Silicon-containing resist underlayer film-forming composition containing polyfunctional sulfonic acid

Abstract

A silicon-containing composition for forming a resist underlayer film, which contains: component [A]: a polysiloxane; component (B): sulfuric acid, polyfunctional sulfonic acid, or a salt thereof; and component [C]: a solvent.

Description

Technical Field

[0001] The present invention relates to a resist underlayer film-forming composition containing silicon, which contains a polyfunctional sulfonic acid. Background Art

[0002] Microfabrication has been performed by photolithography using photoresists in the manufacture of semiconductor devices. The microfabrication is a method of forming microscopic concavities and convexities on the surface of a substrate corresponding to the pattern by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating the thin film with active light such as ultraviolet rays through a mask pattern depicting a pattern of a semiconductor device, developing the thin film, and etching the substrate using the obtained photoresist pattern as a protective film.

[0003] As semiconductor devices become more integrated, the active light used also tends to be shortened from KrF excimer laser (248nm) to ArF excimer laser (193nm), and further research has been conducted on exposure techniques using EUV (Extreme Ultra violet) and electron beams. As the wavelength of active light becomes shorter, the influence of the reflection of active light from the semiconductor substrate is becoming a major problem, and a method of providing a resist bottom film called an anti-reflective coating (Bottom Anti-Reflective Coating, BARC) between the photoresist and the processed substrate is widely used. As such a resist bottom film, a bottom film containing silicon, etc., has been proposed (Patent Document 1, etc.).

[0004] With the miniaturization of resist patterns in the most advanced semiconductor devices in recent years, the demand for thin-film resists has become more significant. In particular, in a three-layer process consisting of a resist film, a resist underlayer film containing silicon, and an organic underlayer film, the resist on the resist underlayer film containing silicon is required to have good lithography properties.

[0005] In recent years, the development of lithography technology using metal oxide resists (MOR) which have better etching resistance than conventional chemically amplified resists has been actively carried out for further fine pattern formation of the above-mentioned resists. In the future, further miniaturization will require thinner film thickness of the resist, but the present metal oxide resist (MOR) (hereinafter also referred to as "metal-containing resist") has sufficient etching resistance for fine pattern formation processing even in a thin film, and therefore has been expected to be used as a material for the next generation EUV lithography technology in recent years.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2007-163846 Summary of the invention

[0009] Problems to be solved by the invention

[0010] In semiconductor device processing, in order to improve productivity, as one of the methods for shortening exposure time, high sensitivity of resist is required. In particular, in semiconductor device processing using the most advanced EUV lithography technology, this requirement is strong because EUV exposure time affects productivity.

[0011] The present invention has been made in view of such circumstances, and an object of the present invention is to provide a resist underlayer film-forming composition containing silicon that can improve the sensitivity of a resist.

[0012] Means for solving problems

[0013] The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved, and have completed the present invention having the following gist.

[0014] That is, the present invention includes the following aspects.

[0015] [1] A silicon-containing composition for forming a resist underlayer film, comprising:

[0016] [A] Ingredient: polysiloxane;

[0017] [B] component: sulfuric acid, polyfunctional sulfonic acid, or salts thereof; and

[0018] [C] Ingredient: Solvent.

[0019] [2] The silicon-containing resist underlayer film forming composition according to [1], wherein the polyfunctional sulfonic acid is a compound represented by the following formula (A).

[0020]

[0021] (In formula (A), n represents an integer of 1 to 3. 1 It represents an n+1-valent organic group having 1 to 15 carbon atoms.

[0022] [3] The silicon-containing resist underlayer film forming composition according to [1] or [2], wherein the salt in the component [B] is an ammonium salt, an imidazole Salt, pyridine Salt, sulfonium salt, Salt, and iodine Any of the salts.

[0023] [4] The silicon-containing resist underlayer film-forming composition according to any one of [1] to [3], wherein the polysiloxane as the component [A] is a modified polysiloxane in which a part of the silanol groups is alcohol-modified or acetal-protected.

[0024] [5] The silicon-containing resist underlayer film-forming composition according to any one of [1] to [4], wherein the component [C] contains an alcohol solvent.

[0025] [6] The silicon-containing resist underlayer film-forming composition according to [5], wherein the component [C] contains propylene glycol monoalkyl ether.

[0026] [7] The silicon-containing resist underlayer film-forming composition according to any one of [1] to [6], further comprising component [D]: a curing catalyst.

[0027] [8] The resist underlayer film-forming composition containing silicon according to any one of [1] to [7], further comprising component [E]: nitric acid.

[0028] [9] The silicon-containing resist underlayer film-forming composition according to any one of [1] to [8], wherein the component [C] contains water.

[0029]

[10] The silicon-containing resist underlayer film forming composition according to any one of [1] to [9], which is used for forming a resist underlayer film for EUV lithography.

[0030]

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

[10] .

[0031]

[12] A semiconductor processing substrate comprising:

[0032] semiconductor substrate; and

[0033]

[11] The resist underlayer film containing silicon.

[0034]

[13] A method for manufacturing a semiconductor device, comprising the following steps:

[0035] A step of forming an organic lower layer film on a substrate;

[0036] a step of forming a resist underlayer film on the organic underlayer film using the resist underlayer film-forming composition containing silicon as described in any one of [1] to

[10] ; and

[0037] A step of forming a resist film containing a metal on the resist underlayer film.

[0038]

[14] The method for manufacturing a semiconductor element according to

[13] , wherein the metal-containing resist film is formed by a metal-containing resist for EUV lithography.

[0039]

[15] The method for manufacturing a semiconductor element according to

[13] or

[14] , wherein in the step of forming the resist underlayer film, a silicon-containing resist underlayer film-forming composition filtered through a nylon filter is used.

[0040]

[16] A pattern forming method comprising the following steps:

[0041] A step of forming an organic lower layer film on a semiconductor substrate;

[0042] A step of coating the resist underlayer film-forming composition containing silicon described in any one of [1] to

[10] on the organic underlayer film and firing the composition to form a resist underlayer film;

[0043] forming a resist film containing a metal on the resist underlayer film;

[0044] The process of exposing and developing the metal-containing resist film to obtain a resist pattern;

[0045] A step of using the resist pattern as a mask to etch the resist underlayer film; and

[0046] A step of etching the organic underlayer film using the patterned resist underlayer film as a mask.

[0047]

[17] The pattern forming method according to

[16] further comprises a step of removing the resist underlayer film by a wet method using a chemical solution after the step of etching the organic underlayer film.

[0048]

[18] According to the pattern forming method described in

[16] or

[14] , the above-mentioned metal-containing resist film is formed by a metal-containing resist for EUV lithography.

[0049] Effects of the Invention

[0050] According to the present invention, a resist underlayer film-forming composition containing silicon that can improve the sensitivity of a resist can be provided.

[0051] Furthermore, according to the present invention, a method for producing a silicon-containing resist underlayer film, a semiconductor processing substrate, a semiconductor element, and a patterning method can be provided, using the silicon-containing resist underlayer film-forming composition. DETAILED DESCRIPTION

[0052] (Resist underlayer film-forming composition containing silicon)

[0053] The silicon-containing resist underlayer forming composition of the present invention contains polysiloxane as the component [A], sulfuric acid, polyfunctional sulfonic acid, or salts thereof as the component [B], and a solvent as the component [C], and further contains other components as necessary.

[0054] The present inventors have found that a resist underlayer film capable of improving the sensitivity of the resist can be formed by including sulfuric acid, a polyfunctional sulfonic acid, or a salt thereof as the component [B] in a resist underlayer-forming composition containing silicon including polysiloxane.

[0055] <[A] Component: Polysiloxane>

[0056] The polysiloxane as the component [A] is not particularly limited as long as it is a polymer having a siloxane bond.

[0057] The polysiloxane may include a modified polysiloxane in which a part of the silanol groups is modified, for example, a modified polysiloxane in which a part of the silanol groups is modified with alcohol or protected with acetal.

[0058] In another example, the polysiloxane includes a hydrolysis condensate of a hydrolyzable silane, and may include a modified polysiloxane in which at least a part of the silanol groups of the hydrolysis condensate are alcohol-modified or acetal-protected. The hydrolyzable silane involved in the hydrolysis condensate may include one or more hydrolyzable silanes.

[0059] The polysiloxane may have a cage-type, ladder-type, linear-type, or branched-type main chain structure. Commercially available polysiloxanes may be used as the polysiloxane.

[0060] In the present invention, the "hydrolysis condensate" of the hydrolyzable silane, i.e., the product of hydrolysis and condensation, includes not only polyorganosiloxane polymers which are condensates in which condensation is completely completed, but also polyorganosiloxane polymers which are partially hydrolysis condensates in which condensation is not completely completed. Such partially hydrolysis condensates are polymers obtained by hydrolysis and condensation of the hydrolyzable silane, just like the condensates in which condensation is completely completed, but partially stop at hydrolysis and do not condense, so that Si-OH groups remain. In addition, the resist underlayer film-forming composition containing silicon may also contain uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and monomers (hydrolyzable silanes) in addition to the hydrolysis condensates.

[0061] In addition, in this specification, "hydrolyzable silane" may be simply referred to as "silane compound".

[0062] Examples of the polysiloxane include hydrolysis-condensation products of hydrolyzable silanes containing at least one type of hydrolyzable silane represented by the following formula (1).

[0063] <<Formula (1)>>

[0064] R 1 a Si(R 2 ) 4-a (1)

[0065] In formula (1), R 1 It is a group bonded to a silicon atom, and independently represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents an organic group having an epoxy group, an organic group having an acryl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof.

[0066] In addition, R 2 is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0067] a represents an integer of 0-3.

[0068] <<<R 1 >>>

[0069] The alkyl group may be linear, branched or cyclic, and the number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and further preferably 10 or less.

[0070] Specific examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-butyl, Pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl and 1-ethyl-2-methyl-n-propyl, etc.

[0071] In addition, in this specification, "i" means "iso", "s" means "secondary", and "t" means "tertiary".

[0072] Specific examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl. Cycloalkyl groups such as cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl; and bridged ring cycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl and bicyclodecyl.

[0073] The aryl group may be any one of a phenyl group, a monovalent group derived by removing one hydrogen atom of a condensed ring aromatic hydrocarbon compound, and a monovalent group derived by removing one hydrogen atom of 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.

[0074] For example, the aryl group includes an aryl group having 6 to 20 carbon atoms, and as an example, phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 1-naphthyl, 2-naphthyl, 5-naphthyl, 2- 1-pyrenyl, 2-pyrenyl, pentacene, benzopyrenyl, benzo[9,10]phenanthryl; biphenyl-2-yl (o-biphenyl), biphenyl-3-yl (m-biphenyl), biphenyl-4-yl (p-biphenyl), p-terphenyl-4-yl, m-terphenyl-4-yl, o-terphenyl-4-yl, 1,1′-binaphthyl-2-yl, 2,2′-binaphthyl-1-yl, etc., but are not limited to these.

[0075] The aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups include the same as those mentioned above. The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0076] Specific examples of the aralkyl group include, but are not limited to, phenylmethyl (benzyl), 2-phenylethylene, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, and 10-phenyl-n-decyl.

[0077] The halogenated alkyl group, halogenated aryl group, and halogenated aralkyl group are alkyl groups, aryl groups, and aralkyl groups substituted with one or more halogen atoms, respectively. Specific examples of such alkyl groups, aryl groups, and aralkyl groups include the same as those described above.

[0078] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0079] The number of carbon atoms in the haloalkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and further preferably 10 or less.

[0080] Specific examples of the halogenated alkyl group include, but are not limited to, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropane-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group.

[0081] The number of carbon atoms in the halogenated aryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0082] Specific examples of the halogenated aryl group include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-1-naphthyl , 4-fluoro-1-naphthyl, 6-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8-difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, heptafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, heptafluoro-2-naphthyl, and the like. In addition, groups in which the fluorine atom (fluoro group) in these groups is arbitrarily substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group) can be mentioned, but are not limited to these.

[0083] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0084] Specific examples of the halogenated aralkyl group include 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl and 2,3,4,5,6-pentafluorobenzyl. In addition, examples include groups in which the fluorine atom (fluoro group) in these groups is arbitrarily substituted with a chlorine atom (chloro group), a bromine atom (bromo group) or an iodine atom (iodo group), but the present invention is not limited to these.

[0085] The alkoxyalkyl group, alkoxyaryl group, and alkoxyaralkyl group are each an alkyl group, an aryl group, and an aralkyl group substituted with one or more alkoxy groups, and specific examples of such an alkyl group, an aryl group, and an aralkyl group include the same as those described above.

[0086] Examples of the alkoxy group as a substituent include an alkoxy group having at least one alkyl moiety in a linear, branched, or cyclic form having 1 to 20 carbon atoms.

[0087] Examples of the linear or branched alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-butoxy, Pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy, etc.

[0088] Examples of the cyclic alkoxy group include cyclopropyloxy, cyclobutyloxy, 1-methyl-cyclopropyloxy, 2-methyl-cyclopropyloxy, cyclopentyloxy, 1-methyl-cyclobutyloxy, 2-methyl-cyclobutyloxy, 3-methyl-cyclobutyloxy, 1,2-dimethyl-cyclopropyloxy, 2,3-dimethyl-cyclopropyloxy, 1-ethyl-cyclopropyloxy, 2-ethyl-cyclopropyloxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutyloxy, 2-ethyl-cyclobutyloxy, 3-ethyl-cyclobutyloxy, 1,2-dimethyl-cyclobutyloxy, 1,3-dimethyl-cyclopentyloxy, Methyl-cyclobutyloxy, 2,2-dimethyl-cyclobutyloxy, 2,3-dimethyl-cyclobutyloxy, 2,4-dimethyl-cyclobutyloxy, 3,3-dimethyl-cyclobutyloxy, 1-n-propyl-cyclopropyloxy, 2-n-propyl-cyclopropyloxy, 1-isopropyl-cyclopropyloxy, 2-isopropyl-cyclopropyloxy, 1,2,2-trimethyl-cyclopropyloxy, 1,2,3-trimethyl-cyclopropyloxy, 2,2,3-trimethyl-cyclopropyloxy, 1-ethyl-2-methyl-cyclopropyloxy, 2-ethyl-1-methyl-cyclopropyloxy, 2-ethyl-2-methyl-cyclopropyloxy and 2-ethyl-3-methyl-cyclopropyloxy, etc.

