Silicon-containing resist underlayer film formation composition

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

[Technical Field]

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

[0002] Conventionally, microfabrication using lithography with photoresists has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating it with active light such as ultraviolet light through a mask pattern on which the semiconductor device pattern is drawn, developing the photoresist, and then etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the pattern. As semiconductor devices become more highly integrated, the wavelengths of the active light used are also tending to be shorter, from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). Furthermore, exposure techniques using EUV (Extreme Ultraviolet) and electron beams are being investigated. With the shortening of the wavelength of active light, the effect of reflection of active light from the semiconductor substrate has become a major problem. As a result, a method of placing a resist underlayer film called a bottom anti-reflective coating (BARC) between the photoresist and the substrate to be processed has become widely applied. For example, underlayer films containing silicon have been proposed as such resist underlayer films (Patent Document 1, etc.).

[0003] With the miniaturization of resist patterns in cutting-edge semiconductor devices in recent years, the demand for thinner resists has become increasingly pronounced. In particular, in a three-layer process consisting of a resist film, a silicon-containing resist underlayer, and an organic underlayer, not only is the thinning of the resist required, but the thinning of the silicon-containing resist underlayer is also required, as is good lithographic properties of the resist on the silicon-containing resist underlayer. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2007-163846 [Overview of the project] [Problems that the invention aims to solve]

[0005] As a result of further thinning of the resist film and the resist underlayer film mentioned above, pattern collapse and deterioration of pattern shape are now frequently observed even in systems where good resist patterns could previously be formed. In recent semiconductor manufacturing processes, where the thinning of the films used for patterns is becoming increasingly pronounced, the ability of the resist underlayer film to impart good lithographic properties is crucial.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a silicon-containing resist underlayer composition for forming a silicon-containing resist underlayer that can obtain a good resist pattern without pattern collapse, even with a resist underlayer that is thinner than conventional ones, such as a film thickness of 10 nm or less. [Means for solving the problem]

[0007] From a first perspective, the present invention is: [A] The weight-average molecular weight obtained by gel permeation chromatography (GPC) analysis in terms of polystyrene is 1,800 or less, and Polysiloxanes, and [B] solvent This invention relates to a silicon-containing resist underlayer film formation composition containing the above. The second aspect relates to the silicon-containing resist underlayer film forming composition described in the first aspect, wherein the [A] polysiloxane is a polysiloxane in which the proportion of molecules with a molecular weight exceeding 2,000 is less than 35% in the integrated molecular weight distribution curve obtained by gel permeation chromatography (GPC) analysis in polystyrene equivalent. The third aspect relates to a silicon-containing resist underlayer film forming composition according to the first or second aspect, wherein the [A] polysiloxane has a weight-average molecular weight of 1,100 or more and 1,800 or less. The fourth aspect relates to a silicon-containing resist underlayer film formation composition according to any one of the first to third aspects, which is capable of forming patterns even with a resist underlayer film of thickness of 10 nm or less. The fifth aspect relates to a silicon-containing resist underlayer film forming composition according to any one of the first to fourth aspects, wherein the [A]polysiloxane comprises at least one hydrolyzable silane hydrolyzate condensate containing at least one hydrolyzable silane represented by the following formula (1), a modified hydrolyzate condensate in which at least a portion of the silanol groups of the condensate are alcohol-modified, a modified hydrolyzate condensate in which at least a portion of the silanol groups of the condensate are acetal-protected, and at least one selected from the group consisting of the condensate and the dehydration reaction product of the alcohol. [ka] (In the formula, R 1This group is a group bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an 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 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. (where 'a' represents an integer between 0 and 3.) The sixth aspect relates to a silicon-containing resist underlayer film formation composition according to any one of the first to fifth aspects, which does not contain a curing catalyst. The seventh aspect relates to a silicon-containing resist underlayer film forming composition according to any one of the first to sixth aspects, wherein the solvent [B] above contains water. The eighth aspect relates to a silicon-containing resist underlayer film forming composition according to any one of the first to seventh aspects, further comprising a pH adjusting agent. The ninth aspect relates to a silicon-containing resist underlayer film forming composition according to any one of the first to eighth aspects, wherein the [C] standard boiling point is 230.0°C or higher and contains a glycol compound represented by the following formula (2). [ka] (In the formula, R 3 and R 4 Each of these 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. The tenth aspect relates to a silicon-containing resist underlayer film forming composition according to any one of the first to ninth aspects, further comprising a surfactant. The eleventh aspect relates to a silicon-containing resist underlayer film forming composition according to any one of the first to tenth aspects, further comprising a metal oxide. The twelfth aspect relates to a silicon-containing resist underlayer film formation composition described in any one of the first to eleventh aspects, for use in forming a resist underlayer film for EUV lithography. The thirteenth aspect relates to a resist underlayer film, which is a cured product of a silicon-containing resist underlayer film forming composition described in any one of the first to twelfth aspects. The 14th aspect relates to the resist underlayer film described in the 13th aspect, having a film thickness of 10 nm or less. The 15th aspect relates to a semiconductor processing substrate comprising a semiconductor substrate and a resist underlayer film as described in the 13th or 14th aspect. From the 16th perspective, A process of forming an organic underlayer film on a substrate, A step of forming a silicon-containing resist underlayer on the above organic underlayer using a silicon-containing resist underlayer forming composition described in any one of the first to twelfth aspects, The process includes the step of forming a resist film on the silicon-containing resist underlayer film described above. This relates to a method for manufacturing semiconductor devices. The 17th aspect relates to the manufacturing method described in the 16th aspect, wherein in the step of forming the silicon-containing resist underlayer film described above, the silicon-containing resist underlayer film forming composition filtered with a nylon filter is used. The 18th aspect relates to a resist underlayer film obtained by applying a silicon-containing resist underlayer film formation composition described in any one of the 1st to 12th aspects onto a semiconductor substrate and firing it. The 19th aspect relates to a method for manufacturing a semiconductor device, comprising the steps of: applying a silicon-containing resist underlayer film forming composition described in any one of the 1st to 12th aspects onto a semiconductor substrate and firing it to form a resist underlayer film; applying a resist film forming composition on 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 with the resist pattern; and processing the semiconductor substrate with the patterned resist underlayer film. The 20th aspect relates to a method for manufacturing a semiconductor device, comprising the steps of: forming an organic underlayer film on a semiconductor substrate; applying a resist underlayer film forming composition described in any one of the 1st to 12th aspects thereon and firing it to form a resist underlayer film; applying a resist film forming composition thereon 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 an organic underlayer film with the patterned resist underlayer film; and processing a semiconductor substrate with the patterned organic underlayer film. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a silicon-containing resist underlayer film formation composition that can form a silicon-containing resist underlayer film that can obtain a good resist pattern without pattern collapse even if the film thickness is 10 nm or less. Furthermore, according to the present invention, it is possible to provide a silicon-containing resist underlayer film formation composition that can be suitably used in lithography processes where further thinning and miniaturization are required. [Modes for carrying out the invention]

[0009] The present invention relates to a composition for forming a silicon-containing resist underlayer film that can prevent the collapse of resist patterns associated with the thinning of semiconductor systems, and to a silicon-containing resist underlayer film formation composition (hereinafter also simply referred to as "resist underlayer film formation composition") that contains [A] a polysiloxane of 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 [A]polysiloxane is not particularly limited, as long as it is a polymer having siloxane bonds.

[0011] The [A]polysiloxane in this invention is a polysiloxane with a weight-average molecular weight of 1,800 or less, obtained by gel permeation chromatography (GPC) analysis on a polystyrene basis. For example, in one embodiment, a polysiloxane with a weight-average molecular weight of 1,100 or more and 1,800 or less can be used. Furthermore, the [A]polysiloxane of the present invention is a polysiloxane in which the proportion of molecules with a molecular weight exceeding 2,500 is less than 20% in the integrated molecular weight distribution curve obtained in polystyrene equivalent by gel permeation chromatography (GPC) analysis. For example, in one embodiment, a polysiloxane in which the proportion of molecules with a molecular weight of 2,000 or more is less than 35% in the above integrated molecular weight distribution curve can be used. Alternatively, for example, a polysiloxane in which the proportion of molecules with a molecular weight of 1,800 or less is 60% or more, or the proportion of molecules with a molecular weight of 1,400 or less is 40% or more, can be used. Furthermore, the polydispersity Mw / Mn of [A]polysiloxane can be, for example, less than 1.30. The silicon-containing resist underlayer film formation composition of the present invention is characterized by using a polysiloxane with a weight-average molecular weight of 1,800 or less, so to speak, a low molecular weight polysiloxane, in which the proportion of polysiloxanes with a molecular weight exceeding 2,500 is suppressed. By using such a low molecular weight polysiloxane, it is possible to create a composition that can form a silicon-containing resist underlayer film that can prevent the collapse of the resist pattern that may occur due to the thinning of the resist film. For example, even when the resist underlayer film of the present invention has a thickness of 10 nm or less, it can suppress pattern defects such as pattern peeling, pattern collapse, and contact between patterns in the resist pattern of the upper layer, and is a resist underlayer film formation composition that can form a pattern with a good shape.

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

[0013] In this invention, the "hydrolyzed condensate" of the above-mentioned hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only polyorganosiloxane polymers which are condensates in which condensation is completely completed, but also polyorganosiloxane polymers which are partially hydrolyzed condensates in which condensation is not completely completed. Such partially hydrolyzed condensates are polymers obtained by hydrolysis and condensation of a hydrolyzable silane compound, similar to condensates in which condensation is completely completed, but the hydrolysis stops only partially and condensation does not occur, and therefore Si-OH groups remain. Furthermore, the silicon-containing resist underlayer film forming composition of this invention may contain, in addition to hydrolyzed condensates, uncondensed hydrolysates (complete hydrolysates, partially hydrolysates) and monomers (hydrolyzable silane compounds). In this specification, "hydrolyzable silane" may also be simply referred to as "silane compound."

