Composition for forming silicon-containing resist underlayer film

Abstract

[Problem] To provide a composition for forming a silicon-containing underlayer film, said composition being for forming a silicon-containing resist underlayer film such that it is possible to obtain a good resist pattern without pattern collapse even if the resist underlayer film has a thinner thickness compared to conventional products, such as a film thickness of 10 nm or less. [Solution] This composition for forming a silicon-containing resist underlayer film contains: [A] a polysiloxane whose weight-average molecular weight obtained with polystyrene conversion via gel permeation chromatography (GPC) analysis is 1,800 or less, and whose ratio of molecular weights greater than 2,500 in an integral molecular weight distribution curve obtained with polystyrene conversion via gel permeation chromatography (GPC) analysis is less than 20%; and [B] a solvent.

Description

Silicon-containing resist underlayer film forming composition

[0001] The present invention relates to a composition for forming a resist underlayer film, and provides a composition for forming a silicon-containing resist underlayer film that can form a silicon-containing resist underlayer film having good lithography properties that can suppress pattern collapse and the like, even when used together with a thin resist film or when a thin resist underlayer film is formed and used.

[0002] Conventionally, microfabrication using photoresist has been performed in the manufacture of semiconductor devices by lithography. This microfabrication method involves forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating the photoresist with active light such as ultraviolet light through a mask pattern on which a semiconductor device pattern is drawn, developing the photoresist, and etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities corresponding to the pattern on the substrate surface. As semiconductor devices become increasingly highly integrated, the active light used tends to be shorter in wavelength, from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). Furthermore, exposure techniques using EUV (extreme ultraviolet) and electron beams are being considered. As the wavelength of actinic rays becomes shorter, the influence of reflection of actinic rays from semiconductor substrates becomes a major problem, and a method of providing a resist underlayer film called an anti-reflective coating (Bottom Anti-Reflective Coating, BARC) between a photoresist and a substrate to be processed has become widely used. As such a resist underlayer film, for example, an underlayer film containing silicon or the like has been proposed (Patent Document 1, etc.).

[0003] With the recent trend toward finer resist patterns in cutting-edge semiconductor devices, the demand for thinner resist films has become more pronounced. In particular, in three-layer processes consisting of a resist film, a silicon-containing resist underlayer film, and an organic underlayer film, not only thinner resist films but also thinner silicon-containing resist underlayer films are required, and good lithography properties are also required for the resist on the silicon-containing resist underlayer film.

[0004] Japanese Patent Application Laid-Open No. 2007-163846

[0005] Due to the further thinning of the resist film and resist underlayer film described above, even in systems that have previously been able to form good resist patterns, pattern collapse and deterioration of pattern shape are now occasionally observed. In recent semiconductor manufacturing processes, where the films used for patterns are becoming significantly thinner, the ability of resist underlayer films to impart good lithography properties is important.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming a silicon-containing resist underlayer film, which is used to form a silicon-containing resist underlayer film that can provide a good resist pattern without pattern collapse, even when the resist underlayer film is thinner than conventional ones, for example, has a film thickness of 10 nm or less.

[0007]

[0003] In a first aspect, the present invention relates to a composition for forming a silicon-containing resist underlayer film, comprising: [A] a polysiloxane having a weight-average molecular weight of 1,800 or less, as determined by gel permeation chromatography (GPC) analysis and calculated as equivalent to polystyrene, and having a proportion of molecular weights exceeding 2,500 of less than 20% in an integrated molecular weight distribution curve, as determined by gel permeation chromatography (GPC) analysis and calculated as equivalent to polystyrene, and [B] a solvent. In a second aspect, the present invention relates to the composition for forming a silicon-containing resist underlayer film according to the first aspect, wherein the polysiloxane [A] is a polysiloxane having a proportion of molecular weights exceeding 2,000 of less than 35% in an integrated molecular weight distribution curve, as determined by gel permeation chromatography (GPC) analysis and calculated as equivalent to polystyrene. In a third aspect, the present invention relates to the composition for forming a silicon-containing resist underlayer film according to the first or second aspect, wherein the polysiloxane [A] has a weight-average molecular weight of 1,100 or more and 1,800 or less.

[0013] As a fourth aspect, the present invention relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to third aspects, which is a composition capable of forming a pattern even with a resist underlayer film having a thickness of 10 nm or less.

[0014] As a fifth aspect, the present invention relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to fourth aspects, in which the polysiloxane [A] comprises at least one selected from the group consisting of a hydrolysis condensate of a hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1), a modified product of the hydrolysis condensate in which at least a portion of the silanol groups of the condensate have been modified with an alcohol, a modified product of the hydrolysis condensate in which at least a portion of the silanol groups of the condensate have been acetal-protected, and a dehydration reaction product of the condensate and an alcohol: (In the formula, R １are groups bonded to a silicon atom, and each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof; R ２ are groups or atoms bonded to a silicon atom and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, and a represents an integer of 0 to 3.) A sixth aspect relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to fifth aspects, which does not contain a curing catalyst. A seventh aspect relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to sixth aspects, in which the solvent [B] contains water. An eighth aspect relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to seventh aspects, which further contains a pH adjuster. A ninth aspect relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to eighth aspects, which contains [C] a glycol compound having a normal boiling point of 230.0°C or higher and represented by the following formula (2): (In the formula, R ３ and R ４each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 3 to 4 carbon atoms, and n represents an integer of 3 or greater.) A tenth aspect relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to ninth aspects, further comprising a surfactant. An eleventh aspect relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to tenth aspects, further comprising a metal oxide. A twelfth aspect relates to the composition for forming a silicon-containing resist underlayer film according to any one of the first to eleventh aspects, which is used for forming a resist underlayer film for EUV lithography. A thirteenth aspect relates to a resist underlayer film that is a cured product of the composition for forming a silicon-containing resist underlayer film according to any one of the first to twelfth aspects. A fourteenth aspect relates to the resist underlayer film according to the thirteenth aspect, which has a film thickness of 10 nm or less.

[0023] A fifteenth aspect relates to a semiconductor processing substrate comprising a semiconductor substrate and the resist underlayer film according to the thirteenth or fourteenth aspect. A sixteenth aspect relates to a method for manufacturing a semiconductor device, the method comprising: forming an organic underlayer film on a substrate; forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film-forming composition according to any one of the first to twelfth aspects; and forming a resist film on the silicon-containing resist underlayer film. A seventeenth aspect relates to the manufacturing method according to the sixteenth aspect, in which the silicon-containing resist underlayer film-forming composition is filtered through a nylon filter. An eighteenth aspect relates to a resist underlayer film obtained by applying the silicon-containing resist underlayer film-forming composition according to any one of the first to twelfth aspects onto a semiconductor substrate and baking the composition.As a nineteenth aspect, the present invention relates to a method for manufacturing a semiconductor device, the method including the steps of: applying the silicon-containing resist underlayer film-forming composition according to any one of the first to twelfth aspects onto a semiconductor substrate and baking the composition to form a resist underlayer film; applying a resist film-forming composition onto the underlayer film to form a resist film; exposing the resist film; developing the resist after exposure to obtain a resist pattern; etching the resist underlayer film using the resist pattern; and processing a semiconductor substrate using the patterned resist underlayer film. As a twentieth aspect, the present invention relates to a method for manufacturing a semiconductor device, the method including the steps of: forming an organic underlayer film on a semiconductor substrate; applying the composition for forming a resist underlayer film according to any one of the first to twelfth aspects thereon and baking the composition; forming a resist underlayer film by applying a composition for forming a resist film on the resist underlayer film to form a resist film; exposing the resist film; developing the resist after exposure to light to obtain a resist pattern; etching the resist underlayer film using the resist pattern; etching the organic underlayer film using the patterned resist underlayer film; and processing a semiconductor substrate using the patterned organic underlayer film.

[0008] According to the present invention, it is possible to provide a composition for forming a silicon-containing resist underlayer film, which is capable of forming a silicon-containing resist underlayer film that can provide a good resist pattern without pattern collapse even when the film thickness is 10 nm or less. Furthermore, according to the present invention, it is possible to provide a composition for forming a silicon-containing resist underlayer film that can be suitably used in lithography processes that require further thinning and miniaturization.

[0009] The present invention relates to a composition for forming a silicon-containing resist underlayer film, which is capable of preventing collapse of a resist pattern that accompanies thinning of a semiconductor system, and relates to a composition for forming a silicon-containing resist underlayer film (hereinafter also simply referred to as a "composition for forming a resist underlayer film"), which comprises [A] a polysiloxane having a specific molecular weight and [B] a solvent. The present invention will be described in detail below.

[0010] [A] Polysiloxane In the present invention, the structure of the polysiloxane [A] is not particularly limited as long as it is a polymer having a siloxane bond.

[0011] The polysiloxane [A] of the present invention is a polysiloxane having a weight-average molecular weight of 1,800 or less, as determined by gel permeation chromatography (GPC) analysis and converted into polystyrene. For example, in one embodiment, a polysiloxane having a weight-average molecular weight of 1,100 to 1,800 can be used. Furthermore, the polysiloxane [A] of the present invention is a polysiloxane having a molecular weight exceeding 2,500 in an integrated molecular weight distribution curve determined by gel permeation chromatography (GPC) analysis and converted into polystyrene, with the proportion of molecular weights exceeding 2,500 being less than 20%. For example, in one embodiment, a polysiloxane having a molecular weight of 2,000 or more in an integrated molecular weight distribution curve with the proportion of molecular weights of 2,000 or more being less than 35% can be used. Furthermore, for example, a polysiloxane having a molecular weight of 1,800 or less in an integrated molecular weight distribution curve with the proportion of molecular weights of 1,400 or less in an integrated molecular weight distribution curve with the proportion of molecular weights of 1,800 or less being 60% or more, or a proportion of molecular weights of 1,400 or less being 40% or more can be used. The polydispersity index Mw / Mn of the polysiloxane [A] can be, for example, less than 1.30. The composition for forming a silicon-containing resist underlayer film of the present invention is characterized by using a so-called low-molecular-weight polysiloxane having a weight-average molecular weight of 1,800 or less, as described above, in which the proportion of polysiloxanes having molecular weights exceeding 2,500 is suppressed. The use of such a low-molecular-weight polysiloxane allows for the formation of a composition capable of forming a silicon-containing resist underlayer film that can prevent the collapse of a resist pattern that can occur when a resist film or the like is thinned. For example, the composition for forming a silicon-containing resist underlayer film of the present invention is a resist underlayer film-forming composition that can suppress pattern defects such as pattern peeling, pattern collapse, and contact between patterns in an upper resist pattern, even when used as a resist underlayer film having a thickness of 10 nm or less, and can form a pattern with a good shape.

[0012] The polysiloxane may include a modified polysiloxane in which some of the silanol groups have been modified, such as a polysiloxane modified product in which some of the silanol groups have been alcohol-modified or acetal-protected. The polysiloxane may also include, for example, a hydrolysis condensation product of a hydrolyzable silane, and may include a modified polysiloxane in which at least some of the silanol groups of the hydrolysis condensation product have been alcohol-modified or acetal-protected. The hydrolyzable silane in the hydrolysis condensation product may include one or more hydrolyzable silanes. The polysiloxane may have a cage-type, ladder-type, linear-type, or branched-type main chain structure. Furthermore, commercially available polysiloxanes may be used as the polysiloxane.

[0013] In the present invention, the "hydrolyzed condensate" of the hydrolyzable silane, i.e., the product of hydrolysis and condensation, includes not only polyorganosiloxane polymers that are condensates in which condensation has been completely completed, but also polyorganosiloxane polymers that are partial hydrolyzed condensates in which condensation has not been completely completed. Like the condensates in which condensation has been completely completed, such partial hydrolyzed condensates are polymers obtained by the hydrolysis and condensation of a hydrolyzable silane compound, but they are partially hydrolyzed and not condensed, and therefore Si—OH groups remain. Furthermore, in addition to the hydrolyzed condensate, the composition for forming a silicon-containing resist underlayer film of the present invention may also contain uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and monomers (hydrolyzable silane compounds). In this specification, "hydrolyzable silane" may also be simply referred to as "silane compounds."

[0014] The polysiloxane (A) may be, for example, a hydrolysis condensate of hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1).

[0015] In formula (1), R １are groups bonded to a silicon atom, and each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof. ２ are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, and a represents an integer of 0 to 3.

[0016] In the above formula (1), examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-butyl ... Examples of such groups include 1-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group.

[0017] Cyclic alkyl groups can also be used, and examples of cyclic alkyl groups having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethyl cycloalkyl groups such as 1-n-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclopropyl group; and bridged ring cycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group and bicyclodecyl group.