[0089] Specific examples of the alkoxyalkyl group include lower (having about 5 or less carbon atoms) alkyloxy lower (having about 5 or less carbon atoms) alkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, and ethoxymethyl, but are not limited to these.

[0090] Specific examples of the alkoxyaryl group include, but are not limited to, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, and 7-methoxynaphth-1-yl.

[0091] Specific examples of the alkoxyaralkyl group include 3-(methoxyphenyl)benzyl and 4-(methoxyphenyl)benzyl, but are not limited to these.

[0092] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and further preferably 10 or less.

[0093] Specific examples of the alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl , 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl 2-Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1 ,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutyl vinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl , 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, and bridged ring alkenyl such as bicycloheptenyl (norbornyl) can also be mentioned. ,

[0094] In addition, as the substituents in the above-mentioned alkyl group, aryl group, aralkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group, for example, alkyl group, aryl group, aralkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, alkoxy group, aralkyloxy group and the like are mentioned, and their specific examples and their suitable carbon atom numbers are the same as those mentioned above or below.

[0095] In addition, the aryloxy group mentioned in the substituent is a group in which an aryl group is bonded via an oxygen atom (-O-), and specific examples of such aryl groups include 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 thereof include phenoxy, naphthalene-2-yloxy, etc., but are not limited to these.

[0096] When there are two or more substituents, the substituents may be bonded to each other to form a ring.

[0097] Examples of the organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.

[0098] Examples of the organic group having an acryloyl group include an acryloyloxymethyl group, an acryloyloxyethyl group, and an acryloyloxypropyl group.

[0099] Examples of the organic group having a methacryloyl group include a methacryloyloxymethyl group, a methacryloyloxyethyl group, and a methacryloyloxypropyl group.

[0100] Examples of the organic group having a mercapto group include a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, a mercaptooctyl group, and a mercaptophenyl group.

[0101] Examples of the organic group having an amino group include, but are not limited to, amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl. The organic group having an amino group will be described in detail below.

[0102] Examples of the organic group having an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group. However, groups in which an alkoxy group is directly bonded to a silicon atom are excluded.

[0103] Examples of the organic group having a sulfonyl group include a sulfonylalkyl group and a sulfonylaryl group, but the group is not limited to these.

[0104] Examples of the organic group having a cyano group include a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, and a thiocyanate group.

[0105] As the organic group having an amino group, there can be mentioned an organic group having at least one of a primary amino group, a secondary amino group, and a tertiary amino group. Preferably, a hydrolysis condensate of a counter cation having a tertiary ammonium group formed by hydrolyzing a hydrolyzable silane having a tertiary amino group with a strong acid can be used. In addition to the nitrogen atom constituting the amino group, the organic group may also contain heteroatoms such as an oxygen atom and a sulfur atom.

[0106] As a preferred example of the organic group having an amino group, a group represented by the following formula (A1) can be mentioned.

[0107]

[0108] In formula (A1), R 101 and R 102 Each of them independently represents a hydrogen atom or a hydrocarbon group, and each of L independently represents an alkylene group which may be substituted. * represents a bond.

[0109] Examples of the hydrocarbon group include, but are not limited to, alkyl, alkenyl, and aryl groups. 1 Same as above.

[0110] The alkylene group may be linear or branched, and the number of carbon atoms thereof is usually 1 to 10, preferably 1 to 5. Examples thereof include linear alkylene groups such as methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene.

[0111] Examples of the organic group having an amino group include an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group, but the group is not limited to these.

[0112] <<<R 2 >>>

[0113] As R 2 The alkoxy group in R 1 The alkoxy group exemplified in the description of .

[0114] As R 2 The halogen atoms in R 1 The halogen atoms exemplified in the description of .

[0115] The aralkyloxy group is a monovalent group derived by removing a hydrogen atom from a hydroxyl group of an aralkyl alcohol, and specific examples of the aralkyl group in the aralkyloxy group include the same as those described above.

[0116] The number of carbon atoms in the aralkyloxy group is not particularly limited, but may be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less.

[0117] Specific examples of the aralkyloxy group include phenylmethyloxy (benzyloxy), 2-phenylethyleneoxy, 3-phenyl-n-propyloxy, 4-phenyl-n-butyloxy, 5-phenyl-n-pentyloxy, 6-phenyl-n-hexyloxy, 7-phenyl-n-heptyloxy, 8-phenyl-n-octyloxy, 9-phenyl-n-nonyloxy, and 10-phenyl-n-decyloxy, but are not limited to these.

[0118] The acyloxy group is a monovalent group derived from the carboxyl group (-COOH) of a carboxylic acid compound by removing a hydrogen atom, and typically, alkylcarbonyloxy, arylcarbonyloxy or aralkylcarbonyloxy derived from the carboxyl group of an alkylcarboxylic acid, an arylcarboxylic acid or an aralkylcarboxylic acid by removing a hydrogen atom can be cited, but it is not limited to these. As specific examples of the alkyl group, aryl group and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid and aralkylcarboxylic acid, the same as those mentioned above can be cited.

[0119] Specific examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2,2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, The invention also includes 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and tosylcarbonyloxy.

[0120] <<<Specific examples of the hydrolyzable silane represented by formula (1)>>>

[0121] Specific examples of the hydrolyzable silane represented by the formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropropoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltripenzyloxysilane, methyltriphenethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxy Ethyl triethoxysilane, α-glycidoxypropyl trimethoxysilane, α-glycidoxypropyl triethoxysilane, β-glycidoxypropyl trimethoxysilane, β-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl tripropoxysilane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyl triphenoxysilane, α-glycidoxybutyl trimethoxysilane, α-glycidoxybutyl triethoxysilane, β-glycidoxybutyl triethoxysilane, γ-glycidoxybutyl trimethoxysilane, γ-glycidoxybutyl triethoxysilane, δ-glycidoxybutyl trimethoxysilane, δ -Glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxy Silane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane,γ-Glycidoxypropylmethyldiphenoxysilane, γ-Glycidoxypropylethyldimethoxysilane, γ-Glycidoxypropylethyldiethoxysilane, γ-Glycidoxypropylvinyldimethoxysilane, γ-Glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane silane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiacetoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane, allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-phenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenyl Methoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrichlorosilane, phenethyltriacetoxysilane, phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane,Phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyl Triacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, tert-butoxyphenyltrimethoxysilane, tert-butoxyphenyltriethoxysilane, tert-butoxyphenyltriacetoxysilane, tert-butoxyphenyltrichlorosilane, tert-butoxybenzyltrimethoxysilane, tert-butoxybenzyltriethoxysilane, tert-butoxybenzyltriacetoxysilane, tert-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane Alkane, methoxynaphthyl triacetoxysilane, methoxynaphthyl trichlorosilane, ethoxynaphthyl trimethoxysilane, ethoxynaphthyl triethoxysilane, ethoxynaphthyl triacetoxysilane, ethoxynaphthyl trichlorosilane, γ-chloropropyl trimethoxysilane, γ-chloropropyl triethoxysilane, γ-chloropropyl triacetoxysilane, 3,3,3-trifluoropropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl triethoxysilane, β-cyanoethyl triethoxysilane, thiocyanate propyl triethoxysilane, chloromethyl trimethoxysilane, chloromethyl triethoxysilane, triethoxysilylpropyl diallyl isocyanurate, bicyclo[2,2,1 ] heptenyl triethoxysilane, benzenesulfonylpropyl triethoxysilane, benzenesulfonamidopropyl triethoxysilane, dimethylaminopropyl trimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, silanes represented by the following formulas (A-1) to (A-41),The silanes represented by the following formulas (1-1) to (1-290) are not limited thereto.

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131] In formulae (1-1) to (1-290), T each independently represents an alkoxy group, an acyloxy group, or a halogen group, and preferably represents a methoxy group or an ethoxy group, for example.

[0132] Examples of the polysiloxane [A] include hydrolysis-condensation products of hydrolyzable silanes containing a hydrolyzable silane represented by the following formula (2) together with or instead of the hydrolyzable silane represented by the formula (1).

[0133] <Formula (2)>

[0134] 〔R 3 b Si(R 4 ) 3-b 〕2R 5 c (2)

[0135] In formula (2), R 3 It is a group bonded to a silicon atom, and independently represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents an organic group having an epoxy group, an organic group having an acryl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof.

[0136] In addition, R 4 is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0137] R 5 is a group bonded to a silicon atom, and independently represents an alkylene group or an arylene group.

[0138] b represents 0 or 1, and c represents 0 or 1.

[0139] As R 3 Specific examples of the groups in and their suitable carbon number can be given as follows: 1 The above mentioned groups and carbon atom numbers.

[0140] As R 4 Specific examples of the groups and atoms in the formula (a) and their suitable carbon number can be given as follows: 2 The above mentioned groups and atoms and the number of carbon atoms.

[0141] As R 5 Specific examples of the alkylene group in the term include straight-chain alkylene groups such as methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene; branched-chain alkylene groups such as 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 1,1-dimethylethylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 1,1-dimethyl-1,3-propylene, 1,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, and 1-ethyl-1,3-propylene; and alkylene groups such as methanetriyl, ethane-1,1,2 The invention also includes, but is not limited to, alkanetriyl groups such as butane-1,1,1-triyl, ethane-1,2,2-triyl, ethane-2,2,2-triyl, propane-1,1,1-triyl, propane-1,1,2-triyl, propane-1,2,3-triyl, propane-1,2,2-triyl, propane-1,1,3-triyl, butane-1,1,1-triyl, butane-1,1,2-triyl, butane-1,1,3-triyl, butane-1,2,3-triyl, butane-1,2,4-triyl, butane-1,2,2-triyl, butane-2,2,3-triyl, 2-methylpropane-1,1,1-triyl, 2-methylpropane-1,1,2-triyl and 2-methylpropane-1,1,3-triyl.

[0142] As R 5Specific examples of the arylene group in include 1,2-phenylene, 1,3-phenylene, and 1,4-phenylene; groups derived by removing two hydrogen atoms from the aromatic ring of a condensed ring aromatic hydrocarbon compound, such as 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, 2,3-anthracenediyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl; and groups derived by removing two hydrogen atoms from the aromatic ring of a ring-linked aromatic hydrocarbon compound, such as 4,4'-biphenyldiyl and 4,4"-p-terphenyldiyl, but are not limited thereto.

[0143] b is preferably 0.

[0144] c is preferably 1.

[0145] Specific examples of the hydrolyzable silane represented by formula (2) include methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, butylenebistrimethoxysilane, phenylenebistrimethoxysilane, phenylenebistriethoxysilane, phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane, naphthylenebistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, bismethyldimethoxydisilane, the like, but the present invention is not limited to these.

[0146] Examples of the polysiloxane [A] include hydrolysis-condensation products of hydrolyzable silanes including the hydrolyzable silane represented by the formula (1) and / or the hydrolyzable silane represented by the formula (2) and other hydrolyzable silanes listed below.

[0147] As other hydrolyzable silanes, there are mentioned those having The silane compounds include, but are not limited to, silane compounds having a sulfone group, silane compounds having a sulfonamide group, and silane compounds having a cyclic urea skeleton in the molecule.

[0148] <<The molecule has Silane compounds (hydrolyzable organosilanes)>>

[0149] Expected to have The silane compound containing the hydrolyzable silane can effectively and efficiently promote the crosslinking reaction of the hydrolyzable silane.

[0150] The molecule has A suitable example of the silane compound having a group is represented by formula (3).

[0151] R 11 f R 12 g Si(R 13 ) 4-(f+g) (3)

[0152] R 11 is a group bonded to a silicon atom and represents Base or with Organic base.

[0153] R 12 It is a group bonded to a silicon atom, and independently represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents an organic group having an epoxy group, an organic group having an acryl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more thereof.

[0154] R 13 is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0155] f represents 1 or 2, g represents 0 or 1, and 1≤f+g≤2 is satisfied.

[0156] Specific examples of alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organic groups having an epoxy group, organic groups having an acryloyl group, organic groups having a methacryloyl group, organic groups having a mercapto group, organic groups having an amino group and organic groups having a cyano group, alkoxy groups, aralkyloxy groups, acyloxy groups, and halogen atoms; specific examples of substituents for alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl, and suitable carbon atom numbers thereof; 12 , we can cite the following about R 1 The above-mentioned 13 , we can cite the following about R 2 And the above.

[0157] If more detailed, as Specific examples of the ammonium group include a cyclic ammonium group or a chain ammonium group, and a tertiary ammonium group or a quaternary ammonium group is preferred.

[0158] That is, as Base or with Preferred specific examples of the organic group of the amine group include a cyclic ammonium group or a chain ammonium group or an organic group having at least one of them, and preferably a tertiary ammonium group or a quaternary ammonium group or an organic group having at least one of them.

[0159] In addition, When the group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. In this case, there are cases where the nitrogen atom constituting the ring is directly or via a divalent linking group and the silicon atom is bonded, and there are cases where the carbon atom constituting the ring is directly or via a divalent linking group and the silicon atom is bonded.