[0014] [A] Examples of polysiloxanes include hydrolysis condensates of hydrolyzable silanes containing at least one hydrolyzable silane represented by the following formula (1). [ka]

[0015] In formula (1), R 1 This group is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an 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. Also R 2These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. And 'a' represents an integer between 0 and 3.

[0016] In formula (1) above, examples of alkyl groups include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl Examples include ru-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, for example, as cyclic alkyl groups having 3 to 10 carbon atoms, they include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl Examples include cycloalkyl groups such as -cyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group, as well as crosslinked cyclic cycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0018] The aryl group may be a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused ring aromatic hydrocarbon compound, or a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Examples of aryl groups include aryl groups with 6 to 20 carbon atoms, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-naphthacenyl, 2-naphthacenyl, 5-naphthacenyl, 2-cricenyl, 1-pyrenyl, and 2-pyrenyl groups. Examples include, but are not limited to, the pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group (o-biphenylyl group), biphenyl-3-yl group (m-biphenylyl group), biphenyl-4-yl group (p-biphenylyl group), paraterphenyl-4-yl group, metaterphenyl-4-yl group, orthoterphenyl-4-yl group, 1,1'-binaphthyl-2-yl group, 2,2'-binaphthyl-1-yl group, etc.

[0019] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those 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, phenylmethyl (benzyl) group, 2-phenylethylene group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, and 10-phenyl-n-decyl group.

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

[0021] The number of carbon atoms in the above 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, but are not limited to, monofluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, and perfluoropentyl groups.

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

[0023] The number of carbon atoms in the above-mentioned 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 halogenated aralkyl groups include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, and 2,4,5-trifluorobenzyl group. Examples include the refluorobenzyl group, 2,4,6-trifluorobenzyl group, 2,3,4,5-tetrafluorobenzyl group, 2,3,4,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluorobenzyl group, and 2,3,4,5,6-pentafluorobenzyl group. In addition, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group) are also included, but are not limited to these.

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

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

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

[0027] Examples of the above alkenyl groups include alkenyl groups having 2 to 10 carbon atoms, such as ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, and 1-methyl -2-butenyl group, 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- 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 2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group, as well as bridging cyclic alkenyl groups such as bicycloheptenyl group (norbornyl group).

[0028] Furthermore, examples of 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 of these and their preferred number of carbon atoms are the same as those described above or below. Furthermore, the aryloxy groups mentioned above as substituents are groups in which an aryl group is bonded via an oxygen atom (-O-), and specific examples of such aryl groups are the same as those mentioned above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include, but are not limited to, a phenoxy group and a naphthalene-2-yloxy group. Furthermore, if there are two or more substituents, they may bond together to form a ring.

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

[0030] The above-mentioned aralkyloxy group is a group derived by removing a hydrogen atom from the hydroxyl group of an aralkyl alcohol, and specific examples of such aralkyl groups are the same as those mentioned above. The number of carbon atoms in the above-mentioned 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 above-mentioned aralkyloxy groups include, but are not limited to, phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group, 5-phenyl-n-pentyloxy group, 6-phenyl-n-hexyloxy group, 7-phenyl-n-heptyloxy group, 8-phenyl-n-octyloxy group, 9-phenyl-n-nonyloxy group, and 10-phenyl-n-decyloxy group.

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

[0032] Specific examples of hydrolyzable silanes represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamiloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, and methyltriphenoxysilane. Netyloxysilane, Glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, α-Glycidoxyethyltrimethoxysilane, α-Glycidoxyethyltriethoxysilane, β-Glycidoxyethyltrimethoxysilane, β-Glycidoxyethyltriethoxysilane, α-Glycidoxypropyltrimethoxysilane, α-Glycidoxypropyltriethoxysilane, β-Glycidoxypropyltrimethoxysilane, β-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ- Ricidoxypropyltriethoxysilane, γ-glycidoxypropyltrippropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxysilane (3,4-Epoxycyclohexyl)methyltrimethoxysilane, (3,4-Epoxycyclohexyl)methyltriethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-Epoxycyclohexyl)ethyltributoxysilane, β-(3,4-Epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-Epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane Sisilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ- Ricidoxypropyl vinyldimethoxysilane, γ-glycidoxypropyl vinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimeth Xysilane, Divinyldiethoxysilane, Divinyldichlorosilane, Divinyldiacetoxysilane, γ-Glycidoxypropylvinyldimethoxysilane, γ-Glycidoxypropylvinyldiethoxysilane, Allyltrimethoxysilane, Allyltriethoxysilane, Allyltrichlorosilane, Allyltriacetoxysilane, Allylmethyldimethoxysilane, Allylmethyldiethoxysilane, Allylmethyldichlorosilane, Allylmethyldiacetoxysilane, Allyldimethylmethoxysilane, Allyldimethylethoxysilane, Allyldimethylchlorosilane,Allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane , phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 3-phenyl Diaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxy Sisilane, phenethyltrichlorosilane, phenethyltriacetoxysilane, phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane,Methoxyphenethyltrimethoxysilane, Methoxyphenethyltriethoxysilane, Methoxyphenethyltriacetoxysilane, Methoxyphenethyltrichlorosilane, Ethoxyphenyltrimethoxysilane, Ethoxyphenyltriethoxysilane, Ethoxyphenyltriacetoxysilane, Ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane, i-Propoxyphenyltrimethoxysilane, i-Propoxy i-Powoxyphenyltriacetoxysilane, i-Propoxyphenyltrichlorosilane, i-Propoxybenzyltrimethoxysilane, i-Propoxybenzyltriethoxysilane, i-Propoxybenzyltriacetoxysilane, i-Propoxybenzyltrichlorosilane, t-Butoxyphenyltrimethoxysilane, t-Butoxyphenyltriethoxysilane, t-Butoxyphenyltriacetoxysilane, t-Butoxyphenyltrichlorosilane, t-Butoxybenzyltrimethoxysilane, t-Butoxy Benzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxysibenzyltrichlosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyl Reacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanatetopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane,Examples include, but are not limited to, benzenesulfonamidopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and silanes represented by the following formulas (A-1) to (A-41).

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] Furthermore, as [A]polysiloxane, hydrolyzed condensates of hydrolyzable silanes can be mentioned, which include a hydrolyzable silane represented by formula (1), or, instead of the hydrolyzable silane represented by formula (1), a hydrolyzable silane represented by formula (3) below.

[0037] [ka] In formula (3), R 5is 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 containing 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. Also, R 6 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. R 7 is a group bonded to a silicon atom, and independently of one another, represents an alkylene group or an arylene group. And b represents an integer of 0 or 1, and c represents an integer of 0 or 1.

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

[0039] Specific examples of hydrolyzable silanes 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, as [A]polysiloxane, hydrolyzed condensates of hydrolyzable silanes can be listed, which include hydrolyzable silanes represented by formula (1) and / or hydrolyzable silanes represented by formula (3), as well as other hydrolyzable silanes listed below. 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 compounds containing an onium group in the molecule (hydrolyzable organosilanes)> Silane compounds containing an onium group within their molecule are expected to effectively and efficiently promote the crosslinking reaction of hydrolyzable silanes.

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

[0043] Specific examples of the alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, and organic groups including epoxy groups, acryloyl groups, methacryloyl groups, mercapto groups, amino groups, or cyano groups, as well as alkoxy groups, aralkyloxy groups, acyloxy groups, halogen atoms, and specific examples of substituents of alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, and alkenyl groups, and their preferred number of carbon atoms is R 12 Regarding R 1 Regarding the above, R 13 Regarding R 2 The above points can be listed for each of these.

[0044] More specifically, examples of onium groups include cyclic ammonium groups or linear ammonium groups, with tertiary or quaternary ammonium groups being preferred. In other words, preferred examples of an onium group or an organic group containing it include a cyclic ammonium group or a chain-like 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. Furthermore, 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, the nitrogen atom and silicon atom constituting the ring may be bonded directly or via a divalent linking group, or the carbon atom and silicon atom constituting the ring may be bonded directly or via a divalent linking group.

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

[0046] [ka] In formula (S1), A 1 , A 2 , A 3 and A 4 These represent a base that is independent of each other and can be expressed by any of the following formulas (J1) to (J3), but A 1 ~A 4 At least one of them is a group represented by the following formula (J2). The silicon atom in the above formula (4) is A 1 ~A 4 Depending on which of the following it bonds with, the resulting ring exhibits aromaticity, A 1 ~A 4 The type of bond between each atom and the adjacent atoms that form the ring together is determined to be either a single bond or a double bond.

[0047] [ka] In formulas (J1) to (J3), R 10 Each of these independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide, an aryl halide, an aralkyl halide, or an alkenyl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, alkyl halides, aryl halides, aralkyl halides, and alkenyl groups, and their preferred number of carbon atoms, are the same as those mentioned above.

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

[0049] In formula (S1), n 1 m is an integer from 1 to 8. 1 is 0 or 1, m 2 is a positive integer ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring. m 1 If A is 0, 1 ~A 4 (4+n) 1 A member ring is formed. That is, n 1 When is 1, it is a 5-membered ring, n 1 When is 2, it is a 6-membered ring, n 1 When is 3, it is a 7-membered ring, n 1 When is 4, it is an 8-membered ring, n 1 When is 5, it is a 9-membered ring, n 1 When n is 6, it is a 10-membered ring. 1 When is 7, it is an 11-membered ring, n 1 When the number is 8, a 12-membered ring is formed. m 1 If A is 1, 1 ~A 3 (4+n) 1 ) Member ring and A 4 A fused ring is formed by the fusion of a 6-membered ring containing the compound. A 1 ~A 4 Depending on which of formulas (J1) to (J3) it is, there may or may not be hydrogen atoms on the atoms constituting the ring, but A 1 ~A 4 However, if there is a hydrogen atom on the atom constituting the ring, that hydrogen atom is R 14 It may be replaced by A. 1 ~A4 In the ring constituent atoms other than the ring constituent atoms inside, R 14 It may be substituted. For these reasons, as stated above, m 2 This is selected from integers ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring.

