Film-forming composition

Abstract

The objective of this invention is to provide a composition that effectively functions as a resist underlayer film, exhibiting good solvent resistance to the composition used as the upper resist film, good etching characteristics against fluorine-based gases, and further good photolithography characteristics. A solution is a film-forming composition characterized by comprising a hydrolyzed condensate obtained by hydrolyzing and condensing a hydrolyzable silane compound using two or more acidic compounds, and a solvent, wherein the hydrolyzable silane compound comprises an amino-containing silane as shown in formula (1). (In formula (1), R...) 1 For groups that bond with silicon atoms, each independently represents an organic group containing an amino group, R 2 The group that bonds to a silicon atom represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or represents an organogroup containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group. 3 For groups or atoms bonded to silicon atoms, each can independently represent an alkoxy, aralkyloxy, acyloxy, or halogen atom, where a is an integer from 1 to 2, b is an integer from 0 to 1, and a + b ≤ 2. 1 a R 2 b Si(R 3 ) 4‑(a+b) (1).

Description

Technical Field

[0001] This relates to compositions for film formation. Background Technology

[0002] In the manufacture of semiconductor devices, photolithography using photoresist has long been used for microfabrication. This microfabrication 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 depicting a semiconductor device, developing the film, and then using the resulting photoresist film pattern as a protective film to etch the substrate, thereby forming a micro-unfolding texture on the substrate surface corresponding to the aforementioned pattern.

[0003] In recent years, the thinning of resist films has become increasingly important in cutting-edge semiconductor devices. In particular, in three-layer processes consisting of a resist film, a silicon-containing resist underlayer film, and an organic underlayer film, the Si-HM (Silicon-Hard Mask), which serves as the resist underlayer film, requires not only good photolithography properties but also a good etching rate in wet etching. Therefore, good solubility in wet etching solutions (such as HF) is required.

[0004] In response to these requirements, particularly for EUV (Extreme Ultraviolet) lithography, materials were developed with the aim of improving lithography properties. These materials incorporated a large amount of functional groups with high adhesion to the resist into the polymer and a large amount of photoacid generators into the composition. However, in such materials, the decrease in solubility in wet etching solutions (such as HF) caused by the increase in organic components becomes a major problem.

[0005] In this situation, reports were made containing... Compositions for forming resist underlayer films of silane compounds with anionic groups, and resist underlayer films comprising silane compounds having anionic groups (Patent Document 1 and Patent Document 2).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2010 / 021290

[0009] Patent Document 2: International Publication No. 2010 / 071155 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] The present invention was made in view of the above circumstances, and its object is to provide a composition that can function well as a resist underlayer film having solvent resistance to the composition used as the upper resist film, good etching characteristics against fluorine-based gases, and further good photolithography characteristics.

[0012] Methods for solving problems

[0013] In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research and found that a composition comprising a hydrolyzed condensate obtained by hydrolyzing and condensing a hydrolyzed silane compound containing a specified hydrolyzable silane using two or more acidic compounds, and a solvent, can be used to obtain a resist lower layer film that can function well as a resist film having solvent resistance to the composition used as the upper layer, good etching characteristics against fluorine-based gases, and even better photolithography characteristics. This invention was thus completed.

[0014] That is, in this invention, as a first aspect, there is a composition for film formation, characterized in that it comprises a hydrolytic condensate obtained by hydrolyzing and condensing a hydrolytic silane compound using two or more acidic compounds, and a solvent.

[0015] The above-mentioned hydrolyzable silane compounds include amino-containing silanes as shown in formula (1).

[0016] R 1 a R 2 b Si(R 3 ) 4-(a+b) (1)

[0017] (In equation (1), R) 1 The groups that bond with silicon atoms are represented independently by organic groups containing amino groups.

[0018] R 2 The group to be bonded to a silicon atom represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organic group containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group.

[0019] R 3 These are groups or atoms that bond with silicon atoms, and each can be represented independently as an alkoxy, aralkyloxy, acyloxy, or halogen atom.

[0020] (where a is an integer from 1 to 2, b is an integer from 0 to 1, and a + b ≤ 2.)

[0021] As a second point of view, relating to the film-forming composition described in the first point of view, the two or more acidic compounds comprise two or more selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, heteropolyacid, cyclic compounds formed by carbonyl-linked olefinic alcohols (oxocarbonic acid), organic acids containing sulfonic acid groups, organic acids containing phosphoric acid groups, organic acids containing carboxyl groups, and organic acids containing phenolic hydroxyl groups, in a manner different from each other.

[0022] As a third point of view, relating to the film-forming composition described in the second point of view, the two or more acidic compounds comprise two or more selected from the group consisting of nitric acid, sulfuric acid, cyclic compounds formed by carbonyl-linked olefins, organic acids containing sulfonic acid groups, and organic acids containing carboxyl groups in different ways from each other.

[0023] As a fourth point of view, relating to the membrane forming composition described in the second point of view, the two or more acidic compounds include at least one selected from sulfuric acid and organic acids containing sulfonic acid groups, and at least one selected from hydrochloric acid, nitric acid, phosphoric acid, boric acid, heteropoly acid, cyclic compounds formed by carbonyl-linked olefins, organic acids containing phosphoric acid groups, organic acids containing carboxyl groups, and organic acids containing phenolic hydroxyl groups.

[0024] As a fifth point of view, relating to the film-forming composition of any one of the second to fourth points of view, the cyclic compound formed by carbonyl-linked olefinic alcohol comprises at least one selected from deltic acid, squaric acid and malic acid.

[0025] As a sixth point of view, relating to the film-forming composition of any one of the second to fifth points of view, the organic acid containing a sulfonic acid group comprises at least one selected from aromatic sulfonic acids, saturated aliphatic sulfonic acids, and unsaturated aliphatic sulfonic acids.

[0026] As a seventh point of view, relating to the film-forming composition described in the sixth point of view, the aforementioned organic acid containing a sulfonic acid group comprises at least one selected from aromatic sulfonic acids and saturated aliphatic sulfonic acids.

[0027] As the eighth point of view, relating to the film-forming composition of any one of the second to seventh points, the aforementioned carboxyl-containing organic acid comprises at least one selected from formic acid, oxalic acid, aromatic carboxylic acids, saturated aliphatic carboxylic acids, and unsaturated aliphatic carboxylic acids.

[0028] As a ninth point of view, relating to the film-forming composition described in the eighth point of view, the aforementioned carboxyl-containing organic acid comprises unsaturated aliphatic carboxylic acids.

[0029] As a tenth point of view, relating to the film-forming composition of any one of the first to ninth points of view, the aforementioned amino-containing organic group is a group represented by the following formula (A1).

[0030]

[0031] (In equation (A1), R) 101 and R 102 Each can be represented independently by a hydrogen atom or a hydrocarbon group, with L indicating a substituted alkylene group.

[0032] As the 11th point of view, relating to the film-forming composition described in the 10th point of view, the alkylene group is a straight-chain or branched alkylene group having 1 to 10 carbon atoms.

[0033] As the 12th point of view, it relates to the film forming composition described in any one of the 1st to 11th points of view, which is used to form a photoresist underlayer film used in a photolithography process.

[0034] As the 13th point of view, there is a resist underlayer film obtained from any one of the film-forming compositions described in points 1 to 12.

[0035] As a 14th viewpoint, a method for manufacturing a semiconductor device is provided, comprising the following steps:

[0036] The process of forming an organic lower layer film on a substrate;

[0037] The process of forming a resist underlayer film on the aforementioned organic underlayer film using the film-forming composition described in any one of the first to twelfth viewpoints; and

[0038] The process of forming a resist film on the lower resist film mentioned above.

[0039] The effects of the invention

[0040] By using the film-forming composition of the present invention, not only can films be easily formed by wet processes such as spin coating, but also a film suitable for use as a resist film and an organic underlayer film in a three-layer process can be obtained, which can achieve good photolithography characteristics when used with a resist film and an organic underlayer film, and further exhibits solvent resistance to the composition used as the upper layer for the resist film and good etching characteristics against fluorine-based gases.

[0041] By using such a film-forming composition, it is expected that more reliable semiconductor devices can be manufactured. Detailed Implementation

[0042] The present invention will now be described in further detail.

[0043] It should be noted that the film-forming composition of the present invention comprises a hydrolytic condensate of a hydrolyzable silane compound. However, this hydrolytic condensate contains not only a siloxane polymer as a condensate in which condensation is fully completed, but also a siloxane polymer as a partially hydrolyzed condensate in which condensation is not fully completed. Such partially hydrolyzed condensates, like the fully condensed condensates, are polymers obtained through the hydrolysis and condensation of silane compounds, but the hydrolysis is partially stopped, and no condensation occurs; therefore, Si-OH groups remain.

[0044] Furthermore, in this invention, the term "solid component" refers to any component in the composition other than the solvent.

[0045] The membrane forming composition of the present invention comprises a hydrolyzed condensate obtained by hydrolyzing and condensing a hydrolyzable silane compound using two or more acidic compounds, wherein the hydrolyzable silane compound comprises an amino-containing silane as shown in formula (1).

[0046] R 1 a R 2 b Si(R 3 ) 4-(a+b) (1)

[0047] In equation (1), R 1 The group that bonds with silicon atoms represents an organic group containing an amino group, R. 2 The group that bonds to a silicon atom represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or represents an organogroup containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group. 3 A group or atom that is bonded to a silicon atom, and is independently represented by an alkoxy, aralkyloxy, acyloxy, or halogen atom, where a is an integer from 1 to 2 and b is an integer from 0 to 1, and a+b≤2.

[0048] The alkyl group in formula (1) is a monovalent group derived from an alkane by removing one hydrogen atom. It can be any of the straight-chain, branched, or cyclic groups. 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 even more preferably 10 or less.

[0049] Specific examples of straight-chain or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, etc. Examples of ethyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these.

[0050] Specific examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl Cycloalkyl groups such as butyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, etc., as well as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl, etc., but not limited to these.

[0051] The aryl group in formula (1) can be any of the following: a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused-ring aromatic hydrocarbon compound, or a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0052] Specific examples include phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 9-phenanthyl, 1-tetraphenyl, 2-tetraphenyl, 5-tetraphenyl, 2- 1-Pyrene, 2-Pyrene, pentaphenyl, benzo[a]pyrene, triphenylene; biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, m-terphenyl-4-yl, o-terphenyl-4-yl, 1,1'-binaphthyl-2-yl, 2,2'-binaphthyl-1-yl, etc., but not limited to these.

[0053] In formula (1), the aralkyl group is an alkyl group that has been substituted with an aryl group. Specific examples of such aryl and alkyl groups can be given as those described above. The number of carbon atoms in the aralkyl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0054] Specific examples of aralkyl groups include phenylmethyl (benzyl), 2-phenylethylidene, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, 10-phenyl-n-decyl, etc., but are not limited to these.

[0055] The haloalkyl in formula (1) is an alkyl group in which a halogen atom has been substituted. As a specific example of such an alkyl group, the same as those mentioned above can be given.

[0056] The number of carbon atoms in the haloalkyl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0057] Examples of halogen atoms and halogen atoms in formula (1) include fluorine, chlorine, bromine, and iodine.

[0058] Specific examples of haloalkyl groups include 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-hexafluoropropane-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, etc., but are not limited to these.

[0059] In formula (1), the halogenated aryl group is an aryl group substituted with a halogen atom. As a specific example of such an aryl group and halogen atom, the same as above can be given.

[0060] The number of carbon atoms in the haloaryl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0061] Specific examples of halogenated aryl groups include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl. Fluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-1-naphthyl, 4-fluoro-1-naphthyl, 6-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8-difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, heptafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, heptafluoro-2-naphthyl, etc., but not limited to these.

[0062] The halogenated aralkyl group in formula (1) is an aralkyl group in which a halogen atom has been substituted. As a specific example of such an aralkyl group and halogen atom, the same as those mentioned above can be given.

[0063] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0064] Specific examples of haloaryl groups include 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,4,5,6-pentafluorobenzyl, etc., but are not limited to these.

[0065] In formula (1), the alkoxyalkyl group is an alkoxy-substituted alkyl group. The alkoxy-substituted alkyl group can be any of the straight-chain, branched, or cyclic forms. Specific examples of such alkyl groups can be the same as those described above. The number of carbon atoms in the alkoxyalkyl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0066] Specific examples of alkoxy groups substituted on the alkyl group in an alkoxyalkyl group and alkoxy groups of formula (1) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy, 4-methyl-n-pentoxy, etc. The list includes chain- or branched alkoxy, cyclopropoxy, cyclobutoxy, 1-methyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, etc. Methyl-cyclopropoxy, cyclopentoxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentoxy, 2-methyl-cyclopentoxy, 3-methyl-cyclopentoxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3-dimethyl-cyclobutoxy, 2,2-dimethyl-cyclobutoxy, 2,3-di Cyclic alkoxy groups such as methyl-cyclobutoxy, 2,4-dimethyl-cyclobutoxy, 3,3-dimethyl-cyclobutoxy, 1-n-propyl-cyclopropoxy, 2-n-propyl-cyclopropoxy, 1-isopropyl-cyclopropoxy, 2-isopropyl-cyclopropoxy, 1,2,2-trimethyl-cyclopropoxy, 1,2,3-trimethyl-cyclopropoxy, 2,2,3-trimethyl-cyclopropoxy, 1-ethyl-2-methyl-cyclopropoxy, 2-ethyl-1-methyl-cyclopropoxy, 2-ethyl-2-methyl-cyclopropoxy, and 2-ethyl-3-methyl-cyclopropoxy, but not limited to these.

[0067] Specific examples of alkoxyalkyl groups include, but are not limited to, lower alkyloxyalkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, and 2-ethoxyethyl.

[0068] In formula (1), the alkoxyaryl group is an aryl group substituted with an alkoxy group. Specific examples of such alkoxy and aryl groups can be given 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.

[0069] Specific examples of alkoxyaryl groups include 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, 7-methoxynaphth-1-yl, etc., but are not limited to these.

[0070] In formula (1), the alkoxyaryl group is an aryl group substituted with an alkoxy group. Specific examples of such alkoxy and aryl groups can be given 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.

[0071] Specific examples of alkoxyaryl groups include 3-(methoxyphenyl)benzyl, 4-(methoxyphenyl)benzyl, etc., but are not limited to these.

[0072] The alkenyl group in formula (1) can be either 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 even more preferably 10 or less.

[0073] Specific examples of alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3- Methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2- Methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3-dimethyl 1,3-Dimethyl-2-butenyl, 1,3-Dimethyl-3-butenyl, 1-Isobutylvinyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 2-Isopropyl-2-propenyl, 3,3-Dimethyl-1-butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 1-n-Propyl-1-propenyl, 1-n-Propyl-2-propenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2- Methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, etc., but not limited to these.

[0074] Examples of organic groups containing epoxy groups in formula (1) include epoxypropoxymethyl, epoxypropoxyethyl, epoxypropoxypropyl, epoxypropoxybutyl, epoxycyclohexyl, etc., but are not limited to these.

[0075] Examples of organic groups containing an acryloyl group in formula (1) include acryloylmethyl, acryloylethyl, acryloylpropyl, etc., but are not limited to these.

[0076] Examples of organic groups containing a methacryloyl group in formula (1) include methacryloylmethyl, methacryloylethyl, methacryloylpropyl, etc., but are not limited to these.

[0077] Examples of organic groups containing thiol groups in formula (1) include ethyl thiol, butyl thiol, hexyl thiol, octyl thiol, etc., but are not limited to these.

[0078] Examples of organic groups containing cyano groups in formula (1) include cyanoethyl, cyanopropyl, etc., but are not limited to these.

[0079] In formula (1), the aralkyloxy group is a group derived from the hydroxyl group of an aralkyl alcohol by removing a hydrogen atom. As a specific example of such an aralkyl group, the same as described above can be given.

[0080] The number of carbon atoms in the arylalkyloxy group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0081] Specific examples of aralkyloxy groups include phenylmethyloxy (benzyloxy), 2-phenylethyloxy, 3-phenyl-n-propyloxy, 4-phenyl-n-butyloxy, 5-phenyl-n-pentyloxy, 6-phenyl-n-hexyloxy, 7-phenyl-n-heptyloxy, 8-phenyl-n-octyloxy, 9-phenyl-n-nonyloxy, 10-phenyl-n-decyloxy, etc., but are not limited to these.

