Composition for forming a resist underlayer film

Abstract

The objective of this invention is to provide a silicon-containing resist underlayer film forming composition for forming a resist underlayer film in a processing step such as a semiconductor substrate, which can be stripped not only by conventional dry etching methods but also by wet etching methods using solutions such as dilute hydrofluoric acid, buffered hydrofluoric acid, and alkaline solutions. Furthermore, it provides a photolithography resist underlayer film forming composition that exhibits excellent storage stability and leaves minimal residue during dry etching processes. The solution is a resist underlayer film forming composition comprising a hydrolyzed condensate of a hydrolyzable silane mixture, wherein the hydrolyzable silane mixture comprises a hydrolyzable silane as shown in formula (1) and an alkyltrialkoxysilane, and the content of the alkyltrialkoxysilane in the hydrolyzable silane mixture is 0 mol% or more and less than 40 mol% based on the total molar number of all hydrolyzable silanes contained in the hydrolyzable silane mixture. (In formula (1), R...) 1 "A group that bonds to a silicon atom" indicates an organogroup comprising at least one group or skeleton selected from succinic anhydride, vinyl, phenyl, and isocyanuric acid skeletons, R 2 For groups that bond with silicon atoms, each can independently represent a substituted alkyl group, etc., R 3 For groups or atoms bonded to silicon atoms, each can be represented independently as an alkoxy, aralkyloxy, acyloxy, or halogen atom, where 'a' represents 1, 'b' represents an integer from 0 to 2, and 4−(a+b) represents an integer from 1 to 3. 1 a R 2 b Si(R 3 ) 4‑(a+b) (1).

Description

Technical Field

[0001] This invention relates to a composition for forming a resist underlayer film, providing a silicon-containing composition for forming a silicon-containing resist underlayer film that can form a low-uneven pattern in fine patterning, can be easily peeled off by a stripping solution that does not damage the semiconductor substrate, the coating-type organic underlayer film required in the patterning process, or the carbon-based CVD film, and can maintain peelability after dry etching. 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 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 photoresist pattern, and then etching the substrate with the resulting photoresist pattern as a protective film, thereby forming a micro-unfolding texture on the substrate surface corresponding to the aforementioned pattern.

[0003] In recent years, with the advancement of high integration in semiconductor devices, the active light used has also tended to be shorter-wavelengthd, shifting from KrF excimer lasers (248nm) to ArF excimer lasers (193nm). As the wavelength of active light shortens, the impact of its reflection from the semiconductor substrate is becoming a significant problem. Therefore, the method of placing a bottom-layer anti-reflective coating (BARC) between the photoresist and the substrate being processed is widely adopted.

[0004] As the lower layer film between the aforementioned semiconductor substrate and the photoresist, a film known as a hard mask containing metallic elements such as silicon and titanium is used. In this case, the composition of the photoresist and the hard mask differs greatly, therefore the rate at which they are removed by dry etching depends heavily on the type of gas used in the dry etching process. Furthermore, by appropriately selecting the type of gas, the hard mask can be removed by dry etching without a significant reduction in the thickness of the photoresist film. Thus, in the manufacture of semiconductor devices in recent years, a photoresist lower layer film is placed between the semiconductor substrate and the photoresist to achieve various effects, primarily anti-reflective properties.

[0005] While compositions for resist underlayers have been studied to date, the development of new materials for resist underlayers is desired due to the diversity of required properties. Examples disclosed include a coating-type BPSG (borophosphorus glass) film-forming composition containing a structure with a specific silica backbone, which addresses the formation of a film capable of wet etching (Patent Document 1); and a silicon-containing resist underlayer composition containing a carbonyl structure, which addresses the removal of mask residue after photolithography (Patent Document 2).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2016-74774

[0009] Patent Document 2: International Publication No. 2018 / 181989 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] In cutting-edge semiconductor devices, multilayer processes are widely used through miniaturization of ion implantation layers. Typically, for multilayer processes, the transfer to the next layer is sometimes performed using dry etching, as described above. The final substrate processing, removal of mask residues such as resist films, and removal of the underlying film containing the resist are also performed using dry etching and ashing. However, dry etching and ashing processes cause considerable damage to the substrate, requiring improvements.

[0012] The present invention was made in view of the above circumstances, and its object is to provide a silicon-containing photoresist underlayer film forming composition for forming a photoresist underlayer film in a processing step such as a semiconductor substrate, which can be stripped not only by conventional dry etching methods, but also by wet etching methods using solutions such as dilute hydrofluoric acid, buffered hydrofluoric acid, and alkaline solutions. Furthermore, the present invention provides a silicon-containing photoresist underlayer film forming composition that has excellent storage stability and leaves little residue in the dry etching process.

[0013] Methods for solving problems

[0014] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the membrane obtained by the composition containing a hydrolytic condensate (polysiloxane) obtained from a hydrolyzable silane having a specific structure such as a succinic anhydride backbone can be easily removed by a chemical solution such as an alkaline solution. Furthermore, by controlling the structure of the hydrolytic condensate derived from alkyltrialkoxysilane, the residue removal of the membrane obtained by dry etching is improved, thereby completing the present invention.

[0015] That is, as a first aspect of the present invention, there is a composition for forming a resist underlayer film, which comprises a hydrolytic condensate of a hydrolyzable silane mixture, wherein the hydrolyzable silane mixture comprises a hydrolyzable silane of formula (1) and an alkyltrialkoxysilane.

[0016] The content of alkyltrialkoxysilane in the above hydrolyzable silane mixture is based on the total molar number of all hydrolyzable silanes contained in the above hydrolyzable silane mixture being 0 mol% or more and less than 40 mol%.

[0017] R 1 a R 2 b Si(R 3 ) 4-(a+b) (1)

[0018] (In equation (1),

[0019] R 1 The term "group that bonds with silicon atoms" refers to an organic group comprising at least one group or skeleton selected from succinic anhydride skeleton, alkenyl, aryl, and groups shown in formulas (1-2) below.

[0020]

[0021] In equation (1-2),

[0022] X 101 The group represents any one of the groups shown in formulas (1-3) to (1-5) below, and the carbon atom of the ketone group in formulas (1-4) and (1-5) below is related to the R in formula (1-2). 102 The nitrogen atoms that are bound together,

[0023]

[0024] (In equations (1-3) to (1-5), R) 103 ~R 107 Each of these can independently represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or an organogroup containing an epoxy or sulfonyl group.

[0025] R 101 Each can independently represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or an organic group containing an epoxy or sulfonyl group.

[0026] R 102 Each can be independently represented as an alkylene group, a hydroxyalkylene group, a sulfur bond (-S-), an ether bond (-O-), or an ester bond (-C(=O)-O- or -OC(=O)-).

[0027] R 2 The group that bonds to a silicon atom can independently represent a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organogroup comprising an epoxy group, acryloyl group, methacryl group, mercapto group, amino group, amide group, alkoxy group, sulfonyl group, or cyano group, or a combination thereof.

[0028] 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.

[0029] a represents 1, b represents an integer from 0 to 2, and 4 - (a + b) represents an integer from 1 to 3.

[0030] As a second point of view, relating to the composition for forming a resist underlayer film as described in the first point of view, the above-mentioned R 1 "A group that bonds to a silicon atom" indicates an organic group that contains at least one group or skeleton selected from succinic anhydride skeleton, vinyl skeleton, phenyl skeleton and isocyanuric acid skeleton.

[0031] As a third point of view, relating to the composition for forming a resist underlayer film as described in the first or second point of view, the above-mentioned hydrolyzable silane mixture further comprises the hydrolyzable silane shown in the following formula (2).

[0032] R 4 c Si(R 5 ) 4-c (2)

[0033] (In equation (2),

[0034] R 4 The group that bonds to a silicon atom can independently represent a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organogroup comprising an epoxy group, acryloyl group, methacryl group, mercapto group, amino group, amide group, alkoxy group, sulfonyl group, or cyano group, or a combination thereof.

[0035] R 5 These are groups or atoms that bond with silicon atoms, and each can be represented independently as an alkoxy, aralkyloxy, acyloxy, or halogen atom.

[0036] c represents an integer from 0 to 3.

[0037] As a fourth point of view, relating to the composition for forming a photoresist underlayer film as described in any one of the first to third points of view, the content of the compound represented by the above formula (1) in the above hydrolyzable silane mixture is 5 mol% or more based on the total molar number of all hydrolyzable silanes contained in the above hydrolyzable silane mixture.

[0038] As a fifth point of view, the composition for forming a resist underlayer film as described in the fourth point of view comprises R 1 Compounds containing an organic group with a succinic anhydride skeleton are represented by the compound shown in formula (1).

[0039] As a sixth point of view, relating to the composition for forming a resist underlayer film as described in the fifth point of view, the R in the above-mentioned hydrolyzable silane mixture 1 The content of the compound represented by formula (1) containing an organic group with a succinic anhydride skeleton is based on the total number of moles of all hydrolyzable silanes contained in the above-mentioned hydrolyzable silane mixture being 1 mol% or more.

[0040] As the seventh point of view, the composition for forming a resist underlayer film as described in any one of the first to fifth points of view is a composition with a pH of 2 to 5.

[0041] As the eighth point of view, a pattern forming method is provided, which includes the following steps:

[0042] The process of forming an organic lower layer film on a semiconductor substrate;

[0043] The process of coating a resist underlayer film forming composition as described in any one of the first to seventh viewpoints onto the above-mentioned organic underlayer film and firing it to form a silicon-containing resist underlayer film;

[0044] The process of coating a resist film forming composition onto the silicon-containing resist lower layer film to form a resist film;

[0045] The process of exposing and developing the above-mentioned resist film to obtain a resist pattern;

[0046] The process of using a resist pattern as a mask to etch the silicon-containing resist underlayer film;

[0047] The process of etching the organic underlying film using a patterned silicon-containing photoresist underlayer as a mask.

[0048] As a ninth point of view, the pattern forming method described in the eighth point of view further includes, after the step of etching the organic underlayer film, a step of removing the silicon-containing resist underlayer film by using a wet method with a chemical solution.

[0049] As a tenth point of view, relating to the pattern forming method described in the ninth point of view, the aforementioned liquid is an alkaline liquid.

[0050] The effects of the invention

[0051] In this invention, by using a hydrolytic condensate obtained from a silane compound with a specific structure comprising a succinic anhydride skeleton, an alkenyl group such as vinyl, an aryl group such as phenyl, or an isocyanuric acid skeleton as a component of a composition for forming a resist underlayer film, the removal performance obtained by wet methods can be improved in films formed from this composition, even for silicon-based films. Furthermore, by using a hydrolytic condensate obtained from a silane compound comprising a succinic anhydride skeleton as a component, the removal performance obtained by wet methods can be further improved.

[0052] Therefore, when using the resist underlayer film forming composition of the present invention to perform pattern forming, semiconductor substrate processing, etc., using photoresist films, etc., the residue of the mask after processing, such as the resist film and the underlayer film containing the resist underlayer film, can be easily removed by the solution, and semiconductor devices with less substrate damage can be manufactured.

[0053] Furthermore, according to the present invention, by controlling the structural proportion derived from alkyltrialkoxysilane in the above-mentioned hydrolytic condensate, the residue removal property obtained by etching can be improved when a film formed from a composition containing the condensate is dry-etched.

[0054] Furthermore, according to the present invention, by adjusting the pH of the composition for forming the resist underlayer film, for example by using nitric acid as a hydrolysis catalyst during the manufacture of the hydrolysis condensate, the pH of the composition can be made to a specific range, thereby achieving a precursor solution containing the hydrolysis condensate with excellent preservation stability, and thus producing a composition for forming the resist underlayer film with excellent preservation stability. Detailed Implementation

[0055] The present invention targets compositions for forming silicon-containing photoresist underlayers that can be peeled off by wet methods, and is characterized by including products (hydrolysis condensates) obtained by hydrolysis condensation of a mixture of hydrolyzable silanes containing hydrolyzable silanes with specific structures.

[0056] [Hydrolysis condensate of a mixture of hydrolyzable silanes]

[0057] The composition for forming the resist underlayer film of the present invention comprises a hydrolytic condensate of a mixture of hydrolyzable silanes.

[0058] Here, in this invention, the hydrolysis condensate includes not only a polyorganosiloxane polymer as a condensate with complete condensation, but also a partially hydrolyzed condensate as a partially hydrolyzed condensate. Such partially hydrolyzed condensates, like the fully condensed condensates, are polymers obtained through the hydrolysis and condensation of hydrolyzable silane compounds, but partially refractory at the point where hydrolysis ceases, thus retaining Si-OH groups. Furthermore, the resist underlayer film forming composition of this invention may also contain, in addition to the hydrolysis condensate, uncondensed hydrolysates (completely hydrolyzed products, partially hydrolyzed products) and monomers (hydrolyzable silane compounds).

[0059] It should be noted that in this specification, "hydrolyzable silane" is sometimes simply referred to as "silane compound". Furthermore, as described later, the above-mentioned hydrolyzable silane mixture contains the hydrolyzable silane shown in formula (1) below, and may contain other hydrolyzable silanes such as tetraalkoxysilane and alkyltrialkoxysilane as needed. However, when alkyltrialkoxysilane is included as another silane compound, its content is based on the total moles (100 mol%) of silane compounds in the above-mentioned hydrolyzable silane mixture being less than 40 mol%, that is, the proportion of alkyltrialkoxysilane in the mixture is 0 mol% or more and less than 40 mol%. The ability to control the removal rate of etching residue by controlling the proportion of alkyltrialkoxysilane is a discovery made for the first time by the inventors.

