Plasma-treated silicon-containing resist underlayer film, composition for forming silicon-containing resist underlayer film, and laminate

Abstract

A plasma-treated silicon-containing resist underlayer film comprising a polysiloxane.

Description

Plasma-treated silicon-containing resist underlayer film, silicon-containing resist underlayer film formation composition, and laminate

[0001] The present invention relates to a plasma-treated silicon-containing resist underlayer film, a silicon-containing resist underlayer film formation composition, and a laminate.

[0002] Traditionally, microfabrication using photoresist lithography has been employed in the manufacturing of semiconductor devices. Microfabrication is a processing method in which a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, and then active light such as ultraviolet light is irradiated onto it through a mask pattern on which the semiconductor device pattern is drawn, developing the photoresist, and the substrate is etched using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the pattern. In recent years, as the integration density of semiconductor devices has increased, the active light used has tended to be shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). With the shortening of the wavelength of active light, the effect of reflection of the active light from the semiconductor substrate has become a major problem, and a method of placing a resist underlayer film called an anti-reflective coating (Bottom Anti-Reflective Coating, BARC) between the photoresist and the substrate to be processed has become widely applied.

[0003] As a microfabrication technology, mass production of 10 nm node devices is underway using double patterning in ArF immersion lithography. Furthermore, mass production of 7 nm node devices using double patterning in ArF immersion lithography is also progressing. For the next-generation technology of 5 nm node mass production, extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm has been partially put into practical use.

[0004] In advanced microfabrication, miniaturization is difficult with resist films alone, and the miniaturization process is becoming impossible without utilizing a hard mask formed in the layer beneath the resist film. In this situation, one method of utilizing a hard mask as a resist underlayer is the multilayer resist method. In this method, an underlayer film with different etching selectivity from the resist film, such as a silicon-containing resist underlayer film, is interposed between the resist film and the substrate to be processed. After obtaining a pattern on the resist film, the resist pattern is used as an etching mask to transfer the pattern to the silicon-containing resist underlayer film by dry etching. Furthermore, the silicon-containing resist underlayer film is used as an etching mask to transfer the pattern to the substrate to be processed or to a core film for the spacer process by dry etching.

[0005] As a composition for forming a silicon-containing resist underlayer film applicable to multilayer resist methods, a resist underlayer film forming composition has been proposed that contains a silicon-containing compound obtained by hydrolysis, condensation, or both of these processes of a specific silicon compound (see, for example, Patent Document 1).

[0006] Japanese Patent Publication No. 2014-157242

[0007] The properties required of a silicon-containing resist underlayer film include, for example, that it does not intermix with the film formed on top (i.e., it is insoluble in the solvent used to form the upper film), has excellent etching resistance, and has high film density. The present invention has been made in view of the above circumstances, and aims to provide a silicon-containing resist underlayer film forming composition that can form a silicon-containing resist underlayer film with excellent etching resistance and high film density, as well as a plasma-treated silicon-containing resist underlayer film and a laminate using the silicon-containing resist underlayer film forming composition.

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

[0009] In other words, the present invention encompasses the following aspects: [1] A plasma-treated silicon-containing resist underlayer film containing polysiloxane. [2] A film density of 1.8 g / cm³. ３ The above is the plasma-treated silicon-containing resist underlayer film described in [1]. [3] O of the silicon-containing resist underlayer film before plasma treatment ２ or CF ４ In relation to the etching rate, the O of the plasma-treated silicon-containing resist underlayer film after plasma treatment ２ or CF ４ [1] A plasma-treated silicon-containing resist underlayer film according to [1], wherein the etching rate is 0.95 times or less. [4] A silicon-containing resist underlayer film forming composition for forming a plasma-treated silicon-containing resist underlayer film according to any one of [1] to [3], comprising the polysiloxane and a solvent. [5] A silicon-containing resist underlayer film forming composition according to [4], wherein the polysiloxane is a hydrolysis condensate of a hydrolyzable silane (Si-1), and the hydrolyzable silane (Si-1) comprises 30 mol% or more of a hydrolyzable silane represented by the following formula (A). (In formula (A), R is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.) [6] The silicon-containing resist underlayer film forming composition according to [4], wherein the polysiloxane is a hydrolysis condensate of a hydrolyzable silane (Si-1), and the hydrolyzable silane (Si-1) comprises a hydrolyzable silane represented by the following formula (B). (In formula (B), R １１ R is a group that bonds to a silicon atom and independently represents an organic group having 1 to 45 carbon atoms. １２(where a is a group or atom bonded to a silicon atom, and independently of each other, represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer from 1 to 3.) [7] The silicon-containing resist underlayer film forming composition according to any one of [4] to [6], wherein the polysiloxane has at least one of a double bond and a triple bond. [8] The silicon-containing resist underlayer film forming composition according to any one of [4] to [7], wherein the polysiloxane comprises a polysiloxane modified product in which at least a portion of the silanol groups are alcohol-modified or acetal-protected. [9] The silicon-containing resist underlayer film forming composition according to any one of [4] to [8], wherein the solvent comprises an alcohol-based solvent or water.

[10] The silicon-containing resist underlayer film forming composition according to [9], wherein the alcohol-based solvent comprises a propylene glycol monoalkyl ether.

[11] The silicon-containing resist underlayer film forming composition according to any one of [4] to

[10] , comprising an inorganic acid.

[12] The resist underlayer film formation composition according to

[11] , wherein the inorganic acid comprises hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, or boric acid.

[13] The silicon-containing resist underlayer film formation composition according to any one of [4] to

[12] , used in EUV lithography.

[14] A laminate comprising a semiconductor substrate and a plasma-treated silicon-containing resist underlayer film according to any one of [1] to [3].

[0010] According to the present invention, a silicon-containing resist underlayer film formation composition is available that can form a silicon-containing resist underlayer film with excellent etching resistance and increased film density, as well as a plasma-treated silicon-containing resist underlayer film and a laminate using the silicon-containing resist underlayer film formation composition.

[0011] Figure 1 is a schematic cross-sectional view of one example of a laminate. Figure 2 is a schematic cross-sectional view of another example of a laminate. Figure 3 is a schematic cross-sectional view of another example of a laminate. Figure 4 is a schematic cross-sectional view of another example of a laminate. Figure 5 is a schematic cross-sectional view of another example of a laminate. Figure 6 is a schematic cross-sectional view of another example of a laminate.

[0012] [Plasma-treated silicon-containing underlayer resist film] The plasma-treated silicon-containing underlayer resist film of the present invention comprises polysiloxane.

[0013] (Polysiloxane) For example, polysiloxane contains 30 mol% or more of Q units based on all units, preferably 45 mol% or more, and more preferably 60 mol% or more. The upper limit of the proportion of Q units relative to all units in polysiloxane is not particularly limited; the proportion of Q units may be, for example, 100 mol% or less, 90 mol% or less, or 85 mol% or less.

[0014] Here, the term "all units" refers to the total of M units, D units, T units, and Q units that constitute polysiloxane. Note that polysiloxane does not need to include all of M units, D units, T units, and Q units. The M unit is (R) ３ SiO １／２ refers to the siloxy unit represented by . Here, each R independently represents a hydrogen atom or an organic group. The number described after (R) (here, 3) means that three hydrogen atoms or organic groups are bonded to the silicon atom. That is, the M unit has one silicon atom, three hydrogen atoms or organic groups, and one oxygen atom O ＊ . More specifically, the M unit has three hydrogen atoms or organic groups bonded to one silicon atom, and an oxygen atom O bonded to one silicon atom ＊ . The D unit is (R) ２ SiO ２／２ (each R independently represents a hydrogen atom or an organic group), which means a siloxy unit represented by . That is, the D unit has one silicon atom, two hydrogen atoms or organic groups bonded to the silicon atom, and an oxygen atom O bonded to another silicon atom ＊ and is a unit having two of said oxygen atoms. The T unit is RSiO ３／２ (R represents a hydrogen atom or an organic group), which means a siloxy unit represented by . That is, the T unit has one silicon atom, one hydrogen atom or organic group bonded to the silicon atom, and an oxygen atom O bonded to another silicon atom ＊It is a unit that has three of these. The Q unit is SiO ２ This refers to the siloxy unit represented by . In other words, the Q unit has one silicon atom and an oxygen atom O bonded to another silicon atom. ＊ It is a unit that has four of these elements.

[0015] The polysiloxane preferably contains 5 mol% or more of T units relative to the total units, more preferably 10 mol% or more, and particularly preferably 20 mol% or more. There is no particular upper limit to the ratio of T units to the total units in the polysiloxane, and the ratio of T units may be, for example, 100 mol% or less, 70 mol% or less, 55 mol% or less, or 40 mol% or less.

[0016] The polysiloxane preferably contains 70 mol% to 100 mol% of the total Q and T units relative to the total units, more preferably 80 mol% to 100 mol%, and particularly preferably 90 mol% to 100 mol%.

[0017] Polysiloxanes preferably have at least one of a double bond and a triple bond. Examples of double bonds include carbon-carbon double bonds. Examples of triple bonds include carbon-carbon triple bonds and carbon-nitrogen triple bonds.

[0018] The polysiloxane may include a modified polysiloxane in which some of the silanol groups have been modified, for example, a modified polysiloxane in which some of the silanol groups have been alcohol-modified or acetal-protected. The polysiloxane may also include, as an example, a hydrolysis condensate of a hydrolyzable silane, and may include a modified polysiloxane in which at least some of the silanol groups of the hydrolysis condensate have been alcohol-modified or acetal-protected. The hydrolyzable silane in the hydrolysis condensate may include one or more hydrolyzable silanes. Commercially available polysiloxanes can be used as the polysiloxane.

[0019] In this invention, the "hydrolyzed condensate" of hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only polyorganosiloxane polymers, which are condensates in which condensation is completely completed, but also polyorganosiloxane polymers, which are partially hydrolyzed condensates in which condensation is not completely completed. Such partially hydrolyzed condensates are polymers obtained by hydrolysis and condensation of hydrolyzable silane, similar to condensates in which condensation is completely completed, but the hydrolysis stops only partially and condensation does not occur, and therefore Si-OH groups remain. In addition to hydrolyzed condensates, uncondensed hydrolysates (complete hydrolysates, partially hydrolysates) and monomers (hydrolyzable silanes) may remain in the surface modifier. In this specification, "hydrolyzable silane" may also be simply referred to as "silane compound." In this specification, "polysiloxane" may also be referred to as "hydrolyzed condensate."