[0082] In formula (1), the acyloxy group is a group derived from the carboxyl group of a carboxylic acid compound by removing a hydrogen atom. Typically, examples include alkylcarbonyloxy, arylcarbonyloxy, or aralkylcarbonyloxy derived from the carboxyl group of an alkylcarboxylic acid, arylcarboxylic acid, or aralkylcarboxylic acid, but this is not a limitation. Specific examples of alkyl, aryl, and aralkyl groups in such alkylcarboxylic acids, arylcarboxylic acids, and aralkylcarboxylic acids can be given as those described above.

[0083] Specific examples of acyloxy groups include methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, isobutyl carbonyloxy, sec-butyl carbonyloxy, tert-butyl carbonyloxy, n-pentyl carbonyloxy, 1-methyl-n-butyl carbonyloxy, 2-methyl-n-butyl carbonyloxy, 3-methyl-n-butyl carbonyloxy, 1,1-dimethyl-n-propyl carbonyloxy, 1,2-dimethyl-n-propyl carbonyloxy, 2,2-dimethyl-n-propyl carbonyloxy, 1-ethyl-n-propyl carbonyloxy, n-hexyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-pentyl carbonyloxy, 4-methyl The compounds include, but are not limited to, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, toluenesulfonylcarbonyloxy, etc.

[0084] The organic group containing an amino group in formula (1) is not particularly limited as long as it contains an amino group, but as a preferred example, the group shown in the following formula (A1) can be cited.

[0085]

[0086] In equation (A1), R 101 and R 102 Each of the two groups represents a hydrogen atom or a hydrocarbon group independently, and each of the two groups represents a alkylene group that can be substituted.

[0087] Examples of hydrocarbon groups in formula (A1) include alkyl, alkenyl, and aryl groups, but they are not limited to these.

[0088] Specific examples of such alkyl, alkenyl, and aryl groups can be given as those identical to those described above.

[0089] From the perspective of achieving excellent photolithography characteristics with good reproducibility, R101 and R 102 Preferably, the atom is hydrogen, alkyl, or aryl; more preferably, it is hydrogen, alkyl with 1 to 5 carbon atoms, or aryl with 6 to 10 carbon atoms; and even more preferably, it is R. 101 For hydrogen atoms, R 102 It 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 All are alkyl groups having 1 to 5 carbon atoms or aryl groups having 6 to 10 carbon atoms, with R being further preferred. 101 and R 102 Both are hydrogen atoms.

[0090] Furthermore, as the alkylene group in formula (A1), examples similar to those described above can be linear or branched, and the number of carbon atoms is typically 1 to 10, preferably 1 to 5.

[0091] Preferably, the alkylene compounds are straight-chain alkylene compounds such as methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene.

[0092] a is an integer from 1 to 2, b is an integer from 0 to 1, and satisfies a+b≤2. However, from the viewpoints of excellent photolithography characteristics, solvent resistance of the composition for resisting the film, and a suitable balance of etching rates, it is preferable that b is 0, more preferably that a is 1, and b is 0.

[0093] The content of the amino-containing silane in the above-mentioned hydrolyzable silane compound (1) is arbitrary, but from the viewpoint of achieving excellent photolithography characteristics with good reproducibility, it is preferably 0.01 mol% to 20 mol%, more preferably 0.1 mol% to 5 mol%, and other hydrolyzable silanes are used as the remainder.

[0094] The membrane forming composition of the present invention aims to adjust membrane properties such as membrane density. As the above-mentioned hydrolyzable silane compound, it may contain at least one of the following hydrolyzable silanes as other hydrolyzable silanes, together with the amino-containing silane shown in formula (1).

[0095] R 4 d Si(R 5 ) 4-d (2)

[0096] [R 6 e Si(R 7 ) 3-e ]2Yf (3)

[0097] In equation (2), R 4 A group that is bonded to a silicon atom via a Si-C bond, which independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a 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.

[0098] In addition, R 5 These are groups or atoms that bond with silicon atoms, and each of them independently represents an alkoxy, aralkyloxy, acyloxy, or halogen atom.

[0099] d represents an integer from 0 to 3.

[0100] As mentioned above, R 4 Specific examples of the groups and atoms in R, and their suitable number of carbon atoms, can be given regarding R. 2 The aforementioned groups and atoms, as well as the number of carbon atoms.

[0101] As mentioned above, R 5 Specific examples of the groups and atoms in R, and their suitable number of carbon atoms, can be given regarding R. 3 The aforementioned groups and atoms, as well as the number of carbon atoms.

[0102] In equation (3), R 6 A group that is bonded to a silicon atom via a Si-C bond, which independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a 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.

[0103] In addition, R 7 These are groups or atoms that bond with silicon atoms, and each of them independently represents an alkoxy, aralkyloxy, acyloxy, or halogen atom.

[0104] Y represents a group bonded to a silicon atom via a Si-C bond, and each group independently represents an alkylene or arylene group.

[0105] e represents an integer of 0 or 1, and f represents an integer of 0 or 1.

[0106] As mentioned above, R 6 and R 7 Specific examples of the groups and atoms in the above text, and their suitable number of carbon atoms, can be given by citing the above groups and atoms and the number of carbon atoms.

[0107] Furthermore, specific examples of alkylene groups in Y mentioned above include straight-chain alkylene groups such as methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene; branched alkylene groups such as 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 1,1-dimethylethylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 1,1-dimethyl-1,3-propylene, 1,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, and 1-ethyl-1,3-propylene; and alkylene groups such as methanetriylene and ethane-1 ,1,2-triyl, ethane-1,2,2-triyl, ethane-2,2,2-triyl, propane-1,1,1-triyl, propane-1,1,2-triyl, propane-1,2,3-triyl, propane-1,2,2-triyl, propane-1,1,3-triyl, butane-1,1,1-triyl, butane-1,1,2-triyl, butane-1,1,3-triyl, butane-1,2,3-triyl, butane-1,2,4-triyl, butane-1,2,2-triyl, butane-2,2,3-triyl, 2-methylpropane-1,1,1-triyl, 2-methylpropane-1,1,2-triyl, 2-methylpropane-1,1,3-triyl, etc., alkane triyl groups, but not limited to these.

[0108] Specific examples of the arylene groups in Y mentioned above include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthodiyl, 1,8-naphthodiyl, 2,6-naphthodiyl, 2,7-naphthodiyl, 1,2-anthratriyl, 1,3-anthratriyl, 1,4-anthratriyl, 1,5-anthratriyl, 1,6-anthratriyl, 1,7-anthratriyl, 1,8-anthratriyl, 2,3-anthratriyl, 2,6-anthratriyl, 2,7-anthratriyl, 2,9-anthratriyl, 2,10-anthratriyl, 9,10-anthratriyl groups derived from the removal of two hydrogen atoms from the aromatic ring of a fused-ring aromatic hydrocarbon compound; 4,4'-biphenyldiyl, 4,4”-p-terphenyldiyl groups derived from the removal of two hydrogen atoms from the aromatic ring of a ring-linked aromatic hydrocarbon compound, etc., but are not limited to these.

[0109] e is preferably 0 or 1, more preferably 0. f is preferably 1.

[0110] Specific examples of hydrolyzable silanes represented by formula (2) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethoxysilane, epoxypropoxymethyltrimethoxysilane, and epoxypropoxymethyltriethoxysilane. γ-glycidyl silane, α-glycidyl ethyl trimethoxysilane, α-glycidyl ethyl triethoxysilane, β-glycidyl ethyl trimethoxysilane, β-glycidyl ethyl triethoxysilane, α-glycidyl propyl trimethoxysilane, α-glycidyl propyl triethoxysilane, β-glycidyl propyl trimethoxysilane, β-glycidyl propyl triethoxysilane, γ-glycidyl propyl trimethoxysilane, γ-glycidyl propyl triethoxysilane, γ-glycidyl propyl triethoxysilane, γ-glycidyl propyl tripropoxysilane, γ- Epoxypropoxypropyltributoxysilane, γ-epoxypropoxypropyltriphenoxysilane, α-epoxypropoxybutyltrimethoxysilane, α-epoxypropoxybutyltriethoxysilane, β-epoxypropoxybutyltriethoxysilane, γ-epoxypropoxybutyltrimethoxysilane, γ-epoxypropoxybutyltriethoxysilane, δ-epoxypropoxybutyltrimethoxysilane, δ-epoxypropoxybutyltriethoxysilane, (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)ethyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β ...4-Epoxycyclohexyl)butyltriethoxysilane, epoxypropoxymethylmethyldimethoxysilane, epoxypropoxymethylmethyldiethoxysilane, α-epoxypropoxyethylmethyldimethoxysilane, α-epoxypropoxyethylmethyldiethoxysilane, β-epoxypropoxyethylmethyldimethoxysilane, β-epoxypropoxyethylethyldimethoxysilane, α-epoxypropoxypropylmethyldimethoxysilane, α-epoxypropoxypropylmethyldiethoxysilane, β-epoxypropoxypropylmethyldimethoxysilane, β-epoxypropoxypropylethyldimethoxysilane, γ-epoxypropoxypropylmethyldimethoxysilane, γ-epoxypropoxypropylmethyldiethoxysilane, γ-epoxypropoxypropylmethyldipropoxysilane, γ-epoxypropoxypropylmethyldipropoxysilane, γ-epoxypropoxypropylmethyldipropoxysilane, γ-epoxypropoxypropylmethyldipropoxysilane, γ-epoxypropoxypropylmethyldipropoxysilane -Glycyloxypropylmethyldibutoxysilane, γ-glycyloxypropylmethyldiphenoxysilane, γ-glycyloxypropylethyldimethoxysilane, γ-glycyloxypropylethyldiethoxysilane, γ-glycyloxypropylvinyldimethoxysilane, γ-glycyloxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane Alkane, methoxybenzyltrichlorosilane, methoxyphenylethyltrimethoxysilane, methoxyphenylethyltriethoxysilane, methoxyphenylethyltriacetoxysilane, methoxyphenylethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltriacetoxysilane Isopropoxybenzyltrichlorosilane, tert-butoxyphenyltrimethoxysilane, tert-butoxyphenyltriethoxysilane, tert-butoxyphenyltriacetoxysilane, tert-butoxyphenyltrichlorosilane, tert-butoxybenzyltrimethoxysilane, tert-butoxybenzyltriethoxysilane, tert-butoxybenzyltriacetoxysilane, tert-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallyl isocyanurate, bicyclo(2,2,1)heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonamidepropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyldimethoxysilane Ethoxysilanes, phenylmethyldiethoxysilanes, γ-chloropropylmethyldimethoxysilanes, γ-chloropropylmethyldiethoxysilanes, dimethyldiacetoxysilanes, γ-methacryloyloxypropylmethyldimethoxysilanes, γ-methacryloyloxypropylmethyldiethoxysilanes, γ-mercaptopropylmethyldimethoxysilanes, γ-mercaptopropylmethyldiethoxysilanes, methylvinyldimethoxysilanes, methylvinyldiethoxysilanes, and silanes shown in formulas (A-1) to (A-41) below, but not limited thereto.

[0111]

[0112]

[0113] Specific examples of hydrolyzable silanes represented by formula (3) include methylene bis(trimethoxysilane), methylene bis(trichlorosilane), methylene bis(triacetoxysilane), ethyl bis(triethoxysilane), ethyl bis(trichlorosilane), ethyl bis(triacetoxysilane), propylene bis(triethoxysilane), butyl bis(trimethoxysilane), phenyl bis(trimethoxysilane), phenyl bis(triethoxysilane), phenyl bis(methyl)ethoxysilane, phenyl bis(methyl)ethoxysilane, naphthyl bis(trimethoxysilane), bis(trimethoxyethyl)silane, bis(triethoxyethyl)silane, bis(ethyl)ethoxyethyl)silane, bis(methyl)methoxyethyl)silane, etc., but are not limited to these.

[0114] In this invention, when the hydrolyzable silane compound from which the hydrolysis condensate is obtained contains other hydrolyzable silanes besides the amino-containing silane shown in formula (1), the content of the other hydrolyzable silanes in the hydrolyzable silane compound is generally 80 mol% to 99.99 mol%, preferably 95 mol% to 99.9 mol%.

[0115] From the viewpoint of maintaining / improving the resist properties of the resist film by increasing the crosslinking density of the film obtained by the film forming composition of the present invention and suppressing the diffusion of the resist film components into the obtained film, the above-mentioned hydrolyzable silane compound preferably includes the hydrolyzable silane shown in formula (2), more preferably includes the hydrolyzable silane shown in formula (2) with 3 functionalities and the hydrolyzable silane shown in formula (2) with 4 functionalities, more preferably includes at least one of alkyltrialkoxysilane and aryltrialkoxysilane with tetraalkoxysilane, and even more preferably includes at least one of methyltrialkoxysilane and phenyltrialkoxysilane with tetraalkoxysilane.

[0116] In this case, the ratio of the hydrolyzable silane represented by the 3-functional formula (2) to the hydrolyzable silane represented by the 4-functional formula (2) is typically 10:90 to 90:10 in molar ratio, preferably 70:30 to 20:80.

[0117] In the hydrolysis and condensation of the hydrolytic silane compound contained in the film-forming composition of the present invention for obtaining the hydrolytic condensate, two or more acidic compounds are used.

[0118] As two or more acidic compounds, as long as they are structurally different from each other, there are no particular restrictions on each other, and they can be either inorganic acids or organic acids.

[0119] Examples of inorganic acids include hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, and heteropoly acids, but they are not limited to these.

[0120] Examples of heteropoly acids include phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicomolybdic acid, and phosphotungmolybdic acid.

[0121] Among them, from the viewpoint of achieving excellent photolithography characteristics with good reproducibility and improving the storage stability of the hydrolyzed condensate solution, nitric acid, phosphoric acid, and sulfuric acid are preferred, and nitric acid is more preferred.

[0122] Organic acids have acidic groups such as sulfonic acid groups, phosphoric acid groups, carboxyl groups, and phenolic hydroxyl groups within their molecules. Multiple acidic groups can exist in an organic acid, and these multiple acidic groups can be the same or different from each other.

[0123] In a preferred embodiment of the present invention, examples of organic acids containing sulfonic acid groups include aromatic sulfonic acids, saturated aliphatic sulfonic acids, and unsaturated aliphatic sulfonic acids.

[0124] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, aromatic sulfonic acids and saturated aliphatic sulfonic acids are preferred.

[0125] Aromatic sulfonic acids are substances in which at least one hydrogen atom of an aromatic compound is replaced by a sulfonic acid group. The number of carbon atoms in the aromatic ring constituting 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 by halogen atoms such as fluorine, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, alkenyl groups such as vinyl, halogenated alkyl groups such as trifluoromethyl, and halogenated alkenyl groups such as perfluorovinyl. Usually, the number of substituents is 0 to 3.

[0126] 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.

[0127] Examples of aromatic sulfonic acids typically include unsubstituted aromatic sulfonic acids, alkyl or alkenyl aromatic sulfonic acids, haloalkyl or haloalkenyl aromatic sulfonic acids, haloaromatic sulfonic acids, etc., but are not limited to these.

[0128] From the viewpoints of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted aromatic sulfonic acid or alkyl aromatic sulfonic acid is preferred, and alkyl aromatic sulfonic acid is more preferred.

[0129] Specific examples of unsubstituted aromatic sulfonic acids include 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, pyrenesulfonic acid, etc., but are not limited to these.

[0130] 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(tert-butyl)benzenesulfonic acid, 3,5-bis(isopropyl)benzenesulfonic acid, 2,4,6-tris(tert-butyl)benzenesulfonic acid, 2,4,6-tris(isopropyl)benzenesulfonic acid, and 5,8-dibutylbenzenesulfonic acid. -2-Naphthalenesulfonic acid, 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., but not limited to these.

[0131] Specific examples of halogenated alkyl or halogenated alkenyl aromatic sulfonic acids 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, 4-triiodomethylbenzenesulfonic acid. Sulfonic 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, 4-perfluorovinylbenzenesulfonic acid, etc., but not limited to these.

[0132] 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, and 2,6-diiodobenzenesulfonic acid. Sulfonic acid, 2,4,6-trifluorobenzenesulfonic 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, fluoroanthracitesulfonic acid, chloroanthracitesulfonic acid, bromoanthracitesulfonic acid, iodoanthracitesulfonic acid, etc., but not limited to these.

[0133] From the viewpoint of achieving excellent resist properties with good reproducibility, when the substituent of the aromatic ring in the aromatic sulfonic acid is a halogen atom, it is preferably a fluorine atom; when it is an alkyl group, it is preferably an alkyl group with 1 to 3 carbon atoms; more preferably methyl or ethyl; and even more preferably methyl.