[0160] In one embodiment of a suitable embodiment, R as a group bonded to a silicon atom is 11 It is a heteroaromatic cyclic ammonium group represented by the following formula (S1).

[0161]

[0162] In formula (S1), A 1 , A 2 , A 3 and A 4 Each independently represents a group represented by any one of the following formulas (J1) to (J3), A 1 ~A 4 At least one of them is a group represented by the following formula (J2), and according to the silicon atom in formula (3) and A 1 ~A 4 Which combination of A is determined in such a way that the formed ring shows aromaticity 1 ~A 4 The bond between each of the atoms adjacent to each other and forming a ring together is a single bond or a double bond. * indicates a bonding bond.

[0163]

[0164] In formula (J1) to formula (J3), R 10 Each independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group or an alkenyl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, the halogenated alkyl group, the halogenated aryl group, the halogenated aralkyl group and the alkenyl group and their suitable carbon number are the same as those mentioned above. * represents a bonding bond.

[0165] In formula (S1), R 14 Each of them 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. 14 If there are two or more, two R 14 Can combine with each other to form a ring, 2 R14 The formed ring may be a bridged ring structure, in which case the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, or the like.

[0166] Specific examples of such alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups and alkenyl groups and their suitable carbon atom numbers are the same as those mentioned above.

[0167] In formula (S1), n 1 is an integer from 1 to 8, m 1 is 0 or 1, m 2 It is 0 or a positive integer from 1 to the maximum number of substitutions that can be made on a single ring or multiple rings.

[0168] In m 1 When it is 0, the structure contains A 1 ~A 4 (4+n 1 )-membered ring. That is, in n 1 When it is 1, it forms a 5-membered ring. 1 When it is 2, it forms a 6-membered ring. 1 When it is 3, it forms a 7-membered ring. 1 When it is 4, it forms an 8-membered ring. 1 When it is 5, it forms a 9-membered ring. 1 When it is 6, it forms a 10-membered ring. 1 When it is 7, it forms an 11-membered ring. 1 When it is 8, it forms a 12-membered ring.

[0169] In m 1 When it is 1, it contains A 1 ~A 3 (4+n 1 )-membered ring and containing A 4 The 6-membered ring forms a fused ring.

[0170] A 1 ~A 4 Depending on which of the formulas (J1) to (J3) it is, there may be a case where the atoms constituting the ring have hydrogen atoms or a case where the atoms do not have hydrogen atoms. 1 ~A 4 When there is a hydrogen atom on an atom constituting the ring, the hydrogen atom may be replaced by R 14 In addition, R 14 Can be substituted for except A 1 ~A 4 Based on this situation, as described above, m 2 is selected from 0 or an integer from 1 to the maximum number of substitutions that can be made on the monocyclic or polycyclic rings.

[0171] The bond of the heteroaromatic cyclic ammonium group represented by formula (S1) exists on any carbon atom or nitrogen atom existing in such a monocyclic or condensed ring, and is directly bonded to the silicon atom, or is bonded via a linker to form an organic group having cyclic ammonium, which is bonded to the silicon atom.

[0172] Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group, but the linking group is not limited to these.

[0173] Specific examples of the alkylene group and the arylene group and their suitable carbon atom numbers are the same as those mentioned above.

[0174] In addition, the alkenylene group is a divalent group derived by further removing one hydrogen atom from the alkenyl group, and specific examples of such alkenyl groups include the same as those described above. The number of carbon atoms in the alkenylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0175] Specific examples thereof include vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, and 2-pentenylene, but are not limited to these.

[0176] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a heteroaromatic cyclic ammonium group represented by formula (S1) include silanes represented by the following formulae (I-1) to (I-50), but are not limited thereto.

[0177]

[0178]

[0179]

[0180] In another example, R as a group bonded to the silicon atom in formula (3) 11 It may be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).

[0181]

[0182] In formula (S2), A 5 , A 6 , A 7 and A 8 Each independently represents a group represented by any one of the following formulas (J4) to (J6), A 5 ~A 8 At least one of them is a group represented by the following formula (J5). 5 ~A 8Which combination of A is determined in such a way that the formed ring shows non-aromaticity? 5 ~A 8 The bonds between each atom and its adjacent atoms forming a ring are single or double bonds. * indicates a bonding bond.

[0183]

[0184] In formula (J4) to formula (J6), R 10 Each independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group or an alkenyl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, the halogenated alkyl group, the halogenated aryl group, the halogenated aralkyl group and the alkenyl group and their suitable carbon number are the same as those mentioned above. * represents a bonding bond.

[0185] In formula (S2), R 15 Each of them 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. 15 If there are two or more, two R 15 Can combine with each other to form a ring, 2 R 15 The formed ring may be a bridged ring structure, in which case the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, or the like.

[0186] Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group and alkenyl group and their suitable carbon atom numbers are the same as those mentioned above.

[0187] In formula (S2), n 2 is an integer from 1 to 8, m 3 is 0 or 1, m 4 It is 0 or a positive integer from 1 to the maximum number of substitutions that can be made on a single ring or multiple rings.

[0188] In m 3 When it is 0, the structure contains A 5 ~A 8 (4+n 2 )-membered ring. That is, in n 2 When it is 1, it forms a 5-membered ring. 2 When it is 2, it forms a 6-membered ring. 2 When it is 3, it forms a 7-membered ring. 2 When it is 4, it forms an 8-membered ring. 2 When it is 5, it forms a 9-membered ring. 2 When it is 6, it forms a 10-membered ring. 2 When it is 7, it forms an 11-membered ring. 2 When it is 8, it forms a 12-membered ring.

[0189] In m 3 When it is 1, it contains A 5 ~A 7 (4+n 2 )-membered ring and containing A 8 The 6-membered ring forms a fused ring.

[0190] A 5 ~A 8 Depending on which of the formulas (J4) to (J6) it is, there may be a case where the atoms constituting the ring have hydrogen atoms or a case where the atoms do not have hydrogen atoms. 5 ~A 8 When there is a hydrogen atom on an atom constituting the ring, the hydrogen atom may be replaced by R 15 In addition, R 15 Can be substituted for A 5 ~A 8 Ring-constituting atoms other than the ring-constituting atoms in.

[0191] Based on this situation, as mentioned above, m 4 An integer selected from 0 or from 1 to the maximum number of substitutions that can be made on the monocyclic or polycyclic rings.

[0192] The bonding bond of the heteroaliphatic cyclic ammonium group represented by formula (S2) exists on any carbon atom or nitrogen atom existing in such a monocyclic or condensed ring, and is directly bonded to the silicon atom, or is bonded via a linker to form an organic group having cyclic ammonium, which is bonded to the silicon atom.

[0193] Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group. Specific examples of the alkylene group, the arylene group, and the alkenylene group and their suitable carbon atom numbers are the same as those mentioned above.

[0194] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a heteroaliphatic cyclic ammonium group represented by formula (S2) include silanes represented by the following formulas (II-1) to (II-30), but are not limited thereto.

[0195]

[0196]

[0197] In still another example, R as a group bonded to the silicon atom in formula (3) 11 It may be a chain ammonium group represented by the following formula (S3).

[0198]

[0199] In formula (S3), R 10Each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group or an alkenyl group, and specific examples of the alkyl group, the aryl group, the aralkyl group, the halogenated alkyl group, the halogenated aryl group, the halogenated aralkyl group and the alkenyl group and their suitable carbon number are the same as those mentioned above. * represents a bond.

[0200] The chain ammonium group represented by the formula (S3) is directly bonded to the silicon atom, or is bonded via a linker to form an organic group having a chain ammonium group, which is bonded to the silicon atom.

[0201] Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group. Specific examples of the alkylene group, the arylene group, and the alkenylene group include the same as those described above.

[0202] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a chain ammonium group represented by formula (S3) include silanes represented by the following formulas (III-1) to (III-28), but are not limited thereto.

[0203]

[0204]

[0205] <<Silane compound having sulfone group or sulfonamide group (hydrolyzable organosilane)>>

[0206] Examples of the silane compound having a sulfone group and the silane compound having a sulfoneamide group include compounds represented by the following formulas (B-1) to (B-36), but are not limited thereto.

[0207] In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

[0208]

[0209]

[0210] <<Silane compounds having a cyclic urea skeleton in the molecule (hydrolyzable organosilane)>>

[0211] Examples of the hydrolyzable organosilane having a cyclic urea skeleton in the molecule include hydrolyzable organosilane represented by the following formula (4-1).

[0212] R 401 x R 402 y Si(R 403 ) 4-(x+y) (4-1)

[0213] In formula (4-1), R 401is a group bonded to a silicon atom, and each independently represents a group represented by the following formula (4-2).

[0214] R 402 It is a group bonded to a silicon atom and represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a halogenated alkyl group which may be substituted, a halogenated aryl group which may be substituted, a halogenated aralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents an organic group having an epoxy group, an organic group having an acryl group, an organic group having a methacryloyl group, an organic group having a mercapto group, or an organic group having a cyano group, or a combination of two or more thereof.

[0215] R 403 The groups or atoms bonded to the silicon atom each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom.

[0216] x is 1 or 2, y is 0 or 1, and x+y≤2.

[0217] R 402 alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organic groups having epoxy groups, organic groups having acryl groups, organic groups having methacryloyl groups, organic groups having mercapto groups, and organic groups having cyano groups, and R 403 The alkoxy group, aralkyloxy group, acyloxy group and halogen atom, as well as specific examples of these substituents and suitable carbon number can be cited as those for R 1 and R 2 And the same as above.

[0218]

[0219] In formula (4-2), R 404 each independently represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an organic group having an epoxy group, or an organic group having a sulfonyl group, and R 405 Each independently represents an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-) or an ester bond (-CO-O- or -O-CO-). * represents a bonding bond.

[0220] In addition, R 404 Specific examples of the alkyl group which may be substituted, the alkenyl group which may be substituted, and the organic group having an epoxy group and suitable carbon number thereof can be given as those for R 1 The same as above, but in addition to these, as R 404The alkyl group which may be substituted is preferably an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group, and specific examples thereof include allyl group, 2-vinylethyl group, 3-vinylpropyl group, 4-vinylbutyl group and the like.

[0221] The organic group having a sulfonyl group is not particularly limited as long as it contains a sulfonyl group, and examples thereof include an alkylsulfonyl group which may be substituted, an arylsulfonyl group which may be substituted, an aralkylsulfonyl group which may be substituted, a halogenated alkylsulfonyl group which may be substituted, a halogenated arylsulfonyl group which may be substituted, a halogenated aralkylsulfonyl group which may be substituted, an alkoxyalkylsulfonyl group which may be substituted, an alkoxyarylsulfonyl group which may be substituted, an alkoxyaralkylsulfonyl group which may be substituted, and an alkenylsulfonyl group which may be substituted.

[0222] The alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl groups in these groups, as well as specific examples of these substituents and suitable carbon number thereof, can be cited as those mentioned above for R. 1 And the same as above.

[0223] The alkylene group is a divalent group derived by further removing one hydrogen atom from the alkyl group, and can be any of a linear, branched, and cyclic group. Specific examples of such alkylene groups include 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, more preferably 20 or less, and further preferably 10 or less.

[0224] In addition, R 405 The alkylene group may have one or more selected from the group consisting of a sulfide bond, an ether bond, and an ester bond at its terminal or in the middle, preferably in the middle.

[0225] Specific examples of the alkylene group include straight-chain alkylene groups such as methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene; branched-chain alkylene groups such as methylethylene, 1-methyl1,3-propylene, 2-methyl1,3-propylene, 1,1-dimethylethylene, 1-methyl1,4-butylene, 2-methyl1,4-butylene, 1,1-dimethyl1,3-propylene, 1,2-dimethyl1,3-propylene, 2,2-dimethyl1,3-propylene, and 1-ethyl1,3-propylene; and 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2- Cyclic alkylene groups such as cyclohexanediyl and 1,3-cyclohexanediyl, and alkylene groups containing ether groups such as -CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2OCH2CH2SCH2CH2-, but are not limited to these.

[0226] The hydroxyalkylene group is a group in which at least one hydrogen atom of the above-mentioned alkylene group is replaced by a hydroxyl group. Specific examples thereof include hydroxymethylene, 1-hydroxyethylene, 2-hydroxyethylene, 1,2-dihydroxyethylene, 1-hydroxy1,3-propylene, 2-hydroxy1,3-propylene, 3-hydroxy1,3-propylene, 1-hydroxy1,4-butylene, 2-hydroxy1,4-butylene, 3-hydroxy1,4-butylene, 4-hydroxy1,4-butylene, 1,2-dihydroxy1,4-butylene, 1,3-dihydroxy1,4-butylene, 1,4-dihydroxy1,4-butylene, 2,3-dihydroxy1,4-butylene, 2,4-dihydroxy1,4-butylene, and 4,4-dihydroxy1,4-butylene, but are not limited thereto.

[0227] In formula (4-2), X 401 Each independently represents any one of the groups represented by the following formulae (4-3) to (4-5), and the carbon atom of the keto group in the following formulae (4-4) and (4-5) and R in the formula (4-2) 405 The bound nitrogen atoms are bound.

[0228]

[0229] In formula (4-3) to formula (4-5), R 406 ~R 410 Each of them independently represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an organic group having an epoxy group or a sulfonyl group. Specific examples of the alkyl group which may be substituted, the alkenyl group which may be substituted, and the organic group having an epoxy group or a sulfonyl group and suitable carbon number thereof can be given as those described above with respect to R. 1 In addition, specific examples of organic groups having a sulfonyl group and suitable carbon number can be given as those for R 404 The same as above. * indicates a bonding bond.

[0230] Among them, from the viewpoint of achieving excellent lithographic properties with good reproducibility, X 401 Preferred is a group represented by formula (4-5).

