Composition for forming silicon-containing resist underlayer film and method for manufacturing semiconductor element

Abstract

Provided is a composition for forming a silicon-containing resist underlayer film, containing: (A) a polysiloxane; (B) a polyether-modified silicone oil; and (C) a solvent.

Description

Composition for forming a silicon-containing resist underlayer film and method for manufacturing a semiconductor device

[0001] This invention relates to a silicon-containing resist underlayer film formation composition and a method for manufacturing a semiconductor device.

[0002] Conventionally, microfabrication using lithography with resist compositions has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with an active light such as ultraviolet light through a mask pattern on which the device pattern is drawn, developing the film, and then etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the photoresist pattern. In recent years, with the increasing integration density of semiconductor devices, the active light used has also evolved. In addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. Consequently, poor resist pattern formation due to influence from the semiconductor substrate has become a major problem. Therefore, in order to solve this problem, methods of providing a resist underlayer film between the resist and the semiconductor substrate are being widely investigated.

[0003] A resist underlayer film can be manufactured by coating a resist underlayer film formation composition containing polymers, solvents, etc., onto a semiconductor substrate and firing it. Due to the diversification of semiconductor manufacturing processes, there is a demand for properties such as small film thickness differences and good coverage (planarization) for various layouts in stepped substrates.

[0004] For example, Patent Document 1 proposes a resist underlayer film formation composition containing a surfactant having a perfluoroalkyl substructure, for the purpose of improving the surface planarity of the coated film.

[0005] International Publication No. 2015 / 122296 brochure

[0006] Fluorine-containing surfactants are effective in improving planarity during film formation. However, perfluoroalkyl and polyfluoroalkyl compounds, known as PFAS (Per and Polyfluoroalkyl substances), are restricted substances under the European REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) regulations, and it is expected that regulations on their use will become increasingly stringent in the future. Therefore, there is a strong demand for the use of surfactants that do not fall under the category of PFAS.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a silicon-containing resist underlayer film formation composition having good planarization properties and using a non-fluorine-based additive, and a method for manufacturing a semiconductor device using the silicon-containing resist underlayer film formation composition.

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

[0009] In other words, the present invention encompasses the following: [1] A composition for forming a silicon-containing resist underlayer film, comprising: [A] component: polysiloxane, [B] component: polyether-modified silicone oil, and [C] component: solvent. [2] The silicon-containing resist underlayer film forming composition according to [1], wherein the [B] component is a polymer represented by the following formula (1). (In equation (1), a and b are independent numbers from 1 to 20, and Q represents the following equation. The units of a and b may be random or blocks. Q = -R) １ (EO) ｃ (PO) ｄ R ２ In the formula, R １ R is an oxyalkylene group with 1 to 6 carbon atoms, EO is an ethylene oxy group, PO is a propylene oxy group, R ２≠ 0. ≠ (In formula (2), R ３ R represents a group bonded to a silicon atom, independently of each other, representing an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an amide 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 thereof. ４(where a is a group or atom bonded to a silicon atom, and independently of each other, represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, and a represents an integer from 0 to 3.) [4] A silicon-containing resist underlayer film forming composition according to any one of [1] to [3], wherein the [C] component comprises water. [5] A silicon-containing resist underlayer film forming composition according to any one of [1] to [4], wherein the [C] component comprises an alcohol-based solvent. [6] A silicon-containing resist underlayer film forming composition according to any one of [1] to [5], wherein the [C] component comprises a propylene glycol monoalkyl ether. [7] A silicon-containing resist underlayer film forming composition according to any one of [1] to [6], further comprising nitric acid. [8] A silicon-containing resist underlayer film forming composition according to any one of [1] to [7], which does not contain a curing catalyst. [9] A silicon-containing resist underlayer film forming composition according to any one of [1] to [8], further comprising a pH adjuster.

[10] A silicon-containing resist underlayer film forming composition according to any one of [1] to [9], further comprising a metal oxide.

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

[10] , for use in EUV lithography.

[12] A method for manufacturing a semiconductor device, comprising the steps of: forming an organic underlayer film on a substrate; forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition according to any one of [1] to

[11] ; and forming a resist film on the silicon-containing resist underlayer film.

[13] A method for manufacturing a semiconductor device according to

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

[0010] According to the present invention, it is possible to provide a silicon-containing resist underlayer film formation composition that has good planarization properties and uses a non-fluorine-based additive, and a method for manufacturing a semiconductor device using the silicon-containing resist underlayer film formation composition.

[0011] (Composition for Forming Silicon-Containing Resist Lower Layer Film) The composition for forming a silicon-containing resist lower layer film of the present invention contains a [A] component, a [B] component, and a [C] component. The composition for forming a silicon-containing resist lower layer film may contain nitric acid, a pH adjuster, a metal oxide, and the like. By containing the [A] component, the [B] component, and the [C] component, the composition for forming a silicon-containing resist lower layer film can improve the hump height and achieve good planarization.

[0012] <[A] Component> The [A] component is a polysiloxane. The polysiloxane is not particularly limited as long as it is a polymer having a siloxane bond. Examples of the polysiloxane include at least one hydrolyzable condensate of a hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (2), a modified product of the condensate in which at least a part of the silanol groups possessed by the condensate are alcohol-modified, a modified product of the condensate in which at least a part of the silanol groups possessed by the condensate are acetal-protected, and at least one selected from the group consisting of dehydration reaction products of the condensate and an alcohol.

[0013] (In formula (2), R ３ is a group bonded to a silicon atom, and independently of each other, represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an amide 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 thereof, and R ４(where a is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, and a represents an integer from 0 to 3.)

[0014] Note R ３ It is not a hydrolyzable group. a is an integer from 0 to 3, preferably 1 or 2, and more preferably 1.

[0015] -R ３ - The alkyl group may be linear, branched, or cyclic, and its carbon number is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3 Examples include methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. In this specification, "i" means "iso", "s" means "sec", and "t" means "tert".

[0016] Specific examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, and 2,4-dimethyl-cyclobutyl group. Examples include cycloalkyl groups such as methyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group, as well as crosslinked cyclic cycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0017] The aryl group may be any of the following: a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused ring aromatic hydrocarbon compound, or a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. For example, aryl groups with 6 to 20 carbon atoms can be given as aryl groups, and examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 5-naphthacenyl group, 2-crisenyl group, 1-pyrenyl group, 2-pyrenyl group, Examples include, but are not limited to, the pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group (o-biphenylyl group), biphenyl-3-yl group (m-biphenylyl group), biphenyl-4-yl group (p-biphenylyl group), paraterphenyl-4-yl group, metaterphenyl-4-yl group, orthoterphenyl-4-yl group, 1,1'-binaphthyl-2-yl group, 2,2'-binaphthyl-1-yl group, etc.

[0018] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those mentioned above. The number of carbon atoms in an aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aralkyl groups include, but are not limited to, phenylmethyl group (benzyl group), 2-phenylethylene group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, and 10-phenyl-n-decyl group.

[0019] Alkyl halogenated groups, aryl halogenated groups, and aralkyl halogenated groups are, respectively, alkyl groups, aryl groups, and aralkyl groups substituted with one or more halogen atoms. Specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those mentioned above.

[0020] The number of carbon atoms in the alkyl halogen is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of alkyl halogens include, but are not limited to, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, bromodifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3-bromopropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 1,1,1,3,3,3-hexafluoropropan-2-yl group, 3-bromo-2-methylpropyl group, 4-bromobutyl group, and perfluoropentyl group.

[0021] The number of carbon atoms in the aryl halide group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aryl halide groups include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2-fluoro-1-naphthyl group, and 3-fluorophenyl group. Examples include fluoro-1-naphthyl group, 4-fluoro-1-naphthyl group, 6-fluoro-1-naphthyl group, 7-fluoro-1-naphthyl group, 8-fluoro-1-naphthyl group, 4,5-difluoro-1-naphthyl group, 5,7-difluoro-1-naphthyl group, 5,8-difluoro-1-naphthyl group, 5,6,7,8-tetrafluoro-1-naphthyl group, heptafluoro-1-naphthyl group, 1-fluoro-2-naphthyl group, 5-fluoro-2-naphthyl group, 6-fluoro-2-naphthyl group, 7-fluoro-2-naphthyl group, 5,7-difluoro-2-naphthyl group, heptafluoro-2-naphthyl group, etc., and groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group), but are not limited to these.

[0022] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of halogenated aralkyl groups include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, and 2,4,5-trifluorobenzyl group. Examples include the refluorobenzyl group, 2,4,6-trifluorobenzyl group, 2,3,4,5-tetrafluorobenzyl group, 2,3,4,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluorobenzyl group, and 2,3,4,5,6-pentafluorobenzyl group. Furthermore, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group) are also included, but are not limited to these.

[0023] Alkoxyalkyl groups, alkoxyaryl groups, and alkoxyaralkyl groups are alkyl groups, aryl groups, and aralkyl groups, respectively, that are substituted with one or more alkoxy groups. Specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those mentioned above.

[0024] Examples of alkoxy groups as substituents include alkoxy groups having at least one alkyl moiety of linear, branched, and cyclic structures with 1 to 20 carbon atoms. Examples of linear or branched alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 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-pentyloxy, 2-methyl-n-pentyloxy, 3- Examples include methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group.Examples of cyclic alkoxy groups include cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3 Examples include dimethylcyclobutoxy group, 2,2-dimethylcyclobutoxy group, 2,3-dimethylcyclobutoxy group, 2,4-dimethylcyclobutoxy group, 3,3-dimethylcyclobutoxy group, 1-n-propylcyclopropoxy group, 2-n-propylcyclopropoxy group, 1-i-propylcyclopropoxy group, 2-i-propylcyclopropoxy group, 1,2,2-trimethylcyclopropoxy group, 1,2,3-trimethylcyclopropoxy group, 2,2,3-trimethylcyclopropoxy group, 1-ethyl-2-methylcyclopropoxy group, 2-ethyl-1-methylcyclopropoxy group, 2-ethyl-2-methylcyclopropoxy group, and 2-ethyl-3-methylcyclopropoxy group.