[0020] The polysiloxane is preferably a hydrolysis condensate of a hydrolyzable silane (Si-1). The hydrolyzable silane (Si-1) includes, for example, a hydrolyzable silane represented by the following formula (A). The hydrolyzable silane (Si-1) contains, for example, 30 mol% or more of the hydrolyzable silane represented by the following formula (A). (In formula (1), R is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.)

[0021] When hydrolyzing and condensing hydrolyzable silane (Si-1) to obtain polysiloxane, the proportion of hydrolyzable silane represented by formula (A) in the hydrolyzable silane (Si-1) is, for example, 30 mol% or more, preferably 45 mol% or more, and more preferably 60 mol% or more. The upper limit of the proportion of hydrolyzable silane represented by formula (A) in the hydrolyzable silane (Si-1) when hydrolyzing and condensing hydrolyzable silane (Si-1) to obtain polysiloxane is not particularly limited, and the proportion may be, for example, 100 mol% or less, 90 mol% or less, or 85 mol% or less.

[0022] In formula (A), R is a hydrolyzable group. Examples of alkoxy groups in R in formula (A) include alkoxy groups having 1 to 4 carbon atoms. The aralkyloxy group in R in formula (A) is a monovalent group derived by removing a hydrogen atom from the hydroxyl group of an aralkyl alcohol. The number of carbon atoms in the aralkyloxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less. Specific examples of aralkyloxy groups include, but are not limited to, phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group, 5-phenyl-n-pentyloxy group, 6-phenyl-n-hexyloxy group, 7-phenyl-n-heptyloxy group, 8-phenyl-n-octyloxy group, 9-phenyl-n-nonyloxy group, and 10-phenyl-n-decyloxy group. The acyloxy group in R in formula (A) is a monovalent group derived by removing a hydrogen atom from the carboxyl group (-COOH) of a carboxylic acid compound. Typical examples include, but are not limited to, alkylcarbonyloxy groups, arylcarbonyloxy groups, or aralkylcarbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of an alkylcarboxylic acid, arylcarboxylic acid, or aralkylcarboxylic acid.Specific examples of acyloxy groups include acyloxy groups having 2 to 20 carbon atoms, such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, i-butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group, 3-methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, and 2-methyl-n-pentylcarbonyloxy group. Examples include vonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, and tosylcarbonyloxy group. Examples of halogen atoms in formula (A) include fluorine, chlorine, bromine, and iodine. Among these, an alkoxy group is preferred for R, and an alkoxy group having 1 to 4 carbon atoms is more preferred.

[0023] Examples of hydrolyzable silanes represented by formula (A) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxysilane.

[0024] Hydrolyzable silanes (Si-1) include, for example, hydrolyzable silanes represented by the following formula (B). (In formula (B), R １１ R is a group that bonds to a silicon atom and independently represents an organic group having 1 to 45 carbon atoms. １２ (where a is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer from 1 to 3.)

[0025] a is preferably 1 or 2, and more preferably 1.

[0026] R １１ For example, it has at least one of a double bond and a triple bond. Examples of double bonds include a carbon-carbon double bond. Examples of triple bonds include a carbon-carbon triple bond and a carbon-nitrogen triple bond.

[0027] <<R in equation (B) １２ >> R in equation (B) １２ R in formula (B) is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. １２ Specific and preferred examples include those given in the explanation of R in formula (A).

[0028] <<R in equation (B) １１ >> R in equation (B) １１ R is a group that bonds to a silicon atom and independently represents an organic group having 1 to 45 carbon atoms. １１ R in formula (B) is not a hydrolyzable group. １１For example, this may represent an organic group having a cyclic urea skeleton, such as an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, an optionally substituted alkenyl group, or an organic group having a cyclic urea skeleton; or an organic group having an optionally ring-opened epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of these.

[0029] The alkyl group may be linear, branched, or cyclic, and its carbon number is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3 Examples include methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group. In this specification, "i" means "iso", "s" means "sec", and "t" means "tert".

[0030] Specific examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, and 2,4-dimethyl-cyclobutyl group. Examples include cycloalkyl groups such as methyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group, as well as crosslinked cyclic cycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0031] The aryl group may be any of the following: a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused ring aromatic hydrocarbon compound, or a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. For example, aryl groups with 6 to 20 carbon atoms can be given as aryl groups, and examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 5-naphthacenyl group, 2-crisenyl group, 1-pyrenyl group, 2-pyrenyl group, Examples include, but are not limited to, the pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group (o-biphenylyl group), biphenyl-3-yl group (m-biphenylyl group), biphenyl-4-yl group (p-biphenylyl group), paraterphenyl-4-yl group, metaterphenyl-4-yl group, orthoterphenyl-4-yl group, 1,1'-binaphthyl-2-yl group, 2,2'-binaphthyl-1-yl group, etc.

[0032] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those mentioned above. The number of carbon atoms in an aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aralkyl groups include, but are not limited to, phenylmethyl group (benzyl group), 2-phenylethylene group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, and 10-phenyl-n-decyl group.

[0033] Alkyl halogenated groups, aryl halogenated groups, and aralkyl halogenated groups are, respectively, alkyl groups, aryl groups, and aralkyl groups substituted with one or more halogen atoms. Specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those mentioned above.

[0034] The number of carbon atoms in the alkyl halogen is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of alkyl halogens include, but are not limited to, monofluoromethyl group, difluoromethyl group, trifluoromethyl group, bromodifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 1,1-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3-bromopropyl group, 2,2,3,3-tetrafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 1,1,1,3,3,3-hexafluoropropan-2-yl group, 3-bromo-2-methylpropyl group, 4-bromobutyl group, and perfluoropentyl group.

[0035] The number of carbon atoms in the aryl halide group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aryl halide groups include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2,3,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2-fluoro-1-naphthyl group, and 3-fluorophenyl group. Examples include fluoro-1-naphthyl group, 4-fluoro-1-naphthyl group, 6-fluoro-1-naphthyl group, 7-fluoro-1-naphthyl group, 8-fluoro-1-naphthyl group, 4,5-difluoro-1-naphthyl group, 5,7-difluoro-1-naphthyl group, 5,8-difluoro-1-naphthyl group, 5,6,7,8-tetrafluoro-1-naphthyl group, heptafluoro-1-naphthyl group, 1-fluoro-2-naphthyl group, 5-fluoro-2-naphthyl group, 6-fluoro-2-naphthyl group, 7-fluoro-2-naphthyl group, 5,7-difluoro-2-naphthyl group, heptafluoro-2-naphthyl group, etc., and groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group), but are not limited to these.

[0036] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of halogenated aralkyl groups include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, and 2,4,5-trifluorobenzyl group. Examples include the refluorobenzyl group, 2,4,6-trifluorobenzyl group, 2,3,4,5-tetrafluorobenzyl group, 2,3,4,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluorobenzyl group, and 2,3,4,5,6-pentafluorobenzyl group. Furthermore, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group) are also included, but are not limited to these.

[0037] Alkoxyalkyl groups, alkoxyaryl groups, and alkoxyaralkyl groups are alkyl groups, aryl groups, and aralkyl groups, respectively, that are substituted with one or more alkoxy groups. Specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those mentioned above.

[0038] Examples of alkoxy groups as substituents include alkoxy groups having at least one alkyl moiety of linear, branched, and cyclic structures with 1 to 20 carbon atoms. Examples of linear or branched alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3- Examples include methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group.Examples of cyclic alkoxy groups include cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3 Examples include dimethylcyclobutoxy group, 2,2-dimethylcyclobutoxy group, 2,3-dimethylcyclobutoxy group, 2,4-dimethylcyclobutoxy group, 3,3-dimethylcyclobutoxy group, 1-n-propylcyclopropoxy group, 2-n-propylcyclopropoxy group, 1-i-propylcyclopropoxy group, 2-i-propylcyclopropoxy group, 1,2,2-trimethylcyclopropoxy group, 1,2,3-trimethylcyclopropoxy group, 2,2,3-trimethylcyclopropoxy group, 1-ethyl-2-methylcyclopropoxy group, 2-ethyl-1-methylcyclopropoxy group, 2-ethyl-2-methylcyclopropoxy group, and 2-ethyl-3-methylcyclopropoxy group.

[0039] Specific examples of alkoxyalkyl groups include, but are not limited to, lower alkyloxy lower alkyl groups (approximately 5 or fewer carbon atoms) such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, and ethoxymethyl group. Specific examples of alkoxyaryl groups include, but are not limited to, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-(1-ethoxy)phenyl group, 3-(1-ethoxy)phenyl group, 4-(1-ethoxy)phenyl group, 2-(2-ethoxy)phenyl group, 3-(2-ethoxy)phenyl group, 4-(2-ethoxy)phenyl group, 2-methoxynaphthalen-1-yl group, 3-methoxynaphthalen-1-yl group, 4-methoxynaphthalen-1-yl group, 5-methoxynaphthalen-1-yl group, 6-methoxynaphthalen-1-yl group, and 7-methoxynaphthalen-1-yl group. Specific examples of alkoxyaralkyl groups include, but are not limited to, the 3-(methoxyphenyl)benzyl group and the 4-(methoxyphenyl)benzyl group.

[0040] The alkenyl group may be linear or branched, and its carbon number is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of alkenyl groups include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1- Butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group , 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl- 2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3, 3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl -1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cy Examples include clopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group, as well as bridging cyclic alkenyl groups such as bicycloheptenyl group (norbornyl group).

[0041] Furthermore, examples of substituents in the alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, and alkenyl groups include alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, aryloxy groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, alkoxy groups, and aralkyloxy groups. Specific examples of these substituents and their preferred carbon numbers are the same as those described above or below. The aryloxy group mentioned in the substituents is a group in which an aryl group is bonded via an oxygen atom (-O-). Specific examples of such aryl groups are the same as those described above. The carbon number of the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include phenoxy groups and naphthalene-2-yloxy groups, but are not limited to these. In addition, if there are two or more substituents, they may bond to each other to form a ring.

[0042] Organic groups having an epoxy group that may be ring-opened include glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group, epoxycyclohexyl group, or groups in which the epoxy group is ring-opened. Organic groups having an acryloyl group include acryloyloxymethyl group, acryloyloxyethyl group, acryloyloxypropyl group, etc. Organic groups having a methacryloyl group include methacryloyloxymethyl group, methacryloyloxyethyl group, methacryloyloxypropyl group, etc. Organic groups having a mercapto group include mercaptoethyl group, mercaptobutyl group, mercaptohexyl group, mercaptooctyl group, mercaptophenyl group, etc. Organic groups having an amino group include, but are not limited to, amino group, aminomethyl group, aminoethyl group, aminophenyl group, dimethylaminoethyl group, dimethylaminopropyl group, etc. More details about organic groups having an amino group will be described later. Examples of organic groups having an alkoxy group include, but are not limited to, methoxymethyl and methoxyethyl groups. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded. Examples of organic groups having a sulfonyl group include, but are not limited to, sulfonyl alkyl groups and sulfonylaryl groups. Examples of organic groups having a cyano group include cyanoethyl, cyanopropyl, cyanophenyl, and thiocyanate groups.