[0060] [The silane compound (hydrolyzable silane) shown in formula (1)]

[0061] The hydrolytic condensate used in the resist underlayer film forming composition of the present invention can be a hydrolytic condensation product of a mixture of hydrolyzable silanes containing silane compounds represented by the following formula (1).

[0062] R 1 a R 2 b Si(R 3 ) 4-(a+b) (1)

[0063] R 1 "A group that binds to silicon atoms" means an organic group that contains at least one group or skeleton selected from succinic anhydride skeleton, alkenyl, aryl and groups shown in formulas (1-2) below.

[0064] As mentioned above, R 1 There are no particular limitations on the organic groups, as long as they contain the above-mentioned skeleton or groups.

[0065] In addition, R 1It can be a group containing multiple and / or more alkenyl, aryl, and further groups as shown in formula (1-2), in which case the above groups or skeletons can be replaced by the same or different kinds of the above groups or skeletons.

[0066] It should be noted that groups comprising a succinic anhydride skeleton, alkenyl, aryl, and groups shown in formulas (1-2), groups in which the hydrogen atoms of alkoxy, aralkyloxy, and acyloxy groups directly bonded to silicon atoms are replaced by the aforementioned groups or skeletons, and groups comprising... Examples of salt compounds, etc. Except for salt structures (such as compounds listed as formulas (I-1) to (I-50), (II-1) to (II-30), (III-1) to (III-28), etc.) and groups containing sulfonyl or sulfonamide groups as aryl groups (such as compounds listed as formulas (B-1) to (B-36).

[0067] For example, the succinic anhydride skeleton, alkenyl, aryl and the group shown in formula (1-2) can be not only the skeleton itself or the group itself, but also, in particular, an organogroup obtained by substituting one or more hydrogen atoms in the alkyl group with at least one selected from the succinic anhydride skeleton, alkenyl, aryl and the group shown in formula (1-2).

[0068] The alkyl group in which the hydrogen atom is replaced by the succinic anhydride skeleton, etc., is not particularly limited and can be any of straight-chain, branched, or cyclic. The number of carbon atoms can usually be 40 or less, for example 30 or less, more for example 20 or less, and even less than 10.

[0069] Specific examples of the aforementioned 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. The following are examples of methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but are not limited to these.

[0070] Furthermore, specific examples of the aforementioned 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, 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., cycloalkyl groups, dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl, etc., but not limited to these.

[0071] Furthermore, as mentioned above, R 1The alkenyl group in the text can be substituted with other alkenyl groups, such as those with 2 to 10 carbon atoms. More specifically, examples 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-di Methyl-1-butenyl, 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 Examples of alkenyl groups include 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, and 3-cyclohexenyl. Cross-linked cyclic alkenyl groups such as dicycloheptenyl (norbornel) can also be cited.

[0072] As mentioned above, R 1 The aryl group in the text can be substituted with other aryl groups, such as those with 6 to 20 carbon atoms. More specifically, examples include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-mercaptophenyl, o-methoxyphenyl, p-methoxyphenyl, p-aminophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, and 9-phenanthyl.

[0073] In addition, examples of groups containing the above-mentioned aryl group include substituted aralkyl groups, substituted halogenated aryl groups, substituted halogenated aralkyl groups, substituted alkoxy aryl groups, and substituted alkoxy aralkyl groups.

[0074] The aryl group mentioned above is an alkyl group that has been replaced by an aryl group. As specific examples of such aryl and alkyl groups, substances identical to those mentioned above can be given.

[0075] 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.

[0076] Specific examples of aralkyl groups include, but are not limited to, 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, and 10-phenyl-n-decyl.

[0077] The aforementioned haloaryl group is an aryl group that has been replaced by a halogen atom. As a specific example of such an aryl group, a substance identical to the one described above can be given.

[0078] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0079] 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.

[0080] 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.

[0081] The aforementioned halogenated aralkyl group is an aralkyl group that has been replaced by a halogen atom. As a specific example of such an aralkyl group and halogen atom, substances identical to those described above can be given.

[0082] 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.

[0083] 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.

[0084] The above-mentioned alkoxyaryl group is an aryl group that has been substituted with an alkoxy group. As a specific example of such an aryl group, substances identical to those described above can be given.

[0085] Examples of alkoxy groups include those having a straight-chain, branched, or cyclic alkyl moiety having 1 to 20 carbon atoms. Examples of straight-chain or branched alkoxy groups include, for example, 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-hexoxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-propoxy. Pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc. In addition, examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-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-cyclopropoxy Butoxy, 2,2-dimethyl-cyclobutoxy, 2,3-dimethyl-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, etc., but not limited to these.

[0086] The number of carbon atoms in the alkoxyaryl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0087] Specific examples of alkoxyaryl groups include, for example, 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.

[0088] The above-mentioned alkoxyaryl group is an aryl group that has been substituted with an alkoxy group. As specific examples of such alkoxy and aryl groups, substances identical to those described above can be given.

[0089] The number of carbon atoms in the alkoxyaryl group is not particularly limited, but it is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0090] Specific examples of alkoxyaryl groups include 3-(methoxyphenyl)benzyl, 4-(methoxyphenyl)benzyl, etc., but are not limited to these.

[0091] Furthermore, in the groups shown in the following formulas (1-2),

[0092]

[0093] X 101 Each of the following formulas (1-3) to (1-5) can be represented independently, and the carbon atom of the ketone group in formulas (1-4) and (1-5) is related to the R in formula (1-2). 102 The nitrogen atoms that are bound together are bound together.

[0094]

[0095] In equations (1-3) to (1-5), R 103 ~R 107 The hydrogen atom, the substituted alkyl group, the substituted alkenyl group, or the organogroup containing an epoxy or sulfonyl group can be independently represented, and specific examples of substituted alkyl groups and substituted alkenyl groups, as well as suitable carbon atom numbers, can be given in relation to R. 1 Examples of alkyl groups include those in which hydrogen atoms are replaced by a succinic anhydride skeleton, as well as the same substances described above that are alkenyl groups.

[0096] In addition, examples of organic groups containing epoxy groups include epoxypropoxymethyl, epoxypropoxyethyl, epoxypropoxypropyl, epoxypropoxybutyl, epoxycyclohexyl, etc., but are not limited to these.

[0097] Examples of organic groups containing a sulfonyl group include sulfonylalkyl and sulfonylaryl groups, but are not limited to these.

[0098] In the above equation (1-2), R 101 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. 102 Each can be represented independently as an alkylene group, a hydroxyalkylene group, a sulfur bond (-S-), an ether bond (-O-), or an ester bond (-C(=O)-O- or -OC(=O)-).

[0099] Here, specific examples of substituted alkyl groups, substituted alkenyl groups, organogroups containing epoxy groups or epoxy groups, suitable carbon number, etc., can be given in relation to R. 103 ~R 107 The substances mentioned above are the same as those mentioned above. In addition to these, alkyl groups that can be substituted are preferably alkyl groups in which the terminal hydrogen atom is replaced by a vinyl group, and specific examples include allyl, 2-vinylethyl, 3-vinylpropyl, 4-vinylbutyl, etc.

[0100] The aforementioned 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 include substances identical 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.

[0101] In addition, R 102 The alkylene group may have one or more of the following at its end or in the middle, preferably in the middle: a sulfur bond, an ether bond, and an ester bond.

[0102] Specific examples of alkylene compounds include straight-chain alkylene compounds such as methylene, ethylene, trimethylene, methyl ethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched-chain alkylene compounds such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; and cyclic alkylene compounds such as 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl. CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2CH2-, -CH2CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2CH2SCH2CH2-, -CH2CH2SCH2CH2CH2-, -CH2CH2CH2SCH2CH2CH2-, -CH2OCH2CH2SCH2-, etc., including alkylene groups such as ether groups, but not limited to these.

[0103] The hydroxyalkylene group is a group 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-hydroxytrimethylene, 2-hydroxytrimethylene, 3-hydroxytrimethylene, 1-hydroxytetramethylene, 2-hydroxytetramethylene, 3-hydroxytetramethylene, 4-hydroxytetramethylene, 1,2-dihydroxytetramethylene, 1,3-dihydroxytetramethylene, 1,4-dihydroxytetramethylene, 2,3-dihydroxytetramethylene, 2,4-dihydroxytetramethylene, 4,4-dihydroxytetramethylene, etc., but are not limited to these.

[0104] In the above, as R 1 Preferably, it comprises a skeleton selected from succinic anhydride, vinyl, phenyl, and isocyanuric acid (in formula (1-2), X 101 At least one of the groups represented by formulas (1-5).

[0105] In equation (1), R 2 The group that is bonded to a silicon atom, independently of each other, represents a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organic group containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, amide group, alkoxy group, sulfonyl group, or cyano group, or a combination thereof.

[0106] It should be noted that, in this invention, the CH2=CH- structure contained in the acryloyl group is different from that of R. 1 The vinyl group in the definition is distinguished.

[0107] Examples of the aforementioned alkyl groups include straight-chain or branched alkyl groups having 1 to 10 carbon atoms, such as 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, etc. 3-Methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc.

[0108] Alternatively, cyclic alkyl groups can be used, for example, cyclic alkyl groups with 3 to 10 carbon atoms, such as 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 The compounds include 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl, etc.

[0109] Haloalkyl refers to alkyl groups that have been replaced by halogen atoms.

[0110] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Furthermore, examples of alkyl groups include substances identical to those described above.

[0111] 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.

[0112] 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.

[0113] Alkoxyalkyl refers to an alkyl group that has been substituted with an alkoxy group. Specific examples of such alkyl groups and alkoxy groups can be given as substances identical to those described above.

[0114] 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.

[0115] Specific examples of alkoxyalkyl groups include, but are not limited to, lower alkyloxyalkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, and ethoxymethyl.

[0116] Examples of substituents among the aforementioned alkyl, haloalkyl, or alkoxyalkyl groups include, for example, alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkoxyaralkyl, alkenyl, alkoxy, aralkyloxy, etc. Among these, substances with the same number of carbon atoms as those described above can be cited as specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, alkoxy, aralkyloxy, and their suitable number of carbon atoms.

[0117] Furthermore, the aryloxy group mentioned above is a group in which an aryl group is bonded via an oxygen atom (-O-). Specific examples of such aryl groups include substances identical to those described above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include phenoxy groups and naphth-2-yloxy groups, but the group is not limited to these.

[0118] Furthermore, when there are two or more substituents, the substituents can combine with each other to form a ring.

[0119] Examples of the above-mentioned organic groups containing epoxy groups include epoxypropoxymethyl, epoxypropoxyethyl, epoxypropoxypropyl, epoxypropoxybutyl, epoxycyclohexyl, etc., but are not limited to these.

[0120] Examples of organic groups containing an acryloyl group include acryloylmethyl, acryloylethyl, and acryloylpropyl, but are not limited to these.

[0121] Examples of organic groups containing a methacryloyl group include methacryloylmethyl, methacryloylethyl, and methacryloylpropyl, but these are not limited to these.

[0122] Examples of organic groups containing thiol groups include ethyl thiol, butyl thiol, hexyl thiol, octyl thiol, etc., but are not limited to these.

[0123] Examples of organic groups containing amino groups include amino, aminomethyl, aminoethyl, dimethylaminoethyl, and dimethylaminopropyl, but are not limited to these.

[0124] Examples of organic groups containing alkoxy groups include, but are not limited to, methoxymethyl and methoxyethyl. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded.

[0125] Examples of organic groups containing a sulfonyl group include the aforementioned sulfonylalkyl and sulfonylaryl groups, but are not limited to these.

[0126] Examples of organic groups containing a cyano group include cyanoethyl and cyanopropyl, but are not limited to these.

[0127] In equation (1), R 3 The groups or atoms that bond with silicon atoms are independently represented by alkoxy, aralkyloxy, acyloxy, or halogen atoms. Examples of substances identical to those described above can be cited as alkoxy or halogen atoms.

[0128] Arylalkyloxy groups are groups derived from the hydroxyl group of aralkyl alcohols by removing a hydrogen atom. Specific examples of such aralkyl groups include substances identical to those described above.

[0129] 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.

[0130] 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.

[0131] An acyloxy group is a group derived from the carboxylic acid group of a carboxylic acid compound by removing a hydrogen atom. Typically, examples include alkyl carbonyloxy, aryl carbonyloxy, or aralkyl carbonyloxy derived from the carboxylic acid group of an alkyl carboxylic acid, aryl carboxylic acid, or aralkyl carboxylic acid by removing a hydrogen atom, but it is not limited to these. As specific examples of alkyl, aryl, and aralkyl groups in such alkyl carboxylic acids, aryl carboxylic acids, and aralkyl carboxylic acids, substances identical to those described above can be given.

[0132] Specific examples of acyloxy groups include those with 2 to 20 carbon atoms. Examples 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-n-pentyl... Carbonyloxy, 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, and toluenesulfonylcarbonyloxy, etc., but not limited to these.

[0133] In the above formula (1), a represents 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3.

[0134] b preferably represents 0 or 1, and more preferably 0.