[0231] From the perspective of achieving excellent lithographic properties with good reproducibility, R 404 and R 406 ~R 410 At least one of the groups is preferably an alkyl group in which a terminal hydrogen atom is substituted with a vinyl group.

[0232] The hydrolyzable organosilane represented by formula (4-1) may be a commercially available product or may be synthesized by a known method described in International Publication No. 2011 / 102470 or the like.

[0233] Specific examples of the hydrolyzable organosilane represented by the formula (4-1) include silanes represented by the following formulae (4-1-1) to (4-1-29), but are not limited to these.

[0234]

[0235]

[0236]

[0237] [A] The polysiloxane may be a hydrolysis-condensation product of a hydrolyzable silane containing other silane compounds than those exemplified above, within a range not impairing the effects of the present invention.

[0238] As described above, as the polysiloxane [A], a modified polysiloxane in which at least a part of the silanol groups is modified can be used. For example, a modified polysiloxane in which a part of the silanol groups is modified with alcohol or a modified polysiloxane protected with acetal can be used.

[0239] Examples of the modified polysiloxane include a reaction product obtained by reacting at least a part of the silanol groups in the hydrolyzable silane hydrolysis condensate with a hydroxyl group of an alcohol, a dehydration reaction product of the condensate and an alcohol, and a modified product in which at least a part of the silanol groups in the condensate are protected with an acetal group.

[0240] As the alcohol, a monohydric alcohol may be used, and examples thereof include methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-pentanol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3 -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.

[0241] In addition, 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.

[0242] The reaction between the silanol group of the condensate and the hydroxyl group of the alcohol is carried out by contacting the polysiloxane with the alcohol and reacting them 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 groups are blocked. In this case, the alcohol as a blocking agent can be used as a solvent in the composition containing the polysiloxane.

[0243] The dehydration reaction product of polysiloxane and alcohol composed of a hydrolysis condensate of a hydrolyzable silane can be produced by reacting polysiloxane with alcohol in the presence of an acid as a catalyst, capping the silanol groups with alcohol, and removing the generated water by dehydration to the outside of the reaction system.

[0244] As the acid, an organic acid having an acid dissociation constant (pka) of -1 to 5, preferably 4 to 5 can be used. For example, the acid can include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, and the like, particularly benzoic acid, isobutyric acid, acetic acid, and the like.

[0245] As the acid, an acid having a boiling point of 70 to 160° C. may be used, and examples thereof include trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid.

[0246] As such, the acid is preferably an acid having any physical property such as an acid dissociation constant (pka) of 4 to 5 or a boiling point of 70 to 160° C. That is, an acid with weak acidity or an acid with strong acidity but low boiling point can be used.

[0247] Furthermore, as the acid, any one of the properties of the acid dissociation constant and the boiling point can be utilized.

[0248] The acetal protection of the silanol group of the condensate can be performed using vinyl ether, for example, vinyl ether represented by the following formula (5) can be used, and by reacting these, a partial structure represented by the following formula (6) can be introduced into the polysiloxane.

[0249]

[0250] In formula (5), R 1a , R 2a , and R 3a Each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 4a represents an alkyl group having 1 to 10 carbon atoms, R 2a With R 4a They may be bonded to each other to form a ring. Examples of the alkyl group include those exemplified above.

[0251]

[0252] In formula (6), R 1’ , R 2’ , and R 3’ Each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 4’ represents an alkyl group having 1 to 10 carbon atoms, R 2’ With R 4’ In formula (6), * represents a bond with an adjacent atom. Examples of the adjacent atom include an oxygen atom of a siloxane bond, an oxygen atom of a silanol group, and R derived from formula (1). 1 The alkyl group includes the ones exemplified above.

[0253] As the vinyl ether represented by formula (5), for example, aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, and cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran can be used. 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 particularly preferably used.

[0254] The acetal protection of the silanol group can be carried out using polysiloxane, vinyl ether, and propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, 1,4-dimethoxybenzene, etc. as a solvent. Aprotic solvents such as alkane, pyridine The reaction is carried out in the presence of a catalyst such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0255] Furthermore, the blocking and acetal protection of these silanol groups with alcohols can be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane described later.

[0256] In a preferred embodiment of the present invention, the polysiloxane [A] comprises a hydrolyzable silane represented by formula (1), and optionally a hydrolyzable silane represented by formula (2), and other hydrolyzable silanes, and at least one of hydrolysis condensates of hydrolyzable silanes and modified products thereof.

[0257] In a preferred embodiment, the polysiloxane [A] comprises a dehydration reaction product of a hydrolysis condensate and an alcohol.

[0258] The hydrolysis condensate of the hydrolyzable silane (which may also include a modified product) may have a weight average molecular weight of, for example, 500 to 1,000,000. From the viewpoint of suppressing the precipitation of the hydrolysis condensate in the composition, the weight average molecular weight may be preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving both storage stability and coating properties, the weight average molecular weight may be preferably 700 or more, and more preferably 1,000 or more.

[0259] In addition, weight average molecular weight is the molecular weight obtained by GPC analysis in terms of polystyrene. GPC analysis can be performed using, for example, a GPC device (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), the column temperature being 40°C, tetrahydrofuran being used as an eluent (eluting solvent), the flow rate (flow velocity) being set to 1.0 mL / min, and a standard sample being carried out using polystyrene (Shodex (registered trademark) manufactured by Showa Denko K.K.).

[0260] The hydrolysis-condensation product of the hydrolyzable silane is obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane).

[0261] The silane compound (hydrolyzable silane) contains an alkoxy group, aralkyloxy group, acyloxy group, or halogen atom directly bonded to a silicon atom, that is, an alkoxysilyl group, aralkyloxysilyl group, acyloxysilyl group, or halosilyl group (hereinafter referred to as a hydrolyzable group).

[0262] In the hydrolysis of these hydrolyzable groups, water is usually used in an amount of 0.1 to 100 mol, for example 0.5 to 100 mol, preferably 1 to 10 mol, per 1 mol of the hydrolyzable group.

[0263] During the hydrolysis and condensation, a hydrolysis catalyst may be used or may be used without the use for the purpose of promoting the reaction. When a hydrolysis catalyst is used, usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, may be used per 1 mol of the hydrolyzable group.

[0264] The reaction temperature for hydrolysis and condensation is usually in the range of room temperature or higher and below the reflux temperature of the organic solvent that can be used for hydrolysis at normal pressure, and can be, for example, 20 to 110°C, or 20 to 80°C.

[0265] The hydrolysis may be complete hydrolysis, that is, all hydrolyzable groups are converted into silanol groups, or partial hydrolysis, that is, unreacted hydrolyzable groups remain.

[0266] Examples of the hydrolysis catalyst that can be used when performing hydrolysis for condensation include metal chelates, organic acids, inorganic acids, organic bases, and inorganic bases.

[0267] Examples of the metal chelate compound as the hydrolysis catalyst include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-isopropoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-tert-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di-isopropoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium , di-sec-butoxy·bis(acetylacetonate)titanium, di-tert-butoxy·bis(acetylacetonate)titanium, monoethoxy·tri(acetylacetonate)titanium, mono-n-propoxy·tri(acetylacetonate)titanium, mono-isopropoxy·tri(acetylacetonate)titanium, mono-n-butoxy·tri(acetylacetonate)titanium, mono-sec-butoxy·tri(acetylacetonate)titanium, mono-tert-butoxy·tri(acetylacetonate)titanium, tetra(acetylacetonate)titanium, triethoxy·mono(ethyl acetoacetate)titanium, tri-n-propoxy·mono(ethyl acetoacetate)titanium, tri-isopropoxy ethyl acetoacetate titanium, tri-n-butoxy mono(ethyl acetoacetate titanium), tri-sec-butoxy mono(ethyl acetoacetate titanium), tri-tert-butoxy mono(ethyl acetoacetate titanium), diethoxy bis(ethyl acetoacetate titanium), di-n-propoxy bis(ethyl acetoacetate titanium), di-isopropoxy bis(ethyl acetoacetate titanium), di-n-butoxy bis(ethyl acetoacetate titanium), di-sec-butoxy bis(ethyl acetoacetate titanium), di-tert-butoxy bis(ethyl acetoacetate titanium, mono(ethyl acetoacetate) titanium, tri-n-butoxy mono(ethyl acetoacetate) titanium, tri-sec-butoxy mono(ethyl acetoacetate) titanium, tri-tert-butoxy mono(ethyl acetoacetate) titanium, Titanium chelates such as ethoxy tris(ethyl acetoacetate)titanium, mono-n-propoxy tris(ethyl acetoacetate)titanium, mono-isopropoxy tris(ethyl acetoacetate)titanium, mono-n-butoxy tris(ethyl acetoacetate)titanium, mono-sec-butoxy tris(ethyl acetoacetate)titanium, mono-tert-butoxy tris(ethyl acetoacetate)titanium, tetrakis(ethyl acetoacetate), mono(acetylacetonate) tris(ethyl acetoacetate)titanium, bis(acetylacetonate) bis(ethyl acetoacetate)titanium, tris(acetylacetonate) mono(ethyl acetoacetate)titanium;triethoxy zirconium mono(acetylacetonate), tri-n-propoxy zirconium mono(acetylacetonate), tri-isopropoxy zirconium mono(acetylacetonate), tri-n-butoxy zirconium mono(acetylacetonate), tri-sec-butoxy zirconium mono(acetylacetonate), tri-tert-butoxy zirconium mono(acetylacetonate), diethoxy zirconium bis(acetylacetonate), di-n-propoxy zirconium bis(acetylacetonate), di-isopropoxy zirconium bis(acetylacetonate), di-n-butoxy zirconium bis(acetylacetonate), di-sec-butoxy zirconium bis(acetylacetonate), di-tert-butoxy · Zirconium bis(acetylacetonate), zirconium monoethoxy tris(acetylacetonate), zirconium mono-n-propoxy tris(acetylacetonate), zirconium mono-isopropoxy tris(acetylacetonate), zirconium mono-n-butoxy tris(acetylacetonate), zirconium mono-sec-butoxy tris(acetylacetonate), zirconium mono-tert-butoxy tris(acetylacetonate), zirconium tetra(acetylacetonate), zirconium triethoxy mono(ethyl acetoacetate), zirconium tri-n-propoxy mono(ethyl acetoacetate), zirconium tri-isopropoxy mono(ethyl acetoacetate), zirconium tri-n-butoxy mono(ethyl acetoacetate) ester) zirconium, tri-sec-butoxy mono(ethyl acetoacetate) zirconium, tri-tert-butoxy mono(ethyl acetoacetate) zirconium, diethoxy bis(ethyl acetoacetate) zirconium, di-n-propoxy bis(ethyl acetoacetate) zirconium, di-isopropoxy bis(ethyl acetoacetate) zirconium, di-n-butoxy bis(ethyl acetoacetate) zirconium, di-sec-butoxy bis(ethyl acetoacetate) zirconium, di-tert-butoxy bis(ethyl acetoacetate) zirconium, monoethoxy tris(ethyl acetoacetate) zirconium, mono-n-propoxy tris(ethyl acetoacetate) Zirconium, zirconium mono-isopropoxy tris(ethyl acetoacetate), zirconium mono-n-butoxy tris(ethyl acetoacetate), zirconium mono-sec-butoxy tris(ethyl acetoacetate), zirconium mono-tert-butoxy tris(ethyl acetoacetate), zirconium tetra(ethyl acetoacetate), zirconium mono(acetylacetonate) tris(ethyl acetoacetate), zirconium bis(acetylacetonate) bis(ethyl acetoacetate), zirconium tris(acetylacetonate) mono(ethyl acetoacetate); aluminum chelates such as aluminum tris(acetylacetonate), aluminum tris(ethyl acetoacetate); etc., but not limited to these. ;

[0268] Examples of organic acids used as the hydrolysis catalyst include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0269] Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and the like, but the present invention is not limited thereto.

[0270] Examples of the organic base as the hydrolysis catalyst include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picolinium, 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.

[0271] Examples of the inorganic base as the hydrolysis catalyst include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like, but the present invention is not limited to these.

[0272] Among these catalysts, metal chelates, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.

[0273] Among them, in the present invention, nitric acid can be used as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, the molecular weight change of the hydrolysis condensate can be suppressed. It is known that the stability of the hydrolysis condensate in the liquid depends on the pH of the solution. After in-depth research, it was found that by using an appropriate amount of nitric acid, the pH of the solution becomes a stable region.

[0274] In addition, as described above, nitric acid can be used when obtaining a modified product of the hydrolysis condensate, for example, when the silanol group is blocked with an alcohol. Therefore, it is also preferred from the viewpoint of being a substance that can contribute to the reaction of both the hydrolysis and condensation of the hydrolyzable silane and the alcohol blocking of the hydrolysis condensate.

[0275] In the case of hydrolysis and condensation, an organic solvent may be used as a solvent. Specific examples thereof include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, and n-pentylnaphthalene; hydrocarbon solvents; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonanol, sec-tetradecyl alcohol, sec-heptanol Alkyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol and other monohydric alcohol solvents; ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol and other polyhydric alcohol solvents; acetone, methyl ethyl ketone, methyl- Ketone solvents such as n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone acetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, di Alkane, dimethyl alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether solvents such as ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid Benzyl ester, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxytriethylene glycol acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, propionic acid Ester solvents such as isopentyl ester, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, cyclopentane sulfone, and 1,3-propane sultone, but are not limited to these. These solvents can be used alone or in combination of two or more.

[0276] After the hydrolysis and condensation reactions are completed, the reaction solution is directly or diluted or concentrated, neutralized, and treated with an ion exchange resin, so that the hydrolysis catalyst such as the acid and alkali used for the hydrolysis and condensation can be removed. In addition, before or after such treatment, alcohol, water, the hydrolysis catalyst used, etc., which are by-products, can be removed from the reaction solution by vacuum distillation, etc.

