Membrane Forming Composition

Abstract

[Problem] To provide a composition which provides a film capable of satisfactorily functioning as a resist underlayer film having resistance to a solvent for a composition of a resist film formed as an upper layer, good etching characteristics with respect to fluorine gas, and good lithography characteristics. [Solution] A film-forming composition characterized by including a solvent and a hydrolyzed condensate obtained by hydrolyzing and condensating a hydrolyzable silane compound by using two or more acidic compounds, wherein the hydrolyzable silane compound includes an amino group-containing silane represented by formula (1) below. (In formula (1), R1 is a group which binds to a silicon atom, and represents a mutually independent organic base which contains an amino group. R2 is a group which can bind to a silicon atom, and represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a halogenated alkyl group which may be substituted, a halogenated aryl group which may be substituted, a halogenated aralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or represents an organic group including an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group. R3 is a group or atom which binds to a silicon atom and represents a mutually independent alkoxy group, an alkyloxy group, an acyloxy group, or a halogen atom. a is an integer from 1-2 and b is an integer from 0-1, satisfying a + b ≤ 2.)

Description

[Technical Field]

[0001] This relates to a film-forming composition. [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 material 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 film, and then etching the substrate using the resulting photoresist film pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the pattern.

[0003] In recent years, with the remarkable trend towards thinner resist films in cutting-edge semiconductor devices, particularly in three-layer processes consisting of a resist film, a silicon-containing resist underlayer, and an organic underlayer, the Si-HM (Silicon-Hard Mask) underlayer requires not only good lithography properties but also a good etching rate in wet etching. Therefore, good solubility in wet etching solutions (such as HF) is essential. In response to these demands, particularly in EUV (Extreme Ultraviolet) lithography, development has been underway to improve lithographic properties by introducing large amounts of functional groups with high adhesion to the resist into the polymer, or by adding large amounts of photoacid generators to the composition. However, a major problem with such materials is the decrease in solubility in wet etching solutions (such as HF) due to the increase in organic components.

[0004] Under these circumstances, compositions for forming resist underlayer films containing silane compounds having an onium group and resist underlayer films containing silane compounds having anionic groups have been reported (Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2010 / 021290 [Patent Document 2] International Publication No. 2010 / 071155 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention has been made in view of the above circumstances, and aims to provide a composition for a resist film formed as an upper layer that has good resistance to solvents, good etching properties to fluorine-based gases, and good lithography properties, and that can function well as a resist underlayer film. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the present inventors have found that a composition comprising a hydrolysis condensate obtained by hydrolyzing and condensing a hydrolyzable silane compound containing a predetermined hydrolyzable silane using two or more acidic compounds, and a solvent, provides a film that can function well as a resist underlayer film having good solvent resistance, good etching properties to fluorine-based gases, and even better lithography properties for the resist film composition formed as the upper layer, thus completing the present invention.

[0008] In other words, the present invention, in first view, is a film-forming composition comprising a hydrolysis condensate obtained by hydrolyzing and condensing a hydrolyzable silane compound using two or more acidic compounds, and a solvent, The present invention relates to a film-forming composition characterized in that the above hydrolyzable silane compound contains an amino group-containing silane represented by the following formula (1). [ka] (In formula (1), R 1These are groups that bond to silicon atoms, and independently of each other, they represent organic groups containing amino groups. R 2 This represents a group bonded to a silicon atom, and may represent an optionally substituted alkyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted halogenated alkyl group, optionally substituted halogenated aryl group, optionally substituted halogenated aralkyl group, optionally substituted alkoxyalkyl group, optionally substituted alkoxyaryl group, optionally substituted alkoxyaralkyl group, or optionally substituted alkenyl group, or an organic group containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group. R 3 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. (where a is an integer between 1 and 2, and b is an integer between 0 and 1, satisfying a + b ≤ 2.) The second aspect relates to the film-forming composition described in the first aspect, wherein the two or more acidic compounds described above are selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, heteropoly acid, oxocarbon acid, sulfonic acid group-containing organic acid, phosphoric acid group-containing organic acid, carboxyl group-containing organic acid, and phenolic hydroxyl group-containing organic acid, so as to be different from each other. The third aspect relates to the film-forming composition described in the second aspect, wherein the two or more acidic compounds described above are selected from the group consisting of nitric acid, sulfuric acid, oxocarbonic acid, sulfonic acid group-containing organic acid, and carboxyl group-containing organic acid, in a manner that is distinct from one another. The fourth aspect relates to the film-forming composition described in the second aspect, wherein the two or more acidic compounds described above include at least one selected from the group consisting of sulfuric acid and sulfonic acid group-containing organic acids, and at least one selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, boric acid, heteropoly acid, oxocarbon acid, phosphoric acid group-containing organic acid, carboxyl group-containing organic acid, and phenolic hydroxyl group-containing organic acid. The fifth aspect relates to a film-forming composition according to any one of the second to fourth aspects, wherein the oxocarbon acid contains at least one selected from delta acid, squalic acid, and rhozonic acid. The sixth aspect relates to a film-forming composition according to any one of the second to fifth aspects, wherein the above-mentioned sulfonic acid group-containing organic acid includes at least one selected from aromatic sulfonic acid, saturated aliphatic sulfonic acid, and unsaturated aliphatic sulfonic acid. The seventh aspect relates to the film-forming composition according to the sixth aspect, wherein the sulfonic acid group-containing organic acid comprises at least one selected from aromatic sulfonic acids and saturated aliphatic sulfonic acids. The eighth aspect relates to a film-forming composition according to any one of the second to seventh aspects, wherein the carboxyl group-containing organic acid includes at least one selected from formic acid, oxalic acid, aromatic carboxylic acid, saturated aliphatic carboxylic acid, and unsaturated aliphatic carboxylic acid. The ninth aspect relates to the film-forming composition described in the eighth aspect, wherein the carboxyl group-containing organic acid includes an unsaturated aliphatic carboxylic acid. The tenth aspect relates to a film-forming composition according to any one of the first to ninth aspects, wherein the organic group containing the above-mentioned amino group is a group represented by the following formula (A1). [ka] (In formula (A1), R 101 and R 102 (Each of the two elements independently represents a hydrogen atom or a hydrocarbon group, and L represents an optionally substituted alkylene group.) The eleventh aspect relates to the film-forming composition according to the tenth aspect, wherein the alkylene group is a linear or branched alkylene group having 1 to 10 carbon atoms. The twelfth aspect relates to a film-forming composition according to any one of the first to eleventh aspects, which is used for forming a resist underlayer film used in the lithography process. The thirteenth aspect relates to a resist underlayer film obtained from a film-forming composition described in any one of the first to twelfth aspects. From the 14th perspective, the process involves forming an organic underlayer film on the substrate, A step of forming a resist underlayer on the above organic underlayer using a film-forming composition described in any one of the first to twelfth viewpoints, The process of forming a resist film on the above resist underlayer film and This relates to a method for manufacturing semiconductor devices including [specific components]. [Effects of the Invention]

[0009] By using the film-forming composition of the present invention, it is possible to easily form films using wet processes such as spin coating, achieve good lithography properties when used together with a resist film and an organic underlayer in a three-layer process, and obtain a suitable film as a resist underlayer that exhibits good solvent resistance and good etching properties to fluorine-based gases for the resist film composition formed as the upper layer. By using such film-forming compositions, it is expected that more reliable semiconductor devices can be manufactured. [Modes for carrying out the invention]

[0010] The present invention will be described in more detail below. Furthermore, the film-forming composition of the present invention contains hydrolyzed condensates of hydrolyzable silane compounds. These hydrolyzed condensates include not only siloxane polymers, which are condensates in which condensation is completely completed, but also siloxane 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 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, in this invention, "solid content" refers to components in the composition other than the solvent.

[0011] The film-forming composition of the present invention comprises a hydrolysis condensate obtained by hydrolyzing and condensing a hydrolyzable silane compound using two or more acidic compounds, wherein the hydrolyzable silane compound comprises an amino group-containing silane represented by formula (1). [ka]

[0012] In formula (1), R 1 R is a group that bonds to a silicon atom and represents an organic group containing an amino group. 2 R is a group bonded to a silicon atom and represents an optionally substituted alkyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted halogenated alkyl group, optionally substituted halogenated aryl group, optionally substituted halogenated aralkyl group, optionally substituted alkoxyalkyl group, optionally substituted alkoxyaryl group, optionally substituted alkoxyaralkyl group, or optionally substituted alkenyl group, or an organic group containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group. 3 A is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, where a is an integer between 1 and 2, b is an integer between 0 and 1, and a + b ≤ 2.

[0013] The alkyl group in formula (1) is a monovalent group derived by removing one hydrogen atom from an alkane, and may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.

[0014] 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, 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.

[0015] Specific examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, and 2,4-dimethyl-cyclobutyl group. Examples of cycloalkyl groups include, but are not limited to, cycloalkyl groups such as 2-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, and 2-ethyl-3-methylcyclopropyl group, as well as bicycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0016] The aryl group in formula (1) 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. 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-chrysenyl 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.

[0017] The aralkyl group in formula (1) is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those described above. The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aralkyl groups include, but are not limited to, phenylmethyl (benzyl) group, 2-phenylethylene group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, and 10-phenyl-n-decyl group.

[0018] In formula (1), the halogenated alkyl group is an alkyl group 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 in this context and in formula (1) include fluorine, chlorine, bromine, and iodine atoms. 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.

[0019] The aryl halide group in formula (1) is an aryl group substituted with a halogen atom, and 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. 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.

[0020] In formula (1), the aralkyl halide is an aralkyl group substituted with a halogen atom, and 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. 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.

[0021] In formula (1), the alkoxyalkyl group is an alkyl group substituted with an alkoxy group. The alkyl group substituted with the alkoxy group in the alkoxyalkyl group may be linear, branched, or cyclic. Specific examples of such alkyl groups are the same as those described 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. Specific examples of alkoxy groups that substitute for alkyl groups in alkoxyalkyl groups and alkoxy groups in formula (1) 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, 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 Linear or branched alkoxy groups such as xy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1 -ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,Examples of cyclic alkoxy groups include, but are not limited to, 3-dimethylcyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-isopropyl-cyclopropoxy group, 2-isopropyl-cyclopropoxy group, 1,2,2-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. 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, and 2-ethoxyethyl group.

[0022] The alkoxyaryl group in formula (1) is an aryl group substituted with an alkoxy group, and specific examples of such alkoxy and aryl groups are the same as those described above. The number of carbon atoms in the alkoxyaryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of 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.

[0023] The alkoxyaralkyl group in formula (1) is an aralkyl group substituted with an alkoxy group, and specific examples of such alkoxy and aralkyl groups are the same as those described above. The number of carbon atoms in the alkoxyaralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of alkoxyaralkyl groups include, but are not limited to, the 3-(methoxyphenyl)benzyl group and the 4-(methoxyphenyl)benzyl group.

[0024] The alkenyl group in formula (1) 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. 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.

[0025] Examples of organic groups containing an epoxy group in formula (1) include, but are not limited to, glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, and epoxycyclohexyl groups.

[0026] Examples of organic groups containing an acryloyl group in formula (1) include, but are not limited to, acryloylmethyl, acryloylethyl, and acryloylpropyl groups.

[0027] Examples of organic groups containing a methacryloyl group in formula (1) include, but are not limited to, methacryloylmethyl, methacryloylethyl, and methacryloylpropyl groups.

[0028] Examples of organic groups containing a mercapto group in formula (1) include, but are not limited to, ethyl mercapto group, butyl mercapto group, hexyl mercapto group, and octyl mercapto group.

[0029] Examples of organic groups containing a cyano group in formula (1) include, but are not limited to, a cyanoethyl group and a cyanopropyl group.

[0030] The aralkyloxy group in formula (1) is a group derived by removing a hydrogen atom from the hydroxyl group of an aralkyl alcohol, and specific examples of such aralkyl groups are the same as those mentioned above. The number of carbon atoms in the aralkyloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aralkyloxy groups include, but are not limited to, phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group, 5-phenyl-n-pentyloxy group, 6-phenyl-n-hexyloxy group, 7-phenyl-n-heptyloxy group, 8-phenyl-n-octyloxy group, 9-phenyl-n-nonyloxy group, and 10-phenyl-n-decyloxy group.

[0031] The acyloxy group in formula (1) is a group derived by removing a hydrogen atom from the carboxyl group of a carboxylic acid compound. Typically, examples include, but are not limited to, alkylcarbonyloxy groups, arylcarbonyloxy groups, or aralkylcarbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of an alkylcarboxylic acid, arylcarboxylic acid, or aralkylcarboxylic acid. Specific examples of alkyl groups, aryl groups, and aralkyl groups in such alkylcarboxylic acids, arylcarboxylic acids, and aralkylcarboxylic acids are the same as those described above. 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.

[0032] The organic group containing an amino group in formula (1) is not particularly limited as long as it is an organic group containing an amino group, but a preferred example is the group represented by the following formula (A1). [ka]

[0033] In formula (A1), R101 and R 102 each independently represents a hydrogen atom or a hydrocarbon group, and L each independently represents an alkylene group which may be substituted.

[0034] Examples of the hydrocarbon group in formula (A1) include, but are not limited to, an alkyl group, an alkenyl group, an aryl group, etc. Specific examples of such an alkyl group, an alkenyl group and an aryl group are the same as those described above.

[0035] From the viewpoint of reproducibly realizing excellent lithography characteristics, R 101 and R 102 are preferably a hydrogen atom, an alkyl group, an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, and even more preferably, R 101 is a hydrogen atom, R 102 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or R 101 and R 102 are both an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably, R 101 and R 102 are both hydrogen atoms.

[0036] In addition, examples of the alkylene group in formula (A1) are the same as those described above, and it may be linear or branched, and the number of its carbon atoms is usually 1 to 10, preferably 1 to 5. Among them, linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group are preferred.

[0037] a is an integer between 1 and 2, and b is an integer between 0 and 1, satisfying a + b ≤ 2. However, from the viewpoint of excellent lithography characteristics, resistance of the resist film composition to solvents, and a suitable balance of etching rates, it is preferable that b is 0, and more preferably that a is 1 and b is 0.