[0134] Saturated aliphatic sulfonic acid is a substance in which at least one hydrogen atom of an alkane or cycloalkane is replaced by a sulfonic acid group. The number of carbon atoms constituting such an alkane or cycloalkane is not particularly limited, but is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The alkane may also be substituted by halogen atoms such as fluorine, aryl groups such as phenyl, etc. Usually, the number of substituents is 0 to 3.

[0135] Examples of saturated aliphatic sulfonic acids typically include unsubstituted saturated aliphatic sulfonic acids, halo-saturated aliphatic sulfonic acids, and aryl saturated aliphatic sulfonic acids, but are not limited to these.

[0136] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted saturated aliphatic sulfonic acid or halo-saturated aliphatic sulfonic acid is preferred, and halo-saturated aliphatic sulfonic acid is more preferred.

[0137] Specific examples of unsubstituted aliphatic sulfonic acids include 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, heptanesulfonic acid, octadecanesulfonic acid, nonadecananesulfonic acid, eicosanesulfonic acid, dodecanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid, dodecanesulfonic acid, tridecanesulfonic acid, dodecanesulfonic acid, and cycloalkanes such as camphorsulfonic acid, but are not limited to these.

[0138] 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, chloroethanesulfonic acid, dichloroethanesulfonic acid, trichloroethanesulfonic acid, pentachloroethanesulfonic acid, tribromoethanesulfonic acid, pentabromoethanesulfonic acid, triiodoethanesulfonic acid, pentabromoethanesulfonic acid, fluoropropanesulfonic acid, trifluoropropanesulfonic acid, heptafluoropropanesulfonic acid, chloropropanesulfonic acid, trichloropropanesulfonic acid, heptachloropropanesulfonic acid, bromopropanesulfonic acid, tribromopropanesulfonic acid, heptabromopropanesulfonic acid, triiodopropanesulfonic acid, heptabromopropanesulfonic acid, and trifluorobutanesulfonic acid. Nonfluorobutane sulfonic acid, trichlorobutane sulfonic acid, nonchlorobutane sulfonic acid, tribromobutane sulfonic acid, nonbromobutane sulfonic acid, triiodobutane sulfonic acid, noniodobutane sulfonic acid, trifluoropentane sulfonic acid, perfluoropentane sulfonic acid, trichloropentane sulfonic acid, perchloropentane sulfonic acid, tribromopentane sulfonic acid, perbromopentane sulfonic acid, triiodopentane sulfonic acid, periodopentane sulfonic acid, trifluorohexane sulfonic acid, perfluorohexane sulfonic acid, trichlorohexane sulfonic acid Perchlorohexane sulfonic acid, perbromohexane sulfonic acid, periodohexane sulfonic acid, trifluoroheptane sulfonic acid, perfluoroheptane sulfonic acid, trichloroheptane sulfonic acid, perchloroheptane sulfonic acid, perbromoheptane sulfonic acid, periodoheptane sulfonic acid, trifluorooctane sulfonic acid, perfluorooctane sulfonic acid, trichlorooctane sulfonic acid, perchlorooctane sulfonic acid, perbromooctane sulfonic acid, periodooctane sulfonic acid, trifluorononane sulfonic acid, perfluorononane sulfonic acid, trichlorononane sulfonic acid Acids, perchlorononane sulfonic acid, perbromononane sulfonic acid, periodononane sulfonic acid, trifluorodecane sulfonic acid, perfluorodecane sulfonic acid, trichlorodecane sulfonic acid, perchlorodecane sulfonic acid, perbromodecane sulfonic acid, periododecane sulfonic acid, trifluoroundecane sulfonic acid, perfluoroundecane sulfonic acid, trichloroundecane sulfonic acid, perchloroundecane sulfonic acid, perbromoundecane sulfonic acid, periodoundecane sulfonic acid, trifluorododecane sulfonic acid, perfluorododecane sulfonic acid, trichlorododecane sulfonic acid, perchlorododecane sulfonic acid, perbromododecane sulfonic acid, periododecane sulfonic acid, trifluorotridecane sulfonic acid, perfluorotridecane sulfonic acid, perchlorotridecane sulfonic acid, perbromotridecane sulfonic acid, periodotridecane sulfonic acid, trifluorotetradecane sulfonic acid, perfluorotetradecane sulfonic acid, trichlorotetradecane sulfonic acid, perchlorotetradecane sulfonic acid, perbromotetradecane sulfonic acid, per... Iodotetradecanesulfonic acid, trifluoropentadecananesulfonic acid, perfluoropentadecananesulfonic acid, trichloropentadecananesulfonic acid, perchloropentadecananesulfonic acid, perbromopentadecananesulfonic acid, periodopentadecananesulfonic 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, perfluorononadecananesulfonic acid, perchlorononadecananesulfonic acid, perbromononadecananesulfonic acid, periodononadecananesulfonic acid, perfluoroeicosanesulfonic acid, perchloroeicosanesulfonic acid, perbromoeicosanesulfonic acid, periodoeicosanesulfonic acid, perfluoroeicosanesulfonic acid, perchloroeicosanesulfonic acid, perbromoeicosanesulfonic acid, periodoeicosanesulfonic acid, perfluoroeicosanesulfonic acid, perchloroeicosanesulfonic acid, perbromoeicosanesulfonic acid, periodoeicosanesulfonic acid,Perfluorodocosahexadecanesulfonic acid, perchlorodocosahexadecanesulfonic acid, perbromodocosahexadecanesulfonic acid, periododocosahexadecanesulfonic acid, perfluorodocotrianesulfonic acid, perchlorodocotrianesulfonic acid, perbromodocotrianesulfonic acid, periododocotrianesulfonic acid, perfluorodocotraanesulfonic acid, perchlorodocotraanesulfonic acid, perbromodocotraanesulfonic acid, periododocotraanesulfonic acid, etc., but not limited to these.

[0139] Specific examples of aryl saturated aliphatic sulfonic acids include phenylmethanesulfonic acid, diphenylmethanesulfonic acid, triphenylmethanesulfonic acid, 1-phenylethanesulfonic acid, 2-phenylethanesulfonic acid, etc., but are not limited to these.

[0140] From the viewpoint of achieving excellent resist properties with good reproducibility, when the substituent that replaces the alkyl group in the saturated aliphatic sulfonic acid is a halogen atom, it is preferably a fluorine atom; when it is an aryl group, it is preferably an aryl group with 6 to 10 carbon atoms, and more preferably a phenyl group.

[0141] Unsaturated aliphatic sulfonic acid is a substance in which at least one hydrogen atom of an alkene or alkyne is replaced by a sulfonic acid group. The number of carbon atoms constituting such an alkene or alkyne is not particularly limited, but is usually 2 to 10, preferably 2 to 5, and more preferably 2 to 3. The alkene or alkyne may also be substituted by halogen atoms such as fluorine, aryl groups such as phenyl, etc. Usually, the number of such substituents is 0 to 3.

[0142] 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.

[0143] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted unsaturated aliphatic sulfonic acid is preferred.

[0144] Specific examples of unsubstituted unsaturated aliphatic sulfonic acids include vinylsulfonic acid, 2-propene-1-sulfonic acid, 1-butene-1-sulfonic acid, 3-butene-1-sulfonic acid, etc., but are not limited to these.

[0145] In a preferred embodiment of the present invention, examples of organic acids containing phosphoric acid groups include aromatic phosphoric acid, saturated aliphatic phosphoric acid, and unsaturated aliphatic phosphoric acid, but the invention is not limited to these.

[0146] Aromatic phosphoric acid is a substance in which at least one hydrogen atom of an aromatic compound is replaced by a phosphate group. The number of carbon atoms in the aromatic ring constituting 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 also be substituted by halogen atoms such as fluorine, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, alkenyl groups such as vinyl, haloalkyl groups such as trifluoromethyl, and haloalkenyl groups such as perfluorovinyl. Usually, the number of substituents is 0 to 3.

[0147] Furthermore, the number of phosphate groups is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1.

[0148] Examples of aromatic phosphoric acids typically include unsubstituted aromatic phosphoric acids, alkyl or alkenyl aromatic phosphoric acids, haloalkyl or haloalkenyl aromatic phosphoric acids, and haloaromatic phosphoric acids, but are not limited to these.

[0149] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted aromatic phosphoric acid or alkyl aromatic phosphoric acid is preferred.

[0150] Examples of unsubstituted aromatic phosphoric acids include phenyl phosphoric acid, 1-naphthyl phosphoric acid, and 2-naphthyl phosphoric acid, but are not limited to these.

[0151] Specific examples of alkyl or alkenyl aromatic phosphoric acids include, but are not limited to, tolyl phosphoric acid, xylyl phosphoric acid, 2-ethylphenyl phosphoric acid, 3-n-propylphenyl diphosphate, and 4-tert-butylphenyl phosphoric acid.

[0152] Specific examples of halogenated alkyl or halogenated alkenyl aromatic phosphoric acids include 2-trifluoromethylphenylphosphonic acid, 2-trichloromethylphenylphosphonic acid, 2-tribromomethylphenylphosphonic acid, 2-triiodomethylphenylphosphonic acid, 3-trifluoromethylphenylphosphonic acid, 3-trichloromethylphenylphosphonic acid, 3-tribromomethylphenylphosphonic acid, 3-triiodomethylphenylphosphonic acid, 4-trifluoromethylphenylphosphonic acid, 4-trichloromethylphenylphosphonic acid, 4-tribromomethylphenylphosphonic acid, 4-triiodomethylphenylphosphonic acid, 2,6-bis(trifluoromethyl)phenylphosphonic acid, 2,6-bis(trichloromethyl)phenylphosphonic acid, 2,6-bis(tribromomethyl)phenylphosphonic acid, 2,6-bis(triiodomethyl)phenylphosphonic acid, 3,5-bis(trifluoromethyl)phenylphosphonic acid, 3,5-bis(trichloromethyl)phenylphosphonic acid, 3,5-bis(tribromomethyl)phenylphosphonic acid, 3,5-bis(triiodomethyl)phenylphosphonic acid, 4-perfluorovinylphenylphosphonic acid, etc., but are not limited to these.

[0153] Specific examples of haloaromatic phosphoric acids include 2-fluorophenyl phosphoric acid, 3-fluorophenyl phosphoric acid, 4-fluorophenyl phosphoric acid, 2-chlorophenyl phosphoric acid, 3-chlorophenyl phosphoric acid, 4-chlorophenyl phosphoric acid, 2-bromophenyl phosphoric acid, 3-bromophenyl phosphoric acid, 4-bromophenyl phosphoric acid, 2-iodophenyl phosphoric acid, 4-iodophenyl phosphoric acid, 2,4-difluorophenyl phosphoric acid, 2,6-difluorophenyl phosphoric acid, 2,4-dichlorophenyl phosphoric acid, 2,6-dichlorophenyl phosphoric acid, 2,4-dibromophenyl phosphoric acid, 2,6-dibromophenyl phosphoric acid, 2,4-diiodophenyl phosphoric acid, and 2,6-diiodophenyl phosphoric acid. Phosphoric acid, 2,4,6-trifluorophenylphosphoric acid, 3,4,5-trifluorophenylphosphoric acid, 2,4,6-trichlorophenylphosphoric acid, 3,4,5-trichlorophenylphosphoric acid, 2,4,6-tribromophenylphosphoric acid, 3,4,5-tribromophenylphosphoric acid, 2,4,6-triiodophenylphosphoric acid, 3,4,5-triiodophenylphosphoric acid, pentafluorophenylphosphoric acid, pentachlorophenylphosphoric acid, pentabromophenylphosphoric acid, pentaiodophenylphosphoric acid, fluoronaphthylphosphoric acid, chloronaphthylphosphoric acid, bromonaphthylphosphoric acid, iodonaphthylphosphoric acid, fluoroanthraylphosphoric acid, chloroanthraylphosphoric acid, bromoanthraylphosphoric acid, iodoanthraylphosphoric acid, etc., but not limited to these.

[0154] Saturated aliphatic phosphoric acid is a substance in which at least one hydrogen atom of an alkane or cycloalkane is replaced by a phosphate group. The number of carbon atoms constituting such an alkane or cycloalkane is not particularly limited, but is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The alkane may also be substituted with halogen atoms such as fluorine, aryl groups such as phenyl, etc. Usually, the number of substituents is 0 to 3.

[0155] Examples of saturated aliphatic phosphoric acids typically include unsubstituted saturated aliphatic phosphoric acids, halo-saturated aliphatic phosphoric acids, and aryl-saturated aliphatic phosphoric acids, but they are not limited to these.

[0156] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted saturated aliphatic phosphoric acid or halo-saturated aliphatic phosphoric acid are preferred.

[0157] Examples of unsubstituted saturated aliphatic phosphoric acids include methylphosphoric acid and ethylphosphoric acid, but are not limited to these.

[0158] Examples of halogenated saturated aliphatic phosphoric acids include trifluoromethyl phosphoric acid and pentafluoroethyl phosphoric acid, but are not limited to these.

[0159] Specific examples of aryl saturated aliphatic phosphoric acids include phenylmethane phosphoric acid, diphenylmethane phosphoric acid, triphenylmethane phosphoric acid, 1-phenylethane phosphoric acid, 2-phenylethane phosphoric acid, etc., but are not limited to these.

[0160] Unsaturated aliphatic phosphoric acid is a substance in which at least one hydrogen atom of an alkene or alkyne is replaced by a phosphate group. The number of carbon atoms constituting such an alkene or alkyne is not particularly limited, but is usually 2 to 10, preferably 2 to 5, and more preferably 2 to 3. The alkene or alkyne may also be substituted by halogen atoms such as fluorine, aryl groups such as phenyl, etc. Usually, the number of such substituents is 0 to 3.

[0161] Examples of unsaturated aliphatic phosphoric acids include, but are not limited to, unsubstituted unsaturated aliphatic phosphoric acids, halogenated unsaturated aliphatic phosphoric acids, and aryl unsaturated aliphatic phosphoric acids.

[0162] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted unsaturated aliphatic phosphoric acid is preferred.

[0163] Specific examples of unsubstituted unsaturated aliphatic phosphoric acids include vinyl phosphoric acid, 2-propen-1-phosphoric acid, 1-buten-1-phosphoric acid, 3-buten-1-phosphoric acid, etc., but are not limited to these.

[0164] In a preferred embodiment of the present invention, examples of organic acids containing carboxyl groups include formic acid and oxalic acid, as well as aromatic carboxylic acids, saturated aliphatic carboxylic acids, and unsaturated aliphatic carboxylic acids.

[0165] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, aromatic carboxylic acids and unsaturated aliphatic carboxylic acids are preferred.

[0166] Aromatic carboxylic acids are substances in which at least one hydrogen atom of an aromatic compound is replaced by a carboxyl group. The number of carbon atoms in the aromatic ring constituting 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 also be substituted by halogen atoms such as fluorine, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, alkenyl groups such as vinyl, haloalkyl groups such as trifluoromethyl, and haloalkenyl groups such as perfluorovinyl. Usually, the number of substituents is 0 to 3.

[0167] Furthermore, the number of carboxyl groups is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1.

[0168] Examples of aromatic carboxylic acids typically include unsubstituted aromatic carboxylic acids, alkyl or alkenyl aromatic carboxylic acids, haloalkyl or haloalkenyl aromatic carboxylic acids, and haloaromatic carboxylic acids, but are not limited to these.

[0169] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted aromatic carboxylic acids and alkyl aromatic carboxylic acids are preferred.

[0170] Specific examples of unsubstituted aromatic carboxylic acids include benzoic acid, benzo-1,2-dicarboxylic acid, benzo-1,3-dicarboxylic acid, benzo-1,4-dicarboxylic acid, benzo-1,3,5-tricarboxylic acid, 2-naphthoic acid, anthracene carboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,4-carboxylic acid, phenanthrene carboxylic acid, pyrene carboxylic acid, etc., but are not limited to these.