[0277] The hydrolysis condensate (hereinafter also referred to as polysiloxane) obtained by such operation can be obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and it can be directly used for the preparation of a composition for forming a resist underlayer film containing silicon. That is, the reaction solution can be directly (or diluted) used for the preparation of a composition for forming a resist underlayer film containing silicon. In this case, the hydrolysis catalyst, by-products, etc. used for hydrolysis and condensation can remain in the reaction solution as long as they do not impair the effect of the present invention. For example, the nitric acid used for the hydrolysis catalyst and the alcohol blocking of the silanol group can remain in the polymer varnish solution at about 100ppm to 5,000ppm.

[0278] The obtained polysiloxane varnish may be solvent-exchanged or diluted with an appropriate solvent. If the obtained polysiloxane varnish has good storage stability, the organic solvent may be distilled off to make the concentration of the film-forming component 100%. The so-called film-forming component refers to the component obtained by removing the solvent component from all the components of the composition.

[0279] The organic solvent used for solvent replacement and dilution of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane. The dilution solvent is not particularly limited and may be one or more and may be arbitrarily selected and used.

[0280] <[B] Ingredient>

[0281] The component [B] is sulfuric acid, a polyfunctional sulfonic acid, or a salt thereof, and these may be used alone or in combination of two or more.

[0282] The polyfunctional sulfonic acid in the present invention is a compound having two or more sulfonic groups (—SO 3 H).

[0283] As described above, the present inventors have found that a resist underlayer film capable of improving the sensitivity of the resist can be formed by including sulfuric acid, a polyfunctional sulfonic acid, or a salt thereof as the component [B] in a resist underlayer-forming composition containing silicon including polysiloxane.

[0284] As shown in the examples described later, even when a monofunctional sulfonic acid (a compound having one sulfonic group (—SO 3 H)) is used instead of the component [B], the effects of the present invention cannot be obtained.

[0285] The effect of the present invention is significant when a metal-containing resist is used. The present inventors consider the reason as follows. Sulfuric acid, polyfunctional sulfonic acid, and their salts coordinate with the metal of the metal-containing resist to promote the curing of the resist. As a result, the sensitivity of the resist is improved.

[0286] The number of sulfonic groups in the polyfunctional sulfonic acid is not particularly limited, but is preferably 2 to 6, and more preferably 2 to 4. The number of sulfonic groups is usually represented by an integer.

[0287] The molecular weight of the polyfunctional sulfonic acid is not particularly limited, but is preferably 176 to 1,000, and more preferably 176 to 500. The molecular weight of 176 is the molecular weight of methanedisulfonic acid.

[0288] As the polyfunctional sulfonic acid, for example, a compound represented by the following formula (A) is preferred.

[0289]

[0290] (In formula (A), n represents an integer of 1 to 3. 1 It represents an n+1-valent organic group having 1 to 15 carbon atoms.

[0291] R 1 The n+1-valent organic group having 1 to 15 carbon atoms may have a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, etc. in addition to the carbon atom.

[0292] As R 1 The molecular weight of the n+1-valent organic group having 1 to 15 carbon atoms is not particularly limited, but is preferably 12 to 200.

[0293] As n, it can be 1, 2, or 3.

[0294] As the polyfunctional sulfonic acid, for example, the following compounds can be mentioned.

[0295]

[0296] The sulfuric acid, the polyfunctional sulfonic acid, or the salt thereof is not particularly limited, and examples thereof include ammonium salts, imidazoles, Salt, pyridine Salt, sulfonium salt, Salt, iodine Salt, etc.

[0297] In these salts, it is not necessary for all sulfonic groups to be anionized, and it is sufficient that at least one sulfonic group is anionized.

[0298] These salts may be, for example, salts as shown below in specific examples. That is, at least one of the two or more sulfonic groups of the polyfunctional sulfonic acid may be anionized to form a salt.

[0299]

[0300] Even when these salts do not have a sulfonic group (—SO 3 H) in the salt state, a sulfonic group can be generated by, for example, irradiation with light or electron beams or by heat.

[0301] Examples of the ammonium salt include N,N-dimethyl-N-benzylammonium and N,N-diethyl-N-benzylammonium.

[0302] As imidazole Salts include salts of imidazoles and polyfunctional sulfonic acids. Examples of imidazoles include imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 2-phenyl-4-methylimidazole, 2-methyl-4-phenylimidazole, 2-methylbenzimidazole, and 2-phenylbenzimidazole.

[0303] As pyridine The salt includes salts of pyridines and polyfunctional sulfonic acids. Examples of the pyridines include pyridine, picolin, and 4-methylpyridine.

[0304] Examples of the sulfonium salt include aromatic sulfonium salts. Examples of the aromatic sulfonium salt include triphenylsulfonium salt, (2-ethoxy-1-methyl-2-oxoethyl)methyl-2-naphthylsulfonium salt, 4-(methoxycarbonyloxy)phenylbenzylmethylsulfonium salt, 4-acetoxyphenyldimethylsulfonium salt, 4-hydroxyphenylbenzylmethylsulfonium salt, 4-hydroxyphenyl(o-methylbenzyl)methylsulfonium salt, 4-hydroxyphenyl(α-naphthylmethyl)methylsulfonium salt, and diphenyl-4-(phenylthio)phenylsulfonium salt.

[0305] As Salts include, for example, ethyltriphenylphosphine Salt, tetrabutyl Salt, etc.

[0306] As iodine Salts, for example, aromatic iodine Salt. As aromatic iodine Salts, for example, diphenyl iodide Salt, 4-methylphenyl-4-(1-methylethyl)phenyl iodide Salt, Bis(4-tert-butylphenyl)iodide Salt, bis(dodecylphenyl)iodide Salt, etc.

[0307] From the viewpoint of more fully achieving the effects of the present invention, the content of the component [B] in the silicon-containing resist underlayer film-forming composition is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the [A] polysiloxane.

[0308] <[C] Component: Solvent>

[0309] The solvent for the component [C] can be used without particular limitation as long as it can dissolve and mix the component [A], the component [B], and, if necessary, other components contained in the resist underlayer film-forming composition containing silicon.

[0310] As the solvent [C], an alcohol solvent is preferred, an alkylene glycol monoalkyl ether as an alcohol solvent is more preferred, and propylene glycol monoalkyl ether is still more preferred. Since these solvents are also blocking agents for the silanol groups of the polysiloxane, the silicon-containing resist underlayer film-forming composition can be prepared from the solution obtained by preparing the polysiloxane [A] without the need for solvent replacement or the like.

[0311] Examples of the alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether.

[0312] Specific examples of other [C] solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ethyl ester, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate , amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, -methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, γ-butyrolactone, etc. The solvent can be used alone or in combination of two or more.

[0313] In addition, the resist underlayer film-forming composition containing silicon of the present invention may contain water as a solvent. When containing water as a solvent, its content may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less relative to the total mass of the solvent contained in the composition.

[0314] <[D] Component: Curing catalyst>

[0315] The silicon-containing resist underlayer film-forming composition may not contain a curing catalyst, but preferably contains a curing catalyst (component [D]).

[0316] When the resist underlayer film-forming composition containing silicon contains both the component [B] and the component [D], the effect of the present invention brought about by containing the component [B] can be more fully obtained.

[0317] As the curing catalyst, ammonium salts, phosphines, Salt, sulfonium salt, iodine Salt, oxygen Salts, etc. The following salts described as examples of curing catalysts may be added in the form of salts, and may be any of those that form salts in the composition (those that are added as another compound and form salts in the system).

[0318] As ammonium salts, there can be mentioned quaternary ammonium salts having a structure represented by formula (D-1), quaternary ammonium salts having a structure represented by formula (D-2), quaternary ammonium salts having a structure represented by formula (D-3), quaternary ammonium salts having a structure represented by formula (D-4), quaternary ammonium salts having a structure represented by formula (D-5), and tertiary ammonium salts having a structure represented by formula (D-6).

[0319]

[0320] (In the formula, m a Integer from 2 to 11, n a represents an integer from 2 to 3, R 21 represents an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion.)

[0321] R 22 R 23 R 24 R 25 N + Y - Formula (D-2)

[0322] (Where R 22 , R 23 , R 24 and R 25 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion, and R 22 , R 23 , R 24 , and R 25 Each is bonded to a nitrogen atom.)

[0323]

[0324] (Where R 26 and R 27 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion.)

[0325]

[0326] (Where R 28 represents an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion.)

[0327]

[0328] (Where R 29 and R 30 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion.)

[0329]

[0330] (In the formula, m a Integer from 2 to 11, n a represents an integer from 2 to 3, Y - represents an anion.)

[0331] In addition, as Salts include quaternary Salt.

[0332] R 31 R 32 R 33 S + Y - Formula (D-7)

[0333] (Where R 31 , R 32 , R 33 , and R 34 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion, and R 31 , R 32 , R 33 , and R 34 Each is bonded to a phosphorus atom.)

[0334] In addition, examples of the sulfonium salt include tertiary sulfonium salts represented by formula (D-8).

[0335] R 35 R 36 R 37 S + Y - Formula (D-8)

[0336] (Where R 35 , R 36 , and R 37 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion, and R 35 , R 36 , and R 37 Each is bonded to a sulfur atom.)

[0337] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m a Integer from 2 to 11, n a represents an integer of 2 to 3. 21 represents, for example, an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include straight-chain alkyl groups such as ethyl, propyl, and butyl, benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alkoxide (-O - ) and other acid groups.

[0338] The compound of formula (D-2) is R 22 R 23 R 24 R 25 N + Y - The quaternary ammonium salt R 22 , R 23 , R 24 and R 25 For example, it is an alkyl group having 1 to 18 carbon atoms such as ethyl, propyl, butyl, cyclohexyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms such as phenyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alkoxide (-O -The quaternary ammonium salt can be obtained as a commercial product, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0339] The compound of formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 The number of carbon atoms is, for example, 1 to 18, preferably R 26 and R 27 The total number of carbon atoms is 7 or more. 26 Examples include alkyl groups such as methyl, ethyl, and propyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. 27 Examples include aralkyl groups such as benzyl, alkyl groups such as octyl and octadecyl. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alkoxide (-O - The compound can also be obtained as a commercial product, but can be produced by reacting an imidazole compound such as 1-methylimidazole and 1-benzylimidazole with an aralkyl halide, alkyl halide or aryl halide such as benzyl bromide, methyl bromide or bromobenzene.

[0340] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, R 28 For example, it is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include butyl, octyl, benzyl, and lauryl. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alkoxide (-O - ) or the like. The compound can also be obtained as a commercial product, but can be produced, for example, by reacting pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or the like, or an aryl halide. The compound can be exemplified by, for example, N-laurylpyridinium chloride N-Benzylpyridinium bromide wait.

[0341] The compound of formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picolinate, etc., wherein R 29 For example, it is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include methyl, octyl, lauryl, and benzyl. 30 For example, it is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. For example, when the compound represented by formula (D-5) is a quaternary ammonium derived from picolinate, R 30 Methyl. Anion (Y - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alkoxide (-O - ) or the like. The compound can also be obtained as a commercial product, but can be prepared by, for example, reacting a substituted pyridine such as picolinate with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or an aryl halide. The compound can be exemplified by, for example, N-benzylpicolinate Chloride, N-Benzylpicoline Bromide, N-laurylpicoline Chloride, etc.

[0342] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m a Integer from 2 to 11, n a Indicates 2 or 3. In addition, anions (Y - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alkoxide (-O - ) and other acid groups. The present compound can be prepared 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. When formic acid is used, the anion (Y - ) is (HCOO - ), when acetic acid is used, the anion (Y - ) is (CH3COO - ). In addition, when phenol is used, the anion (Y - ) is (C6H5O - ).

[0343] The compound of formula (D-7) is a compound having R 31 R 32 R 33 R 34 P + Y - The structure of the season Salt. 31 , R 32 , R 33 , and R 34 For example, it is an alkyl group having 1 to 18 carbon atoms such as ethyl, propyl, butyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms such as phenyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl. 31 ~R 34 Among the four substituents, three are unsubstituted phenyl or substituted phenyl, such as phenyl and tolyl, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alkoxide (-O - ) and the like. The compound can be obtained as a commercial product, and examples thereof include tetra-n-butyl halides. Tetra-n-propyl halide Tetraalkyl halides Triethylbenzyl halide Trialkylbenzyl halides Triphenylmethyl halides Triphenylethyl halide Triphenyl halogenated monoalkyl Triphenylbenzyl halides Tetraphenyl halides Trimethylphenyl halides or trimethylbenzene monoalkyl halides (In the above, the halogen atom is a chlorine atom or a bromine atom.) A halogenated triphenylmethyl Triphenylethyl halide Triphenyl halogenated monoalkyl Triphenylbenzyl halides Isohalogenated triphenyl monoaryl Halogenated trimethylphenyl monophenyl Isohalogenated trimethylphenyl monoaryl Trimethylol Halide Isohalogenated trimethylbenzyl monoalkyl (The halogen atom is a chlorine atom or a bromine atom).

[0344] In addition, examples of the phosphines include primary phosphines such as methyl phosphine, ethyl phosphine, propyl phosphine, isopropyl phosphine, isobutyl phosphine and phenyl phosphine, secondary phosphines such as dimethyl phosphine, diethyl phosphine, diisopropyl phosphine, diisopentyl phosphine and diphenyl phosphine, and tertiary phosphines such as trimethyl phosphine, triethyl phosphine, triphenyl phosphine, methyldiphenyl phosphine and dimethylphenyl phosphine.