[0018] The aryl group may be any of a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused-ring aromatic hydrocarbon compound, and a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound, and the number of carbon atoms therein is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. For example, the aryl group may be an aryl group having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-naphthacenyl group, a 2-naphthacenyl group, a 5-naphthacenyl group, a 2-chrysenyl group, a 1-pyrenyl group, and a 2-pyrenyl group. , pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group (o-biphenylyl group), biphenyl-3-yl group (m-biphenylyl group), biphenyl-4-yl group (p-biphenylyl group), para-terphenyl-4-yl group, meta-terphenyl-4-yl group, ortho-terphenyl-4-yl group, 1,1'-binaphthyl-2-yl group, 2,2'-binaphthyl-1-yl group and the like, but are not limited to these.

[0019] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups include those described above. The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aralkyl groups include, but are not limited to, a phenylmethyl group (benzyl group), a 2-phenylethylene group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, a 6-phenyl-n-hexyl group, a 7-phenyl-n-heptyl group, an 8-phenyl-n-octyl group, a 9-phenyl-n-nonyl group, and a 10-phenyl-n-decyl group.

[0020] The halogenated alkyl group, halogenated aryl group, and halogenated aralkyl group are alkyl groups, aryl groups, and aralkyl groups substituted with one or more halogen atoms, and specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those mentioned above. Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0021] The number of carbon atoms in the halogenated alkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropan-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group, but are not limited to these.

[0022] The number of carbon atoms in the halogenated aryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of the halogenated aryl group include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,5-trifluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,3,4,5-tetrafluorophenyl group, a 2,3,4,6-tetrafluorophenyl group, a 2,3,5,6-tetrafluorophenyl group, a pentafluorophenyl group, a 2-fluoro-1-naphthyl group, a 3-fluorophenyl group, a 2-fluoro-1-naphthyl ... Examples of the fluorocarbon include 1-naphthyl, 4-fluoro-1-naphthyl, 6-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8-difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, heptafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, and heptafluoro-2-naphthyl. Examples of the fluorocarbon include, but are not limited to, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group).

[0023] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of the halogenated aralkyl group include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,5-trifluorobenzyl group, 2,6 ... Examples of the fluorobenzyl group include a 2,4,6-trifluorobenzyl group, a 2,3,4,5-tetrafluorobenzyl group, a 2,3,4,6-tetrafluorobenzyl group, a 2,3,5,6-tetrafluorobenzyl group, and a 2,3,4,5,6-pentafluorobenzyl group, and also include groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group), but are not limited to these.

[0024] The alkoxyalkyl group, alkoxyaryl group, and alkoxyaralkyl group are alkyl groups, aryl groups, and aralkyl groups substituted with one or more alkoxy groups, and specific examples of such alkyl groups, aryl groups, and aralkyl groups include the same as those described above.

[0025] Examples of the alkoxy group include alkoxy groups having a straight-chain, branched, or cyclic alkyl moiety and having 1 to 20 carbon atoms. Examples of the straight-chain or branched alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, a n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 2-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 2-methyl-n-but ... Examples include a methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.Examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methylcyclopropoxy, 2-methylcyclopropoxy, cyclopentyloxy, 1-methylcyclobutoxy, 2-methylcyclobutoxy, 3-methylcyclobutoxy, 1,2-dimethylcyclopropoxy, 2,3-dimethylcyclopropoxy, 1-ethylcyclopropoxy, 2-ethylcyclopropoxy, cyclohexyloxy, 1-methylcyclopentyloxy, 2-methylcyclopentyloxy, 3-methylcyclopentyloxy, 1-ethylcyclobutoxy, 2-ethylcyclobutoxy, 3-ethylcyclobutoxy, 1,2-dimethylcyclobutoxy, 1,3 dimethylcyclobutoxy group, 2,2-dimethylcyclobutoxy group, 2,3-dimethylcyclobutoxy group, 2,4-dimethylcyclobutoxy group, 3,3-dimethylcyclobutoxy group, 1-n-propylcyclopropoxy group, 2-n-propylcyclopropoxy group, 1-i-propylcyclopropoxy group, 2-i-propylcyclopropoxy group, 1,2,2-trimethylcyclopropoxy group, 1,2,3-trimethylcyclopropoxy group, 2,2,3-trimethylcyclopropoxy group, 1-ethyl-2-methylcyclopropoxy group, 2-ethyl-1-methylcyclopropoxy group, 2-ethyl-2-methylcyclopropoxy group, and 2-ethyl-3-methylcyclopropoxy group.

[0026] Specific examples of the alkoxyalkyl group include, but are not limited to, lower (having about 5 or less carbon atoms) alkyloxy-lower (having about 5 or less carbon atoms) alkyl groups such as a methoxymethyl group, an ethoxymethyl group, a 1-ethoxyethyl group, a 2-ethoxyethyl group, and an ethoxymethyl group. Specific examples of the alkoxyaryl group include, but are not limited to, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-(1-ethoxy)phenyl group, a 3-(1-ethoxy)phenyl group, a 4-(1-ethoxy)phenyl group, a 2-(2-ethoxy)phenyl group, a 3-(2-ethoxy)phenyl group, a 4-(2-ethoxy)phenyl group, a 2-methoxynaphthalen-1-yl group, a 3-methoxynaphthalen-1-yl group, a 4-methoxynaphthalen-1-yl group, a 5-methoxynaphthalen-1-yl group, a 6-methoxynaphthalen-1-yl group, and a 7-methoxynaphthalen-1-yl group. Specific examples of the alkoxyaralkyl group include, but are not limited to, a 3-(methoxyphenyl)benzyl group and a 4-(methoxyphenyl)benzyl group.

[0027] The alkenyl group includes alkenyl groups having 2 to 10 carbon atoms, such as ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group xenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2- propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl- Examples include a 2-propenyl group, a 1-methyl-2-cyclopentenyl group, a 1-methyl-3-cyclopentenyl group, a 2-methyl-1-cyclopentenyl group, a 2-methyl-2-cyclopentenyl group, a 2-methyl-3-cyclopentenyl group, a 2-methyl-4-cyclopentenyl group, a 2-methyl-5-cyclopentenyl group, a 2-methylene-cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group, and also include bridged cyclic alkenyl groups such as a bicycloheptenyl group (norbornyl group).

[0028] Furthermore, examples of the substituents in the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group include alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, alkoxy group, and aralkyloxy group. Specific examples and their preferred numbers of carbon atoms are the same as those described above or below. The aryloxy group exemplified as the substituent is a group in which an aryl group is bonded via an oxygen atom (—O—). Specific examples of such aryl groups are the same as those described above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include, but are not limited to, a phenoxy group and a naphthalene-2-yloxy group. Furthermore, when two or more substituents are present, the substituents may be bonded to each other to form a ring.

[0029] Examples of the organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group. Examples of the organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group. Examples of the organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group. Examples of the organic group having a mercapto group include an ethylmercapto group, a butylmercapto group, a hexylmercapto group, an octylmercapto group, and a mercaptophenyl group. Examples of the organic group containing an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group. Examples of the organic group containing an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group. However, groups in which an alkoxy group is directly bonded to a silicon atom are excluded. Examples of the organic group containing a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group. Examples of the organic group containing a cyano group include a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, and a thiocyanate group.

[0030] The aralkyloxy group is a group derived by removing a hydrogen atom from the hydroxy group of an aralkyl alcohol, and specific examples of such aralkyl groups include those described above. The number of carbon atoms in the aralkyloxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less. Specific examples of the aralkyloxy group include, but are not limited to, a phenylmethyloxy group (benzyloxy group), a 2-phenylethyleneoxy group, a 3-phenyl-n-propyloxy group, a 4-phenyl-n-butyloxy group, a 5-phenyl-n-pentyloxy group, a 6-phenyl-n-hexyloxy group, a 7-phenyl-n-heptyloxy group, an 8-phenyl-n-octyloxy group, a 9-phenyl-n-nonyloxy group, and a 10-phenyl-n-decyloxy group.

[0031] An acyloxy group is a group derived by removing a hydrogen atom from a carboxyl group (—COOH) of a carboxylic acid compound, and typical examples include, but are not limited to, alkylcarbonyloxy groups, arylcarbonyloxy groups, and aralkylcarbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of an alkylcarboxylic acid, arylcarboxylic acid, or aralkylcarboxylic acid. Specific examples of the alkyl group, aryl group, and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid, and aralkylcarboxylic acid are the same as those described above.Specific examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentyl ... Examples thereof include a methylcarbonyloxy group, a 3-methyl-n-pentylcarbonyloxy group, a 4-methyl-n-pentylcarbonyloxy group, a 1,1-dimethyl-n-butylcarbonyloxy group, a 1,2-dimethyl-n-butylcarbonyloxy group, a 1,3-dimethyl-n-butylcarbonyloxy group, a 2,2-dimethyl-n-butylcarbonyloxy group, a 2,3-dimethyl-n-butylcarbonyloxy group, a 3,3-dimethyl-n-butylcarbonyloxy group, a 1-ethyl-n-butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxy group, a 1,1,2-trimethyl-n-propylcarbonyloxy group, a 1,2,2-trimethyl-n-propylcarbonyloxy group, a 1-ethyl-1-methyl-n-propylcarbonyloxy group, a 1-ethyl-2-methyl-n-propylcarbonyloxy group, a phenylcarbonyloxy group, and a tosylcarbonyloxy group.

[0032] Specific examples of the hydrolyzable silane represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, and methyltriphenoxysilane. Netyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxysilane (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane Silane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane Glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimeth silane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiacetoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane,Allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane , phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 3-phenyl aminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane Sisilane, phenethyltrichlorosilane, phenethyltriacetoxysilane, phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane,Methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, i-propoxyphenyltrimethoxysilane, i-propoxy i-Propoxyphenyltriethoxysilane, i-Propoxyphenyltriacetoxysilane, i-Propoxyphenyltrichlorosilane, i-Propoxybenzyltrimethoxysilane, i-Propoxybenzyltriethoxysilane, i-Propoxybenzyltriacetoxysilane, i-Propoxybenzyltrichlorosilane, t-Butoxyphenyltrimethoxysilane, t-Butoxyphenyltriethoxysilane, t-Butoxyphenyltriacetoxysilane, t-Butoxyphenyltrichlorosilane, t-Butoxybenzyltrimethoxysilane, t-Butoxyphenyltrimethoxysilane, Benzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltrichlorosilane triacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanatepropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane,Examples of the silane include, but are not limited to, benzenesulfonamidopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and silanes represented by the following formulas (A-1) to (A-41).

[0033]

[0034]

[0035]

[0036] Further, examples of the polysiloxane (A) include hydrolysis condensates of hydrolyzable silanes containing a hydrolyzable silane represented by the following formula (3) in addition to or instead of the hydrolyzable silane represented by formula (1):

[0037] In formula (3), R ５ are groups bonded to a silicon atom, and each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof. ６are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. ７ are groups bonded to a silicon atom and each independently represent an alkylene group or an arylene group, b represents an integer of 0 or 1, and c represents an integer of 0 or 1.

[0038] The above R ５ Specific examples of each group in the above and their preferred numbers of carbon atoms include R １ The groups and carbon atom numbers described above for the above R ６ Specific examples of the groups and atoms in the above and their preferred numbers of carbon atoms include R ２ The groups, atoms, and number of carbon atoms mentioned above for R ７Specific examples of the alkylene group in the formula (I) include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; and alkylene groups such as methanetriyl, ethane-1,1,2-triyl, ethane-1,2,2-triyl, and ethane- Examples of alkanetriyl groups include, but are not limited to, a 2,2,2-triyl group, a propane-1,1,1-triyl group, a propane-1,1,2-triyl group, a propane-1,2,3-triyl group, a propane-1,2,2-triyl group, a propane-1,1,3-triyl group, a butane-1,1,1-triyl group, a butane-1,1,2-triyl group, a butane-1,1,3-triyl group, a butane-1,2,3-triyl group, a butane-1,2,4-triyl group, a butane-1,2,2-triyl group, a butane-2,2,3-triyl group, a 2-methylpropane-1,1,1-triyl group, a 2-methylpropane-1,1,2-triyl group, and a 2-methylpropane-1,1,3-triyl group.Specific examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group; a 1,5-naphthalenediyl group, a 1,8-naphthalenediyl group, a 2,6-naphthalenediyl group, a 2,7-naphthalenediyl group, a 1,2-anthracenediyl group, a 1,3-anthracenediyl group, a 1,4-anthracenediyl group, a 1,5-anthracenediyl group, a 1,6-anthracenediyl group, a 1,7-anthracenediyl group, a 1,8-anthracenediyl group, a 2,3-anthracenediyl group, Examples of the fused ring aromatic hydrocarbon compound include, but are not limited to, groups derived by removing two hydrogen atoms on the aromatic ring of a fused ring aromatic hydrocarbon compound such as a 2,6-anthracenediyl group, a 2,7-anthracenediyl group, a 2,9-anthracenediyl group, a 2,10-anthracenediyl group, or a 9,10-anthracenediyl group; and groups derived by removing two hydrogen atoms on the aromatic ring of a ring-linked aromatic hydrocarbon compound such as a 4,4'-biphenyldiyl group or a 4,4"-paraterphenyldiyl group. Furthermore, b preferably represents 0 or 1, and more preferably 0. Furthermore, c is preferably 1.