[0171] Specific examples of alkyl or alkenyl aromatic carboxylic acids include o-toluic acid, m-toluic acid, p-toluic acid, p-styrenic acid, p-isopropylbenzoic acid, p-dodecylbenzoic acid, dihexylbenzoic acid, 2,5-dihexylbenzoic acid, 3,5-bis(tert-butyl)benzoic acid, 3,5-bis(isopropyl)benzoic acid, 2,4,6-tris(tert-butyl)benzoic acid, 2,4,6-tris(isopropyl)benzoic acid, 5 ,8-Dibutyl-2-naphthoic acid, 6,7-Dibutyl-2-naphthoic acid, hexylnaphthoic acid, 4-hexyl-1-naphthoic acid, 7-hexyl-1-naphthoic acid, 6-hexyl-2-naphthoic acid, octylnaphthoic acid, 2-octyl-1-naphthoic acid, dinonylnaphthoic acid, 2,7-dinonyl-4-naphthoic acid, dinonylnaphthalenedicarboxylic acid, dodecylnaphthoic acid, 3-dodecyl-2-naphthoic acid, etc., but not limited to these.

[0172] Specific examples of halogenated alkyl or halogenated alkenyl aromatic carboxylic acids include 2-trifluoromethylbenzoic acid, 2-trichloromethylbenzoic acid, 2-tribromomethylbenzoic acid, 2-triiodomethylbenzoic acid, 3-trifluoromethylbenzoic acid, 3-trichloromethylbenzoic acid, 3-tribromomethylbenzoic acid, 3-triiodomethylbenzoic acid, 4-trifluoromethylbenzoic acid, 4-trichloromethylbenzoic acid, 4-tribromomethylbenzoic acid, 4-triiodomethylbenzoic acid. Formic acid, 2,6-bis(trifluoromethyl)benzoic acid, 2,6-bis(trichloromethyl)benzoic acid, 2,6-bis(tribromomethyl)benzoic acid, 2,6-bis(triiodomethyl)benzoic acid, 3,5-bis(trifluoromethyl)benzoic acid, 3,5-bis(trichloromethyl)benzoic acid, 3,5-bis(tribromomethyl)benzoic acid, 3,5-bis(triiodomethyl)benzoic acid, 4-perfluorovinylbenzoic acid, etc., but not limited to these.

[0173] Specific examples of halogenated aromatic carboxylic acids include 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2-bromobenzoic acid, 3-bromobenzoic acid, 4-bromobenzoic acid, 2-iodobenzoic acid, 4-iodobenzoic acid, 2,4-difluorobenzoic acid, 2,6-difluorobenzoic acid, 2,4-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 2,6-dibromobenzoic acid, 2,4-diiodobenzoic acid, and 2,6-diiodobenzoic acid. Formic acid, 2,4,6-trifluorobenzoic acid, 3,4,5-trifluorobenzoic acid, 2,4,6-trichlorobenzoic acid, 3,4,5-trichlorobenzoic acid, 2,4,6-tribromobenzoic acid, 3,4,5-tribromobenzoic acid, 2,4,6-triiodobenzoic acid, 3,4,5-triiodobenzoic acid, pentafluorobenzoic acid, pentachlorobenzoic acid, pentabromobenzoic acid, pentaiodobenzoic acid, fluoronaphthoic acid, chloronaphthoic acid, bromonaphthoic acid, iodonaphthoic acid, fluoroanthracite, chloroanthracite, bromoanthracite, iodoanthracite, etc., but not limited to these.

[0174] From the viewpoint of achieving excellent resist properties with good reproducibility, when the substituent of the aromatic ring in the aromatic carboxylic acid is a halogen atom, it is preferably a fluorine atom; when it is an alkyl group, it is preferably an alkyl group with 1 to 3 carbon atoms; more preferably methyl or ethyl; and even more preferably methyl.

[0175] Saturated aliphatic carboxylic acids are substances in which at least one hydrogen atom of an alkane or cycloalkane is replaced by a carboxyl group. The number of carbon atoms constituting such an alkane or cycloalkane is not particularly limited, but is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. The alkane may also be substituted with halogen atoms such as fluorine, aryl groups such as phenyl, etc. Usually, the number of substituents is 0 to 3.

[0176] Saturated aliphatic carboxylic acids typically include unsubstituted saturated aliphatic carboxylic acids, halosubstituted saturated aliphatic carboxylic acids, hydroxylated saturated aliphatic carboxylic acids, and aryl saturated aliphatic carboxylic acids, but are not limited to these.

[0177] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted saturated aliphatic carboxylic acids and halo-saturated aliphatic carboxylic acids are preferred, and halo-saturated aliphatic carboxylic acids are more preferred.

[0178] 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), and butane... Chain or branched alkyl carboxylic acids such as 2,2-dicarboxylic acid, butane-2,3-dicarboxylic acid, butane-2,4-dicarboxylic acid, pentanecarboxylic acid, hexanecarboxylic acid, heptanecarboxylic acid, octanecarboxylic acid, nonanecarboxylic acid, decanecarboxylic acid, undecanecarboxylic acid, dodecanecarboxylic acid, tridecanecarboxylic acid, tetradecanecarboxylic acid, pentadecanecarboxylic acid, hexadecanecarboxylic acid, heptadecanocarboxylic acid, octadecanecarboxylic acid, nonadecanocarboxylic acid, eicosanecarboxylic acid, dodecanecarboxylic acid, tridecanecarboxylic acid, tetradecanecarboxylic acid, etc., and cycloalkyl carboxylic acids such as camphorcarboxylic acid, but not limited to these.

[0179] 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, trifluoroethanecarboxylic 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, and 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 Acids, 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, trifluorononane Formic acid, perfluorononane carboxylic acid, trichlorononane carboxylic acid, perchlorononane carboxylic acid, perbromononane carboxylic acid, periodononane carboxylic acid, trifluorodecane carboxylic acid, perfluorodecane carboxylic acid, trichlorodecane carboxylic acid, perchlorodecane carboxylic acid, perbromodecane carboxylic acid, periododecane carboxylic acid, trifluoroundecane carboxylic acid, perfluoroundecane carboxylic acid, perchloroundecane carboxylic acid, perbromoundecane carboxylic acid, periodoundecane carboxylic acid, trifluorododecane carboxylic acid, perfluorododecane carboxylic acid, perchlorododecane carboxylic acid, perbromododecane carboxylic acid, periodododecane carboxylic acid, trifluorotridecane carboxylic acid, perfluorotridecane carboxylic acid, perchlorotridecane carboxylic acid, perbromotridecane carboxylic acid, periodotridecane carboxylic acid, trifluorotetradecane carboxylic acid, perfluorotetradecane carboxylic acid, trichlorotetradecane carboxylic acid, all Chlorotetradecanoic acid, perbromotetradecanoic acid, periodotetradecanoic acid, trifluoropentadecanoic acid, perfluoropentadecanoic acid, trichloropentadecanoic acid, perchloropentadecanoic acid, perbromopentadecanoic acid, periodopentadecanoic acid, perfluorohexadecanoic acid, perchlorohexadecanoic acid, perbromohexadecanoic acid, periodohexadecanoic acid, perfluoroheptadecanoic acid, perchloroheptadecanoic acid, perbromoheptadecanoic acid, periodoheptadecanoic acid, perfluorooctadecanoic acid, perchlorooctadecanoic acid, perbromooctadecanoic acid, periodooctadecanoic acid, perfluorononadecanoic acid, perchlorononadecanoic acid, perbromononadecanoic acid, periodononadecanoic acid, perfluoroeicosanecanoic acid, perchloroeicosanecanoic acid, perbromoeicosanecanoic acid, periodoeicosanecanoic acid, perfluorotimocosanecanoic acid, perchlorotimocosanecanoic acid, perchlorotimocosanecanoic acid, perfluoro ...Perbromodococarboxylic acid, periodococarboxylic acid, perfluorodococarboxylic acid, perchlorodococarboxylic acid, perbromodococarboxylic acid, periododococarboxylic acid, perfluorodococarboxylic acid, perchlorodococarboxylic acid, perbromodococarboxylic acid, periododococarboxylic acid, perfluorodocotracocarboxylic acid, perchlorodocotracocarboxylic acid, perbromodocotracocarboxylic acid, periododocotracocarboxylic acid, etc., but not limited to these.

[0180] Specific examples of hydroxyl-saturated aliphatic carboxylic acids include 1,2-dihydroxyethane-1,2-dicarboxylic acid (tartaric acid) and 2-hydroxypropane-1,2,3-tricarboxylic acid (citric acid), but are not limited to these.

[0181] Specific examples of aryl saturated aliphatic carboxylic acids include phenylmethanecarboxylic acid, diphenylmethanecarboxylic acid, triphenylmethanecarboxylic acid, 1-phenylethanecarboxylic acid, 2-phenylethanecarboxylic acid, etc., but are not limited to these.

[0182] From the viewpoint of achieving excellent resist properties with good reproducibility, when the substituent that replaces the alkyl group in the saturated aliphatic carboxylic acid is a halogen atom, it is preferably a fluorine atom; when it is an aryl group, it is preferably an aryl group with 6 to 10 carbon atoms, and more preferably a phenyl group.

[0183] Unsaturated aliphatic carboxylic acids are substances in which at least one hydrogen atom of an alkene or alkyne is replaced by a carboxylic acid group. The number of carbon atoms constituting such an alkene or alkyne is not particularly limited, but is usually 2 to 10, preferably 2 to 5, and more preferably 2 to 3. The alkene or alkyne may also be substituted by halogen atoms such as fluorine, aryl groups such as phenyl, etc. Usually, the number of such substituents is 0 to 3.

[0184] 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.

[0185] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted unsaturated aliphatic carboxylic acids are preferred.

[0186] Specific examples of unsubstituted unsaturated aliphatic carboxylic acids include vinylcarboxylic acid, 2-propen-1-carboxylic acid, 1-buten-1-carboxylic acid, 3-buten-1-carboxylic acid, trans-ethylene-1,2-dicarboxylic acid (fumaric acid), cis-ethylene-1,2-dicarboxylic acid (maleic acid), etc., but are not limited to these.

[0187] In a preferred embodiment of the present invention, hydroxy aromatic compounds can be cited as organic acids containing phenolic hydroxyl groups.

[0188] A hydroxy aromatic compound is a substance in which at least one hydrogen atom of an aromatic compound is replaced by a hydroxyl group. The number of carbon atoms in the aromatic ring constituting 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 also be substituted by halogen atoms such as fluorine, alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl, alkenyl groups such as vinyl, haloalkyl groups such as trifluoromethyl, and haloalkenyl groups such as perfluorovinyl. Usually, the number of substituents is 0 to 3.

[0189] Furthermore, the number of hydroxyl groups is not particularly limited, but is usually 1 to 3, preferably 1 to 2, and more preferably 1.

[0190] Examples of hydroxy aromatic compounds typically include unsubstituted hydroxy aromatic compounds, alkyl or alkenyl hydroxy aromatic compounds, haloalkyl or haloalkenyl hydroxy aromatic compounds, halohydroxy aromatic compounds, etc., but are not limited to these.

[0191] From the perspectives of achieving excellent photolithography characteristics with good reproducibility and the ease of obtaining the compound, unsubstituted hydroxy aromatic compounds are preferred.

[0192] Specific examples of unsubstituted hydroxyl aromatic compounds include phenol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,3,5-trihydroxybenzene, 2-hydroxynaphthalene, hydroxyanthracene, hydroxyphenanthrene, hydroxypyrene, etc., but are not limited to these.

[0193] Specific examples of alkyl or alkenyl hydroxy aromatic compounds include 2,5-dihydroxytoluene, p-hydroxystyrene, 1-isopropyl-4-hydroxybenzene, 1-dodecyl-4-hydroxybenzene, etc., but are not limited to these.

[0194] Specific examples of halogenated alkyl or halogenated alkenyl hydroxyl aromatic compounds include 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(trichloromethyl)phenol, 2,6-bis(tribromomethyl)phenol, 2,6-bis(triiodomethyl)phenol, 3,5-bis(trifluoromethyl)phenol, 3,5-bis(trichloromethyl)phenol, 3,5-bis(tribromomethyl)phenol, 3,5-bis(triiodomethyl)phenol, 4-perfluorovinylphenol, etc., but are not limited to these.

[0195] Specific examples of halogenated hydroxyl aromatic 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, and 2,6-diiodophenol. 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, 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, hydroxyiodoanthracene, etc., but not limited to these.

[0196] Furthermore, as preferred organic acids in this invention, examples include cyclic compounds formed by carbonyl-linked olefins such as dihydroxycyclopropenone, squaric acid, and malic acid.

[0197] In this invention, in one embodiment, from the viewpoint of obtaining excellent photolithographic properties with better reproducibility, the two or more acidic compounds preferably include two or more selected from the group consisting of nitric acid, sulfuric acid, cyclic compounds formed by carbonyl-linked olefins, organic acids containing sulfonic acid groups, and organic acids containing carboxyl groups in different ways. More preferably, they include two or more selected from the group consisting of nitric acid, cyclic compounds formed by carbonyl-linked olefins, organic acids containing sulfonic acid groups, and organic acids containing carboxyl groups in different ways.

[0198] Furthermore, in other embodiments, from the viewpoint of achieving excellent photolithographic characteristics with better reproducibility, the above-mentioned two or more acidic compounds preferably include at least one selected from sulfuric acid and organic acids containing sulfonic acid groups, and at least one selected from hydrochloric acid, nitric acid, phosphoric acid, boric acid, heteropoly acids, cyclic compounds formed by carbonyl-linked olefins, organic acids containing phosphoric acid groups, organic acids containing carboxyl groups, and organic acids containing phenolic hydroxyl groups. More preferably, they include organic acids containing sulfonic acid groups and at least one selected from nitric acid, cyclic compounds formed by carbonyl-linked olefins, and organic acids containing carboxyl groups.

[0199] The hydrolytic condensate contained in the film-forming composition of the present invention is obtained by hydrolysis and condensation of a hydrolytic silane compound containing an amino-containing silane as shown in formula (1) above using the acidic compound described above. By using the amino-containing silane and two or more acidic compounds, a unit containing two or more amine salt structures can be realized as a monomer unit derived from the amino-containing silane in the hydrolytic condensate. As a result, the composition can achieve solvent resistance to the resist film formed as the upper layer, good etching characteristics against fluorine-based gases, and good photolithography characteristics.

[0200] In particular, nitric acid, carboxylic acid compounds, and phenolic compounds can be especially helpful in improving photolithography properties, while sulfuric acid, sulfonic acid compounds, and phosphoric acid compounds can be especially helpful in improving etching properties and wet etching properties against fluorine gases.

[0201] In this invention, the number of acidic compounds used in manufacturing the hydrolysis condensate is not particularly limited as long as it is 2 or more, but from the viewpoint of achieving excellent photolithography characteristics with good reproducibility, it is usually 2 to 5, preferably 2 to 4, more preferably 2 to 3, and even more preferably 2.

[0202] The film-forming composition of the present invention contains a solvent.

[0203] There are no limitations on the solvent's ability to dissolve the above-mentioned and below-mentioned hydrolyzable silanes, their hydrolyzable condensates, and other components.

[0204] Specific examples include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl methanol, 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 ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate. Ethyl lactate, 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 Esters, ethyl 3-methoxypropionate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, 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., and the solvent can be used alone or in combination of two or more.

[0205] The film-forming composition of the present invention may contain water as a solvent, the content of which 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.

[0206] In this invention, the aforementioned hydrolyzable silane may also contain intramolecularly defined... Hydrolyzable organosilanes with a radical. This is achieved through the use of intramolecularly possessing... The base is a hydrolyzable organosilane, which can effectively and efficiently promote the cross-linking reaction of hydrolyzable silanes.

[0207] Such molecules have A suitable example of a hydrolyzable organosilane is represented by the following formula (4).

[0208] R 31 j R 32 k Si(R 33 ) 4-(j+k) (4)

[0209] R 31 These are groups that bond with silicon atoms, and are independent of each other. base or contain Organic groups of the radical, R 32 The group that bonds to a silicon atom represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or represents an organogroup containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, or cyano group. 33 Each group or atom is an independent group or atom bonded to a silicon atom, and can be an alkoxy, aralkyloxy, acyloxy, or halogen atom. j represents 1 or 2, k represents 0 or 1, and satisfies 1≤j+k≤2.

[0210] Specific examples of such alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, alkoxy, halogen atom and organic groups containing epoxy, acryloyl, methacryloyl, mercapto, amino or cyano groups and substituents of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl and alkenyl groups and their suitable carbon number can be given as the same examples as described above.

[0211] If we go into more detail, then as Specific examples of the base include cyclic ammonium groups or chain ammonium groups, preferably tertiary ammonium groups or quaternary ammonium groups.

