Membrane Forming Composition

Abstract

[Problem] To provide a film-forming composition for forming a resist underlayer film for a solvent development type resist that is capable of forming a good resist pattern. [Solution] A film-forming composition which contains a hydrolysis-condensation product of a hydrolyzable silane compound, at least one substance that is selected from the group consisting of an aminoplast crosslinking agent and a phenoplast crosslinking agent, and a solvent, and which is characterized in that the hydrolyzable silane compound contains a hydrolyzable silane represented by formula (1).

Description

[Technical Field]

[0001] The present invention relates to a film-forming composition, a resist underlayer film formed from the film-forming composition, and a method for manufacturing a semiconductor device using the film-forming composition. More specifically, the present invention relates to a film-forming composition for forming a resist underlayer film as a hard mask used as a layer beneath a negative-type photoresist in the lithography process of semiconductor device manufacturing. [Background technology]

[0002] Conventionally, microfabrication using lithography with photoresists has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating it with active light such as ultraviolet light through a mask pattern on which the semiconductor device pattern is drawn, developing the photoresist, and then etching the substrate using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the pattern.

[0003] In recent years, as semiconductor devices have become more highly integrated, the wavelengths of the active light used have also tended to decrease, from KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) to EUV light (13.5 nm). Consequently, the thinning of resist layers has become significant. In particular, in a three-layer process consisting of a resist layer, a silicon-containing resist underlayer, and an organic underlayer, the silicon-containing resist underlayer must be able to suppress resist pattern deformation in order to manufacture highly reliable semiconductor devices with good reproducibility.

[0004] Under these circumstances, a technique for suppressing pattern collapse has been reported, for example, a resist underlayer film formation composition containing a silane compound having an onium group (Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2010 / 021290 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] With the recent advancements in the semiconductor device field, the demand for improved technologies, including those that suppress pattern deformation, is becoming increasingly strong. The present invention has been made in view of the above circumstances, and aims to provide a film-forming composition that, when used in a lithography process together with a resist film, or together with a resist underlayer organic underlayer film and a resist film, can suppress pattern collapse and provide a thin film that can achieve a good pattern. [Means for solving the problem]

[0007] To achieve the above objective, the present inventors conducted extensive research and found that when a film obtained from a composition containing a hydrolysis condensate of a hydrolyzable silane compound having a specific functional group and at least one selected from aminoplast crosslinking agents and phenoplast crosslinking agents is used as a resist underlayer in lithography processes such as EB lithography and EUV lithography, together with a resist film, or together with an organic underlayer and a resist film, pattern collapse can be suppressed and a good pattern can be achieved, thus completing the present invention.

[0008] In other words, the present invention relates, in first view, to a film-forming composition comprising a hydrolysis condensate of a hydrolyzable silane compound, at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents, and a solvent, wherein the hydrolyzable silane compound comprises a hydrolyzable silane represented by the following formula (1). [ka] (In formula (1), R 1This represents an organic group that is bonded to a silicon atom by a Si-C bond and includes at least one structure selected from an alkoxymethylbenzene structure, a phenoxy structure, and an epoxy structure. R 2 This refers to a group bonded to a silicon atom by a Si-C bond, which independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, or a sulfonyl group, or a combination thereof. R 3 These are groups or atoms bonded to a silicon atom, and independently represent a hydroxyl group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. 'a' represents an integer of 1, 'b' represents an integer between 0 and 2, and 'a+b' represents an integer between 1 and 3. The second aspect relates to the film-forming compound described in the first aspect, wherein the organic group containing the phenoxy structure is an organic group containing a phenol structure, an alkoxyalkoxybenzene structure, or an alkoxybenzene structure. The third aspect relates to the film-forming composition described in the first aspect, wherein the organic group containing the alkoxymethylbenzene structure is an organic group containing the (alkoxy)(alkoxymethyl)benzene structure. The fourth aspect relates to a film-forming composition according to any one of the first to third aspects, wherein the above-mentioned hydrolyzable silane compound further comprises a hydrolyzable silane represented by the following formula (2). [ka] (In formula (2), R 11(This refers to a group or atom bonded to a silicon atom, which independently represents a hydroxyl group, alkoxy group, aralkyloxy group, acyloxy group, or halogen atom.) The fifth aspect relates to a film-forming composition according to any one of the first to fourth aspects, wherein the above-mentioned hydrolyzable silane compound further comprises a hydrolyzable silane represented by the following formula (3). [ka] (In formula (3), R 12 This refers to a group bonded to a silicon atom by a Si-C bond, which independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, or a sulfonyl group, or a combination thereof. R 13 (This refers to a group or atom bonded to a silicon atom, which independently represents a hydroxyl group, alkoxy group, aralkyloxy group, acyloxy group, or halogen atom.) The sixth aspect relates to a film-forming composition according to any one of the first to fifth aspects, wherein the hydrolysis condensate contains monomer units of hydrolyzable silane represented by formula (1) in a proportion of 0.1 mol% to 15 mol%. The seventh aspect relates to a film-forming composition according to any one of the first to sixth aspects, further comprising an acid catalyst. The eighth aspect relates to the film-forming composition according to the seventh aspect, wherein the acid catalyst comprises at least one selected from the group consisting of triphenylsulfonium trifluoromethanesulfonate and tris(hydroxyphenyl)sulfonium trifluoromethanesulfonate. The ninth aspect relates to a film-forming composition according to any one of the first to eighth aspects, further comprising a curing catalyst. The tenth aspect relates to the film-forming composition described in the ninth aspect, wherein the curing catalyst comprises at least one selected from the group consisting of ammonium salts, phosphines, phosphonium salts, and sulfonium salts. The eleventh aspect relates to a film-forming composition according to any one of the first to tenth aspects, wherein the hydrolyzable silane represented by formula (1) is (4-(1-ethoxyethoxy)phenyl)trimethoxysilane, or trimethoxy(3-(2-oxyranylmethoxy)propyl)silane, or triethoxy((4-ethoxy-2-methoxyphenoxy)methyl)silane. The twelfth aspect relates to a film-forming composition for forming a resist underlayer film used in a lithography process, as described in any one of the first to eleventh aspects. The thirteenth aspect relates to the film-forming composition described in the twelfth aspect, wherein the lithography step is an EB lithography or EUV lithography step. The fourteenth aspect relates to a resist underlayer film obtained from a film-forming composition described in any one of the first to thirteenth aspects. The 15th aspect relates to a semiconductor processing substrate comprising a semiconductor substrate and a resist underlayer film as described in the 14th aspect. The sixteenth aspect relates to a method for producing a film-forming composition according to any one of the first to thirteenth aspects, comprising the steps of: hydrolyzing and condensing the above hydrolyzable silane compound in the presence of nitric acid to produce the above hydrolyzed condensate; and dissolving the hydrolyzed condensate and at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents in a solvent. The 17th aspect relates to a method for manufacturing a semiconductor device, comprising the steps of: forming a resist underlayer film on a semiconductor substrate using a film-forming composition described in any one of the 1st to 13th aspects; forming a resist film on the resist underlayer film; exposing the resist film; solvent developing the resist film after exposure to obtain a resist pattern; etching the resist underlayer film with the resist pattern; and processing the semiconductor substrate with the patterned resist film and the resist underlayer film. The 18th aspect relates to a method for manufacturing a semiconductor device, comprising the steps of: forming an organic underlayer film on a semiconductor substrate; forming a resist underlayer film on the organic underlayer film using a film-forming composition described in any one of the 1st to 13th aspects; forming a resist film on the resist underlayer film; exposing the resist film; solvent developing the resist film after exposure to obtain a resist pattern; etching the resist underlayer film with the resist pattern; and processing the semiconductor substrate with the patterned resist film and the resist underlayer film. [Effects of the Invention]

[0009] The film formed from the film-forming composition of the present invention, when used as a resist underlayer in lithography processes such as EB lithography and EUV lithography together with a resist film, or together with an organic underlayer and a resist film, can suppress pattern deformation and achieve a good pattern. As a result, it is expected that highly reliable semiconductor devices (semiconductor devices) can be manufactured by using this film-forming composition. The reason why pattern collapse can be suppressed when a film obtained from the film-forming composition of the present invention is used as a resist underlayer is not clear, but it is presumed that the film density is improved by a crosslinking reaction between the hydrolysis condensate contained in the composition and at least one crosslinking agent selected from aminoplus, a crosslinking agent and a phenoplast crosslinking agent, and that the diffusion of acid generated in the resist film to the resist underlayer is suppressed, so that the exposed areas of the resist film become sufficiently hydrophilic and pattern collapse due to negative-type (solvent) development can be suppressed, or that the adhesion between the resist underlayer and the resist film is improved as a crosslinking reaction proceeds between the resist film and the resist underlayer, thus suppressing pattern collapse due to negative-type (solvent) development. [Modes for carrying out the invention]

[0010] The present invention will be described in more detail below.

[0011] [Hydrolyzable silane] The film-forming composition of the present invention comprises a hydrolysis condensate of a hydrolyzable silane compound, at least one selected from aminoplast crosslinking agents and phenoplast crosslinking agents, and a solvent. The hydrolyzable silane compound is characterized by containing a hydrolyzable silane represented by the following formula (1). [ka] R 1 This represents an organic group that is bonded to a silicon atom by a Si-C bond and includes at least one structure selected from an alkoxymethylbenzene structure, a phenoxy structure, and an epoxy structure.

[0012] In one aspect, an organic group containing an epoxy structure is an organic group containing an epoxy group-containing benzene structure.

[0013] The silicon atom may be directly bonded to the carbon atom of the benzene ring or the epoxy group in the alkoxymethylbenzene or phenoxy structure contained in the organic group, or it may be bonded via a linking group such as an alkylene group.