[0043] Examples of organic groups having an amino group include organic groups having at least one of a primary amino group, a secondary amino group, and a tertiary amino group. Hydrolysis condensates obtained by hydrolyzing a hydrolyzable silane having a tertiary amino group with a strong acid to form a countercation having a tertiary ammonium group are preferably used. In addition to the nitrogen atom constituting the amino group, the organic group may also contain heteroatoms such as oxygen atoms and sulfur atoms.

[0044] A preferred example of an organic group having an amino group is the group represented by the following formula (A1).

[0045] In formula (A1), R １０１ and R １０２ R independently represents a hydrogen atom or a hydrocarbon group, and L independently represents an optionally substituted alkylene group. * represents a bond. Examples of hydrocarbon groups include, but are not limited to, alkyl groups, alkenyl groups, and aryl groups. Specific examples of these alkyl groups, alkenyl groups, and aryl groups include R １ The same as those mentioned above can be cited. The alkylene group may be linear or branched, and its carbon number is usually 1 to 10, preferably 1 to 5. Examples of linear alkylene groups include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, and decamethylene group. Examples of organic groups having an amino group include, but are not limited to, amino group, aminomethyl group, aminoethyl group, aminophenyl group, dimethylaminoethyl group, and dimethylaminopropyl group.

[0046] Examples of organic groups having a cyclic urea skeleton include the organic group represented by the following formula (4-2). In formula (4-2), R ４０４ R independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group having an epoxy group or a sulfonyl group. ４０５ These independently represent an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-), or an ester bond (-CO-O- or -O-CO-). * represents a bond. Note that R ４０４ Specific examples of organic groups having an optionally substituted alkyl group, an optionally substituted alkenyl group, and an epoxy group, and preferred carbon numbers, etc., are given by R １２ The same points mentioned above can be cited.

[0047] Also, R ４０５The alkylene group may have one or more selected from sulfide bonds, ether bonds, and ester bonds at its terminal or in the middle, preferably in the middle. Specific examples of alkylene groups include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as methylethylene, 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 alkylenes such as 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutitatindiyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl. ２ OCH ２ -ien-CH ２ CH ２ OCH ２ -ien-CH ２ CH ２ OCH ２ CH ２ -ien-CH ２ CH ２ CH ２ OCH ２ CH ２ -ien-CH ２ CH ２ OCH ２ CH ２ CH ２ -ien-CH ２ CH ２ CH ２ OCH ２ CH ２ CH ２ -ien-CH ２ SCH ２ -ien-CH ２ CH ２ SCH ２ -ien-CH ２ CH ２ SCH ２ CH ２ -ien-CH ２ CH ２ CH２ SCH ２ CH ２ -, -CH ２ CH ２ SCH ２ CH ２ CH ２ -, -CH ２ CH ２ CH ２ SCH ２ CH ２ CH ２ -, -CH ２ OCH ２ CH ２ SCH ２ Examples include, but are not limited to, alkylene groups containing ether groups such as the aforementioned groups.

[0048] A hydroxyalkylene group is a group obtained by substituting at least one hydrogen atom of the aforementioned alkylene group with a hydroxy group. Specific examples thereof include, but are not limited to, hydroxymethylene group, 1-hydroxyethylene group, 2-hydroxyethylene group, 1,2-dihydroxyethylene group, 1-hydroxytrimethylene group, 2-hydroxytrimethylene group, 3-hydroxytrimethylene group, 1-hydroxytetramethylene group, 2-hydroxytetramethylene group, 3-hydroxytetramethylene group, 4-hydroxytetramethylene group, 1,2-dihydroxytetramethylene group, 1,3-dihydroxytetramethylene group, 1,4-dihydroxytetramethylene group, 2,3-dihydroxytetramethylene group, 2,4-dihydroxytetramethylene group, and 4,4-dihydroxytetramethylene group.

[0049] In formula (4-2), X ４０１ each independently represent any one of the groups represented by the following formulas (4-3) to (4-5), and the carbon atom of the ketone group in the following formulas (4-4) and (4-5) is bonded to the nitrogen atom to which R ４０５ in formula (4-2) is bonded.

[0050] In formulas (4-3) to (4-5), R ４０６ to R ４１０Each of these independently represents an organic group having a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an epoxy or sulfonyl group. Specific examples and preferred carbon numbers of organic groups having optionally substituted alkyl groups, optionally substituted alkenyl groups, and epoxy or sulfonyl groups are given in R. １２ The same examples mentioned above can be cited. Furthermore, specific examples of organic groups having a sulfonyl group and preferred carbon numbers are listed in R. ４０４ The same items mentioned above can be cited. * indicates a combination.

[0051] Hydrolyzable silanes having an organic group with a cyclic urea skeleton may be commercially available or synthesized by known methods described in International Publication No. 2011 / 102470, etc.

[0052] Specific examples of hydrolyzable silanes having an organic group with a cyclic urea skeleton include, but are not limited to, the silanes represented by the following formulas (4-1-1) to (4-1-29).

[0053] When hydrolyzing and condensing hydrolyzable silane (Si-1) to obtain polysiloxane, the proportion of hydrolyzable silane represented by formula (B) in the hydrolyzable silane (Si-1) is preferably 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 20 mol% or more. The upper limit of the proportion of hydrolyzable silane represented by formula (B) in the hydrolyzable silane (Si-1) when hydrolyzing and condensing hydrolyzable silane (Si-1) to obtain polysiloxane is not particularly limited, and the proportion may be, for example, 70 mol% or less, 55 mol% or less, or 40 mol% or less.

[0054] When hydrolyzing and condensing hydrolyzable silane (Si-1) to obtain polysiloxane, the total ratio of hydrolyzable silane represented by formula (A) and hydrolyzable silane represented by formula (B) in the hydrolyzable silane (Si-1) is not particularly limited, but is preferably 70 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and particularly preferably 90 mol% to 100 mol%.

[0055] The polysiloxane may be a hydrolysis condensate or modified product thereof of a hydrolyzable silane (Si-1) containing other silane compounds other than those exemplified above, as long as the effects of the present invention are not impaired.

[0056] As mentioned above, as the polysiloxane, a modified product can be used in which at least a portion of the silanol groups of the hydrolysis condensate are modified. For example, a modified product in which a portion of the silanol groups are modified with alcohol or a modified product protected with acetal can be used. Examples of such modified polysiloxanes include reaction products obtained by the reaction of at least a portion of the silanol groups of the hydrolysis condensate of the hydrolyzable silane with the hydroxyl groups of an alcohol, dehydration reaction products of the condensate and an alcohol, and modified products in which at least a portion of the silanol groups of the condensate are protected with acetal groups.

[0057] Monohydric alcohols can be used as the alcohol, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, and 1-hexanol. Examples include 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, and cyclohexanol. Additionally, alkoxy group-containing alcohols such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used.

[0058] The reaction between the silanol group of the hydrolysis condensate and the hydroxyl group of the alcohol is carried out by contacting the hydrolysis condensate with the alcohol and reacting at a temperature of 40 to 160°C, for example 60°C, for 0.1 to 48 hours, for example 24 hours, to obtain a modified product in which the silanol group is capped. In this case, the capping alcohol can be used as a solvent in a composition containing polysiloxane.

[0059] Further, the dehydration reaction product of a hydrolyzable condensate of hydrolyzable silane and an alcohol can be produced by reacting the hydrolysis condensate with an alcohol in the presence of an acid catalyst, capping silanol groups with the alcohol, and removing the water generated by dehydration out of the reaction system. An organic acid having an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5, can be used as the acid. Examples of the acid include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, and acetic acid; among these, benzoic acid, isobutyric acid, and acetic acid can be exemplified. Further, an acid having a boiling point of 70 to 160°C can be used as the acid, and examples thereof include trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. As described above, an acid that has either of the physical properties: an acid dissociation constant (pKa) of 4 to 5, or a boiling point of 70 to 160°C is preferable. That is, an acid with weak acidity, or an acid with strong acidity but low boiling point can be used. And either property based on the acid dissociation constant or boiling point can be used for the acid.

[0060] Acetal protection of silanol groups contained in the hydrolysis condensate can be performed using a vinyl ether, for example, a vinyl ether represented by the following formula (5), and a partial structure represented by the following formula (6) can be introduced into polysiloxane through these reactions.

[0061] In formula (5), R １ａ , R ２ａ , and R ３ａ each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ４ａ represents an alkyl group having 1 to 10 carbon atoms, and R ２ａ and R ４ａ may be bonded to each other to form a ring. Examples of the alkyl group include those exemplified above. In formula (6), R １ ', R ２ ', and R ３ ' each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ４ ' represents an alkyl group having 1 to 10 carbon atoms, R ２ ' and R ４' may be bonded to each other to form a ring. In formula (6), * indicates a bond with an adjacent atom. The adjacent atom is, for example, the oxygen atom of a siloxane bond, the oxygen atom of a silanol group, or R in formula (1). １ Examples of carbon atoms derived from this include the aforementioned examples of alkyl groups.

[0062] Examples of vinyl ethers represented by formula (5) include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, as well as cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran can be used.

[0063] The acetal protection of silanol groups can be carried out using a hydrolysis condensate, a vinyl ether, and an aprotic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, or 1,4-dioxane, with a catalyst such as pyridium p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0064] Furthermore, the capping of these silanol groups with alcohol or acetal protection may be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane, as described later.