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

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

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

[0053] In another example, the group R bonded to the silicon atom in formula (4) above is 11 This can be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).

[0054] [ka] In formula (S2), A 5 , A 6 , A 7 and A 8 These represent a base that is independent of each other and can be expressed by any of the following formulas (J4) to (J6), but A 5 ~A 8 At least one of them is a group represented by the following formula (J5). The silicon atom in the above formula (4) is A 5 ~A 8 Depending on which of the following it bonds with, the resulting ring exhibits non-aromaticity, A 5 ~A 8 The type of bond between each atom and the adjacent atoms that form the ring together is determined to be either a single bond or a double bond.

[0055] [ka] In formulas (J4) to (J6), R 10 Each of these independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide, an aryl halide, an aralkyl halide, or an alkenyl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, alkyl halides, aryl halides, aralkyl halides, and alkenyl groups, and their preferred number of carbon atoms, are the same as those described above.

[0056] In formula (S2), R 15independently of each other, 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, and R 15 when two or more R 15 are present, two R 15 may be bonded to each other to form a ring, and the ring formed by two R may be a bridged ring structure. In such a case, the cyclic ammonium group will have an adamantane ring, a norbornene ring, a spiro ring, etc.

[0057] In formula (S2), n 2 is an integer from 1 to 8, m 3 is 0 or 1, and m 4 is a positive integer from 0 or 1 to the maximum number that can be substituted in a monocyclic or polycyclic ring. When m 3 is 0, a (4 + n 5 )-member ring containing A 8 is formed. That is, when n<obiwan 2 is 1, a 5-member ring is formed; when n 2 is 2, a 6-member ring is formed; when n 2 is 3, a 7-member ring is formed; when n 2 is 4, an 8-member ring is formed; when n 2 is 5, a 9-member ring is formed; when n 2 is 6, a 10-member ring is formed; when n 2 is 7, an 11-member ring is formed; when n 2 is 8, a 12-member ring is formed, respectively. When m 2 is 1, a condensed ring formed by condensing a (4 + n 3 )-member ring containing A 5 ~A 7 and a 6-member ring containing A 2 is formed. A 8 ~A 5 ~A 8Depending on which of formulas (J4) to (J6) it is, there may or may not be hydrogen atoms on the atoms constituting the ring, but A 5 ~A 8 However, if there is a hydrogen atom on the atom constituting the ring, that hydrogen atom is R 15 It may be replaced by A. 5 ~A 8 In the ring constituent atoms other than the ring constituent atoms inside, R 15 It may be substituted. For these reasons, as stated above, m 4 This is selected from integers ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring.

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

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

[0060] In another example, the group R bonded to the silicon atom in formula (4) above is 11 This can be a chain-like ammonium group represented by the following formula (S3).

[0061] [ka] In formula (S3), R 10 Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide, an aryl halide, an aralkyl halide, or an alkenyl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, alkyl halides, aryl halides, aralkyl halides, and alkenyl groups, and their preferred number of carbon atoms, are the same as those described above.

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

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

[0064] <Silane compounds having a sulfone group or a sulfonamide group (hydrolyzable organosilanes)> 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 formula, Me represents a methyl group and Et represents an ethyl group.

[0065] [ka] [ka] [ka]

[0066] <Silane compounds containing a cyclic urea skeleton within the molecule (hydrolyzable organosilanes)> Examples of hydrolyzable organosilanes having a cyclic urea skeleton in their molecule include hydrolyzable organosilanes represented by the following formula (5-1).

[0067] [ka]

[0068] In formula (5-1), R 501 These are groups that bond to silicon atoms and represent groups that are independent of each other and are expressed by the following formula (5-2). R 502 This group is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group. R 503 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. x is either 1 or 2, and y is either 0 or 1, satisfying x + y ≤ 2. The above R 502 Alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, and organic groups including epoxy groups, acryloyl groups, methacryloyl groups, mercapto groups, or cyano groups, and R 503 Specific examples of alkoxy groups, aralkyloxy groups, acyloxy groups, and halogen atoms, as well as their substituents, preferred number of carbon atoms, etc., are as follows: 1 and R 2 The same items mentioned above can be cited in relation to this matter.

[0069] [ka]

[0070] In formula (5-2), R 504 R independently represents an organic group containing a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an epoxy group or a sulfonyl group. 505 These independently represent an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-), or an ester bond (-CO-O- or -O-CO-). Note, R 504 Specific examples of organic groups including optionally substituted alkyl groups, optionally substituted alkenyl groups, and epoxy groups, and preferred number of carbon atoms, etc., are given by R 1 The same things mentioned above can be cited regarding R, but in addition to these, 504 Preferably, the alkyl group may be one in which the terminal hydrogen atom is replaced with a vinyl group. Specific examples include allyl group, 2-vinylethyl group, 3-vinylpropyl group, and 4-vinylbutyl group.

[0071] Organic groups containing a sulfonyl group are not particularly limited as long as they contain a sulfonyl group, and include optionally substituted alkylsulfonyl groups, optionally substituted arylsulfonyl groups, optionally substituted aralkylsulfonyl groups, optionally substituted halogenated alkylsulfonyl groups, optionally substituted halogenated arylsulfonyl groups, optionally substituted halogenated aralkylsulfonyl groups, optionally substituted alkoxyalkylsulfonyl groups, optionally substituted alkoxyarylsulfonyl groups, optionally substituted alkoxyaralkylsulfonyl groups, optionally substituted alkenylsulfonyl groups, and the like. Specific examples of alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, and alkenyl groups in these groups, as well as their substituents, preferred number of carbon atoms, etc., are as follows: 1 The same items mentioned above can be cited in relation to this matter.

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

[0073] Also, R 505 The alkylene group may have one or more selected from sulfide bonds, ether bonds, and ester bonds at its terminal or in the middle, preferably in the middle. Specific examples of alkylene groups include linear alkylene groups such as methylene, ethylene, trimethylene, 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; and 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, and 1,3-cyclobutanediyl. Examples of alkylene groups include cyclic alkylenes such as tandyl groups, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl, as well as ether groups such as -CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2SCH2CH2CH2-, -CH2CH2CH2SCH2CH2CH2-, -CH2OCH2CH2SCH2-, and -CH2OCH2CH2SCH2-, but are not limited to these.

[0074] A hydroxyalkylene group is one in which at least one hydrogen atom of the above-mentioned alkylene group is replaced by a hydroxyl group. Specific examples include, but are not limited to, hydroxymethylene, 1-hydroxyethylene, 2-hydroxyethylene, 1,2-dihydroxyethylene, 1-hydroxytrimethylene, 2-hydroxytrimethylene, 3-hydroxytrimethylene, 1-hydroxytetramethylene, 2-hydroxytetramethylene, 3-hydroxytetramethylene, 4-hydroxytetramethylene, 1,2-dihydroxytetramethylene, 1,3-dihydroxytetramethylene, 1,4-dihydroxytetramethylene, 2,3-dihydroxytetramethylene, 2,4-dihydroxytetramethylene, and 4,4-dihydroxytetramethylene.

[0075] In formula (5-2), X 501 Each of these independently represents one of the groups represented by formulas (5-3) to (5-5) below, and the carbon atoms of the ketone group in formulas (5-4) and (5-5) below are the same as R in formula (5-2). 505 It bonds with the nitrogen atom to which it is bonded.

[0076] [ka]

[0077] In formulas (5-3) to (5-5), R 506 ~R 510 Each of these independently represents an organic group containing a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an epoxy or sulfonyl group. Specific examples and preferred carbon number of organic groups containing optionally substituted alkyl groups, optionally substituted alkenyl groups, and epoxy or sulfonyl groups are given in R. 504 The same items mentioned above can be cited in relation to this matter. In particular, from the perspective of achieving excellent lithography characteristics with good reproducibility, X 501 The base represented by formula (5-5) is preferred.

[0078] From the perspective of achieving excellent lithography characteristics with good reproducibility, R 504 and R 506 ~R 510 Preferably, at least one of the elements is an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group.

[0079] The hydrolyzable organosilane represented by formula (5-1) above may be a commercially available product, or it can be synthesized by known methods described in International Publication No. 2011 / 102470, etc.

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

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

[0082] As mentioned above, as [A]polysiloxane, a modified polysiloxane in which at least a portion of the silanol groups have been modified can be used. For example, a modified polysiloxane in which some of the silanol groups have been alcohol-modified or a modified polysiloxane protected with acetal can be used. Examples of the modified polysiloxane include reaction products obtained by the reaction of at least a portion of the silanol groups of the hydrolyzable silane hydrolysis condensate with the hydroxyl groups of an alcohol, dehydration reaction products of the condensate and an alcohol, and modified products obtained by protecting at least a portion of the silanol groups of the condensate with acetal groups.

[0083] The above alcohols can be monohydric alcohols, 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-hexano Examples include 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, and cyclohexanol. Additionally, alkoxy group-containing alcohols such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used.

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

[0085] Furthermore, the dehydration reaction product of a polysiloxane, which is a hydrolysis condensate of the above-mentioned 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 resulting water from the reaction system. The above-mentioned acid can be an organic acid having an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5. For example, the acid can be trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, etc., with benzoic acid, isobutyric acid, and acetic acid being particularly noteworthy. Furthermore, the acid used can have a boiling point of 70 to 160°C, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. As described above, the acid is preferably one that has either an acid dissociation constant (pKa) of 4 to 5 or a boiling point of 70 to 160°C. In other words, an acid with low acidity or an acid with high acidity but a low boiling point can be used. Furthermore, as an acid, it is possible to utilize either the acid dissociation constant or the boiling point properties.