[0014] In one embodiment, the silicon atom may be directly bonded to the carbon atom of the benzene ring in the epoxy group-containing benzene structure of the organic group, or it may be bonded via a linking group such as an alkylene group.

[0015] Organic groups containing an alkoxymethylbenzene structure are not particularly limited as long as they contain an organic group in which an alkoxymethyl group is directly bonded to benzene. Examples include organic groups containing a methoxymethylbenzene structure, an ethoxymethylbenzene structure, a propiooxymethylbenzene structure, an alkoxyalkoxymethylbenzene structure, an alkylalkoxymethylbenzene structure, an alkenylalkoxymethylbenzene structure, an alkenyloxyalkoxymethylbenzene structure, an alkylyloxyalkoxymethylbenzene structure, an alkylylalkoxymethylbenzene structure, an alkoxymethylbenzene structure of an alkanoate, an alkoxymethylbenzene structure of an alkenoate, an alkoxymethylbenzene structure of an alkynate, an alkylalkoxymethylbenzene carbonate structure, an [(oxyranyl)alkoxy]alkoxymethylbenzene structure, a 1,2-methylenedioxyalkoxymethylbenzene structure, or an alkoxymethylnaphthalene structure.

[0016] The organic group containing the epoxy structure is not particularly limited as long as it contains an epoxy group, and the epoxy group-containing benzene structure is not particularly limited as long as it contains an epoxy group and a benzene ring. Examples of organic groups containing the epoxy structure include alkyl epoxy groups, cycloalkyl epoxy groups, oxatricycloalkyl groups, oxabicycloalkyl groups, alkoxymethyloxyranyl groups, phenoxymethyloxyranyl groups, oxatricycloalkoxymethyloxyranyl groups, and oxabicycloalkoxymethyloxyranyl groups.

[0017] Organic groups containing a phenoxy structure are not particularly limited as long as they contain a benzene structure with an oxygen atom directly bonded to it, but examples include organic groups containing a phenol structure, alkoxybenzene structure, alkoxyalkoxybenzene structure, alkenyloxybenzene structure, phenoxybenzene structure, phenyl alkanoate structure, phenyl alkenoate structure, phenoxyalkylenebenzene structure, alkylphenyl carbonate structure, [(oxyranyl)alkoxy]benzene structure, 1,2-methylenedioxybenzene structure, or alkoxynaphthalene structure. Among these, organic groups containing a phenol structure, an alkoxyphenyl structure, or an alkoxyalkoxyphenyl structure are preferred from the viewpoint of achieving more reproducible suppression of pattern collapse.

[0018] R 2 This refers to a group bonded to a silicon atom by a Si-C bond, which independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, or a sulfonyl group, or a combination thereof. Here, "optionally substituted" means that, for example, the substituents may be substituted with alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, etc., and if there are two or more substituents, the substituents may bond to each other to form a ring.

[0019] The alkyl group can be linear, branched, or cyclic. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.

[0020] Specific examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl 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, and 3-methyl-n-pentyl group. Examples include, but are not limited to, the following groups: 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, 1-ethyl-2-methyl-n-propyl group, etc.

[0021] 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 Examples of cycloalkyl groups include, but are not limited to, cycloalkyl groups such as -cyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-isopropylcyclopropyl group, 2-isopropylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group; bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0022] The aryl group may be a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused ring aromatic hydrocarbon compound, or a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0023] Specific examples include, but are not limited to, 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, pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl 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.

[0024] 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 the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0025] Specific examples of aralkyl groups include, but are not limited to, phenylmethyl (benzyl) group, 2-phenylethylene group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, and 10-phenyl-n-decyl group.

[0026] Alkyl halogens are alkyl groups in which a halogen atom is substituted, and specific examples of such alkyl groups are the same as those mentioned above. 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. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0027] Specific examples of halogenated alkyl groups include, but are not limited to, monofluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, and perfluoropentyl groups.

[0028] Aryl halides are aryl groups in which a halogen atom is substituted. Specific examples of such aryl groups and halogen atoms are the same as those mentioned above. 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.

[0029] Specific examples of aryl halides include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, and 2,3,5,6-tetrafluorophenyl. Examples of such groups include, but are not limited to, the fluoro-1-naphthyl group, pentafluorophenyl group, 2-fluoro-1-naphthyl group, 3-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, and heptafluoro-2-naphthyl group.

[0030] A halogenated aralkyl group is an aralkyl group in which a halogen atom is substituted. Specific examples of such aralkyl groups and halogen atoms are the same as those mentioned above. The number of carbon atoms in the aralkyl halogenated group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0031] Specific examples of halogenated aralkyl groups include, but are not limited to, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, and 2,3,4,5,6-pentafluorobenzyl.

[0032] An alkoxyalkyl group is an alkyl group substituted with an alkoxy group. The alkyl group substituted with the alkoxy group in an alkoxyalkyl group can be linear, branched, or cyclic. Specific examples of such alkyl groups are the same as those mentioned above. The number of carbon atoms in the alkoxyalkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.

[0033] Specific examples of alkoxy groups that substitute for alkyl groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group Xy group, 3-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, 1-ethyl-2-methyl-n-propoxy group Chain-like or branched alkoxy groups such as xy groups, cyclopropoxy groups, cyclobutoxy groups, 1-methyl-cyclopropoxy groups, 2-methyl-cyclopropoxy groups, cyclopentyloxy groups, 1-methyl-cyclobutoxy groups, 2-methyl-cyclobutoxy groups, 3-methyl-cyclobutoxy groups, 1,2-dimethyl-cyclopropoxy groups, 2,3-dimethyl-cyclopropoxy groups, 1-ethyl-cyclopropoxy groups, 2-ethyl-cyclopropoxy groups, cyclohexyloxy groups, 1-methyl-cyclopentyloxy groups, 2-methyl-cyclopentyloxy groups, 3-methyl-cyclopentyloxy groups Tyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-isopropyl-cyclopropoxy group, 2-isopropyl-cyclopropoxy group, 1,2,Examples include, but are not limited to, cyclic alkoxy groups such as 2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group, and 2-ethyl-3-methyl-cyclopropoxy group. Among these, the alkoxy group in the alkoxyalkyl group is preferably a lower alkyloxy group such as a methoxy group or an ethoxy group, with the methoxy group being more preferred.

[0034] Specific examples of alkoxyalkyl groups include, but are not limited to, lower alkyloxy lower alkyl groups such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, and ethoxymethyl group.

[0035] An alkoxyaryl group is an aryl group substituted with an alkoxy group, and specific examples of such alkoxy and aryl groups are the same as those mentioned above.

[0036] Specific examples of alkoxyaryl groups include, but are not limited to, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphthalen-1-yl, 3-methoxynaphthalen-1-yl, 4-methoxynaphthalen-1-yl, 5-methoxynaphthalen-1-yl, 6-methoxynaphthalen-1-yl, and 7-methoxynaphthalen-1-yl groups.

[0037] An alkoxyaralkyl group is an aralkyl group substituted with an alkoxy group, and specific examples of such alkoxy and aralkyl groups are the same as those mentioned above. The number of carbon atoms in the alkoxyalkoxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0038] Specific examples of alkoxyaralkyl groups include, but are not limited to, the 3-(methoxyphenyl)benzyl group and the 4-(methoxyphenyl)benzyl group.

[0039] The alkenyl group may be linear or branched, and its number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.

[0040] Specific examples of alkenyl groups include ethenyl 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-isopropylethenyl 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-isobutylethenyl 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-isopropyl-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-isopropyl- Examples include, but are not limited to, 2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0041] Examples of organic groups containing epoxy groups include, but are not limited to, glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, and epoxycyclohexyl groups.

[0042] Examples of organic groups containing an acryloyl group include, but are not limited to, acryloylmethyl, acryloylethyl, and acryloylpropyl groups.

[0043] Organic groups containing a methacryloyl group include, but are not limited to, methacryloylmethyl, methacryloylethyl, and methacryloylpropyl groups.

[0044] Examples of the organic group containing a mercapto group include, but are not limited to, an ethyl mercapto group, a butyl mercapto group, a hexyl mercapto group, an octyl mercapto group, etc.

[0045] Examples of the organic group containing an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, etc.

[0046] Examples of the organic group containing the above amide group include -CONR 41 R 42 (R 41 and R 42 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group.) The groups represented by are included. Specific examples and preferred numbers of carbon atoms of the alkyl group, alkenyl group and aryl group are the same as those described above. Specific examples of the organic group containing an amide group include, but are not limited to, an amide group, a methyl amide group, a dimethyl amide group, a methyl ethyl amide group, a diethyl amide group, a dipropyl amide group, a diisopropyl amide group, a dibutyl amide group, etc.

[0047] The alkynyl group may be either linear or branched, and the number of its carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and even more preferably 10 or less. Specific examples of the alkynyl group include, but are not limited to, an ethynyl group, a 1-propynyl group, a 2-propynyl group, etc.

[0048] Examples of the organic group containing an alkoxy group include the organic groups containing the alkoxy group described above, and specific examples of the alkoxy group are the same as those described above.

[0049] Examples of organic groups containing a sulfonyl group include sulfonylalkyl groups and sulfonylaryl groups. Specific examples of such alkyl and aryl groups are the same as those mentioned above.

[0050] R 3 This refers to a group or atom bonded to a silicon atom, which independently represents a hydroxyl group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0051] Specific examples of alkoxy groups and preferred carbon atom numbers include R 2 The same items mentioned above can be cited in relation to this matter.