[0025] Specific examples of alkoxyalkyl groups include, but are not limited to, lower alkyloxy lower alkyl groups (approximately 5 or fewer carbon atoms) such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, and ethoxymethyl group. Specific examples of alkoxyaryl groups include, but are not limited to, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-(1-ethoxy)phenyl group, 3-(1-ethoxy)phenyl group, 4-(1-ethoxy)phenyl group, 2-(2-ethoxy)phenyl group, 3-(2-ethoxy)phenyl group, 4-(2-ethoxy)phenyl group, 2-methoxynaphthalen-1-yl group, 3-methoxynaphthalen-1-yl group, 4-methoxynaphthalen-1-yl group, 5-methoxynaphthalen-1-yl group, 6-methoxynaphthalen-1-yl group, and 7-methoxynaphthalen-1-yl group. Specific examples of alkoxyaralkyl groups include, but are not limited to, the 3-(methoxyphenyl)benzyl group and the 4-(methoxyphenyl)benzyl group.

[0026] The alkenyl group may be linear or branched, and its carbon number is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of alkenyl groups include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1- Butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group , 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl- 2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3, 3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl -1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cy Examples include clopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group, as well as bridging cyclic alkenyl groups such as bicycloheptenyl group (norbornyl group).

[0027] Furthermore, examples of substituents in the alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, and alkenyl groups include alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, aryloxy groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, alkoxy groups, and aralkyloxy groups. Specific examples of these substituents and their preferred carbon numbers are the same as those described above or below. The aryloxy group mentioned in the substituents is a group in which an aryl group is bonded via an oxygen atom (-O-). Specific examples of such aryl groups are the same as those described above. The carbon number of the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include phenoxy groups and naphthalene-2-yloxy groups, but are not limited to these. In addition, if there are two or more substituents, they may bond to each other to form a ring.

[0028] Furthermore, specific examples of "alkyl groups that may be substituted" include the group shown in the following structure.

[0029] (In the formula, * represents a bond with a silicon atom.)

[0030] Organic groups having an epoxy group that may be ring-opened include glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group, epoxycyclohexyl group, or groups in which the epoxy group is ring-opened. Organic groups having an acryloyl group include acryloyloxymethyl group, acryloyloxyethyl group, acryloyloxypropyl group, etc. Organic groups having a methacryloyl group include methacryloyloxymethyl group, methacryloyloxyethyl group, methacryloyloxypropyl group, etc. Organic groups having a mercapto group include mercaptoethyl group, mercaptobutyl group, mercaptohexyl group, mercaptooctyl group, mercaptophenyl group, etc. Organic groups having an alkoxy group include, for example, methoxymethyl group and methoxyethyl group, but are not limited to these. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded. Organic groups having a sulfonyl group include, for example, sulfonylalkyl groups and sulfonylaryl groups, but are not limited to these. Examples of organic groups having a cyano group include cyanoethyl group, cyanopropyl group, cyanophenyl group, and thiocyanate group. Examples of organic groups having an amino group include, but are not limited to, amino group, aminomethyl group, aminoethyl group, aminophenyl group, dimethylaminoethyl group, and dimethylaminopropyl group.

[0031] -R ４ - R ４ Examples of alkoxy groups in this context include R ３ The alkoxy group, as exemplified in the explanation, is an example. ４ Examples of halogen atoms in this include R ３ The halogen atoms exemplified in the explanation are examples.

[0032] The aralkyloxy group is a monovalent group derived by removing a hydrogen atom from the hydroxyl group of an aralkyl alcohol. Specific examples of the aralkyl group in the aralkyloxy group are the same as those mentioned above. The number of carbon atoms in the aralkyloxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less. Specific examples of the aralkyloxy group include, but are not limited to, phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group, 5-phenyl-n-pentyloxy group, 6-phenyl-n-hexyloxy group, 7-phenyl-n-heptyloxy group, 8-phenyl-n-octyloxy group, 9-phenyl-n-nonyloxy group, and 10-phenyl-n-decyloxy group.

[0033] Acyloxy groups are monovalent groups derived by removing a hydrogen atom from the carboxyl group (-COOH) of a carboxylic acid compound. Typical examples include, but are not limited to, alkylcarbonyloxy groups, arylcarbonyloxy groups, or aralkylcarbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of alkylcarboxylic acids, arylcarboxylic acids, or aralkylcarboxylic acids. Specific examples of alkyl groups, aryl groups, and aralkyl groups in such alkylcarboxylic acids, arylcarboxylic acids, and aralkylcarboxylic acids are the same as those mentioned above.Specific examples of acyloxy groups include acyloxy groups having 2 to 20 carbon atoms, such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, and 2-methyl-n-pentylcarbonyloxy group. Examples include vonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, and tosylcarbonyloxy group.

[0034] --Specific examples of hydrolyzable silanes represented by formula (2)-- Specific examples of hydrolyzable silanes represented by formula (2) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamiloxysilane, methyltriphenoxysilane, and methyltribenzyloxysilane Methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrippropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycid Xybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane,γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycid Xyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyl Ethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxy Sisilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiacetoxysilane,Allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane, allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyl Nyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 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, phenethyl Phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane,Methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, i-propoxyphenyltrimethoxysilane, i-propoxyphenyltriethoxysilane, i-propoxyphenyltriacetoxysilane, i-propoxyphenyltrichlorosilane, i-p Ropoxybenzyltrimethoxysilane, i-propoxybenzyltriethoxysilane, i-propoxybenzyltriacetoxysilane, i-propoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyl Trimethoxysilane, Methoxynaphthyltriethoxysilane, Methoxynaphthyltriacetoxysilane, Methoxynaphthyltrichlorosilane, Ethoxynaphthyltrimethoxysilane, Ethoxynaphthyltriethoxysilane, Ethoxynaphthyltriacetoxysilane, Ethoxynaphthyltrichlorosilane, γ-Chloropropyltrimethoxysilane, γ-Chloropropyltriethoxysilane, γ-Chloropropyltriacetoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane Putopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanatetopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonamidopropyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane,Examples include, but are not limited to, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and dimethylaminopropyltrimethoxysilane.

[0035] The polysiloxane may include a modified polysiloxane in which some of the silanol groups have been modified, for example, a modified polysiloxane in which some of the silanol groups have been modified with alcohol or are acetal protected. The polysiloxane may also include, as an example, a hydrolysis condensate of a hydrolyzable silane, and may include a modified polysiloxane in which at least some of the silanol groups of the hydrolysis condensate have been modified with alcohol or are acetal protected. The hydrolyzable silane in the hydrolysis condensate may include one or more hydrolyzable silanes. Furthermore, the polysiloxane may have a cage-type, ladder-type, linear-type, or branched-type main chain structure. In addition, commercially available polysiloxanes can be used as the polysiloxane.

[0036] In the present invention, the "hydrolyzed condensate" of hydrolyzable silane, that is, the product of hydrolysis condensation, includes not only polyorganosiloxane polymers which are condensates in which condensation is completely completed, but also polyorganosiloxane polymers which are partially hydrolyzed condensates in which condensation is not completely completed. Such partially hydrolyzed condensates are polymers obtained by hydrolysis and condensation of hydrolyzable silane, just like condensates in which condensation is completely completed, but the hydrolysis stops only partially and condensation does not occur, and therefore Si-OH groups remain. In addition, component [A] may contain uncondensed hydrolysates (complete hydrolysates, partially hydrolysates) or monomers (hydrolyzable silanes) in addition to hydrolyzed condensates. In this specification, "hydrolyzable silane" may also be simply referred to as "silane compound." In this specification, "polysiloxane" may also be referred to as "hydrolyzed condensate."

[0037] The polysiloxane, which is a hydrolysis condensate, can be a hydrolysis condensate of a hydrolyzable silane containing other silane compounds other than those exemplified above, as long as the effects of the present invention are not impaired.

[0038] As mentioned above, a modified polysiloxane in which at least a portion of the silanol groups are modified can be used as the polysiloxane. For example, a modified polysiloxane in which some of the silanol groups are modified with alcohol or a modified polysiloxane protected with acetal can be used. Examples of such modified polysiloxanes include reaction products obtained by the reaction of at least a portion of the silanol groups of a hydrolyzable silane condensate with the hydroxyl groups of an alcohol, dehydration reaction products of the condensate and an alcohol, and modified products in which at least a portion of the silanol groups of the condensate are protected with acetal groups.

[0039] Monohydric alcohols can be used as the alcohol, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, and 1-hexanol. Examples include 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, and cyclohexanol. Additionally, alkoxy group-containing alcohols such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used.

[0040] The reaction between the silanol groups of the condensate and the hydroxyl groups of the alcohol is carried out by contacting the polysiloxane with the alcohol and reacting at a temperature of 40 to 160°C, for example 60°C, for 0.1 to 48 hours, for example 24 hours, to obtain a modified polysiloxane in which the silanol groups are capped. In this case, the capping alcohol can be used as a solvent in a composition containing polysiloxane.

[0041] Furthermore, a dehydration reaction product of polysiloxane, which is a hydrolysis condensate of a hydrolyzable silane, and an alcohol can be produced by reacting the polysiloxane with the alcohol in the presence of an acid catalyst, capping the silanol groups with the alcohol, and removing the resulting water from the reaction system. The acid used is an organic acid with an acid dissociation constant (pka) of -1 to 5, preferably 4 to 5. For example, the acid can be trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, etc., with benzoic acid, isobutyric acid, and acetic acid being particularly noteworthy. In addition, the acid can be an acid with a boiling point of 70 to 160°C, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. Thus, as an acid, it is preferable to have either an acid dissociation constant (pka) of 4 to 5 or a boiling point of 70 to 160°C. That is, an acid with low acidity or an acid with high acidity but a low boiling point can be used. Furthermore, as an acid, it is possible to utilize either the acid dissociation constant or the boiling point properties.

[0042] The acetal protection of the silanol group in the condensate can be carried out using a vinyl ether, for example, a vinyl ether represented by the following formula (5), and these reactions can introduce the substructure represented by the following formula (6) into the polysiloxane.

[0043] 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, R ４ａ R represents an alkyl group having 1 to 10 carbon atoms. ２ａ and R ４ａ These elements may be bonded to each other to form a ring. Examples of alkyl groups can be given above. In formula (6), R １ ', R ２ ', and R ３ ' represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ４ ' represents an alkyl group having 1 to 10 carbon atoms, R ２ 'and R ４' may be bonded to each other to form a ring. In formula (6), * indicates a bond with an adjacent atom. The adjacent atom is, for example, the oxygen atom of a siloxane bond, the oxygen atom of a silanol group, or R in formula (1). １ Examples of carbon atoms derived from this include the aforementioned examples of alkyl groups.