[0086] The acetal protection of the silanol group in the above condensate can be carried out using a vinyl ether, for example, a vinyl ether represented by the following formula (6), and through these reactions, the substructure represented by the following formula (7) can be introduced into the polysiloxane. [ka] 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, and R 4a R represents an alkyl group having 1 to 10 carbon atoms. 2a and R 4a These elements may be bonded to each other to form a ring. The alkyl groups mentioned above are examples of those described above. [ka] In formula (7), R 1 ', R 2 ', and R 3 ' represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 4 ' represents an alkyl group having 1 to 10 carbon atoms, R 2 'and R 4 ' may be bonded to each other to form a ring. In formula (7), the asterisk (*) indicates a bond with an adjacent atom. Adjacent atoms are, for example, the oxygen atom of a siloxane bond, the oxygen atom of a silanol group, or the R in formula (1). 1 Examples of carbon atoms derived from [the above] include the alkyl groups mentioned above.

[0087] Examples of vinyl ethers represented by formula (6) above include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, as well as cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran can be used.

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

[0089] Furthermore, the capping of these silanol groups with alcohol or acetal protection may be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane, as described later.

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

[0091] Generally, the weight-average molecular weight of hydrolyzable silane hydrolysis condensates (including modified products) can be in the range of, for example, 500 to 1,000,000. From the viewpoint of suppressing the precipitation of hydrolysis condensates 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 applicability, it can be preferably 700 or more, more preferably 1,000 or more. In particular, in the present invention, from the viewpoint of preventing the collapse of the resist pattern of the upper layer when a thin film is formed, the weight-average molecular weight of the [A] polysiloxane, that is, the hydrolysis condensate (including modified products) of the above hydrolyzable silane, 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 polystyrene equivalent. GPC analysis can be performed, for example, using a GPC instrument (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product name Shodex® KF803L, KF802, KF801, manufactured by Showa Denko K.K.), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as the standard sample. Furthermore, the proportion of the specific molecular weight mentioned above refers to the proportion in the integrated molecular weight distribution curve obtained by GPC analysis in polystyrene equivalent. Furthermore, the weight-average molecular weight of the hydrolyzed condensate can be adjusted by, for example, the conditions during the hydrolysis and condensation of the hydrolyzable silane described later, such as the solvent used, the reaction temperature, and the reaction time.

[0092] Hydrolyzed silane hydrolysis condensates are obtained by hydrolyzing and condensing the above-mentioned silane compounds (hydrolyzable silanes). The above silane compounds (hydrolyzable silanes) contain alkoxy groups, aralkyloxy groups, acyloxy groups, and halogen atoms that are directly bonded to a silicon atom, namely alkoxysilyl groups, aralkyloxysilyl groups, acyloxysilyl groups, and silyl halogenated groups (hereinafter referred to as hydrolyzable groups). For the hydrolysis of these hydrolyzable groups, typically 0.1 to 100 moles of water, for example 0.5 to 100 moles, preferably 1 to 10 moles, are used per mole of hydrolyzable group. During hydrolysis and condensation, a hydrolysis catalyst may be used to accelerate the reaction, or it may be carried out without one. When a hydrolysis catalyst is used, typically 0.0001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolysis catalyst can be used per mole of hydrolyzable group. The reaction temperature for hydrolysis and condensation is typically in the range of room temperature or higher, and below the reflux temperature at atmospheric pressure of the organic solvent that can be used for hydrolysis, for example, 20 to 110°C, or for example, 20 to 80°C. Hydrolysis may be complete, meaning all hydrolyzable groups may be converted to silanol groups, or it may be partial hydrolysis, meaning some hydrolyzable groups may remain unreacted. Examples of hydrolysis catalysts that can be used for hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0093] Examples of metal chelate compounds used as hydrolysis catalysts include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, and di -i-propoxy bis(acetylacetonate) titanium, di-n-butoxy bis(acetylacetonate) titanium, di-sec-butoxy bis(acetylacetonate) titanium, di-t-butoxy bis(acetylacetonate) titanium, monoethoxy tris(acetylacetonate) titanium, mono-n-propoxy tris(acetylacetonate) titanium, mono-i-propoxy tris(acetylacetonate) titanium, mono-n-butoxy tris(acetylacetonate) titanium, mono-sec-butoxy tris(acetylacetonate) Titanium acetone, mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethylacetoacetate) titanium Titanium diacetate, di-n-propoxy-bis(ethylacetate) titanium, di-i-propoxy-bis(ethylacetate) titanium, di-n-butoxy-bis(ethylacetate) titanium, di-sec-butoxy-bis(ethylacetate) titanium, di-t-butoxy-bis(ethylacetate) titanium, monoethoxy-tris(ethylacetate) titanium, mono-n-propoxy-tris(ethylacetate) titanium, mono-i-propoxy-tris(ethylacetate) titanium,Titanium chelate compounds such as mono-n-butoxytris(ethylacetoacetate)titanium, mono-sec-butoxytris(ethylacetoacetate)titanium, mono-t-butoxytris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonate)tris(ethylacetoacetate)titanium, bis(acetylacetonate)bis(ethylacetoacetate)titanium, tris(acetylacetonate)mono(ethylacetoacetate)titanium; triethoxy-mono(acetylacetoacetate) Zirconium triacetate, tri-n-propoxy mono(acetylacetonate)zirconium, tri-i-propoxy mono(acetylacetonate)zirconium, tri-n-butoxy mono(acetylacetonate)zirconium, tri-sec-butoxy mono(acetylacetonate)zirconium, tri-t-butoxy mono(acetylacetonate)zirconium, diethoxy bis(acetylacetonate)zirconium, di-n-propoxy bis(acetylacetonate)zirconium, di-i-propoxy bis(A Cetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-i-propoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-sec- Butoxytris(acetylacetonate)zirconium, mono-t-butoxytris(acetylacetonate)zirconium, tetrakis(acetylacetonate)zirconium, triethoxymono(ethylacetoacetate)zirconium, tri-n-propoxymono(ethylacetoacetate)zirconium, tri-i-propoxymono(ethylacetoacetate)zirconium, tri-n-butoxymono(ethylacetoacetate)zirconium, tri-sec-butoxymono(ethylacetoacetate)zirconium,Tri-t-butoxy mono(ethyl acetate) zirconium, diethoxy bis(ethyl acetate) zirconium, di-n-propoxy bis(ethyl acetate) zirconium, di-i-propoxy bis(ethyl acetate) zirconium, di-n-butoxy bis(ethyl acetate) zirconium, di-sec-butoxy bis(ethyl acetate) zirconium, di-t-butoxy bis(ethyl acetate) zirconium, monoethoxy tris(ethyl acetate) zirconium, mono-n-propoxy tris(ethyl acetate) zirconium, mono-i-propoxy tris(ethyl acetate) zirconium, mono-n-butoxy Examples of zirconium chelate compounds include, but are not limited to, tris(ethylacetate)zirconium, mono-sec-butoxytris(ethylacetate)zirconium, mono-t-butoxytris(ethylacetate)zirconium, tetrakis(ethylacetate)zirconium, mono(acetylacetonate)tris(ethylacetate)zirconium, bis(acetylacetonate)bis(ethylacetate)zirconium, and tris(acetylacetonate)mono(ethylacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonate)aluminum and tris(ethylacetate)aluminum; etc.

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

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

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

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

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

[0099] In particular, nitric acid can be suitably used as a hydrolysis catalyst in this invention. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, changes in the molecular weight of the hydrolysis condensate can be suppressed. It is known that the stability of the hydrolysis condensate in liquid depends on the pH of the solution. After diligent research, it was found that by using an appropriate amount of nitric acid, the pH of the solution can be brought into a stable range. Furthermore, as mentioned above, nitric acid can also be used when obtaining modified hydrolysis condensates, for example, when capping silanol groups with alcohol. Therefore, it is preferable from the viewpoint that it can contribute to both the hydrolysis and condensation of hydrolyzable silane and the alcohol capping of the hydrolysis condensate.

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

[0101] After the hydrolysis and condensation reactions are complete, the reaction solution can be neutralized, either as is or diluted or concentrated, and then treated with an ion exchange resin to remove the hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation. Alternatively, before or after such treatment, by-products such as alcohol, water, and the hydrolysis catalysts used can be removed from the reaction solution by vacuum distillation or the like.

[0102] The hydrolysis condensate obtained in this manner (hereinafter also referred to as polysiloxane) is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and can be used as is in the preparation of the resist underlayer film formation composition described later. That is, the above reaction solution can be used as is (or diluted) in the preparation of the resist underlayer film formation composition, and in this case, the hydrolysis catalyst and by-products used for hydrolysis and condensation may remain in the reaction solution as long as they do not impair the effects of the present invention. For example, the hydrolysis catalyst and nitric acid used during alcohol capping of silanol groups may remain in the polymer varnish solution at a concentration of about 100 ppm to 5,000 ppm. The resulting polysiloxane varnish may be subjected to solvent replacement or diluted with an appropriate solvent. Furthermore, if its storage stability is not compromised, the organic solvent can be removed from the resulting polysiloxane varnish to obtain a solid content of 100%. The organic solvent used for solvent substitution or dilution of the above-mentioned polysiloxane varnish may be the same as or different from the organic solvent used in the hydrolysis and condensation reaction of the hydrolyzable silane. This dilution solvent is not particularly limited, and one or more types may be arbitrarily selected and used.

[0103] [B] solvent The solvent [B] used in the silicon-containing resist underlayer film forming composition of the present invention is not particularly limited as long as it is a solvent that can dissolve and mix with the above [A] polysiloxane and other components described later. Note that the solvent does not contain the glycol compound [C] described later. Also, even when the reaction solution of the polysiloxane [A] is used as it is (or diluted) for preparing the composition for forming the resist underlayer film, the solvent used for the hydrolysis and condensation of the polysiloxane does not contain the glycol compound [C] described later.