[0039] Specific examples of the hydrolyzable silane represented by formula (3) include, but are not limited to, methylene bistrimethoxysilane, methylene bistrichlorosilane, methylene bistriacetoxysilane, ethylene bistriethoxysilane, ethylene bistrichlorosilane, ethylene bistriacetoxysilane, propylene bistriethoxysilane, butylene bistrimethoxysilane, phenylene bistrimethoxysilane, phenylene bistriethoxysilane, phenylene bismethyldiethoxysilane, phenylene bismethyldimethoxysilane, naphthylene bistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, and bismethyldimethoxydisilane.

[0040] Furthermore, examples of the polysiloxane (A) include hydrolysis condensates of hydrolyzable silanes containing the hydrolyzable silane represented by formula (1) and / or the hydrolyzable silane represented by formula (3) as well as other hydrolyzable silanes listed below. Examples of other hydrolyzable silanes include, but are not limited to, silane compounds having an onium group in the molecule, silane compounds having a sulfone group, silane compounds having a sulfonamide group, and silane compounds having a cyclic urea skeleton in the molecule.

[0041] <Silane Compound Having an Onium Group in the Molecule (Hydrolyzable Organosilane)> A silane compound having an onium group in the molecule is expected to be able to effectively and efficiently promote the crosslinking reaction of a hydrolyzable silane.

[0042] A suitable example of the silane compound having an onium group in the molecule is represented by formula (4). R １１ R is a group bonded to a silicon atom and represents an onium group or an organic group containing an onium group. １２ are groups bonded to silicon atoms, and each independently represent an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, or a combination thereof. １３ are groups or atoms bonded to a silicon atom, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, f represents 1 or 2, and g represents 0 or 1, and 1≦f+g≦2 is satisfied.

[0043] Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, and organic groups containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, an alkoxy group, an aralkyloxy group, an acyloxy group, and a halogen atom; and specific examples of the substituents of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group, and their preferred numbers of carbon atoms, include R １２ Regarding R １ The above with respect to R １３ Regarding R ２ Regarding the above, each of the above can be mentioned.

[0044] More specifically, specific examples of the onium group include a cyclic ammonium group or a chain ammonium group, with a tertiary ammonium group or a quaternary ammonium group being preferred. That is, suitable specific examples of the onium group or the organic group containing it include a cyclic ammonium group or a chain ammonium group, or an organic group containing at least one of these, with a tertiary ammonium group or a quaternary ammonium group or an organic group containing at least one of these being preferred. Note that when the onium group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. In this case, there are cases where the nitrogen atom constituting the ring and the silicon atom are bonded directly or via a divalent linking group, and cases where the carbon atom constituting the ring and the silicon atom are bonded directly or via a divalent linking group.

[0045] In one preferred embodiment of the present invention, R １１ is a heteroaromatic cyclic ammonium group represented by the following formula (S1).

[0046] In formula (S1), A １ , A ２ , A ３ and A４ are each independently a group represented by any one of the following formulas (J1) to (J3), １ ~A ４ At least one of the silicon atoms in the above formula (4) is a group represented by the following formula (J2): １ ~A ４ A is bonded to the ring so that the resulting ring exhibits aromaticity. １ ~A ４ It is determined whether the bond between each of them and the adjacent atom that together constitutes the ring is a single bond or a double bond.

[0047] In formulas (J1) to (J3), R １０ are each independently a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, or an alkenyl group, and specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, and alkenyl group and suitable numbers of carbon atoms therefor are the same as those described above.

[0048] In formula (S1), R １４ each independently represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, or a hydroxy group; R １４ If there are two or more R １４ may be bonded to each other to form a ring, and two R １４ The ring formed by may be a bridged ring structure, and in such a case, the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, etc. Specific examples of such alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, and alkenyl groups, and suitable numbers of carbon atoms therefor, are the same as those described above.

[0049] In formula (S1), n １ is an integer from 1 to 8, and m １ is 0 or 1, m２ is a positive integer from 0 or 1 to the maximum number of substitutions possible on a monocyclic or polycyclic ring. １ If is 0, A １ ~A ４ (4+n １ That is, an n-membered ring is formed. １ is 1, a five-membered ring; １ is 2, a 6-membered ring, １ is 3, a 7-membered ring, １ When n is 4, it is an 8-membered ring. １ is 5, a 9-membered ring; １ When n is 6, it is a 10-membered ring. １ When n is 7, it is an 11-membered ring. １ When m is 8, a 12-membered ring is formed. １ If is 1, then A １ ~A ３ (4+n １ )-membered ring and A ４ A fused ring is formed by condensing with a 6-membered ring containing A. １ ~A ４ may or may not have a hydrogen atom on an atom constituting the ring, depending on which of formulas (J1) to (J3) it is, １ ~A ４ has a hydrogen atom on an atom constituting the ring, the hydrogen atom is １４ Also, A may be replaced by １ ~A ４ A ring-constituting atom other than the ring-constituting atom in １４ For this reason, as described above, m ２ is selected from 0 or an integer from 1 to the maximum number of substitutions possible on a monocyclic or polycyclic ring.

[0050] The bond of the heteroaromatic cyclic ammonium group represented by the formula (S1) is present on any carbon atom or nitrogen atom present in such a single ring or fused ring, and is directly bonded to a silicon atom, or a linking group is bonded to form an organic group containing cyclic ammonium, which is then bonded to a silicon atom.Such linking groups include, but are not limited to, alkylene groups, arylene groups, alkenylene groups, etc.Specific examples of alkylene groups and arylene groups and their preferred carbon atom numbers are the same as those described above.

[0051] An alkenylene group is a divalent group derived by removing one more hydrogen atom from an alkenyl group, and specific examples of such alkenyl groups include those described above. The number of carbon atoms in the alkenylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include, but are not limited to, vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, and 2-pentenylene groups.

[0052] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (4) having the heteroaromatic cyclic ammonium group represented by formula (S1) above include, but are not limited to, silanes represented by formulas (I-1) to (I-50) below.

[0053] In another example, R １１ can be a heteroaliphatic cyclic ammonium group represented by the following formula (S2):

[0054] In formula (S2), A ５ , A ６ , A ７ and A ８ are each independently a group represented by any one of the following formulas (J4) to (J6), ５ ~A ８At least one of the silicon atoms in the formula (4) is a group represented by the following formula (J5): ５ ~A ８ A is bonded to the ring so that the resulting ring exhibits non-aromaticity. ５ ~A ８ It is determined whether the bond between each of them and the adjacent atom that together constitutes the ring is a single bond or a double bond.

[0055] In formulas (J4) to (J6), R １０ are each independently a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, or an alkenyl group, and specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, and alkenyl group and suitable numbers of carbon atoms therefor are the same as those described above.

[0056] In formula (S2), R １５ each independently represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, or a hydroxy group; R １５ If there are two or more R １５ may be bonded to each other to form a ring, and two R １５ The ring formed by may be a bridged ring structure, and in such a case, the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, etc. Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group and alkenyl group and suitable numbers of carbon atoms therefor are the same as those described above.

[0057] In formula (S2), n ２ is an integer from 1 to 8, and m ３ is 0 or 1, m ４ is a positive integer from 0 or 1 to the maximum number of substitutions possible on a monocyclic or polycyclic ring. ３ If is 0, A５ ~A ８ (4+n ２ That is, an n-membered ring is formed. ２ is 1, a five-membered ring; ２ is 2, a 6-membered ring, ２ is 3, a 7-membered ring, ２ When n is 4, it is an 8-membered ring. ２ is 5, a 9-membered ring; ２ When n is 6, it is a 10-membered ring. ２ When n is 7, it is an 11-membered ring. ２ When m is 8, a 12-membered ring is formed. ３ If is 1, then A ５ ~A ７ (4+n ２ )-membered ring and A ８ A fused ring is formed by condensing with a 6-membered ring containing A. ５ ~A ８ may or may not have a hydrogen atom on an atom constituting the ring, depending on which of formulas (J4) to (J6) it is. ５ ~A ８ has a hydrogen atom on an atom constituting the ring, the hydrogen atom is １５ Also, A may be replaced by ５ ~A ８ A ring-constituting atom other than the ring-constituting atom in １５ For this reason, as described above, m ４ is selected from 0 or an integer from 1 to the maximum number of substitutions possible on a monocyclic or polycyclic ring.

[0058] The bond of the heteroaliphatic cyclic ammonium group represented by the above formula (S2) is present on any carbon atom or nitrogen atom present in such a single ring or fused ring, and is directly bonded to a silicon atom, or is bonded to a linking group to form an organic group containing cyclic ammonium, which is then bonded to a silicon atom. Examples of such linking groups include alkylene groups, arylene groups, and alkenylene groups, and specific examples of the alkylene groups, arylene groups, and alkenylene groups and their preferred numbers of carbon atoms are the same as those described above.

[0059] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (4) having the heteroaliphatic cyclic ammonium group represented by formula (S2) above include, but are not limited to, silanes represented by formulas (II-1) to (II-30) below.

[0060] In yet another example, R １１ can be a chain ammonium group represented by the following formula (S3).

[0061] In formula (S3), R １０ are each independently a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, or an alkenyl group, and specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, and alkenyl group and suitable numbers of carbon atoms therefor are the same as those described above.

[0062] The chain ammonium group represented by formula (S3) is directly bonded to a silicon atom, or is bonded to a linking group to form an organic group containing the chain ammonium group, which is then bonded to a silicon atom. Examples of such linking groups include alkylene groups, arylene groups, and alkenylene groups, and specific examples of the alkylene groups, arylene groups, and alkenylene groups are the same as those described above.

[0063] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (4) having a chain ammonium group represented by formula (S3) above include, but are not limited to, silanes represented by formulas (III-1) to (III-28) below.

[0064] <Silane Compound Having a Sulfone Group or a Sulfonamide Group (Hydrolyzable Organosilane)> Examples of silane compounds having a sulfone group and silane compounds having a sulfonamide group include, but are not limited to, compounds represented by the following formulas (B-1) to (B-36): In the following formulas, Me represents a methyl group, and Et represents an ethyl group.

[0065]

[0066] <Silane Compound Having a Cyclic Urea Skeleton in the Molecule (Hydrolyzable Organosilane)> Examples of hydrolyzable organosilanes having a cyclic urea skeleton in the molecule include hydrolyzable organosilanes represented by the following formula (5-1).

[0067]

[0068] In formula (5-1), R ５０１ are groups bonded to silicon atoms, and each independently represents a group represented by the following formula (5-2): ５０２ are groups bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group. ５０３ are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. x is 1 or 2, and y is 0 or 1, and x + y ≦ 2 is satisfied. ５０２alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, and organic groups containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, as well as R ５０３ Specific examples of the alkoxy group, aralkyloxy group, acyloxy group and halogen atom, as well as the preferred number of carbon atoms of these substituents, are given in R １ and R ２ The same factors as those mentioned above can be mentioned.

[0069]

[0070] In formula (5-2), R ５０４ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy group or a sulfonyl group; R ５０５ are each independently an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-), or an ester bond (-CO-O- or -O-CO-). ５０４ Specific examples of the organic group including the optionally substituted alkyl group, the optionally substituted alkenyl group, and the epoxy group, and the preferred number of carbon atoms, etc. are given in R １ The same as those mentioned above can be mentioned with respect to R ５０４ The optionally substituted alkyl group is preferably an alkyl group in which a terminal hydrogen atom is substituted with a vinyl group, and specific examples thereof include an allyl group, a 2-vinylethyl group, a 3-vinylpropyl group, and a 4-vinylbutyl group.