[0044] Examples of vinyl ethers represented by formula (5) include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, as well as cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran can be used.

[0045] The acetal protection of silanol groups can be carried out using a polysiloxane, a vinyl ether, and an aprotic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, or 1,4-dioxane, with a catalyst such as pyridium p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0046] Furthermore, the capping of these silanol groups with alcohol or acetal protection may be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane, as described later.

[0047] In a preferred embodiment of the present invention, the polysiloxane comprises at least one hydrolysis condensate and modified product thereof of a hydrolyzable silane, which comprises a compound represented by formula (2) and optionally other hydrolyzable silanes. In a preferred embodiment, the polysiloxane comprises a dehydration product of a hydrolysis condensate and an alcohol.

[0048] Polysiloxanes, which are hydrolyzed condensates (including modified products) of hydrolyzable silanes, can have a weight-average molecular weight of, for example, 500 to 1,000,000. From the viewpoint of suppressing the precipitation of hydrolyzed condensates in the composition, the weight-average molecular weight can preferably be 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving both storage stability and coatability, it can preferably be 500 or more, more preferably 600 or more. The weight-average molecular weight is the molecular weight obtained in polystyrene equivalent by GPC analysis. GPC analysis can be performed, for example, using a GPC instrument (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product name Shodex® KF803L, KF802, KF801, manufactured by Showa Denko K.K.), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate of 1.0 mL / min, and polystyrene (Shodex®, manufactured by Showa Denko K.K.) as the standard sample.

[0049] Hydrolyzable silane hydrolysis condensates are obtained by hydrolyzing and condensing the aforementioned silane compounds (hydrolyzable silanes). The aforementioned silane compounds (hydrolyzable silanes) contain alkoxy groups, aralkyloxy groups, acyloxy groups, or halogen atoms directly bonded to a silicon atom, i.e., alkoxysilyl groups, aralkyloxysilyl groups, acyloxysilyl groups, or silyl halogenated groups (hereinafter referred to as hydrolyzable groups). For the hydrolysis of these hydrolyzable groups, typically 0.1 to 100 moles of water, for example 0.5 to 100 moles, preferably 1 to 10 moles, are used per mole of hydrolyzable groups. During hydrolysis and condensation, a hydrolysis catalyst may be used to accelerate the reaction, or the hydrolysis and condensation may be carried out without one. When a hydrolysis catalyst is used, typically 0.0001 to 10 moles of the hydrolysis catalyst, preferably 0.001 to 1 mole, can be used per mole of hydrolyzable groups. The reaction temperature for hydrolysis and condensation is usually in the range of room temperature or higher and below the reflux temperature at atmospheric pressure of the organic solvent that can be used for hydrolysis, for example, 20 to 110°C or 20 to 80°C. Hydrolysis may be complete, i.e., all hydrolyzable groups may be converted to silanol groups, or it may be partial hydrolysis, i.e., some hydrolyzable groups may remain unreacted. Examples of hydrolysis catalysts that can be used for hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0050] Examples of metal chelate compounds used as hydrolysis catalysts include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, and di -i-propoxy bis(acetylacetonate) titanium, di-n-butoxy bis(acetylacetonate) titanium, di-sec-butoxy bis(acetylacetonate) titanium, di-t-butoxy bis(acetylacetonate) titanium, monoethoxy tris(acetylacetonate) titanium, mono-n-propoxy tris(acetylacetonate) titanium, mono-i-propoxy tris(acetylacetonate) titanium, mono-n-butoxy tris(acetylacetonate) titanium, mono-sec-butoxy tris(acetylacetonate) Titanium acetone, mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethylacetoacetate) titanium Titanium acetate, di-n-propoxy-bis(ethylacetate) titanium, di-i-propoxy-bis(ethylacetate) titanium, di-n-butoxy-bis(ethylacetate) titanium, di-sec-butoxy-bis(ethylacetate) titanium, di-t-butoxy-bis(ethylacetate) titanium, monoethoxy-tris(ethylacetate) titanium, mono-n-propoxy-tris(ethylacetate) titanium, mono-i-propoxy-tris(ethylacetate) titanium,Titanium chelate compounds such as mono-n-butoxy tris(ethyl acetate) titanium, mono-sec-butoxy tris(ethyl acetate) titanium, mono-t-butoxy tris(ethyl acetate) titanium, tetrakis(ethyl acetate) titanium, mono(acetylacetonate) tris(ethyl acetate) titanium, bis(acetylacetonate) bis(ethyl acetate) titanium, tris(acetylacetonate) mono(ethyl acetate) titanium, and triethoxy mono(acetylacetonate) titanium; triethoxy mono(acetylacetonate) Zirconium triacetate, tri-n-propoxy mono(acetylacetonate) zirconium, tri-i-propoxy mono(acetylacetonate) zirconium, tri-n-butoxy mono(acetylacetonate) zirconium, tri-sec-butoxy mono(acetylacetonate) zirconium, tri-t-butoxy mono(acetylacetonate) zirconium, diethoxy bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium, di-i-propoxy bis(A Cetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-i-propoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-sec- Butoxy tris(acetylacetonate) zirconium, mono-t-butoxy tris(acetylacetonate) zirconium, tetrakis(acetylacetonate) zirconium, triethoxy mono(ethylacetoacetate) zirconium, tri-n-propoxy mono(ethylacetoacetate) zirconium, tri-i-propoxy mono(ethylacetoacetate) zirconium, tri-n-butoxy mono(ethylacetoacetate) zirconium, tri-sec-butoxy mono(ethylacetoacetate) zirconium,Tri-t-butoxy mono(ethylacetate) zirconium, diethoxy bis(ethylacetate) zirconium, di-n-propoxy bis(ethylacetate) zirconium, di-i-propoxy bis(ethylacetate) zirconium, di-n-butoxy bis(ethylacetate) zirconium, di-sec-butoxy bis(ethylacetate) zirconium, di-t-butoxy bis(ethylacetate) zirconium, monoethoxy tris(ethylacetate) zirconium, mono-n-propoxy tris(ethylacetate) zirconium, mono-i-propoxy tris(ethylacetate) zirconium, mono-n-butoxy Examples of zirconium chelate compounds include, but are not limited to, zirconium chelate compounds such as tris(ethylacetate)zirconium, mono-sec-butoxytris(ethylacetate)zirconium, mono-t-butoxytris(ethylacetate)zirconium, tetrakis(ethylacetate)zirconium, mono(acetylacetonate)tris(ethylacetate)zirconium, bis(acetylacetonate)bis(ethylacetate)zirconium, and tris(acetylacetonate)mono(ethylacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonate)aluminum and tris(ethylacetate)aluminum;

[0051] Examples of organic acids used as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, etc.

[0052] Examples of inorganic acids used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0053] Examples of organic bases used as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0054] Examples of inorganic bases used as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0055] Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used individually or in combination of two or more.

[0056] In particular, nitric acid can be suitably used as a hydrolysis catalyst in this invention. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, changes in the molecular weight of the hydrolyzed condensate can be suppressed. It is known that the stability of the hydrolyzed condensate in solution depends on the pH of the solution. After diligent research, it was found that by using an appropriate amount of nitric acid, the pH of the solution becomes stable. Furthermore, as mentioned above, nitric acid can also be used when obtaining modified products of the hydrolyzed condensate, for example, when capping the silanol group with alcohol, and is therefore preferable from the viewpoint that it can contribute to both the hydrolysis and condensation of hydrolyzable silane and the alcohol capping of the hydrolyzed condensate.

[0057] When hydrolysis and condensation occur, organic solvents may be used as solvents. Specific examples include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbencene, i-propylbencene, diethylbenzene, i- Aromatic hydrocarbon solvents such as butylbenzene, triethylbenzene, di-i-propylbencene, and n-amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, and 2-ethylbutanol n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, Monoalcohol solvents such as phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin;Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenthone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl Ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and other ether-based solvents;Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol Examples of ester solvents include monomethyl ether, dipropylene glycol acetate monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents include dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesultone, but are not limited to these. These solvents can be used individually or in combination of two or more. ;

[0058] After the hydrolysis and condensation reactions are complete, the reaction solution can be neutralized, either as is or diluted or concentrated, and then treated with an ion exchange resin to remove the hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation. Alternatively, before or after such treatment, by-products such as alcohol, water, and the hydrolysis catalysts used can be removed from the reaction solution by vacuum distillation or the like.

[0059] The hydrolysis condensate obtained in this way is obtained in the form of polysiloxane varnish dissolved in an organic solvent, and can be used directly in the preparation of a surface modifier. That is, the reaction solution can be used as is (or diluted) in the preparation of a surface modifier, and in this case, the hydrolysis catalyst and by-products used in the hydrolysis and condensation may remain in the reaction solution as long as they do not impair the effects of the present invention. For example, the hydrolysis catalyst and nitric acid used during alcohol capping of silanol groups may remain in the polymer varnish solution at a concentration of about 100 ppm to 5,000 ppm. The obtained polysiloxane varnish may be solvent-substituted or diluted with an appropriate solvent. The obtained polysiloxane varnish can also be desiccanted to obtain a film-forming component concentration of 100%, provided that its storage stability is not poor. The film-forming component refers to the components of the composition excluding the solvent component. The organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used in the hydrolysis and condensation reaction of the hydrolyzable silane. The dilution solvent is not particularly limited, and one or more types can be arbitrarily selected and used.

[0060] The content of component [A] in the silicon-containing resist underlayer film formation composition is not particularly limited, but is preferably 0.01% to 10% by mass, more preferably 0.05% to 5% by mass, and particularly preferably 0.1% to 3% by mass. Furthermore, the content of component [A] in the silicon-containing resist underlayer film formation composition is preferably 70% to 99.9% by mass, more preferably 80% to 99.5% by mass, and even more preferably 90% to 99% by mass, relative to the film constituent components. Here, film constituent components refer to components other than the solvent in the silicon-containing resist underlayer film formation composition.

[0061] <Component [B]> Component [B] is a polyether-modified silicone oil. Component [B] is a fluorine-free, non-fluorine-based additive. The silicon-containing resist underlayer film forming composition of this embodiment contains component [B], and therefore does not fall under the category of PFAS and has good planarization properties.