[0065] Hydrolyzable silane hydrolysis condensates are obtained by hydrolyzing and condensing the aforementioned silane compounds (hydrolyzable silanes). The aforementioned silane compounds (hydrolyzable silanes) contain alkoxy groups, aralkyloxy groups, acyloxy groups, or halogen atoms directly bonded to a silicon atom, i.e., alkoxysilyl groups, aralkyloxysilyl groups, acyloxysilyl groups, or silyl halogenated groups (hereinafter referred to as hydrolyzable groups). For the hydrolysis of these hydrolyzable groups, typically 0.1 to 100 moles of water, for example 0.5 to 100 moles, preferably 1 to 10 moles, are used per mole of hydrolyzable groups. During hydrolysis and condensation, a hydrolysis catalyst may be used to accelerate the reaction, or the hydrolysis and condensation may be carried out without one. When a hydrolysis catalyst is used, typically 0.0001 to 10 moles of the hydrolysis catalyst, preferably 0.001 to 1 mole, can be used per mole of hydrolyzable groups. The reaction temperature for hydrolysis and condensation is usually in the range of room temperature or higher and below the reflux temperature at atmospheric pressure of the organic solvent that can be used for hydrolysis, for example, 20 to 110°C or 20 to 80°C. Hydrolysis may be complete, i.e., all hydrolyzable groups may be converted to silanol groups, or it may be partial hydrolysis, i.e., some hydrolyzable groups may remain unreacted. Examples of hydrolysis catalysts that can be used for hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0066] Examples of metal chelate compounds used as hydrolysis catalysts include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, and di -i-propoxy bis(acetylacetonate) titanium, di-n-butoxy bis(acetylacetonate) titanium, di-sec-butoxy bis(acetylacetonate) titanium, di-t-butoxy bis(acetylacetonate) titanium, monoethoxy tris(acetylacetonate) titanium, mono-n-propoxy tris(acetylacetonate) titanium, mono-i-propoxy tris(acetylacetonate) titanium, mono-n-butoxy tris(acetylacetonate) titanium, mono-sec-butoxy tris(acetylacetonate) Titanium acetone, mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethylacetoacetate) titanium Titanium acetate, di-n-propoxy-bis(ethylacetate) titanium, di-i-propoxy-bis(ethylacetate) titanium, di-n-butoxy-bis(ethylacetate) titanium, di-sec-butoxy-bis(ethylacetate) titanium, di-t-butoxy-bis(ethylacetate) titanium, monoethoxy-tris(ethylacetate) titanium, mono-n-propoxy-tris(ethylacetate) titanium, mono-i-propoxy-tris(ethylacetate) titanium,Titanium chelate compounds such as mono-n-butoxy tris(ethyl acetate) titanium, mono-sec-butoxy tris(ethyl acetate) titanium, mono-t-butoxy tris(ethyl acetate) titanium, tetrakis(ethyl acetate) titanium, mono(acetylacetonate) tris(ethyl acetate) titanium, bis(acetylacetonate) bis(ethyl acetate) titanium, tris(acetylacetonate) mono(ethyl acetate) titanium, and triethoxy mono(acetylacetonate) titanium; triethoxy mono(acetylacetonate) Zirconium triacetate, tri-n-propoxy mono(acetylacetonate) zirconium, tri-i-propoxy mono(acetylacetonate) zirconium, tri-n-butoxy mono(acetylacetonate) zirconium, tri-sec-butoxy mono(acetylacetonate) zirconium, tri-t-butoxy mono(acetylacetonate) zirconium, diethoxy bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium, di-i-propoxy bis(A Cetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-i-propoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-sec- Butoxy tris(acetylacetonate) zirconium, mono-t-butoxy tris(acetylacetonate) zirconium, tetrakis(acetylacetonate) zirconium, triethoxy mono(ethylacetoacetate) zirconium, tri-n-propoxy mono(ethylacetoacetate) zirconium, tri-i-propoxy mono(ethylacetoacetate) zirconium, tri-n-butoxy mono(ethylacetoacetate) zirconium, tri-sec-butoxy mono(ethylacetoacetate) zirconium,Tri-t-butoxy mono(ethylacetate) zirconium, diethoxy bis(ethylacetate) zirconium, di-n-propoxy bis(ethylacetate) zirconium, di-i-propoxy bis(ethylacetate) zirconium, di-n-butoxy bis(ethylacetate) zirconium, di-sec-butoxy bis(ethylacetate) zirconium, di-t-butoxy bis(ethylacetate) zirconium, monoethoxy tris(ethylacetate) zirconium, mono-n-propoxy tris(ethylacetate) zirconium, mono-i-propoxy tris(ethylacetate) zirconium, mono-n-butoxy Examples of zirconium chelate compounds include, but are not limited to, zirconium chelate compounds such as tris(ethylacetate)zirconium, mono-sec-butoxytris(ethylacetate)zirconium, mono-t-butoxytris(ethylacetate)zirconium, tetrakis(ethylacetate)zirconium, mono(acetylacetonate)tris(ethylacetate)zirconium, bis(acetylacetonate)bis(ethylacetate)zirconium, and tris(acetylacetonate)mono(ethylacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonate)aluminum and tris(ethylacetate)aluminum;

[0067] Examples of organic acids used as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, meritic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, etc.

[0068] Examples of inorganic acids used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0069] Examples of organic bases used as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0070] Examples of inorganic bases used as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0071] Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used individually or in combination of two or more.

[0072] In particular, nitric acid can be suitably used as a hydrolysis catalyst in the present invention. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, changes in the molecular weight of the hydrolysis condensate or its modified product can be suppressed. It is known that the stability of the hydrolysis condensate or its modified product in liquid depends on the pH of the solution. After diligent research, it was found that by using an appropriate amount of nitric acid, the pH of the solution becomes stable. Furthermore, as mentioned above, nitric acid can also be used when obtaining a modified product of the hydrolysis condensate, for example, when capping the silanol group with alcohol, and is therefore preferable from the viewpoint that it can contribute to both the hydrolysis and condensation of hydrolyzable silane and the alcohol capping of the hydrolysis condensate.

[0073] When hydrolysis and condensation occur, organic solvents may be used as solvents. Specific examples include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbencene, i-propylbencene, diethylbenzene, i- Aromatic hydrocarbon solvents such as butylbenzene, triethylbenzene, di-i-propylbencene, and n-amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, and 2-ethylbutanol n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, Monoalcohol solvents such as phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin;Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenthone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl Ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and other ether-based solvents;Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol Examples of ester solvents include monomethyl ether, dipropylene glycol acetate monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents include N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents include dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesultone, but are not limited to these. These solvents can be used individually or in combination of two or more. ;

[0074] After the hydrolysis and condensation reactions are complete, the reaction solution can be neutralized, either as is or diluted or concentrated, and then treated with an ion exchange resin to remove the hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation. Alternatively, before or after such treatment, by-products such as alcohol, water, and the hydrolysis catalysts used can be removed from the reaction solution by vacuum distillation or the like.

[0075] The hydrolysis condensate or its modified product (hereinafter also referred to as polysiloxane) obtained in this manner can be obtained in the form of a polysiloxane varnish dissolved in an organic solvent and can be used as is in the preparation of a composition for forming a silicon-containing resist underlayer film. That is, the reaction solution can be used as is (or diluted) in the preparation of a composition for forming a silicon-containing resist underlayer film, and in this case, the hydrolysis catalyst and by-products used for hydrolysis and condensation may remain in the reaction solution as long as they do not impair the effects of the present invention. For example, the hydrolysis catalyst and nitric acid used during alcohol capping of silanol groups may remain in the polymer varnish solution at a concentration of about 100 ppm to 5,000 ppm. The obtained polysiloxane varnish may be solvent-substituted or diluted with an appropriate solvent. The obtained polysiloxane varnish can also be decontaminated to obtain a film-forming component concentration of 100%, provided that its storage stability is not poor. The film-forming component refers to the components of the composition excluding the solvent component. The organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used in the hydrolysis and condensation reactions of the hydrolyzable silane. This dilution solvent is not particularly limited, and one or more types may be arbitrarily selected and used.

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

[0077] [Composition for forming a silicon-containing resist underlayer film] The silicon-containing resist underlayer film formation composition comprises a polysiloxane and a solvent. The silicon-containing resist underlayer film formation composition is a silicon-containing resist underlayer film formation composition for forming a plasma-treated silicon-containing resist underlayer film.

[0078] <Component [A]: Polysiloxane> The polysiloxane mentioned above is an example of polysiloxane. Note that the polysiloxane contained in the silicon-containing resist underlayer film forming composition is usually a polysiloxane that has not been plasma-treated.

[0079] <Component [B]: Solvent> The solvent contained in the silicon-containing resist underlayer film forming composition may be an organic solvent or water. As water, pure water, ultrapure water, ion-exchanged water, etc., can be used.

[0080] The organic solvent is preferably an alcohol-based solvent, more preferably an alkylene glycol monoalkyl ether that is an alcohol-based solvent, and even more preferably a propylene glycol monoalkyl ether. Since these organic solvents also act as capping agents for the silanol groups of the hydrolysis condensate, a silicon-containing resist underlayer film-forming composition can be prepared from a solution obtained by preparing [A]polysiloxane without the need for solvent substitution or the like. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether.

[0081] Other specific examples of organic solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, and 2-hydroxy-2-methyl propyl ether acetate. Ethyl propyl ethyl ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether 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 dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, acetic acid Methyl, 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,Examples of suitable organic solvents include ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. Organic solvents can be used individually or in combination of two or more.

[0082] <Component [C]: Curing catalyst> The silicon-containing resist underlayer film formation composition may or may not contain a curing catalyst.

[0083] Here, "not containing a curing catalyst" in the present invention refers to the absence of a curing catalyst in the silicon-containing resist underlayer film formation composition. However, if a curing catalyst is not detected when the silicon-containing resist underlayer film formation composition is subjected to compositional analysis (e.g., mass spectrometry, IR analysis, gas chromatography analysis, etc.), it also falls under the category of "not containing a curing catalyst" in the present invention.

[0084] As curing catalysts, ammonium salts, phosphines, phosphonium salts, sulfonium salts, etc., can be used. The salts listed below as examples of curing catalysts may be added in salt form, or they may form salts in the composition (added as separate compounds and forming salts in the system).

[0085] As an ammonium salt, formula (D-1): (In the formula, m ａ n represents an integer between 2 and 11, and n ａ represents an integer between 2 and 3, R ２１ Y represents an alkyl group, an aryl group, or an aralkyl group. － ) represents an anion. quaternary ammonium salts having a structure represented by ),

[0086] Formula (D-2): (In the formula, R ２２ , R ２３ , R ２４ and R ２５ These independently represent an alkyl group, an aryl group, or an aralkyl group, Y － represents an anion, and R ２２ , R ２３ , R ２４ , and R ２５ Each of these is bonded to a nitrogen atom. ) A quaternary ammonium salt having a structure represented by ),

[0087] Formula (D-3): (In the formula, R ２６ and R ２７ These independently represent an alkyl group, an aryl group, or an aralkyl group, Y － ) represents an anion. quaternary ammonium salts having a structure represented by ),

[0088] Formula (D-4): (In the formula, R ２８ Y represents an alkyl group, an aryl group, or an aralkyl group. － ) represents an anion. quaternary ammonium salts having a structure represented by ),

[0089] Formula (D-5): (In the formula, R ２９ and R ３０ These independently represent an alkyl group, an aryl group, or an aralkyl group, Y － ) represents an anion. quaternary ammonium salts having a structure represented by ),

[0090] Formula (D-6): (In the formula, m ａ n represents an integer between 2 and 11, and n ａ represents an integer between 2 and 3, Y － Examples of tertiary ammonium salts having a structure represented by (where represents an anion) include:

[0091] Furthermore, as a phosphonium salt, formula (D-7): (In the formula, R ３１ , R ３２ , R３３ , and R ３４ These independently represent an alkyl group, an aryl group, or an aralkyl group, Y － represents an anion, and R ３１ , R ３２ , R ３３ , and R ３４ Each of these is bonded to a phosphorus atom. Examples of quaternary phosphonium salts represented by ( ) can be given.