[0038] The content of the amino group-containing silane represented by formula (1) in the above hydrolyzable silane compound is arbitrary, but from the viewpoint of reproducibly achieving excellent lithography properties, it is preferably 0.01 mol% to 20 mol%, more preferably 0.1 mol% to 5 mol%, with the remainder being other hydrolyzable silanes.

[0039] The film-forming composition of the present invention may, for the purpose of adjusting film properties such as film density, contain, as the above-mentioned hydrolyzable silane compound, an amino group-containing silane represented by formula (1), and at least one other hydrolyzable silane selected from, for example, the hydrolyzable silane represented by formula (2) and the hydrolyzable silane represented by formula (3).

[0040] [ka]

[0041] In formula (2), R 4 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 amide group, an alkoxy group, or a sulfonyl group, or a combination thereof. Also R 5These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. d represents an integer between 0 and 3.

[0042] The above R 4 Specific examples of each group and atom in R, and their preferred number of carbon atoms, are as follows: 2 The above-mentioned groups, atoms, and number of carbon atoms can be cited in relation to this. The above R 5 Specific examples of each group and atom in R, and their preferred number of carbon atoms, are as follows: 3 The above-mentioned groups, atoms, and number of carbon atoms can be listed in relation to this.

[0043] In formula (3), R 6 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 amide group, an alkoxy group, or a sulfonyl group, or a combination thereof. Also R 7 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. Y is a group that is bonded to a silicon atom by a Si-C bond, and independently represents either an alkylene group or an arylene group. e represents an integer of 0 or 1, and f represents an integer of 0 or 1.

[0044] The above R 6 and R 7Specific examples of each group and atom in this, as well as their preferred number of carbon atoms, can be listed above. Furthermore, specific examples of alkylene groups in Y above include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, etc., branched alkylene groups such as 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group, etc., methanetriyl group, ethane-1,1,2-triyl group, ethane-1,2,2-triyl group, etc. Examples of alkanetriyl groups include, but are not limited to, tan-2,2,2-triyl group, propane-1,1,1-triyl group, propane-1,1,2-triyl group, propane-1,2,3-triyl group, propane-1,2,2-triyl group, propane-1,1,3-triyl group, butane-1,1,1-triyl group, butane-1,1,2-triyl group, butane-1,1,3-triyl group, butane-1,2,3-triyl group, butane-1,2,4-triyl group, butane-1,2,2-triyl group, butane-2,2,3-triyl group, 2-methylpropane-1,1,1-triyl group, 2-methylpropane-1,1,2-triyl group, 2-methylpropane-1,1,3-triyl group, etc. Specific examples of the arylene group in Y above include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group; 1,5-naphthalenediyl group, 1,8-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 1,2-anthracenediyl group, 1,3-anthracenediyl group, 1,4-anthracenediyl group, 1,5-anthracenediyl group, 1,6-anthracenediyl group, 1,7-anthracenediyl group, 1,8-anthracenediyl group, 2, Examples include, but are not limited to, groups derived by removing two hydrogen atoms from the aromatic ring of fused ring aromatic hydrocarbon compounds such as 3-anthracenediyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl groups; and groups derived by removing two hydrogen atoms from the aromatic ring of ring-linked aromatic hydrocarbon compounds such as 4,4'-biphenyldiyl and 4,4"-paraterphenyldiyl groups. e is preferably 0 or 1, more preferably 0. f is preferably 1.

[0045] Specific examples of hydrolyzable silanes represented by formula (2) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltrimethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamiloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, and methyltriphenoxysilane. Netyloxysilane, Glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, α-Glycidoxyethyltrimethoxysilane, α-Glycidoxyethyltriethoxysilane, β-Glycidoxyethyltrimethoxysilane, β-Glycidoxyethyltriethoxysilane, α-Glycidoxypropyltrimethoxysilane, α-Glycidoxypropyltriethoxysilane, β-Glycidoxypropyltrimethoxysilane, β-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ- Ricidoxypropyltriethoxysilane, γ-glycidoxypropyltrippropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxysilane (3,4-Epoxycyclohexyl)methyltrimethoxysilane, (3,4-Epoxycyclohexyl)methyltriethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-Epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-Epoxycyclohexyl)ethyltributoxysilane, β-(3,4-Epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-Epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyl Dimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxy Silane, γ-glycidoxypropyl vinyldimethoxysilane, γ-glycidoxypropyl vinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyl Triacetoxysilane, Methoxybenzyltrichlorosilane, Methoxyphenethyltrimethoxysilane, Methoxyphenethyltriethoxysilane, Methoxyphenethyltriacetoxysilane, Methoxyphenethyltrichlorosilane, Ethoxyphenyltrimethoxysilane, Ethoxyphenyltriethoxysilane, Ethoxyphenyltriacetoxysilane, Ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane,i-propoxyphenyltrimethoxysilane, i-propoxyphenyltriethoxysilane, i-propoxyphenyltriacetoxysilane, i-propoxyphenyltrichlorosilane, i-propoxybenzyltrimethoxysilane, i-propoxybenzyltriethoxysilane, i-propoxybenzyltriacetoxysilane, i-propoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t -Butoxybenzyltrimethoxysilane, t-Butoxybenzyltriethoxysilane, t-Butoxybenzyltriacetoxysilane, t-Butoxybenzyltrichlorosilane, Methoxynaphthyltrimethoxysilane, Methoxynaphthyltriethoxysilane, Methoxynaphthyltriacetoxysilane, Methoxynaphthyltrichlorosilane, Ethoxynaphthyltrimethoxysilane, Ethoxynaphthyltriethoxysilane, Ethoxynaphthyltriacetoxysilane, Ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyl Pyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacrylateoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo(2,2,1)heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonamidopropyltrieth Xysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane,Examples include, but are not limited to, methyl vinyl diethoxysilane and silanes represented by formulas (A-1) to (A-41) below.

[0046] [ka]

[0047] [ka]

[0048] [ka]

[0049] Specific examples of hydrolyzable silanes represented by formula (3) include, but are not limited to, methylene bistrimethoxysilane, methylene bistrichlorosilane, methylene bistriacetoxysilane, ethylene bistriethoxysilane, ethylene bistrichlorosilane, ethylene bistriacetoxysilane, propylene bistriethoxysilane, butylene bistrimethoxysilane, phenylene bistrimethoxysilane, phenylene bistriethoxysilane, phenylene bismethyldiethoxysilane, phenylene bismethyldimethoxysilane, naphthylene bistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, and bismethyldimethoxydisilane.

[0050] In the present invention, when the hydrolyzable silane compound that yields the hydrolysis condensate contains other hydrolyzable silanes other than the amino group-containing silane represented by formula (1), the content of the other hydrolyzable silanes in the hydrolyzable silane compound is usually 80 mol% to 99.99 mol%, preferably 95 mol% to 99.9 mol%.

[0051] From the viewpoint of improving the crosslinking density of the film obtained from the film-forming composition of the present invention, suppressing the diffusion of components of the resist film into the obtained film, and maintaining and improving the resist properties of the resist film, the hydrolyzable silane compound preferably comprises a hydrolyzable silane represented by formula (2), more preferably comprises a trifunctional hydrolyzable silane represented by formula (2) and a tetrafunctional hydrolyzable silane represented by formula (2), even more preferably comprises at least one selected from alkyltrialkoxysilane and aryltrialkoxysilane and a tetraalkoxysilane, and still more preferably comprises at least one selected from methyltrialkoxysilane and phenyltrialkoxysilane and a tetraalkoxysilane. In this case, the ratio of the hydrolyzable silane represented by formula (2) for the trifunctional compound to the hydrolyzable silane represented by formula (2) for the tetrafunctional compound is typically 10:90 to 90:10, preferably 70:30 to 20:80, in molar ratio.

[0052] Two or more acidic compounds are used for the hydrolysis and condensation of the hydrolyzable silane compound to obtain the hydrolysis condensate contained in the film-forming composition of the present invention. The two or more acidic compounds are not particularly limited as long as they are structurally different from each other, and may be either inorganic acids or organic acids.

[0053] Examples of inorganic acids include, but are not limited to, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, and heteropoly acids.

[0054] Examples of heteropoly acids include phosphomolybdic acid, silicic acid, phosphotungstic acid, silicatungstic acid, and phosphotungstomolybdic acid.

[0055] Among these, nitric acid, phosphoric acid, and sulfuric acid are preferred, with nitric acid being more preferred, from the viewpoint of achieving excellent lithographic properties with good reproducibility and improving the storage stability of the hydrolysis condensate solution.

[0056] Organic acids are those that have acidic groups such as sulfonic acid groups, phosphoric acid groups, carboxyl groups, and phenolic hydroxyl groups in their molecules. Multiple acidic groups may be present in the organic acid, and these multiple acidic groups may be identical or different from one another.

[0057] In a preferred embodiment of the present invention, examples of sulfonic acid group-containing organic acids include aromatic sulfonic acids, saturated aliphatic sulfonic acids, and unsaturated aliphatic sulfonic acids. Among these, aromatic sulfonic acids and saturated aliphatic sulfonic acids are preferred from the viewpoint of reproducibly achieving excellent lithographic properties and from the viewpoint of the availability of the compounds.

[0058] Aromatic sulfonic acids are those in which at least one hydrogen atom of an aromatic compound is substituted with a sulfonic acid group. The number of carbon atoms constituting the aromatic ring of such an aromatic compound is not particularly limited, but is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10. The aromatic ring may be substituted with substituents such as halogen atoms like fluorine, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups, alkenyl groups such as vinyl groups, halogenated alkyl groups such as trifluoromethyl groups, and halogenated alkenyl groups such as perfluorovinyl groups. The number of such substituents is usually 0 to 3. Furthermore, the number of sulfonic acid groups is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1.

[0059] Typical examples of aromatic sulfonic acids include, but are not limited to, unsubstituted aromatic sulfonic acids, alkyl or alkenyl aromatic sulfonic acids, halogenated alkyl or halogenated alkenyl aromatic sulfonic acids, and halogenated aromatic sulfonic acids. In particular, from the viewpoint of achieving excellent lithographic properties with good reproducibility and the ease of obtaining the compounds, unsubstituted aromatic sulfonic acids and alkyl aromatic sulfonic acids are preferred, and alkyl aromatic sulfonic acids are more preferred.

[0060] Specific examples of unsubstituted aromatic sulfonic acids include, but are not limited to, benzenesulfonic acid, benzene-1,2-disulfonic acid, benzene-1,3-disulfonic acid, benzene-1,4-disulfonic acid, benzene-1,3,5-trisulfonic acid, 2-naphthalenesulfonic acid, anthracenesulfonic acid, phenanthrenesulfonic acid, and pyrenesulfonic acid.

[0061] Specific examples of alkyl or alkenyl aromatic sulfonic acids include p-toluenesulfonic acid, p-styrenesulfonic acid, p-isopropylbenzenesulfonic acid, p-dodecylbenzenesulfonic acid, dihexylbenzenesulfonic acid, 2,5-dihexylbenzenesulfonic acid, 3,5-bis(t-butyl)benzenesulfonic acid, 3,5-bis(isopropyl)benzenesulfonic acid, 2,4,6-tris(t-butyl)benzenesulfonic acid, 2,4,6-tris(isopropyl)benzenesulfonic acid, and 5,8-dibutyl-2-naphthalenesulfone. Examples include, but are not limited to, acids, 6,7-dibutyl-2-naphthalenesulfonic acid, hexylnaphthalenesulfonic acid, 4-hexyl-1-naphthalenesulfonic acid, 7-hexyl-1-naphthalenesulfonic acid, 6-hexyl-2-naphthalenesulfonic acid, octylnaphthalenesulfonic acid, 2-octyl-1-naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, 2,7-dinonyl-4-naphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylnaphthalenesulfonic acid, 3-dodecyl-2-naphthalenesulfonic acid, etc.

[0062] Specific examples of alkyl halides or alkenyl halides include 2-trifluoromethylbenzenesulfonic acid, 2-trichloromethylbenzenesulfonic acid, 2-tribromomethylbenzenesulfonic acid, 2-triiodomethylbenzenesulfonic acid, 3-trifluoromethylbenzenesulfonic acid, 3-trichloromethylbenzenesulfonic acid, 3-tribromomethylbenzenesulfonic acid, 3-triiodomethylbenzenesulfonic acid, 4-trifluoromethylbenzenesulfonic acid, 4-trichloromethylbenzenesulfonic acid, 4-tribromomethylbenzenesulfonic acid, and 4-tri Examples include, but are not limited to, iodomethylbenzenesulfonic acid, 2,6-bis(trifluoromethyl)benzenesulfonic acid, 2,6-bis(trichloromethyl)benzenesulfonic acid, 2,6-bis(tribromomethyl)benzenesulfonic acid, 2,6-bis(triiodomethyl)benzenesulfonic acid, 3,5-bis(trifluoromethyl)benzenesulfonic acid, 3,5-bis(trichloromethyl)benzenesulfonic acid, 3,5-bis(tribromomethyl)benzenesulfonic acid, 3,5-bis(triiodomethyl)benzenesulfonic acid, and 4-perfluorovinylbenzenesulfonic acid.

[0063] Specific examples of halogenated aromatic sulfonic acids include 2-fluorobenzenesulfonic acid, 3-fluorobenzenesulfonic acid, 4-fluorobenzenesulfonic acid, 2-chlorobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2-bromobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 4-bromobenzenesulfonic acid, 2-iodobenzenesulfonic acid, 4-iodobenzenesulfonic acid, 2,4-difluorobenzenesulfonic acid, 2,6-difluorobenzenesulfonic acid, 2,4-dichlorobenzenesulfonic acid, 2,6-dichlorobenzenesulfonic acid, 2,4-dibromobenzenesulfonic acid, 2,6-dibromobenzenesulfonic acid, 2,4-diiodobenzenesulfonic acid, 2,6-diiodobenzenesulfonic acid, and 2,4,6-trifluorobenzenesulfonic acid. Examples include, but are not limited to, fluorocarbon acid, 3,4,5-trifluorobenzenesulfonic acid, 2,4,6-trichlorobenzenesulfonic acid, 3,4,5-trichlorobenzenesulfonic acid, 2,4,6-tribromobenzenesulfonic acid, 3,4,5-tribromobenzenesulfonic acid, 2,4,6-triiodobenzenesulfonic acid, 3,4,5-triiodobenzenesulfonic acid, pentafluorobenzenesulfonic acid, pentachlorobenzenesulfonic acid, pentabromobenzenesulfonic acid, pentaiodobenzenesulfonic acid, fluoronaphthalenesulfonic acid, chloronaphthalenesulfonic acid, bromonaphthalenesulfonic acid, iodonaphthalenesulfonic acid, fluoroanthracenesulfonic acid, chloroanthracenesulfonic acid, bromoanthracenesulfonic acid, iodoanthracenesulfonic acid, etc.