[0062] [B] Component is, for example, a polymer represented by the following formula (1).

[0063] (In equation (1), a and b are independent numbers between 1 and 20, and Q represents the following equation. The unit of b may be random or block. Q = -R) １ (EO) ｃ (PO) ｄ R ２ In the formula, R １ R is an oxyalkylene group with 1 to 6 carbon atoms, EO is an ethylene oxy group, PO is a propylene oxy group, R ２ represents a hydrogen atom or a methyl group, and c and d each independently represent a number between 0 and 10, with cd ≠ 0. EO and PO may be random or blocky.

[0064] In formula (1), a is a number from 1 to 20, preferably from 1 to 15, and more preferably from 1 to 10. In formula (1), b is a number from 1 to 20, preferably from 1 to 15, and more preferably from 1 to 10. In formula (1), the unit of b may be random or a block.

[0065] In Q, R １ R is an oxyalkylene group having 1 to 6 carbon atoms. １ The number of carbon atoms is preferably 1 to 3. In Q, R ２is a hydrogen atom or a methyl group, with a methyl group being preferred. In Q, EO represents an ethylene oxy group, and PO represents a propylene oxy group. In Q, c is a number from 0 to 10, preferably 1 to 5. In Q, d is a number from 0 to 10, preferably 1 to 5. In Q, cd ≠ 0. In Q, EO and PO may be random or in a block.

[0066] Component [B] is a silane compound different from component [A]. The weight-average molecular weight of component [B] is not particularly limited, but is preferably 500 to 1,000,000, more preferably 600 to 500,000, even more preferably 700 to 400,000, even more preferably 800 to 300,000, even more preferably 1,000 to 200,000, even more preferably 1,500 to 100,000, and particularly preferably 2,000 to 50,000. The weight-average molecular weight of component [B] can be determined by the same method as the weight-average molecular weight of the polysiloxane in component [A] described above.

[0067] [B] Component may be a commercially available product. Examples of commercially available [B] components include DOWSIL® SH28 Paint Additive, DOWSIL® L-7001 Fluid, DOWSIL® FZ-2104 Fluid, DOWSIL® BY16-036 Fluid, DOWSIL® SF8428 Fluid, DOWSIL® 501W Additive, DOWSIL® L-7002 Fluid, and DOWSIL® SF8427 Fluid, all manufactured by Dow Toray Industries, Inc.

[0068] The content of component [B] in the silicon-containing resist underlayer film forming composition is usually 3.0% by mass or less, preferably 2.0% by mass or less, relative to the solid content of the silicon-containing resist underlayer film forming composition. The lower limit of the content of component [B] is, for example, 0.1% by mass, relative to the solid content of the silicon-containing resist underlayer film forming composition. Furthermore, the content of component [B] in the silicon-containing resist underlayer film forming composition is usually 3.0 parts by mass or less, preferably 2.0 parts by mass or less, per 100 parts by mass of component [A] of the silicon-containing resist underlayer film forming composition. The lower limit of the content of component [B] is, for example, 0.1 parts by mass per 100 parts by mass of component [A] of the silicon-containing resist underlayer film forming composition. Component [B] may be added alone or in combination of two or more types.

[0069] <Component [C]> Component [C] is a solvent. Any solvent that can dissolve and mix components [A], [B], and other components contained in the silicon-containing resist underlayer film forming composition as needed is not particularly limited.

[0070] Examples of solvents include organic solvents and water. Examples of organic solvents include alcohols, carboxylic acids having a hydroxyl group, linear or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic acid esters (monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers).

[0071] Examples of alcohols include alcohol-based solvents such as monoalcohol-based solvents and polyhydric alcohol-based solvents. Examples of monoalcohol-based solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, and n-octano Examples of polyhydric alcohol solvents include 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol. Examples of polyhydric alcohol solvents include ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin.

[0072] Examples of carboxylic acids having a hydroxyl group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, and methyl 2-hydroxy-3-methylbutyrate.

[0073] Examples of linear or cyclic alkyl ketones include methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0074] An example of a cyclic lactone is γ-butyrolactone.

[0075] Examples of alkylene glycol alkyl ethers include alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether. Examples of alkylene glycol dialkyl ethers include 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, and propylene glycol dibutyl ether.

[0076] Examples of alkylene glycol monoalkyl ether carboxylic acid esters include monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene glycol monoalkyl ether acetates. Examples of alkylene glycol monoalkyl ether acetates 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, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate. Examples of alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers include 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0077] Other specific examples of solvents include toluene, xylene, ethoxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, 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 Examples of solvents include methyl 3-methoxy-2-methylpropionate, ethyl methoxyethyl, ethyl ethoxyethyl, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, methyl 3-methoxybutyl acetate, 3-methoxypropyl acetate, methyl-3-methoxybutyl acetate, methyl-3-methoxybutyl propionate, methyl-3-methoxybutyl butyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 4-methyl-2-pentanol. These solvents can be used individually or in combination of two or more.

[0078] Among these solvents, water-containing solvents are preferred, and alcohol-based solvents are preferred. Furthermore, among these solvents, alkylene glycol alkyl ethers are preferred, and propylene glycol alkyl ethers are more preferred.

[0079] The content of component [C] in the silicon-containing resist underlayer film forming composition is not particularly limited, but is preferably 50% to 99.99% by mass, more preferably 75% to 99.95% by mass, and particularly preferably 90% to 99.9% by mass.

[0080] <Other Additives> Various additives can be added to silicon-containing resist underlayer films depending on the application of the composition. Examples of additives include acids, curing catalysts, stabilizers (organic acids, water, alcohol, etc.), organic polymers, acid generators, pH adjusters, metal oxides, rheology adjusters, adhesion aids, etc., which are known additives that are added to materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, anti-reflective films, and pattern reversal films. Examples of various additives are given below, but the composition is not limited to these.

[0081] -Acid- The silicon-containing resist underlayer film forming composition preferably contains an acid. The acid may be added during the preparation of the silicon-containing resist underlayer film forming composition, or it may be used as a hydrolysis catalyst or during alcohol capping of silanol groups in the production of component [A] described above, and the remaining acid in the polysiloxane varnish can be treated as such.

[0082] Examples of acids include organic acids and inorganic acids. Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, sorbic acid, acrylic acid, methacrylic acid, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, phenolsulfonic acid, 5-sulfosalicylic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid. Examples of inorganic acids include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. Among these acids, inorganic acids are preferred, and nitric acid is more preferred.

[0083] The amount of acid added (residual acid amount) can be, for example, 0.0001% to 1% by mass, or 0.001% to 0.1% by mass, or 0.005% to 0.05% by mass, based on the total mass of the silicon-containing resist underlayer film forming composition.

[0084] -Curing catalyst- The silicon-containing resist underlayer film formation composition may or may not contain a curing catalyst.

[0085] The silicon-containing resist underlayer film formation composition of this embodiment contains polysiloxane as component [A]. Since the polysiloxane of this embodiment contains a hydrolysis condensate of a hydrolyzable silane, a curing catalyst is not required. For this reason, it is preferable that the silicon-containing resist underlayer film formation composition of this embodiment does not contain a curing catalyst.

[0086] Here, "not containing a curing catalyst" in the present invention refers to the absence of a curing catalyst in the silicon-containing resist underlayer film formation composition. However, if a curing catalyst is not detected when the silicon-containing resist underlayer film formation composition is subjected to compositional analysis (e.g., mass spectrometry, IR analysis, gas chromatography analysis, etc.), it also falls under the category of "not containing a curing catalyst" in the present invention.

[0087] As curing catalysts, ammonium salts, phosphines, phosphonium salts, sulfonium salts, iodonium salts, oxonium salts, etc., can be used. The salts listed below as examples of curing catalysts may be added in salt form, or they may form salts in the composition (added as separate compounds and forming salts in the system).

[0088] As an ammonium salt, formula (D-1): (In the formula, m ａ n represents an integer between 2 and 11, and n ａ represents an integer between 2 and 3, R ２１ Y represents an alkyl group, an aryl group, or an aralkyl group. － ) represents an anion. quaternary ammonium salts having a structure represented by ),

[0089] Formula (D-2): (In the formula, R ２２ , R ２３ , R ２４ and R ２５ These independently represent an alkyl group, an aryl group, or an aralkyl group, Y － represents an anion, and R ２２ , R ２３ , R ２４ , and R ２５ Each of these is bonded to a nitrogen atom.) Quaternary ammonium salts having a structure represented by ),

[0090] Formula (D-3): (In the formula, R ２６ and R ２７ These independently represent an alkyl group, an aryl group, or an aralkyl group, Y － ) represents an anion. quaternary ammonium salts having a structure represented by ),

[0091] Formula (D-4): (In the formula, R ２８ Y represents an alkyl group, an aryl group, or an aralkyl group. － ) represents an anion. quaternary ammonium salts having a structure represented by ),

[0092] Formula (D-5): (In the formula, R ２９ and R ３０ These independently represent an alkyl group, an aryl group, or an aralkyl group, Y － ) represents an anion. quaternary ammonium salts having a structure represented by ),

[0093] Formula (D-6): (In the formula, m ａ n represents an integer between 2 and 11, and n ａ represents an integer between 2 and 3, Y － Examples of tertiary ammonium salts having a structure represented by (where represents an anion) include:

[0094] Furthermore, as a phosphonium salt, formula (D-7): (In the formula, R ３１ , R ３２ , R ３３ , and R ３４represents an alkyl group, an aryl group, or an aralkyl group independently of one another, and Y － represents an anion, and R ３１ , R ３２ , R ３３ , and R ３４ are each bonded to a phosphorus atom. Examples thereof include quaternary phosphonium salts represented by ().

[0095] Further, examples of the sulfonium salt include a compound of formula (D-8): (In the formula, R ３５ , R ３６ , and R ３７ represent an alkyl group, an aryl group, or an aralkyl group independently of one another, and Y － represents an anion, and R ３５ , R ３６ , and R ３７ are each bonded to a sulfur atom. Examples thereof include tertiary sulfonium salts represented by ().