[0092] Furthermore, as a sulfonium salt, formula (D-8): (In the formula, R ３５ , R ３６ , and R ３７ These independently represent an alkyl group, an aryl group, or an aralkyl group, Y － represents an anion, and R ３５ , R ３６ , and R ３７ Each of these is bonded to a sulfur atom. Examples of tertiary sulfonium salts represented by ( ) can be given.

[0093] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m ａ n represents an integer between 2 and 11, and n ａ R represents an integer between 2 and 3. ２１ This represents, for example, an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. Examples include linear alkyl groups such as ethyl, propyl, and butyl groups, as well as benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl groups. Also, an anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acidic groups include those listed above.

[0094] The compound of formula (D-2) is R２２ R ２３ R ２４ R ２５ N ＋ Y － This is a quaternary ammonium salt represented by . The R of this quaternary ammonium salt ２２ , R ２３ , R ２４ and R ２５ These are, for example, C1-C18 alkyl groups such as ethyl, propyl, butyl, cyclohexyl, and cyclohexylmethyl groups, C6-C18 aryl groups such as phenyl groups, or C7-C18 aralkyl groups such as benzyl groups. Anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acidic groups include ) and others. These quaternary ammonium salts are commercially available, and examples include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0095] The compound of formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, and R ２６ and R ２７ The number of carbon atoms is, for example, 1 to 18, R ２６ and R ２７ It is preferable that the total number of carbon atoms is 7 or more. For example, R ２６ Examples of R include alkyl groups such as methyl, ethyl, and propyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups. ２７ Examples include aralkyl groups such as benzyl groups, octyl groups, and octadecyl groups. Anions (Y － ) is a chloride ion (Cl－ ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acidic groups include ). This compound can be obtained commercially, but it can also be produced by reacting imidazole compounds such as 1-methylimidazole and 1-benzylimidazole with aralkyl halides, alkyl halides, and aryl halides such as benzyl bromide, methyl bromide, and benzene bromide.

[0096] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ２８ This is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples include a butyl group, an octyl group, a benzyl group, and a lauryl group. Anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting pyridine with an alkyl halide or aryl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0097] The compound of formula (D-5) is a quaternary ammonium salt derived from substituted pyridines such as picoline, and R ２９This is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples include a methyl group, an octyl group, a lauryl group, a benzyl group, etc. ３０ For example, R is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. For example, if the compound represented by formula (D-5) is a quaternary ammonium derived from picoline, then R ３０ It is a methyl group. Anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting a substituted pyridine such as picoline with an alkyl halide or aryl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0098] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, m ａ n represents an integer between 2 and 11, and n ａ This indicates 2 or 3. Also, the anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O －Examples of acidic groups include (Y). This compound can be produced by the reaction of an amine with a weak acid such as a carboxylic acid or phenol. Examples of carboxylic acids include formic acid and acetic acid, and when formic acid is used, an anion (Y － ) is (HCOO － ) and when acetic acid is used, the anion (Y － ) is (CH ３ COO － ) Also, when phenol is used, the anion (Y － ) is (C ６ H ５ O － )

[0099] The compound of formula (D-7) is R ３１ R ３２ R ３３ R ３４ P ＋ Y － It is a quaternary phosphonium salt having the structure R ３１ , R ３２ , R ３３ , and R ３４ For example, C1-C18 alkyl groups such as ethyl, propyl, butyl, and cyclohexylmethyl groups, C6-C18 aryl groups such as phenyl groups, or C7-C18 aralkyl groups such as benzyl groups, preferably R ３１ ~R ３４ Three of the four substituents are unsubstituted or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. Also, the anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O －Examples of acidic groups include ) and others. This compound is available commercially, and examples include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritrilmonoarylphosphonium halide, or tritrilmonoalkylphosphonium halide (in all cases, the halogen atom is a chlorine atom or a bromine atom). Particularly preferred are triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, tritrilmonoarylphosphonium halides such as tritrilmonophenylphosphonium halide, and tritrilmonoalkylphosphonium halides such as tritrilmonomethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).

[0100] Furthermore, examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0101] The compound of formula (D-8) is R ３５ R ３６ R ３７ S ＋ Y － It is a tertiary sulfonium salt having the structure R ３５ , R ３６ , and R ３７For example, C1-C18 alkyl groups such as ethyl, propyl, butyl, and cyclohexylmethyl groups, C6-C18 aryl groups such as phenyl groups, or C7-C18 aralkyl groups such as benzyl groups, preferably R ３５ ~R ３７ Two of the three substituents are unsubstituted or substituted phenyl groups, such as phenyl or tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. Also, the anion (Y － ) is a chloride ion (Cl － ), bromide ions (Br － ), iodide ion (I － ) and other halide ions, as well as carboxylates (-COO － ), sulfonate (-SO ３ － ), Alcorato (-O － Examples of acid groups include maleate anions and nitrate anions. This compound is available commercially, and examples include trialkylsulfonium halides such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halide, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halide and diphenylethylsulfonium halide, triphenylsulfonium halide (in all cases, the halogen atom is a chlorine atom or a bromine atom), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmonoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate and diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. In addition, triphenylsulfonium halide and triphenylsulfonium carboxylate can be preferably used.

[0102] The content of the curing catalyst [C] in the silicon-containing resist underlayer film forming composition is not particularly limited, and may be 0.1 to 30 parts by mass, 0.5 to 25 parts by mass, or 1 to 20 parts by mass per 100 parts by mass of [A] polysiloxane.

[0103] <Component [E]: Inorganic Acid> The composition for forming a silicon-containing resist underlayer film preferably contains [E] an inorganic acid. Examples of inorganic acids include hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, and boric acid. [E] an inorganic acid may be added during the preparation of the composition for forming a silicon-containing resist underlayer film, or it may be used as a hydrolysis catalyst or during alcohol capping of silanol groups in the production of the polysiloxane described above, and the residue remaining in the polysiloxane varnish can be treated as [E] an inorganic acid.

[0104] [E] The amount of inorganic acid added (residual nitric acid) can be, for example, 0.0001% to 1% by mass, or 0.001% to 0.1% by mass, or 0.005% to 0.05% by mass, based on the total mass of the silicon-containing resist underlayer film forming composition.

[0105] <Other Additives> Various additives can be added to silicon-containing resist underlayer films depending on the application of the composition. Examples of additives include crosslinking agents, stabilizers (organic acids, water, alcohol, etc.), organic polymers, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology adjusters, adhesion aids, etc. These are known additives that are incorporated into materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, anti-reflective films, and pattern reversal films. Examples of various additives are given below, but the composition is not limited to these.

[0106] <<Stabilizers>> Stabilizers may be added for purposes such as stabilizing hydrolyzable silane hydrolysis condensates. Specific examples include organic acids, water, alcohols, or combinations thereof. Examples of organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Among these, oxalic acid and maleic acid are preferred. When organic acids are added, the amount added is 0.1 to 5.0% by mass relative to the mass of the hydrolyzable silane hydrolysis condensate. These organic acids can also function as pH adjusters. Preferred alcohols are those that easily evaporate upon heating after coating. Examples include methanol, ethanol, propanol, i-propanol, and butanol. When alcohols are added, the amount added can be 1 to 20 parts by mass per 100 parts by mass of the silicon-containing resist underlayer film forming composition.

[0107] <<Organic Polymers>> By adding organic polymers to a silicon-containing resist underlayer film formation composition, the dry etching rate (decrease in film thickness per unit time), as well as the damping coefficient and refractive index of the film formed from the composition can be adjusted. There are no particular restrictions on the organic polymer, and various organic polymers (condensation polymers and addition polymers) can be appropriately selected depending on the purpose of addition. Specific examples include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be suitably used when such functionality is required. Specific examples of such organic polymers include, but are not limited to, addition polymerization polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthyl methacrylate, anthyl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenyl maleimide as structural units, as well as condensation polymerization polymers such as phenol novolac and naphthol novolac.

[0108] When an addition polymerization polymer is used as an organic polymer, the polymer may be either a homopolymer or a copolymer. Addition polymerization monomers are used in the production of addition polymerization polymers, and specific examples of such addition polymerization monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0109] Specific examples of acrylic acid ester compounds include, but are not limited to, methyl acrylate, ethyl acrylate, n-hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthyl methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate.

[0110] Specific examples of methacrylic acid ester compounds include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthyl methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate.

[0111] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-antrylcrylamide.

[0112] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-antlylmethacrylamide.

[0113] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

[0114] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0115] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0116] When a condensation polymer is used as an organic polymer, examples of such polymers include condensation polymers of glycol compounds and dicarboxylic acid compounds. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, and butylene glycol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Other examples include, but are not limited to, polyesters, polyamides, and polyimides such as polypyromellitrimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate. If the organic polymer contains a hydroxyl group, this hydroxyl group can undergo a crosslinking reaction with hydrolysis condensates, etc.

[0117] The weight-average molecular weight of an organic polymer can typically be between 1,000 and 1,000,000. When incorporating an organic polymer, in order to fully obtain the functional effects of the polymer while suppressing precipitation in the composition, its weight-average molecular weight can be set to, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000. Such organic polymers may be used individually or in combination of two or more.

[0118] When a silicon-containing resist underlayer film forming composition contains an organic polymer, the amount of the organic polymer cannot be specified in general terms as it is determined appropriately considering the function of the organic polymer, etc. However, it can usually be in the range of 1 to 200% by mass relative to the mass of [A]polysiloxane. From the viewpoint of suppressing precipitation in the composition, for example, it can be 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less. From the viewpoint of obtaining the full effect, for example, it can be 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0119] <<Acid Generator>> Examples of acid generators include thermal acid generators and photoacid generators, with photoacid generators being preferred. Examples of photoacid generators include, but are not limited to, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. Depending on the type, photoacid generators, such as carboxylates like nitrates and maleates in the onium salt compounds described later, and hydrochlorides, can also function as curing catalysts. Examples of thermal acid generators include, but are not limited to, tetramethylammonium nitrate.