[0135] Specific examples of the compounds shown in formula (1) above include, for example: silane compounds containing a succinic anhydride skeleton such as [(3-trimethoxysilyl)propyl]succinic anhydride, [(3-triethoxysilyl)propyl]succinic anhydride, [(3-trimethoxysilyl)ethyl]succinic anhydride, and [(3-trimethoxysilyl)butyl]succinic anhydride; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane. Divinyldiacetoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiacetoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane, allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-styryltrimethoxysilane, and other silane compounds containing alkenyl (vinyl) groups;Phenylacetoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane Triphenylchlorosilane, 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenylethyltrimethoxysilane, phenylethyltriethoxysilane, phenylethyltrichlorosilane, phenylethyltriacetoxysilane, phenylethylmethyldimethoxysilane, phenylethylmethyldiethoxysilane, phenylethylmethyldichlorosilane, phenylethyldiacetoxysilane, and other silane compounds containing phenyl groups;Methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenylethyltrimethoxysilane, methoxyphenylethyltriethoxysilane, methoxyphenylethyltriacetoxysilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane Alkane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, tert-butoxyphenyltrimethoxysilane, tert-butoxyphenyltriethoxysilane, tert-butoxyphenyltriacetoxysilane, tert-butoxyphenyltrichlorosilane, tert-butoxybenzyltrimethoxysilane, tert-butoxybenzyltriethoxysilane, tert-butoxybenzyltriacetoxysilane, tert-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, etc., containing substituted aryl groups; etc.

[0136] Furthermore, as a specific example of the silane compound shown in formula (1) above, R in the formula 1 Silane compounds containing organic groups as shown in formulas (1-2) above can be commercially available or synthesized by known methods as described in International Publication No. 2011 / 102470, etc.

[0137] Hereinafter, as specific examples of silane compounds containing organic groups containing the groups shown in formulas (1-2) above, compounds shown in formulas (1-2-1) to (1-2-29) will be given, but are not limited to these.

[0138]

[0139]

[0140]

[0141] Furthermore, as silane compounds represented by the above formula (1), examples include silane compounds containing aryl groups represented by formulas (A-1) to (A-41).

[0142]

[0143]

[0144] [Other silane compounds (hydrolyzable silanes)]

[0145] In this invention, for the purpose of adjusting membrane properties such as membrane density, at least one of the following (other hydrolyzable silanes) can be used in the above-described hydrolyzable silane mixture, together with the silane compound shown in formula (1) below, and further, the silane compound shown in formula (3) below. Among these other hydrolyzable silanes, the silane compound shown in formula (2) is preferred.

[0146] R 4 c Si(R 5 ) 4-c (2)

[0147] In equation (2), R 4 The group that is bonded to a silicon atom, independently of each other, represents a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organic group containing an epoxy group, acryloyl group, methacryloyl group, mercapto group, amino group, amide group, alkoxy group, sulfonyl group, or cyano group, or a combination thereof.

[0148] In addition, R 5 These are groups or atoms that bond with silicon atoms, and are independently represented as alkoxy, aralkyloxy, acyloxy, or halogen atoms.

[0149] Therefore, c represents an integer from 0 to 3.

[0150] As mentioned above, R 4 Specific examples of the groups in R and their suitable number of carbon atoms can be given. 2 The above-mentioned groups and number of carbon atoms.

[0151] As mentioned above, R 5 Specific examples of the groups in R and their suitable number of carbon atoms can be given. 3 The aforementioned groups and atoms, as well as the number of carbon atoms.

[0152] Furthermore, c preferably represents 0 or 1, and more preferably 0.

[0153] [R] 6 d Si(R 7 ) 3-d 〕2Y e (3)

[0154] In equation (3), R 6 The group to be bonded to a silicon atom, independently of each other, 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 organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof.

[0155] In addition, R 7 These are groups or atoms that bond with silicon atoms, and are independently represented as alkoxy, aralkyloxy, acyloxy, or halogen atoms.

[0156] Y represents a group bonded to a silicon atom, which independently represents either an alkylene group or an arylene group.

[0157] Furthermore, d represents an integer of 0 or 1, and e represents an integer of 0 or 1.

[0158] As mentioned above, R 6 Specific examples of the groups in R and their suitable number of carbon atoms can be given. 2 The above-mentioned groups and number of carbon atoms.

[0159] As mentioned above, R 7 Specific examples of the groups in R and their suitable number of carbon atoms can be given. 3 The aforementioned groups and atoms, as well as the number of carbon atoms.

[0160] Furthermore, specific examples of alkylene groups in Y mentioned above include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; and alkylene groups such as methanetriyl, ethane-1,1,2-triyl, ethane-1,2,2-triyl, and 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 alkane triyl, etc., but not limited to these.

[0161] In addition, specific examples of arylene groups 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, etc., which are derived by removing two hydrogen atoms from the aromatic ring of a fused-ring aromatic hydrocarbon compound; 4,4'-biphenyldiyl, 4,4”-p-terphenyldiyl, etc., which are derived by removing two hydrogen atoms from the aromatic ring of a ring-linked aromatic hydrocarbon compound, etc., but are not limited to these.

[0162] Furthermore, d preferably represents 0 or 1, and more preferably 0.

[0163] Further, e is preferably 1.

[0164] Specific examples of the hydrolyzable silanes shown in formula (2) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltribenzyloxysilane, methyltriphenylethoxysilane, epoxypropoxymethyltrimethoxysilane, and epoxypropoxysilane. γ-Oxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxy... β-(3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)ethyl ...4-Epoxycyclohexyl)butyltriethoxysilane, epoxypropoxymethylmethyldimethoxysilane, epoxypropoxymethylmethyldiethoxysilane, α-epoxypropoxyethylmethyldimethoxysilane, α-epoxypropoxyethylmethyldiethoxysilane, β-epoxypropoxyethylmethyldimethoxysilane, β-epoxypropoxyethylethyldimethoxysilane, α-epoxypropoxypropylmethyldimethoxysilane, α-epoxypropoxypropylmethyldiethoxysilane, β-epoxy γ-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, γ-chloro propyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, bicyclo(2,2,1)heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonyl... Amamidopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, etc., but not limited to these.

[0165] Specific examples of the silane compounds shown in formula (3) include methylene bistrimethoxysilane, methylene bistrichlorosilane, methylene bistriacetoxysilane, ethyl bistriethoxysilane, ethyl bistrichlorosilane, ethyl bistriacetoxysilane, propyl bistriethoxysilane, butyl bistrimethoxysilane, phenyl bistrimethoxysilane, phenyl bistriethoxysilane, phenyl bismethyldiethoxysilane, phenyl bismethyldimethoxysilane, naphthyl bistrimethoxysilane, bistrimethoxyethylsilane, bistriethoxyethylsilane, bisethyldiethoxyethylsilane, bismethyldimethoxyethylsilane, etc., but are not limited to these.

[0166] Among them, from the viewpoint of increasing the crosslinking density of the film obtained by the composition of the present invention, inhibiting the diffusion of the components of the resist film into the obtained film, and maintaining / improving the resist properties of the resist film, tetramethoxysilane, tetraethoxysilane, and other 4-functional silanes are preferred.

[0167] In this invention, the above-mentioned hydrolyzable silane mixture may contain molecules with intramolecular... Silane compounds with a styrene group (hydrolyzable organosilanes). This is achieved through the use of intramolecularly possessing... The silane compounds (hydrolyzable organosilanes) can effectively and efficiently promote the cross-linking reaction of hydrolyzable silanes.

[0168] Such molecules have A suitable example of a hydrolyzable organosilane (hydrolyzable organosilane) is represented by formula (4).

[0169] R 11 f R 12 g Si(R 13 ) 4-(f+g) (4)

[0170] R 11 A group that bonds with silicon atoms, indicating base or contain Organic groups of radicals.

[0171] R 12 The group that is bonded to a silicon atom, independently of each other, 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 organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, or a combination thereof.

[0172] R 13 These are groups or atoms that bond with silicon atoms, and are independently represented as alkoxy, aralkyloxy, acyloxy, or halogen atoms.

[0173] f represents 1 or 2, g represents 0 or 1, and satisfies 1 ≤ f + g ≤ 2.

[0174] Specific examples of the above-mentioned alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organogroups including epoxy, acryloyl, methacryloyl, mercapto, amino, or cyano groups, alkoxy, aralkyloxy, acyloxy, halogen atoms, further examples of substituents of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl, and their suitable carbon atom numbers, with respect to R 12 Examples of R can be given. 2 Regarding the aforementioned substances, concerning R... 13 Examples of R can be given. 3 The aforementioned substances.

[0175] If described in more detail, as Specific examples of the group include cyclic ammonium groups or chain ammonium groups, preferably tertiary ammonium groups or quaternary ammonium groups.

[0176] 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.

[0177] 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 bonded to the silicon atom directly or through a divalent linker, and cases where the carbon atom constituting the ring is bonded to the silicon atom directly or through a divalent linker.

[0178] In one example of a suitable embodiment of the invention, R is a group that bonds with silicon atoms. 11 It is a heteroaromatic cyclic ammonium group as shown in the following formula (S1).

[0179]

[0180] In equation (S1), A 1 A 2 A 3 and A 4 Each of the following formulas (J1) to (J3) represents a group independently, but A 1 ~A 4 At least one of them is a group represented by the following formula (J2). Based on the silicon atom in the above formula (4) and A 1 ~A 4 Which combination, in the way the ring it forms, displays aromaticity, is used to determine A. 1 ~A 4The bonds between each atom and its adjacent atoms that together form a ring are either single bonds or double bonds.

[0181]

[0182] In equations (J1) to (J3), R 10 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 substances as described above.

[0183] In equation (S1), R 14 Each of these can independently represent alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, or hydroxyl, in R 14 When there are more than two, two R 14 They can combine to form a ring, 2 Rs 14 The resulting ring can be a cross-linked ring structure. In such cases, the cyclic ammonium group can have adamantane rings, norbornene rings, spiro rings, etc.

[0184] As specific examples of such alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl and alkenyl groups and their suitable number of carbon atoms, the same substances as described above can be cited.

[0185] In equation (S1), n 1 m is an integer from 1 to 8. 1 m is 0 or 1 2 It is a positive integer ranging from 0 or 1 to the largest number that can be replaced by a single ring or multiple rings.

[0186] 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.

[0187] In m 1 When the value is 1, a structure containing A is formed. 1 ~A3 (4+n) 1 ) Metacyclic rings and containing A 4 Fused rings are obtained by the fusion of 6-membered rings.

[0188] 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 have hydrogen atoms, in A? 1 ~A 4 When the atoms constituting the ring have hydrogen atoms, those hydrogen atoms can be replaced by R. 14 In addition, R 14 It can also replace A 1 ~A 4 The rings within the atom constitute the atom, while the rings outside the atom constitute the atom. Based on this situation, as described above, m 2 Selected from 0 or 1 to the largest number that can be replaced by a single ring or multiple rings.

[0189] The bonding bonds of the heteroaromatic cyclic ammonium group shown in the above formula (S1) exist in any carbon or nitrogen atom present in 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.

[0190] Examples of such linking groups include alkylene, arylene, and alkenylene, but they are not limited to these.

[0191] As specific examples of alkylene and arylene groups and their suitable number of carbon atoms, substances identical to those described above can be cited.

[0192] Furthermore, the alkenyl group is a divalent group derived by removing one hydrogen atom from an alkenyl group. Specific examples of such alkenyl groups include substances identical to those described above. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0193] Specific examples include vinylidene, 1-methylvinylidene, propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, etc., but are not limited to these.

[0194] Specific examples of silane compounds (hydrolyzable organosilanes) having the heteroaromatic cyclic ammonium group shown in formula (S1) shown above include silanes shown in formulas (I-1) to (I-50) below, but are not limited to these.

[0195]

[0196]

[0197]

[0198] In another example, R is a group that bonds to the silicon atom in formula (4) above. 11 It can be a heteroaliphatic cyclic ammonium group as shown in the following formula (S2).

[0199]

[0200] In equation (S2), A 5 A 6 A 7 and A 8 Each of the following formulas (J4) to (J6) represents a group independently, but A 5 ~A 8 At least one of them is a group represented by the following formula (J5). Based on the silicon atom in the above formula (4) and A 5 ~A 8 Which combination, in a way that the formed ring exhibits non-aromaticity, determines A. 5 ~A 8 Whether the bonds between each atom and its adjacent atoms forming a ring are single or double bonds.

[0201]

[0202] In equations (J4) to (J6), R 10 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 substances identical to those described above.

[0203] In equation (S2), R 15 Each of these can independently represent alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl, or hydroxyl, in R 15 When there are more than two, two R 15 They can combine to form a ring, 2 Rs 15 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.

[0204] As specific examples of the above-mentioned alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl and alkenyl groups and their suitable number of carbon atoms, substances identical to those described above can be given.

[0205] In equation (S2), n 2m is an integer from 1 to 8. 3 m is 0 or 1 4 It is a positive integer ranging from 0 or 1 to the largest number that can be replaced by a single ring or multiple rings.

[0206] 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.

[0207] 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 Fused rings are obtained by the fusion of 6-membered rings.

[0208] According to A 5 ~A 8 Which of equations (J4) to (J6) has the case where the atoms constituting the ring have hydrogen atoms, and the case where they do not have hydrogen atoms, in A 5 ~A 8 When the atoms constituting the ring have hydrogen atoms, those hydrogen atoms can be replaced by R. 15 In addition, R 15 It can also replace A 5 ~A 8 The rings in the middle constitute atoms, while the rings outside the atoms constitute atoms.

[0209] Given this situation, as mentioned above, m 4 Selected from 0 or 1 to the largest number that can be replaced by a single ring or multiple rings.