[0104] [B]Specific examples of solvents 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), propylene glycol monoethyl ether Cete, 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-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, etc. can be mentioned, and the solvent can be used alone or in combination of two or more kinds.

[0105] In addition, 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, its content can be, for example, 30% by mass or less, preferably 20% by mass or less, 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 can contain a glycol compound (also referred to as a high-boiling glycol compound) represented by the following general formula (2) and having a standard boiling point of 230.0°C or higher. In this specification, the "standard boiling point" refers to the boiling point at 1 atm (101325 Pa) (Normal Boiling Point, NBP). As described above, in the present invention, the above [C] glycol compound does not correspond to the above [B] solvent.

[0107] The glycol compound described above contributes to suppressing the occurrence of defects caused by fine particles that may be generated during the formation of the resist underlayer film during the coating of the resist underlayer film formation composition when forming a silicon-containing resist underlayer film. The above-mentioned coating defects are believed to be caused in part by the volatilization of solvents contained in the resist underlayer film formation composition and the generation of fine particles (solid matter) due to the solidification (condensation, etc.) of polymer components such as polysiloxane contained in the composition. Such solvent volatilization and generation of solid matter can occur not only during storage of the resist underlayer film formation composition but also during the formation of the resist underlayer film. In other words, in actual field operations related to resist underlayer film formation, coating film formation by a coating device may be carried out continuously, and in this case, not only solvent volatilization but also the generation of fine particles can occur within the discharge nozzle of the coating device. By including the above-mentioned high-boiling-point glycol compound in the silicon-containing resist underlayer film forming composition, the stability of the composition within the discharge nozzle of the coating apparatus is improved, and the generation of fine particles within the nozzle is prevented, thereby suppressing the occurrence of defects in the coated film.

[0108] [ka] In formula (2), R 3 and R 4 Each of these 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. Note that there are multiple R's. 3 These may be the same or different.

[0109] The above R 3 and R 4 Examples of alkyl groups having 1 to 4 carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl groups; and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and t-butyl groups. Also, the above R 3 and R 4Examples of acyl groups having 3 to 4 carbon atoms in this context include ethyl carbonyl group (propionyl group) and propyl carbonyl group (butyryl group). n is an integer greater than or equal to 3, with its upper limit being, for example, 7. Among these, R 4 The C1 to C4 alkyl group or the C3 to C4 acyl group is preferred, and R 3 A hydrogen atom or a methyl group is preferred.

[0110] Specific examples of glycol compounds represented by formula (2) above that have 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), heptaethylene glycol monomethyl ether (standard boiling point: >300°C), etc., but are not limited to these compounds.

[0111] When using the above-mentioned [C] glycol compound, the amount it is blended can be less than 1% by mass based on the total mass of the silicon-containing resist underlayer film forming composition, and its lower limit can be 0.01% by mass. By blending the [C] glycol compound within the above range, the silicon-containing resist underlayer film forming composition of the present invention is preferable because the film obtained from the composition is expected to have solvent resistance and effectively suppress the occurrence of defects.

[0112] Furthermore, when an organic solvent corresponding to the [C] glycol compound is used as a solvent during the production of the aforementioned [A] polysiloxane, that is, during the hydrolysis and condensation of the hydrolyzable silane, and the reaction solution is used as is for the preparation of the resist underlayer film forming composition, the organic solvent corresponding to the [C] glycol compound remaining in the reaction solution can be included as the above-mentioned [C] glycol compound.

[0113] [Silicon-containing composition for forming a resist underlayer film] The silicon-containing resist underlayer film forming composition of the present invention comprises [A] polysiloxane, [B] solvent, optionally [C] glycol compound, and may further contain other components described later. The concentration of solids in the resist underlayer film forming composition may be, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, or 0.5 to 20.0% by mass, relative to the total mass of the composition. The above solids refer to the components of the composition excluding [B] solvent components and [C] glycol compounds from the total components of the composition. The content of the above [A] polysiloxane in the solid content is usually 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention described above with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and still more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the additives described later. Furthermore, the resist underlayer film forming composition 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 manufactured by mixing the above-mentioned [A] polysiloxane, [B] solvent, and [C] glycol compound, and other components if any are included. In this case, a solution containing [A] polysiloxane may be prepared in advance and this solution may be mixed with [B] solvent, [C] glycol compound, and other components. Alternatively, the reaction solution used to prepare [A] polysiloxane can be used directly to prepare the resist underlayer film forming composition, in which case the [C] glycol compound may be added during the production of the polysiloxane. The mixing order is not particularly limited. For example, a solution containing [A] polysiloxane may be mixed with [B] solvent, and then [C] glycol compound and other components may be added to the mixture; or the solution containing [A] polysiloxane, [B] solvent, [C] glycol compound, and other components may be mixed simultaneously. If necessary, additional [B] solvent may be added at the end, or some components that are relatively soluble in [B] solvent may be left out of the mixture and added at the end. However, from the viewpoint of suppressing aggregation and separation of constituent components and preparing a composition with excellent uniformity with good reproducibility, it is preferable to prepare a solution in which [A] polysiloxane is well dissolved in advance and use this to prepare the composition. Note that [A] polysiloxane may aggregate or precipitate when mixed with [B] solvent, [C] glycol compounds, and other components, depending on the type and amount of [B] solvent mixed with it, as well as the amount and properties of these components. Also, when preparing a composition using a solution in which [A] polysiloxane is dissolved, note that it is necessary to determine the concentration of the [A] polysiloxane solution and the amount used so that the amount of [A] polysiloxane in the final composition is the desired amount. During the preparation of the composition, heating may be used as appropriate, provided that the components do not decompose or deteriorate.

[0115] In the present invention, the composition for forming a resist underlayer film may be filtered using a sub-micrometer-order filter or the like during the manufacturing process or after all components have been mixed. The material of the filter used is not limited, but for example, a nylon filter or a fluororesin filter can be used.

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

[0117] [Other additives] The silicon-containing resist underlayer film forming composition of the present invention can be blended with various additives depending on the application of the composition. Examples of the above-mentioned additives include known additives that are incorporated into materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, anti-reflective films, and pattern reversal films. These additives include 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 surfactants, fluorine surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology adjusters, and adhesion aids. The following are examples of various additives, but they are not limited to these.

[0118] <Curing catalyst> The silicon-containing resist underlayer film formation composition of the present invention may be a composition that does not contain a curing catalyst, but it may also contain a curing catalyst. As the curing catalyst mentioned above, ammonium salts, phosphines, phosphonium salts, sulfonium salts, etc., can be used. The salts listed below as examples of curing catalysts may be added in salt form, or they may form salts in the above composition (added as separate compounds and forming salts in the system).

[0119] As the ammonium salt, the formula (D-1):

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0120] Furthermore, the above phosphonium salt is given by formula (D-7): [ka] (In the formula, R 31 , R 32 , R 33 , and R 34 P represents an alkyl or aryl group, P represents a phosphorus atom, and Y represents a phosphorus atom. - represents an anion, and R 31 , R 32 , R 33 , and R 34 Examples of quaternary phosphonium salts can be given, which are represented as follows (where each is bonded to a phosphorus atom).

[0121] Furthermore, the above sulfonium salt is given by formula (D-8): [ka] (In the formula, R 35 , R 36 , and R 37 S represents an alkyl or aryl group, S represents a sulfur atom, and Y represents a sulfur atom. - represents an anion, and R 35 , R 36 , and R 37Examples of tertiary sulfonium salts can be given, which are represented as (where each is bonded to a sulfur atom).

[0122] The compound of formula (D-1) above is a quaternary ammonium salt derived from an amine, and m a n represents an integer between 2 and 11, where n a R represents an integer between 2 and 3. 21 This represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10, or an aryl group having 6 to 18 carbon atoms, for example, linear alkyl groups such as ethyl, propyl, and butyl groups, or benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl groups. Also, an anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include those listed above.

[0123] The compound of formula (D-2) above is R 22 R 23 R 24 R 25 N + Y - This is a quaternary ammonium salt represented by . The R of this quaternary ammonium salt 22 , R 23 , R 24 and R 25 This is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O -Examples of acidic groups include ) and others. These quaternary ammonium salts are commercially available, and examples include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0124] The compound of formula (D-3) above is a quaternary ammonium salt derived from a 1-substituted imidazole, and R 26 and R 27 The number of carbon atoms is 1 to 18, R 26 and R 27 It is preferable that the total number of carbon atoms is 7 or more. For example, R 26 R 27 Examples include the benzyl group, octyl group, and octadecyl group. Anions (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include ). This compound can be obtained commercially, but it can also be produced by reacting imidazole compounds such as 1-methylimidazole and 1-benzylimidazole with alkyl halides or aryl halides such as benzyl bromide and methyl bromide.

[0125] The compound of formula (D-4) above is a quaternary ammonium salt derived from pyridine, and R 28 The C1 group 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, for example, a butyl group, an octyl group, a benzyl group, and a lauryl group. The anion (Y - ) is a chloride ion (Cl -), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting pyridine with an alkyl halide or aryl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0126] The compound of formula (D-5) above is a quaternary ammonium salt derived from substituted pyridines 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, for example, a methyl group, an octyl group, a lauryl group, a benzyl group, etc. 30 R 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 derived from picoline, for example, 30 It is a methyl group. Anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting a substituted pyridine such as picoline with an alkyl halide or aryl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0127] The compound of formula (D-6) above is a tertiary ammonium salt derived from an amine, and m a n represents an integer between 2 and 11, where n a This represents an integer between 2 and 3. Also, the anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include (Y). This compound can be produced by the reaction of an amine with a weak acid such as a carboxylic acid or phenol. Examples of carboxylic acids include formic acid and acetic acid, and when formic acid is used, an anion (Y - ) is (HCOO - ) and when acetic acid is used, the anion (Y - ) is (CH3COO - ) is also used. In addition, when phenol is used, the anion (Y - ) is (C6H5O - )

[0128] The compound of formula (D-7) above is R 31 R 32 R 33 R 34 P + Y - It is a quaternary phosphonium salt having the structure R 31 , R 32 , R 33 , and R 34 is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, preferably R 31 ~R 34 Of the four substituents, three are phenyl groups or substituted phenyl groups, for example, 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. Also, the anion (Y - ) is a chloride ion (Cl- ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include ) and others. This compound is available commercially, and examples include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritrilmonoarylphosphonium halide, or tritrilmonoalkylphosphonium halide (in all cases, the halogen atom is a chlorine atom or a bromine atom). Particularly preferred are triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, tritrilmonoarylphosphonium halides such as tritrilmonophenylphosphonium halide, and tritrilmonoalkylphosphonium halides such as tritrilmonomethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).