[0052] The aralkyloxy group is a group derived by removing a hydrogen atom from the hydroxyl group of an aralkyl alcohol. A specific example of such an aralkyl group is R 2 The same items mentioned above can be cited in relation to this matter. The number of carbon atoms in the aralkyloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0053] Specific examples of aralkyloxy groups include, but are not limited to, phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group, 5-phenyl-n-pentyloxy group, 6-phenyl-n-hexyloxy group, 7-phenyl-n-heptyloxy group, 8-phenyl-n-octyloxy group, 9-phenyl-n-nonyloxy group, and 10-phenyl-n-decyloxy group.

[0054] Acyloxy groups are groups derived by removing a hydrogen atom from the carboxyl group of a carboxyl group-containing compound. Typically, examples include, but are not limited to, alkylcarbonyloxy groups, arylcarbonyloxy groups, or aralkylcarbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of 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 include R 2 The same items mentioned above can be cited in relation to this matter.

[0055] Specific examples of acyloxy groups include methyl carbonyloxy group, ethyl carbonyloxy group, n-propyl carbonyloxy group, isopropyl carbonyloxy group, n-butyl carbonyloxy group, isobutyl carbonyloxy group, s-butyl carbonyloxy group, t-butyl carbonyloxy group, n-pentyl carbonyloxy group, 1-methyl-n-butyl carbonyloxy group, 2-methyl-n-butyl carbonyloxy group, 3-methyl-n-butyl carbonyloxy group, 1,1-dimethyl-n-propyl carbonyloxy group, 1,2-dimethyl-n-propyl carbonyloxy group, 2,2-dimethyl-n-propyl carbonyloxy group, 1-ethyl-n-propyl carbonyloxy group, n-hexyl carbonyloxy group, 1-methyl-n-pentyl carbonyloxy group, 2-methyl-n-pentyl carbonyloxy group, and 3-methyl-n-pentylcarbonyloxy group. Examples of carbonyloxy groups include, but are not limited to, phenylcarbonyloxy groups, 4-methyl-n-pentylcarbonyloxy groups, 1,1-dimethyl-n-butylcarbonyloxy groups, 1,2-dimethyl-n-butylcarbonyloxy groups, 1,3-dimethyl-n-butylcarbonyloxy groups, 2,2-dimethyl-n-butylcarbonyloxy groups, 2,3-dimethyl-n-butylcarbonyloxy groups, 3,3-dimethyl-n-butylcarbonyloxy groups, 1-ethyl-n-butylcarbonyloxy groups, 2-ethyl-n-butylcarbonyloxy groups, 1,1,2-trimethyl-n-propylcarbonyloxy groups, 1,2,2-trimethyl-n-propylcarbonyloxy groups, 1-ethyl-1-methyl-n-propylcarbonyloxy groups, 1-ethyl-2-methyl-n-propylcarbonyloxy groups, phenylcarbonyloxy groups, tosylcarbonyloxy groups, etc.

[0056] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0057] a is 1 or 2, and b is 0 or 1, satisfying a+b≦2. However, from the viewpoint of more reproducibly suppressing pattern collapse, it is preferable that a is 1, and more preferably that a is 1 and b is 0.

[0058] The following are specific examples of hydrolyzable silanes represented by formula (1), but are not limited to these. In each formula, T independently represents a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, preferably a hydroxyl group, a methoxy group, and an ethoxy group.

[0059] Below, R 1 Specific examples of hydrolyzable silanes represented by formula (1), where is an organic group containing an alkoxymethylbenzene structure, are (1-A-1) to (1-A-27), but are not limited to these. [ka] [ka]

[0060] Below, R 1 Specific examples of hydrolyzable silanes represented by formula (1), where is an organic group containing a phenoxy structure, are (1-B-1) to (1-B-66), but are not limited to these. [ka] [ka] [ka] [ka]

[0061] Below, R 1 Specific examples of hydrolyzable silanes represented by formula (1), where is an organic group containing an epoxy structure, include (1-C-1) to (1-C-10), but are not limited to these. [ka]

[0062] In the present invention, for the purpose of adjusting film properties such as film density, the above hydrolyzable silane compound may include at least one selected from the hydrolyzable silane represented by formula (2) and the hydrolyzable silane represented by formula (3), along with the hydrolyzable silane represented by formula (1). [ka]

[0063] R in equation (2) 11 and R in equation (3) 13 Each of these is a group or atom bonded to a silicon atom, and independently represents a hydroxyl group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. Specific examples of alkoxy groups, aralkyloxy groups, and acyloxy groups, and preferred carbon atom numbers, are as follows: 3 The same examples mentioned above can be cited. Furthermore, specific examples of halogen atoms include R 3 The same as those mentioned above can be cited. Among these, hydroxyl groups, methoxy groups, or ethoxy groups are preferred.

[0064] R in equation (3) 12 This refers to a group bonded to a silicon atom by a Si-C bond, which independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, or a sulfonyl group, or a combination thereof. Specific examples and preferred number of carbon atoms for alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, epoxy groups, acryloyl groups, methacryloyl groups, mercapto groups, amino groups, amide groups, alkoxy groups, and sulfonyl groups include R 2 The same items mentioned above can be cited in relation to this matter.

[0065] Specific examples of hydrolyzable silanes represented by formula (2) include, but are not limited to, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, and tetran-butoxysilane. Among these, tetramethoxysilane and tetraethoxysilane are preferred from the viewpoint of reproducibly suppressing pattern collapse.

[0066] Specific examples of hydrolyzable silanes represented by formula (3) include methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamiloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methoxyphenyltrimethoxysilane, methyltriethoxysilane Xyphenyltriethoxysilane, Methoxyphenyltriacetoxysilane, Methoxyphenyltrichlorosilane, Methoxybenzyltrimethoxysilane, Methoxybenzyltriethoxysilane, Methoxybenzyltriacetoxysilane, Methoxybenzyltrichlorosilane, Methoxyphenethyltrimethoxysilane, Methoxyphenethyltriethoxysilane, Methoxyphenethyltriacetoxysilane, Methoxyphenethyltrichlorosilane, Ethoxyphenyltrimethoxysilane, Ethoxyphenyltriethoxysilane, Ethoxyphenyltriacetoxysilane Toxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxy Poxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane,Examples include, but are not limited to, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, and chloromethyltriethoxysilane. Among these, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane are preferred from the viewpoint of reproducibly suppressing pattern collapse.

[0067] [Hydrolyzed condensate] The hydrolysis condensate contained in the film-forming composition of the present invention can be obtained by hydrolysis and condensation of a hydrolyzable silane compound containing a hydrolyzable silane represented by formula (1). In this invention, the term "hydrolyzed condensate" 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 compounds, similar to condensates in which condensation is completely completed, but the hydrolysis stops only partially and condensation does not occur, and therefore Si-OH groups remain. Furthermore, the film-forming composition of the present invention may contain, in addition to hydrolyzed condensates, uncondensed hydrolyzates (complete hydrolyzates, partially hydrolyzed condensates) and monomers (hydrolyzable silane compounds).

[0068] The hydrolysis condensate contained in the film-forming composition of the present invention is a hydrolysis condensate obtained using a hydrolysis silane compound containing at least one hydrolyzable silane represented by formula (1) as a raw material. A preferred example is a hydrolysis condensate obtained using a hydrolysis silane compound containing at least one hydrolyzable silane represented by formula (1) and at least one hydrolyzable silane represented by formula (2) as a raw material, or a hydrolysis condensate obtained using a hydrolysis silane compound containing at least one hydrolyzable silane represented by formula (1) and at least one hydrolyzable silane represented by formula (3) as a raw material. A more preferred example is a hydrolysis condensate obtained using a hydrolysis silane compound containing at least one hydrolyzable silane represented by formula (1), at least one hydrolyzable silane represented by formula (2), and at least one hydrolyzable silane represented by formula (3) as a raw material.

[0069] The hydrolyzable silanes represented by formulas (1) to (3) used in the present invention have an alkoxy group, aralkyloxy group, acyloxy group, or halogen atom directly bonded to a silicon atom, and contain a hydrolyzable group which is an alkoxysilyl group, aralkyloxysilyl group, acyloxysilyl group, or silyl halogenated group. For its hydrolysis and condensation, typically 0.5 moles to 100 moles, preferably 1 mole to 10 moles, of water are used per mole of hydrolyzable group.

[0070] The reaction temperature during hydrolysis and condensation is not particularly limited as long as the hydrolysis and condensation proceed, but it is usually between 20 and 80°C.