[0345] The compound of formula (D-8) is a compound having R 35 R 36 R 37 S + Y - The structure of tertiary sulfonium salt. 35 , R 36 , and R 37 For example, it is an alkyl group having 1 to 18 carbon atoms such as ethyl, propyl, butyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms such as phenyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl. 35 ~R 37 Two of the three substituents are unsubstituted phenyl or substituted phenyl, such as phenyl and tolyl, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. - ) can be exemplified by chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alkoxide (-O - ), maleic acid anion, nitrate anion and other acid groups. The compound can be obtained as a commercial product, for example, trialkylsulfonium halides such as tri-n-butylsulfonium halides, tri-n-propylsulfonium halides, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halides, diphenylmethylsulfonium halides, diphenylethylsulfonium halides and other diphenylmonoalkylsulfonium halides, triphenylsulfonium halides (above, the halogen atom is a chlorine atom or a bromine atom), tri-n-butylsulfonium carboxylates, trialkylsulfonium carboxylates such as tri-n-propylsulfonium carboxylates, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylates, diphenylmethylsulfonium carboxylates, diphenylethylsulfonium carboxylates and diphenylmonoalkylsulfonium carboxylates, triphenylsulfonium carboxylates. In addition, triphenylsulfonium halides and triphenylsulfonium carboxylates can be preferably used.

[0346] Furthermore, a nitrogen-containing silane compound may be added as a curing catalyst. Examples of the nitrogen-containing silane compound include silane compounds containing an imidazole ring, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0347] From the viewpoint of more fully achieving the effects of the present invention, the content of the curing catalyst [D] in the silicon-containing resist underlayer film-forming composition is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 25 parts by mass, and even more preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the polysiloxane [A].

[0348] From the viewpoint of more fully achieving the effects of the present invention, the mass ratio ([D] component) to the [B] component in the silicon-containing resist underlayer film-forming composition is preferably 0.1:1.0 to 1.0:0.1, more preferably 0.2:1.0 to 1.0:0.1, and even more preferably 0.5:1.0 to 1.0:0.15.

[0349] <[E] Ingredient: Nitric acid>

[0350] The silicon-containing resist underlayer film-forming composition preferably contains [E] nitric acid.

[0351] [B] Nitric acid can be added when preparing the silicon-containing resist underlayer film-forming composition, but it can also be treated as a hydrolysis catalyst in the production of the above-mentioned polysiloxane, or used when the silanol group is blocked by alcohol, and the substance remaining in the polysiloxane varnish can be treated as [E] nitric acid.

[0352] The blending amount of [B] nitric acid (residual nitric acid amount) can be, for example, 0.0001% by mass to 1% by mass, or 0.001% by mass to 0.1% by mass, or 0.005% by mass to 0.05% by mass based on the total mass of the silicon-containing resist underlayer film-forming composition.

[0353] <[F] Component: amine, hydroxide>

[0354] From the viewpoint of more fully achieving the effects of the present invention, the resist underlayer film-forming composition containing silicon preferably contains [F] at least one selected from amines and hydroxides.

[0355] Examples of the amine include ammonia; primary amines such as monomethanolamine, monoethanolamine, monopropanolamine, methylamine, ethylamine, propylamine, and butylamine; secondary amines such as dimethylamine, ethylmethylamine, and diethylamine; tertiary amines such as trimethylamine, triethylamine, tripropylamine, dimethylethylamine, methyldiisopropylamine, diisopropylethylamine, diethylethanolamine, and triethanolamine; amines such as ethylenediamine and tetramethylethylenediamine; cyclic amines such as pyridine and morpholine, and the like.

[0356] Examples of the hydroxide include inorganic alkali hydroxides and organic alkali hydroxides.

[0357] Examples of the inorganic alkali hydroxide include sodium hydroxide and potassium hydroxide.

[0358] Examples of the organic base hydroxide include tetraalkylammonium hydroxide, triarylsulfonium hydroxide, diaryliodonium Hydroxides, etc. Examples of tetraalkylammonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Examples of triarylsulfonium hydroxides include triphenylsulfonium hydroxide and tri(tert-butylphenyl)sulfonium hydroxide. Examples of diaryliodonium hydroxides include tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Hydroxides, for example diphenyl iodide Hydroxide, bis(tert-butylphenyl) iodide Hydroxide, etc.

[0359] The content of the component [F] in the silicon-containing resist underlayer film-forming composition is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the polysiloxane [A].

[0360] <Other additives>

[0361] The resist underlayer film-forming composition containing silicon may be blended with various additives depending on the application of the composition.

[0362] Examples of additives include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology modifiers, adhesion promoters, and the like, which are known additives that are mixed with materials (compositions) for forming various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, antireflective films, and pattern reversal films.

[0363] In addition, various additives are exemplified below, but are not limited to these.

[0364] <<Stabilizer>>

[0365] The stabilizer can be added for the purpose of stabilizing the hydrolysis-condensation product of the hydrolyzable silane mixture, and specific examples thereof include organic acids, water, alcohols, or combinations thereof.

[0366] As organic acids, for example, oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, salicylic acid, etc. can be cited. Among them, oxalic acid and maleic acid are preferred. When an organic acid is added, its addition amount is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the hydrolyzable silane mixture. These organic acids can also act as pH adjusters.

[0367] As water, pure water, ultrapure water, ion-exchanged water or the like can be used. When used, the amount thereof added can be 1 to 20 parts by mass based on 100 parts by mass of the resist underlayer film-forming composition containing silicon.

[0368] The alcohol is preferably an alcohol that is easily dispersed by heating after coating, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol, etc. When alcohol is added, the amount thereof added may be 1 to 20 parts by mass based on 100 parts by mass of the resist underlayer film-forming composition containing silicon.

[0369] <<Organic polymer>>

[0370] The organic polymer is added to the resist underlayer film-forming composition containing silicon, so that the dry etching rate (the amount of film thickness reduction per unit time), attenuation coefficient, refractive index, etc. of the film (resist underlayer film) formed by the composition can be adjusted. There is no particular limitation on the organic polymer, and it can be appropriately selected from various organic polymers (condensation polymers and addition polymers) according to the purpose of its addition.

[0371] Specific examples thereof include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate.

[0372] In the present invention, an organic polymer containing an aromatic ring or heteroaromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, a quinoxaline ring, etc., which functions as a light absorbing site, can also be suitably used when such a function is required. Specific examples of such an organic polymer include addition polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as structural units, and condensation polymers such as phenol novolac and naphthol novolac, but are not limited thereto.

[0373] When an addition polymer is used as the organic polymer, the polymer may be either a homopolymer or a copolymer.

[0374] 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, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0375] Specific examples of the acrylate compound include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracenemethyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, and glycidyl acrylate, but are not limited to these.

[0376] Specific examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate, but are not limited to these.

[0377] Specific examples of the acrylamide compound include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide, but are not limited to these.

[0378] Specific examples of the methacrylamide compound include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-benzyl methacrylamide, N-phenyl methacrylamide, N,N-dimethyl methacrylamide, and N-anthryl methacrylamide, but are not limited thereto.

[0379] Specific examples of the vinyl compound include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc., but are not limited to these.

[0380] Specific examples of the styrene compound include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene, but are not limited to these.

[0381] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but the maleimide is not limited thereto.

[0382] When a polycondensate is used as a polymer, such a polymer may be, for example, a polycondensate of a diol compound and a dicarboxylic acid compound. As the diol compound, diethylene glycol, 1,6-hexanediol, butanediol, etc. may be mentioned. As the dicarboxylic acid compound, succinic acid, adipic acid, terephthalic acid, maleic anhydride, etc. may be mentioned. In addition, polyesters, polyamides, and polyimides such as poly-1,2,4,5-pyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate may be mentioned, but are not limited to these.

[0383] When the organic polymer contains a hydroxyl group, the hydroxyl group can undergo a cross-linking reaction with a hydrolysis condensate or the like.

[0384] The weight average molecular weight of the organic polymer can be generally 1,000 to 1,000,000. When the organic polymer is mixed, the weight average molecular weight can be, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000, from the viewpoint of fully obtaining the effect of the function as the polymer and suppressing precipitation in the composition.

[0385] Such organic polymers may be used alone or in combination of two or more.

[0386] When the silicon-containing resist underlayer film-forming composition contains an organic polymer, the content thereof is appropriately determined in consideration of the function of the organic polymer and the like and therefore cannot be generally specified, but generally, it can be in the range of 1 to 200% by mass relative to the mass of the [A] polysiloxane, and from the viewpoint of suppressing precipitation in the composition, it can be, for example, 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less, and from the viewpoint of sufficiently obtaining the effect, it can be, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0387] <<Acid Generator>>

[0388] Examples of the acid generator include a thermal acid generator and a photoacid generator, and a photoacid generator can be preferably used.

[0389] Examples of the photoacid generator include sulfonium salts, Salt, ammonium salt, iodine Salt, oxygen Salt, etc. Salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, etc., but are not limited to these. In addition, the photoacid generator depends on its type, for example, Among salt compounds, nitrates, carboxylates such as maleates, and hydrochlorides can also function as curing catalysts.

[0390] Examples of the thermal acid generator include tetramethylammonium nitrate, but the present invention is not limited thereto.

[0391] As Specific examples of salt compounds include diphenyl iodide Hexafluorophosphate, diphenyl iodide Trifluoromethanesulfonate, diphenyl iodide Nonafluorobutane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Camphorsulfonate, bis(4-tert-butylphenyl)iodide Trifluoromethanesulfonate and other iodine Sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate (nitrate), triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride are also included, but are not limited to these.

[0392] Specific examples of the sulfonyl imide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide, but are not limited thereto.

[0393] Specific examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane, but are not limited thereto.

[0394] When the silicon-containing resist underlayer film-forming composition contains an acid generator, the content thereof cannot be generally specified because it is appropriately determined in consideration of the type of the acid generator, etc., but is usually in the range of 0.01 to 5 mass % relative to the mass of the [A] polysiloxane, and is preferably 3 mass % or less, more preferably 1 mass % or less, from the viewpoint of suppressing the precipitation of the acid generator in the composition, and is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, from the viewpoint of sufficiently obtaining the effect, etc.

[0395] The acid generator may be used alone or in combination of two or more. A photoacid generator and a thermal acid generator may be used in combination.

[0396] <<Surfactant>>

[0397] Surfactants are effective in suppressing the generation of pinholes, streaks, etc. when a silicon-containing resist underlayer film-forming composition is applied to a substrate. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, and the like. More specifically, examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan monostearate. Sorbitan fatty acid esters such as monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; and other nonionic surfactants; commercial products Names: EF301, EF303, and EF352 (registered trademarks) (manufactured by Mitsubishi Microelectronics Co., Ltd. (formerly Mitsubishi Microelectronics Co., Ltd.)), trade names: EF301 (Note: Registered trademarks) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Co., Ltd.), FC430, FC431 (manufactured by スリーエムジャパン Co., Ltd. )), trade name Asahigard (registered trademark) AG710 (manufactured by AGC Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Semichem Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these.

[0398] The surfactant may be used alone or in combination of two or more.

[0399] When the silicon-containing resist underlayer film-forming composition contains a surfactant, the content thereof may be generally 0.0001 to 5% by mass, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass, based on the mass of the [A] polysiloxane.

[0400] <<Rheology modifier>>

[0401] The rheology modifier is mainly added to improve the fluidity of the resist lower film-forming composition containing silicon, and is particularly added in the baking process to improve the uniformity of the film thickness of the formed film and the filling property of the composition into the inside of the hole. As specific examples, phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, adipic acid derivatives such as di-n-butyl adipate, di-isobutyl adipate, di-isooctyl adipate, octyldecyl adipate, maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate, or stearic acid derivatives such as stearic acid n-butyl stearate and glyceryl stearate can be cited.

[0402] When these rheology control agents are used, the amount thereof added is usually less than 30% by mass based on the total film-forming components of the resist underlayer film-forming composition containing silicon.

[0403] <<Adhesive additive>>

[0404] The adhesion aid is mainly added for the purpose of improving the adhesion between a substrate or a resist and a film (resist underlayer film) formed from a resist underlayer film-forming composition containing silicon, and particularly for the purpose of suppressing / preventing peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole. Heterocyclic compounds such as azole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds.

[0405] When using these adhesion promoters, the amount added is usually less than 5 mass %, preferably less than 2 mass % based on the film-forming components of the silicon-containing resist underlayer film-forming composition.

[0406] <<pH adjuster>>

[0407] In addition, as the pH adjuster, other acids other than the organic acid having one or more carboxylic acid groups mentioned as the above stabilizer can be mentioned. When the pH adjuster is used, the amount thereof added can be 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass relative to 100 parts by mass of the [A] polysiloxane.

[0408] <<Metal Oxides>>

[0409] In addition, examples of metal oxides that can be added to the silicon-containing resist underlayer film forming composition include, but are not limited to, oxides of 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).

[0410] The concentration of the film-forming component in the resist underlayer film-forming composition containing silicon may be, for example, 0.01 to 50 mass %, 0.01 to 30 mass %, 0.01 to 25 mass %, or 0.01 to 20.0 mass % based on the total mass of the composition.

[0411] The content of [A] polysiloxane in the film-forming component is usually 20% to 100% by mass, but from the viewpoint of obtaining the effect of the present invention with good reproducibility, etc., the lower limit is preferably 50% by mass, more preferably 60% by mass, more preferably 70% by mass, and further preferably 80% by mass, and the upper limit is preferably 99% by mass, and the remainder may be additives described later.

[0412] The resist underlayer film-forming composition containing silicon preferably has a pH of 1-5, and more preferably has a pH of 2-4.

[0413] In the present invention, in the middle of manufacturing the resist underlayer film-forming composition containing silicon, or after all the components are mixed, filtration can be performed using a submicron filter or the like. There is no limitation on the material type of the filter used at this time, and for example, a polyethylene filter, a nylon filter, a fluororesin filter, a polyimide filter, etc. can be used.