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

[0130] The compound of formula (D-8) above 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, for example, 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. Also, the anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O -Examples of acid groups include maleate anions and nitrate anions. This compound is available commercially, and examples include trialkylsulfonium halides such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halide, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halide and diphenylethylsulfonium halide, triphenylsulfonium halide (in all cases, the halogen atom is either a chlorine atom or a bromine atom), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmonoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate and diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. In addition, triphenylsulfonium halide and triphenylsulfonium carboxylate can be preferably used.

[0131] Furthermore, in this invention, a nitrogen-containing silane compound can be added as a curing catalyst. Examples of nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilipropyl)-4,5-dihydroimidazole.

[0132] When a curing catalyst is used, the 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 [A]polysiloxane.

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

[0134] <Organic polymers> By adding the above-mentioned organic polymer compound to the resist underlayer film forming composition, the dry etching rate (amount of film thickness reduction per unit time), as well as the damping coefficient and refractive index of the film (resist underlayer film) formed from the composition can be adjusted. There are no particular restrictions on the organic polymer compound, and it can be appropriately selected from various organic polymers (condensation polymers and addition polymers) depending on the purpose of its addition. Specific examples include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be suitably used when such functionality is required. Specific examples of such organic polymer compounds include, but are not limited to, addition polymerization polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as structural units, and condensation polymerization polymers such as phenol novolac and naphthol novolac.

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

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

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

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

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

[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 acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

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

[0144] The weight-average molecular weight of the above organic polymer compound can usually be between 1,000 and 1,000,000. When incorporating an organic polymer compound, in order to fully obtain the functional effects of the polymer while suppressing precipitation in the composition, its weight-average molecular weight can be set to, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000. Such organic polymer compounds may be used individually or in combination of two or more.

[0145] When the silicon-containing resist underlayer film forming composition of the present invention contains an organic polymer compound, its content cannot be specified in general terms as it is determined appropriately considering the function of the organic polymer compound, etc. However, it can usually be in the range of 1 to 200% by mass relative to the mass of the above [A] polysiloxane. From the viewpoint of suppressing precipitation in the composition, for example, it can be 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less. From the viewpoint of obtaining the full effect, for example, it can be 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0146] <Acid Generator> Examples of acid generators include thermal acid generators and photoacid generators, with photoacid generators being preferred. Examples of photoacid generators include, but are not limited to, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. Furthermore, depending on the type, some photoacid generators, such as carboxylates (nitrates, maleates, etc.) and hydrochlorides of onium salt compounds (described later), can also function as curing catalysts. Examples of thermal acid generators include, but are not limited to, tetramethylammonium nitrate.

[0147] Specific examples of iodonium salt compounds include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride.

[0148] Specific examples of sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

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

[0150] When the silicon-containing resist underlayer film forming composition of the present invention contains an acid generator, the amount of the acid generator cannot be specified in general terms as it is determined appropriately considering the type of acid generator, etc. However, it is usually in the range of 0.01 to 5% by mass relative to the mass of [A]polysiloxane, preferably 3% by mass or less, more preferably 1% by mass or less, from the viewpoint of suppressing the precipitation of the acid generator in the composition, and preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of obtaining the full effect. The acid generator can be used alone or in combination of two or more types, and a photoacid generator and a thermoacid generator may be used in combination.

[0151] <Surfactants> Surfactants are effective in suppressing the occurrence of pinholes, striations, etc., when the above-mentioned resist underlayer film forming composition is applied to a substrate. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorine 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 tri Nonionic surfactants such as oleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters; trade names F-Top (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.)); trade names Megafac (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation); Florard F Examples of fluorinated surfactants include C430, FC431 (manufactured by 3M Japan Ltd.), the product name Asahi Guard (registered trademark) AG710 (manufactured by AGC Inc.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these. Surfactants can be used individually or in combination of two or more types.

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

[0153] <Rheological modifier> The above-mentioned rheology modifiers are mainly added to improve the fluidity of the resist underlayer film formation composition, and in particular during the baking process, to improve the uniformity of the film thickness formed and to enhance the filling of the composition into the holes. Specific examples include phthalate derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate; adipic acid derivatives such as di-normal butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyl decyl adipate; maleic acid derivatives such as di-normal butyl malate, diethyl malate, and dinonyl malate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate. When these rheological modifiers are used, the amount added is usually less than 30% by mass relative to the total solid content of the resist underlayer film forming composition.

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

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

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

[0157] <Metal oxides> Furthermore, examples of metal oxides 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 more metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and metalloids such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0158] [Manufacturing method for semiconductor devices] Hereinafter, as one aspect of the present invention, a method for manufacturing a semiconductor device (semiconductor element) using the silicon-containing resist underlayer film formation composition 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 elements [for example, semiconductor substrates such as silicon wafers coated with silicon oxide films, silicon nitride films, or silicon oxidoxide-nitride films, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates on which ITO (indium tin oxide) films or IZO (indium zinc oxide) films are formed, plastic (polyimide, PET, etc.) substrates, substrates coated with low-dielectric constant materials (low-k materials), flexible substrates, etc.] by an appropriate coating method such as a spinner or coater, and then the composition is cured into a film by firing using a heating means such as a hot plate, thereby forming a resist underlayer film. Hereinafter, in this specification, the resist underlayer film refers to a film formed from the silicon-containing resist underlayer film forming composition of the present invention. The firing conditions are appropriately selected from among a firing temperature of 40°C to 400°C, or 80°C to 250°C, and a firing time of 0.3 minutes to 60 minutes. Preferably, the firing temperature is 150°C to 250°C and the firing time is 0.5 minutes to 2 minutes. Generally, the thickness of the resist underlayer can be, for example, about 10 nm to 1,000 nm. As mentioned above, in recent years, with the trend towards thinner resists, there is a demand for thinner resist underlayers. Therefore, the present invention targets not only resist underlayers with a thickness of 10 nm to 1,000 nm, but also resist underlayers with a thickness of 10 nm or less. By using the silicon-containing resist underlayer formation composition of the present invention, the cured resist underlayer of the present invention can suppress pattern defects such as the collapse of the resist pattern formed on the upper layer, even if its thickness is 10 nm or less. For example, the resist underlayer of the present invention can have a thickness of 1 nm to 10 nm. Furthermore, a resist underlayer formation composition that has been filtered with a nylon filter can be used as the resist underlayer formation composition used when forming the resist underlayer. Here, a resist underlayer formation composition that has been filtered with a nylon filter refers to a composition that has been filtered with a nylon filter either during the manufacturing process of the resist underlayer formation composition or after all components have been mixed.

[0160] In addition, in other embodiments of the present invention, an organic underlayer film may be formed on the substrate, and then the resist underlayer film may be formed on top of it. There are no particular restrictions on the organic underlayer film used here; any film that has been conventionally used in lithography processes can be arbitrarily selected and used. By providing an organic underlayer film, a resist underlayer film on top of that, and a resist film described later on top of that on the substrate, the pattern width of the photoresist film is narrowed, and even when the photoresist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas described later. For example, the silicon-containing resist underlayer film of the present invention can be processed by using a fluorine-based gas having a sufficiently fast etching rate for the photoresist film as the etching gas, the organic underlayer film can be processed by using an oxygen-based gas having a sufficiently fast etching rate for the silicon-containing resist underlayer film of the present invention as the etching gas, and the substrate can be processed by using a fluorine-based gas having a sufficiently fast etching rate for the organic underlayer film as the etching gas. The substrates and coating methods that can be used in this case are the same as those described above.

[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, that is, by applying a coating-type resist material (for example, a photoresist film forming composition) onto the resist underlayer film and firing it. The thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0162] The photoresist material used for the resist film formed on the above-mentioned 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-type and positive-type photoresist materials can be used. Examples include a positive-type photoresist material consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist material consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, a chemically amplified photoresist material consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist material, an alkali-soluble binder and a photoacid generator, and a chemically amplified photoresist material consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate, a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist material and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (manufactured by Cypree), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), AR2772JN (manufactured by JSR Corporation), and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, examples of fluorine-containing polymer-based photoresist materials, such as those described in Proc.SPIE, Vol.3999, 330-334 (2000), Proc.SPIE, Vol.3999, 357-364 (2000), and Proc.SPIE, Vol.3999, 365-374 (2000), can be cited.