[0210] The bonding bonds of the heteroaliphatic cyclic ammonium group shown in the above formula (S2) exist in any carbon or nitrogen atom present in such a monocyclic or fused ring, directly bonded to silicon atoms, or bonded to linking groups to form an organic group containing cyclic ammonium, which is bonded to silicon atoms.

[0211] Examples of such linking groups include alkylene, arylene, or alkenyl groups, and examples of alkylene, arylene, and alkenyl groups and their suitable number of carbon atoms include substances similar to those described above.

[0212] Specific examples of silane compounds (hydrolyzable organosilanes) having the heteroaliphatic cyclic ammonium group shown in formula (S2) shown above can be silanes shown in formulas (II-1) to (II-30) below, but are not limited to these.

[0213]

[0214]

[0215] In another example, R is a group that bonds to the silicon atom in formula (4) above. 11 It can be a chain-like ammonium group as shown in the following formula (S3).

[0216]

[0217] In equation (S3), R 10 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, substances identical to those described above can be cited.

[0218] 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.

[0219] Examples of such linking groups include alkylene, arylene, or alkenyl groups, and specific examples of alkylene, arylene, and alkenyl groups include substances similar to those described above.

[0220] Specific examples of silane compounds (hydrolyzable organosilanes) having the chain-like ammonium group shown in formula (S3) shown above include silanes shown in formulas (III-1) to (III-28) below, but are not limited to these.

[0221]

[0222]

[0223] Furthermore, the resist lower film forming composition of the present invention may further include, in the above-mentioned hydrolyzable silane mixture, a silane compound having a sulfone group or a silane compound having a sulfonamide group. Specific examples are given below, but the invention is not limited to these.

[0224] In the following formula, Me represents methyl and Et represents ethyl.

[0225]

[0226]

[0227]

[0228] In addition to the examples above, other silane compounds (hydrolyzable silanes) may be included in the above-described hydrolyzable silane mixture without impairing the effects of the present invention.

[0229] As described above, the resist underlayer film forming composition of the present invention comprises the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture.

[0230] In a preferred embodiment of the present invention, the resist underlayer film forming composition of the present invention comprises at least the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture.

[0231] In a preferred embodiment of the present invention, the hydrolytic condensate contained in the resist underlayer film forming composition of the present invention comprises, in addition to the silane shown in formula (1), at least the hydrolytic silane shown in formula (2), and other hydrolytic silanes as needed, the hydrolytic condensate obtained.

[0232] For example, the above-mentioned hydrolysis condensate can be a hydrolysis condensate of a hydrolysis silane mixture containing, for example, the total amount of silane compounds contained in the hydrolysis silane mixture, at a ratio of 5 mol% or more, preferably at a ratio of 10 mol% or more, the silane compounds shown in formula (1).

[0233] In a more preferred embodiment, the above-mentioned hydrolysis condensate can be a compound represented by formula (1), containing R. 1 The compound containing an organic group with a succinic anhydride skeleton is used as a hydrolytic condensate of the necessary hydrolytic silane mixture. In this case, R can be included based on the total amount of silane compounds contained in the hydrolytic silane mixture, for example, at a proportion of 1 mol% or more, preferably 5 mol% or more. 1 The hydrolytic condensate of a mixture of hydrolyzable silanes containing an organic group of the succinic anhydride skeleton.

[0234] In hydrolyzable silane mixtures, when using silane compounds other than those shown in formula (1) (hydrolyzable silanes), the amount of the silane compound shown in formula (1) added relative to the total amount of silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture (100 mol%) can be, for example, 5 mol% or more, preferably 10 mol% or more. From the viewpoint of obtaining the above-described effects of the present invention with good reproducibility, the use of R is particularly preferred. 1 The compound represented by formula (1) containing an organic group with a succinic anhydride skeleton is required and can be based on the total amount of silane compounds contained in the hydrolyzable silane mixture, for example, typically 0.1 mol% or more, preferably 0.5 mol% or more, more preferably 1 mol% or more, even more preferably 3 mol% or more, further preferably 5 mol% or more, and can also typically be 10 mol% or less, preferably 8 mol% or less, more preferably 6 mol% or less, and even more preferably 5.5 mol% or less.

[0235] In hydrolyzable silane mixtures, when using silane compounds of formula (2) (excluding alkyltrialkoxysilanes) and silane compounds of formula (3), the amount of these silane compounds added relative to the total amount of silane compounds (hydrolyzable silanes) contained in the hydrolyzable silane mixture can typically be 60 mol% to 90 mol%, but as mentioned above, from the viewpoint of improving the removal of residues obtained by etching when dry etching a film formed from a composition containing the condensate of the mixture, the amount of alkyltrialkoxysilane added is less than 40 mol%, i.e., more than 0 mol% and less than 40 mol%.

[0236] Furthermore, the intramolecular structure shown in formula (4) is used in hydrolyzable silane mixtures. In the case of a hydrolyzable organosilane, the amount of the organosilane added relative to the total amount of the silane compound (hydrolyzable silane) is typically 0.01 mol% or more, preferably 0.1 mol% or more, typically 30 mol% or less, and preferably 10 mol% or less.

[0237] The weight-average molecular weight of the hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture can be, for example, 500 to 1,000,000. From the viewpoint of suppressing the precipitation of the hydrolyzed condensate in the composition, it is preferable to have a weight-average molecular weight of 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of combining storage stability and coatability, it is preferable to have a weight-average molecular weight of 700 or more, and more preferably 1,000 or more.

[0238] It should be noted that the weight-average molecular weight is the molecular weight obtained from GPC analysis and converted to polystyrene. GPC analysis can be performed as follows: for example, using a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Corporation), setting the column temperature to 40°C, using tetrahydrofuran as the eluent, setting the flow rate to 1.0 mL / min, and using polystyrene (manufactured by Showa Denko Corporation) as the standard sample.

[0239] The hydrolysis condensate of the above-mentioned hydrolyzable silane mixture is obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane).

[0240] The aforementioned silane compounds (hydrolyzable silanes) contain alkoxy, aralkyloxy, acyloxy, and halogen atoms that are directly bonded to silicon atoms, namely, alkoxysilyl, aralkyloxysilyl, acyloxysilyl, and halosilyl groups as hydrolyzable groups.

[0241] In the hydrolysis of these hydrolyzable groups, 0.5 to 100 moles of water are typically used for each mole of the hydrolyzable group, preferably 1 to 10 moles of water.

[0242] During hydrolysis and condensation, a hydrolysis catalyst may be used to promote the reaction, or the hydrolysis and condensation may be carried out without using one. When a hydrolysis catalyst is used, 0.0001 to 10 moles of hydrolyzable group are typically used, preferably 0.001 to 1 mole of hydrolysis catalyst.

[0243] The reaction temperature for hydrolysis and condensation is typically above room temperature and below the reflux temperature of the organic solvent used for hydrolysis at atmospheric pressure, for example, 20–110°C, or even 20–80°C.

[0244] Hydrolysis can be complete, meaning all hydrolyzable groups are converted into silanol groups, or it can be partial, meaning that unreacted hydrolyzable groups remain.

[0245] Examples of hydrolysis catalysts that can be used to perform hydrolysis and condensation include metal chelates, organic acids, inorganic acids, organic bases, and inorganic bases.

[0246] Examples of metal chelates that can serve as hydrolysis catalysts 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, and di-n-butoxy-bis(acetylacetone)titanium. 2-Sec-Butoxy·bis(acetylacetone)titanium, 2-Ter-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-Ter-Butoxy·tri(acetylacetone)titanium, Tetra(acetylacetone)titanium, Triethoxy·Mono(ethyl acetoacetate)titanium, Tri-n-Propoxy·Mono(ethyl acetoacetate)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, mono... Titanium chelates include ethoxytris(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(ethyl acetoacetate)zirconium, tri-n-propoxy·mono(ethyl acetoacetate)zirconium, tri-isopropoxy·mono(ethyl acetoacetate)zirconium, tri-n-butoxy·mono(ethyl acetoacetate)zirconium Zirconium trioxide (acid), tri-sec-butoxy-mono(ethyl acetoacetic acid)zirconium, tri-tert-butoxy-mono(ethyl acetoacetic acid)zirconium, diethoxy-bis(ethyl acetoacetic acid)zirconium, di-n-propoxy-bis(ethyl acetoacetic acid)zirconium, di-isopropoxy-bis(ethyl acetoacetic acid)zirconium, di-n-butoxy-bis(ethyl acetoacetic acid)zirconium, di-sec-butoxy-bis(ethyl acetoacetic acid)zirconium, di-tert-butoxy-bis(ethyl acetoacetic acid)zirconium, monoethoxy-tri(ethyl acetoacetic acid)zirconium, mono-n-propoxy-tri(ethyl acetoacetic acid) 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 tri(acetylacetone)-mono(ethyl acetoacetate), etc.; aluminum chelates include aluminum tri(acetylacetone) and aluminum tri(ethyl acetoacetate), etc., but are not limited to these.

[0247] Organic acids that can serve as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0248] Inorganic acids that can act as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0249] Examples of organic bases that can serve as hydrolysis catalysts include, but are not limited to, 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, and benzyltriethylammonium hydroxide.

[0250] Inorganic bases that can act as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0251] Among these catalysts, metal chelates, organic acids, and inorganic acids are preferred. They can be used alone or in combination of two or more.

[0252] In this invention, nitric acid can be suitably used as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, the molecular weight change of the hydrolysis condensate can be suppressed. It is known that the stability of hydrolysis condensates in liquids depends on the pH of the solution. In-depth studies have shown that by using an appropriate amount of nitric acid, the pH of the solution is within a stable range.

[0253] During hydrolysis and condensation, organic solvents can be used as solvents. Specific examples include aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; and 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, n-heptanol, 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 alkanols, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, 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, methyl- Ketone solvents including 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, 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 (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, Ether solvents such as propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methylamyl acetate, 2-ethylbutyl acetate, etc. 2-Ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl 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, ethylene glycol diacetate, methoxytri(ethylene glycol) acetate, ethyl propionate, n-butyl propionate, isopentyl propionate Ester solvents include esters such as diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; sulfur-containing solvents include dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesulfonyl lactone, but are not limited to these. These solvents can be used alone or in combination of two or more.

[0254] After the hydrolysis and condensation reactions are completed, the reaction solution is neutralized by direct, dilution, or concentration, and then treated with an ion exchange resin to remove hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation. Furthermore, before or after such treatment, byproducts such as alcohols, water, and the hydrolysis catalysts used can be removed from the reaction solution by means such as vacuum distillation.

[0255] The hydrolyzed condensate (hereinafter also referred to as polysiloxane) obtained through this operation is obtained as a polysiloxane varnish dissolved in an organic solvent, and can be used directly as a composition for forming the lower layer of the resist film described later. The obtained polysiloxane varnish can also be subjected to solvent displacement, or it can be diluted with a suitable solvent. It should be noted that if the obtained polysiloxane varnish does not deteriorate in its storage stability, the organic solvent can also be removed by distillation to make the solids concentration 100%.

[0256] The organic solvents used in the solvent replacement and dilution of the aforementioned polysiloxane varnish can be the same as or different from the organic solvents used in the hydrolysis and condensation reactions of the hydrolyzable silane mixture. There are no particular limitations on the dilution solvent; it can be one or more types, and any choice can be made.

[0257] [Composition for forming the underlayer of the resist]

[0258] The resist underlayer film forming composition of the present invention comprises the hydrolysis condensate (polysiloxane) of the above-mentioned hydrolyzable silane mixture and a solvent, and may further comprise other components described below.

[0259] The concentration of the solid component in the composition for forming the lower layer of the resist film, relative to the total mass of the composition, can be, for example, 0.1–50% by mass, 0.1–30% by mass, 0.1–25% by mass, or 0.5–20.0% by mass. As described above, the solid component refers to the component remaining after removing the solvent component from all components of the composition.

[0260] The content of the hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture in the solid component is usually 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, further preferably 80% by mass, and the upper limit is preferably 99% by mass, and the remainder may be additives described later.

[0261] Furthermore, the content of the hydrolyzed condensate of the above-mentioned hydrolyzed silane mixture in the composition can be, for example, 0.5 to 20.0% by mass.

[0262] Furthermore, the composition for forming the lower layer film of the resist preferably has a pH of 2 to 5, and more preferably a pH of 3 to 4.

[0263] The composition for forming the lower layer of the resist film can be manufactured by mixing the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture, a solvent, and other components as needed. In this case, a solution containing the hydrolytic condensate can be prepared in advance, and this solution can be mixed with the solvent and other components.

[0264] 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, a solution containing hydrolysate condensates, solvent, and other components can be mixed simultaneously.

[0265] If necessary, solvent can be added last, or a component that is readily soluble in solvent can be added last, even if it is not present in the mixture beforehand. 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 hydrolysates, etc., beforehand and use it to prepare the composition. It should be noted that hydrolysates, etc., may aggregate or precipitate when mixed, depending on the type and amount of solvent, the amount and properties of other components, etc. Furthermore, when preparing the composition using a solution of hydrolysates, etc., it is necessary to determine the concentration and amount of the solution of hydrolysates, etc., in a way that the final composition contains the desired amount of hydrolysates, etc.

[0266] In the preparation of the composition, appropriate heating may be applied within a range that does not cause the components to decompose or deteriorate.