[0414] The silicon-containing resist underlayer film-forming composition of the present invention can be suitably used as a resist underlayer film-forming composition used in a photolithography process.

[0415] (Resist underlayer film, semiconductor processing substrate, pattern forming method, and semiconductor element manufacturing method)

[0416] The resist underlayer film of the present invention is a cured product of the silicon-containing resist underlayer film-forming composition of the present invention.

[0417] The semiconductor processing substrate of the present invention includes, for example, the silicon-containing resist underlayer film of the present invention.

[0418] The method for manufacturing a semiconductor device of the present invention includes, for example, the following steps:

[0419] A step of forming an organic lower layer film on a substrate;

[0420] a step of forming a resist underlayer film on an organic underlayer film using the resist underlayer film-forming composition containing silicon of the present invention; and

[0421] A step of forming a resist film containing a metal on the resist underlayer film.

[0422] The pattern forming method of the present invention includes, for example, the following steps:

[0423] A step of forming an organic lower layer film on a semiconductor substrate;

[0424] A step of coating the resist underlayer film-forming composition containing silicon of the present invention on the organic underlayer film and firing the composition to form a resist underlayer film;

[0425] A step of forming a resist film containing a metal on the resist underlayer film;

[0426] A process of exposing and developing a resist film containing a metal to obtain a resist pattern;

[0427] A step of using the resist pattern as a mask to etch the resist underlayer film; and

[0428] A step of etching the organic underlayer film using the patterned resist underlayer film as a mask.

[0429] Hereinafter, as one embodiment of the present invention, a semiconductor processing substrate, a pattern forming method, and a method for manufacturing a semiconductor element using the silicon-containing resist underlayer film of the present invention or the silicon-containing resist underlayer film-forming composition of the present invention are described.

[0430] First, the resist underlayer film-forming composition containing silicon of the present invention is applied by a suitable coating method such as a spin coater or a coater on a substrate used for manufacturing precision integrated circuit elements (for example, a semiconductor substrate such as a silicon wafer coated with a silicon oxide film, a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (including alkali-free glass, low-alkali glass, and crystallized glass), a glass substrate formed with an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film, a plastic (polyimide, PET, etc.) substrate, a substrate coated with a low dielectric constant material (low-k material), a flexible substrate, etc.), and then the resist underlayer film is formed by firing the composition using a heating means such as a hot plate to form a cured product. Hereinafter, in this specification, the so-called resist underlayer film refers to the resist underlayer film containing silicon of the present invention or a film formed from the resist underlayer film-forming composition containing silicon of the present invention.

[0431] The calcination conditions are appropriately selected from a calcination temperature of 40°C to 400°C, or 80°C to 250°C, and a calcination time of 0.3 to 60 minutes, preferably a calcination temperature of 150°C to 250°C, and a calcination time of 0.5 to 2 minutes.

[0432] The thickness of the resist underlayer film formed here is, for example, 10 nm to 1,000 nm, or 20 nm to 500 nm, or 50 nm to 300 nm, or 100 nm to 200 nm, or 10 to 150 nm.

[0433] In addition, as the resist underlayer film-forming composition containing silicon used in the formation of the resist underlayer film, a resist underlayer film-forming composition containing silicon that has been filtered through a nylon filter can be used. The resist underlayer film-forming composition containing silicon that has been filtered through a nylon filter here refers to a composition that has been filtered through a nylon filter during the process of manufacturing the resist underlayer film-forming composition containing silicon or after all components have been mixed.

[0434] One aspect of the present invention is an aspect in which an organic underlayer film is formed on a substrate and then a resist underlayer film is formed thereon. However, there may be an aspect in which the organic underlayer film is not provided depending on circumstances.

[0435] The organic underlayer film used here is not particularly limited and can be arbitrarily selected from those conventionally used in photolithography processes.

[0436] By providing an organic lower film on a substrate, providing a resist lower film thereon, and further providing a metal-containing resist film described later thereon, the pattern width of the metal-containing resist film is narrowed, and even when the metal-containing resist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas described later. For example, by using a fluorine-based gas having a sufficiently fast etching rate with respect to the metal-containing resist film as an etching gas, the resist lower film can be processed, and by using an oxygen-based gas having a sufficiently fast etching rate with respect to the resist lower film as an etching gas, the organic lower film can be processed, and by further using a fluorine-based gas having a sufficiently fast etching rate with respect to the organic lower film as an etching gas, the substrate can be processed.

[0437] In addition, the substrate and coating method that can be used at this time are the same as those mentioned above.

[0438] Next, a layer of a resist material containing a metal (a metal-containing resist film) is formed on the resist underlayer film. The metal-containing resist film can be formed by a known method, that is, by applying a coating type resist material (a metal-containing resist film forming composition) as a metal-containing resist on the resist underlayer film and firing it.

[0439] The film thickness of the metal-containing resist film is, for example, 5 nm to 10,000 nm, or 5 nm to 1,000 nm, or 5 nm to 40 nm.

[0440] A resist containing a metal is also called a metal oxide resist (metal oxide resist (MOR)), and a representative example thereof is a tin oxide-based resist.

[0441] As a metal oxide resist material, for example, a coating composition described in Japanese Patent Application Publication No. 2019-113855, which includes a metal oxo-hydroxyl (oxo-hydroxo) network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond, can be mentioned.

[0442] An example of a metal-containing resist uses a peroxide ligand as a radiation sensitivity stabilizing ligand. The peroxide-based metal oxygen-hydroxy compound is described in detail in the patent document described in paragraph

[0011] of the Japanese Publication No. 2019-532489. As the patent document, for example, U.S. Patent No. 9,176,377B2, U.S. Patent Application Publication No. 2013 / 0224652A1, U.S. Patent No. 9,310,684B2, U.S. Patent Application Publication No. 2016 / 0116839A1, and U.S. Patent Application Publication No. 15 / 291738 can be cited.

[0443] Next, the metal-containing resist film formed on the upper layer of the resist lower film is exposed through a predetermined mask (photomask). During the 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.

[0444] After the exposure, post-exposure baking may be performed as necessary. The post-exposure baking is performed under conditions appropriately selected from a heating temperature of 70° C. to 250° C. and a heating time of 0.3 minutes to 10 minutes.

[0445] In addition, in the present invention, an organic solvent can be used as a developer, and development is performed by a developer (solvent) after exposure. Thus, for example, when a negative metal-containing resist film is used, the metal-containing resist film of the unexposed portion is removed to form a pattern of the metal-containing resist film.

[0446] Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxy Butyl 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, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. are exemplified. Furthermore, a surfactant or the like may be added to these developers. As the conditions for development, the temperature is appropriately selected from 5° C. to 50° C. and the time is appropriately selected from 10 seconds to 600 seconds.

[0447] The resist lower layer film (middle layer) is removed using the pattern of the metal-containing resist film (upper layer) formed in this way as a protective film, and then the organic lower layer film (lower layer) is removed using the film composed of the patterned metal-containing resist film and the patterned resist lower layer film (middle layer) as a protective film. Finally, the substrate is processed using the patterned resist lower layer film (middle layer) and the patterned organic lower layer film (lower layer) as protective films.

[0448] The removal (patterning) of the resist lower layer film (middle layer) using the pattern of the metal-containing resist film (upper layer) as a protective film is performed by dry etching, and gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used.

[0449] In addition, in the dry etching of the resist lower film, it is preferred to use halogen-based gases. For dry etching using halogen-based gases, the resist film containing metal is not easily removed. In contrast, a large number of resist lower films containing silicon atoms are rapidly removed by halogen-based gases. Therefore, the reduction of the film thickness of the resist film containing metal accompanying the dry etching of the resist lower film can be suppressed. And then, as a result, the resist film containing metal can be used with a thin film. Therefore, the dry etching of the resist lower film preferably adopts fluorine-based gases, and as fluorine-based gases, for example, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc. can be cited, but are not limited to these.

[0450] In the case where there is an organic lower film between the substrate and the resist lower film, the removal (patterning) of the organic lower film (lower layer) is preferably performed by dry etching using an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.) with a film composed of (a metal-containing resist film (upper layer) patterned in the case of remaining) and) a patterned resist lower film (intermediate layer) as a protective film. This is because the resist lower film of the present invention, which contains a large amount of silicon atoms, is not easily removed by dry etching using an oxygen-based gas.

[0451] Then, processing (patterning) of the (semiconductor) substrate using the patterned resist underlayer film (intermediate layer) and, if necessary, the patterned organic underlayer film (underlayer) as a protective film is preferably performed by dry etching using a fluorine-based gas.

[0452] Examples of the fluorine-based gas include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0453] After the organic underlayer film is removed (patterned) or after the substrate is processed (patterned), the resist underlayer film can be removed. The resist underlayer film can be removed by dry etching or wet etching (wet method).

[0454] Dry etching of the resist underlayer film preferably uses fluorine-based gases as mentioned in patterning, such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc., but is not limited to these.

[0455] As the chemical solution used for wet etching of the resist underlayer film, there can be mentioned alkaline solutions such as dilute hydrofluoric acid (HF), buffered hydrofluoric acid (HF and NH4F mixed solution), aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical solution), aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution). In addition, as the alkaline solution, in addition to the above-mentioned ammonia hydrogen peroxide aqueous solution (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide water and water, there can also be mentioned a solution containing ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidine Hydroxide, 1-propyl-1-methylpyrrolidine Hydroxide, 1-butyl-1-methylpiperidinium Hydroxide, 1-propyl-1-methylpiperidinium Hydroxide, methylpiperidin Aqueous solution of 1 to 99% by mass of mepiquat hydroxide, trimethylsulfonium hydroxide, hydrazine, ethylenediamine, or guanidine. These solutions may also be used in combination.

[0456] In addition, an organic anti-reflection film can be formed on the upper layer of the resist underlayer film before the formation of the metal-containing resist film. There is no particular limitation on the anti-reflection film composition used therein, and for example, any material conventionally used in the photolithography process can be selected and used. In addition, the anti-reflection film can be formed by conventional methods, for example, coating and firing using a spin coater or a coating machine.

[0457] Furthermore, the substrate to which the silicon-containing resist underlayer film-forming composition is applied may have an organic or inorganic antireflection film formed on its surface by a CVD method or the like, or the resist underlayer film may be formed thereon. Even when the resist underlayer film of the present invention is formed thereon after an organic underlayer film is formed on a substrate, the substrate used may have an organic or inorganic antireflection film formed on its surface by a CVD method or the like.

[0458] The resist underlayer film formed from the resist underlayer film-forming composition containing silicon may also absorb the light used in the photolithography process depending on the wavelength of the light. In such a case, it can function as an antireflection film having the effect of preventing reflected light from the substrate.

[0459] Furthermore, the resist underlayer film can also be used as a layer for preventing interaction between the substrate and the metal-containing resist film, a layer having the function of preventing the material used for the metal-containing resist film or the substance generated when the metal-containing resist film is exposed to light from having an adverse effect on the substrate, a layer having the function of preventing the diffusion of substances generated from the substrate into the metal-containing resist film during heating and firing, and a barrier layer for reducing the poisoning effect of the metal-containing resist film caused by the dielectric layer of the semiconductor substrate, etc.

[0460] The resist underlayer film can be applied to a substrate having a through hole formed therein used in a dual damascene process, and can be used as a hole filling material (embedded material) that can fill the hole without a gap. In addition, it can also be used as a planarizing material for planarizing the surface of a semiconductor substrate having uneven surfaces.

[0461] In addition, the resist lower film of the present invention can also be, for example, not mixed with the EUV resist film containing metal, and prevent undesired exposure light, such as UV (ultraviolet) light, DUV (deep ultraviolet) light (ArF light, KrF light) from reflecting from the substrate or interface during EUV exposure (wavelength 13.5nm) in addition to being the lower film of the EUV resist film containing metal and as a hard mask. Therefore, in order to form the lower anti-reflection film of the EUV resist film containing metal, the resist lower film forming composition containing silicon of the present invention can be used appropriately. That is, it can be used as the lower layer of the EUV resist film containing metal and effectively prevent reflection. When used as an EUV resist lower film, the process can be carried out in the same way as the photoresist lower film.

[0462] By using the semiconductor processing substrate including the resist underlayer film of the present invention described above and a semiconductor substrate, the semiconductor substrate can be suitably processed.

[0463] In addition, according to the method for manufacturing a semiconductor element as described above, which includes the steps of forming an organic underlayer film, forming a resist underlayer film on the organic underlayer film using the resist underlayer film forming composition containing silicon of the present invention, and forming a resist film containing metal on the resist underlayer film, it is possible to achieve high-precision processing of semiconductor substrates with good reproducibility, and therefore stable manufacturing of semiconductor elements can be expected.

[0464] Example

[0465] Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[0466] In addition, in the examples, the apparatus and conditions used for analyzing the physical properties of the samples are as follows.

[0467] (1) Molecular weight determination

[0468] The molecular weight of the polysiloxane used in the present invention is a molecular weight obtained in terms of polystyrene obtained by GPC analysis.

[0469] The measurement conditions of GPC are as follows: using a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC columns (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as an eluent (elution solvent), a flow rate (flow velocity) of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as a standard sample.

[0470] (2) 1 H-NMR

[0471] Use JEOL's NMR equipment 1 H-NMR (400 MHz) was used for evaluation using d6-acetone as a solvent.

[0472] [1] Synthesis of polymer (hydrolysis condensation product)

[0473] 20.8 g of tetraethoxysilane, 7.6 g of methyltriethoxysilane, and 52.9 g of propylene glycol monoethyl ether were added to a 300 ml flask, and 8.4 g of a 0.2 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0474] After the dropwise addition, the flask was transferred to an oil bath adjusted to 60° C. and refluxed for 20 hours. Then, ethanol and water as reaction by-products were removed by vacuum distillation and concentrated to obtain an aqueous solution of a hydrolysis condensate (polymer).