[0071] Typically, a catalyst is used during hydrolysis and condensation. Examples of such catalysts include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases, and these may be used individually or in combination of two or more. Examples of metal chelate compounds used as catalysts for hydrolysis and condensation include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-isopropoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-s-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, and di-n-propoxy bis(acetylacetonate) Titanium, di-isopropoxy-bis(acetylacetonate)titanium, di-n-butoxy-bis(acetylacetonate)titanium, di-s-butoxy-bis(acetylacetonate)titanium, di-t-butoxy-bis(acetylacetonate)titanium, monoethoxy-tris(acetylacetonate)titanium, mono-n-propoxy-tris(acetylacetonate)titanium, mono-isopropoxy-tris(acetylacetonate)titanium, mono-n-butoxy-tris(acetylacetonate)titanium, mono-s-butoxy-tris(acetylacetonate)titanium Titanium acetylacetonate, mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-isopropoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-s-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethylacetoacetate) Titanium di-n-propoxy bis(ethyl acetate) titanium, di-isopropoxy bis(ethyl acetate) titanium, di-n-butoxy bis(ethyl acetate) titanium, di-s-butoxy bis(ethyl acetate) titanium, di-t-butoxy bis(ethyl acetate) titanium, monoethoxy tris(ethyl acetate) titanium, mono-n-propoxy tris(ethyl acetate) titanium, mono-isopropoxy tris(ethyl acetate) titanium,Titanium chelate compounds such as mono-n-butoxy tris(ethyl acetate) titanium, mono-s-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, and tris(acetylacetonate) mono(ethyl acetate) titanium; triethoxy mono(acetylacetonate) zil Zirconium, tri-n-propoxy mono(acetylacetonate)zirconium, tri-isopropoxy mono(acetylacetonate)zirconium, tri-n-butoxy mono(acetylacetonate)zirconium, tri-s-butoxy mono(acetylacetonate)zirconium, tri-t-butoxy mono(acetylacetonate)zirconium, diethoxy bis(acetylacetonate)zirconium, di-n-propoxy bis(acetylacetonate)zirconium, di-isopropoxy bis(acetylacetonate)zirconium Di-n-butoxy bis(acetylacetonate) zirconium, di-s-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-isopropoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-s-butoxy tris(acetylacetonate) zirconium M, mono-t-butoxy tris(acetylacetonate) zirconium, tetrakis(acetylacetonate) zirconium, triethoxy mono(ethylacetoacetate) zirconium, tri-n-propoxy mono(ethylacetoacetate) zirconium, tri-isopropoxy mono(ethylacetoacetate) zirconium, tri-n-butoxy mono(ethylacetoacetate) zirconium, tri-s-butoxy mono(ethylacetoacetate) zirconium, tri-t-butoxy mono(ethylacetoacetate) zirconium,Diethoxy-bis(ethylacetate)zirconium, di-n-propoxy-bis(ethylacetate)zirconium, di-isopropoxy-bis(ethylacetate)zirconium, di-n-butoxy-bis(ethylacetate)zirconium, di-s-butoxy-bis(ethylacetate)zirconium, di-t-butoxy-bis(ethylacetate)zirconium, monoethoxy-tris(ethylacetate)zirconium, mono-n-propoxy-tris(ethylacetate)zirconium, mono-isopropoxy-tris(ethylacetate)zirconium, mono-n-butoxy-tris(ethylacetate) Examples of zirconium chelate compounds include zirconium, mono-s-butoxy tris(ethylacetate)zirconium, mono-t-butoxy tris(ethylacetate)zirconium, tetrakis(ethylacetate)zirconium, mono(acetylacetonate)tris(ethylacetate)zirconium, bis(acetylacetonate)bis(ethylacetate)zirconium, tris(acetylacetonate)mono(ethylacetate)zirconium, etc.; and aluminum chelate compounds such as tris(acetylacetonate)aluminum and tris(ethylacetate)aluminum, etc., but are not limited to these.

[0072] Examples of organic acids used as catalysts for hydrolysis and condensation 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, 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, and the like. Examples of inorganic acids used as catalysts for hydrolysis and condensation include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid. In a preferred embodiment of the present invention, the hydrolyzable silane compound is hydrolyzed and condensed in the presence of nitric acid to produce a hydrolysis condensate.

[0073] Examples of organic bases used as catalysts for hydrolysis and condensation 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. Examples of inorganic bases used as catalysts for hydrolysis and condensation include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, with nitric acid being particularly preferred.

[0074] Typically, the hydrolysis and condensation of hydrolyzable silane compounds are carried out in a solvent. Solvents used for hydrolysis and condensation include, for example, aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, n-amylnaphthalene, and trimethylbenzene; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, s-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, s-hexanol, and 2-ethylbutanol. Monoalcohol solvents such as tanol, s-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, s-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, s-undecyl alcohol, trimethylnonyl alcohol, s-tetradecyl alcohol, s-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, 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-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and phenthion; ethyl ether, isopropyl 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 Ether-based solvents such as mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, s-butyl acetate, n-pentyl acetate, s-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 mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monopropyl ether acetate Examples of ester solvents include ethyl ethers, dipropylene glycol acetate monomethyl ether, dipropylene glycol acetate monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, isoamyl 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-methylpyrrolidone; 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. Among these, ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and phenthone are preferred in terms of the storage stability of the solution.

[0075] When using a silane other than the hydrolyzable silane represented by formula (1) as the hydrolyzable silane, the amount of the hydrolyzable silane represented by formula (1) is usually 0.1 mol% or more of the total hydrolyzable silanes. However, from the viewpoint of obtaining the above effects of the present invention with good reproducibility, it is preferably 0.5 mol% or more, more preferably 1 mol% or more, and even more preferably 5 mol% or more. When using hydrolyzable silane represented by formula (2), the amount used can be typically 99.9 mol% or less, preferably 50 mol% to 80 mol%, and more preferably 60 mol% to 80 mol%, of the total hydrolyzable silane. When using hydrolyzable silane represented by formula (3), the amount added can be typically 99.9 mol% or less, preferably 0.1 mol% to 50 mol%, and more preferably 10 mol% to 30 mol%, of the total hydrolyzable silane. In a preferred embodiment, the hydrolysis condensate contained in the film-forming composition of the present invention is obtained using a hydrolyzable silane represented by formula (1) along with other hydrolyzable silanes as the hydrolyzable silane, and such a hydrolysis condensate preferably contains monomer units of the hydrolyzable silane represented by formula (1) in an amount of 0.1 mol% to 20 mol%, more preferably 0.1 mol% to 15 mol%, and even more preferably 0.1 mol% to 10 mol%, of the total monomer units, and the remainder contains monomer units of other hydrolyzable silanes, preferably monomer units of the hydrolyzable silane represented by formula (2) and monomer units of the hydrolyzable silane represented by formula (3).

[0076] The weight-average molecular weight of the hydrolysis condensate in the present invention is usually 500 to 1,000,000, but from the viewpoint of suppressing the precipitation of the hydrolysis condensate in the composition, it is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less, and from the viewpoint of achieving both storage stability and applicability, it is preferably 700 or more, and more preferably 1,000 or more. The weight-average molecular weight is the molecular weight obtained by converting it to polystyrene using GPC analysis. GPC analysis can be performed, for example, using a GPC instrument (product name HLC-8220GPC, manufactured by Tosoh Corporation) and a GPC column (product names Shodex KF803L, KF802, KF801, manufactured by Showa Denko K.K.), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as the standard sample.

[0077] Under the conditions described above, a hydrolyzable silane compound can be hydrolyzed and condensed to produce a hydrolyzed condensate. After the reaction is complete, the acid catalyst used for hydrolysis and condensation can be removed from the reaction solution by neutralizing it, either as is, diluted, or concentrated, or by treating it with an ion exchange resin. Alternatively, by-products such as alcohol, water, and catalyst can be removed from the reaction solution by vacuum distillation or other methods before or after such treatment. If necessary, after such purification, the hydrolysis condensate can be obtained as a solid or as a solution containing the hydrolysis condensate by distilling off all or part of the solvent from the solution containing the hydrolysis condensate.

[0078] [Crosslinking agent] The film-forming composition of the present invention comprises at least one crosslinking agent selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents. When the aminoplast crosslinking agent and the phenoplast crosslinking agent are exposed to high temperatures during thermal curing, a crosslinking reaction proceeds between them and the hydrolysis condensate used in the present invention.

[0079] The amount of aminoplast crosslinking agent and phenoplast crosslinking agent contained in the film-forming composition of the present invention is typically 0.01 to 40% by mass in total relative to the hydrolysis condensate. From the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 0.05% by mass, preferably 0.1% by mass, more preferably 1% by mass, and even more preferably 2% by mass. From the viewpoint of suppressing the precipitation of the crosslinking agent in the composition and preparing a composition with excellent storage stability, the upper limit is preferably 30% by mass, more preferably 25% by mass, even more preferably 20% by mass, and even more preferably 15% by mass.

[0080] The aminoplast crosslinking agent is not particularly limited as long as it has two or more methoxymethylene groups in one molecule, and examples include the following compounds (A-1) to (A-10), with 1,3,4,6-tetrakis(methoxymethyl)tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione (A-1) being a representative example. Other examples include compounds such as methoxymethylated glycoluryl, butoxymethylated glycoluryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and butoxymethylated thiourea. [ka]

[0081] The phenoplast crosslinking agent is not particularly limited as long as it has two or more hydroxymethylene groups in one molecule. Examples include the following compounds (B-1) to (B-32), with 3,3',5,5'-tetrakis(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol (B-24) being a representative example. [ka] [ka]

[0082] [solvent] The film-forming composition of the present invention contains a solvent. Such solvents are not limited as long as they dissolve the solids. In this invention, "solids" refers to components other than the solvent contained in the composition.

[0083] Specific examples of solvents used in the present invention include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyethyl acetate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethyl Ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate,Isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyethyl, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl, ethyl ethoxyethyl, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methyl Examples of suitable solvents include butylpropionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. The solvent can be used individually or in combination of two or more.

[0084] Furthermore, the film-forming composition of the present invention may contain water as a solvent, and the amount of water is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, relative to the solvent contained in the composition.

[0085] [Acid catalyst] The film-forming composition of the present invention may contain an acid generator as an acid catalyst. By including such an acid catalyst, it becomes possible to efficiently promote crosslinking between the hydrolysis condensate and the aminoplast crosslinking agent or phenoplast crosslinking agent. As a result, pattern collapse can be suppressed with greater reproducibility. Examples of acid generators include thermal acid generators and photoacid generators. The thermal acid generator produces acid when the film-forming composition is heated, and the photoacid generator produces acid when the film-forming composition is exposed to light. Therefore, no acid is generated during storage of the film-forming composition, improving storage stability, and the curing process can be accelerated when the film hardens.

[0086] Examples of thermal acid generators included in the film-forming composition of the present invention include, but are not limited to, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other alkyl organic sulfonates. Examples of photoacid generators include, but are not limited to, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0087] Specific examples of onium salt compounds include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, tris(4-hydroxyphenyl)sulfonium trifluoromethanesulfonate (tris(4-hydroxyphenyl)sulfonium trifluoromethanesulfonate), and triphenylsulfonium trifluoromethanesulfonate (triphenylsulfonium trifluoromethanesulfonate).