[0096] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, and m ａ represents an integer of 2 to 11, and n ａ represents an integer of 2 to 3. R ２１ of this quaternary ammonium salt 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. Examples thereof include linear alkyl groups such as an ethyl group, a propyl group, and a butyl group, and benzyl group, a cyclohexyl group, a cyclohexylmethyl group, a dicyclopentadienyl group, and the like. Further, the anion (Y － ) includes halide ions such as a chloride ion (Cl － ), a bromide ion (Br － ), and an iodide ion (I － ), and acid groups such as a carboxylate (—COO － ), a sulfonate (—SO ３ － ), and an alcoholate (—O － ).

[0097] The compound of formula (D-2) is R ２２ R ２３ R２４ R ２５ N ＋ Y － is a quaternary ammonium salt represented by. In this quaternary ammonium salt, R ２２ 、R ２３ 、R ２４ and R ２５ are, for example, an alkyl group having 1 to 18 carbon atoms such as an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group. The anion (Y － ) includes halide ions such as chloride ion (Cl － ), bromide ion (Br － ), iodide ion (I － ), and acid groups such as carboxylate (-COO － ), sulfonate (-SO ３ － ), and alcoholate (-O － ). This quaternary ammonium salt can be obtained as a commercially available product, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trimethyloctylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, and the like.

[0098] The compound of formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, and the number of carbon atoms of R ２６ and R ２７ is, for example, 1 to 18, and the total number of carbon atoms of R ２６ and R ２７ is preferably 7 or more. For example, R ２６ can be exemplified by an alkyl group such as a methyl group, an ethyl group, a propyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ２７ can be exemplified by an aralkyl group such as a benzyl group, an alkyl group such as an octyl group, an octadecyl group. The anion (Y － ) includes chloride ion (Cl － ), bromide ion (Br －), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acidic groups include ). This compound can be obtained commercially, but it can also be produced by reacting imidazole compounds such as 1-methylimidazole and 1-benzylimidazole with aralkyl halides, alkyl halides, and aryl halides such as benzyl bromide, methyl bromide, and benzene bromide.

[0099] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ２８ This is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples include a butyl group, an octyl group, a benzyl group, and a lauryl group. Anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting pyridine with an alkyl halide or aryl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0100] The compound of formula (D-5) is a quaternary ammonium salt derived from substituted pyridines such as picoline, and R ２９This is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples include a methyl group, an octyl group, a lauryl group, a benzyl group, etc. ３０ For example, R is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. For example, if the compound represented by formula (D-5) is a quaternary ammonium derived from picoline, then R ３０ It is a methyl group. Anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting a substituted pyridine such as picoline with an alkyl halide or aryl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0101] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m ａ n represents an integer between 2 and 11, and n ａ This indicates 2 or 3. Also, the anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O －Examples of acidic groups include (Y). This compound can be produced by the reaction of an amine with a weak acid such as a carboxylic acid or phenol. Examples of carboxylic acids include formic acid and acetic acid, and when formic acid is used, an anion (Y － ) is (HCOO － ) and when acetic acid is used, the anion (Y － ) is (CH ３ COO － ) Also, when phenol is used, the anion (Y － ) is (C ６ H ５ O － )

[0102] The compound of formula (D-7) is R ３１ R ３２ R ３３ R ３４ P ＋ Y － It is a quaternary phosphonium salt having the structure R ３１ , R ３２ , R ３３ , and R ３４ For example, C1-C18 alkyl groups such as ethyl, propyl, butyl, and cyclohexylmethyl groups, C6-C18 aryl groups such as phenyl groups, or C7-C18 aralkyl groups such as benzyl groups, preferably R ３１ ~R ３４ Three of the four substituents are unsubstituted or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group 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. Also, the anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O －Examples of acidic groups include ) and others. This compound is available commercially, and examples include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritrilmonoarylphosphonium halide, or tritrilmonoalkylphosphonium halide (in all cases, the halogen atom is a chlorine atom or a bromine atom). Particularly preferred are triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, tritrilmonoarylphosphonium halides such as tritrilmonophenylphosphonium halide, and tritrilmonoalkylphosphonium halides such as tritrilmonomethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).

[0103] Furthermore, examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0104] The compound of formula (D-8) is R ３５ R ３６ R ３７ S ＋ Y － It is a tertiary sulfonium salt having the structure R ３５ , R ３６ , and R ３７For example, C1-C18 alkyl groups such as ethyl, propyl, butyl, and cyclohexylmethyl groups, C6-C18 aryl groups such as phenyl groups, or C7-C18 aralkyl groups such as benzyl groups, preferably R ３５ ~R ３７ Two of the three substituents are unsubstituted or substituted phenyl groups, such as phenyl or tolyl groups, and the remaining one is an alkyl group 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. Also, the anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acid groups include maleate anions and nitrate anions. This compound is available commercially, and examples include trialkylsulfonium halides such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halide, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halide and diphenylethylsulfonium halide, triphenylsulfonium halide (in all cases, the halogen atom is a chlorine atom or a bromine atom), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmonoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate and diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. In addition, triphenylsulfonium halide and triphenylsulfonium carboxylate can be preferably used.

[0105] Furthermore, a nitrogen-containing silane compound can be added as a curing catalyst. Examples of nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilipropyl)-4,5-dihydroimidazole.

[0106] When the silicon-containing resist underlayer film forming composition contains a curing catalyst, the content of the curing catalyst 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, per 100 parts by mass of component [A].

[0107] - Stabilizers - Stabilizers may be added for purposes such as stabilizing the hydrolysis condensate of the hydrolyzable silane mixture. Specific examples include organic acids, water, alcohols, or combinations thereof. Examples of organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Among these, oxalic acid and maleic acid are preferred. When adding organic acids, the amount added is 0.1 to 5.0% by mass relative to the mass of the hydrolysis condensate of the hydrolyzable silane mixture. These organic acids can also function as pH adjusters. As water, pure water, ultrapure water, or deionized water can be used. When used, the amount added can be 0.1 to 20 parts by mass per 100 parts by mass of the silicon-containing resist underlayer film forming composition. As alcohols, those that easily evaporate upon heating after coating are preferred. Examples include methanol, ethanol, propanol, i-propanol, and butanol. When alcohol is added, the amount added may be 0.1 to 20 parts by mass per 100 parts by mass of the silicon-containing resist underlayer film forming composition.

[0108] -Organic Polymers- By adding organic polymers to a silicon-containing resist underlayer film forming composition, the dry etching rate (decrease in film thickness per unit time), as well as the damping coefficient and refractive index of the resist underlayer film formed from the silicon-containing resist underlayer film forming composition, can be adjusted. There are no particular restrictions on the organic polymer, and various organic polymers (condensation polymers and addition polymers) can be appropriately selected depending on the purpose of addition. Specific examples 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. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be suitably used when such functionality is required. Specific examples of such organic polymers include, but are not limited to, addition polymerization polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthyl methacrylate, anthyl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenyl maleimide as structural units, as well as condensation polymerization polymers such as phenol novolac and naphthol novolac.

[0109] When an addition polymerization polymer is used as an organic polymer, the polymer may be either a homopolymer or a copolymer. Addition polymerization monomers are used in the production of addition polymerization polymers, and specific examples of such addition polymerization monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0110] Specific examples of acrylic acid ester compounds include, but are not limited to, methyl acrylate, ethyl acrylate, n-hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthyl methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate.

[0111] Specific examples of methacrylic acid ester compounds include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthyl 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-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate.

[0112] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-antrylcrylamide.

[0113] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-antlylmethacrylamide.

[0114] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

[0115] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0116] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0117] When a condensation polymer is used as an organic polymer, examples of such polymers include condensation polymers of glycol compounds and dicarboxylic acid compounds. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, and butylene glycol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Other examples include, but are not limited to, polyesters, polyamides, and polyimides such as polypyromellitrimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate. If the organic polymer contains a hydroxyl group, this hydroxyl group can undergo a crosslinking reaction with hydrolysis condensates, etc.

[0118] The weight-average molecular weight of an organic polymer can typically be between 1,000 and 1,000,000. When incorporating an organic polymer, in order to fully obtain the functional effects of the polymer while suppressing precipitation in the composition, its weight-average molecular weight can be set to, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000. Such organic polymers may be used individually or in combination of two or more.

[0119] When a silicon-containing resist underlayer film forming composition contains an organic polymer in combination with component [A], the amount of the organic polymer cannot be specified in general, as it is determined appropriately considering the function of the organic polymer, etc. However, it can usually be in the range of 1 to 200% by mass relative to the mass of component [A]. From the viewpoint of suppressing precipitation in the composition, for example, it can be 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less. From the viewpoint of obtaining the full effect, for example, it can be 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0120] - Acid Generators - Examples of acid generators include thermal acid generators and photoacid generators, with photoacid generators being preferred. Examples of photoacid generators include, but are not limited to, onium salt compounds such as sulfonium salts, phosphonium salts, ammonium salts, iodonium salts, and oxonium salts, sulfonimide compounds, and disulfonyldiazomethane compounds. Depending on the type, photoacid generators, such as carboxylate salts like nitrates and maleates in the onium salt compounds described later, and hydrochlorides, can also function as curing catalysts. Examples of thermal acid generators include, but are not limited to, tetramethylammonium nitrate.

[0121] Specific examples of onium salt compounds include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride.

[0122] Specific examples of sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0123] Specific examples of disulfonyl diazomethane compounds include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0124] When a silicon-containing resist underlayer film forming composition contains an acid generator, the amount of the acid generator cannot be specified in general terms as it is determined appropriately considering the type of acid generator, etc. However, it is usually in the range of 0.01 to 5% by mass relative to the mass of component [A], preferably 3% by mass or less, more preferably 1% by mass or less, from the viewpoint of suppressing the precipitation of the acid generator in the composition, and preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of obtaining its effect sufficiently. The acid generator can be used alone or in combination of two or more types, and a photoacid generator and a thermal acid generator may be used in combination.

[0125] - Rheology Modifiers - Rheology modifiers are mainly added to improve the fluidity of compositions for forming silicon-containing resist underlayer films, and in particular during the baking process, to improve the uniformity of the film thickness formed and to enhance the filling of the composition into the holes. Specific examples include phthalate derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate; adipic acid derivatives such as dinormal butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyl decyl adipate; maleic acid derivatives such as dinormal butyl malate, diethyl malate, and dinonyl malate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. When these rheology modifiers are used, the amount added is usually less than 30% by mass of the total film-forming components of the silicon-containing resist underlayer film-forming composition.