[0475] Propylene glycol monoethyl ether was further added, and the concentration was adjusted to 20% by mass in terms of solid residue at 150° C. as a solvent ratio of 100% of propylene glycol monoethyl ether, and filtered using a nylon filter (pore size 0.1 μm). The obtained polymer had a structure represented by the following formula (E1), and its weight average molecular weight obtained by GPC was Mw2,300 in terms of polystyrene.

[0476]

[0477] (Synthesis example 2)

[0478] 20.8 g of tetraethoxysilane, 5.1 g of methyltriethoxysilane, 2.8 g of phenyltrimethoxysilane, and 53.4 g of propylene glycol monoethyl ether were added to a 300 ml flask, and 8.4 g of a 0.2 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0479] After the dropwise addition, the flask was transferred to an oil bath adjusted to 60° C. and refluxed for 20 hours. Then, ethanol, methanol, and water as reaction by-products were removed by reduced pressure distillation and concentrated to obtain an aqueous solution of a hydrolysis condensate (polymer).

[0480] Propylene glycol monoethyl ether was further added, and the concentration was adjusted to 20% by mass in terms of solid residue at 150° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and filtered using a nylon filter (pore size 0.1 μm). The obtained polymer had a structure represented by the following formula (E2), and its weight average molecular weight obtained by GPC was Mw2,700 in terms of polystyrene.

[0481]

[0482] (Synthesis example 3)

[0483] 20.8 g of tetraethoxysilane, 5.1 g of methyltriethoxysilane, 3.7 g of 5-(triethoxysilyl)-2-norbornene and 53.4 g of propylene glycol monoethyl ether were added to a 300 ml flask, and 8.4 g of a 0.2 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0484] After the dropwise addition, the flask was transferred to an oil bath adjusted to 60° C. and refluxed for 20 hours. Then, ethanol and water as reaction by-products were removed by vacuum distillation and concentrated to obtain an aqueous solution of a hydrolysis condensate (polymer).

[0485] Propylene glycol monoethyl ether was further added, and the concentration was adjusted to 20% by mass in terms of solid residue at 150° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and filtered using a nylon filter (pore size 0.1 μm). The obtained polymer had a structure represented by the following formula (E3), and its weight average molecular weight obtained by GPC was Mw2,200 in terms of polystyrene.

[0486]

[0487] (Synthesis Example 4)

[0488] 20.8 g of tetraethoxysilane, 5.1 g of methyltriethoxysilane, 5.9 g of diallyl isocyanuratepropyltriethoxysilane, and 59.1 g of propylene glycol monoethyl ether were added to a 300 ml flask, and 8.4 g of a 0.2 M nitric acid aqueous solution was added dropwise while the resulting mixed solution was stirred with an electromagnetic stirrer.

[0489] After the dropwise addition, the flask was transferred to an oil bath adjusted to 60° C. and refluxed for 20 hours. Then, ethanol and water as reaction by-products were removed by vacuum distillation and concentrated to obtain an aqueous solution of a hydrolysis condensate (polymer).

[0490] Propylene glycol monoethyl ether was further added, and the concentration was adjusted to 20% by mass in terms of solid residue at 150° C. as a solvent ratio of 100% propylene glycol monoethyl ether, and filtered using a nylon filter (pore size 0.1 μm). The obtained polymer had a structure represented by the following formula (E4), and its weight average molecular weight obtained by GPC was Mw2,300 in terms of polystyrene.

[0491]

[0492] [2] Preparation of a silicon-containing composition for forming a resist underlayer film

[0493] The polysiloxane (polymer) obtained in the above-mentioned synthesis example, an acid (additive 1), a curing catalyst (additive 2), sulfuric acid, a sulfonic acid compound, or a salt thereof (additive 3), and a solvent were mixed in the ratios shown in Table 1, and filtered through a 0.1 μm fluororesin filter to prepare silicon-containing resist underlayer film-forming compositions. The amounts of each addition in Table 1 are expressed in parts by mass.

[0494] The hydrolysis condensate (polymer) was prepared as a composition containing a solution obtained in the synthesis example. However, the addition ratio of the polymer in Table 1 does not refer to the addition amount of the polymer solution but indicates the addition amount of the polymer itself.

[0495] The meanings of the abbreviations in Table 1 are as follows.

[0496] <Solvent>

[0497] DIW: Ultrapure Water

[0498] PGEE: Propylene glycol monoethyl ether

[0499] PGME: Propylene glycol monomethyl ether

[0500] <Additive 1>

[0501] MA: Maleic acid

[0502] <Additive 2>

[0503] TPSNO3: Triphenylsulfonium nitrate

[0504] <Additive 3>

[0505] PrDSA: 1,3-propanedisulfonic acid

[0506] BiPhDSA: 4,4-Biphenyldisulfonic acid

[0507] NaphDSA: 1,5-naphthalene disulfonic acid

[0508] SA: sulfuric acid

[0509] TPS-PrDSA: Triphenylsulfonium 1,3-propane disulfonate

[0510] MSA: Methanesulfonic acid

[0511] PTSA: p-Toluenesulfonic acid

[0512] Table 1

[0513]

[0514] * Examples 1 to 8 and Comparative Examples 1 to 3 further contained nitric acid contained in the polymer solution prepared in the Synthesis Example.

[0515] [3] Preparation of organic underlayer film-forming composition

[0516] 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 placed in a 100 ml four-necked flask. Alkane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was stirred and heated to 100°C to dissolve it, thereby initiating polymerization. After 24 hours, the mixture was left to cool to 60°C.

[0517] Chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.) was added to the cooled reaction mixture for dilution, and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) for precipitation.

[0518] The obtained precipitate was filtered and recovered, and the recovered solid was dried at 80° C. for 24 hours in a reduced pressure dryer to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL).

[0519] In addition, PCzFL1 The measurement results of H-NMR are as follows.

[0520] 1 H-NMR (400MHz, DMSO-d6): δ (ppm) 7.03-7.55 (br, 12H), δ7.61-8.10 (br, 4H), δ11.18 (br, 1H)

[0521] The weight average molecular weight Mw of PCzFL obtained by GPC was 2,800 in terms of polystyrene, and the polydispersity M w / Mn is 1.77.

[0522]

[0523] 20 g of PCzFL, 3.0 g of tetramethoxymethyl glycoluril (manufactured by Nippon Science Instruments Co., Ltd. (formerly Mitsui Science Co., Ltd.), trade name: Paudalin 1174) as a crosslinking agent, and pyridine as a catalyst were mixed. 0.30 g of p-toluenesulfonate and 0.06 g of Megaphage R-30 (trade name, manufactured by DIC Corporation) as a surfactant were mixed, and the resulting mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate to prepare a solution. μ The sample was filtered through a polyethylene microfilter with a pore size of 0.05 μ The mixture was filtered through a polyethylene microfilter of 1000 μm to prepare a composition for forming an organic underlayer film.

[0524] [4]Solvent resistance test

[0525] The compositions prepared in Examples 1 to 8 and Comparative Examples 1 to 3 were applied to silicon wafers using a spin coater. They were heated on a hot plate at 215° C. for 1 minute to form resist underlayer films containing Si, and the film thickness of the obtained resist underlayer films was measured. The film thickness was about 10 nm.

[0526] Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was applied to each Si-containing resist lower film and spin-dried. The film thickness of the lower film after coating was measured, and the film thickness before the mixed solvent coating was used as a reference (100%), and the ratio (%) of the change in film thickness after the mixed solvent coating was calculated. The case where the ratio of the film thickness change before and after the mixed solvent coating was 1% or less was evaluated as "good", and the case where the ratio of the film thickness change exceeded 1% was evaluated as "uncured".

[0527] Table 2 shows the obtained results.

[0528] Table 2

[0529] Solvent resistance Example 1 good Example 2 good Example 3 good Example 4 good Example 5 good Example 6 good Example 7 good Example 8 good Comparative Example 1 good Comparative Example 2 good Comparative Example 3 good

[0530] [5] Formation of resist pattern using EUV exposure: Negative organic solvent development

[0531] The organic underlayer film-forming composition was spin-coated on a silicon wafer and heated on a hot plate at 215° C. for 1 minute to form an organic underlayer film (layer A) (film thickness: 90 nm).

[0532] The composition obtained in Example 1 was spin-coated thereon, and heated on a hot plate at 215° C. for 1 minute to form a resist underlayer film (B) layer (film thickness: 10 nm).

[0533] An EUV resist solution (tin oxide resist) was further spin-coated thereon, and heated at 130°C for 1 minute to form an EUV resist layer (C), and then exposed using an EUV exposure apparatus (NXE3300B) manufactured by ASML under conditions of NA = 0.33, σ = 0.67 / 0.90 (outer / inner), and dipole. In addition, during exposure, exposure was performed through a mask set so that the line width and the width between the lines (gap width) of the EUV resist would become 16 nm after the following development, that is, a dense line with a line and space (L / S) of 16 nm = 1 / 1 was formed.

[0534] After exposure, post-exposure heating (PEB, 170° C. for 1 minute) was performed, followed by cooling to room temperature on a cooling plate, development was performed using an organic solvent (propylene glycol monomethyl ether acetate) for 60 seconds, and rinsing was performed to form a resist pattern.

[0535] By the same procedure, resist patterns were formed using each of the compositions obtained in Examples 2 to 8 and Comparative Examples 1 to 3.

[0536] Using a length measurement SEM (CG4100) manufactured by Hitachi HiTech Nologics, the exposure amount when a line size of 16 nm was formed was measured and this was defined as sensitivity. In addition, the size of 60 lines at this time was measured to determine line width roughness (LWR). The results are shown in Table 3.

[0537] Table 3

[0538]

[0539] As shown in Table 3, it can be seen that when a polysiloxane film formed using a resist underlayer film-forming composition containing sulfuric acid, a polyfunctional sulfonic acid, or a salt thereof is used as a resist underlayer film, the sensitivity can be improved compared with a resist underlayer film-forming composition containing silicon not containing sulfuric acid, a polyfunctional sulfonic acid, or a salt thereof (Comparative Example 1). On the other hand, no improvement in sensitivity was observed in the compositions of Comparative Examples 2 to 3 containing a monofunctional sulfonic acid.

Claims

1. A silicon-containing resist underlayer film-forming composition comprising: [A] Ingredient: polysiloxane; [B] component: sulfuric acid, polyfunctional sulfonic acid, or salts thereof; and [C] Ingredient: Solvent.

2. The silicon-containing resist underlayer film-forming composition according to claim 1, wherein the polyfunctional sulfonic acid is a compound represented by the following formula (A): In formula (A), n represents an integer of 1 to 3; R 1 It represents an n+1-valent organic group having 1 to 15 carbon atoms.

3. The silicon-containing resist underlayer film-forming composition according to claim 1, wherein the salt in the component [B] is an ammonium salt, an imidazole Salt, pyridine Salt, sulfonium salt, Salt, and iodine Any of the salts.

4. The silicon-containing resist underlayer film-forming composition according to claim 1, wherein the polysiloxane as the component [A] is a modified polysiloxane in which a part of the silanol groups is alcohol-modified or acetal-protected. 5 . The silicon-containing resist underlayer film-forming composition according to claim 1 , wherein the component [C] contains an alcohol solvent. 6 . The silicon-containing resist underlayer film-forming composition according to claim 5 , wherein the component [C] contains propylene glycol monoalkyl ether. 7 . The silicon-containing resist underlayer film-forming composition according to claim 1 , further comprising a component [D]: a curing catalyst. 8 . The silicon-containing resist underlayer film-forming composition according to claim 1 , further comprising a component [E]: nitric acid. 9 . The silicon-containing resist underlayer film-forming composition according to claim 1 , wherein the component [C] contains water. 10 . The silicon-containing resist underlayer film-forming composition according to claim 1 , which is used for forming a resist underlayer film for EUV lithography. 11 . A silicon-containing resist underlayer film, which is a cured product of the silicon-containing resist underlayer film-forming composition according to claim 1 .

12. A semiconductor processing substrate comprising: semiconductor substrate; and The resist underlayer film containing silicon as claimed in claim 11.

13. A method for manufacturing a semiconductor device, comprising the following steps: A step of forming an organic lower layer film on a substrate; a step of forming a resist underlayer film on the organic underlayer film using the resist underlayer film-forming composition containing silicon according to any one of claims 1 to 10; and A step of forming a resist film containing a metal on the resist underlayer film. 14 . The method for manufacturing a semiconductor element according to claim 13 , wherein the metal-containing resist film is formed of a metal-containing resist for EUV lithography. 15 . The method for manufacturing a semiconductor element according to claim 13 , wherein in the step of forming the resist underlayer film, a resist underlayer film-forming composition containing silicon filtered through a nylon filter is used.

16. A pattern forming method comprising the following steps: A step of forming an organic lower layer film on a semiconductor substrate; A step of applying the resist underlayer film-forming composition containing silicon according to any one of claims 1 to 10 onto the organic underlayer film and firing the composition to form a resist underlayer film; forming a resist film containing a metal on the resist underlayer film; The process of exposing and developing the metal-containing resist film to obtain a resist pattern; A step of using the resist pattern as a mask to etch the resist underlayer film; as well as A step of etching the organic underlayer film using the patterned resist underlayer film as a mask. 17 . The pattern forming method according to claim 16 , further comprising, after the step of etching the organic underlayer film, a step of removing the resist underlayer film by a wet method using a chemical solution. 18 . The pattern forming method according to claim 16 , wherein the metal-containing resist film is formed of a metal-containing resist for EUV lithography.

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