[0088] 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.

[0089] 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. Acid generators can be used individually or in combination of two or more types. That is, a single photoacid generator can be used, or two or more types can be used in combination. Similarly, a single thermal acid generator can be used, or two or more types can be used in combination. Furthermore, a combination of a photoacid generator and a thermal acid generator is also possible.

[0090] Of these, the following photoacid generators are preferred. [ka]

[0091] When the film-forming composition of the present invention contains an acid generator, its content 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 the hydrolysis condensate of the hydrolyzable silane compound. From the viewpoint of suppressing the precipitation of the acid generator in the composition, it is preferably 3% by mass or less, more preferably 1% by mass or less, and from the viewpoint of obtaining its effect sufficiently, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

[0092] [Curing catalyst] The film-forming composition of the present invention may contain a curing catalyst. The curing catalyst is used to react the OH groups remaining in the hydrolysis condensate with Si-O-Si bonds within the hydrolysis condensate, between hydrolysis condensates, or between hydrolysis condensates and hydrolysates. By including a curing catalyst in the film-forming composition of the present invention, pattern collapse can be suppressed with even greater reproducibility. Furthermore, the curing catalyst may also possess the function of an acid catalyst. Ammonium salts, phosphines, phosphonium salts, and sulfonium salts can be used as curing catalysts.

[0093] As an ammonium salt, formula (D-1): [ka] (However, m is an integer between 2 and 11, n1 is an integer between 2 and 3, R 21 Y is an alkyl or aryl group. A - The symbols represent the anions. Quaternary ammonium salts having the structure shown by formula (D-2): [ka] (However, R 22 , R 23 , R 24 and R 25 is an alkyl or aryl group, N is a nitrogen atom, Y is a nitrogen atom. A - Each represents an anion, and R 22 , R 23 , R 24 , and R 25 Each of these is bonded to a nitrogen atom by a CN bond. ) Quaternary ammonium salts having the structure shown, Formula (D-3): [ka] (However, R 26 and R 27 Y is an alkyl or aryl group. A - The symbols represent anions, respectively. ) Quaternary ammonium salts having the structure shown, Formula (D-4): [ka] (However, R 28 Y is an alkyl or aryl group. A -The symbols represent anions, respectively. ) Quaternary ammonium salts having the structure shown, Formula (D-5): [ka] (However, R 29 and R 30 Y is an alkyl or aryl group. A - The symbols represent anions, respectively. ) Quaternary ammonium salts having the structure shown, Formula (D-6): [ka] (However, m is an integer from 2 to 11, n1 is an integer from 2 to 3, H is a hydrogen atom, Y A - Examples include tertiary ammonium salts having the structure shown by (where ) represents anion.

[0094] Furthermore, as a phosphonium salt, formula (D-7): [ka] (However, R 31 , R 32 , R 33 , and R 34 P represents an alkyl or aryl group, P represents a phosphorus atom, and Y represents a phosphorus atom. A - Each represents an anion, and R 31 , R 32 , R 33 , and R 34 These are all linked to the phosphorus atom by CP bonds. An example is the quaternary phosphonium salt represented by ).

[0095] Furthermore, as a sulfonium salt, formula (D-8): [ka] (However, R 35 , R 36 , and R 37represents an alkyl group or an aryl group, S represents a sulfur atom, Y A - represents an anion respectively, and R 35 , R 36 , and R 37 are each bonded to the sulfur atom by a C - S bond. Examples include tertiary sulfonium salts represented by ().

[0096] The compound represented by formula (D - 1) is a quaternary ammonium salt derived from an amine. m represents an integer from 2 to 11, and n1 represents an integer from 2 to 3 respectively. For this quaternary ammonium salt, R 21 represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, or an aryl group. Examples include linear alkyl groups such as an ethyl group, a propyl group, and a butyl group, and aryl groups such as a benzyl group, a cyclohexyl group, a cyclohexylmethyl group, and a dicyclopentadienyl group. Also, the anion (Y A - ) can include halogen ions such as a chloride ion (Cl - ), a bromide ion (Br - ), an iodide ion (I - ), and acid groups such as a carboxylate (-COO - ), a sulfonate (-SO3 - ), and an alcoholate (-O - ).

[0097] The compound represented by formula (D - 2) is a quaternary ammonium salt represented by R 22 R 23 R 24 R 25 N + Y A - For this quaternary ammonium salt, R 22 , R 23 , R 24 and R 25 represent an alkyl group or an aryl group having 1 to 18 carbon atoms. Examples include linear alkyl groups such as an ethyl group, a propyl group, and a butyl group, and aryl groups such as a benzyl group, a cyclohexyl group, a cyclohexylmethyl group, and a dicyclopentadienyl group. The anion (Y A- ) includes halogen ions such as chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ), etc., and acid groups such as carboxylate (-COO - ), sulfonate (-SO3 - ), alcoholate (-O - ), etc. This quaternary ammonium salt can be obtained as a commercially available product. Examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, etc.

[0098] The compound represented by formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, and R 26 and R 27 are an alkyl group having 1 to 18 carbon atoms or an aryl group, and the total number of carbon atoms of R 26 [[ID=​​​​​​​​​​​​​​​​​​​​​​

[0099] The compound represented by formula (D-4) is a quaternary ammonium salt derived from pyridine, and R 28 The group is an alkyl group or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, and examples include a butyl group, octyl group, benzyl group, and lauryl group. Anion (Y A - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - ) and halogen ions such as carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting pyridine with an alkyl halide or aryl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0100] The compound represented by formula (D-5) is a quaternary ammonium salt derived from substituted pyridines such as picoline, and R 29 R is an alkyl group or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, and examples include a methyl group, octyl group, lauryl group, benzyl group, etc. 30 R is an alkyl group having 1 to 18 carbon atoms, or an aryl group. 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 A - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - ) and halogen ions such as carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O- Examples of acidic groups include those listed above. 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 represented by formula (D-6) is a tertiary ammonium salt derived from an amine, where m is an integer from 2 to 11 and n1 is an integer from 2 to 3. Also, the anion (Y A - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - ) and halogen ions such as carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include (Y). It 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 A - ) is (HCOO - ) and when acetic acid is used, the anion (Y A - ) is (CH3COO - ) is also used. In addition, when phenol is used, the anion (Y A - ) is (C6H5O - )

[0102] The compound represented by formula (D-7) is R 31 R 32 R 33 R 34 P + Y A - It is a quaternary phosphonium salt having the structure R 31, R 32 , R 33 , and R 34 R represents an alkyl group or aryl group having 1 to 18 carbon atoms, for example, linear alkyl groups such as ethyl group, propyl group, and butyl group, or benzyl group, cyclohexyl group, cyclohexylmethyl group, and dicyclopentadienyl group. 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 or aryl group having 1 to 18 carbon atoms. Also, the anion (Y A - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - ) and halogen ions such as carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O -Examples of acidic groups include ) and others. This compound is available commercially, and examples include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritrilmonoarylphosphonium halide, or tritrilmonoalkylphosphonium halide (where 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 (where 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 represented by formula (D-8) is R 35 R 36 R 37 S + Y A - It is a tertiary sulfonium salt having the structure R35 , R 36 , and R 37 R represents an alkyl group or aryl group having 1 to 18 carbon atoms, for example, linear alkyl groups such as ethyl group, propyl group, and butyl group, or benzyl group, cyclohexyl group, cyclohexylmethyl group, and dicyclopentadienyl group. Preferably R 35 ~R 37 Three of the four substituents are phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group or aryl group having 1 to 18 carbon atoms. Also, an anion (Y A - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - ) and halogen ions such as carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acid groups include maleate anions and nitrate anions. This compound is commercially available and includes, for example, tetraalkylsulfonium halides such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, trialkylbenzylsulfonium halides such as diethylbenzylsulfonium halide, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halide and diphenylethylsulfonium halide, triphenylsulfonium halide (halogen atom is chlorine atom or bromine atom), tetraalkylphosphonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, trialkylbenzylsulfonium 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, in this invention, a nitrogen-containing silane compound can be added as a curing catalyst. Examples of nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0106] Among these curing catalysts, preferred examples include sulfonium salt compounds such as triphenylsulfonium adamantane carboxylate trifluoroethanesulfonate (sulfonate), triphenylsulfonium p-toluenesulfonate (sulfonate), triphenylsulfonium methanesulfonate (sulfonate), triphenylsulfonium phenolsulfonate (sulfonate), triphenylsulfonium nitrate (nitrate), triphenylsulfonium maleate, bis(triphenylsulfonium) maleate, triphenylsulfonium hydrochloride, triphenylsulfonium acetate, triphenylsulfonium trifluoroacetate, triphenylsulfonium salicylate, triphenylsulfonium benzoate, and triphenylsulfonium hydroxide, with triphenylsulfonium nitrate being particularly preferred. The curing catalyst is present in an amount of 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass, per 100 parts by mass of polyorganosiloxane.

[0107] [Stabilizer] Furthermore, the film-forming composition of the present invention may contain organic acids, water, alcohol, etc., for purposes such as stabilizing hydrolysis condensates contained in the film-forming composition.

[0108] Specific examples of organic acids that the film-forming composition of the present invention may contain for the above purpose include, but are not limited to, oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, salicylic acid, etc. Among these, oxalic acid and maleic acid are preferred. If the film-forming composition of the present invention contains an organic acid, its content is 0.1% to 5.0% by mass relative to the total mass of the hydrolysis condensate.