[0212] That is, as base or contain Suitable specific examples of the organic group of the group may be cyclic ammonium group or chain ammonium group or an organic group containing at least one of them, preferably tertiary ammonium group or quaternary ammonium group or an organic group containing at least one of them.

[0213] It should be noted that, in When the group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as a ring-forming atom. In this case, there are cases where the nitrogen atom constituting the ring is directly bonded to the silicon atom or bonded through a divalent linker, and cases where the carbon atom constituting the ring is directly bonded to the silicon atom or bonded through a divalent linker.

[0214] In one example of a suitable embodiment of the invention, R 31 It is a heteroaromatic cyclic ammonium group as shown in the following formula (S1).

[0215]

[0216] A 1 A 2 A 3 and A 4 Each of the groups represented independently by any one 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), according to the silicon atom in formula (4) and A 1 ~A 4 Which combination, A 1 ~A 4 The bonds between each atom and its adjacent atoms forming the ring are either single or double bonds, determined by the aromaticity of the ring.

[0217]

[0218] R 30 The terms "single bond", "hydrogen atom", "alkyl", "aryl", "aralkyl", "haloalkyl", "haloaryl", "haloaralkyl" or "alkenyl" can be used to represent each other independently. Examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl and alkenyl and their suitable number of carbon atoms can be given as the same as those described above.

[0219] R 34 Each of these can independently represent alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, or hydroxyl, in R 34 When there are more than two, two R 34 They can combine to form a ring, 2 Rs 34 The formed ring can be a cross-linked ring structure. In such cases, the cyclic ammonium group can have adamantane ring, norbornene ring, spiro ring, etc.

[0220] As specific examples of such alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, and alkenyl groups, and their suitable carbon number, the same examples as those described above can be given.

[0221] n 1 m is an integer from 1 to 8. 1 m is 0 or 1 2 It is a positive integer from 0 or 1 to the largest number that can be substituted on a single ring or multiple rings.

[0222] In m 1 When the value is 0, it constitutes a combination of A. 1 ~A 4 (4+n) 1 A ring of elements. That is, in n... 1 When the value is 1, a 5-membered ring is formed; in n... 1 When the number is 2, a 6-membered ring is formed. 1 When the number is 3, it forms a 7-membered ring, and in n 1 When the sum is 4, it forms an 8-membered ring, and in n... 1 When the sum is 5, a 9-membered ring is formed, and in n... 1 When the sum is 6, a 10-membered ring is formed, and at n... 1 When 7 elements are formed, an 11-membered ring is formed. At n... 1 A 12-membered ring is formed when the number of elements is 8.

[0223] In m 1 When the value is 1, a structure containing A is formed. 1 ~A 3 (4+n) 1 ) Metacyclic rings and containing A 4 A condensed ring formed by the condensation of six-membered rings.

[0224] According to A 1 ~A 4 Which of equations (J1) to (J3) has the case where the atoms constituting the ring have hydrogen atoms, and the case where they do not? A 1 ~A 4 When the atoms constituting the ring have hydrogen atoms, those hydrogen atoms can be replaced by R. 34 In addition, R 34 It can replace A 1 ~A 4 The rings within the atom constitute atoms other than the rings that constitute atoms. Based on this situation, as described above, m 2 An integer selected from 0 or 1 to the largest number that can be substituted on a single or multiple rings.

[0225] The bonding bonds of the heteroaromatic cyclic ammonium group shown in formula (S1) exist on any carbon or nitrogen atom present on such a monocyclic or fused ring, directly bonded to silicon atoms, or bonded to a linker group to form an organic group containing cyclic ammonium, which is bonded to silicon atoms.

[0226] Examples of such linking groups include alkylene, arylene, and alkenyl groups, but they are not limited to these.

[0227] Specific examples of alkylene and arylene groups and their suitable carbon number can be given as the same examples as those described above.

[0228] An alkenyl group is a divalent group derived by further removing one hydrogen atom from an alkenyl group. As a specific example of such an alkenyl group, the same examples as those mentioned above can be given.

[0229] The number of carbon atoms in the alkenyl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0230] Specific examples include vinylidene, 1-methylvinylidene, propenylidene, 1-butenylidene, 2-butenylidene, 1-pentenylidene, 2-pentenylidene, etc., but are not limited to these.

[0231] Specific examples of hydrolyzable organosilanes of formula (4) having heteroaromatic cyclic ammonium groups as shown in formula (S1) are given, but are not limited thereto.

[0232]

[0233]

[0234]

[0235] In another suitable embodiment of the invention, R 31 It is a heteroaliphatic cyclic ammonium group as shown in the following formula (S2).

[0236]

[0237] A 5 A 6 A 7 and A 8 Each of the groups represented independently by any one 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), according to the silicon atom in formula (4) and A 5 ~A 8 Which combination, A 5 ~A 8 The bonds between each atom and its adjacent atoms forming the ring are either single or double bonds, determined by the non-aromatic nature of the ring.

[0238]

[0239] R 30 The terms "single bond", "hydrogen atom", "alkyl", "aryl", "aralkyl", "haloalkyl", "haloaryl", "haloaralkyl" or "alkenyl" can be used to represent each other independently. Examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl and alkenyl and their suitable number of carbon atoms can be given as the same as those described above.

[0240] R 35 Each of these can independently represent alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, or hydroxyl, in R 35 When there are more than two, two R 35 They can combine to form a ring, 2 Rs 35 The formed ring can be a cross-linked ring structure. In such cases, the cyclic ammonium group can have adamantane ring, norbornene ring, spiro ring, etc.

[0241] As specific examples of such alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, and alkenyl groups, and their suitable carbon number, the same examples as those described above can be given.

[0242] n 2 m is an integer from 1 to 8. 3 m is 0 or 1 4 It is a positive integer from 0 or 1 to the largest number that can be substituted on a single ring or multiple rings.

[0243] In m 3 When the value is 0, it constitutes a combination of A. 5 ~A 8 (4+n) 2 A ring of elements. That is, in n... 2 When the value is 1, a 5-membered ring is formed; in n... 2 When the number is 2, a 6-membered ring is formed. 2 When the number is 3, it forms a 7-membered ring, and in n 2 When the sum is 4, it forms an 8-membered ring, and in n... 2 When the sum is 5, a 9-membered ring is formed, and in n... 2 When the sum is 6, a 10-membered ring is formed, and at n... 2 When 7 elements are formed, an 11-membered ring is formed. At n... 2 A 12-membered ring is formed when the number of elements is 8.

[0244] In m 3 When the value is 1, a structure containing A is formed. 5 ~A 7 (4+n) 2 ) Metacyclic rings and containing A 8 A condensed ring formed by the condensation of six-membered rings.

[0245] According to A 5 ~A8 Which of equations (J4) to (J6) is correct? There are cases where the atoms constituting the ring have hydrogen atoms, and cases where they do not. However, in A... 5 ~A 8 When the atoms constituting the ring have hydrogen atoms, those hydrogen atoms can be replaced by R. 35 In addition, R 35 It can replace A 5 ~A 8 The rings in the middle constitute atoms, while the rings outside the atoms constitute atoms.

[0246] Given this situation, as mentioned above, m 4 An integer selected from 0 or 1 to the largest number that can be substituted on a single or multiple rings.

[0247] The heteroaliphatic cyclic ammonium group shown in formula (S2) has a bonding bond that exists on any carbon or nitrogen atom present on such a monocyclic or fused ring, which is directly bonded to silicon atoms or bonded to a linker group to form an organic group containing cyclic ammonium, which is bonded to silicon atoms.

[0248] Examples of such linking groups include alkylene, arylene, or alkenylene, and examples of alkylene, arylene, and alkenylene, and their suitable number of carbon atoms, are the same as those described above.

[0249] Specific examples of hydrolyzable organosilanes of formula (4) having heteroaliphatic cyclic ammonium groups as shown in formula (S2) are given, but are not limited thereto.

[0250]

[0251]

[0252] In another suitable embodiment of the invention, R 31 It is a chain-like ammonium group as shown in the following formula (S3).

[0253]

[0254] R 30 The hydrogen atom, alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl or alkenyl can be represented independently of each other. As specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl and alkenyl and their suitable number of carbon atoms, the same examples as those described above can be given.

[0255] The chain-like ammonium group shown in formula (S3) is directly bonded to silicon atoms, or bonded to a linker group to form an organic group containing the chain-like ammonium group, which is bonded to silicon atoms.

[0256] Examples of such linking groups include alkylene, arylene, or alkenyl groups, and specific examples of alkylene, arylene, and alkenyl groups are the same as those described above.

[0257] Specific examples of hydrolyzable organosilanes of formula (4) having chain-like ammonium groups as shown in formula (S3) are given, but are not limited thereto.

[0258]

[0259]

[0260] The film-forming composition of the present invention may further include silanes having sulfone groups or silanes having sulfonamide groups as hydrolyzable silanes.

[0261] The following are specific examples, but are not limited to these.

[0262]

[0263]

[0264]

[0265] In this invention, the above-mentioned hydrolyzable silane compound may also include hydrolyzable organosilanes having an intramolecular cyclic urea skeleton. As a specific example, it is not limited to this, but the hydrolyzable organosilane shown in the following formula (5-1) can be cited.

[0266] R 501 x R 502 y Si (R 503 ) 4-(x+y) (5-1)

[0267] In equation (5-1), R 501 For groups that bond with silicon atoms, the groups shown in formula (5-2) are represented independently of each other, R 502 The group that bonds to a silicon atom represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or represents an organogroup containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group. 503 For groups or atoms bonded to silicon atoms, each independently represents an alkoxy, aralkyloxy, acyloxy, or halogen atom, where x is 1 or 2, y is 0 or 1, and x + y ≤ 2, R 502Alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organogroups including epoxy, acryloyl, methacryloyl, mercapto, or cyano, and R 503 Specific examples of alkoxy, aralkyloxy, acyloxy, and halogen atoms, as well as their substituents and suitable carbon numbers, can be cited in relation to R. 2 and R 3 The examples above are the same as those above.

[0268]

[0269] In equation (5-2), R 504 Each of the following can independently represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or an organogroup containing an epoxy or sulfonyl group. 505 Each can be represented independently as an alkylene group, a hydroxyalkylene group, a sulfur bond (-S-), an ether bond (-O-), or an ester bond (-CO-O- or -O-CO-).

[0270] It should be noted that R 504 Specific examples of substituted alkyl groups, substituted alkenyl groups, and organogroups containing epoxy groups, and suitable carbon numbers, can be given in relation to R. 2 And the examples above are the same as those, except for them, as R 504 The substituted alkyl group is preferably an alkyl group in which the terminal hydrogen atom is replaced by a vinyl group, and specific examples include allyl, 2-vinylethyl, 3-vinylpropyl, 4-vinylbutyl, etc.

[0271] As an organic group containing a sulfonyl group, there are no particular limitations as long as it contains a sulfonyl group. Examples include substituted alkylsulfonyl groups, substituted arylsulfonyl groups, substituted aralkylsulfonyl groups, substituted haloalkylsulfonyl groups, substituted haloarylsulfonyl groups, substituted haloarylalkylsulfonyl groups, substituted alkoxyalkylsulfonyl groups, substituted alkoxyarylsulfonyl groups, substituted alkoxyarylalkylsulfonyl groups, substituted alkenylsulfonyl groups, etc. Specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaryl, alkoxyalkyl, alkoxyaryl, alkoxyaryl, and alkenyl groups, as well as their substituents and suitable carbon number, can be given in relation to R. 2 The examples above are the same as those above.

[0272] The alkylene group is a divalent group derived by further removing one hydrogen atom from the aforementioned alkyl group. It can be any of the following: linear, branched, or cyclic. Specific examples of such alkylene groups can be given as examples similar to 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 even more preferably 10 or less.

[0273] In addition, R 505 The alkylene group may have one or more of the following at its end or in the middle, preferably in the middle: a thioether bond, an ether bond, and an ester bond.

[0274] Specific examples of alkylene compounds include straight-chain alkylene compounds such as methylene, ethylene, 1,3-propylene, methyl ethylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene, and 1,10-decylene; branched-chain alkylene compounds such as 1-methyl-1,3-propylene, 2-methyl-1,3-propylene, 1,1-dimethylethylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 1,1-dimethyl-1,3-propylene, 1,2-dimethyl-1,3-propylene, 2,2-dimethyl-1,3-propylene, and 1-ethyl-1,3-propylene; and 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, and 1,2-cyclopropanediyl. -cyclohexanediyl, 1,3-cyclohexanediyl and other cyclic alkylene groups, -CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2CH2-, -CH2CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2SCH2CH2CH2-, -CH2CH2CH2SCH2CH2CH2-, -CH2OCH2CH2SCH2- and other alkylene groups including ether groups, but not limited thereto.

[0275] A hydroxyalkylene group is a substance in which at least one hydrogen atom of the aforementioned alkylene group is replaced by a hydroxyl group. Specific examples include hydroxymethylene, 1-hydroxyethylene, 2-hydroxyethylene, 1,2-dihydroxyethylene, 1-hydroxy-1,3-propylene, 2-hydroxy-1,3-propylene, 3-hydroxy-1,3-propylene, 1-hydroxy-1,4-butylene, 2-hydroxy-1,4-butylene, 3-hydroxy-1,4-butylene, 4-hydroxy-1,4-butylene, 1,2-dihydroxy-1,4-butylene, 1,3-dihydroxy-1,4-butylene, 1,4-dihydroxy-1,4-butylene, 2,3-dihydroxy-1,4-butylene, 2,4-dihydroxy-1,4-butylene, 4,4-dihydroxy-1,4-butylene, etc., but are not limited to these.

[0276] In equation (5-2), X 501 The groups represented independently by formulas (5-3) to (5-5) below, and the carbon atom of the ketone group in formulas (5-4) and (5-5) below is the same as the R in formula (5-2). 505 The nitrogen atoms that are bound together are bound together.

[0277]

[0278] In equations (5-3) to (5-5), R 506 ~R 510 Examples of hydrogen atoms or substituted alkyl groups, substituted alkenyl groups, or organogroups containing epoxy or sulfonyl groups, and suitable carbon atom numbers, can be given in relation to R. 504 The examples above are the same as those above.

[0279] From the viewpoint of achieving excellent photolithography characteristics with good reproducibility, the group shown in formula (5-5) is preferred.

[0280] From the perspective of achieving excellent photolithography characteristics with good reproducibility, R 504 and R 506 ~R 510 At least one of the preferred terminal hydrogen atoms is an alkyl group that has been replaced by a vinyl group.

[0281] The hydrolyzable organosilane shown in formula (5-1) above can be commercially available or synthesized by known methods as described in International Publication No. 2011 / 102470, etc.

[0282] The following are specific examples of hydrolyzable organosilanes represented by formula (5-1), but are not limited to these examples.

[0283]

[0284]

[0285]

[0286] In a preferred embodiment of the present invention, the hydrolytic condensate contained in the membrane forming composition of the present invention comprises a hydrolytic condensate obtained by using at least an amino-containing silane of formula (1) and other silanes of formula (2). In another preferred embodiment of the present invention, the hydrolytic condensate contained in the membrane forming composition of the present invention comprises a hydrolytic condensate obtained by using at least an amino-containing silane of formula (1) and other silanes of formula (2) and a hydrolyzable organosilane of formula (5-1).

[0287] The weight-average molecular weight of the hydrolysate in this invention is typically 500 to 1,000,000, but from the viewpoint of suppressing the precipitation of the hydrolysate in the composition, it is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving both storage stability and coatability, it is preferably 700 or more, and more preferably 1,000 or more.

[0288] It should be noted that the weight-average molecular weight is the molecular weight obtained by GPC analysis and converted to polystyrene. GPC analysis can be performed using, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Corporation), a GPC column (trade name Shodex KF803L, KF802, KF801, manufactured by Showa Denko Corporation), with the column temperature set at 40°C, tetrahydrofuran used as the eluent, a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko Corporation) used as the standard sample.

[0289] The membrane-forming composition of the present invention may also contain organic acids, water, alcohols, etc., for purposes such as stabilizing its hydrolysate.

[0290] Specific examples of organic acids that can be included in the membrane-forming composition of the present invention for the above-mentioned purposes include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid, but are not limited thereto. Among these, oxalic acid and maleic acid are preferred.

[0291] When 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 hydrolysate condensate.

[0292] The alcohols that can be included in the film-forming composition of the present invention for the above-mentioned purposes are preferably alcohols that are easily evaporated by heating after coating. Specific examples include lower aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, and butanol.