[0064] From the viewpoint of reproducibly achieving excellent resist properties, when the substituent of the aromatic ring in the aromatic sulfonic acid is a halogen atom, a fluorine atom is preferred, and when it is an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.

[0065] A saturated aliphatic sulfonic acid is an alkane or cycloalkane compound in which at least one hydrogen atom is substituted with a sulfonic acid group. The number of carbon atoms constituting such an alkane or cycloalkane compound is not particularly limited, but is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The alkane compound may also be substituted with substituents such as halogen atoms like fluorine or aryl groups like phenyl groups, and the number of such substituents is usually 0 to 3.

[0066] Typical examples of saturated aliphatic sulfonic acids include, but are not limited to, unsubstituted saturated aliphatic sulfonic acids, halogenated saturated aliphatic sulfonic acids, and aryl saturated aliphatic sulfonic acids. In particular, from the viewpoint of achieving excellent lithographic characteristics with good reproducibility and from the viewpoint of the availability of compounds, unsubstituted saturated aliphatic sulfonic acids and halogenated saturated aliphatic sulfonic acids are preferred, and halogenated saturated aliphatic sulfonic acids are more preferred.

[0067] Specific examples of unsubstituted aliphatic sulfonic acids include, but are not limited to, chain-like or branched alkanesulfonic acids such as methanesulfonic acid, methanedisulfonic acid, ethanesulfonic acid, ethanedisulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, undecanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid, tetradecanesulfonic acid, pentadecanesulfonic acid, hexadecanesulfonic acid, heptadecanesulfonic acid, octadecanesulfonic acid, nonadecanesulfonic acid, eicosanesulfonic acid, henicosanesulfonic acid, docosanesulfonic acid, tricosanesulfonic acid, tetraconesulfonic acid, and cycloalkanesulfonic acids such as camphorsulfonic acid.

[0068] Specific examples of halogenated saturated aliphatic sulfonic acids include fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, chloromethanesulfonic acid, dichloromethanesulfonic acid, trichloromethanesulfonic acid, bromomethanesulfonic acid, dibromomethanesulfonic acid, tribromomethanesulfonic acid, iodomethanesulfonic acid, diiodomethanesulfonic acid, triiodomethanesulfonic acid, fluoroethanesulfonic acid, difluoroethanesulfonic acid, trifluoroethanesulfonic acid, pentafluoroethanesulfonic acid, and chloroethanesulfonic acid. Dichloroethanesulfonic acid, trichloroethanesulfonic acid, pentachloroethanesulfonic acid, tribromoethanesulfonic acid, pentabromoethanesulfonic acid, triiodoethanesulfonic acid, pentaiodoethanesulfonic acid, fluoropropanesulfonic acid, trifluoropropanesulfonic acid, heptafluoropropanesulfonic acid, chloropropanesulfonic acid, trichloropropanesulfonic acid, heptachloropropanesulfonic acid, bromopropanesulfonic acid, tribromopropanesulfonic acid, heptabromopropanesulfonic acid, triiodopropanesulfonic acid Heptaiodopropanesulfonic acid, trifluorobutanesulfonic acid, nonafluorobutanesulfonic acid, trichlorobutanesulfonic acid, nonachlorobutanesulfonic acid, tribromobutanesulfonic acid, nonabromobutanesulfonic acid, triiodobutanesulfonic acid, nonaiodobutanesulfonic acid, trifluoropentanesulfonic acid, perfluoropentanesulfonic acid, trichloropentanesulfonic acid, perchloropentanesulfonic acid, tribromopentanesulfonic acid, perbromopentanesulfonic acid, triiodopentanesulfonic acid, periodopentanesulfonic acid Sulfonic acid, trifluorohexanesulfonic acid, perfluorohexanesulfonic acid, trichlorohexanesulfonic acid, perchlorohexanesulfonic acid, perbromohexanesulfonic acid, periodohexanesulfonic acid, trifluoroheptanesulfonic acid, perfluoroheptanesulfonic acid, trichloroheptanesulfonic acid, perchloroheptanesulfonic acid, perbromoheptanesulfonic acid, periodoheptanesulfonic acid, trifluorooctanesulfonic acid, perfluorooctanesulfonic acid, trichlorooctanesulfonic acid, perchlorooctanesulfonic acid,Perbromooctanesulfonic acid, periodooctanesulfonic acid, trifluorononanesulfonic acid, perfluorononanesulfonic acid, trichlorononanesulfonic acid, perchlorononanesulfonic acid, perbromonanonanesulfonic acid, periodononanesulfonic acid, trifluorodecanesulfonic acid, perfluorodecanesulfonic acid, trichlorodecanesulfonic acid, perchlorodecanesulfonic acid, perbromodecanesulfonic acid, periododecanesulfonic acid, trifluoroundecanesulfonic acid, perfluoroundecanesulfonic acid, trichloroundecanesulfonic acid Acid, perchloroundecanesulfonic acid, perbromoundecanesulfonic acid, periodoundecanesulfonic acid, trifluorododecanesulfonic acid, perfluorododecanesulfonic acid, trichlorododecanesulfonic acid, perchlorododecanesulfonic acid, perbromodododecanesulfonic acid, periodododecanesulfonic acid, trifluorotridecanesulfonic acid, perfluorotridecanesulfonic acid, trichlorotridecanesulfonic acid, perchlorotridecanesulfonic acid, perbromotridecanesulfonic acid, periodotridecanesulfonic acid, trifluorotetrade Cansulfonic acid, perfluorotetradecanesulfonic acid, trichlorotetradecanesulfonic acid, perchlorotetradecanesulfonic acid, perbromotetradecanesulfonic acid, periodotetradecanesulfonic acid, trifluoropentadecanesulfonic acid, perfluoropentadecanesulfonic acid, trichloropentadecanesulfonic acid, perchloropentadecanesulfonic acid, perbromopentadecanesulfonic acid, periodopentadecanesulfonic acid, perfluorohexadecanesulfonic acid, perchlorohexadecanesulfonic acid, perbromohexadecanesulfonic acid, Periodohexadecanesulfonic acid, perfluoroheptadecanesulfonic acid, perchloroheptadecanesulfonic acid, perbromoheptadecanesulfonic acid, periodoheptadecanesulfonic acid, perfluorooctadecanesulfonic acid, perchlorooctadecanesulfonic acid, perbromooctadecanesulfonic acid, periodooctadecanesulfonic acid, perfluorononadecanesulfonic acid, perchlorononadecanesulfonic acid, perbromononadecanesulfonic acid, periodononadecanesulfonic acid, perfluoroicosanesulfonic acid, perchloroicosanesulfonic acid,Examples include, but are not limited to, perbromoicosanesulfonic acid, periodoicosanesulfonic acid, perfluorohenicosanesulfonic acid, perchlorohenicosanesulfonic acid, perbromohenicosanesulfonic acid, periodohenicosanesulfonic acid, perfluorodocosanesulfonic acid, perchlorodocosanesulfonic acid, perbromododocosanesulfonic acid, periododocosanesulfonic acid, perfluorotricosanesulfonic acid, perchlorotricosanesulfonic acid, perbromotricosanesulfonic acid, periodotricosanesulfonic acid, perfluorotetraconasesulfonic acid, perchlorotetraconasesulfonic acid, perbromotetraconasesulfonic acid, and periodotetraconasesulfonic acid.

[0069] Specific examples of aryl saturated aliphatic sulfonic acids include, but are not limited to, phenylmethanesulfonic acid, diphenylmethanesulfone, triphenylmethanesulfonic acid, 1-phenylethanesulfonic acid, and 2-phenylethanesulfonic acid.

[0070] From the viewpoint of reproducibly achieving excellent resist properties, when the substituent substituted for the alkyl in saturated aliphatic sulfonic acid is a halogen atom, a fluorine atom is preferred; when it is an aryl group, an aryl group having 6 to 10 carbon atoms is preferred, and phenyl is more preferred.

[0071] An unsaturated aliphatic sulfonic acid is an alkene or alkyne compound in which at least one hydrogen atom is substituted with a sulfonic acid group. The number of carbon atoms constituting such an alkene or alkyne compound is not particularly limited, but is usually 2 to 10, preferably 2 to 5, and more preferably 2 to 3. The alkene or alkyne compound may also be substituted with substituents such as halogen atoms like fluorine or aryl groups like phenyl groups, and the number of such substituents is usually 0 to 3.

[0072] Examples of unsaturated aliphatic sulfonic acids include, but are not limited to, unsubstituted unsaturated aliphatic sulfonic acids, halogenated unsaturated aliphatic sulfonic acids, and aryl unsaturated aliphatic sulfonic acids. Among these, unsubstituted unsaturated aliphatic sulfonic acids are preferred from the viewpoint of achieving excellent lithographic properties with good reproducibility and from the viewpoint of the availability of the compounds.

[0073] Specific examples of unsubstituted unsaturated aliphatic sulfonic acids include, but are not limited to, vinyl sulfonic acid, 2-propene-1-sulfonic acid, 1-butene-1-sulfonic acid, and 3-butene-1-sulfonic acid.

[0074] In one preferred embodiment of the present invention, examples of phosphate group-containing organic acids include, but are not limited to, aromatic phosphates, saturated aliphatic phosphates, and unsaturated aliphatic phosphates.

[0075] Aromatic phosphoric acid is obtained by substituting at least one hydrogen atom of an aromatic compound with phosphoric acid. The number of carbon atoms constituting the aromatic ring of such an aromatic compound is not particularly limited, but is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10. The aromatic ring may be substituted with substituents such as halogen atoms like fluorine, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups, alkenyl groups such as vinyl groups, halogenated alkyl groups such as trifluoromethyl groups, and halogenated alkenyl groups such as perfluorovinyl groups. The number of such substituents is usually 0 to 3. Furthermore, the number of phosphate groups is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1.

[0076] Examples of aromatic phosphoric acids include, but are not limited to, unsubstituted aromatic phosphoric acids, alkyl or alkenyl aromatic phosphoric acids, alkyl or alkenyl halogenated aromatic phosphoric acids, and halogenated aromatic phosphoric acids. Among these, unsubstituted aromatic phosphoric acid and alkyl aromatic phosphoric acid are preferred from the viewpoint of achieving excellent lithographic properties with good reproducibility and from the viewpoint of the availability of the compounds.

[0077] Specific examples of unsubstituted aromatic phosphates include, but are not limited to, phenyl phosphate, 1-naphthyl phosphate, and 2-naphthyl phosphate.

[0078] Specific examples of alkyl or alkenyl aromatic phosphates include, but are not limited to, tolyl phosphate, xylyl phosphate, 2-ethylphenyl phosphate, 3-n-propylphenyldiphosphate, and 4-t-butylphenyl phosphate.

[0079] Specific examples of alkyl or alkenyl halogenated aromatic phosphates include, but are not limited to, 2-trifluoromethylphenyl phosphate, 2-trichloromethylphenyl phosphate, 2-tribromomethylphenyl phosphate, 2-triiodomethylphenyl phosphate, 3-trifluoromethylphenyl phosphate, 3-trichloromethylphenyl phosphate, 3-tribromomethylphenyl phosphate, 3-triiodomethylphenyl phosphate, 4-trifluoromethylphenyl phosphate, 4-trichloromethylphenyl phosphate, 4-tribromomethylphenyl phosphate, 4-triiodomethylphenyl phosphate, 2,6-bis(trifluoromethyl)phenyl phosphate, 2,6-bis(tribromomethyl)phenyl phosphate, 2,6-bis(triiodomethyl)phenyl phosphate, 3,5-bis(trifluoromethyl)phenyl phosphate, 3,5-bis(trichloromethyl)phenyl phosphate, 3,5-bis(tribromomethyl)phenyl phosphate, 3,5-bis(triiodomethyl)phenyl phosphate, 4-perfluorovinylphenyl phosphate, etc.

[0080] Specific examples of halogenated aromatic phosphates include 2-fluorophenyl phosphate, 3-fluorophenyl phosphate, 4-fluorophenyl phosphate, 2-chlorophenyl phosphate, 3-chlorophenyl phosphate, 4-chlorophenyl phosphate, 2-bromophenyl phosphate, 3-bromophenyl phosphate, 4-bromophenyl phosphate, 2-iodophenyl phosphate, 4-iodophenyl phosphate, 2,4-difluorophenyl phosphate, 2,6-difluorophenyl phosphate, 2,4-dichlorophenyl phosphate, 2,6-dichlorophenyl phosphate, 2,4-dibromophenyl phosphate, 2,6-dibromophenyl phosphate, 2,4-diiodophenyl phosphate, 2,6-diiodophenyl phosphate, and 2,4,6-trifluorophenyl phosphate. Examples include, but are not limited to, acids, 3,4,5-trifluorophenyl phosphate, 2,4,6-trichlorophenyl phosphate, 3,4,5-trichlorophenyl phosphate, 2,4,6-tribromophenyl phosphate, 3,4,5-tribromophenyl phosphate, 2,4,6-triiodophenyl phosphate, 3,4,5-triiodophenyl phosphate, pentafluorophenyl phosphate, pentachlorophenyl phosphate, pentabromophenyl phosphate, pentaiodophenyl phosphate, fluoronaphthyl phosphate, chloronaphthyl phosphate, bromonaphthyl phosphate, iodonaphthyl phosphate, fluoroanthracenyl phosphate, chloroanthracenyl phosphate, bromoanthracenyl phosphate, iodoanthracenyl phosphate, etc.

[0081] A saturated aliphatic phosphoric acid is an alkane or cycloalkane compound in which at least one hydrogen atom is substituted with phosphoric acid. The number of carbon atoms constituting such an alkane or cycloalkane compound is not particularly limited, but is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The alkane compound may also be substituted with substituents such as halogen atoms like fluorine or aryl groups like phenyl groups, and the number of such substituents is usually 0 to 3.