[0109] The water that may be included in the film-forming composition of the present invention for the above purpose can be pure water, ultrapure water, ion-exchanged water, etc. If the film-forming composition of the present invention contains water, its content may be 1 to 20 parts by mass per 100 parts by mass of the film-forming composition. Water may serve both as a stabilizer and a solvent.

[0110] The alcohol that may be included in the film-forming composition of the present invention for the above purpose is preferably one that evaporates easily upon heating after application. Specific examples include lower aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, and butanol. If the film-forming composition of the present invention contains alcohol, the amount of alcohol is 1 to 20 parts by mass per 100 parts by mass of the film-forming composition. The alcohol may serve as both a stabilizer and a solvent.

[0111] [pH adjuster] Furthermore, the film-forming composition of the present invention may contain a pH adjusting agent as needed. As the pH adjusting agent, bisphenol S or a bisphenol S derivative may be added. The amount of bisphenol S or a bisphenol S derivative is 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, per 100 parts by mass of the hydrolysis condensate.

[0112] The following are specific examples of bisphenol S and bisphenol S derivatives (C-1) to (C-23), but are not limited to these. [ka]

[0113] [Surfactants] Furthermore, the film-forming composition of the present invention may optionally contain a surfactant. Surfactants are particularly effective in suppressing the occurrence of pinholes, striations, and the like when the film-forming composition of the present invention is applied to a substrate as a composition for forming an underlayer film of a lithography resist. Specific examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monopalmitate. Examples of nonionic surfactants include polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc.); and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these. Surfactants can be used individually or in combination of two or more types.

[0114] When the film-forming composition of the present invention contains a surfactant, its content is usually in the range of 0.0001 parts by mass to 5 parts by mass per 100 parts by mass of the hydrolysis condensate. However, from the viewpoint of suppressing precipitation in the composition, it is preferably 1 part by mass or less, and from the viewpoint of obtaining its effect sufficiently, it is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more.

[0115] Furthermore, the film-forming composition of the present invention may contain rheology modifiers, adhesion aids, etc. Rheology modifiers are effective in improving the fluidity of the film-forming composition. Adhesion aids are effective in improving the adhesion between the resist underlayer film obtained from the film-forming composition of the present invention and an organic underlayer film, a semiconductor substrate, or a resist.

[0116] The film-forming composition of the present invention can be produced by mixing the hydrolysis condensate of the above-mentioned hydrolyzable silane with at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents, a solvent, and other components if any are included. In this case, a solution containing the hydrolysis condensate, etc., may be prepared in advance and this solution may be mixed with the solvent and other components. The mixing order is not particularly limited. For example, a solvent may be added to a solution containing hydrolysis condensates, etc., and mixed, and then other components may be added to the mixture. Alternatively, the solution containing hydrolysis condensates, etc., the solvent, and the other components may be mixed simultaneously. If necessary, additional solvent may be added at the end, or some components that are relatively soluble in the solvent may be omitted from the mixture and added at the end. However, from the viewpoint of suppressing aggregation and separation of constituent components and preparing a composition with excellent uniformity and reproducibility, it is preferable to prepare a solution in which the hydrolysis condensates, etc. are well dissolved in advance and use this to prepare the composition. Note that hydrolysis condensates, etc. may aggregate or precipitate when mixed with other components, depending on the type and amount of solvent mixed together, and the amount and properties of other components. Also, when preparing a composition using a solution in which hydrolysis condensates, etc. are dissolved, note that it is necessary to determine the concentration of the hydrolysis condensate solution and the amount used so that the amount of hydrolysis condensates, etc. in the final composition is the desired amount. During the preparation of the composition, heating may be used as appropriate, provided that the components do not decompose or deteriorate.

[0117] In the present invention, the film-forming composition may be filtered using a sub-micrometer-order filter or the like during the manufacturing process or after all components have been mixed.

[0118] The concentration of solids in the film-forming composition of the present invention is usually 0.1% to 50% by mass relative to the mass of the composition, but is preferably 30% or less by mass, and more preferably 25% or less by mass, from the viewpoint of suppressing the precipitation of solids. From the viewpoint of reproducibly obtaining the effects of the present invention described above, the proportion of hydrolyzable silane compound hydrolysis condensates in the solid content is usually 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and still more preferably 90% by mass or more.

[0119] The film-forming composition of the present invention can be suitably used as a composition for forming a resist underlayer film in a lithography process including a negative-type development process.

[0120] In one embodiment of the present invention, a resist underlayer film forming composition, comprising the film-forming composition of the present invention, is applied to a substrate used in the manufacture of a semiconductor device (for example, a silicon wafer substrate, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, and a low-k material coated substrate, etc.) by an appropriate coating method such as a spinner or coater, and then fired to form the resist underlayer film of the present invention. The firing conditions are usually selected as appropriate from a firing temperature of 80°C to 250°C and a firing time of 0.3 minutes to 60 minutes, but preferably a firing temperature of 150°C to 250°C and a firing time of 0.5 minutes to 2 minutes.

[0121] The resist underlayer film of the present invention may further contain a metal oxide. Examples of such metal oxides 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).

[0122] The thickness of the resist underlayer film of the present invention 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.

[0123] Next, a photoresist film is formed on the resist underlayer film of the present invention. The photoresist film can be formed by a well-known method, namely by coating the photoresist composition onto the resist underlayer film of the present invention and firing it. The thickness of the photoresist film is, for example, 50 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm.

[0124] In another aspect of the present invention, an organic underlayer film can be formed on a substrate, followed by the formation of the resist underlayer film of the present invention, and then a photoresist film on top of that. This narrows the pattern width of the photoresist film, and even when the photoresist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, the resist underlayer film of the present invention can be processed using a fluorine-based gas that can achieve a sufficiently fast etching rate for the photoresist film as the etching gas, the organic underlayer film can be processed using an oxygen-based gas that can achieve a sufficiently fast etching rate for the resist underlayer film of the present invention as the etching gas, and the substrate can be processed using a fluorine-based gas that can achieve a sufficiently fast etching rate for the organic underlayer film as the etching gas.

[0125] The photoresist material used in the photoresist film formed on the resist underlayer film of the present invention is not particularly limited as long as it is sensitive to the light used for exposure. Both negative-type and positive-type photoresist materials can be used, and specific examples include, but are not limited to, a positive-type photoresist material consisting of a 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 film, 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 film 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.), and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, fluorine-containing polymer-based photoresists, such as those described in Proc.SPIE, Vol.3999, 330-334(2000), Proc.SPIE, Vol.3999, 357-364(2000), and Proc.SPIE, Vol.3999, 365-374(2000), can also be suitably used.

[0126] Next, exposure is performed through a predetermined mask. For exposure, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), etc., can be used. After exposure, post-exposure baking can be performed as needed. Post-exposure baking is carried out under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0127] In this invention, instead of a photoresist material, an electron beam lithography resist or an EUV lithography resist material can be used as the resist material. For electron beam lithography, both negative and positive resist materials can be used. Specific examples include, but are not limited to, 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 film; 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; 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. For EUV lithography, methacrylate resin-based resist materials can be used.

[0128] Next, development is performed using a developer (for example, an alkaline developer). This removes the photoresist material from the exposed areas, if, for example, a positive-type photoresist material is used, and a photoresist film pattern is formed. Specific examples of developing solutions include, but are not limited to, 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.

[0129] In this invention, an organic solvent can be used as the developer. That is, development is performed with the developer (organic solvent) after exposure. As a result, for example, when a negative-type photoresist material is used, the photoresist film in the unexposed areas is removed, and a photoresist film pattern is formed. Specific examples of organic solvents that can be used as such developers include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl Formate acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, Examples of such substances include, but are not limited to, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc.

[0130] If necessary, the developing solution may contain surfactants or other additives.

[0131] Development is carried out under conditions appropriately selected from a temperature of 5°C to 50°C and a development time of 10 seconds to 600 seconds.

[0132] Then, using the pattern of the photoresist film (upper layer) formed in this manner as a protective film, the resist underlayer film (intermediate layer) of the present invention is removed. Next, using the film consisting of the patterned photoresist film and the resist underlayer film (intermediate layer) of the present invention as a protective film, the organic underlayer film (lower layer) is removed. Finally, using the patterned resist underlayer film (intermediate layer) and organic underlayer film (lower layer) of the present invention as protective films, the semiconductor substrate is processed.

[0133] First, the resist underlayer (intermediate layer) of the present invention in the area where the photoresist film has been removed is removed by dry etching to expose the semiconductor substrate. For dry etching the resist underlayer film of the present invention, gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. For dry etching of the resist underlayer, it is preferable to use a halogen-based gas. Dry etching with halogen-based gases generally does not effectively remove photoresist films composed of organic materials. In contrast, the resist underlayer of the present invention, which contains a large amount of silicon atoms, is rapidly removed by halogen-based gases. Therefore, the reduction in the thickness of the photoresist film associated with dry etching of the resist underlayer can be suppressed. As a result, it becomes possible to use the photoresist film as a thin film. Dry etching of the resist underlayer is preferably performed using a fluorine-based gas. Examples of fluorine-based gases include, but are not limited to, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0134] Subsequently, the organic underlayer film is removed using a protective film consisting of the patterned photoresist film and the resist underlayer film of the present invention. The organic underlayer film (underlayer) is preferably removed by dry etching with an oxygen-based gas. This is because the resist underlayer film of the present invention, which contains many silicon atoms, is difficult to remove by dry etching with an oxygen-based gas.

[0135] Finally, the semiconductor substrate is processed. Preferably, the semiconductor substrate is processed by dry etching using a fluorine-based gas. Examples of fluorinated gases include, but are not limited to, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0136] An organic anti-reflective coating can be formed on top of the resist underlayer of the present invention before the formation of the photoresist film. There are no particular restrictions on the anti-reflective coating composition used; for example, any composition conventionally used in lithography processes can be arbitrarily selected and used, and the anti-reflective coating can be formed by conventional methods, such as coating with a spinner or coater and firing.