[0120] Specific examples of onium salt compounds include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride.

[0121] Specific examples of sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0122] Specific examples of disulfonyl diazomethane compounds include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0123] When a silicon-containing resist underlayer film forming composition contains an acid generator, the amount of the acid generator cannot be specified in general terms as it is determined appropriately considering the type of acid generator, etc. However, it is usually in the range of 0.01 to 5% by mass relative to the mass of [A]polysiloxane, preferably 3% by mass or less, more preferably 1% by mass or less, from the viewpoint of suppressing the precipitation of the acid generator in the composition, and preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of obtaining the full effect. The acid generator can be used alone or in combination of two or more types, and a photoacid generator and a thermoacid generator may be used in combination.

[0124] <<Surfactants>> Surfactants are effective in suppressing the occurrence of pinholes, striations, etc., when a silicon-containing resist underlayer film formation composition is applied to a substrate. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, and UV-curable surfactants. More specifically, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate. Nonionic surfactants such as oleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters; trade names F-Top® EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.)); trade names Megafac® F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation); Florard F Examples of fluorine-based surfactants include C430, FC431 (manufactured by 3M Japan Ltd.), Asahi Guard® AG710 (manufactured by AGC Inc.), Surflon® S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these. Surfactants can be used individually or in combination of two or more.

[0125] If the silicon-containing resist underlayer film forming composition contains a surfactant, its content is usually 0.0001 to 5% by mass, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass, relative to the mass of [A]polysiloxane.

[0126] <<Rheology Modifiers>> Rheology modifiers are mainly added to improve the fluidity of compositions for forming a silicon-containing resist underlayer film, and in particular during the baking process, to improve the uniformity of the film thickness formed and to enhance the filling of the composition into the holes. Specific examples include phthalate derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate; adipic acid derivatives such as dinormal butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyl decyl adipate; maleic acid derivatives such as dinormal butyl malate, diethyl malate, and dinonyl malate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. When these rheology modifiers are used, the amount added is usually less than 30% by mass of the total film-forming components of the silicon-containing resist underlayer film-forming composition.

[0127] <<Adhesion Aids>> Adhesion aids are added primarily to improve adhesion to the substrate or adjacent layers (e.g., surface modification layers). Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; and γ-chloropropyltrimethoxysilane. Examples of adhesive aids include other silanes such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. When these adhesive aids are used, the amount added is usually less than 5% by mass, preferably less than 2% by mass, relative to the film-forming component of the silicon-containing resist underlayer film-forming composition.

[0128] <<pH Adjusting Agents>> In addition to the organic acids listed above as stabilizers, other acids having one or more carboxylic acid groups can be used as pH adjusting agents. When pH adjusting agents are used, the amount added may be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass per 100 parts by mass of [A] polysiloxane.

[0129] <<Metal Oxides>> Examples of metal oxides that can be added to silicon-containing resist underlayer films include, but are not limited to, oxides of one or more metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and metalloids such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0130] The concentration of the film-forming component in the silicon-containing resist underlayer film-forming composition can be, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, or 0.5 to 20.0% by mass, relative to the total mass of the composition. The content of [A]polysiloxane in the film-forming component is usually 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and still more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the additives described later. Furthermore, the silicon-containing resist underlayer film-forming composition preferably has a pH of 2 to 5, and more preferably a pH of 3 to 4.

[0131] In the present invention, the silicon-containing resist underlayer film forming composition may be filtered using a sub-micrometer-order filter or the like during the manufacturing process or after all components have been mixed. The material of the filter used is not limited, but for example, a nylon filter or a fluororesin filter can be used.

[0132] The silicon-containing resist underlayer film formation composition of the present invention can be suitably used as an underlayer film formation composition for use in lithography processes.

[0133] The silicon-containing resist underlayer film formation composition of the present invention is preferably used in EUV lithography.

[0134] [Method for manufacturing a plasma-treated silicon-containing resist underlayer film] The method for manufacturing a plasma-treated silicon-containing resist underlayer film includes, for example, a coating step, a firing step, and a plasma treatment step. The coating step is a step of applying a silicon-containing resist underlayer film forming composition onto a semiconductor substrate or onto an organic underlayer film disposed on a semiconductor substrate to obtain a coated film. The firing step is a step of firing (heating) the coated film to obtain a silicon-containing resist underlayer film before plasma treatment. The plasma treatment step is a step of performing plasma treatment on the silicon-containing resist underlayer film before plasma treatment to obtain a plasma-treated silicon-containing resist underlayer film.

[0135] A plasma-treated silicon-containing resist underlayer film can be formed, for example, as follows, using the silicon-containing resist underlayer film forming composition according to the present invention.

[0136] Semiconductor substrates used in the manufacture of semiconductor devices (e.g., silicon wafer substrates, silicon dioxide coated substrates (SiO ２A silicon-containing resist underlayer film forming composition according to one embodiment of the present invention is applied to a substrate (such as a semiconductor substrate), silicon nitride substrate (SiN substrate), silicon oxide nitride substrate (SiON substrate), titanium nitride substrate (TiN substrate), tungsten substrate (W substrate), glass substrate, ITO substrate, polyimide substrate, and low-dielectric material (low-k material) coated substrate, or to an organic underlayer film disposed on a semiconductor substrate, by an appropriate coating method such as a spinner or coater, and then fired using a heating means such as a hot plate to form a silicon-containing resist underlayer film before plasma treatment. The firing conditions are appropriately selected from a firing temperature of 80°C to 800°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 500°C and the firing time is 0.5 to 2 minutes. Air may be used as the atmospheric gas during firing, or an inert gas such as nitrogen or argon may be used. In one embodiment, it is particularly preferable that the oxygen concentration is 1% or less. The thickness of the silicon-containing resist underlayer film formed here can be, for example, 1 to 10,000 nm, 1 to 1,000 nm, 5 to 1,000 nm, 10 to 500 nm, 20 to 400 nm, or 30 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of the quartz imprint mold (mold replica) can be fabricated.

[0137] There are no particular restrictions on the organic underlayer film placed on the semiconductor substrate; it can be arbitrarily selected and used from those conventionally used in lithography processes.

[0138] Plasma irradiation can be performed using known methods. For example, in Japanese Patent No. 5746670, "Improvement of the wiggling profile of spin-on carbon hard mask by H ２ One example is the method described in "Plasma Treatment" (J. Vac. Sci. Technol. B26(1), Jan / Feb 2008, pp. 67-71).

[0139] For plasma treatment conditions, for example, the source power is preferably 0 to 20,000 W, more preferably 1 to 20,000 W, and even more preferably 1 to 5,000 W. The bias voltage (bias power) is preferably 0 to 20,000 V, more preferably 1 to 20,000 V, and even more preferably 1 to 5,000 V. The pressure is preferably 0 to 20,000 mTorr, and more preferably 0 to 10,000 mTorr. The gas supply flow rate is preferably 1 to 5,000 sccm. The temperature is preferably -100 to 600°C, and more preferably -10 to 300°C. The time is preferably 1 to 1,200 seconds.

[0140] For example, the gas atmosphere used during plasma processing is N ２ NF ３ , H ２ Examples include noble gases such as He, and fluorocarbons; more preferably, He, Ar, N ２ , Ne, NF ３ , H ２ CF ４ CHF ３ ,CH ２ F ２ ,CH ３ F, C ４ F ６ , C ４ F ８ These are some examples. These gases may also be used in mixtures of two or more types.

[0141] The irradiation device is not particularly limited as long as it is capable of plasma irradiation, but for example, the Teilius SP and Tactras Vigus manufactured by Tokyo Electron Corporation can be used. It is possible to select the device and set the conditions in order to more significantly achieve the effects of the present invention.

[0142] By subjecting the formed silicon-containing resist underlayer film to plasma treatment, a plasma-treated silicon-containing resist underlayer film according to one aspect of the present invention can be obtained. Because the plasma-treated silicon-containing resist underlayer film has undergone plasma treatment, it exhibits changes in film properties compared to the silicon-containing resist underlayer film before plasma treatment. Plasma treatment can, for example, improve the etching resistance of the silicon-containing resist underlayer film and increase the hardness and density of the film. Here, the film thickness of the plasma-treated silicon-containing resist underlayer film is, for example, 1 to 10,000 nm, or 1 to 1,000 nm, or 5 to 1,000 nm, or 10 to 500 nm, or 20 to 400 nm, or 30 to 300 nm. The range in which film properties such as etching resistance change due to plasma treatment is, for example, the surface of the silicon-containing resist underlayer film, or from the surface to 1 nm, or from the surface to 5 nm, or from the surface to 20 nm, or from the surface to 100 nm, or from the surface to the bottom, using the film after plasma treatment as a reference. The film properties of the silicon-containing resist underlayer can be continuously changed in the film thickness direction.

[0143] The film density of the plasma-treated silicon-containing resist underlayer film at room temperature (e.g., 25°C) is 1.8 g / cm³. ３ The above is preferable, specifically 1.83 g / cm³. ３ The above is more preferable, 1.85 g / cm³ ３ The above is even more preferable. There is no particular upper limit to the membrane density, but the membrane density is, for example, 2.5 g / cm³. ３ The following applies: The film density of the plasma-treated silicon-containing resist underlayer film is determined, for example, using the measuring apparatus described in the examples.

[0144] Furthermore, by applying a silicon-containing resist underlayer film forming composition, which is one aspect of the present invention, to a semiconductor substrate having stepped portions and portions without steps (a so-called stepped substrate) and firing it, the step difference between the stepped portions and the portions without steps can be reduced.

[0145] The silicon-containing resist underlayer film can be improved in etching resistance by plasma treatment. ２ or CF ４ The O2 of the plasma-treated silicon-containing resist underlayer film after plasma treatment, relative to the etching rate. ２ or CF ４ The etching rate is preferably 0.95 times or less, more preferably 0.9 times or less, and even more preferably 0.85 times or less. The lower limit of the etching rate of the silicon-containing resist underlayer film after plasma treatment relative to the etching rate of the silicon-containing resist underlayer film before plasma treatment is not particularly limited, but for example, it is 0.05 times. The etching rate of the silicon-containing resist underlayer film before plasma treatment and the etching rate of the silicon-containing resist underlayer film after plasma treatment can be determined, for example, by the method described in the examples.

[0146] The gas used for plasma treatment preferably contains at least a noble gas, nitrogen, and hydrogen. Examples of noble gases include helium, neon, and argon.