[0126] - Adhesion Aids - Adhesion aids are added primarily to improve the adhesion between the substrate or resist and the film (resist underlayer film) formed from the silicon-containing resist underlayer film forming composition, and especially to suppress and prevent the 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; and γ-chloropropyltrimethoxysilane. Examples of adhesive aids include other silanes such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. When these adhesive aids are used, the amount added is usually less than 5% by mass, preferably less than 2% by mass, relative to the film-forming component of the silicon-containing resist underlayer film-forming composition.

[0127] - pH adjuster - In addition to acids having one or more carboxylic acid groups, such as the organic acids mentioned above as stabilizers, other pH adjusters can be used. When a pH adjuster is used, the amount added may be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass per 100 parts by mass of component [A].

[0128] -Metal Oxides- Examples of metal oxides that can be added to silicon-containing resist underlayer film formation compositions include, but are not limited to, oxides of one or more metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and metalloids such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0129] The concentration of the film-forming component in the silicon-containing resist underlayer film-forming composition can be, for example, 0.01 to 50% by mass, 0.01 to 30% by mass, 0.01 to 25% by mass, or 0.01 to 20.0% by mass, relative to the total mass of the composition. The content of component [A] in the film-forming component is usually 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and still more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the aforementioned additives. Furthermore, the silicon-containing resist underlayer film-forming composition preferably has a pH of 1 to 5, and more preferably a pH of 2 to 4.

[0130] The silicon-containing resist underlayer film formation composition can be manufactured by mixing component [A], component [B], and component [C], and optionally other components, if any. In this case, a solution containing component [A] may be prepared in advance and this solution may be mixed with component [B], component [C], and other components. During the preparation of the silicon-containing resist underlayer film formation composition, heating may be used as appropriate, within a range that does not cause the components to decompose or deteriorate.

[0131] The silicon-containing resist underlayer film formation composition may be filtered using a sub-micrometer-order filter during the manufacturing process or after all components have been mixed. The material of the filter used is not limited, but examples include polyethylene filters, nylon filters, fluororesin filters, polyimide filters, etc.

[0132] (Method for manufacturing semiconductor devices) The silicon-containing resist underlayer film in this embodiment is a cured product of the silicon-containing resist underlayer film forming composition of the present invention.

[0133] The laminate of this embodiment comprises, for example, a semiconductor substrate and a silicon-containing resist underlayer film of this embodiment.

[0134] The method for manufacturing a semiconductor device of the present invention includes, for example, the steps of: forming an organic underlayer film on a substrate; forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition of the present invention; and forming a resist film on the silicon-containing resist underlayer film.

[0135] The pattern formation method of this embodiment includes, for example, the steps of: forming an organic underlayer film on a semiconductor substrate; applying the silicon-containing resist underlayer film formation composition of the present invention onto the organic underlayer film and firing it to form a silicon-containing resist underlayer film; forming a resist film on the silicon-containing resist underlayer film; exposing and developing the resist film to obtain a resist pattern; using the resist pattern as a mask to etch the silicon-containing resist underlayer film; and using the patterned silicon-containing resist underlayer film as a mask to etch the organic underlayer film.

[0136] Hereinafter, as an embodiment of the present invention, a laminate, a pattern formation method, and a method for manufacturing a semiconductor device using the silicon-containing resist underlayer film formation composition of the present invention will be described.

[0137] First, the silicon-containing resist underlayer film forming composition of the present invention is applied to a substrate used in the manufacture of precision integrated circuit elements [for example, semiconductor substrates such as silicon wafers coated with silicon oxide films, silicon nitride films, or silicon oxidizite films, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates on which ITO (indium tin oxide) films or IZO (indium zinc oxide) films are formed, plastic (polyimide, PET, etc.) substrates, substrates coated with low dielectric constant materials (low-k materials), flexible substrates, etc.] by an appropriate coating method such as a spinner or coater. Then, the composition is cured by firing using a heating means such as a hot plate to form a resist underlayer film. Hereinafter, in this specification, the silicon-containing resist underlayer film refers to a film formed from the silicon-containing resist underlayer film forming composition of the present invention. The firing conditions are appropriately selected from a firing temperature of 40°C to 400°C or 80°C to 250°C and a firing time of 0.3 minutes to 60 minutes. Preferably, the firing temperature is 150°C to 250°C and the firing time is 0.5 minutes to 2 minutes. The thickness of the resist underlayer film formed here 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. When forming the resist underlayer film, a silicon-containing resist underlayer film formation composition that has been filtered with a nylon filter can be used. Here, a silicon-containing resist underlayer film formation composition that has been filtered with a nylon filter refers to a composition that has been filtered with a nylon filter at an intermediate stage in the manufacturing of the silicon-containing resist underlayer film formation composition, or after all components have been mixed.

[0138] In the process of forming a silicon-containing resist underlayer film, it is preferable to use a silicon-containing resist underlayer film forming composition that has been filtered. The material of the filter used at this time is not limited, but for example, polyethylene filters, nylon filters, fluororesin filters, polyimide filters, etc., can be used.

[0139] In one aspect of the present invention, an organic underlayer film is formed on a substrate, and then a silicon-containing resist underlayer film is formed on top of it. However, in some cases, the organic underlayer film may not be provided. There are no particular restrictions on the organic underlayer film used here, and it can be arbitrarily selected from those that have been conventionally used in lithography processes. By providing an organic underlayer film, a silicon-containing resist underlayer film on top of that, and a resist film described later on top of that on the substrate, the pattern width of the photoresist film is narrowed. Even when the photoresist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas described later. For example, the silicon-containing resist underlayer film can be processed by using a fluorine-based gas with a sufficiently fast etching rate for the photoresist film as the etching gas, the organic underlayer film can be processed by using an oxygen-based gas with a sufficiently fast etching rate for the silicon-containing resist underlayer film as the etching gas, and the substrate can be processed by using a fluorine-based gas with a sufficiently fast etching rate for the organic underlayer film as the etching gas. The substrates and coating methods that can be used in this case are the same as those described above.

[0140] Next, a layer of, for example, a photoresist material (resist film) is formed on the silicon-containing resist underlayer film. The resist film can be formed by a well-known method, that is, for example, by coating a coating-type resist material (resist film forming composition) onto the silicon-containing resist underlayer film and firing it. The thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0141] The photoresist material used for the resist film formed on the silicon-containing resist underlayer is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative-type and positive-type photoresist materials can be used. Examples include a positive-type photoresist material consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist material consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, a chemically amplified photoresist material consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist material, an alkali-soluble binder and a photoacid generator, and a chemically amplified photoresist material consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate, a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist material and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (manufactured by Cypree), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), AR2772JN (manufactured by JSR Corporation), and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, examples include fluorine-containing atom polymer-based photoresist materials, such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0142] Furthermore, instead of a photoresist film, an electron beam lithography resist film (also referred to as an electron beam resist film) or an EUV lithography resist film (also referred to as an EUV resist film) can be used as the resist film formed on the silicon-containing resist underlayer.

[0143] For forming electron beam resist films, both negative and positive materials can be used as electron beam resist materials. Specific examples include: chemically amplified resist materials consisting of an acid generator and a binder having a group that decomposes with acid to change the alkali dissolution rate; chemically amplified resist materials consisting of an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes with acid to change the alkali dissolution rate of the resist material; chemically amplified resist materials consisting of an acid generator, a binder having a group that decomposes with acid to change the alkali dissolution rate, and a low-molecular-weight compound that decomposes with acid to change the alkali dissolution rate of the resist material; non-chemically amplified resist materials consisting of a binder having a group that decomposes with electron beam to change the alkali dissolution rate; and non-chemically amplified resist materials consisting of a binder having a portion that is cut by electron beam to change the alkali dissolution rate. When using these electron beam resist materials, a resist film pattern can be formed in the same way as when using a photoresist material with an electron beam as the irradiation source. Furthermore, methacrylate resin-based resist materials can be used as EUV resist materials for forming EUV resist films.

[0144] The resist material may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MORs), and a typical example is a tin oxide-based resist. An example of a metal oxide resist material is a coating composition containing a metal oxo-hydroxo network having an organic ligand via a metal-carbon bond and / or metal-carboxylate bond, as described in Japanese Patent Application Publication No. 2019-113855. An example of a metal-containing resist uses a peroxo ligand as a radiosensitizing stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described in the patent document described in paragraph

[0011] of Publication No. 2019-532489, for example. Examples of such patent documents include 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.

[0145] Next, the resist film formed on the upper layer of the silicon-containing resist underlayer film is exposed through a predetermined mask (rectil). For exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and F ２ Excimer lasers (wavelength 157 nm), EUV lasers (wavelength 13.5 nm), electron beams, etc., can be used. After exposure, post-exposure baking can be performed as needed. Post-exposure baking is performed under conditions appropriately selected from heating temperatures of 70°C to 150°C and heating times of 0.3 minutes to 10 minutes.

[0146] Next, development is performed using a developer (e.g., an alkaline developer). This removes the photoresist film from the exposed areas, for example, when a positive-type photoresist film is used, thus forming a photoresist pattern. Examples of developers (alkaline developers) include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants can be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0147] Furthermore, in this invention, an organic solvent can be used as the developer, and development is performed with the developer (solvent) after exposure. As a result, for example, when a negative-type photoresist film is used, the photoresist film in the unexposed areas is removed, and a pattern of the photoresist film is formed. Examples of developers (organic solvents) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, 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, and 3-ethyl-3-methoxybutyl acetate. Butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate Alacetate, 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 pyruvate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate,Examples of developing agents include isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Furthermore, surfactants can be added to these developing solutions. Development conditions include a temperature of 5°C to 50°C and a development time of 10 to 600 seconds, which can be appropriately selected.

[0148] The pattern of the photoresist film (upper layer) formed in this manner is used as a protective film to remove the resist underlayer film (intermediate layer). Next, the film consisting of the patterned photoresist film and the patterned resist underlayer film (intermediate layer) is used as a protective film to remove the organic underlayer film (lower layer). Finally, the patterned photoresist film (upper layer), the patterned resist underlayer film (intermediate layer), and the patterned organic underlayer film (lower layer) are used as protective films to process the substrate.