[0082] Typical examples of saturated aliphatic phosphates include, but are not limited to, unsubstituted saturated aliphatic phosphates, halogenated saturated aliphatic phosphates, and aryl saturated aliphatic phosphates. In particular, unsubstituted saturated aliphatic phosphates and halogenated saturated aliphatic phosphates are preferred from the viewpoint of achieving excellent lithographic properties with good reproducibility and from the viewpoint of the availability of the compounds.

[0083] Specific examples of unsubstituted saturated aliphatic phosphates include, but are not limited to, methyl phosphate and ethyl phosphate.

[0084] Specific examples of halogenated saturated aliphatic phosphates include, but are not limited to, trifluoromethyl phosphate and pentafluoroethyl phosphate.

[0085] Specific examples of aryl saturated aliphatic phosphates include, but are not limited to, phenylmethane phosphate, diphenylmethane phosphate, triphenylmethane phosphate, 1-phenylethane phosphate, and 2-phenylethane phosphate.

[0086] An unsaturated aliphatic phosphoric acid is an alkene or alkyne compound in which at least one hydrogen atom is substituted with phosphoric acid. The number of carbon atoms constituting such an alkene or alkyne compound is not particularly limited, but is usually 2 to 10, preferably 2 to 5, and more preferably 2 to 3. The alkene or alkyne compound may also be substituted with substituents such as halogen atoms like fluorine or aryl groups like phenyl groups, and the number of such substituents is usually 0 to 3.

[0087] Examples of unsaturated aliphatic phosphates include, but are not limited to, unsubstituted unsaturated aliphatic phosphates, halogenated unsaturated aliphatic phosphates, and aryl unsaturated aliphatic phosphates. Among these, unsubstituted unsaturated aliphatic phosphates are preferred from the viewpoint of achieving excellent lithographic properties with good reproducibility and from the viewpoint of the availability of the compound.

[0088] Specific examples of unsubstituted unsaturated aliphatic phosphates include, but are not limited to, vinyl phosphate, 2-propene-1-phosphate, 1-butene-1-phosphate, and 3-butene-1-phosphate.

[0089] In one preferred embodiment of the present invention, examples of carboxyl group-containing organic acids include formic acid and oxalic acid, as well as aromatic carboxylic acids, saturated aliphatic carboxylic acids, unsaturated aliphatic carboxylic acids, and the like. In particular, aromatic carboxylic acids and unsaturated aliphatic carboxylic acids are preferred from the viewpoint of achieving excellent lithographic properties with good reproducibility and from the viewpoint of the availability of the compounds.

[0090] Aromatic carboxylic acids are those in which at least one hydrogen atom of an aromatic compound is substituted with a carboxyl group. The number of carbon atoms constituting the aromatic ring of such an aromatic compound is not particularly limited, but is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10. The aromatic ring may be substituted with substituents such as halogen atoms like fluorine, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups, alkenyl groups such as vinyl groups, halogenated alkyl groups such as trifluoromethyl groups, and halogenated alkenyl groups such as perfluorovinyl groups. The number of such substituents is usually 0 to 3. Furthermore, the number of carboxyl groups is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1.

[0091] Typical examples of aromatic carboxylic acids include, but are not limited to, unsubstituted aromatic carboxylic acids, alkyl or alkenyl aromatic carboxylic acids, alkyl or alkenyl halogenated aromatic carboxylic acids, and halogenated aromatic carboxylic acids. Among these, unsubstituted aromatic carboxylic acids and alkyl aromatic carboxylic acids are preferred from the viewpoint of achieving excellent lithographic properties with good reproducibility and from the viewpoint of the availability of the compounds.

[0092] Specific examples of unsubstituted aromatic carboxylic acids include, but are not limited to, benzoic acid, benzene-1,2-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, benzene-1,3,5-tricarboxylic acid, 2-naphthalenecarboxylic acid, anthracenecarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,4-carboxylic acid, phenanthrenecarboxylic acid, and pyrenecarboxylic acid.

[0093] Specific examples of alkyl or alkenyl aromatic carboxylic acids include o-toluenecarboxylic acid, m-toluenecarboxylic acid, p-toluenecarboxylic acid, p-styrenecarboxylic acid, p-isopropylbenzenecarboxylic acid, p-dodecylbenzenecarboxylic acid, dihexylbenzenecarboxylic acid, 2,5-dihexylbenzenecarboxylic acid, 3,5-bis(t-butyl)benzenecarboxylic acid, 3,5-bis(isopropyl)benzenecarboxylic acid, 2,4,6-tris(t-butyl)benzenecarboxylic acid, 2,4,6-tris(isopropyl)benzenecarboxylic acid, and 5,8-dibutyl Examples include, but are not limited to, -2-naphthalenecarboxylic acid, 6,7-dibutyl-2-naphthalenecarboxylic acid, hexylnaphthalenecarboxylic acid, 4-hexyl-1-naphthalenecarboxylic acid, 7-hexyl-1-naphthalenecarboxylic acid, 6-hexyl-2-naphthalenecarboxylic acid, octylnaphthalenecarboxylic acid, 2-octyl-1-naphthalenecarboxylic acid, dinonylnaphthalenecarboxylic acid, 2,7-dinonyl-4-naphthalenecarboxylic acid, dinonylnaphthalenedicarboxylic acid, dodecylnaphthalenecarboxylic acid, and 3-dodecyl-2-naphthalenecarboxylic acid.

[0094] Specific examples of alkyl or alkenyl halogenated aromatic carboxylic acids include, but are not limited to, 2-trifluoromethylbenzenecarboxylic acid, 2-trichloromethylbenzenecarboxylic acid, 2-tribromomethylbenzenecarboxylic acid, 2-triiodomethylbenzenecarboxylic acid, 3-trifluoromethylbenzenecarboxylic acid, 3-trichloromethylbenzenecarboxylic acid, 3-tribromomethylbenzenecarboxylic acid, 3-triiodomethylbenzenecarboxylic acid, 4-trifluoromethylbenzenecarboxylic acid, 4-trichloromethylbenzenecarboxylic acid, 4-tribromomethylbenzenecarboxylic acid, 4-triiodomethylbenzenecarboxylic acid, 2,6-bis(trifluoromethyl)benzenecarboxylic acid, 2,6-bis(trichloromethyl)benzenecarboxylic acid, 2,6-bis(tribromomethyl)benzenecarboxylic acid, 2,6-bis(triiodomethyl)benzenecarboxylic acid, 3,5-bis(trifluoromethyl)benzenecarboxylic acid, 3,5-bis(trichloromethyl)benzenecarboxylic acid, 3,5-bis(tribromomethyl)benzenecarboxylic acid, 3,5-bis(triiodomethyl)benzenecarboxylic acid, and 4-perfluorovinylbenzenecarboxylic acid.

[0095] Specific examples of halogenated aromatic carboxylic acids include 2-fluorobenzenecarboxylic acid, 3-fluorobenzenecarboxylic acid, 4-fluorobenzenecarboxylic acid, 2-chlorobenzenecarboxylic acid, 3-chlorobenzenecarboxylic acid, 4-chlorobenzenecarboxylic acid, 2-bromobenzenecarboxylic acid, 3-bromobenzenecarboxylic acid, 4-bromobenzenecarboxylic acid, 2-iodobenzenecarboxylic acid, 4-iodobenzenecarboxylic acid, 2,4-difluorobenzenecarboxylic acid, 2,6-difluorobenzenecarboxylic acid, 2,4-dichlorobenzenecarboxylic acid, 2,6-dichlorobenzenecarboxylic acid, 2,4-dibromobenzenecarboxylic acid, 2,6-dibromobenzenecarboxylic acid, 2,4-diiodobenzenecarboxylic acid, 2,6-diiodobenzenecarboxylic acid, and 2,4,6-trifluorobenzenecarboxylic acid. Examples include, but are not limited to, benzoic acid, 3,4,5-trifluorobenzenecarboxylic acid, 2,4,6-trichlorobenzenecarboxylic acid, 3,4,5-trichlorobenzenecarboxylic acid, 2,4,6-tribromobenzenecarboxylic acid, 3,4,5-tribromobenzenecarboxylic acid, 2,4,6-triiodobenzenecarboxylic acid, 3,4,5-triiodobenzenecarboxylic acid, pentafluorobenzenecarboxylic acid, pentachlorobenzenecarboxylic acid, pentabromobenzenecarboxylic acid, pentaiodobenzenecarboxylic acid, fluoronaphthalenecarboxylic acid, chloronaphthalenecarboxylic acid, bromonaphthalenecarboxylic acid, iodonaphthalenecarboxylic acid, fluoroanthracenecarboxylic acid, chloroanthracenecarboxylic acid, bromoanthracenecarboxylic acid, iodoanthracenecarboxylic acid, etc.

[0096] From the viewpoint of reproducibly achieving excellent resist properties, when the substituent of the aromatic ring in an aromatic carboxylic acid is a halogen atom, a fluorine atom is preferred, and when it is an alkyl group, an alkyl group having 1 to 3 carbon atoms is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.

[0097] A saturated aliphatic carboxylic acid is an alkane or cycloalkane compound in which at least one hydrogen atom is substituted with a carboxyl group. The number of carbon atoms constituting such an alkane or cycloalkane compound is not particularly limited, but is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The alkane compound may also be substituted with substituents such as halogen atoms such as fluorine or aryl groups such as phenyl groups, and the number of such substituents is usually 0 to 3.

[0098] Typical examples of saturated aliphatic carboxylic acids include, but are not limited to, unsubstituted saturated aliphatic carboxylic acids, halogenated saturated aliphatic carboxylic acids, hydroxy saturated aliphatic carboxylic acids, and aryl saturated aliphatic carboxylic acids. In particular, from the viewpoint of achieving excellent lithographic properties with good reproducibility and the ease of obtaining the compounds, unsubstituted saturated aliphatic carboxylic acids and halogenated saturated aliphatic carboxylic acids are preferred, and halogenated saturated aliphatic carboxylic acids are more preferred.

[0099] Specific examples of unsubstituted aliphatic carboxylic acids include methanecarboxylic acid, methanedicarboxylic acid (malonic acid), ethanecarboxylic acid, ethane-1,1-dicarboxylic acid, ethane-1,2-dicarboxylic acid (succinic acid), propanecarboxylic acid, propane-1,1-dicarboxylic acid, propane-1,2-dicarboxylic acid, propane-2,2-dicarboxylic acid, propane-1,3-dicarboxylic acid, (glutaric acid), butanecarboxylic acid, butane-1,1-dicarboxylic acid, butane-1,2-dicarboxylic acid, butane-1,3-dicarboxylic acid, butane-1,4-dicarboxylic acid (adipic acid), butane-2,2-dicarboxylic acid, butane-2,3-dicarboxylic acid, butane-2,4- Examples include, but are not limited to, chain-like or branched alkanecarboxylic acids such as dicarboxylic acids, pentanecarboxylic acid, hexanecarboxylic acid, heptanecarboxylic acid, octanecarboxylic acid, nonanecarboxylic acid, decanocarboxylic acid, undecanocarboxylic acid, dodecanocarboxylic acid, tridecanocarboxylic acid, tetradecanocarboxylic acid, pentadecanocarboxylic acid, hexadecanecarboxylic acid, heptadecanecarboxylic acid, octadecanocarboxylic acid, nonadecanecarboxylic acid, eicosanecarboxylic acid, henicosanecarboxylic acid, docosanecarboxylic acid, tricosanecarboxylic acid, tetraconsanatecarboxylic acid, and cycloalkanecarboxylic acids such as camphorcarboxylic acid.

[0100] Specific examples of halogenated saturated aliphatic carboxylic acids include fluoromethanecarboxylic acid, difluoromethanecarboxylic acid, trifluoromethanecarboxylic acid, chloromethanecarboxylic acid, dichloromethanecarboxylic acid, trichloromethanecarboxylic acid, bromomethanecarboxylic acid, dibromomethanecarboxylic acid, tribromomethanecarboxylic acid, iodomethanecarboxylic acid, diiodomethanecarboxylic acid, triiodomethanecarboxylic acid, fluoroethanecarboxylic acid, difluoroethanecarboxylic acid, triiodomethanecarboxylic acid, pentafluoroethanecarboxylic acid, chloroethanecarboxylic acid, dichloroethanecarboxylic acid, trichloroethanecarboxylic acid, pentachloroethanecarboxylic acid, tribromoethanecarboxylic acid, pentabromoethanecarboxylic acid, triiodoethanecarboxylic acid, pentaiodoethanecarboxylic acid, fluoropropanecarboxylic acid, trifluoropropanecarboxylic acid, heptafluoropropanecarboxylic acid, chloropropanecarboxylic acid, trichloropropanecarboxylic acid, heptachloropropanecarboxylic acid, bromopropanecarboxylic acid, tribromopropanecarboxylic acid, heptabromopropanecarboxylic acid, triiodopropanecarboxylic acid Heptaiodopropanecarboxylic acid, trifluorobutanecarboxylic acid, nonafluorobutanecarboxylic acid, trichlorobutanecarboxylic acid, nonachlorobutanecarboxylic acid, tribromobutanecarboxylic acid, nonabromobutanecarboxylic acid, triiodobutanecarboxylic acid, nonaiodobutanecarboxylic acid, trifluoropentanecarboxylic acid, perfluoropentanecarboxylic acid, trichloropentanecarboxylic acid, perchloropentanecarboxylic acid, tribromopentanecarboxylic acid, perbromopentanecarboxylic acid, triiodopentanecarboxylic acid, periodopentanecarboxylic acid, trifluorohexanecarboxylic acid, perfluorohexanecarboxylic acid, trichlorohexanecarboxylic acid, perchlorohexanecarboxylic acid, perbromohexanecarboxylic acid, periodohexanecarboxylic acid, trifluoroheptanecarboxylic acid, perfluoroheptanecarboxylic acid, trichloroheptanecarboxylic acid, perchloroheptanecarboxylic acid, perbromoheptanecarboxylic acid, periodoheptanecarboxylic acid, trifluorooctanecarboxylic acid, perfluorooctanecarboxylic acid, perchlorooctanecarboxylic acid,Perbromooctanecarboxylic acid, periodooctanecarboxylic acid, trifluorononanocarboxylic acid, perfluorononanocarboxylic acid, trichlorononanocarboxylic acid, perchlorononanocarboxylic acid, perbromononanecarboxylic acid, periodononanocarboxylic acid, trifluorodecanecarboxylic acid, perfluorodecanecarboxylic acid, trichlorodecanecarboxylic acid, perchlorodecanecarboxylic acid, perbromodecanecarboxylic acid, periododecanecarboxylic acid, trifluoroundecanecarboxylic acid, perfluoroundecanecarboxylic acid, trichloroundecanecarboxylic acid, perchloroundecanecarboxylic acid, perbromoundecanecarboxylic acid, periodondecanecarboxylic acid, trifluorododecanecarboxylic acid, perfluorododecanecarboxylic acid, trichlorododecanecarboxylic acid, perchlorododecanecarboxylic acid, perbromododecanecarboxylic acid, periodondecanecarboxylic acid, trifluorotridecanecarboxylic acid, perfluorotridecanecarboxylic acid, trichlorotridecanecarboxylic acid, perchlorotridecanecarboxylic acid, perbromotridecanecarboxylic acid, periodondecanecarboxylic acid, trifluorotetrade Canocarboxylic acid, perfluorotetradecanecarboxylic acid, trichlorotetradecanecarboxylic acid, perchlorotetradecanecarboxylic acid, perbromotetradecanecarboxylic acid, periodotetradecanecarboxylic acid, trifluoropentadecanecarboxylic acid, perfluoropentadecanecarboxylic acid, trichloropentadecanecarboxylic acid, perchloropentadecanecarboxylic acid, perbromopentadecanecarboxylic acid, periodopentadecanecarboxylic acid, perfluorohexadecanecarboxylic acid, perchlorohexadecanecarboxylic acid, perbromohexadecanecarboxylic acid, Periodohexadecanecarboxylic acid, perfluoroheptadecanecarboxylic acid, perchloroheptadecanecarboxylic acid, perbromoheptadecanecarboxylic acid, periodoheptadecanecarboxylic acid, perfluorooctadecanecarboxylic acid, perchlorooctadecanecarboxylic acid, perbromooctadecanecarboxylic acid, periodooctadecanecarboxylic acid, perfluorononadecanecarboxylic acid, perchlorononadecanecarboxylic acid, perbromononadecanecarboxylic acid, periodononadecanecarboxylic acid, perfluoroicosanecarboxylic acid, perchloroicosanecarboxylic acid,Examples include, but are not limited to, perbromoicosanecarboxylic acid, periodoicosanecarboxylic acid, perfluorohenicosanecarboxylic acid, perchlorohenicosanecarboxylic acid, perbromohenicosanecarboxylic acid, periodohenicosanecarboxylic acid, perfluorodocosanecarboxylic acid, perchlorodocosanecarboxylic acid, perbromododocosanecarboxylic acid, periododocosanecarboxylic acid, perfluorotricosanecarboxylic acid, perchlorotricosanecarboxylic acid, perbromotricosanecarboxylic acid, periodotricosanecarboxylic acid, perfluorotetraconosecarboxylic acid, perchlorotetraconosecarboxylic acid, perbromotetraconosecarboxylic acid, and periodotetraconosecarboxylic acid.