[0147] A method for manufacturing a plasma-treated silicon-containing resist underlayer film according to one aspect of the present invention preferably further includes a step of firing the semiconductor substrate on which the plasma-treated silicon-containing resist underlayer film is formed at 400°C or higher after plasma treatment.

[0148] [Laminate] The laminate of the present invention comprises a semiconductor substrate and a plasma-treated silicon-containing resist underlayer film of the present invention. The laminate may also include an organic underlayer film. The organic underlayer film is disposed, for example, between the semiconductor substrate and the plasma-treated silicon-containing resist underlayer film.

[0149] The semiconductor substrate is not particularly limited as long as it is a substrate used in the manufacture of semiconductor devices, for example, a silicon wafer substrate, a silicon dioxide coated substrate (SiO ２Examples include substrates, silicon nitride substrates (SiN substrates), silicon oxide nitride substrates (SiON substrates), titanium nitride substrates (TiN substrates), tungsten substrates (W substrates), glass substrates, ITO substrates, polyimide substrates, and substrates coated with low dielectric constant materials (low-k materials).

[0150] The thickness of the plasma-treated silicon-containing resist underlayer film is, for example, 1 to 10,000 nm, or 1 to 1,000 nm, or 5 to 1,000 nm, or 10 to 500 nm, or 20 to 400 nm, or 30 to 300 nm.

[0151] One example of a method for forming a plasma-treated silicon-containing resist underlayer film is the method for manufacturing a plasma-treated silicon-containing resist underlayer film described above.

[0152] The following describes an example of the structure of the laminate using diagrams. Figure 1 is a schematic cross-sectional view of an example of a laminate. The laminate in Figure 1 comprises a semiconductor substrate 1 and a plasma-treated silicon-containing resist underlayer film 2.

[0153] Figure 2 is a schematic cross-sectional view of another example of a laminate. The laminate in Figure 2 comprises a semiconductor substrate 1, an organic underlayer film 3, and a plasma-treated silicon-containing resist underlayer film 2 in that order.

[0154] Figure 3 is a schematic cross-sectional view of another example of a laminate. The laminate in Figure 3 comprises, in this order, a semiconductor substrate 1, an organic underlayer film 3, a plasma-treated silicon-containing resist underlayer film 2, and a resist film 4.

[0155] Figure 4 is a schematic cross-sectional view of another example of a laminate. The laminate in Figure 4 comprises, in this order, a semiconductor substrate 1, an organic underlayer film 3, a plasma-treated silicon-containing resist underlayer film 2, an organic underlayer film 5, and a resist film 4.

[0156] Figure 5 is a schematic cross-sectional view of another example of a laminate. The laminate in Figure 5 comprises, in this order, a semiconductor substrate 1, an organic underlayer film 3, a plasma-treated silicon-containing resist underlayer film 2, a surface modification layer 6, and a resist film 4.

[0157] Figure 6 is a schematic cross-sectional view of another example of a laminate. The laminate in Figure 6 comprises, in this order, a semiconductor substrate 1, a plasma-treated silicon-containing resist underlayer film 2, an organic underlayer film 5, and a resist film 4.

[0158] The surface modification layer is a thin layer, and an example of the surface modification layer described in International Publication No. 2024 / 009993 is an example of this layer.

[0159] [Method for manufacturing a semiconductor device and method for forming a pattern] A method for manufacturing a semiconductor device according to one aspect of the present invention includes the steps of: forming an organic underlayer film on a semiconductor substrate; forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition of the present invention (step 1-1); forming a plasma-treated silicon-containing resist underlayer film by plasma-treating the silicon-containing resist underlayer film (step 1-2); and forming a resist film on the plasma-treated silicon-containing resist underlayer film (step 1-3).

[0160] The pattern formation method of the present invention includes, for example, the steps of: forming an organic underlayer film on a semiconductor substrate; applying the silicon-containing resist underlayer film formation composition of the present invention onto the organic underlayer film and firing it to form a silicon-containing resist underlayer film (step 2-1); forming a plasma-treated silicon-containing resist underlayer film by plasma-treating the silicon-containing resist underlayer film (step 2-2); forming a resist film on the plasma-treated silicon-containing resist underlayer film (step 2-3); and exposing and developing the resist film to obtain a resist pattern (step 2-4).

[0161] The pattern formation method may further include the steps of: etching a plasma-treated silicon-containing resist underlayer film using a resist pattern as a mask; and etching an organic underlayer film using the patterned plasma-treated silicon-containing resist underlayer film as a mask.

[0162] Hereinafter, as an embodiment of the present invention, a pattern formation method and a method for manufacturing a semiconductor device using the silicon-containing resist underlayer film formation composition of the present invention will be described.

[0163] Steps 1-1 and 1-2 described above can be carried out, for example, by the method described above for manufacturing a plasma-treated silicon-containing resist underlayer film. Steps 2-1 and 2-2 described above can be carried out, for example, by the method described above for manufacturing a plasma-treated silicon-containing resist underlayer film.

[0164] In one aspect of the present invention, an organic underlayer film is formed on a substrate, and then a silicon-containing resist underlayer film is formed on top of it. However, in some cases, the organic underlayer film may not be provided.

[0165] In steps 1-3 and 2-3, a layer of photoresist material (resist film) is formed on the plasma-treated silicon-containing resist underlayer film. The resist film can be formed by a well-known method, that is, for example, by coating a coating-type resist material (resist film forming composition) onto the silicon-containing resist underlayer film and firing it. The thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0166] The photoresist material used for the resist film formed on the plasma-treated silicon-containing resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative-type and positive-type photoresist materials can be used. Examples include a positive-type photoresist material consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist material consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, a chemically amplified photoresist material consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist material, an alkali-soluble binder and a photoacid generator, and a chemically amplified photoresist material consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate, a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist material and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (manufactured by Cypree), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), AR2772JN (manufactured by JSR Corporation), and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, examples include fluorine-containing atom polymer-based photoresist materials, such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0167] Furthermore, instead of a photoresist film, an electron beam lithography resist film (also referred to as an electron beam resist film) or an EUV lithography resist film (also referred to as an EUV resist film) can be used as the resist film formed on the plasma-treated silicon-containing resist underlayer film.

[0168] For forming electron beam resist films, both negative and positive materials can be used as electron beam resist materials. Specific examples include: chemically amplified resist materials consisting of an acid generator and a binder having a group that decomposes with acid to change the alkali dissolution rate; chemically amplified resist materials consisting of an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes with acid to change the alkali dissolution rate of the resist material; chemically amplified resist materials consisting of an acid generator, a binder having a group that decomposes with acid to change the alkali dissolution rate, and a low-molecular-weight compound that decomposes with acid to change the alkali dissolution rate of the resist material; non-chemically amplified resist materials consisting of a binder having a group that decomposes with electron beams to change the alkali dissolution rate; and non-chemically amplified resist materials consisting of a binder having a portion that is cut by an electron beam to change the alkali dissolution rate. When using these electron beam resist materials, a resist film pattern can be formed in the same way as when using a photoresist material with an electron beam as the irradiation source. Furthermore, methacrylate resin-based resist materials can be used as EUV resist materials for forming EUV resist films.

[0169] The resist material may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MORs), and a typical example is a tin oxide-based resist. An example of a metal oxide resist material is a coating composition containing a metal oxo-hydroxo network having an organic ligand via a metal-carbon bond and / or metal-carboxylate bond, as described in Japanese Patent Application Publication No. 2019-113855. An example of a metal-containing resist uses a peroxo ligand as a radiosensitizing stabilizing ligand. Details of peroxo-based metal oxo-hydroxo compounds are described in the patent document described in paragraph

[0011] of Publication No. 2019-532489, for example. Examples of such patent documents include U.S. Patent No. 9,176,377B2, U.S. Patent Application Publication No. 2013 / 0224652A1, U.S. Patent No. 9,310,684B2, U.S. Patent Application Publication No. 2016 / 0116839A1, and U.S. Patent Application Publication No. 15 / 291738.

[0170] In step 2-4, the resist film formed on the upper layer of the plasma-treated silicon-containing resist underlayer film is exposed through a predetermined mask (reticle). For exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), and F ２Excimer lasers (wavelength 157 nm), EUV (wavelength 13.5 nm), electron beams, etc., can be used. After exposure, post-exposure baking can be performed as needed. Post-exposure baking is performed under conditions appropriately selected from heating temperatures of 70°C to 150°C and heating times of 0.3 minutes to 10 minutes. Next, development is performed with a developer (e.g., an alkaline developer). This removes the photoresist film from the exposed areas, for example, when a positive-type photoresist film is used, and forms a photoresist film pattern. Examples of developers (alkaline developers) include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants can be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50°C and a development time of 10 to 600 seconds.

[0171] The present invention will be described in more detail below with reference to synthesis examples and embodiments, but the present invention is not limited to the embodiments described below.

[0172] The apparatus and conditions used for analyzing the physical properties of the samples in the examples are as follows: (1) Molecular weight measurement The molecular weight of the polysiloxane used in the present invention is the molecular weight obtained in polystyrene equivalent by GPC analysis. The GPC measurement conditions were, for example, a GPC apparatus (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product name Shodex® KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow rate) of 1.0 mL / min, and a standard sample of polystyrene (manufactured by Showa Denko K.K.).

[0173] [1] Synthesis of polymers (hydrolyzed condensates) (Synthesis Example 1) 8.41 g of tetraethoxysilane, 6.48 g of methyltriethoxysilane, 1.04 g of 5-(triethoxysilyl)bicyclo[2.2.1]hept-2-ene, and 23.9 g of propylene glycol monoethyl ether were placed in a 500 mL flask, and 10.1 g of aqueous nitric acid solution (0.2 mol / L) was added dropwise while stirring the resulting mixture with a magnetic stirrer. After addition, the flask was transferred to an oil bath prepared at 60°C and the mixture was reacted for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolyzed condensate (polymer) solution. Propylene glycol monoethyl ether was further added to the solution, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with propylene glycol monoethyl ether as the solvent ratio, and the solution was filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was 2681 in polystyrene equivalents according to GPC.

[0174]

[0175] (Synthesis Example 2) 10.4 g of tetraethoxysilane, 3.18 g of methyltriethoxysilane, 0.71 g of phenyltrimethoxysilane, and 21.5 g of propylene glycol monoethyl ether were placed in a 500 mL flask, and 9.01 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise to the resulting mixture while stirring with a magnetic stirrer. After addition, the flask was transferred to an oil bath prepared at 60°C and reacted for 20 hours. Subsequently, the reaction by-products methanol, ethanol, and water were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was further added to the solution, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with propylene glycol monoethyl ether as the solvent ratio, and the solution was filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was 2440 in polystyrene equivalent by GPC.