[0071] The organic group containing a sulfonyl group is not particularly limited as long as it contains a sulfonyl group, and examples thereof include an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted aralkylsulfonyl group, an optionally substituted halogenated alkylsulfonyl group, an optionally substituted halogenated arylsulfonyl group, an optionally substituted halogenated aralkylsulfonyl group, an optionally substituted alkoxyalkylsulfonyl group, an optionally substituted alkoxyarylsulfonyl group, an optionally substituted alkoxyaralkylsulfonyl group, an optionally substituted alkenylsulfonyl group, etc. Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group in these groups, as well as preferred numbers of carbon atoms, etc. are described in R １ The same factors as those mentioned above can be mentioned.

[0072] R ５０５ The alkylene group is a divalent group derived by removing one more hydrogen atom from the alkyl group, and may be linear, branched, or cyclic. Specific examples of such alkylene groups include those mentioned above. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0073] Also, R ５０５The alkylene group may have one or more bonds selected from a sulfide bond, an ether bond and an ester bond at its terminal or in the middle, preferably in the middle. Specific examples of the alkylene group include linear alkylene groups such as methylene, ethylene, trimethylene, methylethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkylene groups such as 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl; and -CH ２ OCH ２ -, -CH ２ CH ２ OCH ２ -, -CH ２ CH ２ OCH ２ CH ２ -, -CH ２ CH ２ CH ２ OCH ２ CH ２ -, -CH ２ CH ２ OCH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ OCH ２ CH ２ CH ２ -, -CH ２ SCH ２ -, -CH ２ CH ２ SCH ２ -, -CH ２ CH ２ SCH ２ CH ２ -, -CH ２ CH ２ CH２ SCH ２ CH ２ -, -CH ２ CH ２ SCH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ SCH ２ CH ２ CH ２ -, -CH ２ OCH ２ CH ２ SCH ２ Examples of alkylene groups include, but are not limited to, alkylene groups containing ether groups such as -.

[0074] The hydroxyalkylene group is an alkylene group in which at least one hydrogen atom has been replaced with a hydroxy group. Specific examples thereof include, but are not limited to, a hydroxymethylene group, a 1-hydroxyethylene group, a 2-hydroxyethylene group, a 1,2-dihydroxyethylene group, a 1-hydroxytrimethylene group, a 2-hydroxytrimethylene group, a 3-hydroxytrimethylene group, a 1-hydroxytetramethylene group, a 2-hydroxytetramethylene group, a 3-hydroxytetramethylene group, a 4-hydroxytetramethylene group, a 1,2-dihydroxytetramethylene group, a 1,3-dihydroxytetramethylene group, a 1,4-dihydroxytetramethylene group, a 2,3-dihydroxytetramethylene group, a 2,4-dihydroxytetramethylene group, and a 4,4-dihydroxytetramethylene group.

[0075] In formula (5-2), X ５０１ each independently represents any one of the groups represented by the following formulas (5-3) to (5-5), and the carbon atom of the ketone group in the following formulas (5-4) and (5-5) is R ５０５ It bonds to the nitrogen atom to which it is bonded.

[0076]

[0077] In formulas (5-3) to (5-5), R ５０６ ~R ５１０are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy group or a sulfonyl group. Specific examples of the optionally substituted alkyl group, the optionally substituted alkenyl group, and the organic group containing an epoxy group or a sulfonyl group, as well as suitable numbers of carbon atoms, etc., are given in R ５０４ Among them, from the viewpoint of realizing excellent lithography characteristics with good reproducibility, X ５０１ is preferably a group represented by formula (5-5).

[0078] From the viewpoint of realizing excellent lithography characteristics with good reproducibility, R ５０４ and R ５０６ ~R ５１０ At least one of the groups is preferably an alkyl group in which a terminal hydrogen atom is substituted with a vinyl group.

[0079] The hydrolyzable organosilane represented by the above formula (5-1) may be a commercially available product, or may be synthesized by a known method described in, for example, WO 2011 / 102470.

[0080] Specific examples of the hydrolyzable organosilane represented by formula (5-1) include, but are not limited to, silanes represented by the following formulas (5-1-1) to (5-1-29).

[0081] The polysiloxane (A) may be a hydrolysis condensate of a hydrolyzable silane containing a silane compound other than those exemplified above, as long as the effects of the present invention are not impaired.

[0082] As described above, the polysiloxane (A) can be a modified polysiloxane in which at least a portion of the silanol groups have been modified. For example, a polysiloxane modified product in which a portion of the silanol groups have been modified with alcohol or a polysiloxane modified product in which the silanol groups have been protected with acetal can be used. Examples of the modified polysiloxane include a reaction product obtained by reacting at least a portion of the silanol groups of the hydrolysis condensate of the hydrolyzable silane with hydroxy groups of an alcohol, a dehydration reaction product of the condensate with an alcohol, and a modified product in which at least a portion of the silanol groups of the condensate have been protected with acetal groups.

[0083] The alcohol may be a monohydric alcohol, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, or the like. Examples of alcohol include 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, and cyclohexanol. Further, for example, alkoxy group-containing alcohols such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used.

[0084] The reaction between the silanol groups of the condensate and the hydroxyl groups of the alcohol can be carried out by contacting the polysiloxane with the alcohol and reacting for 0.1 to 48 hours, for example, 24 hours, at a temperature of 40 to 160° C., for example, 60° C., to obtain a modified polysiloxane in which the silanol groups are capped. In this case, the alcohol capping agent can be used as a solvent in the composition containing the polysiloxane.

[0085] Furthermore, a dehydration reaction product of a polysiloxane formed by the hydrolysis and condensation of the hydrolyzable silane and an alcohol can be produced by reacting the polysiloxane with an alcohol in the presence of an acid catalyst, capping the silanol groups with the alcohol, and removing the water generated by dehydration from the reaction system. The acid can be an organic acid having an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5. Examples of the acid include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, and acetic acid, among which benzoic acid, isobutyric acid, and acetic acid are particularly preferred. Furthermore, the acid can have a boiling point of 70 to 160°C, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. Thus, the acid preferably has an acid dissociation constant (pKa) of 4 to 5 or a boiling point of 70 to 160°C. In other words, either a weak acidity or a strong acidity with a low boiling point can be used. As the acid, any of the properties such as the acid dissociation constant and boiling point can be used.

[0086] The silanol groups in the condensate can be acetal protected using a vinyl ether, for example, a vinyl ether represented by the following formula (6). By this reaction, a partial structure represented by the following formula (7) can be introduced into the polysiloxane. In formula (6), R １ａ , R ２ａ , and R ３ａ each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ４ａ represents an alkyl group having 1 to 10 carbon atoms; R ２ａ and R ４ａ may be bonded to each other to form a ring. Examples of the alkyl group include those mentioned above. In formula (7), R １ ', R ２ ', and R ３ Each of R′ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; ４ ' represents an alkyl group having 1 to 10 carbon atoms; R ２ ' and R ４The * symbols in formula (7) indicate bonds with adjacent atoms. Examples of adjacent atoms include oxygen atoms in siloxane bonds, oxygen atoms in silanol groups, and R in formula (1). １ Examples of the alkyl group include the carbon atoms derived from the following.

[0087] Examples of the vinyl ether represented by the formula (6) include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, and cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, and 2,3-dihydrofuran are preferably used.

[0088] The acetal protection of the silanol groups can be carried out using a polysiloxane, the vinyl ether, and an aprotic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, or 1,4-dioxane, and using a catalyst such as pyridium paratoluenesulfonate, trifluoromethanesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0089] The capping of the silanol groups with an alcohol or the acetal protection may be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane described below.

[0090] In a preferred embodiment of the present invention, the polysiloxane [A] comprises at least one of a hydrolyzed silane hydrolyzed condensate and a modified product thereof, which contains a hydrolyzable silane represented by formula (1), and optionally a hydrolyzable silane represented by formula (3), and other hydrolyzable silanes. In a preferred embodiment, the polysiloxane [A] comprises a dehydration product of the hydrolyzed condensate and an alcohol.

[0091] Generally, the weight-average molecular weight of the hydrolyzed condensate of hydrolyzable silane (which may include modified products) can be, for example, in the range of 500 to 1,000,000. From the viewpoint of suppressing precipitation of the hydrolyzed condensate in the composition, the weight-average molecular weight can be 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving both storage stability and coatability, the weight-average molecular weight can be preferably 700 or more, more preferably 1,000 or more. In particular, in the present invention, from the viewpoint of preventing collapse of the upper layer resist pattern when thinned, the weight-average molecular weight of the polysiloxane [A], i.e., the hydrolyzed condensate of the hydrolyzable silane (which may include modified products), is 1,800 or less, and the proportion of polysiloxanes with a molecular weight exceeding 2,500 is less than 20%. The weight-average molecular weight is the molecular weight obtained by GPC analysis in terms of polystyrene. GPC analysis can be performed using, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation) and a GPC column (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), with a column temperature of 40°C, tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as a standard sample. The percentage of the specific molecular weight mentioned above refers to the percentage in the integrated molecular weight distribution curve obtained in polystyrene equivalent terms by GPC analysis. The weight-average molecular weight of the hydrolysis-condensation product can be adjusted, for example, by the conditions during hydrolysis and condensation of the hydrolyzable silane described below, such as the solvent used and the reaction temperature and time.

[0092] The hydrolysis condensate of hydrolyzed silane can be obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane). The above-mentioned silane compound (hydrolyzable silane) contains an alkoxy group, aralkyloxy group, acyloxy group, or halogen atom directly bonded to a silicon atom, i.e., an alkoxysilyl group, aralkyloxysilyl group, acyloxysilyl group, or halogenated silyl group (hereinafter referred to as a hydrolyzable group). To hydrolyze these hydrolyzable groups, typically 0.1 to 100 moles, for example, 0.5 to 100 moles, and preferably 1 to 10 moles, of water are used per mole of hydrolyzable group. During the hydrolysis and condensation, a hydrolysis catalyst may be used, or the hydrolysis and condensation may be performed without the use of a hydrolysis catalyst, for example, to promote the reaction. When a hydrolysis catalyst is used, typically 0.0001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolysis catalyst can be used per mole of hydrolyzable group. The reaction temperature during hydrolysis and condensation is usually in the range of from room temperature to the reflux temperature of the organic solvent used for hydrolysis at normal pressure, for example, 20 to 110°C, or for example, 20 to 80°C. The hydrolysis may be complete, i.e., all hydrolyzable groups are converted to silanol groups, or partial, i.e., unreacted hydrolyzable groups may remain. Examples of hydrolysis catalysts that can be used during hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0093] Examples of metal chelate compounds as hydrolysis catalysts include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di -i-propoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium, di-sec-butoxy bis(acetylacetonate)titanium, di-t-butoxy bis(acetylacetonate)titanium, monoethoxy tris(acetylacetonate)titanium, mono-n-propoxy tris(acetylacetonate)titanium, mono-i-propoxy tris(acetylacetonate)titanium, mono-n-butoxy tris(acetylacetonate)titanium, mono-sec-butoxy tris(acetylacetonate) titanium acetate), mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethoxy di-n-propoxy bis(ethylacetoacetate) titanium, di-i-propoxy bis(ethylacetoacetate) titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethylacetoacetate) titanium, mono-n-propoxy tris(ethylacetoacetate) titanium, mono-i-propoxy tris(ethylacetoacetate) titanium,Titanium chelate compounds such as mono-n-butoxy tris(ethylacetoacetate)titanium, mono-sec-butoxy tris(ethylacetoacetate)titanium, mono-t-butoxy tris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonate)tris(ethylacetoacetate)titanium, bis(acetylacetonate)bis(ethylacetoacetate)titanium, and tris(acetylacetonate)mono(ethylacetoacetate)titanium; triethoxy mono(acetylacetonate) tri-n-propoxy mono(acetylacetonate) zirconium, tri-i-propoxy mono(acetylacetonate) zirconium, tri-n-butoxy mono(acetylacetonate) zirconium, tri-sec-butoxy mono(acetylacetonate) zirconium, tri-t-butoxy mono(acetylacetonate) zirconium, diethoxy bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium, di-i-propoxy bis(acetylacetonate) zirconium cetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-i-propoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-sec- Butoxy tris(acetylacetonate)zirconium, mono-t-butoxy tris(acetylacetonate)zirconium, tetrakis(acetylacetonate)zirconium, triethoxy mono(ethylacetoacetate)zirconium, tri-n-propoxy mono(ethylacetoacetate)zirconium, tri-i-propoxy mono(ethylacetoacetate)zirconium, tri-n-butoxy mono(ethylacetoacetate)zirconium, tri-sec-butoxy mono(ethylacetoacetate)zirconium,Tri-t-butoxy mono(ethylacetoacetate)zirconium, diethoxy bis(ethylacetoacetate)zirconium, di-n-propoxy bis(ethylacetoacetate)zirconium, di-i-propoxy bis(ethylacetoacetate)zirconium, di-n-butoxy bis(ethylacetoacetate)zirconium, di-sec-butoxy bis(ethylacetoacetate)zirconium, di-t-butoxy bis(ethylacetoacetate)zirconium, monoethoxy tris(ethylacetoacetate)zirconium, mono-n-propoxy tris(ethylacetoacetate)zirconium, mono-i-propoxy tris(ethylacetoacetate)zirconium, mono-n-butoxy Examples of the chelate compounds include, but are not limited to, zirconium chelate compounds such as tris(ethylacetoacetate)zirconium, mono-sec-butoxy tris(ethylacetoacetate)zirconium, mono-t-butoxy tris(ethylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, mono(acetylacetonato)tris(ethylacetoacetate)zirconium, bis(acetylacetonato)bis(ethylacetoacetate)zirconium, and tris(acetylacetonato)mono(ethylacetoacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethylacetoacetate)aluminum.