[0163] Furthermore, instead of a photoresist film, an electron beam lithography resist film (also referred to as an electron beam resist film) or an EUV lithography resist film (also referred to as an EUV resist film) can be used as the resist film formed on the above-mentioned resist underlayer film. In other words, the silicon-containing resist underlayer film formation composition of the present invention can be used for forming a resist underlayer film for electron beam lithography or for forming a resist underlayer film for EUV lithography. It is particularly suitable as a resist underlayer film formation composition for EUV lithography. Both negative and positive electron beam resist materials can be used as the electron beam resist material. Specific examples include: chemically amplified resist materials consisting of an acid generator and a binder having a group that decomposes with acid to change the alkali dissolution rate; chemically amplified resist materials consisting of an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes with acid to change the alkali dissolution rate of the resist material; chemically amplified resist materials consisting of an acid generator, a binder having a group that decomposes with acid to change the alkali dissolution rate, and a low-molecular-weight compound that decomposes with acid to change the alkali dissolution rate of the resist material; non-chemically amplified resist materials consisting of a binder having a group that decomposes with electron beam to change the alkali dissolution rate; and non-chemically amplified resist materials consisting of a binder having a portion that is cut by electron beam to change the alkali dissolution rate. When using these electron beam resist materials, a resist film pattern 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, a predetermined mask (re) is applied to the resist film formed on the upper layer of the resist underlayer film. Chiku Exposure is performed through a laser. For exposure, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), electron beam, etc. can be used. After exposure, post-exposure baking can be performed as needed. Post-exposure baking is carried out under conditions appropriately selected from heating temperatures of 70°C to 150°C and heating times of 0.3 minutes to 10 minutes.

[0165] Next, development is performed using a developer (for example, an alkaline developer). This removes the photoresist film from the exposed areas, for example, if a positive-type photoresist film is used, and a pattern of the photoresist film is formed. Examples of developer solutions (alkaline developers) include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants can be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0166] Furthermore, in this invention, an organic solvent can be used as the developer, and development is performed with the developer (solvent) after exposure. As a result, for example, when a negative-type photoresist film is used, the photoresist film in the unexposed areas is removed, and a pattern of the photoresist film is formed. Examples of developers (organic solvents) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 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 acetate Alacetate, 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 include ethyl acetate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. Furthermore, surfactants and other additives can be added to these developers.For development, the temperature should be between 5°C and 50°C, and the development time should be selected appropriately from 10 seconds to 600 seconds.

[0167] The pattern of the photoresist film (upper layer) formed in this manner is used as a protective layer to remove the resist underlayer film (intermediate layer). Then, the patterned resist underlayer film (intermediate layer) is used as a protective layer to remove the organic underlayer film (lower layer). Finally, the patterned resist underlayer film (intermediate layer) and the patterned organic underlayer film (lower layer) are used as protective layers to process the substrate.

[0168] The removal (patterning) of the resist underlayer (intermediate layer), which is performed using the pattern of the resist layer (upper layer) as a protective layer, is carried out by dry etching, and gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. Furthermore, it is preferable to use halogen-based gases for dry etching of the resist underlayer. In dry etching with halogen-based gases, resist films (photoresist films) made of organic materials are generally difficult to remove. In contrast, silicon-containing resist underlayers, which contain many silicon atoms, are quickly removed by halogen-based gases. Therefore, the reduction in the thickness of the photoresist film that occurs with dry etching of the resist underlayer can be suppressed. As a result, it becomes possible to use the photoresist film as a thin film. Accordingly, it is preferable to use fluorine-based gases for dry etching of the resist underlayer. Examples of fluorine-based gases include, but are not limited to, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

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

[0170] Subsequently, the processing (patterning) of the (semiconductor) substrate, which is carried out using a patterned resist underlayer film (intermediate layer) and, optionally, a patterned organic underlayer film (underlayer) as protective films, is preferably performed by dry etching with a fluorine-based gas. Examples of fluorinated gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0171] After the removal (patterning) of the above-mentioned organic underlayer film, or after the processing (patterning) of the substrate, the resist underlayer film may be removed. The resist underlayer film can be removed by dry etching or wet etching. Dry etching of the resist underlayer film is preferably performed using a fluorine-based gas, as mentioned in the patterning section above. Examples include, but are not limited to, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2). Examples of chemicals used for wet etching of the resist underlayer include dilute hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (a mixed solution of HF and NH4F), an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM solution), and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 solution), among other alkaline solutions. In addition to the aforementioned ammonia hydrochloride (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide, and water, other examples of alkaline solutions include aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepicato hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These solutions can also be used in combination.

[0172] Furthermore, an organic anti-reflective coating can be formed on top of the resist underlayer before the resist film is formed. There are no particular restrictions on the anti-reflective coating composition used; for example, any composition conventionally used in lithography processes can be arbitrarily selected and used, and the anti-reflective coating can be formed by conventional methods, such as coating with a spinner or coater and firing.

[0173] Furthermore, the substrate on which the silicon-containing resist underlayer film forming composition of the present invention is applied may have an organic or inorganic anti-reflective coating formed on its surface by CVD or the like, and the resist underlayer film can be formed on top of it. Even when an organic underlayer film is formed on the substrate and then the resist underlayer film of the present invention is formed on top of it, the substrate used may also have an organic or inorganic anti-reflective coating formed on its surface by CVD or the like.

[0174] The resist underlayer formed from the silicon-containing resist underlayer formation composition of the present invention may also have absorption properties for certain wavelengths of light used in the lithography process. In such cases, it can function as an anti-reflective film that prevents reflected light from the substrate. Furthermore, the above-mentioned resist underlayer can also be used as a layer to prevent interaction between the substrate and the resist film (photoresist film, etc.), a layer that has the function of preventing adverse effects on the substrate by materials used in the resist film or substances generated during exposure to the resist film, a layer that has the function of preventing diffusion of substances generated from the substrate into the upper resist film during heating and firing, and a barrier layer to reduce the poisoning effect of the resist film by the semiconductor substrate dielectric layer.

[0175] The above resist underlayer film can be applied to a substrate with via holes formed in a dual damascene process and can be used as a hole-filling material (filling material) that can completely fill the holes. It can also be used as a planarizing material to flatten the surface of an uneven semiconductor substrate. Furthermore, the above-mentioned resist underlayer film can be used not only as a hard mask underlayer for an EUV resist film, but also as an anti-reflective underlayer for an EUV resist film. For example, it can prevent reflection of undesirable exposure light, such as UV (ultraviolet) light or DUV (deep ultraviolet) light (ArF light, KrF light), from the substrate or interface during EUV exposure (wavelength 13.5 nm), without intermixing with the EUV resist film. 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 way as for a photoresist underlayer film.

[0176] The semiconductor processing substrate comprising the resist underlayer film of the present invention described above and a semiconductor substrate can be used to suitably process a semiconductor substrate. Furthermore, according to a semiconductor device manufacturing method that 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, as described above, highly accurate semiconductor substrate processing can be achieved with good reproducibility, and therefore stable manufacturing of semiconductor devices can be expected. [Examples]

[0177] The present invention will be described in more detail below with reference to synthesis examples and embodiments, but the present invention is not limited to the embodiments described below.

[0178] The apparatus and conditions used for analyzing the physical properties of the sample in the examples are as follows. (1) Molecular weight measurement The molecular weight of the polysiloxane used in this invention is the molecular weight obtained in terms of polystyrene by GPC analysis. GPC measurement conditions can be followed, for example, using a GPC instrument (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product name Shodex® KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as the standard sample. (2) 1 H-NMR JEOL Nuclear Magnetic Resonance Spectrometer 1 The results were evaluated using 1H-NMR (400 MHz) with d6-acetone as the solvent.

[0179] [1] Synthesis of polymers (hydrolyzed condensates) (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 mixture with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol, methanol, and water, were removed by vacuum distillation, and the mixture was concentrated to obtain an aqueous solution of the hydrolyzed condensate (polymer). Furthermore, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The mixture was then filtered through a nylon filter (pore size 0.1 μm). The resulting polymer contained a polysiloxane (P1) with a structure represented by the following formula (E1), and its weight-average molecular weight was Mw 1,300 in terms of polystyrene as determined by GPC. [ka]

[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 mixture with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol, methanol, and water, were removed by vacuum distillation, and the mixture was concentrated to obtain an aqueous solution of the hydrolyzed condensate (polymer). Furthermore, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The mixture was then filtered through a nylon filter (pore size 0.1 μm). The resulting polymer contained a polysiloxane (P2) with the structure represented by the above formula (E1), and its weight-average molecular weight was Mw 1,800 in terms of polystyrene as determined 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 mixture with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol, methanol, and water, were removed by vacuum distillation, and the mixture was concentrated to obtain an aqueous solution of the hydrolyzed condensate (polymer). Furthermore, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The mixture was then filtered through a nylon filter (pore size 0.1 μm). The resulting polymer contained a polysiloxane (P3) with the structure represented by the above formula (E1), and its weight-average molecular weight was Mw2,200 in terms of polystyrene as determined 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 mixture with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol, methanol, and water, were removed by vacuum distillation, and the mixture was concentrated to obtain an aqueous solution of the hydrolyzed condensate (polymer). Furthermore, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The mixture was then filtered through a nylon filter (pore size 0.1 μm). The resulting polymer contained a polysiloxane (P4) with the structure represented by the above formula (E1), and its weight-average molecular weight was Mw2,600 in terms of polystyrene as determined 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 mixture with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol, methanol, and water, were removed by vacuum distillation, and the mixture was concentrated to obtain an aqueous solution of the hydrolyzed condensate (polymer). Furthermore, propylene glycol monoethyl ether was added, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The mixture was then filtered through a nylon filter (pore size 0.1 μm). The resulting polymer contained a polysiloxane (P5) with the structure represented by the above formula (E1), and its weight-average molecular weight was Mw 2,900 in terms of polystyrene as determined 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 polysiloxanes with a molecular weight range greater than 2500.

[0185] [Table 1]

[0186] [2] Preparation of compositions for forming a resist underlayer film The polysiloxane (polymer), acid (additive 1), condensation catalyst (additive 2), high-boiling point glycol compound (additive 3), and solvent obtained in the above synthesis example are shown. 2 The resist underlayer film formation compositions were prepared by mixing the materials in the proportions shown and filtering them through a 0.1 μm fluororesin filter. 2 The amounts of each additive are shown in parts by mass. Note that the hydrolysis condensate (polymer) was prepared as a solution containing the condensate obtained in the synthesis example, but the table 2 The polymer addition ratio shown refers to the amount of polymer itself added, not the amount of polymer solution added. Furthermore, DIW refers to ultrapure water, PGEE refers to propylene glycol monoethyl ether, and PGME refers to propylene glycol monomethyl ether. Furthermore, MA represents maleic acid, IMTEOS represents triethoxysilylpropyl-4,5-dihydroimidazole, TPSNO3 represents triphenylsulfonium nitrate, and TEGEE represents triethylene glycol monoethyl ether.