[0293] When the film-forming composition of the present invention contains an alcohol, the content of the alcohol is 1 to 20 parts by mass relative to 100 parts by mass of the composition.

[0294] The film-forming composition of the present invention may further include organic polymer compounds, acid-generating agents, surfactants, etc., as needed.

[0295] The organic polymer compounds that the film-forming compositions of the present invention can contain are appropriately selected from a variety of organic polymers (condensation polymers and addition polymers) depending on their purpose of addition.

[0296] Specific examples include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyvinyl ether, phenolic varnish, naphthol varnish, polyether, polyamide, and polycarbonate.

[0297] In this invention, organic polymers containing aromatic 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 used when such functionality is required. Specific examples of such organic polymer compounds include addition polymers containing addition monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as their structural units, as well as condensation polymers such as phenolic varnishes and naphtholic varnishes, but are not limited thereto.

[0298] When using addition polymers as organic polymer compounds, the polymer compound can be either a homopolymer or a copolymer.

[0299] The manufacture of addition polymers uses addition polymerizable monomers. Specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, etc.

[0300] Specific examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene 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-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0301] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0302] 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-anthraylacrylamide.

[0303] 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-anthraylmethacrylamide.

[0304] Specific examples of vinyl compounds include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc., but are not limited to these.

[0305] Specific examples of styrene compounds include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetystyrene, etc., but are not limited to these.

[0306] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but are not limited to these.

[0307] When using condensation polymers as the polymer, examples of such polymers include condensation polymers of diol compounds and dicarboxylic acid compounds. Examples of diol compounds include diethylene glycol, 1,6-hexanediol, and butanediol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Furthermore, examples of polyesters, polyamides, and polyimides include, but are not limited to, poly(pyromellitic terephthalamide), poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate.

[0308] When an organic polymer compound contains a hydroxyl group, that hydroxyl group can undergo a cross-linking reaction with hydrolytic condensates, etc.

[0309] The weight-average molecular weight of the organic polymer compound contained in the film-forming composition of the present invention is generally 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. From the viewpoint of fully obtaining the effect of functioning as a polymer, it is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more.

[0310] Such organic polymer compounds can be used alone or in combination of two or more.

[0311] When the film-forming composition of the present invention contains an organic polymer compound, its content is appropriately determined by considering the function of the organic polymer compound, etc., and therefore cannot be specified in general terms. However, it is generally in the range of 1% to 200% by mass relative to the mass of the hydrolytic condensate of the hydrolytic 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 sufficient 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.

[0312] When the film-forming composition of the present invention contains an acid-generating agent, examples of such an acid-generating agent include thermal acid-generating agents and photo-acid-generating agents.

[0313] As a photoacid-producing agent, examples include Salt compounds, sulfonylimide compounds, disulfonyldiazomethane compounds, etc., but not limited to these.

[0314] As A specific example of a salt compound is diphenyliodide. Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate, bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Sulfonate compounds, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro n-butane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium trifluoromethane sulfonate, and other sulfonate compounds, but not limited to these.

[0315] Specific examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide, but are not limited to these.

[0316] Specific examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, etc., but are not limited to these.

[0317] Acid-producing agents can be used alone or in combination of two or more.

[0318] When the film-forming composition of the present invention contains an acid-generating agent, its content is appropriately determined by considering the type of acid-generating agent, etc., and therefore cannot be specified in general. However, it is generally in the range of 0.01% to 5% by mass relative to the mass of the hydrolytic condensate of the hydrolyzable silane. From the viewpoint of suppressing the precipitation of the acid-generating agent in the composition, it is preferably 3% by mass or less, more preferably 1% by mass or less. From the viewpoint of fully obtaining its effect, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

[0319] The surfactant is particularly effective in suppressing the generation of pinholes, streaks, etc., when the film-forming composition of the present invention is coated onto a substrate as a photoresist lower layer film-forming composition.

[0320] Specific examples of such surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol tristearate. Nonionic surfactants such as stearates, polyoxyethylene sorbitol fatty acid esters, etc.; trade names: Efttop EF301, EF303, EF352 (manufactured by Tokem Prodact Co., Ltd.); trade names: Megafack F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Co., Ltd.); Florad FC430 Fluorinated surfactants such as FC431 (manufactured by Sumitomo Slyem Co., Ltd.), trade names Asahigard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd.), and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), but not limited to these.

[0321] Surfactants can be used alone or in combination of two or more.

[0322] When the film-forming composition of the present invention contains a surfactant, its content is generally in the range of 0.0001 parts by mass to 5 parts by mass relative to 100 parts by mass of the hydrolysate (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 sufficient effect, it is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more.

[0323] The film-forming composition of the present invention preferably does not contain a curing catalyst as an additive. This is because if it is included as an additive, a portion of the additive will migrate into the resist film during resist film formation and subsequent heating, sometimes causing property degradation; this situation is avoided.

[0324] Furthermore, the film-forming composition of the present invention may include rheology modifiers, adhesive additives, pH adjusters, etc. Rheology modifiers are effective in improving the flowability of the film-forming composition. Adhesive additives 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.

[0325] Bisphenol S or its derivatives can be added as a pH adjuster. The content of bisphenol S or its derivatives is 0.01 to 20 parts by weight, or 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight relative to 100 parts by weight of the hydrolysate (polyorganosiloxane).

[0326] The following are specific examples of bisphenol S and bisphenol S derivatives, but are not limited to these.

[0327]

[0328] The hydrolytic condensate used in this invention can be obtained by hydrolyzing and condensing the above-mentioned hydrolytic silane compound.

[0329] Hydrolysis, as described above, can be either complete or partial. As mentioned above, the hydrolyzed condensate contained in the film-forming composition of the present invention may include a partially hydrolyzed product along with the fully hydrolyzed product. Furthermore, hydrolyzable silanes as monomers may remain in the composition.

[0330] In this invention, as described above, the hydrolysis and condensation of the hydrolyzable silane compound uses two or more acidic compounds. From the viewpoint of better reproducibility and obtaining the effects of this invention, the amount of the two or more acidic compounds used is determined such that for every 1 mole of hydrolyzable group of the hydrolyzable silane compound, the amount of acidic groups of the two or more acidic compounds is typically 0.001 mol to 10 mol, preferably 0.002 mol to 5 mol, more preferably 0.003 mol to 3 mol, even more preferably 0.005 mol to 2 mol, and even more preferably 0.007 mol to 1 mol.

[0331] The hydrolyzable silane compound used in this invention has an alkoxy, aralkyloxy, acyloxy, or halogen atom directly bonded to a silicon atom, and contains a hydrolyzable group as an alkoxysilyl, aralkyloxysilyl, acyloxysilyl, or halosilyl group. In this hydrolysis, 0.5 to 100 moles of water are typically used per mole of hydrolyzable group, preferably 1 to 10 moles.

[0332] Hydrolysis catalysts can be used to promote hydrolysis and condensation.

[0333] Specific examples include metal chelates, organic bases, and inorganic bases, but are not limited to these.

[0334] The hydrolysis catalyst can be used alone or in combination of two or more. Regarding the amount used, it is usually 0.001 mol to 10 mol per mol of hydrolytic group, preferably 0.001 mol to 1 mol.

[0335] Specific examples of metal chelates include triethoxy-mono(acetylacetone)titanium, tri-n-propoxy-mono(acetylacetone)titanium, tri-isopropoxy-mono(acetylacetone)titanium, tri-n-butoxy-mono(acetylacetone)titanium, tri-sec-butoxy-mono(acetylacetone)titanium, tri-tert-butoxy-mono(acetylacetone)titanium, diethoxy-bis(acetylacetone)titanium, di-n-propoxy-bis(acetylacetone)titanium, di-isopropoxy-bis(acetylacetone)titanium, di-n-butoxy-bis(acetylacetone)titanium, and di-... -sec-butoxy·bis(acetylacetone)titanium, di-tert-butoxy·bis(acetylacetone)titanium, monoethoxy·tri(acetylacetone)titanium, mono-n-propoxy·tri(acetylacetone)titanium, mono-isopropoxy·tri(acetylacetone)titanium, mono-n-butoxy·tri(acetylacetone)titanium, mono-sec-butoxy·tri(acetylacetone)titanium, mono-tert-butoxy·tri(acetylacetone)titanium, tetra(acetylacetone)titanium, triethoxy·mono(ethyl acetoacetic acid)titanium, tri-n-propoxy·mono(ethyl acetoacetic acid)titanium, tri-isopropoxy Titanium mono(ethyl acetoacetate), tri-n-butoxy-mono(ethyl acetoacetate) titanium, tri-sec-butoxy-mono(ethyl acetoacetate) titanium, tri-tert-butoxy-mono(ethyl acetoacetate) titanium, diethoxy-bis(ethyl acetoacetate) titanium, di-n-propoxy-bis(ethyl acetoacetate) titanium, di-isopropoxy-bis(ethyl acetoacetate) titanium, di-n-butoxy-bis(ethyl acetoacetate) titanium, di-sec-butoxy-bis(ethyl acetoacetate) titanium, di-tert-butoxy-bis(ethyl acetoacetate) titanium, monoethyl acetoacetate Titanium chelates include oxytris(ethyl acetoacetate)titanium, mono-n-propoxytris(ethyl acetoacetate)titanium, mono-isopropoxytris(ethyl acetoacetate)titanium, mono-n-butoxytris(ethyl acetoacetate)titanium, mono-sec-butoxytris(ethyl acetoacetate)titanium, mono-tert-butoxytris(ethyl acetoacetate)titanium, tetra(ethyl acetoacetate)titanium, mono(acetylacetone)tris(ethyl acetoacetate)titanium, bis(acetylacetone)bis(ethyl acetoacetate)titanium, and tris(acetylacetone)mono(ethyl acetoacetate)titanium.Triethoxy-mono(acetylacetone)zirconium, tri-n-propoxy-mono(acetylacetone)zirconium, tri-isopropoxy-mono(acetylacetone)zirconium, tri-n-butoxy-mono(acetylacetone)zirconium, tri-sec-butoxy-mono(acetylacetone)zirconium, tri-tert-butoxy-mono(acetylacetone)zirconium, diethoxy-bis(acetylacetone)zirconium, di-n-propoxy-bis(acetylacetone)zirconium, di-isopropoxy-bis(acetylacetone)zirconium, di-n-butoxy-bis(acetylacetone)zirconium, di-sec-butoxy-bis(acetylacetone)zirconium, di-tert-butoxy • Di(acetylacetone)zirconium, monoethoxy·tri(acetylacetone)zirconium, mono-n-propoxy·tri(acetylacetone)zirconium, mono-isopropoxy·tri(acetylacetone)zirconium, mono-n-butoxy·tri(acetylacetone)zirconium, mono-sec-butoxy·tri(acetylacetone)zirconium, mono-tert-butoxy·tri(acetylacetone)zirconium, tetra(acetylacetone)zirconium, triethoxy·mono(ethylacetoacetate)zirconium, tri-n-propoxy·mono(ethylacetoacetate)zirconium, tri-isopropoxy·mono(ethylacetoacetate)zirconium, tri-n-butoxy·mono(ethylacetoacetate)zirconium Zirconium acetate, tri-sec-butoxy-mono(ethyl acetoacetate)zirconium, tri-tert-butoxy-mono(ethyl acetoacetate)zirconium, diethoxy-bis(ethyl acetoacetate)zirconium, di-n-propoxy-bis(ethyl acetoacetate)zirconium, di-isopropoxy-bis(ethyl acetoacetate)zirconium, di-n-butoxy-bis(ethyl acetoacetate)zirconium, di-sec-butoxy-bis(ethyl acetoacetate)zirconium, di-tert-butoxy-bis(ethyl acetoacetate)zirconium, monoethoxy-tri(ethyl acetoacetate)zirconium, mono-n-propoxy-tri(ethyl acetoacetate)zirconium Zirconium chelates include zirconium, mono-isopropoxy-tris(ethyl acetoacetate)zirconium, mono-n-butoxy-tris(ethyl acetoacetate)zirconium, mono-sec-butoxy-tris(ethyl acetoacetate)zirconium, mono-tert-butoxy-tris(ethyl acetoacetate)zirconium, tetra(ethyl acetoacetate)zirconium, mono(acetylacetone)tris(ethyl acetoacetate)zirconium, bis(acetylacetone)bis(ethyl acetoacetate)zirconium, tris(acetylacetone)mono(ethyl acetoacetate)zirconium, etc.; aluminum chelates include tris(acetylacetone)aluminum, tris(ethyl acetoacetate)aluminum, etc., but are not limited to these.

[0336] Specific examples of organic bases include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picolinide, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, etc., but are not limited to these.

[0337] Specific examples of inorganic bases include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide, but are not limited to these.

[0338] Among them, metal chelates are preferred as hydrolysis catalysts.

[0339] Organic solvents can be used as solvents during hydrolysis and condensation. 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; and aromatic solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, and n-pentylnaphthalene. Aromatic hydrocarbon solvents; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol Monohydric alcohol solvents such as phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol; acetone, methyl ethyl ketone, and methyl-n-propylene glycol. Ketone solvents including 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, acetone-acetone, diacetone alcohol, acetophenone, fentanyl ketone, etc.; ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, etc. Alkane, dimethyl di Alkane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-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, ethoxytris(ethylene glycol), tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ... Ether solvents such as methyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, and cyclohexyl acetate. Esters, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetyl glycol, methoxytris(ethylene glycol), ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate Ester solvents such as di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesulfonyl lactone, etc., but not limited to these. These solvents can be used alone or in combination of two or more.

[0340] Among them, 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, acetone-acetone, diacetone alcohol, acetophenone, and fenestrate are preferred in terms of solution storage stability.

[0341] The reaction temperature for hydrolysis and condensation is usually 20℃~80℃.

[0342] When using a silane other than the amino-containing silane shown in formula (1) as the hydrolyzable silane, the amount of amino-containing silane shown in formula (1) added is generally 0.1 mol% or more in all hydrolyzable silanes, but from the viewpoint of obtaining the above-mentioned 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.

[0343] When using other silanes represented by formula (2) or formula (3) as hydrolyzable silanes, the amount of these other silanes added is generally 0.1 mol% or more, preferably 1 mol% or more, more preferably 5 mol% or more, generally 99.9 mol% or less, preferably 99 mol% or less, more preferably 95 mol% or less in total hydrolyzable silanes.

[0344] When using the hydrolyzable organosilane shown in formula (4) as the hydrolyzable silane, the amount of the organosilane added is generally 0.01 mol% or more, preferably 0.1 mol% or more, generally 30 mol% or less, and preferably 10 mol% or less in the total hydrolyzable silane.

[0345] When using the hydrolyzable organosilane shown in formula (5-1) as the hydrolyzable silane, the amount of the organosilane added is generally 0.1 mol% or more, preferably 0.3 mol% or more, generally 50 mol% or less, and preferably 30 mol% or less in the total hydrolyzable silane.

[0346] Hydrolyzable condensates can be produced by hydrolyzing and condensing hydrolyzable silane compounds under the conditions described above.

[0347] After the reaction is complete, the reaction solution is neutralized by either undiluted or diluted / concentrated, and then treated with an ion exchange resin, thereby removing the acid catalyst used in the hydrolysis. Furthermore, byproducts such as alcohols, water, and catalysts can be removed from the reaction solution before or after such treatment by means of vacuum distillation.

[0348] If necessary, the hydrolyzed condensate can be obtained as a solid or as a solution containing the hydrolyzed condensate by removing all or part of the solvent from the solution containing the hydrolyzed condensate by distillation after such purification.

[0349] The film-forming composition of the present invention can be manufactured by mixing the hydrolytic condensate of the above-mentioned hydrolyzable silane compound, a solvent, and, where other components are included, the other components. In this case, a solution containing the hydrolytic condensate, etc., can be prepared in advance, and the solution can be mixed with the solvent and other components.

[0350] There is no particular restriction on the mixing order. For example, a solvent can be added to a solution containing hydrolysate condensates, and other components can be added to the mixture. Alternatively, the solution containing hydrolysate condensates, the solvent, and other components can be mixed simultaneously.

[0351] If necessary, a further solvent may be added at the end, or a component that is not readily soluble in the solvent may be added last. However, from the viewpoint of suppressing the aggregation and separation of constituent components and preparing a homogeneous composition with good reproducibility, it is preferable to prepare a well-dissolved solution of the hydrolysate or the like beforehand and use it to prepare the composition. It should be noted that the hydrolysate or the like may aggregate or precipitate when mixed, depending on the type and amount of solvent being mixed, the amount and properties of other components, etc. Furthermore, when preparing the composition using a solution of the hydrolysate or the like, it is important to determine the concentration and amount of the solution of the hydrolysate or the like in a way that the final composition contains the desired amount of the hydrolysate or the like.