[0094] Examples of organic acids that can be used as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0095] Examples of inorganic acids that can be used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0096] Examples of organic bases as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0097] Examples of inorganic bases as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like.

[0098] Of these catalysts, metal chelate compounds, organic acids and inorganic acids are preferred, and these may be used alone or in combination of two or more.

[0099] Among these, in the present invention, nitric acid can be preferably used as the hydrolysis catalyst. The use of nitric acid can improve the storage stability of the reaction solution after hydrolysis and condensation, and in particular, can suppress changes in the molecular weight of the hydrolysis condensate. It has been found that the stability of the hydrolysis condensate in a liquid depends on the pH of the solution. As a result of extensive investigation, it has been found that the pH of the solution falls within a stable range when an appropriate amount of nitric acid is used. Furthermore, as described above, nitric acid can also be used when obtaining a modified product of the hydrolysis condensate, for example, when capping silanol groups with an alcohol, and is therefore preferred from the viewpoint of being able to contribute to both the hydrolysis and condensation of hydrolyzable silanes and the alcohol capping of the hydrolysis condensate.

[0100] When carrying out the hydrolysis and condensation, an organic solvent may be used as the solvent, and specific examples thereof include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, Aromatic hydrocarbon solvents such as i-butylbenzene, triethylbenzene, di-i-propylbenzene, and n-amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, and 2-ethylbutanol. alcohol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol monoalcohol-based solvents such as phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol-based solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin;Ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, and ethylene glycol dibutyl ether-based solvents such as ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran;Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol acetate Examples of solvents include, but are not limited to, ester-based solvents such as methyl ether, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglyceride, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more. ;

[0101] After completion of the hydrolysis and condensation reactions, the reaction solution can be used as is or after dilution or concentration, neutralized, and treated with an ion exchange resin to remove the hydrolysis catalyst, such as an acid or a base, used in the hydrolysis and condensation. Before or after such treatment, by-product alcohol and water, the hydrolysis catalyst, etc., can be removed from the reaction solution by vacuum distillation or the like.

[0102] The hydrolysis condensate (hereinafter also referred to as polysiloxane) thus obtained is in the form of a polysiloxane varnish dissolved in an organic solvent, which can be used directly in the preparation of a composition for forming a resist underlayer film, as described below. That is, the reaction solution can be used directly (or diluted) to prepare a composition for forming a resist underlayer film. At this time, the hydrolysis catalyst used in the hydrolysis and condensation, by-products, etc., may remain in the reaction solution as long as the effects of the present invention are not impaired. For example, the hydrolysis catalyst or the nitric acid used in the alcohol capping of silanol groups may remain in the polymer varnish solution at approximately 100 ppm to 5,000 ppm. The resulting polysiloxane varnish may be subjected to solvent substitution or diluted with an appropriate solvent. The resulting polysiloxane varnish can be evaporated to a solids concentration of 100% if its storage stability is not adversely affected. The organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used in the hydrolysis and condensation reaction of the hydrolyzable silane. The dilution solvent is not particularly limited, and one or more kinds may be arbitrarily selected and used.

[0103] [B] Solvent The solvent [B] used in the composition for forming a silicon-containing resist underlayer film of the present invention can be any solvent that can dissolve and mix the polysiloxane [A] and the other components described below. Note that the solvent [B] does not include the glycol compound [C] described below. Furthermore, even when the reaction solution of the polysiloxane [A] is used as is (or diluted) to prepare the composition for forming a resist underlayer film, the solvent used for the hydrolysis and condensation of the polysiloxane does not include the glycol compound [C] described below.

[0104] Specific examples of the solvent [B] include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol (4-methyl-2-pentanol), propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), and propylene glycol monoethyl ether acetate. acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, 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 dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate,Isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, and the solvents can be used alone or in combination of two or more.

[0105] The composition for forming a silicon-containing resist underlayer film of the present invention may contain water as a solvent. When water is contained as a solvent, the content of water can be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total mass of the solvents contained in the composition.

[0106] [C] Glycol Compound The composition for forming a silicon-containing resist underlayer film of the present invention may contain [C] a glycol compound (also referred to as a high-boiling-point glycol compound) having a normal boiling point of 230.0°C or higher and represented by the following general formula (2). In this specification, the term "normal boiling point" refers to the boiling point at 1 atmosphere (101,325 Pa) (Normal Boiling Point, NBP). As described above, in the present invention, the glycol compound [C] does not fall under the category of the solvent [B].

[0107] The glycol compound contributes to suppressing defects caused by fine particles that may occur during the formation of a silicon-containing resist underlayer film by coating the resist underlayer film-forming composition. The coating defects are believed to be caused, among other things, by the evaporation of the solvent contained in the resist underlayer film-forming composition and the generation of fine particles (solids) due to the solidification (condensation, etc.) of polymer components such as polysiloxane contained in the composition. Such solvent evaporation and solid generation can occur not only during storage of the resist underlayer film-forming composition but also during the formation of the resist underlayer film. In other words, in actual resist underlayer film formation processes, coating film formation can be continuously performed using a coating device, and during this process, not only solvent evaporation but also the generation of fine particles can occur within the discharge nozzle of the coating device. The inclusion of the high-boiling-point glycol compound in the silicon-containing resist underlayer film-forming composition improves the stability of the composition within the discharge nozzle of the coating device, preventing the generation of fine particles within the nozzle, thereby suppressing the occurrence of defects in the coating film.

[0108] In formula (2), R ３ and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 3 to 4 carbon atoms, and n represents an integer of 3 or more. ３ may be the same or different.

[0109] The above R ３ and R ４ Examples of the alkyl group having 1 to 4 carbon atoms in the above R include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl; and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and t-butyl. ３ and R ４ Examples of the acyl group having 3 to 4 carbon atoms in R include an ethylcarbonyl group (propionyl group), a propylcarbonyl group (butyryl group), etc. n is an integer of 3 or more, and its upper limit is, for example, 7. ４is preferably an alkyl group having 1 to 4 carbon atoms or an acyl group having 3 to 4 carbon atoms, and R ３ is preferably a hydrogen atom or a methyl group.

[0110] Among the glycol compounds represented by the above formula (2), specific examples of compounds having a standard boiling point of 230.0°C or higher include triethylene glycol (standard boiling point: 276°C), triethylene glycol monomethyl ether (standard boiling point: 248°C), triethylene glycol monoethyl ether (standard boiling point: 255°C), triethylene glycol monobutyl ether (standard boiling point: 271°C), tripropylene glycol monomethyl ether (standard boiling point: 242°C), tetraethylene glycol monomethyl ether (standard boiling point: 325°C), pentaethylene glycol monomethyl ether (standard boiling point: >300°C), and heptaethylene glycol monomethyl ether (standard boiling point: >300°C), but are not limited to these compounds.

[0111] When the glycol compound [C] is used, the blending amount thereof can be less than 1 mass % based on the total mass of the composition for forming a silicon-containing resist underlayer film, and the lower limit thereof can be 0.01 mass %. By blending the glycol compound [C] in the above range, the composition for forming a silicon-containing resist underlayer film of the present invention is suitable because it is expected that the film obtained from the composition will have solvent resistance and will effectively suppress the occurrence of defects.

[0112]

[0049] When the above-described polysiloxane (A) is produced, i.e., when the hydrolyzable silane is hydrolyzed and condensed, an organic solvent corresponding to the glycol compound (C) is used as a solvent, and the reaction solution is used as is for preparing a composition for forming a resist underlayer film, the organic solvent corresponding to the glycol compound (C) remaining in the reaction solution can be included as is as the glycol compound (C).

[0113] [Composition for Forming Silicon-Containing Resist Underlayer Film] The composition for forming a silicon-containing resist underlayer film of the present invention contains the polysiloxane [A] and the solvent [B], and may optionally contain a glycol compound [C], and may further contain other components described below. The concentration of the solids content in the composition for forming a resist underlayer film can be, for example, 0.1 to 50 mass%, 0.1 to 30 mass%, 0.1 to 25 mass%, or 0.5 to 20.0 mass%, relative to the total mass of the composition. The solids content refers to the components of the composition excluding the solvent component [B] and the glycol compound [C]. The content of the polysiloxane [A] in the solids content is usually 20 to 100 mass%, but from the viewpoint of reproducibly achieving the effects of the present invention, the lower limit is preferably 50 mass%, more preferably 60 mass%, even more preferably 70 mass%, and even more preferably 80 mass%, and the upper limit is preferably 99 mass%, with the remainder being the additives described below. The composition for forming a resist underlayer film preferably has a pH of 2 to 5, and more preferably a pH of 3 to 4.

[0114] The resist underlayer film-forming composition can be produced by mixing the polysiloxane [A], the solvent [B], the glycol compound [C], and, if any, other components. In this case, a solution containing the polysiloxane [A] may be prepared in advance, and this solution may be mixed with the solvent [B], the glycol compound [C], and other components. Alternatively, the reaction solution used to prepare the polysiloxane [A] may be used directly to prepare the resist underlayer film-forming composition. In this case, the glycol compound [C] may be added during the production of the polysiloxane. The order of mixing is not particularly limited. For example, the solvent [B] may be added to the solution containing the polysiloxane [A] and mixed, and then the glycol compound [C] and other components may be added to the mixture. Alternatively, the solution containing the polysiloxane [A], the solvent [B], the glycol compound [C], and other components may be mixed simultaneously. If necessary, additional solvent [B] may be added at the end, or some components that are relatively soluble in solvent [B] may be omitted from the mixture and added at the end. However, from the viewpoint of suppressing aggregation or separation of the constituent components and reproducibly preparing a composition with excellent uniformity, it is preferable to prepare a solution in which polysiloxane [A] is well dissolved in advance and use this to prepare the composition. Note that polysiloxane [A] may aggregate or precipitate when mixed with other components, depending on the type and amount of solvent [B] to be mixed with it, as well as the amount and properties of glycol compound [C] and other components. Also, when preparing a composition using a solution in which polysiloxane [A] is dissolved, it is necessary to determine the concentration and amount of polysiloxane [A] solution so that the desired amount of polysiloxane [A] is obtained in the final composition. In preparing the composition, heating may be performed as appropriate within a range that does not cause decomposition or deterioration of the components.

[0115] In the present invention, the composition for forming a resist underlayer film may be filtered using a sub-micrometer filter or the like during the production process of the composition for forming a resist underlayer film or after all of the components have been mixed. The material of the filter used here is not particularly limited, and examples thereof include nylon filters and fluororesin filters.

[0116] The composition for forming a silicon-containing resist underlayer film of the present invention can be suitably used as a composition for forming a resist underlayer film used in a lithography process.

[0117] [Other Additives] Various additives can be blended into the silicon-containing resist underlayer film-forming composition of the present invention depending on the intended use of the composition. Examples of the additives include curing catalysts (ammonium salts, phosphines, phosphonium salts, sulfonium salts, nitrogen-containing silane compounds, etc.), crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymer compounds, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology adjusters, adhesion aids, etc., and known additives blended into materials (compositions) for forming various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, anti-reflective films, and pattern reversal films. Examples of various additives are listed below, but are not limited to these.

[0118] <Curing Catalyst> The composition for forming a silicon-containing resist underlayer film of the present invention may be a composition that does not contain a curing catalyst, but may also contain a curing catalyst. The curing catalyst may be an ammonium salt, a phosphine, a phosphonium salt, a sulfonium salt, or the like. The salts listed below, which are listed as examples of curing catalysts, may be added in the form of a salt, or may form a salt in the composition (a compound that is added as a separate compound and forms a salt in the system).