[0101] Specific examples of hydroxysaturated aliphatic carboxylic acids include, but are not limited to, 1,2-dihydroxyethane-1,2-dicarboxylic acid (tartaric acid) and 2-hydroxypropane-1,2,3-tricarboxylic acid (citric acid).

[0102] Specific examples of aryl saturated aliphatic carboxylic acids include, but are not limited to, phenylmethanecarboxylic acid, diphenylmethanesulfone, triphenylmethanecarboxylic acid, 1-phenylethanecarboxylic acid, and 2-phenylethanecarboxylic acid.

[0103] From the viewpoint of reproducibly achieving excellent resist properties, when the substituent substituted for the alkyl in a saturated aliphatic carboxylic acid is a halogen atom, a fluorine atom is preferred; when it is an aryl group, an aryl group having 6 to 10 carbon atoms is preferred, and phenyl is more preferred.

[0104] An unsaturated aliphatic carboxylic acid is an alkene or alkyne compound in which at least one hydrogen atom is substituted with a carboxylic acid group. The number of carbon atoms constituting such an alkene or alkyne compound is not particularly limited, but is usually 2 to 10, preferably 2 to 5, and more preferably 2 to 3. The alkene or alkyne compound may also be substituted with substituents such as halogen atoms like fluorine or aryl groups like phenyl groups, and the number of such substituents is usually 0 to 3.

[0105] Examples of unsaturated aliphatic carboxylic acids include, but are not limited to, unsubstituted unsaturated aliphatic carboxylic acids, halogenated unsaturated aliphatic carboxylic acids, and aryl unsaturated aliphatic carboxylic acids. Among these, unsubstituted unsaturated aliphatic carboxylic acids are preferred from the viewpoint of achieving excellent lithographic properties with good reproducibility and from the viewpoint of the availability of the compounds.

[0106] Specific examples of unsubstituted unsaturated aliphatic carboxylic acids include, but are not limited to, vinyl carboxylic acids, 2-propene-1-carboxylic acid, 1-butene-1-carboxylic acid, 3-butene-1-carboxylic acid, trans-ethylene-1,2-dicarboxylic acid (fumaric acid), and cis-ethylene-1,2-dicarboxylic acid (maleic acid).

[0107] In one preferred embodiment of the present invention, examples of phenolic hydroxyl group-containing organic acids include hydroxyaromatic compounds.

[0108] Hydroxy-aromatic compounds are those in which at least one hydrogen atom of an aromatic compound is substituted with a hydroxyl group. The number of carbon atoms constituting the aromatic ring of such an aromatic compound is not particularly limited, but is usually 6 to 20, preferably 6 to 14, and more preferably 6 to 10. The aromatic ring may be substituted with substituents such as halogen atoms like fluorine, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups, alkenyl groups such as vinyl groups, halogenated alkyl groups such as trifluoromethyl groups, and halogenated alkenyl groups such as perfluorovinyl groups. The number of such substituents is usually 0 to 3. Furthermore, the number of hydroxyl groups is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1.

[0109] Examples of hydroxyaromatic compounds typically include, but are not limited to, unsubstituted hydroxyaromatic compounds, alkyl or alkenyl hydroxyaromatic compounds, alkyl or alkenyl halogenated hydroxyaromatic compounds, and halogenated hydroxyaromatic compounds. Among these, unsubstituted hydroxyaromatic compounds are preferred from the viewpoint of achieving excellent lithographic properties with good reproducibility and from the viewpoint of the availability of the compounds.

[0110] Specific examples of unsubstituted hydroxyaromatic compounds include, but are not limited to, phenol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,3,5-trihydroxybenzene, 2-hydroxynaphthalene, hydroxyanthracene, hydroxyphenanthrene, and hydroxypyrene.

[0111] Specific examples of alkyl or alkenyl hydroxyaromatic compounds include, but are not limited to, 2,5-dihydroxytoluene, p-hydroxystyrene, 1-isopropyl-4-hydroxybenzene, and 1-dodecyl-4-hydroxybenzene.

[0112] Specific examples of alkyl halides or alkenylhydroxyaromatic halides include, but are not limited to, 2-trifluoromethylphenol, 2-trichloromethylphenol, 2-tribromomethylphenol, 2-triiodomethylphenol, 3-trifluoromethylphenol, 3-trichloromethylphenol, 3-tribromomethylphenol, 3-triiodomethylphenol, 4-trifluoromethylphenol, 4-trichloromethylphenol, 4-tribromomethylphenol, 4-triiodomethylphenol, 2,6-bis(trifluoromethyl)phenol, 2,6-bis(tribromomethyl)phenol, 2,6-bis(triiodomethyl)phenol, 3,5-bis(trifluoromethyl)phenol, 3,5-bis(tribromomethyl)phenol, 3,5-bis(triiodomethyl)phenol, 3,5-bis(triiodomethyl)phenol, 4-perfluorovinylphenol, etc.

[0113] Specific examples of halogenated hydroxyaromatic compounds include 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-iodophenol, 4-iodophenol, 2,4-difluorophenol, 2,6-difluorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, 2,4-dibromophenol, 2,6-dibromophenol, 2,4-diiodophenol, 2,6-diiodophenol, 2,4,6-trifluorophenol, and 3,4,5-trifluoro Examples include, but are not limited to, phenol, 2,4,6-trichlorophenol, 3,4,5-trichlorophenol, 2,4,6-tribromophenol, 3,4,5-tribromophenol, 2,4,6-triiodophenol, 3,4,5-triiodophenol, pentafluorophenol, pentachlorophenol, pentabromophenol, pentaiodophenol, fluorohydroxynaphthalene, chlorohydroxynaphthalene, bromohydroxynaphthalene, hydroxyiodonaphthalene, fluorohydroxyanthracene, chlorohydroxyanthracene, bromohydroxyanthracene, and hydroxyiodonaphthalene.

[0114] Furthermore, preferred organic acids in the present invention include oxocarbon acids such as delta acid, squalane acid, and rhozonic acid.

[0115] In one embodiment of the present invention, from the viewpoint of obtaining excellent lithography characteristics with better reproducibility, the two or more acidic compounds preferably include two or more selected differently from the group consisting of nitric acid, sulfuric acid, oxocarbonic acid, sulfonic acid group-containing organic acid, and carboxyl group-containing organic acid, and more preferably include two or more selected differently from the group consisting of nitric acid, oxocarbonic acid, sulfonic acid group-containing organic acid, and carboxyl group-containing organic acid.

[0116] In another embodiment, from the viewpoint of achieving excellent lithography characteristics with greater reproducibility, the two or more acidic compounds preferably include at least one selected from the group consisting of sulfuric acid and sulfonic acid group-containing organic acids, and at least one selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, boric acid, heteropoly acid, oxocarbon acid, phosphoric acid group-containing organic acid, carboxyl group-containing organic acid, and phenolic hydroxyl group-containing organic acid, and more preferably includes a sulfonic acid group-containing organic acid and at least one selected from the group consisting of nitric acid, oxocarbon acid, and carboxyl group-containing organic acid.

[0117] The hydrolysis condensate contained in the film-forming composition of the present invention is obtained by hydrolysis and condensation of a hydrolyzable silane compound containing an amino group-containing silane represented by formula (1) described above using the acidic compound described above. By using the amino group-containing silane and two or more acidic compounds, it is possible to realize a unit containing two or more amine salt structures as a monomer unit derived from the amino group-containing silane in the hydrolysis condensate. As a result, the composition for the resist film formed as the upper layer can achieve solvent resistance, good etching properties to fluorine-based gases, and good lithography properties. In particular, nitric acid, carboxylic acid compounds, and phenolic compounds can contribute especially to improving lithography properties, while sulfuric acid, sulfonic acid compounds, and phosphoric acid compounds can contribute especially to improving etching properties against fluorinated gases and wet etching properties.

[0118] In the present invention, the number of acidic compounds used in producing the hydrolysis condensate is not particularly limited as long as it is two or more, but from the viewpoint of reproducibly achieving excellent lithography properties, it is usually 2 to 5, preferably 2 to 4, more preferably 2 to 3, and even more preferably 2.

[0119] The film-forming composition of the present invention contains a solvent. Such solvents are not limited insofar as they dissolve the hydrolyzable silanes, their hydrolysis condensates, and other components described above and below.

[0120] Specific examples 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 ethyl hydroxyethyl ethyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol 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 acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate Examples of solvents include methyl ester, 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, γ-butyrolactone, etc. The solvent can be used alone or in combination of two or more.

[0121] The film-forming composition of the present invention may contain water as a solvent, and its content is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, relative to the solvent contained in the composition.

[0122] In the present invention, the hydrolyzable silane may include a hydrolyzable organosilane having an onium group in its molecule. By using a hydrolyzable organosilane having an onium group in its molecule, the crosslinking reaction of the hydrolyzable silane can be effectively and efficiently promoted.

[0123] A suitable example of a hydrolyzable organosilane having such an onium group in its molecule is represented by the following formula (4).

[0124] [ka]

[0125] R 31R is a group that bonds to a silicon atom, and independently of each other, it is an onium group or an organic group containing it. 32 R is a group that bonds to a silicon atom and represents an optionally substituted alkyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted halogenated alkyl group, optionally substituted halogenated aryl group, optionally substituted halogenated aralkyl group, optionally substituted alkoxyalkyl group, optionally substituted alkoxyaryl group, optionally substituted alkoxyaralkyl group, or optionally substituted alkenyl group, or an organic group containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, or cyano group. 33 k is a group or atom that is independently bonded to a silicon atom, and is an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, where j represents 1 or 2, k represents 0 or 1, and 1 ≤ j + k ≤ 2. Such organic groups containing 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, halogen atoms and epoxy groups, acryloyl groups, methacryloyl groups, mercapto groups, amino groups or cyano groups, as well as specific examples of substituents of alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups and alkenyl groups, and their preferred number of carbon atoms are the same as those described above.

[0126] More specifically, examples of onium groups include cyclic ammonium groups or linear ammonium groups, with tertiary or quaternary ammonium groups being preferred. In other words, preferred examples of an onium group or an organic group containing it include a cyclic ammonium group or a chain-like ammonium group or an organic group containing at least one of these, with a tertiary ammonium group or a quaternary ammonium group or an organic group containing at least one of these being preferred. Furthermore, when the onium group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. In this case, there are two possibilities: the nitrogen atom and silicon atom constituting the ring are bonded directly or via a divalent linking group; or the carbon atom and silicon atom constituting the ring are bonded directly or via a divalent linking group.

[0127] In one preferred embodiment of the present invention, R 31 This is a heteroaromatic cyclic ammonium group represented by the following formula (S1).

[0128] [ka]

[0129] A 1 , A 2 , A 3 and A 4 These represent a group that is independent of each other and can be expressed by any of the following formulas (J1) to (J3), but A 1 ~A 4 At least one of them is a group represented by the following formula (J2), and the silicon atom in formula (4) is A 1 ~A 4 Depending on which of the following is combined, A 1 ~A 4 The type of bond between each atom and the adjacent atoms that together form the ring—whether it is a single bond or a double bond—determines whether the resulting ring exhibits aromaticity.

[0130] [ka]

[0131] R 30Each of these independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide, an aryl halide, an aralkyl halide, or an alkenyl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, alkyl halides, aryl halides, aralkyl halides, and alkenyl groups, and their preferred number of carbon atoms, are the same as those described above.