[0352] In the preparation of the composition, appropriate heating can be applied within a range that does not decompose or deteriorate the components.

[0353] In this invention, the membrane forming composition can be filtered using a submicron-sized filter or the like during the manufacturing process of the composition or after all the components have been mixed.

[0354] The concentration of the solid component in the film-forming composition of the present invention is generally 0.1% to 50% by mass relative to the mass of the composition, but from the viewpoint of suppressing the precipitation of the solid component, it is preferably 30% by mass or less, and more preferably 25% by mass or less.

[0355] From the viewpoint of obtaining the effects of the present invention with good reproducibility, the proportion of hydrolyzable silane compound hydrolysate in the solid component is generally 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 even more preferably 90% by mass or more.

[0356] The film-forming composition of the present invention is suitable for use as a composition for forming a resist underlayer film in a photolithography process.

[0357] In one aspect of the present invention, a resist underlayer film forming composition composed of the film forming composition of the present invention is coated onto a substrate used in the manufacture of a semiconductor device (e.g., 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.) using a suitable coating method such as a spin coater or a coating machine, and then fired to form the resist underlayer film of the present invention.

[0358] The firing conditions are usually selected from a firing temperature of 80℃ to 250℃ and a firing time of 0.3 minutes to 60 minutes, but the preferred firing temperature is 150℃ to 250℃ and the firing time is 0.5 minutes to 2 minutes.

[0359] The resist underlayer of the present invention may further contain metal oxides.

[0360] Examples of such metal oxides include, but are not limited to, oxides of one or more of the following metals: 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).

[0361] The thickness of the lower resist 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.

[0362] Next, a photoresist film, for example, is formed on the resist underlayer of the present invention. The photoresist film can be formed by a known method, namely, coating a photoresist film forming composition onto the resist underlayer of the present invention and then 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.

[0363] In other embodiments of the present invention, an organic underlayer film can be formed on the substrate, followed by the formation of the resist underlayer film of the present invention, and then a photoresist film can be formed on top of that. Thus, even when the pattern width of the photoresist film is narrowed, and a thin layer of photoresist film is applied to prevent pattern collapse, substrate processing can still be performed by selecting an appropriate etching gas. For example, a fluorine-based gas that achieves a sufficiently fast etching rate relative to the photoresist film can be used as the etching gas to process the resist underlayer film of the present invention. Furthermore, an oxygen-based gas that achieves a sufficiently fast etching rate relative to the resist underlayer film of the present invention can be used as the etching gas to process the organic underlayer film. Even further, a fluorine-based gas that achieves a sufficiently fast etching rate relative to the organic underlayer film can be used as the etching gas to process the substrate.

[0364] It should be noted that the substrates and coating methods that can be used at this time can be the same as those mentioned above.

[0365] As for the material of the photoresist film formed on the photoresist lower layer film of the present invention, there is no particular limitation as long as it is a photosensitive material used for exposure. Both negative and positive photoresist materials can be used. Specific examples include a positive photoresist material composed of phenolic varnish resin and 1,2-naphthoquinone diazonyl sulfonate; a chemically amplified photoresist material composed of an adhesive having groups that increase the alkali dissolution rate through acid decomposition and a photoacid generator; a chemically amplified photoresist material composed of a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist through acid decomposition, an alkali-soluble adhesive, and a photoacid generator; and a chemically amplified photoresist material composed of an adhesive having groups that increase the alkali dissolution rate of the photoresist through acid decomposition, a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist through acid decomposition, and a photoacid generator, etc., but it is not limited to these.

[0366] Specific examples that can be obtained as commodities include APEX-E manufactured by Shipra, PAR710 manufactured by Sumitomo Chemical Co., Ltd., and SEPR430 manufactured by Shin-Etsu Chemical Industry Co., Ltd., but are not limited to these.

[0367] In addition, fluorinated atom polymer 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), may also be suitable.

[0368] Next, exposure is performed using a specified mask. Exposure can be performed using a KrF excimer laser (wavelength 248nm), an ArF excimer laser (wavelength 193nm), or an F2 excimer laser (wavelength 157nm), etc.

[0369] After exposure, post-exposure baking can be performed as needed. Post-exposure baking is performed under conditions where the heating temperature is appropriately selected from 70℃ to 150℃ and the heating time is from 0.3 minutes to 10 minutes.

[0370] In this invention, as a photoresist material, an electron beam lithography photoresist material or an EUV lithography photoresist material can be used instead of a photoresist material.

[0371] As resist materials for electron beam lithography, both negative and positive types can be used. Specific examples include chemically amplified resist materials composed of an acid-generating agent and a binder having groups that change the rate of alkali dissolution through acid decomposition; chemically amplified resist materials composed of an alkali-soluble binder, an acid-generating agent, and a low-molecular-weight compound that changes the rate of alkali dissolution through acid decomposition; chemically amplified resist materials composed of an acid-generating agent, a binder having groups that change the rate of alkali dissolution through acid decomposition, and a low-molecular-weight compound that changes the rate of alkali dissolution through acid decomposition; non-chemically amplified resist materials composed of a binder having groups that change the rate of alkali dissolution through electron beam decomposition; and non-chemically amplified resist materials composed of a binder having portions where the rate of alkali dissolution changes when cut by electron beams, etc., but are not limited to these. When using these electron beam lithography resist materials, the irradiation source can be an electron beam, and a resist pattern can be formed in the same way as when using photoresist materials.

[0372] As a resist material for EUV lithography, methacrylate resin-based resist materials can be used.

[0373] Next, development is performed using a developer (e.g., an alkaline developer). Thus, when using, for example, a positive photoresist material, the exposed portion of the photoresist film is removed, forming a pattern of the photoresist film.

[0374] Specific examples of developing solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, as well as alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine, but are not limited to these.

[0375] In this invention, an organic solvent can be used as the developer. That is, development is performed using the developer (organic solvent) after exposure. As a result, when using, for example, a negative photoresist material, the photoresist film in the unexposed areas is removed, forming a pattern of the photoresist film.

[0376] Specific examples of organic solvents that can be used as such developing solutions include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4 2-Propoxybutylacetic acid ester, 2-Methoxypentylacetic acid ester, 3-Methoxypentylacetic acid ester, 4-Methoxypentylacetic acid ester, 2-Methyl-3-Methoxypentylacetic acid ester, 3-Methyl-3-Methoxypentylacetic acid ester, 3-Methyl-4-Methoxypentylacetic acid ester, 4-Methyl-4-Methoxypentylacetic acid ester, Propylene glycol diacetate, Methyl formate, Ethyl formate, Butyl formate, Propyl formate, Ethyl lactate, Butyl lactate, Propyl lactate Ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc., but not limited to these.

[0377] Depending on the requirements, the developer may also contain surfactants, etc.

[0378] Development is carried out under conditions appropriately selected from 5°C to 50°C and 10 seconds to 600 seconds.

[0379] Next, the pattern of the photoresist film (upper layer) formed in this manner is used as a protective film to remove the photoresist lower layer (intermediate layer) of the present invention. Then, the film composed of the patterned photoresist film and the photoresist lower layer (intermediate layer) of the present invention is used as a protective film to remove the organic lower layer (lower layer). Finally, the patterned photoresist lower layer (intermediate layer) and organic lower layer (lower layer) of the present invention are used as protective films to process the semiconductor substrate.

[0380] First, the lower resist film (intermediate layer) of the present invention, from which the photoresist film has been removed, is removed by dry etching, exposing the semiconductor substrate.

[0381] The dry etching of the resist underlayer film of the present invention can use 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.

[0382] Dry etching of the photoresist underlayer is preferably performed using a halogen-based gas. With halogen-based gases, the photoresist film, which is essentially composed of organic matter, is difficult to remove. In contrast, the photoresist underlayer of this invention, which contains a large number of silicon atoms, is rapidly removed by a halogen-based gas. Therefore, the reduction in the thickness of the photoresist film accompanying the dry etching of the photoresist underlayer can be suppressed. Consequently, the photoresist film can be used as a thin film. Dry etching of the photoresist underlayer is preferably performed using a fluorine-based gas. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2), but are not limited to these.

[0383] Then, the organic underlayer film is removed using a film consisting of the patterned photoresist film and the photoresist underlayer film of the present invention as a protective film. The organic underlayer film (underlayer) is preferably removed by dry etching using an oxygen-based gas. This is because the photoresist underlayer film of the present invention, which contains a large number of silicon atoms, is not easily removed by dry etching using an oxygen-based gas.

[0384] Finally, the semiconductor substrate is processed. The semiconductor substrate is preferably processed by dry etching using a fluorine-based gas.

[0385] Examples of fluorine-based gases include, but are not limited to, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0386] The upper layer of the photoresist lower layer of the present invention can form an organic antireflective film before the formation of the photoresist film. There are no particular limitations on the antireflective film composition used herein; for example, any material conventionally used in photolithography processes can be selected. Furthermore, the antireflective film can be formed by conventional methods, such as coating and firing using a spin coater or a coating machine.

[0387] A substrate coated with the resist underlayer film forming composition of the present invention may have an organic or inorganic antireflective film formed by CVD or the like on its surface, or the resist underlayer film of the present invention may be formed thereon. In the case where an organic underlayer film is formed on a substrate, and then the resist underlayer film of the present invention is formed thereon, the substrate may also have an organic or inorganic antireflective film formed by CVD or the like on its surface.

[0388] The photoresist underlayer film formed by the composition for forming the photoresist underlayer film of the present invention sometimes absorbs light according to the wavelength of the light used in the photolithography process. Furthermore, in such cases, it can function as an anti-reflective film that prevents reflected light from the substrate. Furthermore, the photoresist underlayer film of the present invention can also be used as a layer for preventing interaction between the substrate and the photoresist film, a layer that prevents adverse effects on the substrate from the material used in the photoresist film or substances generated during exposure of 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 for reducing the poisoning effect of the photoresist film caused by the dielectric layer of the semiconductor substrate.

[0389] The resist underlayer film formed by the resist underlayer film formation composition of the present invention can be applied to substrates with through-holes used in dual damascene processes as a hole-filling material (embedded material) that can fill the holes without gaps. Furthermore, it can also be used as a planarization material for planarizing the surface of semiconductor substrates with uneven surfaces.

[0390] In addition to its function as a hard mask, the lower layer film of the EUV resist can also be used for the following purposes. To form an EUV resist lower layer antireflective film that does not mix with the EUV resist film and prevents undesirable exposure light, such as the aforementioned deep ultraviolet (DUV) light, from reflecting off the substrate or interface during EUV exposure, the resist lower layer film forming composition of the present invention can be used. It can effectively prevent reflection as a lower layer film for EUV resist films. When used as an EUV resist lower layer film, the process can be performed in the same manner as for a photoresist lower layer film.

[0391] The film-forming composition of the present invention described above is suitable for use in the manufacture of semiconductor devices. According to the semiconductor device manufacturing method of the present invention, for example, a process including a step of forming an organic underlayer film on a substrate; a step of forming a resist underlayer film on the organic underlayer film using the film-forming composition of any one of claims 1 to 12; and a step of forming a resist film on the resist underlayer film, the semiconductor device manufacturing method can be expected to produce semiconductor devices with high reliability.

[0392] Example

[0393] The present invention will be described in more detail below with examples of synthesis and embodiments, but the present invention is not limited to the following.

[0394] It should be noted that the weight-average molecular weight is the molecular weight obtained by GPC analysis and converted to polystyrene. The GPC analysis used a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Corporation) and a GPC column (trade name Shodex KF803L, KF802, KF801, manufactured by Showa Denko Corporation), with the column temperature set at 40°C, tetrahydrofuran used as the eluent, the flow rate set at 1.0 mL / min, and polystyrene (manufactured by Showa Denko Corporation) used as the standard sample.

[0395] [1] Synthesis of polymers (hydrolysis condensates)

[0396] (Synthesis example 1)

[0397] 20.2 g of tetraethoxysilane [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 added to a 300 mL flask and stirred. While stirring the resulting solution with an electromagnetic 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.

[0398] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Then, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent. It should be noted that the solids concentration of the obtained concentrate, converted from the solids residue after heating at 140°C, exceeds 20% by mass.

[0399] Next, propylene glycol monoethyl ether was added to the resulting concentrate to adjust the concentration to 20% by mass, based on the solids residue after heating at 140°C, thus obtaining a solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent (solids concentration 20% by mass). The resulting polymer contains the structure shown in formula (E1), and its weight-average molecular weight (Mw) is 1,800 when converted to polystyrene obtained by GPC.

[0400]

[0401] (Synthesis example 2)

[0402] Instead of 10.2 g of a 0.2 mol / L aqueous solution of p-toluenesulfonic acid [manufactured by Tokyo Chemical Industry Co., Ltd.], 10.2 g of a 0.2 mol / L aqueous solution of p-toluenesulfonic acid was used. Otherwise, a solution of the hydrolyzed condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1. The resulting polymer contained the structure shown in formula (E2), and its weight-average molecular weight (Mw) was 1,900 when converted to polystyrene obtained by GPC.

[0403]

[0404] (Synthesis example 3)

[0405] Instead of 10.2 g of a 0.2 mol / L aqueous solution of camphor sulfonic acid [manufactured by Tokyo Chemical Industry Co., Ltd.], 10.2 g of such solution was used. Otherwise, a solution of the hydrolyzed condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1. The resulting polymer contained the structure shown in formula (E3), and its weight-average molecular weight (Mw) was 2,000 when converted to polystyrene obtained by GPC.

[0406]

[0407] (Synthesis Example 4)

[0408] Instead of 10.2 g of nitric acid aqueous solution (concentration 0.2 mol / L), 10.2 g of trifluoroacetic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used. Otherwise, a solution of the hydrolyzed condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1. The resulting polymer contained the structure shown in formula (E4), and its weight-average molecular weight (Mw) was 2,200 when converted to polystyrene obtained by GPC.

[0409]

[0410] (Synthesis Example 5)

[0411] Instead of 10.2 g of nitric acid aqueous solution (concentration 0.2 mol / L), 10.2 g of maleic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used. Otherwise, a solution of the hydrolysis condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1. The resulting polymer contains the structure shown in formula (E5), and its weight-average molecular weight (Mw) is 2,400 when converted to polystyrene obtained by GPC.

[0412]

[0413] (Synthesis Example 6)

[0414] Instead of 10.2 g of nitric acid aqueous solution (concentration 0.2 mol / L), 10.2 g of a square acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was used. Otherwise, a solution of the hydrolysis condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1. The resulting polymer contained the structure shown in formula (E6), and its weight-average molecular weight (Mw) was 2,400 when converted to polystyrene obtained by GPC.

[0415]

[0416] (Synthesis Example 7)

[0417] 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 added to a 300 mL flask and stirred. While stirring the resulting solution with an electromagnetic 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.

[0418] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Then, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent. It should be noted that the solids concentration of the obtained concentrate, converted from the solids residue after heating at 140°C, exceeds 20% by mass.

[0419] Next, propylene glycol monoethyl ether was added to the resulting concentrate to adjust the concentration to 20% by mass, based on the solids residue after heating at 140°C, thus obtaining a solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent (solids concentration 20% by mass). The resulting polymer contains the structure shown in formula (E7), and its weight-average molecular weight (Mw) is 1,800 when converted to polystyrene obtained by GPC.

[0420]

[0421] (Synthesis Example 8)

[0422] 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 isocyanurate-propyltriethoxysilane [manufactured by Nissan Chemical Co., Ltd.], and 48.3 g of propylene glycol monoethyl ether were added to a 300 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, a mixed solution of 9.74 g of nitric acid aqueous solution (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.], 9.74 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.], and 0.35 g of dimethylaminopropyltrimethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise.

[0423] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Then, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent. It should be noted that the solids concentration of the obtained concentrate, converted from the solids residue after heating at 140°C, exceeds 20% by mass.

[0424] Next, propylene glycol monoethyl ether was added to the resulting concentrate to adjust the concentration to 20% by mass, based on the solids residue after heating at 140°C, thus obtaining a solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent (solids concentration 20% by mass). The resulting polymer contains the structure shown in formula (E8), with a weight-average molecular weight (Mw) of 2,000 converted from polystyrene obtained by GPC.