[0119] The ammonium salt is represented by the formula (D-1): (In the formula, m ａ is an integer from 2 to 11, n ａ is an integer of 2 or 3, R ２１ represents an alkyl group or an aryl group, Y － represents an anion.), a quaternary ammonium salt having a structure represented by formula (D-2): (In the formula, R ２２ , R ２３ , R２４ and R ２５ represents an alkyl group or an aryl group, N represents a nitrogen atom, Y represents a － represents an anion, and R ２２ , R ２３ , R ２４ , and R ２５ are each bonded to a nitrogen atom), a quaternary ammonium salt having a structure represented by formula (D-3): (In the formula, R ２６ and R ２７ represents an alkyl group or an aryl group, N represents a nitrogen atom, Y represents a － represents an anion), a quaternary ammonium salt having a structure represented by formula (D-4): (In the formula, R ２８ represents an alkyl group or an aryl group, N represents a nitrogen atom, Y represents a － represents an anion), a quaternary ammonium salt having a structure represented by formula (D-5): (In the formula, R ２９ and R ３０ represents an alkyl group or an aryl group, N represents a nitrogen atom, Y represents a － represents an anion), a quaternary ammonium salt having a structure represented by formula (D-6): (In the formula, m ａ is an integer from 2 to 11, n ａ represents an integer of 2 or 3, H represents a hydrogen atom, N represents a nitrogen atom, Y － represents an anion).

[0120] The phosphonium salt may also be a compound represented by the formula (D-7): (In the formula, R ３１ , R ３２ , R ３３ , and R ３４ represents an alkyl group or an aryl group, P represents a phosphorus atom, Y represents a － represents an anion, and R ３１ , R ３２ , R ３３ , and R ３４ are each bonded to a phosphorus atom).

[0121] The sulfonium salt may also be a compound represented by the formula (D-8): (In the formula, R ３５ , R ３６ , and R ３７ represents an alkyl group or an aryl group, S represents a sulfur atom, Y － represents an anion, and R ３５ , R ３６ , and R ３７ are each bonded to a sulfur atom).

[0122] The compound of the above formula (D-1) is a quaternary ammonium salt derived from an amine, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3. R of this quaternary ammonium salt ２１ represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples thereof include linear alkyl groups such as ethyl, propyl, and butyl, as well as benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl groups. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and the like.

[0123] The compound of the above formula (D-2) is R ２２ R ２３ R ２４ R ２５ N ＋ Y － The R of this quaternary ammonium salt is ２２ , R ２３ , R ２４ and R ２５ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. －) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － The quaternary ammonium salt is commercially available, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0124] The compound of the above formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, and R ２６ and R ２７ has 1 to 18 carbon atoms, and R ２６ and R ２７ The total number of carbon atoms in R is preferably 7 or more. ２６ represents a methyl group, an ethyl group, a propyl group, a phenyl group, or a benzyl group, R ２７ Examples of the anion (Y － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － Although this compound is commercially available, it can also be produced by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with an alkyl halide or aryl halide such as benzyl bromide or methyl bromide.

[0125] The compound of the above formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ２８ is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples thereof include a butyl group, an octyl group, a benzyl group, and a lauryl group. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and other acid groups. This compound is commercially available, but can also be produced by reacting pyridine with an alkyl halide or aryl halide, such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0126] The compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine, such as picoline, and R ２９ R is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples thereof include a methyl group, an octyl group, a lauryl group, and a benzyl group. ３０ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and in the case of a quaternary ammonium group derived from, for example, picoline, R ３０ is a methyl group. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O －) and other acid groups. This compound is commercially available, but can also be produced by reacting a substituted pyridine such as picoline with an alkyl halide or aryl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0127] The compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － The compound can be produced by reacting an amine with a weak acid such as a carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. When formic acid is used, an anion (Y － ) is (HCOO － ) and when acetic acid is used, the anion (Y － ) is (CH ３ COO － ) When phenol is used, the anion (Y － ) is (C ６ H ５ O － )

[0128] The compound of the above formula (D-7) is R ３１ R ３２ R ３３ R ３４ P ＋ Y － It is a quaternary phosphonium salt having the structure: R ３１ , R ３２ , R ３３ , and R３４ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and preferably R ３１ ~R ３４ Three of the four substituents are phenyl groups or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and other acid groups. This compound is commercially available, and examples thereof include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halides, tetraphenylphosphonium halides, tritolylmonoarylphosphonium halides, and tritolylmonoalkylphosphonium halides (all of which the halogen atom is a chlorine atom or a bromine atom). In particular, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, tritolylmonoarylphosphonium halides such as tritolylmonophenylphosphonium halide, and tritolylmonoalkylphosphonium halides (the halogen atom is a chlorine atom or a bromine atom) are preferred.

[0129] Examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0130] The compound of the above formula (D-8) is R ３５ R ３６ R ３７ S ＋ Y － It is a tertiary sulfonium salt having the structure: R ３５ , R ３６ , and R ３７ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, preferably R ３５ ~R ３７ Two of the three substituents are phenyl groups or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O －Examples of suitable acid groups include trialkylsulfonium halides such as tri-n-butylsulfonium halides and tri-n-propylsulfonium halides, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halides, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halides and diphenylethylsulfonium halides, triphenylsulfonium halides (all of which the halogen atom is a chlorine atom or a bromine atom), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmonoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate and diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. Furthermore, triphenylsulfonium halides and triphenylsulfonium carboxylates are preferably used.

[0131] In the present invention, a nitrogen-containing silane compound can be added as a curing catalyst, such as an imidazole ring-containing silane compound, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0132] When a curing catalyst is used, its amount is 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass, per 100 parts by mass of the polysiloxane (A).

[0133] <Stabilizer> The stabilizer may be added for purposes such as stabilizing the hydrolysis condensate of the hydrolyzable silane mixture. Specific examples of the stabilizer include organic acids, water, alcohols, and combinations thereof. Examples of the organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Among these, oxalic acid and maleic acid are preferred. When an organic acid is added, the amount added is 0.1 to 5.0% by mass relative to the mass of the hydrolysis condensate of the hydrolyzable silane mixture. These organic acids can also function as pH adjusters. Examples of the water that can be used include pure water, ultrapure water, and ion-exchanged water. When used, the amount added can be 1 to 20 parts by mass per 100 parts by mass of the composition for forming a resist underlayer film. The alcohol is preferably one that easily evaporates (volatilizes) upon heating after application, such as methanol, ethanol, propanol, i-propanol, and butanol. When alcohol is added, the amount added can be 1 to 20 parts by mass with respect to 100 parts by mass of the composition for forming a resist underlayer film.

[0134] <Organic Polymer> The organic polymer compound can be added to the resist underlayer film-forming composition to adjust the dry etching rate (amount of film thickness reduction per unit time), attenuation coefficient, refractive index, etc. of the film (resist underlayer film) formed from the composition. The organic polymer compound is not particularly limited and can be appropriately selected from various organic polymers (condensation polymerization polymers and addition polymerization polymers) depending on the purpose of addition. Specific examples include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing moieties can also be suitably used when such a function is required. Specific examples of such organic polymer compounds include, but are not limited to, addition polymerization polymers containing, as structural units, addition-polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthrylmethyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide, and condensation polymerization polymers such as phenol novolac and naphthol novolac.

[0135] When an addition polymerization polymer is used as the organic polymer compound, the polymer compound may be either a homopolymer or a copolymer. An addition polymerizable monomer is used to produce the addition polymerization polymer, and specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0136] Specific examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, glycidyl acrylate, and the like, but are not limited to these.

[0137] Specific examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, and the like, but are not limited to these.

[0138] Specific examples of the acrylamide compound include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

[0139] Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited to these.

[0140] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0141] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0142] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0143] When a condensation polymerization polymer is used as the polymer, examples of such a polymer include a condensation polymerization polymer of a glycol compound and a dicarboxylic acid compound. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, butylene glycol, etc. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, maleic anhydride, etc. Examples of polyesters, polyamides, and polyimides such as polypyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, but are not limited to these. When the organic polymer compound contains a hydroxy group, this hydroxy group may undergo a crosslinking reaction with a hydrolysis condensate or the like.

[0144] The weight-average molecular weight of the organic polymer compound can usually be 1,000 to 1,000,000. When an organic polymer compound is incorporated, from the viewpoint of suppressing precipitation in the composition while fully obtaining the functional effect of the polymer, the weight-average molecular weight can be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000. Such organic polymer compounds may be used alone or in combination of two or more.

[0145] When the composition for forming a silicon-containing resist underlayer film of the present invention contains an organic polymer compound, its content cannot be generally specified because it is determined appropriately in consideration of the function and the like of the organic polymer compound. However, it can usually be in the range of 1 to 200% by mass, relative to the mass of the polysiloxane (A). From the viewpoint of inhibiting precipitation in the composition, for example, it can be set to 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less. From the viewpoint of fully obtaining the effect, for example, it can be set to 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0146] <Acid Generator> Examples of the acid generator include thermal acid generators and photoacid generators, and photoacid generators can be preferably used. Examples of the photoacid generator include, but are not limited to, onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, etc. Note that the photoacid generator may also function as a curing catalyst depending on the type, for example, carboxylates such as nitrates and maleates of onium salt compounds described below, or hydrochlorides. Examples of the thermal acid generator include, but are not limited to, tetramethylammonium nitrate.

[0147] Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride. However, the present invention is not limited to these.

[0148] Specific examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited to these.

[0149] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like.

[0150] When the composition for forming a silicon-containing resist underlayer film of the present invention contains an acid generator, its content cannot be generally defined because it is determined appropriately taking into account the type of acid generator and the like, but is usually in the range of 0.01 to 5 mass % relative to the mass of the polysiloxane (A). From the viewpoint of suppressing precipitation of the acid generator in the composition, it is preferably 3 mass % or less, more preferably 1 mass % or less, and from the viewpoint of fully obtaining its effects, it is preferably 0.1 mass % or more, more preferably 0.5 mass % or more. The acid generators can be used alone or in combination of two or more, and a photoacid generator and a thermal acid generator may be used in combination.

[0151] <Surfactant> The surfactant is effective in suppressing the occurrence of pinholes, striations, etc. when the composition for forming a resist underlayer film is applied to a substrate. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, and UV-curable surfactants. More specifically, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate; Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as oleate and polyoxyethylene sorbitan tristearate, trade names of EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.)), trade names of MEGAFAC (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Fluorad F Examples of suitable surfactants include, but are not limited to, fluorine-based surfactants such as C430 and FC431 (manufactured by 3M Japan Ltd.), Asahiguard (registered trademark) AG710 (manufactured by AGC Corporation), and Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants can be used singly or in combination of two or more.

[0152] When the composition for forming a silicon-containing resist underlayer film of the present invention contains a surfactant, the content thereof is usually 0.0001 to 5 mass %, preferably 0.001 to 4 mass %, and more preferably 0.01 to 3 mass %, relative to the mass of the polysiloxane (A).

[0153] <Rheology Adjuster> The rheology adjuster is added primarily to improve the fluidity of the resist underlayer film-forming composition, thereby improving the film thickness uniformity of the formed film and enhancing the ability of the composition to fill holes, particularly during the baking process. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate; adipic acid derivatives such as di-n-butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. When these rheology adjusters are used, the amount added is typically less than 30% by mass based on the total solids content of the resist underlayer film-forming composition.

[0154] <Adhesion Aid> The adhesion aid is added mainly for the purpose of improving the adhesion between the substrate or resist and the film (resist underlayer film) formed from the composition for forming a resist underlayer film, and particularly for the purpose of suppressing or preventing peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; γ-chloropropyltrimethoxysilane; Examples of the adhesion promoter include other silanes such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. When these adhesion promoters are used, the amount added is usually less than 5 mass %, and preferably less than 2 mass %, based on the total solids content of the composition for forming a resist underlayer film.

[0155] <pH Adjuster> In addition to the acids having one or more carboxylic acid groups, such as the organic acids listed above as the <Stabilizer>, bisphenol S or a bisphenol S derivative can be added as a pH adjuster. When a pH adjuster is used, the amount added can be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass per 100 parts by mass of the polysiloxane [A].

[0156] Specific examples of bisphenol S and bisphenol S derivatives include, but are not limited to, compounds represented by the following formulae (C-1) to (C-23).

[0157] <Metal Oxide> Examples of the metal oxide that can be added to the silicon-containing resist underlayer film-forming composition of the present invention include, but are not limited to, oxides of one or a combination of two or more of metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and semimetals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0158] [Method for Manufacturing a Semiconductor Device] Hereinafter, as one embodiment of the present invention, a method for manufacturing a semiconductor device (semiconductor element) using the composition for forming a silicon-containing resist underlayer film of the present invention and a pattern formation method will be described.