[0137] The substrate on which the resist underlayer film forming composition comprising the film-forming composition of the present invention is coated may have an organic or inorganic anti-reflective coating formed on its surface by CVD or the like, and the resist underlayer film of the present invention can be formed on it. Even when an organic underlayer film is formed on the substrate and then the resist underlayer film of the present invention is formed on it, the substrate used may have an organic or inorganic anti-reflective coating formed on its surface by CVD or the like.

[0138] The resist underlayer formed from the resist underlayer formation composition of the present invention may also have absorption properties for certain wavelengths of light used in the lithography process. In such cases, it can function as an anti-reflective film that prevents reflected light from the substrate. Furthermore, the resist underlayer of the present invention can also be used as a layer to prevent interaction between the substrate and the photoresist film, a layer that prevents adverse effects on the substrate from materials used in the photoresist film or substances generated during exposure to the photoresist film, a layer that prevents the diffusion of substances generated from the substrate to the upper photoresist film during heating and firing, and a barrier layer to reduce the poisoning effect of the photoresist film by the semiconductor substrate dielectric layer.

[0139] The resist underlayer film formed from the resist underlayer film formation composition of the present invention can be applied to a substrate with via holes formed in a dual damascene process and 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. In addition to its function as a hard mask, the underlayer film of the EUV resist can also be used for the following purposes. The resist underlayer film forming composition of the present invention can be used to form an underlayer anti-reflection film for an EUV resist that can prevent reflection from the substrate or interface of undesirable exposure light, such as the deep ultraviolet (DUV) light mentioned above, during EUV exposure, without intermixing with the EUV resist. It can efficiently prevent reflection as an underlayer film for an EUV resist. When used as an underlayer film for an EUV resist, the process can be carried out in the same way as for an underlayer film for a photoresist.

[0140] The semiconductor processing substrate comprising the resist underlayer film of the present invention described above and a semiconductor substrate can be used to suitably process a semiconductor substrate. Furthermore, according to a method for manufacturing a semiconductor device, which includes the steps of forming an organic underlayer film on a semiconductor substrate, forming a resist underlayer film on the organic underlayer film using the film-forming composition of the present invention, forming a resist film on the resist underlayer film, exposing the resist film, solvent developing the resist film after exposure to obtain a resist pattern, etching the resist underlayer film with the resist pattern, and processing the semiconductor substrate with the patterned resist film and the resist underlayer film, it is possible to achieve highly accurate and reproducible processing of semiconductor substrates, thus enabling stable manufacturing of semiconductor devices. [Examples]

[0141] The present invention will be described more specifically below with reference to synthesis examples and embodiments, but the present invention is not limited to the following.

[0142] (Synthesis Example 1) 11.1 g of tetraethoxysilane, 2.72 g of methyltriethoxysilane, 2.18 g of (4-(1-ethoxyethoxy)phenyl)trimethoxysilane, and 24.1 g of acetone were placed in a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 13.8 g of aqueous nitric acid solution (concentration 0.01 mol / L) was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 85°C and refluxed for 1200 minutes. After the reaction mixture was cooled to room temperature, 61 g of propylene glycol monoethyl ether and 6 g of water were added, and then, under reduced pressure, acetone, methanol, ethanol, and water were removed by distillation to obtain a concentrated hydrolysis condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was more than 20% by mass in terms of solid residue when heated at 140°C. Next, propylene glycol monoethyl ether was added to the obtained concentrate, and the concentration was adjusted to 13% by mass in terms of solid residue when heated at 140°C, thereby obtaining a solution of hydrolysis condensate (polymer) with propylene glycol monoethyl ether as the solvent (solid content concentration 13% by mass). The obtained polymer contained the structure represented by formula (E1), and its weight-average molecular weight (Mw) was 2,400 in terms of polystyrene as determined by GPC. [ka]

[0143] (Synthesis Example 2) A solution of the hydrolysis condensate (polymer) (solid content concentration 13% by mass) was obtained by the same method as in Synthesis Example 1, except that 1.80 g of trimethoxy(3-(2-oxyranylmethoxy)propyl)silane was used instead of 2.18 g of (4-(1-ethoxyethoxy)phenyl)trimethoxysilane. The obtained polymer contained the structure represented by formula (E2), and its weight-average molecular weight (Mw) was 7,000 in polystyrene terms by GPC. [ka]

[0144] (Synthesis Example 3) A solution (solid content concentration: 13% by mass) of a hydrolytic condensate (polymer) was obtained in the same manner as in Synthesis Example 1, except that 1.80 g of trimethoxy(3-(2-oxiranylmethoxy)propyl)silane was used instead of 2.18 g of (4-(1-ethoxyethoxy)phenyl)trimethoxysilane. The resulting polymer contained a structure represented by formula (E3), and its weight average molecular weight (Mw) was 4,000 in terms of polystyrene by GPC.

Chemical formula

[0145] (Synthesis Example 4) A solution (solid content concentration: 13% by mass) of a hydrolytic condensate (polymer) was obtained in the same manner as in Synthesis Example 1, except that 2.63 g of triethoxy((4-methoxymethyl-2-methoxyphenoxy)methyl)silane was used instead of 2.18 g of (4-(1-ethoxyethoxy)phenyl)trimethoxysilane. The resulting polymer contained a structure represented by formula (E4), and its weight average molecular weight (Mw) was 3,000 in terms of polystyrene by GPC.

Chemical formula

[0146] [2] Preparation of Composition for Film Formation (Examples 1 to 12, Comparative Examples 1 to 4) The hydrolytic condensates (polymers), additives (stabilizers), curing catalysts (condensing agents), photoacid generators (acid catalysts for organic crosslinking), crosslinking agents, and solvents obtained in the above Synthesis Examples 1 to 4 were mixed at the ratios shown in Table 1 and filtered through a 0.1-μm fluororesin filter to prepare the compositions for film formation of Examples 1 to 12, respectively. Also, the hydrolytic condensates (polymers), crosslinking agents (condensing agents), photoacid generators (acid catalysts for organic crosslinking), and solvents obtained in the above Synthesis Examples 1 to 3 were mixed at the ratios shown in Table 2 and filtered through a 0.1-μm fluororesin filter to prepare the compositions for film formation of Comparative Examples 1 to 4, respectively. The addition ratios of the polymers in Tables 1 and 2 indicate the amounts of the polymers themselves, not the amounts of the polymer solutions added.

[0147] Each addition amount is shown in parts by mass. MA is maleic acid as an additive, TPSNO3 is a curing catalyst, which refers to triphenylsulfonium nitrate, TPSTf as a photoacid generator (acid catalyst for organic crosslinking) refers to triphenylsulfonium trifluoromethanesulfonate, and THPSTf refers to tris(4-hydroxyphenyl)sulfonium trifluoromethanesulfonate. Also, PL as a crosslinking agent refers to 1,3,4,6-tetrakis(methoxymethyl)tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione, and TMOM-BP refers to 3,3’,5,5’-tetrakis(methoxymethyl)-[1,1’-biphenyl]-4,4’-diol. Also, PGMEA as a solvent refers to propylene glycol monomethyl ether acetate, PGME refers to propylene glycol monomethyl ether, PGEE refers to propylene glycol monoethyl ether, and DIW refers to ultrapure water (deionized water).

[0148]

Table 1

Table 2

[0149] (Adjustment of the Composition for Forming the Organic Lower Layer Film A) Under a nitrogen atmosphere, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL four-necked flask. 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was added and the mixture was stirred. The temperature was raised to 100°C to dissolve the mixture and begin polymerization. After 24 hours, the mixture was allowed to cool to 60°C, then diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.), and reprecipitation was performed in methanol (168 g, manufactured by Kanto Chemical Co., Ltd.). The resulting precipitate was filtered and dried in a vacuum dryer at 80°C for 24 hours to obtain 9.37 g of the target polymer (formula (EA1), hereinafter abbreviated as PCzFL). [ka] PCzFL 1 The results of the 1H-NMR measurement were as follows: 1 H-NMR(400MHz,DMSO-d6):δ7.03-7.55(br,12H),δ7.61-8.10(br,4H),δ11.18(br,1H) The weight-average molecular weight (Mw) of PCzFL, measured in polystyrene equivalent by GPC, was 2800, and the polydispersity (Mw / Mn) was 1.77. To 20 g of the obtained polymer, 3.0 g of tetramethoxymethyl glycoluryl (manufactured by Mitsui Cytec Co., Ltd., trade name Powderlink 1174) was added as a crosslinking agent, 0.30 g of pyridinium p-toluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (manufactured by Dainippon Ink and Chemicals, Inc., trade name) as a surfactant. This mixture was then dissolved in 88 g of propylene glycol monomethyl ether acetate to prepare a solution. Subsequently, the solution was 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 organic underlayer film A for use in multilayer lithography processes.

[0150] (Preparation of composition for forming organic underlayer film B) Under a nitrogen atmosphere, 2-epoxy-4-(2-oxyranyl)cyclohexyl adduct (40.0 g, manufactured by Daicel Chemical Industries, Ltd., trade name: EHPE3150), 9-anthracenecarboxylic acid (20.3 g), benzoic acid (13.7 g, Kanto Chemical Co., Ltd., Grade 1), BTEAC (1.5 g, manufactured by Tokyo Chemical Industry Co., Ltd.), and PGME (g, mol) as a solvent were added to a 100 mL four-necked flask and mixed. The mixture was refluxed at 142°C for 20 hours. After the reaction, ion exchange was performed by stirring with an ion exchange resin for 4 hours, and a yellow solution was obtained after filtration. GPC analysis of the obtained polymer showed that the weight-average molecular weight was 4100 on a standard polystyrene basis. To 5 g of the obtained polymer solution (polymer solids content 16% by weight), 0.2 g of tetraethoxymethyl glycoluryl, 0.03 g of pyridinium-p-toluenesulfonate, 0.0008 g of Megafac [trademark registered] R-30 (manufactured by DIC Corporation, trade name), 6.4 g of propylene glycol monomethyl ether, and 4.5 g of propylene glycol monomethyl ether acetate were mixed to form a solution. Subsequently, the solution was 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 the organic sublayer B used in the multilayer lithography process.