[0267] In this invention, filtration can be performed using a submicron-sized filter or the like during the manufacturing process of the composition for forming the lower layer of the resist film, or after all the components have been mixed.

[0268] The resist underlayer film formation composition of the present invention is suitable for use as a resist underlayer film formation composition used in photolithography processes.

[0269] [Solvent]

[0270] The solvent used in the resist lower film forming composition of the present invention can be used without particular restriction as long as it is a solvent that can dissolve the above-mentioned solid components.

[0271] There are no limitations as long as such a solvent can dissolve the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture and other components.

[0272] Specific examples include methyl cellolytic acetate, ethyl cellolytic acetate, propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl methanol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxylate, and 2-hydroxy-3-methylbutyric acid. Methyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, lactate Butyl acetate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, methyl 3-methoxypropionate Ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-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-methyl-2-pyrrolidone, 4-methyl-2-pentanol, γ-butyrolactone, etc. Solvents can be used alone or in combination of two or more.

[0273] Furthermore, the resist underlayer film forming composition of the present invention may contain water as a solvent. When water is contained as a solvent, its content relative to the total mass of the solvent contained in the composition may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0274] [Other additives]

[0275] In the resist lower film forming composition of the present invention, various additives can be mixed according to the intended use of the composition.

[0276] Examples of such additives include, for instance, curing catalysts (ammonium salts, phosphine derivatives, etc.). Known additives include salts, matte salts, nitrogen-containing silane compounds, etc.), crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymer compounds, acid-producing agents, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, UV-curable surfactants, etc.), pH adjusters, rheology modifiers, adhesive aids, etc., which are blended into materials (compositions) that form resist underlayer films, antireflective films, pattern reversal films, etc., and can be used in the manufacture of semiconductor devices.

[0277] It should be noted that the following examples illustrate various additives, but are not limited to them.

[0278] <Cure-up Catalyst>

[0279] As the above-mentioned curing catalyst, ammonium salts, phosphine compounds, etc. can be used. Salts, matte salts, etc. It should be noted that the following salts described as solidification catalysts may be added in the form of salts, or may be any of the substances that form salts in the above composition (substances that are added as other compounds and form salts in the system).

[0280] Examples of ammonium salts include quaternary ammonium salts having the structure shown in formula (D-1), quaternary ammonium salts having the structure shown in formula (D-2), quaternary ammonium salts having the structure shown in formula (D-3), quaternary ammonium salts having the structure shown in formula (D-4), quaternary ammonium salts having the structure shown in formula (D-5), and tertiary ammonium salts having the structure shown in formula (D-6).

[0281]

[0282] (In the formula, m represents 2 to 11, n represents an integer from 2 to 3, and R...) 21 (Y- indicates an alkyl or aryl group.)

[0283] R 22 R23 R 24 R 25 N + Y - Equation (D-2)

[0284] (where R is in the formula) 22 R 23 R 24 and R 25 Indicates alkyl or aryl, N represents a nitrogen atom, Y- represents an anion, and R 22 R 23 R 24 and R 25 (Both are bonded to nitrogen atoms via CN bonds)

[0285]

[0286] (where R is in the formula) 26 and R 27 (Indicates alkyl or aryl, N represents nitrogen atom, Y- represents anion)

[0287]

[0288] (where R is in the formula) 28 (Indicates alkyl or aryl, N represents nitrogen atom, Y- represents anion)

[0289]

[0290] (where R is in the formula) 29 and R 30 (Indicates alkyl or aryl, N represents nitrogen atom, Y- represents anion)

[0291]

[0292] (In the formula, m represents 2 to 11, n represents an integer from 2 to 3, H represents a hydrogen atom, N represents a nitrogen atom, and Y- represents an anion.)

[0293] In addition, as mentioned above Salt, as exemplified by the quaternary form shown in equation (D-7), can be used as a reference. Salt.

[0294] R 31 R 32 R 33 R 34 p + Y - Equation (D-7)

[0295] (where R is in the formula) 31 R 32 R 33 and R34 The symbol represents an alkyl or aryl group, P represents a phosphorus atom, Y- represents an anion, and R... 31 R 32 R 33 and R 34 (Both are bonded to phosphorus atoms via CP bonds)

[0296] Furthermore, as the aforementioned matte salt, the tertiary matte salt shown in formula (D-8) can be cited as an example.

[0297] R 35 R 36 R 37 S + Y - Equation (D-8)

[0298] (where R is in the formula) 35 R 36 and R 37 The symbol represents an alkyl or aryl group, S represents a sulfur atom, Y- represents an anion, and R... 35 R 36 and R 37 (Both are bonded to sulfur atoms via CS bonds)

[0299] The compound of formula (D-1) above is a quaternary ammonium salt derived from an amine, where m represents 2 to 11 and n represents an integer from 2 to 3. The R of this quaternary ammonium salt... 21 The alkyl group, representing 1 to 18 carbon atoms (preferably 2 to 10), or the aryl group, representing 6 to 18 carbon atoms, can be exemplified by linear alkyl groups such as ethyl, propyl, and butyl, benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. Furthermore, the anion (γ-) can be exemplified by halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), as well as acid groups such as carboxylate (-COO-), sulfonate (-SO3-), and alcohol (-O-).

[0300] The compound of formula (D-2) above is R. 22 R 23 R 24 R 25 The N+Y- represents a quaternary ammonium salt. The R of this quaternary ammonium salt... 22 R 23 R 24 and R 25It is an alkyl group with 1 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms. Examples of anions (γ-) include halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), as well as acid groups such as carboxylate (-COO-), sulfonate (-SO3-), and alcohol (-O-). This quaternary ammonium salt is commercially available, and examples include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0301] The compound of formula (D-3) above is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 The number of carbon atoms is 1 to 18, preferably R. 26 and R 27 The total number of carbon atoms is 7 or more. For example, R 26 Examples include methyl, ethyl, propyl, phenyl, benzyl, R 27 Examples of examples include benzyl, octyl, and octadecyl. Anions (γ-) can include halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), as well as acid groups such as carboxylate (-COO-), sulfonate (-SO3-), and alcohol (-O-). This compound can also be obtained commercially, but it can be prepared, for example, by reacting imidazole compounds such as 1-methylimidazole and 1-benzylimidazole with alkyl halides such as benzyl bromide and methyl bromide, or aryl halides.

[0302] The compound of formula (D-4) above is a quaternary ammonium salt derived from pyridine, R 28 It is an alkyl group with 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms, such as butyl, octyl, benzyl, and lauryl. Anion (Y - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - The compound contains acid groups such as α, β ... N-Benzylpyridine bromide wait.

[0303] The compounds of formula (D-5) above are quaternary ammonium salts derived from substituted pyridines, such as picolino, R 29It is an alkyl group with 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms, such as methyl, octyl, lauryl, benzyl, etc. R 30 R is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, for example, in the case of a quaternary ammonium derived from picolino, 30 It is a methyl group. Anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - The compound contains acid groups such as ) and ). This compound is also available commercially, but can be prepared, for example, by reacting substituted pyridines such as picolinate with alkyl halides or aryl halides such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, and benzyl bromide. An example of this compound is N-benzylpicolinate. Chloride, N-benzylpicoline bromide, N-laurylpicoline Chlorides, etc.

[0304] The compound of formula (D-6) above is a tertiary ammonium salt derived from an amine, where m represents 2 to 11 and n represents an integer from 2 to 3. Furthermore, the anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - This compound can be produced by reacting amines with weak acids such as carboxylic acids and phenols. Examples of carboxylic acids include formic acid and acetic acid. When formic acid is used, the anion (Y)... - ) is (HCOO) - In the case of using acetic acid, the anion (Y) - (CH3COO) - Furthermore, in the case of using phenol, the anion (Y) - (C6H5O) - ).

[0305] The compound of formula (D-7) above is a compound having R 31 R 32 R 33 R 34 P + Y - The structure of the season Salt. R 31 R 32 R 33 and R 34 It is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, preferably R. 31 ~R 34 Of the four substituents, three are phenyl or substituted phenyl groups, such as phenyl or tolyl, and the remaining one is an alkyl group with 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms. Additionally, the anion (Y...) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - (e.g., acid groups). This compound is available as a commercially available product; examples include tetrabutyl halide. Tetrapropylhalogenated isohalogenated tetraalkyl , triethylbenzyl halide isohalogenated trialkylbenzyl , triphenylmethyl halogenated , triphenyl ethyl halide Isohalogenated triphenylmonyl , triphenylbenzyl halide Tetraphenylhalide , Trimethylyl monoaryl halogenated or halogenated tricresyl monoalkyl (The halogen atom is either a chlorine atom or a bromine atom). A particularly preferred option is triphenylmethyl halide. , triphenyl ethyl halide Isohalogenated triphenylmonyl , triphenylbenzyl halide isohalogenated triphenyl monoaryl , Trimethylbenzene Halogenated Isohyetalized trimethylolyl monoaryl , Trimethylhalogenated Isohyetalized trimethylyl monoalkyl (The halogen atom is either a chlorine atom or a bromine atom).

[0306] In addition, examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0307] The compound of formula (D-8) above is a compound having R 35 R 36 R 37 S + Y - Tertiary sulfonium salts with a structure of R. 35 R 36 and R 37 It is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, preferably R. 35 ~R 37 Two of the three substituents are phenyl or substituted phenyl groups, such as phenyl or tolyl, and the remaining substituent is an alkyl group with 1 to 18 carbon atoms or an aryl group with 6 to 18 carbon atoms. Additionally, the anion (Y) - Examples include chloride ions (Cl). - ), bromide ions (Br) - ), iodide ions (I) - Halogen ions, carboxylate ions (-COO) and other halides - ), sulfonate (-SO3) - ), alcohol radical (-O) - The compound contains acid groups such as maleic acid anion and nitrate anion. Examples of commercially available compounds include tri-n-butylsulfonium halide, tri-n-propylsulfonium halide, dialkylbenzylsulfonium halide, diphenylmethylsulfonium halide, diphenylethylsulfonium halide, triphenylmonoalkylsulfonium halide (where the halogen atom is a chlorine or bromine atom), tri-n-butylsulfonium carboxylates, trialkylsulfonium carboxylates, dialkylbenzylsulfonium carboxylates, diphenylmethylsulfonium carboxylates, diphenylethylsulfonium carboxylates, and triphenylmonoalkylsulfonium carboxylates. Triphenylsulfonium halide and triphenylsulfonium carboxylates are also preferred.

[0308] Furthermore, nitrogen-containing silane compounds can be added as curing catalysts in this invention. Examples of nitrogen-containing silane compounds include silane compounds containing an imidazole ring, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0309] When using a curing catalyst, the amount is 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass relative to 100 parts by mass of polysiloxane.

[0310] <Stabilizer>

[0311] The stabilizers described above can be added for purposes such as stabilizing the hydrolytic condensate of the hydrolyzable silane mixture. As specific examples, organic acids, water, alcohols, or combinations thereof can be added.

[0312] Examples of the aforementioned organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Oxalic acid and maleic acid are preferred. When an organic acid is added, its amount is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the aforementioned hydrolyzable silane mixture. These organic acids can also function as pH adjusters.

[0313] The water used can be pure water, ultrapure water, ion-exchanged water, etc., and when used, its addition amount can be 1 to 20 parts by mass relative to 100 parts by mass of the composition for forming the lower layer film of the corrosion resist.

[0314] The alcohol is preferably a substance that is easily dispersed (volatile) by heating after coating, and examples include methanol, ethanol, propanol, isopropanol, butanol, etc. When an alcohol is added, the amount added can be 1 to 20 parts by mass relative to 100 parts by mass of the composition for forming the underlayer film of the resist.

[0315] <Organic Polymers>

[0316] By adding the aforementioned organic polymer compound to the composition for forming the resist underlayer film, the dry etching rate (the amount of reduction in film thickness per unit time), as well as the attenuation coefficient, refractive index, etc., of the film (resist underlayer film) formed by the composition can be adjusted. There are no particular limitations on the organic polymer compound used; it can be appropriately selected from various organic polymers (condensation polymers and addition polymers) depending on the purpose of its addition.

[0317] 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.

[0318] 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 to these.

[0319] When using addition polymers as organic polymer compounds, the polymer compound can be either a homopolymer or a copolymer.

[0320] 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.

[0321] 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.

[0322] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene 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.

[0323] 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.

[0324] 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.

[0325] 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.

[0326] Specific examples of styrene compounds include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetystyrene, etc., but are not limited to these.

[0327] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but are not limited to these.

[0328] 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(1,2,4,5-pyromellitictetramethylimide), poly(terephthalamide), polybutylene terephthalate, and polyethylene terephthalate.

[0329] When an organic polymer compound contains a hydroxyl group, that hydroxyl group can undergo a cross-linking reaction with hydrolytic condensates, etc.

[0330] The weight-average molecular weight of the aforementioned organic polymer compounds is typically between 1,000 and 1,000,000. When blending organic polymer compounds, from the viewpoint of fully obtaining the function of a polymer while suppressing precipitation in the composition, their weight-average molecular weight can be, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000.

[0331] Such organic polymer compounds can be used alone or in combination of two or more.

[0332] When the composition for forming the lower layer film of the resist according to the present invention contains an organic polymer compound, its content is appropriately determined in consideration of the function of the organic polymer compound, etc., and therefore cannot be specified in general terms. However, generally, it can be in the range of 1 to 200% by mass relative to the mass of the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture. From the viewpoint of suppressing precipitation in the composition, it can be, for example, 100% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less. From the viewpoint of fully obtaining this effect, it can be, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more.