[0159] First, the silicon-containing resist underlayer film-forming composition of the present invention is applied to a substrate used in the manufacture of precision integrated circuit devices (e.g., a semiconductor substrate such as a silicon wafer coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (including alkali-free glass, low-alkali glass, and crystallized glass), a glass substrate formed with an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film, a plastic (polyimide, PET, etc.) substrate, a low-dielectric constant material (low-k material)-coated substrate, a flexible substrate, etc.) by a suitable application method such as a spinner or coater, and then baked using a heating means such as a hot plate to harden the composition and form a resist underlayer film. Hereinafter, in this specification, the term "resist underlayer film" refers to a film formed from the silicon-containing resist underlayer film-forming composition of the present invention. Baking conditions are appropriately selected from a baking temperature of 40°C to 400°C or 80°C to 250°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 150°C to 250°C, and the baking time is 0.5 to 2 minutes. Generally, the thickness of the resist underlayer film can be, for example, about 10 nm to 1,000 nm. As mentioned above, in recent years, with the trend toward thinner resists, thinner resist underlayer films are also required. The present invention targets not only resist underlayer films having a thickness of 10 nm to 1,000 nm, but also resist underlayer films having a thickness of 10 nm or less. By using the silicon-containing resist underlayer film-forming composition of the present invention, the resist underlayer film of the present invention, which is the cured product thereof, can suppress pattern defects such as collapse of the resist pattern formed on the overlying layer, even if the film thickness is 10 nm or less. For example, the resist underlayer film of the present invention can have a thickness of 1 nm to 10 nm. The resist underlayer film-forming composition used in forming the resist underlayer film can be a resist underlayer film-forming composition filtered through a nylon filter. Here, the composition for forming a resist underlayer film that has been filtered through a nylon filter refers to a composition that has been subjected to nylon filter filtration during the production of the composition for forming a resist underlayer film or after all of the components have been mixed.

[0160] In another embodiment of the present invention, an organic underlayer film may be formed on the substrate, and then the resist underlayer film may be formed thereon. The organic underlayer film used here is not particularly limited and can be selected from those conventionally used in lithography processes. By forming an organic underlayer film on a substrate, a resist underlayer film thereon, and a resist film (described below) on top of that, the pattern width of the photoresist film is narrowed. Even if a thin photoresist film is applied to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas (described below). For example, the silicon-containing resist underlayer film of the present invention can be processed using a fluorine-based gas having a sufficiently high etching rate for the photoresist film as an etching gas. The organic underlayer film can also be processed using an oxygen-based gas having a sufficiently high etching rate for the silicon-containing resist underlayer film as an etching gas. Furthermore, the substrate can be processed using a fluorine-based gas having a sufficiently high etching rate for the organic underlayer film as an etching gas. The substrate and coating method that can be used in this case are the same as those described above.

[0161] Next, a layer of, for example, a photoresist material (resist film) is formed on the resist underlayer film. The resist film can be formed by a well-known method, i.e., by applying a coating-type resist material (e.g., a photoresist film-forming composition) on the resist underlayer film and baking it. The thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0162] The photoresist material used in the resist film formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative and positive photoresist materials can be used. Examples include a positive photoresist material composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist material composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate and a photoacid generator, a chemically amplified photoresist material composed of a low molecular weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator, and a chemically amplified photoresist material composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate, a low molecular weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist material, and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., AR2772JN (trade name) manufactured by JSR Corporation, and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Other examples include fluorine-containing polymer photoresist materials such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0163] Furthermore, for the resist film formed on the resist underlayer film, a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film) can be used instead of a photoresist film. That is, the silicon-containing resist underlayer film-forming composition of the present invention can be used for forming a resist underlayer film for electron beam lithography or a resist underlayer film for EUV lithography. It is particularly suitable as a composition for forming a resist underlayer film for EUV lithography. Either a negative material or a positive material can be used as the electron beam resist material. Specific examples include chemically amplified resist materials comprising an acid generator and a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate; chemically amplified resist materials comprising an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material; chemically amplified resist materials comprising an acid generator, a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material; non-chemically amplified resist materials comprising a binder having a group that decomposes in the presence of an electron beam to change the alkaline dissolution rate; and non-chemically amplified resist materials comprising a binder having a moiety that is cleaved by an electron beam to change the alkaline dissolution rate. When using these electron beam resist materials, resist film patterns can be formed in the same way as when using a photoresist material with an electron beam as the irradiation source. Furthermore, methacrylate resin-based resist materials can be used as the EUV resist material.

[0164] Next, the resist film formed on the upper layer of the resist underlayer film is exposed through a predetermined mask (reticle). For exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), EUV (wavelength 13.5 nm), an electron beam, or the like can be used. After exposure, a post-exposure bake can also be performed as necessary. The post-exposure bake is performed under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0165] Next, development is carried out using a developer (e.g., an alkaline developer). As a result, when a positive photoresist film is used, for example, the exposed portions of the photoresist film are removed, forming a photoresist film pattern. Examples of the developer (alkaline developer) include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0166] In the present invention, an organic solvent can be used as a developer, and development is carried out with the developer (solvent) after exposure. As a result, when a negative photoresist film is used, for example, the photoresist film in the unexposed areas is removed, and a photoresist film pattern is formed.Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl butyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, carbonate Examples of the developer include ethyl, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. Furthermore, a surfactant or the like can also be added to these developers.The conditions for development are suitably selected from the temperature range of 5° C. to 50° C. and the time range of 10 seconds to 600 seconds.

[0167] The resist underlayer film (middle layer) is removed using the pattern of the photoresist film (upper layer) thus formed as a protective film, then the organic underlayer film (lower layer) is removed using the pattern of the patterned resist underlayer film (middle layer) as a protective film, and finally, the substrate is processed using the patterned resist underlayer film (middle layer) and the patterned organic underlayer film (lower layer) as protective films.

[0168] The removal (patterning) of the resist underlayer film (middle layer) is performed using the pattern of the resist film (upper layer) as a protective film by dry etching, using tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ Gases such as fluorine, trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. It is preferable to use a halogen-based gas for dry etching of the resist underlayer film. Resist films (photoresist films) made of organic substances are generally difficult to remove with dry etching using a halogen-based gas. In contrast, silicon-containing resist underlayer films containing a large amount of silicon atoms are quickly removed with a halogen-based gas. Therefore, it is possible to suppress the reduction in the thickness of the photoresist film that accompanies dry etching of the resist underlayer film. As a result, it becomes possible to use a thin photoresist film. Therefore, it is preferable to use a fluorine-based gas for dry etching of the resist underlayer film. Examples of fluorine-based gases include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２) and the like, but are not limited to these.

[0169] When an organic underlayer film is present between the substrate and the resist underlayer film, removal (patterning) of the organic underlayer film (lower layer), which is carried out using a film consisting of the patterned resist film (upper layer) (if any remains) and the patterned resist underlayer film (middle layer) as a protective film, is preferably carried out by dry etching with an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.). This is because the silicon-containing resist underlayer film of the present invention, which contains a large amount of silicon atoms, is difficult to remove by dry etching with an oxygen-based gas.

[0170] Thereafter, the (semiconductor) substrate is processed (patterned) using the patterned resist underlayer film (intermediate layer) (if any) and, if desired, the patterned organic underlayer film (underlayer) as protective films, preferably by dry etching using a fluorine-based gas. Examples of the fluorine-based gas include tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, and difluoromethane (CH ２ F ２ ) etc.

[0171] After removing (patterning) the organic underlayer film or after processing (patterning) the substrate, the resist underlayer film can be removed. The resist underlayer film can be removed by dry etching or wet etching. Dry etching of the resist underlayer film is preferably performed with a fluorine-based gas, as described in the above-mentioned patterning, such as tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２Examples of chemicals used for wet etching of the resist underlayer film include, but are not limited to, dilute hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (HF and NH ４ Examples of suitable alkaline solutions include an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical solution), and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution). Examples of the alkaline solution include the aforementioned ammonia hydrogen peroxide solution (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide, and water, as well as aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepicato hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These chemical solutions can also be used in combination.

[0172] An organic antireflective coating can be formed on the resist underlayer before the formation of the resist film. The antireflective coating composition used therein is not particularly limited, and can be selected from those conventionally used in lithography processes. The antireflective coating can be formed by a conventional method, such as coating with a spinner or coater and baking.

[0173] Furthermore, the substrate onto which the silicon-containing resist underlayer film-forming composition of the present invention is applied may have an organic or inorganic antireflective film formed on its surface by a CVD method or the like, and the resist underlayer film may be formed thereon. Even in the case where an organic underlayer film is formed on a substrate and then the resist underlayer film of the present invention is formed thereon, the substrate used may have an organic or inorganic antireflective film formed on its surface by a CVD method or the like.

[0174] The resist underlayer film formed from the silicon-containing resist underlayer film-forming composition of the present invention may also absorb light depending on the wavelength of the light used in the lithography process. In such cases, it can function as an antireflection film that has the effect of preventing light reflected from the substrate. Furthermore, the resist underlayer film can also be used as a layer for preventing interaction between the substrate and a resist film (such as a photoresist film), a layer that functions to prevent adverse effects on the substrate of materials used in the resist film or substances generated during exposure of the resist film, a layer that functions to prevent diffusion of substances generated from the substrate during heating and baking into an upper resist film, and a barrier layer for reducing the poisoning effect of the resist film due to a dielectric layer on a semiconductor substrate.

[0175] The resist underlayer film can be applied to a substrate having via holes formed therein for use in a dual damascene process, and can be used as a hole-filling material (embedding material) capable of filling the holes without gaps. It can also be used as a planarizing material for planarizing the surface of an uneven semiconductor substrate. Furthermore, the resist underlayer film can be used as an underlayer film for an EUV resist film, not only functioning as a hard mask, but also as an underlayer anti-reflection film for an EUV resist film, preventing reflection from the substrate or interface of undesirable exposure light during EUV exposure (wavelength 13.5 nm), such as UV (ultraviolet) light and DUV (deep ultraviolet) light (ArF light, KrF light), without intermixing with the EUV resist film. In other words, it can efficiently prevent reflection as an underlayer for an EUV resist film. When used as an EUV resist underlayer film, the process can be carried out in the same manner as for a photoresist underlayer film.

[0176] The semiconductor processing substrate, which comprises the resist underlayer film of the present invention and a semiconductor substrate as described above, can be used to suitably process the semiconductor substrate. Furthermore, according to the method for manufacturing a semiconductor device, which includes the steps of forming an organic underlayer film, forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film-forming composition of the present invention, and forming a resist film on the silicon-containing resist underlayer film, high-precision processing of the semiconductor substrate can be realized with good reproducibility, and stable manufacturing of semiconductor devices can be expected.

[0177] The present invention will be explained in more detail below by way of synthesis examples and examples, but the present invention is not limited to the following examples.

[0178] In the examples, the apparatus and conditions used for analyzing the physical properties of samples are as follows. (1) Molecular Weight Measurement The molecular weight of the polysiloxane used in the present invention is the molecular weight obtained by GPC analysis in terms of polystyrene. The GPC measurement conditions are, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as eluent (elution solvent), a flow rate (flow rate) of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as a standard sample. (2) １ H-NMR JEOL nuclear magnetic resonance apparatus １ Evaluation was performed by H-NMR (400 MHz) using d6-acetone as the solvent.

[0179] [1] Synthesis of Polymer (Hydrolyzed Condensate) (Synthesis Example 1) 23.5 g of tetraethoxysilane, 7.2 g of methyltriethoxysilane, 1.6 g of phenyltrimethoxysilane, and 182.8 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.3 g of 0.2 M aqueous nitric acid solution was added dropwise while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60 ° C. and refluxed for 20 hours. Thereafter, the reaction by-products, ethanol, methanol, and water, were distilled off under reduced pressure and concentrated to obtain an aqueous solution of hydrolyzed condensate (polymer). Further, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150 ° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm). The obtained polymer contained polysiloxane (P1) having a structure represented by the following formula (E1), and its weight average molecular weight was Mw 1,300 as calculated in terms of polystyrene by GPC.

[0180] (Synthesis Example 2) 23.5 g of tetraethoxysilane, 7.2 g of methyltriethoxysilane, 1.6 g of phenyltrimethoxysilane, and 129.2 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.3 g of 0.2 M aqueous nitric acid solution was added dropwise while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60 ° C. and refluxed for 20 hours. Thereafter, the reaction by-products, ethanol, methanol, and water, were distilled off under reduced pressure and concentrated to obtain an aqueous solution of hydrolyzed condensate (polymer). Further, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150 ° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm). The obtained polymer contained polysiloxane (P2) having a structure represented by the above formula (E1), and its weight average molecular weight was Mw 1,800 as calculated in terms of polystyrene by GPC.