[0132] R 34 Each independently represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, or a hydroxyl group, R 34 If there are two or more R 34 They may be bonded to each other to form a ring, and two R 34 The ring formed may be a bridging ring structure, in which case the cyclic ammonium group will have an adamantane ring, norbornene ring, spiro ring, etc. Specific examples of such alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, and alkenyl groups, and their preferred number of carbon atoms, are the same as those mentioned above.

[0133] n 1 m is an integer from 1 to 8. 1 is 0 or 1, m 2 is a positive integer ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring. m 1 If A is 0, 1 ~A 4 (4+n) 1 A member ring is formed. That is, n 1 When is 1, it is a 5-membered ring, n 1 When is 2, it is a 6-membered ring, n 1 When is 3, it is a 7-membered ring, n 1 When is 4, it is an 8-membered ring, n 1 When is 5, it is a 9-membered ring, n 1 When n is 6, it is a 10-membered ring. 1When is 7, it is an 11-membered ring, n 1 When the number is 8, a 12-membered ring is formed. m 1 If A is 1, 1 ~A 3 (4+n) 1 ) Member ring and A 4 A fused ring is formed by the fusion of a 6-membered ring containing the compound. A 1 ~A 4 Depending on which of formulas (J1) to (J3) it is, the ring may or may not have hydrogen atoms on the atoms constituting the ring, but A 1 ~A 4 However, if there is a hydrogen atom on the atom constituting the ring, that hydrogen atom is R 34 It may be replaced by A. 1 ~A 4 In the ring constituent atoms other than the ring constituent atoms inside, R 34 It may be substituted. For these reasons, as stated above, m 2 This is selected from integers ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring.

[0134] The bonds of the heteroaromatic cyclic ammonium group represented by formula (S1) are located on any carbon or nitrogen atom present in such a monocyclic or fused ring, and either directly bond to a silicon atom or a linking group is attached to form an organic group containing cyclic ammonium, which then bonds to a silicon atom. Examples of such linking groups include, but are not limited to, alkylene groups, arylene groups, and alkenylene groups. Specific examples of alkylene groups and arylene groups, and their preferred number of carbon atoms, are the same as those mentioned above.

[0135] The alkenylene group is a divalent group derived by removing an additional hydrogen atom from an alkenyl group, and specific examples of such alkenyl groups are the same as those mentioned above. The number of carbon atoms in the alkenylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include, but are not limited to, vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, and 2-pentenylene groups.

[0136] Specific examples of hydrolyzable organosilanes represented by formula (4) having a heteroaromatic cyclic ammonium group represented by formula (S1) are given, but are not limited to these. [ka]

[0137] [ka]

[0138] [ka]

[0139] In another example of a preferred embodiment of the present invention, R 31 This is a heteroaliphatic cyclic ammonium group represented by the following formula (S2). [ka]

[0140] A 5 , A 6 , A 7 and A 8 These represent groups that are independent of each other and can be expressed by any of the following formulas (J4) to (J6), but A 5 ~A 8 At least one of them is a group represented by the following formula (J5), and the silicon atom in formula (4) is A 5 ~A 8 Depending on which of the following is combined, A 5 ~A 8Whether the bond of each with the atom adjacent to each and forming a ring together is a single bond or a double bond is determined so that the formed ring exhibits non-aromaticity.

[0141]

Chemical formula

[0142] R 30 independently of each other represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group or an alkenyl group. Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group and alkenyl group and their preferred number of carbon atoms are the same as those described above. R 35 independently of each other represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group or a hydroxy group. When two or more R 35 are present, two R 35 may be bonded to each other to form a ring, and the ring formed by two R 35 may be a bridged ring structure. In such a case, the cyclic ammonium group will have an adamantane ring, a norbornene ring, a spiro ring, etc. Specific examples of such alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group and alkenyl group and their preferred number of carbon atoms are the same as those described above.

[0143] n 2 is an integer from 1 to 8, m 3 is 0 or 1, and m 4 is a positive integer from 0 or 1 to the maximum number that can be substituted on a monocyclic or polycyclic ring. m 3 is 0, A 5 ~A 8 including (4 + n2 A member ring is formed. That is, n 2 When is 1, it is a 5-membered ring, n 2 When is 2, it is a 6-membered ring, n 2 When is 3, it is a 7-membered ring, n 2 When is 4, it is an 8-membered ring, n 2 When is 5, it is a 9-membered ring, n 2 When n is 6, it is a 10-membered ring. 2 When is 7, it is an 11-membered ring, n 2 When the number is 8, a 12-membered ring is formed. m 3 If A is 1, 5 ~A 7 (4+n) 2 ) Member ring and A 8 A fused ring is formed by the fusion of a 6-membered ring containing the compound. A 5 ~A 8 Depending on which of formulas (J4) to (J6) it is, there may or may not be hydrogen atoms on the atoms constituting the ring, but A 5 ~A 8 However, if there is a hydrogen atom on the atom constituting the ring, that hydrogen atom is R 35 It may be replaced by A. 5 ~A 8 In the ring constituent atoms other than the ring constituent atoms inside, R 35 It may be substituted. For these reasons, as stated above, m 4 This is selected from integers ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring.

[0144] The bonds of the heteroaliphatic cyclic ammonium group represented by formula (S2) are located on any carbon or nitrogen atom present in such a monocyclic or fused ring, and either directly bond to a silicon atom or form an organic group containing a cyclic ammonium group via a linking group, which then bonds to a silicon atom. Examples of such linking groups include alkylene groups, arylene groups, or alkenylene groups. Specific examples of alkylene groups, arylene groups, and alkenylene groups, as well as their preferred number of carbon atoms, are the same as those described above.

[0145] Specific examples of hydrolyzable organosilanes represented by formula (4) having a heteroaliphatic cyclic ammonium group represented by formula (S2) are given, but are not limited to these. [ka]

[0146] [ka]

[0147] In another example of a preferred embodiment of the present invention, R 31 This is a chain-like ammonium group represented by the following formula (S3). [ka]

[0148] R 30 Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide, an aryl halide, an aralkyl halide, or an alkenyl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, alkyl halides, aryl halides, aralkyl halides, and alkenyl groups, and their preferred number of carbon atoms, are the same as those described above.

[0149] The chain-like ammonium group represented by formula (S3) is either directly bonded to a silicon atom, or a linking group is attached to it to form an organic group containing the chain-like ammonium group, which then bonds to the silicon atom. Examples of such linking groups include alkylene groups, arylene groups, or alkenylene groups, and specific examples of alkylene groups, arylene groups, and alkenylene groups are the same as those mentioned above.

[0150] Specific examples of hydrolyzable organosilanes represented by formula (4) having a chain-like ammonium group represented by formula (S3) are given, but are not limited to these. [ka]

[0151] [ka]

[0152] The film-forming composition of the present invention may further contain, as a hydrolyzable silane, a silane having a sulfone group or a silane having a sulfonamide group. The following are some specific examples, but they are not limited to these.

[0153] [ka]

[0154] [ka]

[0155] [ka]

[0156] In the present invention, the above-mentioned hydrolyzable silane compound may include a hydrolyzable organosilane having a cyclic urea skeleton in its molecule. Specific examples, though not limited to these, include hydrolyzable organosilanes represented by the following formula (5-1).

[0157] [ka]

[0158] In formula (5-1), R 501 These are groups that bond to silicon atoms, and independently of each other, they represent groups represented by formula (5-2), and R 502R is a group bonded to a silicon atom and represents an optionally substituted alkyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted halogenated alkyl group, optionally substituted halogenated aryl group, optionally substituted halogenated aralkyl group, optionally substituted alkoxyalkyl group, optionally substituted alkoxyaryl group, optionally substituted alkoxyaralkyl group, or optionally substituted alkenyl group, or an organic group containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group. 503 x is a group or atom bonded to a silicon atom, independently representing an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, x is 1 or 2, y is 0 or 1, and x + y ≤ 2, R 502 Organic groups including alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, and epoxy groups, acryloyl groups, methacryloyl groups, mercapto groups, or cyano groups and R 503 Specific examples of alkoxy groups, aralkyloxy groups, acyloxy groups, halogen atoms, and their substituents, as well as preferred carbon atom numbers, etc., are as follows: 2 and R 3 The same items mentioned above can be cited in relation to this matter.

[0159] [ka]

[0160] In formula (5-2), R 504 Each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy group or a sulfonyl group, and R 505 These independently represent an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-), or an ester bond (-CO-O- or -O-CO-). Note, R504 Specific examples of organic groups including optionally substituted alkyl groups, optionally substituted alkenyl groups, and epoxy groups, and preferred numbers of carbon atoms, etc., are given by R 2 The same things mentioned above can be cited regarding R, but in addition to these, 504 Preferably, the alkyl group that may be substituted is an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group. Specific examples include the allyl group, 2-vinylethyl group, 3-vinylpropyl group, and 4-vinylbutyl group.

[0161] Organic groups containing a sulfonyl group are not particularly limited as long as they contain a sulfonyl group, and include optionally substituted alkylsulfonyl groups, optionally substituted arylsulfonyl groups, optionally substituted aralkylsulfonyl groups, optionally substituted halogenated alkylsulfonyl groups, optionally substituted halogenated arylsulfonyl groups, optionally substituted halogenated aralkylsulfonyl groups, optionally substituted alkoxyalkylsulfonyl groups, optionally substituted alkoxyarylsulfonyl groups, optionally substituted alkoxyaralkylsulfonyl groups, optionally substituted alkenylsulfonyl groups, etc. Specific examples of alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, and alkenyl groups, as well as their substituents, and preferred carbon atom numbers, etc., are as follows: 2 The same items mentioned above can be cited in relation to this matter.

[0162] The alkylene group is a divalent group derived by removing one more hydrogen atom from the alkyl group described above, and may be linear, branched, or cyclic. Specific examples of such alkylene groups are the same as those described above. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.

[0163] Also, R505 The alkylene group may have one or more selected from sulfide bonds, ether bonds, and ester bonds at its terminal or in the middle, preferably in the middle. Specific examples of alkylene groups include linear alkylene groups such as methylene, ethylene, trimethylene, methylethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; and 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, and 1,3-cyclobutanediyl. Examples of alkylene groups include cyclic alkylenes such as tandyl groups, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl, as well as ether groups such as -CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2SCH2CH2CH2-, -CH2CH2CH2SCH2CH2CH2-, -CH2OCH2CH2SCH2-, and -CH2OCH2CH2SCH2-, but are not limited to these.

[0164] A hydroxyalkylene group is one in which at least one hydrogen atom of the above-mentioned alkylene group is replaced by a hydroxyl group. Specific examples include, but are not limited to, hydroxymethylene, 1-hydroxyethylene, 2-hydroxyethylene, 1,2-dihydroxyethylene, 1-hydroxytrimethylene, 2-hydroxytrimethylene, 3-hydroxytrimethylene, 1-hydroxytetramethylene, 2-hydroxytetramethylene, 3-hydroxytetramethylene, 4-hydroxytetramethylene, 1,2-dihydroxytetramethylene, 1,3-dihydroxytetramethylene, 1,4-dihydroxytetramethylene, 2,3-dihydroxytetramethylene, 2,4-dihydroxytetramethylene, and 4,4-dihydroxytetramethylene.

[0165] In formula (5-2), X 501 These independently represent groups represented by the following formulas (5-3) to (5-5), and the carbon atoms of the ketone group in formulas (5-4) and (5-5) are the same as the R in formula (5-2). 505 It bonds with the nitrogen atom to which it is bonded.

[0166] [ka]

[0167] In formulas (5-3) to (5-5), R 506 ~R 510 Each independently represents an organic group containing a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an epoxy group or sulfonyl group. Specific examples and preferred number of carbon atoms for organic groups containing optionally substituted alkyl groups, optionally substituted alkenyl groups, and epoxy groups or sulfonyl groups are given by R. 504 The same items mentioned above can be cited in relation to this matter. In particular, from the viewpoint of reproducibly achieving excellent lithography characteristics, the group represented by formula (5-5) is preferred.

[0168] From the perspective of reproducibly achieving excellent lithography characteristics, R 504 and R 506 or R 510 is preferably an alkyl group in which the hydrogen atom at the terminal is substituted with a vinyl group.

[0169] The hydrolyzable organosilane represented by the above formula (5-1) may be a commercially available product, or can also be synthesized by a known method described in International Publication No. 2011 / 102470 or the like.

[0170] Hereinafter, specific examples of the hydrolyzable organosilane represented by the formula (5-1) are given, but are not limited thereto.

Chemical formula

Chemical formula

Chemical formula

[0171] In a preferred embodiment of the present invention, the hydrolysis condensate contained in the film-forming composition of the present invention includes a hydrolysis condensate obtained by using at least another silane represented by the formula (2) together with the amino group-containing silane represented by the formula (1). In another preferred embodiment of the present invention, the hydrolysis condensate contained in the film-forming composition of the present invention includes a hydrolysis condensate obtained by using at least another silane represented by the formula (2) and the hydrolyzable organosilane represented by the formula (5-1) together with the amino group-containing silane represented by the formula (1).

[0172] The weight average molecular weight of the hydrolysis condensate in the present invention is usually 500 to 1,000,000. From the perspective of suppressing precipitation of the hydrolysis condensate in the composition, etc., it is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the perspective of achieving both storage stability and coating properties, etc., it is preferably 700 or more, 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.

[0173] The film-forming composition of the present invention may contain organic acids, water, alcohol, etc., for purposes such as stabilizing its hydrolysis condensate.

[0174] 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 hydrolyzable silane, its hydrolysate, and its hydrolyzed condensate.

[0175] 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 composition.

[0176] The film-forming composition of the present invention may further contain, if necessary, organic polymer compounds, acid generators, surfactants, and the like.

[0177] The organic polymer compounds that may be included in the film-forming composition of the present invention are appropriately selected from various organic polymers (condensation polymers and addition polymers) depending on the purpose of their addition. Specific examples include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be suitably used when such functionality is required. Specific examples of such organic polymer compounds include, but are not limited to, addition polymerization polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as structural units, and condensation polymerization polymers such as phenol novolac and naphthol novolac.

[0178] When an addition polymerization polymer is used as the organic polymer compound, the polymer compound may be either a homopolymer or a copolymer. Addition polymerizable monomers are used in the production of addition polymers. Specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0179] Specific examples of acrylic acid ester compounds include, but are not limited to, methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthyl methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate.