[0187] [Table 2]

[0188] [3] Preparation of compositions for forming an organic resist underlayer film Under nitrogen, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL four-necked flask. 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was then added and the mixture was stirred. The temperature was raised to 100°C to dissolve the mixture and begin polymerization. After 24 hours, the mixture was allowed to cool to 60°C. The cooled reaction mixture was diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.), and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to precipitate. The obtained precipitate was filtered and recovered, and the recovered solid was dried in a vacuum dryer at 80°C for 24 hours to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL). Note that PCzFL 1 The results of the 1H-NMR measurement were as follows: 1 H-NMR(400MHz,DMSO-d6):δ7.03-7.55(br,12H),δ7.61-8.10(br,4H),δ11.18(br,1H) Furthermore, the weight-average molecular weight Mw of PCzFL was 2,800 when converted to polystyrene using GPC, and the polydispersity Mw / Mn was 1.77. [ka]

[0189] 20 g of PCzFL, 3.0 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd. (formerly Mitsui Scitec Co., Ltd.), trade name Powderlink 1174) as a crosslinking agent, 0.30 g of pyridinium p-toluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (manufactured by DIC Corporation, trade name) as a surfactant were mixed, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm, and then filtered again using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming an organic resist underlayer film for use in multilayer lithography processes.

[0190] [4] Solvent resistance and developer solubility test The compositions prepared in Examples 1-6 and Comparative Examples 1-4 were coated onto silicon wafers using a spinner. The wafers were heated on a hot plate at 215°C for 1 minute to form Si-containing resist underlayer films, and the thickness of the resulting underlayer films was measured. Subsequently, a mixed solvent (7 / 3(V / V)) of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate was applied to each Si-containing resist underlayer film and spin-dried. The film thickness of the underlayer film after application was measured, and the percentage change in film thickness after application of the mixed solvent was calculated, with the film thickness before application of the mixed solvent set as the baseline (100%). Films with a percentage change in film thickness of 1% or less before and after application of the mixed solvent were evaluated as "good," and those with a percentage change in film thickness of more than 1% were evaluated as "not cured." Similarly, an alkaline developer (2.38% aqueous solution of tetramethylammonium hydroxide (TMAH)) was applied to each Si-containing resist underlayer film fabricated on a silicon wafer using the same method, and the film was spin-dried. The film thickness of the underlayer film after application was measured, and the percentage change in film thickness after application was calculated, with the film thickness before application of the developer set as the baseline (100%). Films with a percentage change in film thickness of 1% or less before and after application of the developer were evaluated as "good," while those with a percentage change in film thickness of more than 1% were evaluated as "not cured." The results obtained are shown in Table 3.

[0191] [Table 3]

[0192] [5] Formation of resist pattern by EUV exposure: Positive alkaline development The above-mentioned organic resist underlayer film formation composition was applied onto a silicon wafer using a spinner, and baked on a hot plate at 215°C for 60 seconds to form an organic underlayer film (layer A) with a thickness of 60 nm. On top of that, the composition obtained in Example 1 was spin-coated and heated at 215°C for 1 minute to form a resist underlayer (layer B) with a thickness of 10 nm. Furthermore, an EUV resist solution (methacrylate resin-based resist) was spin-coated onto the material and heated at 130°C for 1 minute to form an EUV resist film (C layer). Subsequently, exposure was performed using an ASML EUV exposure system (NXE3300B) under the conditions of NA=0.33, σ=0.67 / 0.90, and Dipole. During exposure, the material was exposed through a mask set so that the line width and spacing between lines of the EUV resist would be 22 nm after development, i.e., a dense line with a line and space (L / S) of 1 / 1 of 22 nm would be formed. After exposure, post-exposure heating (PEB, 110°C for 1 minute) was performed, followed by cooling to room temperature on a cooling plate. Development was then carried out using an alkaline developer (2.38% TMAH aqueous solution) for 60 seconds, followed by rinsing to form a resist pattern. Using the same procedure, resist patterns were formed using the compositions obtained in Examples 2-4 (film thickness 10 nm), Examples 5-6 (film thickness 5 nm), Comparative Example 1 (film thickness 20 nm), and Comparative Examples 2-4 (film thickness 10 nm). For each obtained pattern, the feasibility of forming a 44nm pitch, 22nm line-and-space pattern was evaluated by confirming the pattern shape through cross-sectional observation of the pattern. In observing the pattern shape, a shape between the footing and undercut, with no significant residue in the space area, was evaluated as "good." An undesirable state where the resist pattern peeled off and collapsed was evaluated as "collapsed." An undesirable state where the upper or lower parts of the resist pattern were in contact with each other was evaluated as "bridged." The results obtained are shown in Table 4.

[0193] [Table 4]

[0194] As shown in Tables 2 to 4, the compositions of Examples 1 to 6, in which the proportion of polysiloxane with a molecular weight of 2500 or more is 19% or less, were confirmed to be solvent-resistant and developer-resistant, capable of forming a resist underlayer film with excellent pattern formation properties for photoresists, and exhibiting excellent patterning characteristics at a film thickness of 5 nm. On the other hand, in the compositions of Comparative Examples 1 to 4, which contain polysiloxanes with a molecular weight exceeding 2500 and a proportion of 30% or more, as shown in Table 4, good patterning characteristics were obtained at a film thickness of 20 nm, but at a film thickness of 10 nm, the patterning shape was evaluated as "fallen," resulting in inferior patterning characteristics.

Claims

1. [A] The weight-average molecular weight obtained by gel permeation chromatography (GPC) analysis in terms of polystyrene is 1,100 or more and 1,800 or less, Polysiloxanes, and [B] Solvent It contains, This composition allows for pattern formation even with a resist underlayer film thickness of 10 nm or less. A composition for forming a silicon-containing resist underlayer film.

2. The above [A] polysiloxane is a polysiloxane in which the proportion of molecules with a molecular weight of over 2,000 is less than 35% in the integrated molecular weight distribution curve obtained by gel permeation chromatography (GPC) analysis in terms of polystyrene. The silicon-containing resist underlayer film formation composition according to claim 1.

3. The above [A] polysiloxane includes at least one selected from the group consisting of a hydrolyzable silane hydrolysis condensate containing at least one hydrolyzable silane represented by the following formula (1), a modified hydrolyzable condensate in which at least a portion of the silanol groups of the condensate are alcohol-modified, a modified hydrolyzable condensate in which at least a portion of the silanol groups of the condensate are acetal-protected, and a dehydration reaction product of the condensate and an alcohol. A silicon-containing resist underlayer film forming composition according to either claim 1 or claim 2. 【Chemistry 1】 (In the formula, R １ This group is a group bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an 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 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. (where 'a' represents an integer between 0 and 3.)

4. A silicon-containing resist underlayer film forming composition according to any one of claims 1 to 3, which does not contain a curing catalyst.

5. The silicon-containing resist underlayer film forming composition according to any one of claims 1 to 4, wherein the solvent [B] above comprises water.

6. A silicon-containing resist underlayer film forming composition according to any one of claims 1 to 5, further comprising a pH adjusting agent.

7. [C] A silicon-containing resist underlayer film forming composition according to any one of claims 1 to 6, comprising a glycol compound having a standard boiling point of 230.0°C or higher and represented by the following formula (2). 【Chemistry 2】 (In the formula, R ３ and R ４ Each of these 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.

8. A silicon-containing resist underlayer film forming composition according to any one of claims 1 to 7, further comprising a surfactant.

9. The silicon-containing material according to any one of claims 1 to 8, further comprising a metal oxide. A composition for forming a resist underlayer film.

10. A silicon-containing resist underlayer film forming composition according to any one of claims 1 to 9, for forming an underlayer film of a resist for EUV lithography.

11. A resist underlayer film, which is a cured product of a silicon-containing resist underlayer film forming composition according to any one of claims 1 to 10.

12. The resist underlayer film according to claim 11, having a film thickness of 10 nm or less.

13. A semiconductor processing substrate comprising a semiconductor substrate and a resist underlayer film according to claim 11 or claim 12.

14. A process of forming an organic underlayer film on a substrate, A step of forming a silicon-containing resist underlayer film on the above organic underlayer film using the silicon-containing resist underlayer film forming composition according to any one of claims 1 to 10, The process includes the step of forming a resist film on the silicon-containing resist underlayer film described above. A method for manufacturing semiconductor devices.

15. In the process of forming the silicon-containing resist underlayer film described above, a silicon-containing resist underlayer film formation composition filtered through a nylon filter is used. The manufacturing method according to claim 14.

16. A resist underlayer film obtained by applying the silicon-containing resist underlayer film forming composition according to any one of claims 1 to 10 onto a semiconductor substrate and firing it.

17. A method for manufacturing a semiconductor device, comprising the steps of: applying a silicon-containing resist underlayer film forming composition according to any one of claims 1 to 10 onto a semiconductor substrate and firing to form a resist underlayer film; applying a resist film forming composition on 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 with the resist pattern; and processing the semiconductor substrate with the patterned resist underlayer film.

18. A method for manufacturing a semiconductor device, comprising the steps of: forming an organic underlayer film on a semiconductor substrate; applying a resist underlayer film forming composition according to any one of claims 1 to 10 thereon and firing to form a resist underlayer film; applying a resist film forming composition 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 an organic underlayer film with the patterned resist underlayer film; and processing a semiconductor substrate with the patterned organic underlayer film.

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