[0151] (Formation of resist pattern by EB exposure: Negative solvent development) The above-mentioned composition for forming the organic underlayer B was spin-coated onto a silicon wafer, and the organic underlayer (layer B) (thickness 200 nm) was formed by heating it on a hot plate at 215°C for 1 minute. On top of that, the film-forming composition of Example 1 was spin-coated and heated on a hot plate at 215°C for 1 minute to form a resist underlayer film (20 nm). Furthermore, an EUV resist solution (hydroxystyrene resin-based resist) is spin-coated onto the surface and heated on a hot plate at 130°C for 1 minute to form an EUV resist film. Then, using an Elionix EB exposure system (ELS-G130), exposure is performed in the 200-800 uC / cm2 exposure range at 40 uC / cm2. 2The image was exposed (depicted) under step conditions. After exposure, post-exposure heating (90°C for 1 minute) was performed, followed by cooling to room temperature on a cooling plate. Development was then carried out using an organic solvent developer (butyl acetate) for 25 seconds, and then rinsing was performed to form a resist pattern. Using a similar procedure, resist patterns were formed using the compositions obtained in Examples 2, 7, 9, and 10, and Comparative Examples 1, 2, and 4. The obtainable resist patterns were evaluated for their ability to form 25nm line-and-space patterns, and the results are shown in Tables 3 to 5. In Tables 3 to 5, as an evaluation of the pattern shape, when the exposure amount was changed in a 50nm pitch line-and-space pattern, patterns with a minimum CD size at which the pattern did not collapse were 20nm or larger were considered defective, and those with a CD size less than 20nm were considered good.

[0152] [Table 3] [Table 4] [Table 5]

[0153] As shown in Tables 3 to 5, good pattern shapes could be achieved by adding phenoplast crosslinking agents and aminoplast crosslinking agents to systems using phenol polymers, by adding aminoplast crosslinking agents to systems using epoxy unit-containing polymers, and by adding aminoplast crosslinking agents to systems using epoxy unit-containing polymer systems.

[0154] (Formation of resist patterns by EUV exposure: Negative solvent development) The above-mentioned composition for forming the organic underlayer A was spin-coated onto a silicon wafer, and the organic underlayer (layer A) (thickness 60 nm) was formed by heating it on a hot plate at 215°C for 1 minute. On top of that, the film-forming composition of Example 3 was spin-coated and heated on a hot plate at 215°C for 1 minute to form a resist underlayer film (20 nm). Further on top of that, an EUV resist solution (hydroxystyrene resin-based resist) was spin-coated and heated on a hot plate at 130°C for 1 minute to form an EUV resist film (C layer). Using an EUV exposure apparatus (NXE3300) manufactured by ASML, exposure (writing) was performed under the conditions of NA = 0.33, σ = 0.671 / 0.902, and Dipole. After exposure, post-exposure heating (90°C for 1 minute) was performed, cooled to room temperature on a cooling plate, developed for 1 minute using an organic solvent developer (butyl acetate), and then rinsed to form a resist pattern. Using the respective compositions obtained in Examples 4 to 6, 8, 11 and 12 and Comparative Example 3 in the same procedure, resist patterns were formed respectively. Regarding the obtained resist patterns, the formation of 20 nm line and space was evaluated, and the results are shown in Table 6. In Table 6, as the evaluation result of the pattern shape, when the exposure dose was changed in a line and space with a pitch of 40 nm in EUV lithography, the minimum CD (Critical Dimension) size at which the pattern did not collapse at the best focus was shown as defective if it was 18 nm or more, and good if it was less than 18 nm. The best focus is the focus at which the pattern contrast appears most clearly when exposed by changing the depth of focus.

[0155]

Table 6

[0156] As shown in Tables 3 to 6, the resist underlayer films formed from the film-forming compositions prepared in Examples 1 to 12 could prevent the pattern collapse of the resist film provided on the upper layer and form good resist patterns as compared with the resist underlayer films formed from the film-forming compositions prepared in Comparative Examples 1 to 4 which do not contain a crosslinking agent in the formation test of negative resist patterns by the above EB exposure and EUV exposure.

Claims

1. A film-forming composition comprising a hydrolysis condensate of a hydrolyzable silane compound catalyzed by an organic acid or inorganic acid, at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents, and a solvent, The above hydrolyzable silane compound consists only of hydrolyzable silanes represented by the following formula (1), hydrolyzable silanes represented by the following formula (2), and hydrolyzable silanes represented by the following formula (3) (except for the hydrolyzable silane represented by the following formula (1)), and The hydrolysis condensate of the above hydrolyzable silane compound contains 0.1 mol% to 20 mol% of the monomer units of the hydrolyzable silane represented by the following formula (1) out of the total monomer units. A film-forming composition characterized by the following features. 【Chemistry 1】 (In formula (1), R １ This represents an organic group that is bonded to a silicon atom by a Si-C bond and includes at least one structure selected from an alkoxymethylbenzene structure, a phenoxy structure, and an epoxy structure. R ２ R represents a group bonded to a silicon atom by a Si-C bond, which independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, or a sulfonyl group, or a combination thereof. ３ These are groups or atoms bonded to a silicon atom, and independently represent a hydroxyl group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. (where a represents an integer of 1, b represents an integer between 0 and 2, and a + b represents an integer between 1 and 3.) 【Chemistry 2】 (In formula (2), R １１ (This refers to a group or atom bonded to a silicon atom, which independently represents a hydroxyl group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.) 【Transformation 3】 (In formula (3), R 12 is a group bonded to a silicon atom by a Si-C bond, and independently represents an optionally substituted alkyl group, an optionally substituted alkyl halide, or an optionally substituted alkenyl group, or an organic group including an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, or a sulfonyl group, or a combination thereof.) R 13 represents a group or atom bonded to a silicon atom, independently of each other, representing a hydroxyl group, alkoxy group, aralkyloxy group, acyloxy group, or halogen atom.

2. The film-forming composition according to claim 1, wherein the organic group containing the phenoxy structure is an organic group containing a phenol structure, an alkoxyalkoxybenzene structure, or an alkoxybenzene structure.

3. The film-forming composition according to claim 1, wherein the organic group containing the alkoxymethylbenzene structure is an organic group containing an (alkoxy)(alkoxymethyl)benzene structure.

4. The film-forming composition according to any one of claims 1 to 3, wherein the hydrolysis condensate contains monomer units of a hydrolyzable silane represented by formula (1) in a proportion of 0.1 mol% to 15 mol%.

5. The film-forming composition according to any one of claims 1 to 4, further comprising an acid catalyst.

6. The film-forming composition according to claim 5, wherein the acid catalyst comprises at least one selected from the group consisting of triphenylsulfonium trifluoromethanesulfonate and tris(hydroxyphenyl)sulfonium trifluoromethanesulfonate.

7. The film-forming composition according to any one of claims 1 to 6, further comprising a curing catalyst.

8. The film-forming composition according to claim 7, wherein the curing catalyst comprises at least one selected from the group consisting of ammonium salts, phosphines, phosphonium salts, and sulfonium salts.

9. The film-forming composition according to any one of claims 1 to 8, wherein the hydrolyzable silane represented by formula (1) is (4-(1-ethoxyethoxy)phenyl)trimethoxysilane, or trimethoxy(3-(2-oxyranylmethoxy)propyl)silane, or triethoxy((4-ethoxy-2-methoxyphenoxy)methyl)silane.

10. A film-forming composition according to any one of claims 1 to 9, which is a resist underlayer film formation composition used in the lithography process.

11. The film-forming composition according to claim 10, wherein the lithography step is an EB lithography or EUV lithography step.

12. Resistance obtained from the film-forming composition according to any one of claims 1 to 11 The lower layer membrane.

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

14. A method for producing a film-forming composition according to any one of claims 1 to 11, A step of hydrolyzing and condensing the above hydrolyzable silane compound in the presence of nitric acid to produce the above hydrolyzable condensate, and A step of dissolving the hydrolysis condensate and at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents in a solvent. A method that includes this.

15. A step of forming a resist underlayer film on a semiconductor substrate using a film-forming composition according to any one of claims 1 to 11, The process of forming a resist film on the above-mentioned resist underlayer film, The process of exposing the above-mentioned resist film, The process involves, after exposure, developing the resist film with a solvent to obtain a resist pattern, The above resist pattern is used in the process of etching the underlying resist layer, A process for processing a semiconductor substrate using a patterned resist film and a resist underlayer film, A method for manufacturing a semiconductor device containing [a specific component].

16. A process of forming an organic underlayer film on a semiconductor substrate, A step of forming a resist underlayer film on the above organic underlayer film using the film-forming composition described in any one of claims 1 to 11, The process of forming a resist film on the above-mentioned resist underlayer film, The process of exposing the above-mentioned resist film, The process involves, after exposure, developing the resist film with a solvent to obtain a resist pattern, The above resist pattern is used in the process of etching the underlying resist layer, A process for processing a semiconductor substrate using a patterned resist film and a resist underlayer film, A method for manufacturing a semiconductor device containing [a specific component].

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