[0180] Specific examples of methacrylate ester compounds include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthylmethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate.

[0181] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-antrylcrylamide.

[0182] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-antrylmethacrylamide.

[0183] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

[0184] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0185] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0186] When a condensation polymer is used as the polymer, examples of such polymers include condensation polymers of glycol compounds and dicarboxylic acid compounds. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, and butylene glycol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Other examples include, but are not limited to, polyesters, polyamides, and polyimides such as polypyromellitrimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate. If an organic polymer compound contains a hydroxyl group, this hydroxyl group can undergo a crosslinking reaction with hydrolysis condensates and the like.

[0187] The weight-average molecular weight of the organic polymer compound that may be contained in the film-forming composition of the present invention is usually 1,000 to 1,000,000, but from the viewpoint of suppressing precipitation in the composition, it is preferably 300,000 or less, more preferably 200,000 or less, and even more preferably 100,000, and from the viewpoint of fully obtaining the functional effects of the polymer, it is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more. Such organic polymer compounds can be used individually or in combination of two or more.

[0188] When the film-forming composition of the present invention contains an organic polymer compound, its content cannot be specified in general terms as it is determined appropriately considering the function of the organic polymer compound, etc. However, it is usually in the range of 1% to 200% by mass relative to the mass of the hydrolysis condensate of the hydrolyzable silane. From the viewpoint of suppressing precipitation in the composition, it is preferably 100% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. From the viewpoint of obtaining the full effect, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 30% by mass or more.

[0189] When the film-forming composition of the present invention contains an acid generator, examples of the acid generator include a thermal acid generator and a photoacid generator. Examples of the photoacid generator include, but are not limited to, onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, and the like.

[0190] Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormalbutanesulfonate, diphenyliodonium perfluoronormaloctanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormalbutanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, etc., but are not limited to these.

[0191] Specific examples of the sulfonimide compound include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalimide, and the like.

[0192] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, and the like. The acid generator can be used individually or in combination of two or more types.

[0193] 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 hydrolyzable silane. 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.

[0194] 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 octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, 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.

[0195] 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 (polyorganosiloxane). 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.

[0196] The film-forming composition of the present invention preferably does not contain a curing catalyst as an additive. This is because if a curing catalyst is included as an additive, a portion of the additive may migrate into the resist film during resist film formation or subsequent heating, potentially causing deterioration of its properties, and this is to be avoided.

[0197] Furthermore, the film-forming composition of the present invention may also contain rheology modifiers, adhesion aids, pH adjusters, 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 the semiconductor substrate, organic underlayer film, or resist film.

[0198] Bisphenol S or a bisphenol S derivative can be added as a pH adjuster. The content 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 (polyorganosiloxane).

[0199] The following are specific examples of bisphenol S and bisphenol S derivatives, but the text is not limited to these. [ka]

[0200] The hydrolysis condensate used in the present invention can be obtained by hydrolyzing and condensing the above-mentioned hydrolyzable silane compound. As described above, hydrolysis may be complete or partial hydrolysis. As stated above, the hydrolysis condensate contained in the film-forming composition of the present invention may contain both complete hydrolysates and partial hydrolysates. Furthermore, hydrolyzable silane monomers may remain in the composition.

[0201] In the present invention, as described above, two or more acidic compounds are used for the hydrolysis and condensation of the hydrolyzable silane compound. From the viewpoint of obtaining the effects of the present invention with better reproducibility, the amount of two or more acidic compounds used is determined such that the amount of acidic groups of the two or more acidic compounds per mole of hydrolyzable groups of the hydrolyzable silane compound is usually 0.001 to 10 moles, preferably 0.002 to 5 moles, more preferably 0.003 to 3 moles, even more preferably 0.005 to 2 moles, and even more preferably 0.007 to 1 mole.

[0202] The hydrolyzable silane compounds 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 hydrolysis, typically 0.5 moles to 100 moles, preferably 1 mole to 10 moles, of water are used per mole of the hydrolyzable group.

[0203] During hydrolysis and condensation, a hydrolysis catalyst may be used to promote hydrolysis and condensation, for example. Specific examples include metal chelate compounds, organic bases, and inorganic bases, but are not limited to these. The hydrolysis catalyst can be used alone or in combination of two or more types, and the amount used is usually 0.001 moles to 10 moles, preferably 0.001 moles to 1 mole, per mole of hydrolyzable group.

[0204] Specific examples of metal chelate compounds 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, di-n-propoxy bis(acetylacetonate)titanium, and 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, 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 S(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, mono-n-butoxy-tris(ethyl acetate) titanium,Titanium chelate compounds such as 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, tris(acetylacetonate) mono(ethyl acetate) titanium, etc.; triethoxy mono(acetylacetonate) 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 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, 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(ethylacetoacetate)zirconium,Di-n-propoxy bis(ethyl acetate) zirconium, di-isopropoxy bis(ethyl acetate) zirconium, di-n-butoxy bis(ethyl acetate) zirconium, di-s-butoxy bis(ethyl acetate) zirconium, di-t-butoxy bis(ethyl acetate) zirconium, monoethoxy tris(ethyl acetate) zirconium, mono-n-propoxy tris(ethyl acetate) zirconium, mono-isopropoxy tris(ethyl acetate) zirconium, mono-n-butoxy tris(ethyl acetate) zirconium, mono-s- Examples of zirconium chelate compounds include butoxytris(ethylacetate)zirconium, mono-t-butoxytris(ethylacetate)zirconium, tetrakis(ethylacetate)zirconium, mono(acetylacetonate)tris(ethylacetate)zirconium, bis(acetylacetonate)bis(ethylacetate)zirconium, and tris(acetylacetonate)mono(ethylacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonate)aluminum and tris(ethylacetate)aluminum. However, these examples are not limited to these.

[0205] Specific examples of organic bases 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.

[0206] Specific examples of inorganic bases include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0207] Among these, metal chelate compounds are preferred as hydrolysis catalysts.

[0208] When hydrolysis and condensation occur, organic solvents may be used as solvents. Specific examples include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbencene, isopropylbencene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbencene, and n-amylnaphthalene; 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-methylbutanol. Monoalcohol solvents such as tylbutanol, s-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, s-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, 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.

[0209] The reaction temperatures for hydrolysis and condensation are typically between 20°C and 80°C.

[0210] When using a silane other than the amino group-containing silane represented by formula (1) as the hydrolyzable silane, the amount of the amino group-containing silane represented by formula (1) is usually 0.1 mol% or more of the total hydrolyzable silane. 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 other silanes represented by formula (2) or formula (3) as hydrolyzable silanes, the amount of these other silanes charged is usually 0.1 mol% or more, preferably 1 mol% or more, more preferably 5 mol% or more, usually 99.9 mol% or less, preferably 99 mol% or less, and more preferably 95 mol% or less, out of the total hydrolyzable silanes. When using a hydrolyzable organosilane represented by formula (4) as the hydrolyzable silane, the amount of organosilane used is usually 0.01 mol% or more, preferably 0.1 mol% or more, and usually 30 mol% or less, preferably 10 mol% or less, out of the total amount of hydrolyzable silanes. When using a hydrolyzable organosilane represented by formula (5-1) as the hydrolyzable silane, the amount of the organosilane used is usually 0.1 mol% or more, preferably 0.3 mol% or more, and usually 50 mol% or less, preferably 30 mol% or less, out of the total amount of hydrolyzable silanes.

[0211] 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 can be removed from the reaction solution by neutralizing it, either as is or after dilution or concentration, and then 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.

[0212] The film-forming composition of the present invention can be produced by mixing the hydrolysis condensate of the above-mentioned hydrolyzable silane compound, a solvent, and other components, if any, those other components. 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.

[0213] 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.

[0214] 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.

[0215] The film-forming composition of the present invention can be suitably used as a composition for forming a resist underlayer film used in the lithography process.

[0216] 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.

[0217] 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).

[0218] 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.

[0219] Next, a photoresist film is formed on the resist underlayer of the present invention. The photoresist film can be formed by a well-known method, namely by applying a photoresist film forming composition on the resist underlayer 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.

[0220] 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. The substrates and coating methods that can be used in this case are the same as those described above.

[0221] The material for the photoresist film formed on the resist underlayer of the present invention is not particularly limited as long as it is sensitive to the light used for exposure. Negative-type photoresist 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, 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 and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist 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 photoresist materials, such as those described in Proc.SPIE, Vol.3999, 330-334(2000), Proc.SPIE, Vol.3999, 357-364(2000), and Proc.SPIE, Vol.3999, 365-374(2000), can also be suitably used.

[0222] 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.

[0223] In this invention, instead of a photoresist material, a resist material for electron beam lithography or a resist material for EUV lithography 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; 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.

[0224] Next, development is performed using a developer (for example, an alkaline developer). This removes the photoresist film from the exposed areas, for example, if a positive-type photoresist material is used, and a photoresist 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.

[0225] 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.

[0226] If necessary, the developing solution may contain surfactants or other additives.

[0227] 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.

[0228] 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.

[0229] 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).

[0230] 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.

[0231] 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).

[0232] 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.

[0233] 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.

[0234] 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 into the 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.

[0235] 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 anti-reflective underlayer film of the 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 film. It can efficiently prevent reflection as an underlayer film of the EUV resist film. When used as an underlayer film of the EUV resist, the process can be carried out in the same way as for an underlayer film of a photoresist.

[0236] The film-forming composition of the present invention described above can be suitably used in the manufacture of semiconductor devices. A semiconductor device manufacturing method of the present invention, for example, a semiconductor device manufacturing method comprising the steps of forming an organic underlayer film on a substrate, forming a resist underlayer film on the organic underlayer film using the film-forming composition described in any one of claims 1 to 12, and forming a resist film on the resist underlayer film, can be expected to produce highly reliable semiconductor devices. [Examples]

[0237] 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. The weight-average molecular weight is the molecular weight obtained by converting it to polystyrene equivalent using GPC analysis. The GPC analysis was performed using a GPC instrument (product name HLC-8220GPC, manufactured by Tosoh Corporation) and GPC columns (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.

[0238] [1] Synthesis of polymers (hydrolyzed condensates) (Synthesis Example 1) 20.2 g of tetrateethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 11.3 g of methyltriethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], and 47.8 g of propylene glycol monoethyl ether were placed in a 300 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, a mixed solution of 10.2 g of nitric acid aqueous solution (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.], 10.2 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.], and 0.37 g of dimethylaminopropyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Subsequently, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of hydrolyzed condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was over 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 20% 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 20% by mass). The obtained polymer contained the structure represented by formula (E1), and its weight-average molecular weight (Mw) was 1,800 in terms of polystyrene as determined by GPC. [ka]

[0239] (Synthesis Example 2) A solution of hydrolysis condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1, except that 10.2 g of p-toluenesulfonic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of 10.2 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L). The obtained polymer contained the structure represented by formula (E2), and its weight-average molecular weight (Mw) was 1,900 in polystyrene equivalent by GPC. [ka]

[0240] (Synthesis Example 3) A solution of hydrolyzed condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1, except that 10.2 g of camphor sulfonic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of 10.2 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L). The obtained polymer contained the structure represented by formula (E3), and its weight-average molecular weight (Mw) was 2,000 in polystyrene equivalent by GPC. [ka]

[0241] (Synthesis Example 4) A solution of hydrolysis condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1, except that 10.2 g of trifluoroacetic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of 10.2 g of nitric acid aqueous solution (concentration 0.2 mol / L). The obtained polymer contained the structure represented by formula (E4), and its weight-average molecular weight (Mw) was 2,200 in polystyrene equivalent by GPC. [ka]

[0242] (Synthesis Example 5) A solution of hydrolysis condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1, except that 10.2 g of maleic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of 10.2 g of nitric acid aqueous solution (concentration 0.2 mol / L). The obtained polymer contained the structure represented by formula (E5), and its weight-average molecular weight (Mw) was 2,400 in polystyrene equivalent by GPC. [ka]

[0243] (Synthesis Example 6) A solution of hydrolysis condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1, except that 10.2 g of aqueous squalic acid solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used instead of 10.2 g of aqueous nitric acid solution (concentration 0.2 mol / L). The obtained polymer contained the structure represented by formula (E6), and its weight-average molecular weight (Mw) was 2,400 in polystyrene equivalent by GPC. [ka]

[0244] (Synthesis Example 7) 19.9 g of tetraethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 9.65 g of methyltriethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.04 g of bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], and 47.9 g of propylene glycol monoethyl ether were placed in a 300 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, a mixed solution of 10.0 g of aqueous nitric acid (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.], 10.0 g of aqueous methanesulfonic acid (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.], and 0.36 g of dimethylaminopropyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Subsequently, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of hydrolyzed condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was over 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 20% 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 20% by mass). The obtained polymer contained the structure represented by formula (E7), and its weight-average molecular weight (Mw) was 1,800 in terms of polystyrene as determined by GPC. [ka]

[0245] (Synthesis Example 8) 19.3 g of tetraethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 9.36 g of methyltriethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 3.19 g of diallyl isocyanuratepropyltriethoxysilane [manufactured by Nissan Chemical Corporation], and 48.3 g of propylene glycol monoethyl ether were placed in a 300 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, a mixed solution of 9.74 g of 0.2 mol / L aqueous nitric acid [manufactured by Kanto Chemical Co., Ltd.], 9.74 g of 0.2 mol / L aqueous methanesulfonic acid [manufactured by Tokyo Chemical Industry Co., Ltd.], and 0.35 g of dimethylaminopropyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Subsequently, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of hydrolyzed condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was over 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 20% 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 20% by mass). The obtained polymer contained the structure represented by formula (E8), and its weight-average molecular weight (Mw) was 2,000 in terms of polystyrene as determined by GPC. [ka]

[0246] (Synthesis Example 9) 19.9 g of tetraethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 9.64 g of methyltriethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.09 g of thiocyanate-topropyltriethoxysilane [manufactured by Gellet], and 48.0 g of propylene glycol monoethyl ether were placed in a 300 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, a mixed solution of 10.0 g of aqueous nitric acid (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.], 10.0 g of aqueous methanesulfonic acid (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.], and 0.36 g of dimethylaminopropyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Subsequently, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of hydrolyzed condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was over 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 20% 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 20% by mass). The obtained polymer contained the structure represented by formula (E9), and its weight-average molecular weight (Mw) was 1,900 in terms of polystyrene as determined by GPC. [ka]