[0333] <Acid-producing agent>

[0334] Examples of acid-producing agents include thermal acid-producing agents and photo-producing acid-producing agents, with photo-producing acid-producing agents being preferred.

[0335] As a photoacid-producing agent, examples include Salt compounds, sulfonylimide compounds, disulfonyldiazomethane compounds, etc., but not limited to these.

[0336] In addition, examples of heat-generating acid agents include tetramethylammonium nitrate, but these are not limited to.

[0337] 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, triphenylsulfonium nitrate (nitrate), triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, triphenylsulfonium chloride, and other sulfonate compounds, but not limited to these.

[0338] 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.

[0339] 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.

[0340] When the composition for forming the lower layer film of the resist of the present invention contains an acid-generating agent, its content is appropriately determined considering the type of acid-generating agent, etc., and therefore cannot be specified in general. However, generally, it is in the range of 0.01 to 5% by mass relative to the mass of the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture. 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, and from the viewpoint of fully obtaining this effect, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

[0341] It should be noted that one type of acid-producing agent can be used alone or in combination of two or more. In addition, photo-acid-producing agents and thermal acid-producing agents can be used together.

[0342] <surfactants>

[0343] When the above-mentioned composition for forming a photoresist underlayer is coated onto a substrate, the surfactant is effective in suppressing the formation of pinholes, streaks, etc. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorinated surfactants, and UV-curable surfactants. More specifically, examples include, for instance, 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, and sorbitol monostearate. Oleate, sorbitol trioleate, sorbitol tristearate, and other sorbitol fatty acid esters; polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol tristearate, and other polyoxyethylene sorbitol fatty acid esters, etc., nonionic surfactants, trade names EF301, EF303, EF352 (registered trademarks) (manufactured by Mitsubishi Microelectronics Co., Ltd. (formerly EF300)), trade name EF301 Trademarks) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Co., Ltd.), FC430, FC431 (manufactured by スリーエムジャパン Co., Ltd.) Fluorinated surfactants, such as Asahigard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimeike Mikaru Corporation), and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), are not limited to these.

[0344] Surfactants can be used alone or in combination of two or more.

[0345] When the composition for forming the lower layer film of the resist of the present invention contains a surfactant, its content relative to the mass of the hydrolytic condensate of the above-mentioned hydrolyzable silane mixture can typically be 0.0001 to 5% by mass, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass.

[0346] <Rheology modifiers>

[0347] The aforementioned rheology modifiers are primarily added to improve the flowability of the composition used to form the lower layer of the resist film, particularly during the baking process, to enhance the uniformity of the film thickness and improve the filling ability of the composition into pores. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, di-isobutyl adipate, di-isooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate.

[0348] When using these rheology modifiers, the amount added is typically less than 30% by mass relative to the total solid content of the composition for forming the resist underlayer film.

[0349] <Adhesive Additives>

[0350] The aforementioned adhesive aid is mainly added to improve the adhesion between the substrate or resist and the film (resist underlayer film) formed by the composition for forming the resist underlayer film, especially for the purpose of inhibiting / preventing the peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium; other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; and benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzo[]. Heterocyclic compounds such as azoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds.

[0351] When using these adhesive additives, the amount added is generally less than 5% by mass, preferably less than 2% by mass, relative to the total solid content of the composition for forming the resist underlayer film.

[0352] <pH adjuster>

[0353] In addition, as a pH adjuster, besides acids having one or more carboxylic acid groups, such as organic acids mentioned above as <stabilizers>, bisphenol S or bisphenol S derivatives may also be added. The amount of bisphenol S or bisphenol S derivatives relative to 100 parts by weight of the hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture is 0.01 to 20 parts by weight, or 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight.

[0354] The following are specific examples of bisphenol S and bisphenol S derivatives, but are not limited to these.

[0355]

[0356] [Pattern forming method and semiconductor device manufacturing method]

[0357] Hereinafter, as one aspect of the present invention, a patterning method using the resist underlayer film forming composition of the present invention and a method for manufacturing a semiconductor device will be described.

[0358] First, the resist underlayer film forming composition of the present invention is coated onto a substrate used in the manufacture of precision integrated circuit components (e.g., semiconductor substrates such as silicon wafers coated with silicon oxide film, silicon nitride film, or silicon nitride oxide film; silicon nitride substrates; quartz substrates; glass substrates (including alkali-free glass, low-alkali glass, and crystal glass); glass substrates with ITO (indium tin oxide) film or IZO (indium zinc oxide) film formed; plastic (polyimide, PET, etc.) substrates; substrates coated with low-k materials; flexible substrates, etc.) using a suitable coating method such as a spin coater or a coating machine. Then, the composition is cured by firing using a heating means such as a hot plate to form a resist underlayer film. Hereinafter, in this specification, the term "resist underlayer film" refers to a film formed by the resist underlayer film forming composition of the present invention.

[0359] The firing conditions are appropriately selected from a firing temperature of 40℃ to 400℃ or 80℃ to 250℃ and a firing time of 0.3 minutes to 60 minutes. The preferred firing temperature is 150℃ to 250℃ and the preferred firing time is 0.5 minutes to 2 minutes.

[0360] The thickness of the underlying resist film formed here is, for example, 10 nm to 1,000 nm, or 20 nm to 500 nm, or 50 nm to 300 nm, or 100 nm to 200 nm, or 10 to 150 nm.

[0361] Although the present invention involves forming an organic lower layer film on the substrate and then forming the photoresist lower layer film thereon, depending on the circumstances, there may also be a solution where the organic lower layer film is not provided.

[0362] There are no particular restrictions on the organic underlying film used here; any material that has been conventionally used in photolithography processes to date can be selected.

[0363] By providing an organic underlayer film on a substrate, a photoresist underlayer film on top of that, and then a photoresist film (described later) on top of that, 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 (described later). For example, using a fluorine-based gas having a sufficiently fast etching rate relative to the photoresist film as the etching gas, the photoresist underlayer film of the present invention can be processed. Furthermore, using an oxygen-based gas having a sufficiently fast etching rate relative to the photoresist underlayer film of the present invention as the etching gas, the organic underlayer film can be processed. Finally, using a fluorine-based gas having a sufficiently fast etching rate relative to the organic underlayer film as the etching gas, substrate processing can be performed.

[0364] It should be noted that the substrate and coating method that can be used at this time can be the same as those described above.

[0365] Next, a layer of photoresist material (resist film) is formed on the aforementioned photoresist underlayer film. The formation of the photoresist film can be carried out using a known method, namely, coating a coating-type photoresist material (e.g., a photoresist film forming composition) onto the photoresist underlayer film and then firing it.

[0366] The thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0367] As for the photoresist material used in the photoresist film formed on the aforementioned photoresist underlayer, there are no particular limitations as long as it is photosensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.). Both negative and positive photoresist materials can be used. For example, there are positive photoresist materials composed of phenolic varnish resin and 1,2-naphthoquinone diazonyl sulfonate; chemically amplified photoresist materials composed of a binder having groups that increase the alkali dissolution rate through acid decomposition and a photoacid generator; chemically amplified photoresist materials composed of a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist material through acid decomposition and an alkali-soluble binder and a photoacid generator; and chemically amplified photoresist materials composed of a binder having groups that increase the alkali dissolution rate of the photoresist material through acid decomposition and a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist material through acid decomposition and a photoacid generator.

[0368] Specific examples that can be obtained as commercially available products include APEX-E manufactured by Shiple Co., Ltd., PAR710 manufactured by Sumitomo Chemical Co., Ltd., AR2772JN manufactured by JSR Co., Ltd., and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these. In addition, examples include fluorinated atom polymer-based photoresist materials as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0369] Furthermore, the resist film formed on the aforementioned resist underlayer film can replace the photoresist film and be used as an electron beam lithography resist film (also called an electron beam lithography resist film) or an EUV lithography resist film (also called an EUV lithography resist film). That is, the silicon-containing resist underlayer film forming composition of the present invention can be used as a resist underlayer film forming composition for electron beam lithography or EUV lithography. In particular, it is suitable as a resist underlayer film forming composition for EUV lithography.

[0370] As the aforementioned electron beam resist materials, 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 due to electron beam interruption. When using these electron beam resist materials, the resist film pattern can be formed by using electron beams as the irradiation source, similar to the case when using photoresist materials.

[0371] In addition, methacrylate resin-based resist materials can be used as the aforementioned EUV resist materials.

[0372] Next, the resist film formed on top of the lower resist film is exposed through a specified mask. Exposure can be performed using KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), electron beam, etc.

[0373] After exposure, post-exposure baking can be performed as needed. Post-exposure baking is performed under conditions that are appropriately selected from a heating temperature of 70℃ to 150℃ and a heating time of 0.3 minutes to 10 minutes.

[0374] Next, development is performed using a developer (e.g., an alkaline developer). Thus, in the case of using, for example, a positive photoresist film, the exposed portions of the photoresist film are removed, forming a pattern of the photoresist film.

[0375] Examples of alkaline developers include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants may be added to these developers. The developing conditions are appropriately selected from a temperature of 5–50°C and a time of 10 to 600 seconds.

[0376] Furthermore, in this invention, an organic solvent can be used as the developer, and development is performed using the developer (solvent) after exposure. Thus, when using, for example, a negative photoresist film, the unexposed portions of the photoresist film are removed, forming a pattern on the photoresist film.

[0377] Examples of organic solvents used as developers 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, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate. Butyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate Examples of developing solutions include 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, and propyl-3-methoxypropionate. Furthermore, surfactants may be added to these developing solutions. For developing conditions, the temperature should be appropriately selected from 5°C to 50°C, and the time should be appropriately selected from 10 seconds to 600 seconds.

[0378] Using the pattern of the photoresist film (upper layer) formed in this way as a protective film, the lower resist film (intermediate layer) is removed. Then, using the film composed of the patterned photoresist film and the patterned lower resist film (intermediate layer) as a protective film, the lower organic film (lower layer) is removed. Finally, using the patterned photoresist film (upper layer), the patterned lower resist film (intermediate layer), and the patterned lower organic film (lower layer) as protective films, the substrate is processed.

[0379] The removal of the lower resist film (intermediate layer), which uses the pattern of the resist film (upper layer) as a protective film, is performed by dry etching. Gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used.

[0380] It should be noted that halogen-based gases are preferably used for dry etching of the resist underlayer. With halogen-based gases, the resist film (photoresist film) which is essentially formed of organic matter is difficult to remove. In contrast, the silicon-containing resist underlayer, which contains a large number of silicon atoms, is rapidly removed by halogen-based gases. Therefore, the reduction in the thickness of the photoresist film accompanying the dry etching of this resist underlayer can be suppressed. Consequently, the photoresist film can be used as a thin film. Therefore, fluorine-based gases are preferably used for dry etching of the resist underlayer. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2), but are not limited to these.

[0381] When an organic underlayer film exists between the substrate and the photoresist underlayer film, the removal of the organic underlayer film (underlayer), which is then performed as a protective film consisting of (in the case of residual patterned photoresist film (upper layer) and) a patterned photoresist underlayer film (intermediate layer), is preferably performed by dry etching using an oxygen-based gas (oxygen, oxygen / carbonyl sulfide (COS) mixture, etc.). 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.

[0382] Finally, the processing of the (semiconductor) substrate, which uses a patterned resist underlayer (intermediate layer) and an organic underlayer (underlayer) patterned as needed as protective films, is preferably performed by dry etching using fluorine-based gases.

[0383] Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0384] In this invention, after the etching (removal) process of the organic underlayer film, the resist underlayer film can be removed using a chemical solution. It should be noted that the removal of the resist underlayer film using a chemical solution can also be performed after substrate processing using the patterned organic underlayer film. In this invention, by incorporating the aforementioned structure derived from silane compounds containing a succinic anhydride framework into the hydrolytic condensate (polysiloxane), the solubility of the film formed from this condensate can be improved under alkaline conditions. For example, it exhibits solubility in alkaline solutions such as aqueous solutions containing ammonia and hydrogen peroxide. It is speculated that the reduced crosslinking density due to the influence of the succinic anhydride framework contributes to promoting alkaline solubility. Therefore, the film exhibits good peelability even after treatment with an alkaline solution, and the resist underlayer film, which allows even silicon-based mask residues such as silicon-containing resist underlayer films, can be easily removed using a chemical solution, thereby enabling the manufacture of semiconductor devices with minimal substrate damage.

[0385] Examples of alkaline solutions include dilute hydrofluoric acid, buffered hydrofluoric acid, aqueous solutions containing hydrochloric acid and hydrogen peroxide (SC-2 solution), aqueous solutions containing sulfuric acid and hydrogen peroxide (SPM solution), aqueous solutions containing hydrofluoric acid and hydrogen peroxide (FPM solution), and aqueous solutions containing ammonia and hydrogen peroxide (SC-1 solution). From the viewpoint of minimizing the impact on the substrate, the use of alkaline solutions is suitable.

[0386] In addition to the ammonia-peroxide solution (SC-1 solution) obtained by mixing ammonia with hydrogen peroxide and water, other alkaline solutions containing 1-99% by mass include ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, and 1-butyl-1-methylpyrrolidine. Hydroxide, 1-propyl-1-methylpyrrolidine Hydroxide, 1-Butyl-1-methylpiperidine Hydroxide, 1-propyl-1-methylpiperidine Hydroxides, mepiquat chloride Aqueous solutions of hydroxides, trimethylsulfonium hydroxides, hydrazines, ethylenediamines, or guanidines.