[0176]

[0177] (Synthesis Example 3) 11.2 g of tetraethoxysilane, 2.83 g of vinyltrimethoxysilane, 0.76 g of phenyltrimethoxysilane, and 21.5 g of propylene glycol monoethyl ether were placed in a 500 mL flask, and 9.01 g of aqueous nitric acid solution (0.2 mol / L) was added dropwise while stirring the resulting mixture with a magnetic stirrer. After addition, the flask was transferred to an oil bath prepared at 60°C and reacted for 20 hours. Subsequently, the reaction by-products methanol, ethanol, and water were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was further added to the solution, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with propylene glycol monoethyl ether as the solvent ratio, and the solution was filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was 2109 in polystyrene equivalents according to GPC.

[0178]

[0179] (Synthesis Example 4) 11.2 g of tetraethoxysilane, 3.41 g of methyltriethoxysilane, 0.83 g of cyanoethyltriethoxysilane, and 23.1 g of propylene glycol monoethyl ether were placed in a 500 mL flask, and 9.64 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise while stirring the resulting mixture with a magnetic stirrer. After addition, the flask was transferred to an oil bath prepared at 60°C and the mixture was reacted for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was further added to the solution, and the concentration was adjusted to 20 mass percent in terms of solid residue at 150°C, with propylene glycol monoethyl ether as the solvent ratio, and the solution was filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was 2220 in polystyrene equivalents according to GPC.

[0180]

[0181] (Synthesis Example 5) 11.1 g of tetraethoxysilane, 3.27 g of methyltriethoxysilane, 1.58 g of 3-(triethoxysilylpropyl)diallyl isocyanurate, and 24.0 g of propylene glycol monoethyl ether were placed in a 500 mL flask. While stirring the mixed solution with a magnetic stirrer, 0.16 g of [3-(N,N-dimethylamino)propyl]trimethoxysilane and 9.63 g of aqueous nitric acid solution (0.2 mol / L) were added dropwise. After addition, the flask was transferred to an oil bath prepared at 60°C and reacted for 20 hours. Subsequently, the reaction by-products, methanol, ethanol, and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was added to the solution, and the concentration was adjusted to 20% by mass in terms of solid residue at 150°C, with 100% propylene glycol monoethyl ether as the solvent ratio. The solution was then filtered through a nylon filter (pore size 0.1 μm). The resulting polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was 3133 in terms of polystyrene as calculated by GPC.

[0182]

[0183] [2] Preparation of compositions for forming silicon-containing resist underlayer films The polymers, additives, and solvents obtained in the above synthesis example were mixed in the proportions shown in Table 1 and filtered through a 0.1 μm fluororesin filter to prepare silicon-containing resist underlayer films (coating solutions). The amounts of each additive in Table 1 are shown in parts by mass. Although the polymer was prepared as a solution containing the condensate obtained in the synthesis example, the polymer addition proportions in Table 1 represent the amount of the polymer itself added, not the amount of polymer solution added.

[0184] The meanings of the abbreviations in Table 1 are as follows: <Additive 1> MA: Maleic acid <Additive 2> TPSNO3: Triphenylsulfonium nitrate <Solvent> PGME: Propylene glycol monomethyl ether PGEE: Propylene glycol monoethyl ether DIW: Deionized water

[0185]

[0186] [3] Evaluation of film density by X-ray reflectivity A silicon-containing resist underlayer film (film thickness 50 nm) was formed by spin-coating coating solution 1 onto a silicon wafer and heating it on a hot plate at 220°C for 1 minute. The fabricated silicon-containing resist underlayer film was subjected to plasma irradiation using an etcher manufactured by Tokyo Electron Ltd. to modify the silicon-containing resist underlayer film. Using the same procedure, silicon-containing resist underlayer films modified by plasma treatment were formed using coating solutions 2 to 5. The film density of each silicon-containing resist underlayer film after plasma irradiation was measured using an X-ray reflectivity measuring device (Smart Lab, manufactured by RIGAKU). The measurement conditions are as follows: [Measurement conditions] Voltage: 45 kV Current: 200 mA Scan range: 0.2-3° Step: 0.0048° The obtained results are shown in Table 2 as Examples 1 to 5.

[0187] Each of the coating solutions 1 to 5 was spin-coated onto a silicon wafer, and a silicon-containing resist underlayer film (thickness 50 nm) was formed by heating on a hot plate at 220°C for 1 minute. The film density of each silicon-containing resist underlayer film was measured using an X-ray reflectivity analyzer (Smart Lab, RIGAKU Corporation). The results obtained are shown in Table 2 as Comparative Examples 1 to 5.

[0188] [4] Evaluation of dry etching rate A silicon-containing resist underlayer film (thickness 50 nm) was formed by spin-coating coating solution 1 onto a silicon wafer and heating it on a hot plate at 220°C for 1 minute. The fabricated silicon-containing resist underlayer film was subjected to plasma irradiation using an etcher manufactured by Tokyo Electron Ltd. to modify the silicon-containing resist underlayer film. Using the same procedure, silicon-containing resist underlayer films modified by plasma treatment were formed using coating solutions 2 to 5. Each silicon-containing resist underlayer film after plasma irradiation was subjected to reactive ion etching using a reactive ion etching apparatus (RIE-10NL manufactured by Samco). ２ Dry etching speed and CF ４Dry etching rate measurements were performed. The etching conditions are as follows: [Etching conditions] Gas type: Oxygen (O ２ ), tetrafluorocarbon (CF ４ ) Processing time: 30 seconds. The results obtained are shown in Table 2 as Examples 1 to 5. The change in etching rate shown here is the value calculated by (etching rate after plasma treatment) / (etching rate without plasma treatment) when using the same coating solution.

[0189] The etching rate without plasma treatment was determined as follows: Each of the coating solutions 1 to 5 was spin-coated onto a silicon wafer, and a silicon-containing resist underlayer film (thickness 50 nm) was formed by heating on a hot plate at 220°C for 1 minute. Each silicon-containing resist underlayer film was then etched using a reactive ion etching apparatus (Samco RIE-10NL). ２ Dry etching speed and CF ４ Dry etching rate measurements were performed. The etching conditions are as follows: [Etching conditions] Gas type: Oxygen (O ２ ), tetrafluorocarbon (CF ４ Processing time: 30 seconds

[0190]

[0191] [5] Formation of resist patterns by EUV exposure A silicon wafer was spin-coated with coating solution 1 and heated on a hot plate at 220°C for 1 minute to form a silicon-containing resist underlayer film (thickness 50 nm). The fabricated silicon-containing resist underlayer film was subjected to plasma irradiation using an etcher manufactured by Tokyo Electron Ltd. to modify the silicon-containing resist underlayer film. Using the same procedure, a silicon-containing resist underlayer film modified by plasma treatment was formed using coating solution 5. Subsequently, a metal resist (metal oxide resist) solution was applied to the modified silicon-containing resist underlayer film and heated at 100°C for 60 seconds to form a metal resist film. Then, exposure was performed using an ASML EUV exposure apparatus (NXE3400) under the conditions of NA = 0.33 and σ = 0.595 / 0.817. After exposure, post-exposure heating (PEB) was performed at 180°C for 60 seconds, followed by cooling to room temperature on a cooling plate. Development and rinsing were then performed with an organic solvent developer. Subsequently, heating was performed at 250°C for 60 seconds to form a resist pattern. For each obtained pattern, the feasibility of forming a 28 nm pitch, 14 nm line pattern was evaluated by observing the pattern shape using a Hitachi High-Technologies Corporation CG4100. In the pattern shape observation, patterns that achieved the desired line pattern were evaluated as "good," while patterns that were unresolved or distorted were evaluated as "poor." The results are shown in Table 3.

[0192]

[0193] As described above, when a plasma-treated silicon-containing resist underlayer film is used, a silicon-containing resist underlayer film with high film density and excellent etching selectivity can be obtained.

[0194] 1. Semiconductor substrate 2. Plasma-treated silicon-containing resist underlayer film 3. Organic underlayer film 4. Resist film 5. Organic underlayer film 6. Surface modification layer

Claims

1. A plasma-treated silicon-containing resist underlayer film containing polysiloxane.

2. The membrane density is 1.8 g / cm³. ３ The plasma-treated silicon-containing resist underlayer film according to claim 1.

3. O of the silicon-containing resist underlayer film before plasma treatment ２ or CF ４ In relation to the etching rate, the O of the plasma-treated silicon-containing resist underlayer film after plasma treatment ２ or CF ４ The plasma-treated silicon-containing resist underlayer film according to claim 1, wherein the etching rate is 0.95 times or less.

4. A silicon-containing resist underlayer film forming composition for forming a plasma-treated silicon-containing resist underlayer film according to claim 1, comprising the polysiloxane and a solvent.

5. The silicon-containing resist underlayer film forming composition according to claim 4, wherein the polysiloxane is a hydrolysis condensate of a hydrolyzable silane (Si-1), and the hydrolyzable silane (Si-1) contains 30 mol% or more of a hydrolyzable silane represented by the following formula (A). (In formula (A), R is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.) 6. The silicon-containing resist underlayer film forming composition according to claim 4, wherein the polysiloxane is a hydrolysis condensate of a hydrolyzable silane (Si-1), and the hydrolyzable silane (Si-1) includes a hydrolyzable silane represented by the following formula (B). (In formula (B), R １１ R is a group that bonds to a silicon atom and independently represents an organic group having 1 to 45 carbon atoms. １２ (where a is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer from 1 to 3.) 7. The silicon-containing resist underlayer film forming composition according to claim 4, wherein the polysiloxane has at least one of a double bond and a triple bond.

8. The silicon-containing resist underlayer film forming composition according to claim 4, wherein the polysiloxane comprises a polysiloxane modified product in which at least a portion of the silanol groups are alcohol-modified or acetal-protected.

9. The silicon-containing resist underlayer film forming composition according to claim 4, wherein the solvent comprises an alcohol-based solvent or water.

10. The silicon-containing resist underlayer film forming composition according to claim 9, wherein the alcohol-based solvent comprises a propylene glycol monoalkyl ether.

11. The silicon-containing resist underlayer film forming composition according to claim 4, comprising an inorganic acid.

12. The resist underlayer film forming composition according to claim 11, wherein the inorganic acid comprises hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, or boric acid.

13. A silicon-containing resist underlayer film formation composition according to claim 4, used in EUV lithography.

14. A laminate comprising a semiconductor substrate and a plasma-treated silicon-containing resist underlayer film according to any one of claims 1 to 3.

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