[0247] (Synthesis Example 10) 19.6 g of tetraethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 9.49 g of methyltriethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 2.70 g of triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane [manufactured by Nissan Chemical Corporation], and 48.2 g of propylene glycol monoethyl ether were placed in a 300 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, a mixed solution of 10.0 g of nitric acid aqueous solution (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.], 10.0 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.], and 0.36 g of dimethylaminopropyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Subsequently, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of hydrolyzed condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was over 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 20% 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 20% by mass). The obtained polymer contained the structure represented by formula (E10), and its weight-average molecular weight (Mw) was 2,400 in terms of polystyrene as determined by GPC. [ka]

[0248] (Synthesis Example 11) 20.1 g of tetraethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 9.77 g of methyltriethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 1.60 g of phenyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], and 47.8 g of propylene glycol monoethyl ether were placed in a 300 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, a mixed solution of 10.0 g of nitric acid aqueous solution (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.], 10.0 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.], and 0.37 g of dimethylaminopropyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Subsequently, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of hydrolyzed condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was over 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 20% 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 20% by mass). The obtained polymer contained the structure represented by formula (E11), and its weight-average molecular weight (Mw) was 1,800 in terms of polystyrene as determined by GPC. [ka]

[0249] (Comparative Synthesis Example 1) 20.3 g of tetraethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 11.6 g of triethoxymethylsilane [manufactured by Tokyo Chemical Industry Co., Ltd.], and 47.7 g of propylene glycol monoethyl ether were placed in a 300 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 20.4 g of nitric acid aqueous solution (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.] was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Subsequently, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of hydrolyzed condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was over 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 20% 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 20% by mass). The obtained polymer contained the structure represented by formula (C1), and its weight-average molecular weight (Mw) was 1,700 in terms of polystyrene as determined by GPC. [ka]

[0250] (Comparative Synthesis Example 2) 20.3 g of tetraethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.], 11.6 g of triethoxymethylsilane [manufactured by Tokyo Chemical Industry Co., Ltd.], and 47.7 g of propylene glycol monoethyl ether were placed in a 300 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 20.4 g of aqueous methanesulfonic acid solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Subsequently, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of hydrolyzed condensate (polymer) with propylene glycol monoethyl ether as the solvent. The solid content concentration of the obtained concentrate was over 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 20% 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 20% by mass). The obtained polymer contained the structure represented by formula (C2), and its weight-average molecular weight (Mw) was 1,900 in terms of polystyrene as determined by GPC. [ka]

[0251] (Comparative Synthesis Example 3) A solution of hydrolysis condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1, except that 20.4 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L) was used instead of 10.2 g of nitric acid aqueous solution (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.] and 10.2 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.]. The obtained polymer contained the structure represented by formula (C3), and its weight-average molecular weight (Mw) was 2,600 in polystyrene equivalent by GPC. [ka]

[0252] (Comparative Synthesis Example 4) A solution of hydrolysis condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1, except that 20.4 g of aqueous nitric acid solution (concentration 0.2 mol / L) was used instead of 10.2 g of aqueous nitric acid solution (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.] and 10.2 g of aqueous methanesulfonic acid solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.]. The obtained polymer contained the structure represented by formula (C4), and its weight-average molecular weight (Mw) was 2,000 in polystyrene equivalent by GPC. [ka]

[0253] [2] Preparation of film-forming compositions The polysiloxane (polymer), acid (additive 1), photoacid generator (additive 2), and solvent obtained in the above synthesis example were mixed in the proportions shown in Table 1, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare the respective film-forming compositions. The amounts of each additive in Table 1 are shown in parts by mass. Note that the polymer addition ratios in Table 1 represent the amount of polymer itself added, not the amount of polymer solution added. Furthermore, DIW refers to ultrapure water, PGEE to propylene glycol monoethyl ether, PGMEA to propylene glycol monoethyl ether acetate, and PGME to propylene glycol monoethyl ether. Furthermore, MA stands for maleic acid, and TPSNO3 stands for triphenylsulfonium nitrate.

[0254] [Table 1]

[0255] [3] Preparation of compositions for forming organic underlayer films Under nitrogen, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 ml four-necked flask. 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was then added and the mixture was stirred. The temperature was raised to 100°C to dissolve the mixture and begin polymerization. After 24 hours, the mixture was allowed to cool to 60°C. The cooled reaction mixture was diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.), and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to precipitate. The 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 represented by formula (3-1) (hereinafter abbreviated as PCzFL). Note that PCzFL 1 The results of the 1H-NMR measurement were as follows: 1 H-NMR(400MHz,DMSO-d6):δ7.03-7.55(br,12H),δ7.61-8.10(br,4H),δ11.18(br,1H) Furthermore, the weight-average molecular weight Mw of PCzFL was 2,800 when converted to polystyrene using GPC, and the polydispersity Mw / Mn was 1.77. [ka]

[0256] 20 g of PCzFL, 3.0 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd. (formerly Mitsui Scitec Co., Ltd.), trade name Powderlink 1174) as a crosslinking agent, 0.30 g of pyridinium p-toluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (manufactured by DIC Corporation, trade name) as a surfactant were mixed, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate. The mixture was then filtered using a polyethylene microfilter with a pore size of 0.10 μm, and then filtered again using a polyethylene microfilter with a pore size of 0.05 μm to prepare an organic underlayer film formation composition for use in multilayer lithography processes.

[0257] [4] Solvent resistance and developer solubility tests The film-forming compositions prepared in Examples 1-11 and Comparative Examples 1 and 4 were applied to silicon wafers using a spinner. The wafers were heated on a hot plate at 215°C for 1 minute to form Si-containing films, and the film thickness of the resulting Si-containing films was measured. Subsequently, a mixed solvent (7 / 3(V / V)) of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate was applied to each Si-containing film and spin-dried. The film thickness of the Si-containing film after drying was measured, and the presence or absence of change in film thickness before and after application of the mixed solvent was evaluated. Using the film thickness before application of the mixed solvent as a baseline, films with a change in film thickness of less than 1% after application were evaluated as "good," and films with a change in film thickness of 1% or more were evaluated as "not cured." Furthermore, an alkaline developer (TMAH 2.38% aqueous solution) was applied to each Si-containing film fabricated on a silicon wafer using the same method, and then spin-dried. The film thickness of the underlying film after drying was measured, and the presence or absence of change in film thickness before and after application of the developer was evaluated. Using the film thickness before application of the developer as a baseline, films with a film thickness change of less than 1% were classified as "good," and films with a film thickness change of 1% or more were classified as "not cured." The results obtained are shown in Table 2.

[0258] [Table 2]

[0259] As shown in Table 2, the films obtained from the film-forming composition of the present invention showed good resistance to solvents and developers.

[0260] [5] Measurement of dry etching rate The following etcher and etching gas were used to measure the dry etching rate. Lam2300 (manufactured by Lam Research): CF4 / CHF3 / N2 (fluorinated gas) RIE-10NR (Samco): O2 (oxygen-based gas) The film-forming compositions obtained in Examples 1 to 11 were each applied onto a silicon wafer using a spinner, and then heated on a hot plate at 215°C for 1 minute to form Si-containing films (film thickness 0.02 μm) in each case. Similarly, the above-mentioned organic underlayer film-forming compositions were applied to silicon wafers using a spinner, and heated on a hot plate at 215°C for 1 minute to form an organic underlayer film (film thickness 0.20 μm). The dry etching rates were measured using O2 gas along with CF4 / CHF3 / N2 gas as etching gases for each obtained silicon wafer with an organic underlayer film, and also using O2 gas as the etching gas for silicon wafers with an organic underlayer film. The results are shown in Table 3. The dry etching rate using O2 gas was expressed as a ratio (resistance) to the dry etching rate of the organic underlayer film.

[0261] [Table 3]

[0262] As shown in Table 3, the films obtained from the film-forming composition of the present invention exhibited a high etching rate against fluorine-based gases and showed good resistance to oxygen-based gases compared to organic underlayer films.

[0263] [6] Measurement of wet etching rate The film-forming compositions obtained in Examples 1 to 11 and Comparative Examples 2 and 5 were applied onto silicon wafers using a spinner, and heated on a hot plate at 215°C for 1 minute to form Si-containing films (film thickness 0.02 μm) in each case. The wet etching rate was measured using an NH3 / HF mixed aqueous solution as the wet etching agent for each of the obtained silicon wafers with Si-containing films. A wet etching rate of 10 nm / min or higher was considered good, and a rate of less than 10 nm / min was considered poor. The results are shown in Table 4.

[0264] [Table 4]

[0265] As shown in Table 4, the films obtained from the film-forming composition of the present invention showed a good wet etch rate with respect to the wet etching solution.

[0266] [7] Formation of resist pattern by EUV exposure: Negative solvent development The above-mentioned organic underlayer film formation composition was spin-coated onto a silicon wafer, and an organic underlayer film (layer A) (thickness 90 nm) was formed by heating it on a hot plate at 215°C for 1 minute. On top of that, the film-forming composition obtained in Example 1 was spin-coated and heated on a hot plate at 215°C for 1 minute to form a resist underlayer film (layer B) (thickness 20 nm). Furthermore, an EUV resist solution (methacrylate resin-based resist) was spin-coated onto the surface, and an EUV resist film (C layer) was formed by heating it on a hot plate at 130°C for 1 minute. Then, it was exposed using an ASML EUV exposure system (NXE3300B) under the conditions of NA=0.33, σ=0.67 / 0.90, and Dipole. After exposure, post-exposure heating (110°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 1 minute, and then rinsing was performed to form a resist pattern. Using a similar procedure, resist patterns were formed using the compositions obtained in Examples 2-11 and Comparative Examples 3 and 4. Then, for each obtained pattern, the feasibility of forming a 44nm pitch, 22nm line-and-space pattern was evaluated by confirming the pattern shape through cross-sectional observation of the pattern. In observing the pattern shape, a shape between the fitting and undercut, with no significant residue in the space area, was evaluated as "good." An undesirable state where the resist pattern was peeling or collapsing was evaluated as "collapsed." An undesirable state where the upper or lower parts of the resist pattern were in contact with each other was evaluated as "bridged." The results obtained are shown in Table 5.

[0267] [Table 5]

[0268] As shown in Table 5, the films obtained from the film-forming composition of the present invention functioned well as resist underlayers and achieved excellent lithography properties.

Claims

1. A film-forming composition comprising a hydrolysis condensate obtained by hydrolysis and condensation of a hydrolyzable silane compound using two or more acidic compounds, and a solvent, A wet-etchable film-forming composition characterized in that the above hydrolyzable silane compound contains an amino group-containing silane represented by the following formula (1). 【Chemistry 1】 [In formula (1), R １ These are groups that bond to silicon atoms, and independently of each other, they represent organic groups containing amino groups. The above-mentioned organic group containing an amino group is given by the following formula (A1) 【Chemistry 2】 (In formula (A1), R 101 and R 102 independently represent a hydrogen atom or a hydrocarbon group, and L represents an optionally substituted alkylene group.) This is a group represented by R ２ This represents a group bonded to a silicon atom, and may represent an optionally substituted alkyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted halogenated alkyl group, optionally substituted halogenated aryl group, optionally substituted halogenated aralkyl group, optionally substituted alkoxyalkyl group, optionally substituted alkoxyaryl group, optionally substituted alkoxyaralkyl group, or optionally substituted alkenyl group, or an organic group containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group. R ３ These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a is an integer between 1 and 2, and b is an integer between 0 and 1, satisfying a + b ≤ 2.

2. The wet-etchable film-forming composition according to claim 1, wherein the two or more acidic compounds described above are selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, heteropoly acid, oxocarbon acid, sulfonic acid group-containing organic acid, phosphoric acid group-containing organic acid, carboxyl group-containing organic acid, and phenolic hydroxyl group-containing organic acid, so as to be different from each other.

3. The wet-etchable film-forming composition according to claim 2, comprising two or more acidic compounds selected from the group consisting of nitric acid, sulfuric acid, oxocarbonic acid, sulfonic acid group-containing organic acid, and carboxyl group-containing organic acid, in a manner that differs from one another.

4. The wet-etchable film-forming composition according to claim 2, wherein the two or more acidic compounds described above include at least one selected from the group consisting of sulfuric acid and sulfonic acid group-containing organic acids, and at least one selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, boric acid, heteropoly acid, oxocarbon acid, phosphoric acid group-containing organic acid, carboxyl group-containing organic acid, and phenolic hydroxyl group-containing organic acid.

5. The wet-etchable film-forming composition according to any one of claims 2 to 4, wherein the oxocarbon acid comprises at least one selected from delta acid, squalic acid, and rhozonic acid.

6. The wet-etchable film-forming composition according to any one of claims 2 to 5, wherein the above-mentioned sulfonic acid group-containing organic acid comprises at least one selected from aromatic sulfonic acid, saturated aliphatic sulfonic acid, and unsaturated aliphatic sulfonic acid.

7. The wet-etchable film-forming composition according to claim 6, wherein the above-mentioned sulfonic acid group-containing organic acid comprises at least one selected from aromatic sulfonic acids and saturated aliphatic sulfonic acids.

8. The wet-etchable film-forming composition according to any one of claims 2 to 7, wherein the carboxyl group-containing organic acid comprises at least one selected from formic acid, oxalic acid, aromatic carboxylic acid, saturated aliphatic carboxylic acid, and unsaturated aliphatic carboxylic acid.

9. The wet-etchable film-forming composition according to claim 8, wherein the carboxyl group-containing organic acid comprises an unsaturated aliphatic carboxylic acid.

10. The wet-etchable film-forming composition according to claim 1, wherein the alkylene group is a linear or branched alkylene group having 1 to 10 carbon atoms.

11. A wet-etchable film-forming composition according to any one of claims 1 to 10, for use in forming a resist underlayer film used in a lithography process.

12. A resist underlayer film obtained from a wet-etchable film-forming composition according to any one of claims 1 to 11.

13. A process of forming an organic underlayer film on a substrate, A step of forming a resist underlayer on the above organic underlayer using the wet-etchable film-forming composition described in any one of claims 1 to 11, The process of forming a resist film on the above resist underlayer film and A method for manufacturing semiconductor devices including [specific components].

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