[0387] Furthermore, an organic antireflective film can be formed on top of the photoresist underlayer 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. Moreover, the antireflective film can be formed using conventional methods, such as coating and firing with a spin coater or coater.

[0388] Furthermore, the 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 a resist underlayer film may be formed thereon. In the case where an organic underlayer film is formed on the 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.

[0389] The resist underlayer film formed by the resist underlayer film formation composition of the present invention may, in addition, absorb the wavelength of the light used in the photolithography process. Furthermore, in such cases, it can function as an antireflective film that prevents reflected light from the substrate.

[0390] Furthermore, the aforementioned photoresist underlayer film can also be used as a layer to prevent interaction between the substrate and the photoresist film (photoresist film, etc.), a layer that prevents the adverse effects of the material used in the photoresist film or substances generated during exposure of the photoresist film on the substrate, a layer that prevents substances generated by the substrate during heating and firing from diffusing to the upper photoresist film, and a barrier layer that reduces the poisoning effect of the photoresist film caused by the dielectric layer of the semiconductor substrate.

[0391] The aforementioned resist underlayer film can be applied to substrates with formed vias used in dual damascene processes, and can be used as a hole-filling material (embedded material) that can fill cavities without gaps. Furthermore, it can also be used as a planarization material for planarizing the surface of semiconductor substrates with uneven surfaces.

[0392] Furthermore, the aforementioned photoresist underlayer film can be used as a underlayer film for EUV photoresist films, or as an antireflective underlayer film for EUV photoresist films that, in addition to functioning as a hard mask, can also be used without mixing with the EUV photoresist film to prevent unwanted exposure light, such as UV (ultraviolet) light and DUV (deep ultraviolet) light (ArF light, KrF light), from being reflected from the substrate or interface during EUV exposure (wavelength 13.5nm). In other words, it can effectively prevent reflection when used as a underlayer film for EUV photoresist films. When used as an EUV photoresist underlayer film, its process can be performed in the same way as that for photoresist underlayer films.

[0393] By using the resist lower layer film and semiconductor substrate of the present invention described above, a semiconductor processing substrate can be suitably processed.

[0394] Furthermore, according to the semiconductor device manufacturing method described above, the processing of semiconductor substrates with high precision and good reproducibility can be achieved, thus ensuring stable manufacturing of semiconductor devices. The semiconductor device manufacturing method described above includes the following steps: a step of forming an organic underlayer film; a step of forming a silicon-containing photoresist underlayer film on the organic underlayer film using the silicon-containing photoresist underlayer film forming composition of the present invention; and a step of forming a photoresist film on the silicon-containing photoresist underlayer film.

[0395] Example

[0396] 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.

[0397] The hydrolytic condensates (polyorganosiloxanes) of the above-mentioned hydrolyzable silanes can yield condensates with a weight average molecular weight of 1,000–1,000,000 or 1,000–100,000. Their molecular weights are obtained by GPC analysis and converted to polystyrene.

[0398] The determination conditions for GPC can be as follows: for example, using a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Co., Ltd.), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Co., Ltd.), a column temperature of 40°C, a tetrahydrofuran eluent, a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko Co., Ltd.) as the standard sample.

[0399] [1] Synthesis Examples 1-19, Comparative Synthesis Examples 1-3, Reference Synthesis Example: Synthesis of Hydrolysis Condensate (Polysiloxane)

[0400] <Synthesis example 1>

[0401] 29.2 g of tetraethoxysilane, 5.8 g of methyltriethoxysilane, 5.1 g of phenyltrimethoxysilane, 2.7 g of 3-(triethoxysilylpropyl)diallyl isocyanurate, 3.3 g of [(3-triethoxysilyl)propyl]succinic anhydride, and 67 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 28 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0402] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0403] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,700.

[0404] It should be noted that in the chemical formulas described in the following synthetic examples / comparative synthetic examples / reference synthetic examples, the numbers next to the siloxane units indicate the molar ratio (total 100).

[0405]

[0406] <Synthesis example 2>

[0407] 29.2 g of tetraethoxysilane, 7.7 g of methyltriethoxysilane, 5.1 g of phenyltrimethoxysilane, 2.7 g of 3-(triethoxysilylpropyl)diallyl isocyanurate, and 67 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 28 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0408] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0409] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,900.

[0410]

[0411] <Synthesis Example 3>

[0412] 29.2 g of tetraethoxysilane, 15.0 g of methyltriethoxysilane, 6.7 g of phenyltrimethoxysilane, 3.5 g of 3-(triethoxysilylpropyl)diallyl isocyanurate, 4.3 g of [(3-triethoxysilyl)propyl]succinic anhydride, and 88 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 35 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0413] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0414] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,600.

[0415]

[0416] <Synthesis example 4>

[0417] 29.2 g of tetraethoxysilane, 17.5 g of methyltriethoxysilane, 6.7 g of phenyltrimethoxysilane, 3.5 g of 3-(triethoxysilylpropyl)diallyl isocyanurate, and 85 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 35 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0418] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0419] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,800.

[0420]

[0421] <Synthesis Example 5>

[0422] 31.2 g of tetraethoxysilane, 5.7 g of methyltriethoxysilane, 5.1 g of phenyltrimethoxysilane, 2.7 g of 3-(triethoxysilylpropyl)diallyl isocyanurate and 67 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 28 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0423] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0424] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,700.

[0425]

[0426] <Synthesis example 6>

[0427] 31.2 g of tetraethoxysilane, 9.1 g of methyltriethoxysilane, 4.6 g of phenyltrimethoxysilane, 2.9 g of 3-(triethoxysilylpropyl)diallyl isocyanurate and 72 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 30 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0428] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0429] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,000.

[0430]

[0431] <Synthesis Example 7>

[0432] 14.6 g of tetraethoxysilane, 3.8 g of methyltriethoxysilane, 2.1 g of phenyltrimethoxysilane, 2.2 g of 3-(triethoxysilylpropyl)diallyl isocyanurate and 34 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 14 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0433] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0434] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,800.

[0435]

[0436] <Synthesis example 8>

[0437] 16.7 g of tetraethoxysilane, 3.4 g of vinyltrimethoxysilane, 2.3 g of phenyltrimethoxysilane, and 33 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 15 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0438] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0439] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,100.

[0440]

[0441] <Synthesis Example 9>

[0442] 31.2 g of tetraethoxysilane, 6.4 g of vinyltrimethoxysilane, 4.3 g of phenyltrimethoxysilane, 0.7 g of [(3-triethoxysilyl)propyl]succinic anhydride, and 64 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 28 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0443] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0444] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,900.

[0445]

[0446] <Synthesis Example 10>

[0447] 29.2 g of tetraethoxysilane, 6.1 g of vinyltrimethoxysilane, 4.1 g of phenyltrimethoxysilane, 1.3 g of [(3-triethoxysilyl)propyl]succinic anhydride, and 61 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 28 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0448] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0449] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,000.

[0450]

[0451] <Synthesis Example 11>

[0452] 16.7 g of tetraethoxysilane, 3.7 g of vinyltrimethoxysilane, 2.4 g of phenyltrimethoxysilane, 1.9 g of [(3-triethoxysilyl)propyl]succinic anhydride, 0.1 g of [3-(N,N-dimethylamino)propyl]trimethoxysilane, and 37 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 16 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0453] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed by distillation under reduced pressure, yielding a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrate exceeds 20% by mass when converted from the solid residue after heating at 150°C.

[0454] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,300.

[0455]

[0456] <Synthesis Example 12>

[0457] 14.6 g of tetraethoxysilane, 2.2 g of vinyltrimethoxysilane, 2.0 g of phenyltrimethoxysilane, 0.7 g of dimethoxymethylvinylsilane, and 29 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 13 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0458] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0459] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,100.

[0460]

[0461] <Synthesis Example 13>

[0462] 14.6 g of tetraethoxysilane, 3.7 g of vinyltrimethoxysilane, 2.0 g of diphenyldimethoxysilane, and 29 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 13 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0463] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0464] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,100.

[0465]

[0466] <Synthesis Example 14>

[0467] 20.8 g of tetraethoxysilane, 4.3 g of vinyltrimethoxysilane, 4.6 g of phenyltrimethoxysilane, 0.5 g of [(3-triethoxysilyl)propyl]succinic anhydride, and 45 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 20 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0468] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0469] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,300.

[0470]

[0471] <Synthesis Example 15>

[0472] 20.8 g of tetraethoxysilane, 4.3 g of vinyltrimethoxysilane, 4.6 g of phenyltrimethoxysilane, 0.5 g of [(3-triethoxysilyl)propyl]succinic anhydride, 0.1 g of [3-(N,N-dimethylamino)propyl]trimethoxysilane, and 45 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 20 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0473] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0474] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,500.

[0475]

[0476] <Synthesis Example 16>

[0477] 20.8 g of tetraethoxysilane, 4.3 g of vinyltrimethoxysilane, 4.6 g of phenyltrimethoxysilane, 0.5 g of [(3-triethoxysilyl)propyl]succinic anhydride, 0.03 g of [3-(N,N-dimethylamino)propyl]trimethoxysilane, and 45 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 20 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0478] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0479] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,300.

[0480]

[0481] <Synthesis Example 17>

[0482] 20.8 g of tetraethoxysilane, 4.3 g of vinyltrimethoxysilane, 4.6 g of phenyltrimethoxysilane, 0.5 g of [(3-triethoxysilyl)propyl]succinic anhydride, 0.01 g of [3-(N,N-dimethylamino)propyl]trimethoxysilane, and 45 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 20 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0483] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0484] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,200.

[0485]

[0486] <Synthesis Example 18>

[0487] 20.8 g of tetraethoxysilane, 4.4 g of vinyltrimethoxysilane, 4.7 g of phenyltrimethoxysilane, 1.2 g of [(3-triethoxysilyl)propyl]succinic anhydride, 0.03 g of [3-(N,N-dimethylamino)propyl]trimethoxysilane, and 45 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 20 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0488] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0489] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,000.

[0490]

[0491] <Synthesis Example 19>

[0492] 20.8 g of tetraethoxysilane, 4.6 g of vinyltrimethoxysilane, 4.9 g of phenyltrimethoxysilane, 2.5 g of [(3-triethoxysilyl)propyl]succinic anhydride, 0.03 g of [3-(N,N-dimethylamino)propyl]trimethoxysilane, and 45 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 20 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0493] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0494] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 2,000.

[0495]

[0496] <Comparative Synthesis Example 1>

[0497] 20.8 g of tetraethoxysilane, 7.6 g of methyltriethoxysilane, and 42 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 19 g of 0.2 mol / L acetic acid aqueous solution was added dropwise.

[0498] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water, nitric acid, and ethanol (a reaction byproduct) were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0499] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,300.

[0500]

[0501] <Comparative Synthesis Example 2>

[0502] 12.5 g of tetraethoxysilane, 10.7 g of methyltriethoxysilane, 3.6 g of phenyltrimethoxysilane, 1.9 g of 3-(triethoxysilylpropyl)diallyl isocyanurate, 2.3 g of [(3-triethoxysilyl)propyl]succinic anhydride, and 46 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with a magnetic stirrer, 18 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0503] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0504] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,800.

[0505]

[0506] <Comparative Synthesis Example 3>

[0507] 12.5 g of tetraethoxysilane, 12.0 g of methyltriethoxysilane, 3.6 g of phenyltrimethoxysilane, 1.9 g of 3-(triethoxysilylpropyl)diallyl isocyanurate, and 45 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 18 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0508] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water and nitric acid, as well as methanol and ethanol as reaction byproducts, were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0509] The resulting polysiloxane is equivalent to the following formula, with the weight-average molecular weight (Mw) obtained from GPC converted to polystyrene as 1,900.

[0510]

[0511] <Reference Synthesis Example>

[0512] 20.8 g of tetraethoxysilane, 7.6 g of methyltriethoxysilane, and 42 g of 1-ethoxy-2-propanol were added to a 100 mL flask and stirred. While stirring the resulting solution with an electromagnetic stirrer, 19 g of 0.2 mol / L nitric acid aqueous solution was added dropwise.

[0513] After the addition, the flask was transferred to an oil bath adjusted to 65°C and allowed to react for 16 hours. Then, the reaction solution was cooled to room temperature, and 100 g of 1-ethoxy-2-propanol was added. Under reduced pressure, water, nitric acid, and ethanol (a reaction byproduct) were removed from the reaction solution by vacuum distillation, thus obtaining a concentrated solution of the hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as the solvent. It should be noted that the solids concentration of the obtained concentrated solution, converted from the solid residue after heating at 150°C, exceeds 20% by mass.

[0514] The resulting polysiloxane is equivalent to the following formula, with a weight-average molecular weight (Mw) obtained from GPC converted to polystyrene, which is 2,700.

[0515]

[0516] [2] Examples 1-19, Reference Example and Comparative Example 1: Evaluation of Storage Stability

[0517] In the concentrated solutions of the hydrolysis condensate (polymer) obtained in Synthesis Examples 1-19, Reference Synthesis Example, and Comparative Synthesis Example 1, 1-ethoxy-2-propanol was added to adjust the concentration so that the solid residue after heating at 150°C was converted to 13% by mass, and a solution of the hydrolysis condensate (polymer) with propylene glycol monoethyl ether as solvent (solid component concentration 13% by mass) was obtained.