[0149] The removal of the resist underlayer (intermediate layer), which is performed using the resist film (upper layer) pattern as a protective layer, is carried out by dry etching, using tetrafluoromethane (CF ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８Gases such as trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. It is preferable to use halogen-based gases for dry etching of the resist underlayer film. In dry etching with halogen-based gases, resist films (photoresist films) made of organic materials are generally difficult to remove. In contrast, silicon-containing resist underlayer films, which contain many silicon atoms, are quickly removed by halogen-based gases. Therefore, the reduction in the thickness of the photoresist film associated with dry etching of the resist underlayer film can be suppressed. As a result, it becomes possible to use the photoresist film as a thin film. Therefore, it is preferable to use fluorine-based gases for dry etching of the resist underlayer film, and examples of fluorine-based gases include tetrafluoromethane (CF4). ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２ Examples include, but are not limited to, these.

[0150] When an organic underlayer film is present between the substrate and the resist underlayer film, the removal of the organic underlayer film (underlayer), which is then carried out using a protective film consisting of a patterned resist underlayer film (intermediate layer) and (if any remaining) a patterned resist underlayer film, is preferably performed by dry etching with an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.). This is because the silicon-containing resist underlayer film of this embodiment, which contains many silicon atoms, is difficult to remove by dry etching with an oxygen-based gas.

[0151] Subsequently, the processing (patterning) of the (semiconductor) substrate, which is carried out using a patterned silicon-containing resist underlayer film (intermediate layer) and optionally a patterned organic underlayer film (underlayer) as protective films, is preferably performed by dry etching with a fluorine-based gas. Examples of fluorine-based gases include tetrafluoromethane (CF4). ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, and difluoromethane (CH ２ F ２ Examples include:

[0152] After the removal (patterning) of the organic underlayer film, or after the processing (patterning) of the substrate, the resist underlayer film may be removed. The removal of the silicon-containing resist underlayer film can be carried out by dry etching or wet etching. Dry etching of the silicon-containing resist underlayer film is preferably performed using a fluorine-based gas, as mentioned in the patterning section, for example, tetrafluoromethane (CF4). ４ ), perfluorocyclobutane (C ４ F ８ ), perfluoropropane (C ３ F ８ ), trifluoromethane, difluoromethane (CH ２ F ２ Examples of chemicals used in wet etching of silicon-containing resist underlayer films include dilute hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (HF and NH). ４Examples of alkaline solutions include a mixed solution of F, an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM solution), an aqueous solution containing ammonia and hydrogen peroxide (SC-1 solution), and a resist stripping solution (ST-120 (manufactured by Tokyo Ohka Co., Ltd.)). In addition to the aforementioned ammonia hydrochloride (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide, and water, other examples of alkaline solutions include aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepicato hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These solutions can also be used in combination.

[0153] Furthermore, an organic anti-reflective coating can be formed on top of the silicon-containing resist underlayer before the resist film is formed. There are no particular restrictions on the anti-reflective coating composition used; for example, any composition that has been conventionally used in lithography processes can be arbitrarily selected and used, and the anti-reflective coating can be formed by conventional methods, such as coating with a spinner or coater and firing.

[0154] Furthermore, the substrate on which the silicon-containing resist underlayer film formation composition is applied may have an organic or inorganic anti-reflective coating formed on its surface by CVD or the like, and the silicon-containing resist underlayer film can be formed on top of it. Even when the silicon-containing resist underlayer film of this embodiment is formed on top of an organic underlayer film formed on the substrate, the substrate used may also have an organic or inorganic anti-reflective coating formed on its surface by CVD or the like.

[0155] The silicon-containing resist underlayer film formed from the silicon-containing resist underlayer film formation composition may also have absorption properties for certain wavelengths of light used in the lithography process. In such cases, it can function as an anti-reflective film that prevents reflected light from the substrate. Furthermore, the silicon-containing resist underlayer film can also be used as a layer to prevent interaction between the substrate and the resist film (photoresist film, etc.), a layer that prevents adverse effects on the substrate from materials used in the resist film or substances generated during exposure to the resist film, a layer that prevents the diffusion of substances generated from the substrate into the resist film during heating and firing, and a barrier layer to reduce the poisoning effect of the resist film by the semiconductor substrate dielectric layer.

[0156] The silicon-containing resist underlayer film can be applied to a substrate with via holes formed in a dual damascene process and can be used as a hole-filling material (filling material) that can completely fill the holes. It can also be used as a planarizing material to flatten the surface of an uneven semiconductor substrate. Furthermore, the silicon-containing resist underlayer film of this embodiment, as an underlayer film for an EUV resist film, can, in addition to functioning as a hard mask, prevent reflection of undesirable exposure light, such as UV (ultraviolet) light or DUV (deep ultraviolet) light (ArF light, KrF light), from the substrate or interface during EUV exposure (wavelength 13.5 nm) without intermixing with the EUV resist film. Therefore, the silicon-containing resist underlayer film forming composition of the present invention can be suitably used to form an anti-reflective underlayer film for an EUV resist film. In other words, it can efficiently prevent reflection as an underlayer for an EUV resist film. When used as an EUV resist underlayer film, the process can be carried out in the same way as for a photoresist underlayer film.

[0157] The laminate comprising the silicon-containing resist underlayer film and a semiconductor substrate as described above can be used to suitably process a semiconductor substrate. Furthermore, a semiconductor device manufacturing method that includes the steps of forming an organic underlayer film, forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition of the present invention, and forming a resist film on the silicon-containing resist underlayer film, as described above, can be expected to enable highly accurate and reproducible processing of semiconductor substrates, thus allowing for stable manufacturing of semiconductor devices.

[0158] The present invention will be described in more detail below with reference to synthesis examples and embodiments, but the present invention is not limited to the embodiments described below.

[0159] In the examples, the apparatus and conditions used for analyzing the physical properties of the samples are as follows: (1) Molecular weight measurement The weight-average molecular weight Mw of the polysiloxane used in the present invention is the weight-average molecular weight obtained in polystyrene equivalent by GPC analysis. The GPC measurement conditions can be, for example, to use a GPC apparatus (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product name Shodex® KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow rate) of 1.0 mL / min, and a standard sample of polystyrene (manufactured by Showa Denko K.K.). (2) １ H-NMR JEOL nuclear magnetic resonance apparatus １ The results were evaluated using 1H-NMR (400 MHz) with d6-acetone as the solvent.

[0160] [1] Synthesis of polymers (hydrolyzed condensates) (Synthesis Example 1) 23.3 g of tetraethoxysilane, 6.84 g of methyltriethoxysilane, 3.3 g of diallyl isocyanuratepropyltriethoxysilane, and 47.9 g of propylene glycol monomethyl ether were placed in a 300 mL flask, and while stirring the mixed solution with a magnetic stirrer, a mixed aqueous solution of 0.33 g of dimethylaminopropyltrimethoxysilane and 20.1 g of aqueous nitric acid solution (0.2 mol / L) was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol, methanol, and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolyzed condensate (polymer) solution. Further addition of propylene glycol monomethyl ether was made, and the concentration was adjusted so that the solvent ratio of propylene glycol monomethyl ether was 20 mass percent in terms of solid residue at 140°C. The weight-average molecular weight of the obtained polymer was Mw 3,000 in polystyrene equivalents using GPC. １ ¹H-NMR revealed that the amount of propylene glycol monomethyl ether capping relative to the Si atoms was 4 mol%. The residual nitric acid content was 1200 ppm.

[0161]

[0162] [2] Preparation of a composition for forming a silicon-containing resist underlayer film <Example 1> A composition for forming a silicon-containing resist underlayer film was prepared by mixing 0.016 g of maleic acid, 39.03 g of propylene glycol monoethyl ether, 1.84 g of propylene glycol monomethyl ether, 5.93 g of ultrapure water, and 0.005 g of polyether-modified silicone oil (manufactured by Dow Toray Industries, Ltd., trade name: DOWSIL® SH 28 Paint Additive) with 2.640 g of a solution containing 0.528 g of polysiloxane (polymer) obtained in Synthesis Example 1 above, and filtering the mixture through a 0.1 μm fluororesin filter. The polyether-modified silicone oil is the polyether-modified silicone of the following formula (1). (In equation (1), a and b are independent numbers between 1 and 20, and Q represents the following equation. The unit of b may be random or block. Q = -R) １ (EO) ｃ (PO) ｄ R ２ In the formula, R １ R is an oxyalkylene group with 1 to 6 carbon atoms, EO is an ethylene oxy group, PO is a propylene oxy group, R ２ represents a hydrogen atom or a methyl group, and c and d each independently represent a number between 0 and 10, with cd ≠ 0. EO and PO may be random or blocky.

[0163] <Example 2> A silicon-containing resist underlayer film formation composition was prepared by mixing 0.016 g of maleic acid, 39.03 g of propylene glycol monoethyl ether, 1.84 g of propylene glycol monomethyl ether, 5.93 g of ultrapure water, and 0.005 g of polyether-modified silicone oil (manufactured by Dow Toray Industries, Ltd., trade name: DOWSIL® L-7001 Fluid) with 2.640 g of a solution containing 0.528 g of polysiloxane (polymer) obtained in Synthesis Example 1 above, and filtering the mixture through a 0.1 μm fluororesin filter. The polyether-modified silicone oil is the polyether-modified silicone of formula (1) above.

[0164] <Example 3> A silicon-containing resist underlayer film formation composition was prepared by mixing 0.016 g of maleic acid, 39.03 g of propylene glycol monoethyl ether, 1.84 g of propylene glycol monomethyl ether, 5.93 g of ultrapure water, and 0.005 g of polyether-modified silicone oil (manufactured by Dow Toray Industries, Ltd., trade name: DOWSIL® L-7002 Fluid) with 2.640 g of a solution containing 0.528 g of polysiloxane (polymer) obtained in Synthesis Example 1 above, and filtering the mixture through a 0.1 μm fluororesin filter. The polyether-modified silicone oil is the polyether-modified silicone of formula (1) above.