[0425]

[0426] (Synthesis Example 9)

[0427] 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-propyltriethoxysilane [manufactured by Gerest Co., Ltd.], and 48.0 g of propylene glycol monoethyl ether were added to a 300 mL flask and stirred. While stirring the resulting solution with an electromagnetic 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.

[0428] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Then, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent. It should be noted that the solids concentration of the obtained concentrate, converted from the solids residue after heating at 140°C, exceeds 20% by mass.

[0429] Next, propylene glycol monoethyl ether was added to the resulting concentrate to adjust the concentration to 20% by mass, based on the solids residue after heating at 140°C, thus obtaining a solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent (solids concentration 20% by mass). The resulting polymer contains the structure shown in formula (E9), and its weight-average molecular weight (Mw) is 1,900 when converted to polystyrene obtained by GPC.

[0430]

[0431] (Synthesis Example 10)

[0432] 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 Co., Ltd.], and 48.2 g of propylene glycol monoethyl ether were added to a 300 mL flask and stirred. While stirring the resulting solution with an electromagnetic 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.

[0433] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Then, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent. It should be noted that the solids concentration of the obtained concentrate, converted from the solids residue after heating at 140°C, exceeds 20% by mass.

[0434] Next, propylene glycol monoethyl ether was added to the resulting concentrate to adjust the concentration to 20% by mass, based on the solids residue after heating at 140°C, thus obtaining a solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent (solids concentration 20% by mass). The resulting polymer contains the structure shown in formula (E10), and its weight-average molecular weight (Mw) is 2,400 when converted to polystyrene obtained by GPC.

[0435]

[0436] (Synthesis Example 11)

[0437] 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 added to a 300 mL flask and stirred. While stirring the resulting solution with an electromagnetic 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.

[0438] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Then, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent. It should be noted that the solids concentration of the obtained concentrate, converted from the solids residue after heating at 140°C, exceeds 20% by mass.

[0439] Next, propylene glycol monoethyl ether was added to the resulting concentrate to adjust the concentration to 20% by mass, based on the solids residue after heating at 140°C, thus obtaining a solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent (solids concentration 20% by mass). The resulting polymer contains the structure shown in formula (E11), and its weight-average molecular weight (Mw) is 1,800 when converted to polystyrene obtained by GPC.

[0440]

[0441] (Comparative Synthesis Example 1)

[0442] 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 added to a 300 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 20.4 g of nitric acid aqueous solution (concentration 0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.] was added dropwise.

[0443] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Then, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent. It should be noted that the solids concentration of the obtained concentrate, converted from the solids residue after heating at 140°C, exceeds 20% by mass.

[0444] Next, propylene glycol monoethyl ether was added to the resulting concentrate to adjust the concentration to 20% by mass, based on the solids residue after heating at 140°C, thus obtaining a solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent (solids concentration 20% by mass). The resulting polymer contains the structure shown in formula (C1), and its weight-average molecular weight (Mw) is 1,700 when converted to polystyrene obtained by GPC.

[0445]

[0446] (Comparative Synthesis Example 2)

[0447] 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 added to a 300 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 20.4 g of methanesulfonic acid aqueous solution (concentration 0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.] was added dropwise.

[0448] After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 240 minutes. Then, under reduced pressure, ethanol, methanol, and water were removed by distillation to obtain a concentrated solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent. It should be noted that the solids concentration of the obtained concentrate, converted from the solids residue after heating at 140°C, exceeds 20% by mass.

[0449] Next, propylene glycol monoethyl ether was added to the resulting concentrate to adjust the concentration to 20% by mass, based on the solids residue after heating at 140°C, thus obtaining a solution of the hydrolyzed condensate (polymer) using propylene glycol monoethyl ether as a solvent (solids concentration 20% by mass). The resulting polymer contains the structure shown in formula (C2), and its weight-average molecular weight (Mw) is 1,900 when converted to polystyrene obtained by GPC.

[0450]

[0451] (Comparative Synthesis Example 3)

[0452] Instead of 10.2 g of nitric acid aqueous solution (0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.] and 10.2 g of methanesulfonic acid aqueous solution (0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.], 20.4 g of methanesulfonic acid aqueous solution (0.2 mol / L) was used. Otherwise, a solution of the hydrolyzed condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1. The resulting polymer contained the structure shown in formula (C3), and its weight-average molecular weight (Mw) was 2,600 when converted to polystyrene obtained by GPC.

[0453]

[0454] (Comparative Synthesis Example 4)

[0455] Instead of 10.2 g of nitric acid aqueous solution (0.2 mol / L) [manufactured by Kanto Chemical Co., Ltd.] and 10.2 g of methanesulfonic acid aqueous solution (0.2 mol / L) [manufactured by Tokyo Chemical Industry Co., Ltd.], 20.4 g of nitric acid aqueous solution (0.2 mol / L) was used. Otherwise, a solution of the hydrolyzed condensate (polymer) (solid content concentration 20% by mass) was obtained by the same method as in Synthesis Example 1. The resulting polymer contained the structure shown in formula (C4), and its weight-average molecular weight (Mw) was 2,000 when converted to polystyrene obtained by GPC.

[0456]

[0457] [2] Preparation of the composition for film formation

[0458] 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 filtered through a 0.1 μm fluoropolymer filter to prepare membrane-forming compositions. The amounts added in Table 1 are expressed in parts by mass.

[0459] It should be noted that the polymer addition ratio in Table 1 does not represent the amount of polymer solution added, but rather the amount of polymer itself added.

[0460] In addition, DIW refers to ultrapure water, PGEE refers to propylene glycol monoethyl ether, PGMEA refers to propylene glycol monomethyl ether acetate, and PGME refers to propylene glycol monomethyl ether.

[0461] Furthermore, MA refers to maleic acid, and TPSNO3 refers to triphenylsulfonium nitrate.

[0462] [Table 1]

[0463] Table 1

[0464]

[0465] [3] Preparation of compositions for forming organic lower layer films

[0466] Under nitrogen atmosphere, carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 ml four-necked flask. 1,4-di(II) The alkane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was stirred and heated to 100°C to dissolve it and begin polymerization. After 24 hours, it was cooled to 60°C.

[0467] Chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.) was added to the cooled reaction mixture for dilution, and the diluted mixture was then added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to precipitate the precipitate.

[0468] The resulting precipitate was filtered and dried at 80°C for 24 hours using a vacuum dryer to obtain 9.37 g of the polymer (hereinafter abbreviated as PCzFL) represented by formula (3-1) as the target.

[0469] It should be noted that PCzFL's 1 The H-NMR measurement results are as follows.

[0470] 1 H-NMR (400MHz, DMSO-d6): δ7.03-7.55 (br, 12H), δ7.61-8.10 (br, 4H), δ11.18 (br, 1H)

[0471] Furthermore, the weight-average molecular weight Mw of PCzFL is 2,800 when converted to polystyrene obtained from GPC, and the polydispersity Mw / Mn is 1.77.

[0472]

[0473] 20g of PCzFL, 3.0g of tetramethoxymethyl urea (manufactured by Japan Cytec Industry Co., Ltd. (formerly Mitsui Cytec Co., Ltd.), trade name Pudalink 1174) as a crosslinking agent, and pyridine as a catalyst were prepared. 0.30 g of p-toluenesulfonate and 0.06 g of Megafack R-30 (manufactured by DIC Corporation, trade name) as a surfactant were mixed and 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 further filtered using a polyethylene microfilter with a pore size of 0.05 μm, thus preparing an organic lower layer film formation composition for use in a multilayer film photolithography process.

[0474] [4] Solvent resistance and developer solubility resistance tests

[0475] The film-forming compositions prepared in Examples 1-11 and Comparative Examples 1 and 4 were respectively coated onto silicon wafers using a spin coater. The wafers were heated at 215°C for 1 minute on a hot plate to form Si-containing films, and the thickness of the resulting Si-containing films was measured.

[0476] Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was coated onto each Si-containing film and rotary dried. The film thickness of the Si-containing films after drying was then measured to evaluate the presence or absence of thickness change before and after solvent coating. Using the film thickness before solvent coating as a baseline, a thickness change of less than 1% after coating was rated as "good," while a thickness change of more than 1% was rated as "uncured."

[0477] Furthermore, on each Si-containing film fabricated on a silicon wafer using the same method, an alkaline developer (TMAH 2.38% aqueous solution) was coated and spin-dried. The thickness of the underlying film after drying was then measured to evaluate the presence or absence of thickness change before and after developer coating. Using the film thickness before developer coating as a baseline, a thickness change of less than 1% was defined as "good," and a thickness change of more than 1% was defined as "uncured."

[0478] The results are shown in Table 2.

[0479] [Table 2]

[0480] [Table 2]

[0481] Composition for film formation Solvent resistance developer resistance Example 1 good good Example 2 good good Example 3 good good Example 4 good good Example 5 good good Example 6 good good Example 7 good good Example 8 good good Example 9 good good Example 10 good good Example 11 good good Comparative Example 1 Uncured Uncured Comparative Example 4 good Uncured

[0482] As shown in Table 2, the films obtained from the film-forming compositions of the present invention exhibit good resistance to solvents and developers.

[0483] [5] Determination of dry etching rate

[0484] The following etcher and etching gas were used to determine the dry etching rate.

[0485] Lam2300 (manufactured by Raman): CF4 / CHF3 / N2 (Fluorine-based gas)

[0486] RIE-10NR (made by Samko): O2 (oxygen gas)

[0487] The film-forming compositions obtained in Examples 1 to 11 were coated onto silicon wafers using a spin coater and heated on a hot plate at 215°C for 1 minute to form Si-containing films (film thickness 0.02 μm).

[0488] In addition, the above-mentioned organic lower layer film forming composition was similarly coated onto a silicon wafer using a spin coater and heated at 215°C for 1 minute on a hot plate to form an organic lower layer film (film thickness 0.20 μm).

[0489] Using the obtained silicon wafers with Si-containing films, the dry etching rates were measured using CF4 / CHF3 / N2 gas as the etching gas, and O2 gas as the etching gas. Additionally, silicon wafers with organic underlayer films were used, with O2 gas as the etching gas. The results are shown in Table 3.

[0490] It should be noted that the dry etching rate using O2 gas is expressed as a ratio (resistance) to the dry etching rate of the organic underlying film.

[0491] [Table 3]

[0492] Table 3

[0493]

[0494] As shown in Table 3, the films obtained from the film-forming compositions of the present invention exhibit high etching rates against fluorine-based gases and good resistance to oxygen-based gases compared to organic underlayer films.

[0495] [6] Determination of wet etching rate

[0496] The film-forming compositions obtained in Examples 1-11 and Comparative Examples 2 and 5 were coated onto silicon wafers using a spin coater and heated on a hot plate at 215°C for 1 minute to form Si-containing films (film thickness 0.02 μm).

[0497] Using the obtained silicon wafers with Si-containing films, the wet etching rate was measured using an NH3 / HF mixed aqueous solution as the wet etching solution. A wet etching rate of 10 nm / min or higher was defined as good, and a rate less than 10 nm / min was defined as poor. The results are shown in Table 4.

[0498] [Table 4]

[0499] [Table 4]

[0500]

[0501] As shown in Table 4, the films obtained from the film-forming compositions of the present invention exhibit good wet etching rates to wet etching solutions.

[0502] [7] Formation of resist patterns using EUV exposure: negative solvent development

[0503] The above-mentioned organic lower layer film forming composition was spin-coated on a silicon wafer and heated at 215°C for 1 minute on a hot plate to form an organic lower layer film (layer A) (film thickness 90 nm).

[0504] On it, the film-forming composition obtained in Example 1 is spin-coated and heated at 215°C for 1 minute on a hot plate to form a resist lower layer film (layer B) (film thickness 20 nm).

[0505] Further, an EUV resist solution (methacrylate resin-based resist) is spin-coated onto it, and heated at 130°C for 1 minute on a hot plate to form an EUV resist film (C layer). Then, it is exposed using an ASML EUV exposure apparatus (NXE3300B) under the conditions of NA=0.33, σ=0.67 / 0.90, and Dipole.

[0506] After exposure, post-exposure heating (110°C for 1 minute) is performed, followed by cooling on a cooling plate to room temperature. The image is then developed with an organic solvent developer (butyl acetate) for 1 minute, and then rinsed to form a resist pattern.

[0507] Using the same steps, resist patterns were formed using the compositions obtained in Examples 2-11 and Comparative Examples 3 and 4.

[0508] Furthermore, regarding the obtained patterns, the formation of 44nm spacing and 22nm lines and gaps was evaluated by confirming the pattern shape observed from the pattern cross-section.

[0509] In observing the pattern shape, a condition where the shape between the footing and the undercut is good and there is no significant residue in the gap is evaluated as "good". A condition where the resist pattern peels off and collapses is evaluated as "collapsed". A condition where the upper or lower part of the resist pattern is in contact with each other is evaluated as "bridging". The results are shown in Table 5.

[0510] [Table 5]

[0511] [Table 5]

[0512]

[0513]

[0514] As shown in Table 5, the film obtained by the film forming composition of the present invention functions well as a resist underlayer, achieving excellent photolithography properties.

Claims

1. A composition for film formation, characterized in that, Include: Hydrolyzed condensates obtained by hydrolyzing and condensing hydrolyzed silane compounds using two or more acidic compounds, and solvent, The hydrolyzable silane compound comprises an amino-containing silane as shown in formula (1). In equation (1), R 1 The groups that bond with silicon atoms are represented independently by organic groups containing amino groups. R 2 The group to be bonded to a silicon atom represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted haloalkyl group, a substituted haloaryl group, a substituted haloaralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a 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 that bond with silicon atoms, and each can be represented independently as an alkoxy, aralkyloxy, acyloxy, or halogen atom. Let a be an integer from 1 to 2, and b be an integer from 0 to 1, satisfying a + b ≤ 2. The amino-containing organic group is a group represented by the following formula (A1). In equation (A1), R 101 and R 102 Each can be represented independently by a hydrogen atom or a hydrocarbon group, and L represents a substituted alkylene group.

2. The membrane forming composition according to claim 1, wherein the two or more acidic compounds comprise two or more selected from the group consisting of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, heteropolyacid, cyclic compounds formed by carbonyl-linked olefins, organic acids containing sulfonic acid groups, organic acids containing phosphoric acid groups, organic acids containing carboxyl groups, and organic acids containing phenolic hydroxyl groups in a manner different from each other.

3. The film-forming composition according to claim 2, wherein the two or more acidic compounds comprise two or more selected from the group consisting of nitric acid, sulfuric acid, cyclic compounds formed by carbonyl-linked olefins, organic acids containing sulfonic acid groups, and organic acids containing carboxyl groups in a manner different from each other.

4. The membrane forming composition according to claim 2, wherein the two or more acidic compounds comprise at least one selected from sulfuric acid and organic acids containing sulfonic acid groups, and at least one selected from hydrochloric acid, nitric acid, phosphoric acid, boric acid, heteropoly acids, cyclic compounds formed by carbonyl-linked olefins, organic acids containing phosphoric acid groups, organic acids containing carboxyl groups, and organic acids containing phenolic hydroxyl groups.

5. The film-forming composition according to any one of claims 2 to 4, wherein the cyclic compound formed by carbonyl-linked olefinic alcohol comprises at least one selected from dihydroxycyclopropenone, squaric acid and malic acid.

6. The film-forming composition according to any one of claims 2 to 4, wherein the organic acid containing a sulfonic acid group comprises at least one selected from aromatic sulfonic acids, saturated aliphatic sulfonic acids, and unsaturated aliphatic sulfonic acids.

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

8. The film-forming composition according to any one of claims 2 to 4, wherein the carboxyl-containing organic acid comprises at least one selected from formic acid, oxalic acid, aromatic carboxylic acids, saturated aliphatic carboxylic acids, and unsaturated aliphatic carboxylic acids.

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

10. The film-forming composition according to claim 9, wherein the alkylene group is a straight-chain or branched alkylene group having 1 to 10 carbon atoms.

11. The film-forming composition according to any one of claims 1 to 4, used to form a resist underlayer film used in a photolithography process.

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

13. A method for manufacturing a semiconductor device, comprising the following steps: The process of forming an organic lower layer film on a substrate; The process of forming a resist underlayer film on the organic underlayer film using the film-forming composition according to any one of claims 1 to 11; and The process of forming a resist film on the lower resist film.

Images