[0518] The resulting solution was stored at 35°C for one week, and the weight-average molecular weight of the hydrolysate condensate in the solution before and after storage was measured. The change rate (%) of the weight-average molecular weight was calculated. A change rate of more than 10% relative to the weight-average molecular weight before storage was evaluated as "poor," and a change rate of less than 10% was evaluated as "good." The results are shown in Table 1.

[0519] [Table 1]

[0520] [Table 1]

[0521] No. The concentrate used Evaluation results Example 1 Synthesis example 1 good Example 2 Synthesis example 2 good Example 3 Synthesis example 3 good Example 4 Synthesis example 4 good Example 5 Synthesis example 5 good Example 6 Synthesis example 6 good Example 7 Synthesis Example 7 good Example 8 Synthesis example 8 good Example 9 Synthesis example 9 good Example 10 Synthesis example 10 good Example 11 Synthesis Example 11 good Example 12 Synthesis example 12 good Example 13 Synthesis example 13 good Example 14 Synthesis Example 14 good Example 15 Synthesis Example 15 good Example 16 Synthesis Example 16 good Example 17 Synthesis Example 17 good Example 18 Synthesis example 18 good Example 19 Synthesis example 19 good Reference Example Reference Synthesis Example good Comparative Example 1 Comparative Synthesis Example 1 bad

[0522] [3] Examples 20-38 and Comparative Examples 2-4: Preparation of compositions (coating solutions) for forming silicon-containing photoresist underlayer films

[0523] In the concentrated solutions of the hydrolytic condensates (polymers) obtained in Synthetic Examples 1-19 and Comparative Synthetic Examples 1-3, the various additives and solvents shown in Table 2 were mixed in the proportions shown in Table 2. The resulting mixtures were filtered through a fluoropolymer filter with a pore size of 0.1 μm to obtain coating solutions. The amounts of each additive in Table 2 are expressed in parts by mass.

[0524] It should be noted that the addition ratio of hydrolyzed condensate (polymer) in Table 2 does not represent the amount of concentrated hydrolyzed condensate (polymer) solution added, but rather the amount of the polymer itself added.

[0525] In addition, in Table 2, PGEE represents 1-ethoxy-2-propanol (propylene glycol monoethyl ether), PGMEA represents 1-methoxy-2-propanol monoacetate (propylene glycol monomethyl ether acetate), and PGME represents 1-methoxy-2-propanol (propylene glycol monomethyl ether).

[0526] In addition, MA represents maleic acid, IMID represents N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, and TPSNO3 represents triphenylsulfonium nitrate.

[0527] [Table 2]

[0528] Table 2

[0529]

[0530] [4] Preparation of compositions for forming organic lower layer films

[0531] 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 the mixture was heated to 100°C to dissolve the solid and initiate polymerization.

[0532] After 24 hours, the reaction mixture was cooled to 60°C and diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.). The diluted reaction mixture was then added dropwise to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) for reprecipitation. The resulting precipitate was recovered by filtration, and the recovered solid was dried at 80°C for 24 hours to obtain 9.37 g of the polymer (hereinafter abbreviated as PCzFL) of formula (X) as the target.

[0533] It should be noted that PCzFL's 1 The results of the H-NMR measurements are as follows.

[0534] 1 H-NMR (400MHz, DMSO-d6): δ7.03-7.55 (br, 12H), δ7.61-8.10 (br, 4H), δ11.18 (br, 1H)

[0535] In addition, the weight-average molecular weight (Mw) of PCzFL, converted to polystyrene obtained from GPC, is 2,800, and the polydispersity Mw / Mn is 1.77.

[0536]

[0537] 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 Megafoc R-30 (manufactured by DIC Corporation, trade name) as a surfactant were mixed and dissolved in 88 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution 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 to prepare an organic lower membrane formation composition.

[0538] [5] Evaluation of resist patterns exposed using ArF: PTD

[0539] The above-mentioned organic lower layer film forming composition is applied to a silicon wafer using a spin coater and heated at 240°C for 60 seconds on a hot plate to form an organic lower layer film (layer A) (film thickness 200 nm).

[0540] The coating solution obtained in Example 20 was spin-coated onto it and heated at 215°C for 1 minute on a hot plate to form a silicon-containing photoresist lower layer film (B layer) (20 nm).

[0541] A commercially available ArF photoresist (manufactured by JSR Corporation, trade name: AR2772JN) was further spin-coated onto the photoresist, and heated at 110°C for 90 seconds on a hot plate to form a photoresist film (C layer) (120nm). Then, an NSR-S307E scanner (wavelength: 193nm, NA: 0.85, σ: 0.85 / 0.93) manufactured by NSR Corporation was used to expose the photoresist by setting a mask with a line width and line spacing of 0.065μm after development, i.e., forming dense lines with a line width of 0.065μm and a gap (L / S) of 1 / 1.

[0542] After exposure, post-exposure heating (110℃ for 1 minute) is performed, followed by cooling on a cooling plate until room temperature. Then, development is carried out using a 2.38% alkaline aqueous solution for 60 seconds, followed by rinsing to form a resist pattern.

[0543] Using the same steps, resist patterns were formed using the coating liquids obtained in Examples 21-38 and Comparative Examples 2-4.

[0544] Regarding the obtained photoresist patterns, the evaluation was based on the pattern shape observed from the pattern cross-section. A pattern without collapse (significant pattern peeling, undercut, or thickened line bases) was rated as "good," while a pattern collapse was rated as "poor." The results are shown in Table 3.

[0545] It should be noted that, in the following description, the example numbers of the resist underlayer film forming compositions used are also treated as example numbers of various evaluations carried out using the composition.

[0546] [6] Evaluation of siloxane bond strength ratio using FT-IR

[0547] The coating solution obtained in Example 20 was spin-coated onto a silicon wafer and heated at 215°C for 1 minute on a hot plate to form a silicon-containing photoresist lower layer film (B layer) (120 nm).

[0548] Using the same steps, silicon-containing photoresist underlayer films were formed using the coating solutions obtained in Examples 21-38 and Comparative Example 2.

[0549] Regarding the obtained silicon-containing photoresist underlayers, Fourier transform infrared spectroscopy (FT / IR-6600 (manufactured by Nippon Spectrophotometer Co., Ltd.)) was used to analyze the layers at wavenumbers of 1000–1250 cm⁻¹. -1 The peak intensities of the observed siloxane bonds were compared. The peak intensities were compared using values ​​normalized to 100, with the intensity of the silicon-containing photoresist underlayer film of Comparative Example 2 set to 100. When the bond strength was higher than that of Comparative Example 2 (e.g., 90 or higher), there was a tendency for decreased solubility. The results are shown in Table 3.

[0550] [7] The removal performance was evaluated using SC-1 solution (ammonia / hydrogen peroxide aqueous solution).

[0551] The coating solution obtained in Example 20 was spin-coated onto a silicon wafer and heated at 215°C for 1 minute on a hot plate to form a silicon-containing photoresist lower layer film (B layer) (20 nm).

[0552] Using the same steps, silicon-containing photoresist underlayer films were formed using the coating solutions obtained in Examples 21-38 and Comparative Example 2.

[0553] The silicon wafers with silicon-containing photoresist underlayers were immersed in SC-1 solution (28% ammonia / 33% hydrogen peroxide / water = 1 / 1 / 40 (v / v / v)) at a liquid temperature adjusted to 60°C for 180 seconds, followed by rinsing with water for 60 seconds and drying. The thickness of the silicon-containing photoresist underlayers after immersion in SC-1 solution was then measured, and the change rate (%) was calculated. A change rate of 90% or more in the thickness of the silicon-containing photoresist underlayers after immersion relative to the thickness before immersion was rated as "good," and a change rate of less than 90% was rated as "poor." The results are shown in Table 3.

[0554] [8] Evaluation of residue after dry etching

[0555] The above-mentioned organic lower layer film forming composition is applied to a silicon wafer using a spin coater and heated at 240°C for 60 seconds on a hot plate to form an organic lower layer film (layer A) (film thickness 70 nm).

[0556] The coating solution obtained in Example 20 was spin-coated onto it and heated at 215°C for 1 minute on a hot plate to form a silicon-containing photoresist lower layer film (B layer) (20 nm).

[0557] Using a dry etcher (LAM-2300) manufactured by Lamrise Co., Ltd., a 20-second dry etching process was performed under CF4 gas conditions to remove the silicon-containing resist underlayer (B layer) from the resulting silicon wafer with the coating. Then, a 5-second dry etching process was performed under O2 / COS gas conditions to remove the organic underlayer (A layer).

[0558] Using the same steps, the coating solutions obtained in Examples 21-38 and Comparative Examples 3 and 4 were used to form a silicon-containing photoresist underlayer film, and the silicon-containing photoresist underlayer film (layer B) and the organic underlayer film (layer A) were removed.

[0559] The surface of a silicon wafer after the removal of the organic underlayer (layer A) and the silicon-containing photoresist underlayer (layer B) was observed using a scanning probe microscope (Hitachi Hitachi, AFM5000). Etching residues with a convex shape exceeding 0.05 μm in width and 2 nm in height were identified and rated as "poor," while those not identified were rated as "good." The results are shown in Table 3.

[0560] [Table 3]

[0561] Table 3

[0562]

Claims

1. A composition for forming a resist underlayer film, comprising a hydrolytic condensate of a mixture of hydrolyzable silanes, said hydrolyzable silane mixture comprising a hydrolyzable silane of formula (1), an alkyltrialkoxysilane, and a hydrolyzable silane of formula (2) below. The content of alkyltrialkoxysilanes in the hydrolyzable silane mixture is based on a total molar percentage of 0 mol% and less than 40 mol% of all hydrolyzable silanes contained in the hydrolyzable silane mixture. In equation (1), R 1 The term "group that bonds with silicon atoms" refers to an organic group comprising at least one group or skeleton selected from succinic anhydride skeleton, alkenyl, aryl, and groups shown in formulas (1-2) below. In equation (1-2), X 101 The group represents any one of the groups shown in formulas (1-3) to (1-5) below, and the carbon atom of the ketone group in formulas (1-4) and (1-5) below is related to the R in formula (1-2). 102 The nitrogen atoms that are bound together, In equations (1-3) to (1-5), R 103 ~R 107 Each can independently represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or an organic group containing an epoxy or sulfonyl group; R 101 Each can independently represent a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or an organic group containing an epoxy or sulfonyl group. R 102 Each can be independently represented as an alkylene group, a hydroxyalkylene group, a sulfur bond (-S-), an ether bond (-O-), or an ester bond (-C(=O)-O- or -OC(=O)-); R 2 The group that bonds to a silicon atom can independently represent a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organogroup comprising an epoxy group, acryloyl group, methacryl group, mercapto group, amino group, amide group, alkoxy group, sulfonyl group, or cyano group, or a combination thereof. 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. a represents 1, b represents an integer from 0 to 2, and 4-(a+b) represents an integer from 1 to 3. In equation (2), R 4 The group that bonds to a silicon atom can independently represent a substituted alkyl group, a substituted haloalkyl group, or a substituted alkoxyalkyl group, or an organogroup comprising an epoxy group, acryloyl group, methacryl group, mercapto group, amino group, amide group, alkoxy group, sulfonyl group, or cyano group, or a combination thereof. R 5 These are groups or atoms that bond with silicon atoms, and each can be represented independently as an alkoxy, aralkyloxy, acyloxy, or halogen atom. c represents an integer from 0 to 3.

2. The composition for forming a resist underlayer film according to claim 1, wherein R 1 "A group that bonds to a silicon atom" indicates an organic group that contains at least one group or skeleton selected from succinic anhydride skeleton, vinyl skeleton, phenyl skeleton and isocyanuric acid skeleton.

3. The composition for forming a resist underlayer film according to claim 1 or 2, wherein the content of the compound represented by formula (1) in the hydrolyzable silane mixture is 5 mol% or more based on the total molar number of all hydrolyzable silanes contained in the hydrolyzable silane mixture.

4. The composition for forming a resist underlayer film according to claim 3, comprising R 1 Compounds containing an organic group with a succinic anhydride skeleton are represented by the compound shown in formula (1).

5. The composition for forming a resist underlayer film according to claim 4, wherein the hydrolyzable silane mixture contains R 1 The content of the compound represented by formula (1) containing an organic group with a succinic anhydride skeleton is 1 mol% or more based on the total number of moles of all hydrolyzable silanes contained in the hydrolyzable silane mixture.

6. The composition for forming a resist underlayer film according to claim 1 or 2, wherein the composition has a pH of 2 to 5.

7. A method for forming a pattern, comprising the following steps: The process of forming an organic lower layer film on a semiconductor substrate; The process of coating the photoresist underlayer film formation composition according to any one of claims 1 to 6 onto the organic underlayer film and firing it to form a photoresist underlayer film containing silicon; The process of coating a resist film forming composition onto the silicon-containing resist lower layer film to form a resist film; The process of exposing and developing the resist film to obtain a resist pattern; The process of using a resist pattern as a mask to etch the silicon-containing resist underlayer film; The process of etching the organic underlying film using a patterned silicon-containing resist underlayer as a mask.

8. The pattern forming method according to claim 7, after the step of etching the organic underlayer film, further comprises: a step of removing the silicon-containing resist underlayer film by using a wet method with a chemical solution.

9. The pattern forming method according to claim 8, wherein the liquid is an alkaline liquid.

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