[0165] <Example 4> A silicon-containing resist underlayer film formation composition was prepared by mixing 0.016 g of maleic acid, 39.03 g of propylene glycol monoethyl ether, 1.84 g of propylene glycol monomethyl ether, 5.93 g of ultrapure water, and 0.005 g of polyether-modified silicone oil (manufactured by Dow Toray Industries, Ltd., trade name: DOWSIL® FZ-2104 Fluid) with 2.640 g of a solution containing 0.528 g of polysiloxane (polymer) obtained in Synthesis Example 1 above, and filtering the mixture through a 0.1 μm fluororesin filter. The polyether-modified silicone oil is the polyether-modified silicone of formula (1) above.

[0166] <Comparative Example 1> A silicon-containing resist underlayer film formation composition was prepared by mixing 0.016 g of maleic acid, 39.03 g of propylene glycol monoethyl ether, 1.84 g of propylene glycol monomethyl ether, and 5.93 g of ultrapure water with 2.640 g of a solution containing 0.528 g of polysiloxane (polymer) obtained in Synthesis Example 1 above, and filtering the mixture through a 0.1 μm fluororesin filter.

[0167] <Comparative Example 2> A silicon-containing resist underlayer film forming composition was prepared by mixing 0.016 g of maleic acid, 39.03 g of propylene glycol monoethyl ether, 1.84 g of propylene glycol monomethyl ether, 5.93 g of ultrapure water, and 0.005 g of acrylic resin-based surfactant (NOF Co., Ltd., trade name: AP-001) with 2.640 g of a solution containing 0.528 g of polysiloxane (polymer) obtained in Synthesis Example 1 above, and filtering the mixture through a 0.1 μm fluororesin filter. The surfactant was a copolymer in which a is 0.35, b is 0.15, c is 0.50, d is 0.001, and n is 2 to 20 in the following formula (IV).

[0168] [3] Preparation of composition for forming an organic resist under film Under nitrogen, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 ml four-necked flask, and 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was added and stirred. The temperature was raised to 100°C to dissolve and start polymerization. After 24 hours, it was allowed to cool to 60°C. Chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.) was added to the cooled reaction mixture to dilute it, and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to precipitate. The obtained precipitate was filtered and dried in a vacuum dryer at 80°C for 24 hours to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL). １ The H-NMR measurement results were as follows: １ H-NMR (400MHz, DMSO-d ６ ): δ7.03-7.55 (br, 12H), δ7.61-8.10 (br, 4H), δ11.18 (br, 1H) Furthermore, the weight-average molecular weight Mw of PCzFL was 2,800 in polystyrene equivalents according to GPC, and the polydispersity Mw / Mn was 1.77.

[0169] 20 g of PCzFL, 3.0 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries, Ltd. (formerly Mitsui Scitec Co., Ltd.), trade name Powderlink 1174) as a crosslinking agent, 0.30 g of pyridinium p-toluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (manufactured by DIC Corporation, trade name) as a surfactant were mixed, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.10 μm, and then filtered again using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming an organic resist underlayer film for use in multilayer lithography processes.

[0170] [4] Solvent Resistance and Developer Solubility Test The silicon-containing resist underlayer film formation compositions prepared in Examples 1-4 and Comparative Examples 1-2 were each coated onto silicon wafers using a spinner. They were heated on a hot plate at 215°C for 1 minute to form Si (silicon)-containing resist underlayer films, and the film thickness of the obtained underlayer films was measured. Subsequently, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was applied to each Si-containing resist underlayer film and spin-dried. The film thickness of the underlayer film after application was measured, and the presence or absence of a change in film thickness before and after application of the mixed solvent was evaluated. Using the film thickness before application of the mixed solvent as a reference, those with a change in film thickness of 1% or less after application were evaluated as "good," and those with a change in film thickness of more than 1% were evaluated as "not cured." Furthermore, an alkaline developer (TMAH 2.38% aqueous solution) was applied to each Si-containing resist underlayer film fabricated on a silicon wafer using the same method, and the film was spin-dried. The film thickness of the underlayer film after application was measured, and the presence or absence of a change in film thickness before and after application of the developer was evaluated. Using the film thickness before application of the developer as a baseline, films with a film thickness change of 1% or less were classified as "good," and films with a film thickness change of more than 1% were classified as "not cured." The results obtained are shown in Table 1.

[0171]

[0172] [EBR Performance Evaluation] Each of the silicon-containing resist underlayer film formation compositions prepared in Examples 1-4 and Comparative Examples 1-2 was applied (spin-coated) onto a 300 mm diameter silicon wafer using a spin coater (CLEAN TRACK LITHIUS Pro) manufactured by Tokyo Electron Limited, and then subjected to EBR (Edge Bead Removal) treatment with OK73 thinner (Tokyo Ohka Kogyo Co., Ltd.). After EBR treatment, the silicon wafers were heated on a hot plate at 215°C for 60 seconds to form a silicon-containing resist underlayer film with a thickness of 23 nm. Subsequently, the wafer edge shape (EBR shape evaluation) was performed using an electron microscope (100x magnification) based on the evaluation criteria below. The results are shown in Table 2. Evaluation criterion "A" indicates a good EBR shape and excellent removeability in EBR treatment. (Evaluation Criteria) A: EBR line uniformity on the silicon-containing resist underlayer is consistent. B: EBR line uniformity on the silicon-containing resist underlayer is not consistent.

[0173]

[0174] [Hump Performance Evaluation] The hump height of the edge shape portion of the silicon-containing resist underlayer film, formed using the same method as for EBR performance evaluation, was measured using a film thickness step meter (Dektak XT) manufactured by Bruker Japan Co., Ltd., and the ratio of hump height to film thickness (hump height ratio) was calculated using the following formula: Hump height ratio = Hump height [nm] ÷ Film thickness [nm] The results are shown in Table 3. The lower the hump height ratio, the better the removal performance by EBR.

[0175]

[0176] From the results in Table 3 above, it can be said that the coating films prepared using the silicon-containing resist underlayer film forming compositions prepared in Examples 1 to 4 exhibit a better Hump height ratio compared to Comparative Examples 1 to 2. Therefore, since Examples 1 to 4 exhibit a better Hump height ratio compared to Comparative Examples 1 to 2, they have excellent removeability by EBR and are useful as silicon-containing resist underlayer film forming compositions.

[0177] [5] Formation of resist pattern by EUV exposure: Positive solvent development The above organic resist underlayer film formation composition was applied onto a silicon wafer using a spinner and baked on a hot plate at 215°C for 60 seconds to obtain an organic underlayer film (layer A) with a thickness of 22 nm. On top of that, the composition obtained in Example 1 was spin-coated and heated at 215°C for 1 minute to form a silicon-containing resist underlayer film (layer B) (20 nm). Further on top of that, an EUV resist solution (methacrylate resin-based resist) was spin-coated and heated at 130°C for 1 minute to form an EUV resist film (layer C), and exposure was performed using an ASML EUV exposure apparatus (NXE3300B) under the conditions of NA = 0.33, σ = 0.67 / 0.90, and Dipole. After exposure, post-exposure heating (PEB, 110°C for 1 minute) was performed, the material was cooled to room temperature on a cooling plate, developed for 30 seconds using TMAH 2.38% developer, rinsed, and a resist pattern was formed. Using the same procedure, resist patterns were formed using the compositions obtained in Examples 2-4 and Comparative Examples 1-2. For each obtained pattern, the feasibility of forming 44 nm pitch, 22 nm line and space patterns was evaluated by checking the pattern shape through cross-sectional observation of the pattern. In observing the pattern shape, a state where the shape is between the footing and undercut and there is no significant residue in the space area was evaluated as "good," an undesirable state where the resist pattern peeled off and collapsed was evaluated as "collapsed," and an undesirable state where the upper or lower parts of the resist pattern were in contact with each other was evaluated as "bridged." The results obtained are shown in Table 4.

[0178]

Claims

[A] Ingredient: Polysiloxane [B] Component: Polyether-modified silicone oil, [C] Component: Solvent A composition for forming a silicon-containing resist underlayer film, containing the following: 　 The silicon-containing resist underlayer film forming composition according to claim 1, wherein the [B] component is a polymer represented by the following formula (1). (In equation (1), a and b are each independent numbers between 1 and 20, and Q represents the following equation. The units of a and b may be random or blocks.) Q-R １ (59) ｃ (0) ｄ 2 ２ In the formula, R １ R is an oxyalkylene group with 1 to 6 carbon atoms, EO is an ethylene oxy group, PO is a propylene oxy group, R ２ represents a hydrogen atom or a methyl group, and c and d each independently represent a number from 0 to 10, with cd ≠ 0. EO and PO may be random or block. 　 The aforementioned component [A] includes at least one selected from the group consisting of a hydrolyzable silane hydrolysis condensate containing at least one hydrolyzable silane represented by the following formula (2), a modified hydrolyzable condensate in which at least a portion of the silanol groups of the condensate are alcohol-modified, a modified hydrolyzable condensate in which at least a portion of the silanol groups of the condensate are acetal-protected, and a dehydration reaction product of the condensate and an alcohol. The silicon-containing resist underlayer film formation composition according to claim 1. (In formula (2), R ３ R represents a group bonded to a silicon atom, independently of each other, representing an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an amide 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 thereof. ４ (where a is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, and a represents an integer from 0 to 3.) 　 The silicon-containing resist underlayer film forming composition according to claim 1, wherein the [C] component contains water. 　 The silicon-containing resist underlayer film forming composition according to claim 1, wherein the [C] component comprises an alcohol-based solvent. 　 The silicon-containing resist underlayer film forming composition according to claim 1, wherein the [C] component comprises a propylene glycol monoalkyl ether. 　 The silicon-containing resist underlayer film forming composition according to claim 1, further comprising nitric acid. 　 A silicon-containing resist underlayer film forming composition according to claim 1, which does not contain a curing catalyst. 　 The silicon-containing resist underlayer film forming composition according to claim 1, further comprising a pH adjusting agent. 　 The silicon-containing resist underlayer film forming composition according to claim 1, further comprising a metal oxide. 　 A silicon-containing resist underlayer film formation composition according to claim 1, for use in EUV lithography. 　 A process of forming an organic underlayer film on a substrate, A step of forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition according to any one of claims 1 to 11, The process includes the step of forming a resist film on the silicon-containing resist underlayer film. A method for manufacturing semiconductor devices. 　 In the process of forming the silicon-containing resist underlayer film, the filtered silicon-containing resist underlayer film forming composition is used. A method for manufacturing a semiconductor device according to claim 12.

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