[0181] (Synthesis Example 3) 23.5 g of tetraethoxysilane, 7.2 g of methyltriethoxysilane, 1.6 g of phenyltrimethoxysilane, and 74.3 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.3 g of 0.2 M aqueous nitric acid solution was added dropwise while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60 ° C. and refluxed for 20 hours. Thereafter, the reaction by-products, ethanol, methanol, and water, were distilled off under reduced pressure and concentrated to obtain an aqueous solution of hydrolyzed condensate (polymer). Further, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150 ° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm). The obtained polymer contained polysiloxane (P3) having a structure represented by the above formula (E1), and its weight average molecular weight was Mw 2,200 as calculated in terms of polystyrene by GPC.

[0182] (Synthesis Example 4) 23.5 g of tetraethoxysilane, 7.2 g of methyltriethoxysilane, 1.6 g of phenyltrimethoxysilane, and 48.5 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.3 g of 0.2 M aqueous nitric acid solution was added dropwise while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60 ° C. and refluxed for 20 hours. Thereafter, the reaction by-products, ethanol, methanol, and water, were distilled off under reduced pressure and concentrated to obtain an aqueous solution of hydrolyzed condensate (polymer). Further, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150 ° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm). The obtained polymer contained polysiloxane (P4) having a structure represented by the above formula (E1), and its weight average molecular weight was Mw 2,600 as calculated in terms of polystyrene by GPC.

[0183] (Synthesis Example 5) 23.5 g of tetraethoxysilane, 7.2 g of methyltriethoxysilane, 1.6 g of phenyltrimethoxysilane, and 39.5 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.3 g of 0.2 M aqueous nitric acid solution was added dropwise while stirring the mixed solution with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 60 ° C. and refluxed for 20 hours. Thereafter, the reaction by-products, ethanol, methanol, and water, were distilled off under reduced pressure and concentrated to obtain an aqueous solution of hydrolyzed condensate (polymer). Further, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150 ° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and the solution was filtered using a nylon filter (pore size 0.1 μm). The obtained polymer contained polysiloxane (P5) having a structure represented by the above formula (E1), and its weight average molecular weight was Mw 2,900 as calculated in terms of polystyrene by GPC.

[0184] Table 1 shows the number average molecular weight (Mn), weight average molecular weight (Mw), and average molecular weight (Mz) of the polymers obtained in Synthesis Examples 1 to 5, as well as the proportion of polysiloxane having a molecular weight range of more than 2,500.

[0185]

[0186] [2] Preparation of Compositions for Forming Resist Underlayer Films The polysiloxane (polymer), acid (additive 1), condensation catalyst (additive 2), high-boiling-point glycol compound (additive 3), and solvent obtained in the above Synthesis Examples were mixed in the proportions shown in Table 1, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare compositions for forming resist underlayer films. The amounts of each additive in Table 1 are shown in parts by mass. Note that, although the hydrolysis condensate (polymer) was prepared as a composition in the form of a solution containing the condensate obtained in the Synthesis Examples, the proportion of polymer added in Table 1 indicates the amount of polymer itself added, not the amount of polymer solution added. DIW refers to ultrapure water, PGEE refers to propylene glycol monoethyl ether, and PGME refers to propylene glycol monomethyl ether, respectively. Furthermore, MA means maleic acid, IMTEOS means triethoxysilylpropyl-4,5-dihydroimidazole, TPSNO3 means triphenylsulfonium nitrate, and TEGEE means triethylene glycol monoethyl ether.

[0187]

[0188] [3] Preparation of Organic Resist Underlayer Film Forming Composition Under nitrogen, a 100 mL four-neck flask was charged with carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and paratoluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and 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 and initiate polymerization. After 24 hours, the mixture was allowed to cool to 60°C. The cooled reaction mixture was diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.), and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to cause precipitation. The resulting precipitate was collected by filtration, and the collected solid was dried in a vacuum dryer at 80°C for 24 hours to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL). １ The results of H-NMR measurement were as follows: １ H-NMR (400MHz, DMSO-d ６ ): δ 7.03-7.55 (br, 12H), δ 7.61-8.10 (br, 4H), δ 11.18 (br, 1H) The weight average molecular weight Mw of PCzFL was 2,800 as calculated in terms of polystyrene by GPC, and the polydispersity Mw / Mn was 1.77.

[0189] 20 g of PCzFL, 3.0 g of tetramethoxymethylglycoluril (trade name Powder Link 1174, manufactured by Nippon Cytec Industries Co., Ltd. (formerly Mitsui Cytec Co., Ltd.)) as a crosslinking agent, 0.30 g of pyridinium paratoluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (trade name, manufactured by DIC Corporation) as a surfactant were mixed, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate to form a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 0.10 μm, and further filtered using a polyethylene microfilter with a pore size of 0.05 μm, to prepare a composition for forming an organic resist underlayer film to be used in a multilayer film lithography process.

[0190] [4] Solvent Resistance and Developer Solubility Tests The compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were each coated onto a silicon wafer using a spinner. The composition was heated on a hot plate at 215°C for 1 minute to form a Si-containing resist underlayer film, and the film thickness of the resulting underlayer film was measured. A mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was then coated onto each Si-containing resist underlayer film and spin-dried. The film thickness of the coated underlayer film was measured, and the percentage change in film thickness after application of the mixed solvent was calculated, with the film thickness before application of the mixed solvent taken as the reference (100%). Films with a film thickness change of 1% or less before and after application of the mixed solvent were evaluated as "good," and films with a film thickness change of more than 1% were evaluated as "not cured." In addition, an alkaline developer (2.38% aqueous solution of tetramethylammonium hydroxide (TMAH)) was applied to each Si-containing resist underlayer film prepared on a silicon wafer in the same manner, followed by spin drying. The film thickness of the underlayer film after application was measured, and the percentage change in film thickness after application of the developer was calculated, with the film thickness before application of the developer being used as the reference (100%). Films with a film thickness change of 1% or less before and after application of the developer were evaluated as "good," and films with a film thickness change of more than 1% were evaluated as "not cured." The results are shown in Table 3.

[0191]

[0192] [5] Formation of Resist Pattern by EUV Exposure: Positive Alkaline Development The above-mentioned composition for forming an organic resist underlayer film was applied to a silicon wafer using a spinner and baked on a hot plate at 215°C for 60 seconds to form an organic underlayer film (layer A) with a film thickness of 60 nm. The composition obtained in Example 1 was spin-coated thereon and heated at 215°C for 1 minute to form a resist underlayer film (layer B) with a film thickness of 10 nm. An EUV resist solution (methacrylate resin-based resist) was further spin-coated thereon and heated at 130°C for 1 minute to form an EUV resist film (layer C). The resulting film was then exposed using an EUV exposure system (NXE3300B) manufactured by ASML under conditions of NA = 0.33, σ = 0.67 / 0.90, and dipole. During exposure, the EUV resist was exposed through a mask configured so that the line width and the line spacing would be 22 nm after development, i.e., so that dense lines with a line-and-space (L / S) ratio of 22 nm were formed. After exposure, the resist was subjected to post-exposure baking (PEB, 110°C for 1 minute), cooled to room temperature on a cooling plate, developed for 60 seconds using an alkaline developer (2.38% TMAH aqueous solution), and rinsed to form a resist pattern. Using the same procedure, resist patterns were formed using the compositions obtained in Examples 2 to 4 (film thickness 10 nm), Examples 5 and 6 (film thickness 5 nm), Comparative Example 1 (film thickness 20 nm), and Comparative Examples 2 to 4 (film thickness 10 nm). The resulting patterns were evaluated for the possibility of forming 44 nm pitch, 22 nm line-and-space patterns by observing the pattern cross-sections to confirm the pattern shape. In observing the pattern shape, a state in which the shape was between footing and undercut and there was no significant residue in the space was rated as "good," an unfavorable state in which the resist pattern was peeled and collapsed was rated as "collapse," and an unfavorable state in which the upper or lower parts of the resist pattern were in contact with each other was rated as "bridge." The results obtained are shown in Table 4.

[0193]

[0194] As shown in Tables 2 to 4, the compositions of Examples 1 to 6, which contained 19% or less of polysiloxane having a molecular weight of 2500 or greater, were confirmed to have solvent resistance and developer resistance, be capable of forming resist underlayer films with excellent photoresist pattern formability, and have excellent patterning properties at a film thickness of 5 nm. On the other hand, the compositions of Comparative Examples 1 to 4, which contained 30% or more of polysiloxane having a molecular weight of more than 2500, provided good patterning properties at a film thickness of 20 nm, but the pattern shape was evaluated as "collapsed" at a film thickness of 10 nm, resulting in poor patterning properties.

Claims

1. A composition for forming a silicon-containing resist underlayer film, comprising [A] a polysiloxane having a weight average molecular weight of 1,800 or less in terms of polystyrene obtained by gel permeation chromatography (GPC) analysis and having a ratio of more than 2,500 in molecular weight of less than 20% in the integrated molecular weight distribution curve obtained by gel permeation chromatography (GPC) analysis in terms of polystyrene, and [B] a solvent.

2. The composition for forming a silicon-containing resist underlayer film according to claim 1, wherein the [A] polysiloxane is a polysiloxane having a ratio of more than 2,000 in molecular weight of less than 35% in the integrated molecular weight distribution curve obtained by gel permeation chromatography (GPC) analysis in terms of polystyrene.

3. The composition for forming a silicon-containing resist underlayer film according to claim 1 or 2, wherein the [A] polysiloxane has a weight average molecular weight of 1,100 or more and 1,800 or less.

4. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 3, which is a composition capable of pattern formation even in a resist underlayer film having a film thickness of 10 nm or less.

5. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 4, wherein the [A] polysiloxane contains at least one selected from the group consisting of a hydrolytic condensate of a hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1), a modified product of the condensate in which at least a part of the silanol groups of the condensate is alcohol-modified, a modified product of the condensate in which at least a part of the silanol groups of the condensate is acetal-protected, and a dehydration reaction product of the condensate and an alcohol. (In the formula, R １is a group bonded to a silicon atom, and independently of one another, represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or represents an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof, R ２ is a group or atom bonded to a silicon atom, and independently of one another, represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, and a represents an integer of 0 to 3.) 6. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 5, which does not contain a curing catalyst.

7. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 6, wherein the above [B] solvent contains water.

8. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 7, further comprising a pH adjuster.

9. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 8, wherein [C] has a standard boiling point of 230.0 °C or higher and contains a glycol compound represented by the following formula (2). (In the formula, R ３ and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group having 3 to 4 carbon atoms, and n represents an integer of 3 or more) 10. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 9, further comprising a surfactant.

11. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 10, further comprising a metal oxide.

12. The composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 11, which is for forming a resist underlayer film for EUV lithography.

13. A resist underlayer film which is a cured product of the composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 12.

14. The resist underlayer film according to claim 13, having a film thickness of 10 nm or less.

15. A semiconductor processing substrate comprising a semiconductor substrate and the resist underlayer film according to claim 13 or claim 14.

16. A method for manufacturing a semiconductor element, comprising: a step of forming an organic underlayer film on a substrate; a step of forming a silicon-containing resist underlayer film using the composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 12 on the organic underlayer film; and a step of forming a resist film on the silicon-containing resist underlayer film.

17. The manufacturing method according to claim 16, wherein in the step of forming the silicon-containing resist underlayer film, a composition for forming a silicon-containing resist underlayer film filtered through a nylon filter is used.

18. A resist underlayer film obtained by applying and baking the composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 12 on a semiconductor substrate.

19. A method for manufacturing a semiconductor device, comprising: a step of applying the composition for forming a silicon-containing resist underlayer film according to any one of claims 1 to 12 on a semiconductor substrate and baking to form a resist underlayer film; a step of applying a composition for forming a resist film on the underlayer film to form a resist film; a step of exposing the resist film; a step of developing the resist after exposure to obtain a resist pattern; a step of etching the resist underlayer film with the resist pattern; and a step of processing the semiconductor substrate with the patterned resist underlayer film.

20. A method for manufacturing a semiconductor device, comprising the steps of forming an organic underlayer film on a semiconductor substrate, applying and baking the composition for forming a resist underlayer film according to any one of claims 1 to 12 thereon to form a resist underlayer film, applying a composition for forming a resist film on the resist underlayer film to form a resist film, exposing the resist film, developing the resist after exposure to obtain a resist pattern, etching the resist underlayer film with the resist pattern, etching the organic underlayer film with the patterned resist underlayer film, and processing the semiconductor substrate with the patterned organic underlayer film.