JP7564503B2 - Method for producing silicon-containing resist underlayer film - Google Patents

Description

The present invention relates to a method for producing a silicon-containing resist underlayer film.

Conventionally, in the manufacture of semiconductor devices, microfabrication by lithography using photoresist has been carried out. The microfabrication is a processing method in which a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, and the thin film is irradiated with active light such as ultraviolet light through a mask pattern on which a semiconductor device pattern is drawn, developed, and the substrate is etched using the obtained photoresist pattern as a protective film, thereby forming fine projections and recesses on the substrate surface corresponding to the pattern.
In recent years, the integration density of semiconductor devices has increased, and the wavelength of the active light used has also tended to be shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). As the wavelength of the active light has become shorter, the effect of the reflection of the active light from the semiconductor substrate has become a major problem, and a method of providing 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 used.

As the underlayer film between the semiconductor substrate and the photoresist, a film known as a hard mask containing metal elements such as silicon and titanium is used. In this case, since there is a large difference in the components of the resist and the hard mask, the speed at which they are removed by dry etching depends greatly on the type of gas used in dry etching. By appropriately selecting the type of gas, the hard mask can be removed by dry etching and patterned without a significant decrease in the thickness of the photoresist. Thus, in recent years, in the manufacture of semiconductor devices, a resist underlayer film has come to be placed between the semiconductor substrate and the photoresist to achieve various effects, including an anti-reflection effect.

In recent years, with the miniaturization of cutting-edge semiconductor devices, a three-layer process is being used in which an organic resist underlayer film is layered on a substrate, a silicon-containing resist underlayer film is layered on top of that, and a resist layer is layered on top of that.Since damage to the substrate by dry etching can be expected in the normal three-layer process, a process for removing the silicon-containing resist underlayer film using a wet method is desired.
For example, there has been a proposal to use an anti-reflective coating material containing a titanium siloxane resin having a crosslinkable organic group, and to remove the film obtained from the material by wet stripping (Patent Document 1, etc.).
In the manufacture of semiconductor devices, for example, ion implantation is employed, in which impurity ions that impart n-type or p-type conductivity to a semiconductor substrate are introduced using a photoresist pattern as a mask. In this case, the impurity ions are implanted into the semiconductor substrate directly or through a thin film formed on the surface of the semiconductor substrate using an ion implantation device (ion doping device). Thereafter, the photoresist pattern is removed by, for example, wet cleaning with sulfuric acid-hydrogen peroxide solution, wet cleaning with ammonia water-hydrogen peroxide solution, or ashing, and a step of removing the silicon-containing resist underlayer film by a wet method is also desired.

In addition, since the depth of focus decreases with the shortening of the exposure wavelength, it is necessary to improve the planarization of the coating formed on the substrate. In order to manufacture semiconductor devices that require finer designs, a planarization technique on the substrate is important, and for example, a method of forming a resist underlayer film formed under the resist by photocuring has been disclosed.
For example, a resist underlayer film-forming composition containing a silicon-based compound having a cationic polymerizable reactive group such as an epoxy group or a vinyl group, a photocationic polymerization initiator, and a photoradical polymerization initiator has been disclosed (see Patent Document 2).

JP 2007-163846 A International Publication No. 2007/066597

The object of the present invention is to provide a method for producing a silicon-containing resist underlayer film that can be used in the manufacture of semiconductor devices and that can be removed by a wet method using a chemical solution, particularly an aqueous sulfuric acid/hydrogen peroxide solution (SPM (a mixed aqueous solution of sulfuric acid and hydrogen peroxide)), even after oxygen gas etching has been performed.

As a result of intensive research conducted by the present inventors to solve the above problems, it was discovered that a photocured film obtained from a polysiloxane containing a siloxane unit containing an organic group having two or more hydroxyl groups and a siloxane unit containing an organic group having an acetoxy group can be removed by a wet method using a chemical solution even after oxygen gas etching treatment, and the present invention was completed.

That is, according to a first aspect, the present invention provides a method for producing a silicon-containing resist underlayer film that is removable by a sulfuric acid/hydrogen peroxide aqueous solution after a dry etching treatment using oxygen gas, comprising:
The present invention relates to a method for producing a silicon-containing resist underlayer film, the method comprising: (A) curing, with ultraviolet light, a coating film of a resist underlayer film-forming composition that contains a hydrolysis condensate of a hydrolyzable silane, the hydrolysis condensate including a siloxane unit having an organic group having two or more hydroxy groups and a siloxane unit having an organic group having an acetoxy group.
As a second aspect, the resist underlayer film forming composition is
The present invention relates to a method for producing a silicon-containing resist underlayer film according to the first aspect, comprising: (B) a crosslinkable compound; and (C) at least one of an acid and an acid generator.
As a third aspect, the present invention relates to the method for producing a silicon-containing resist underlayer film according to the first or second aspect, wherein the aqueous sulfuric acid/hydrogen peroxide solution contains sulfuric acid and hydrogen peroxide in a ratio of sulfuric acid/hydrogen peroxide = 85 to 95 wt %/1 to 10 wt %.

According to the present invention, the resist underlayer film to be produced by the present invention is formed from a composition that contains, as a hydrolysis condensation product of a hydrolyzable silane, a hydrolysis condensation product that includes a siloxane unit containing an organic group having two or more hydroxy groups and a siloxane unit containing an organic group having an acetoxy group, and that may further contain a crosslinkable compound, an acid, and the like.
Conventionally, a co-hydrolysis condensate (polysiloxane) of a tetrafunctional silane such as tetraethoxysilane and a trifunctional silane has been used in a silicon-containing resist underlayer film. Although this has the advantage that the resist underlayer film does not cause intermixing with a resist composition that is overcoated thereon, mainly due to the formation of a crosslinked structure between silanol groups, it is difficult to remove the resist underlayer film with a chemical solution, for example, SPM (a mixed aqueous solution of sulfuric acid and hydrogen peroxide) after processing the underlayer or substrate.
In the present invention, the hydrolysis condensate having two or more hydroxyl groups and acetoxy groups is used in the production of the resist underlayer film, thereby forming a crosslinked structure between hydroxyl groups, between hydroxyl groups and silanol groups, or between hydroxyl groups and a crosslinking compound. Therefore, not only does it not cause intermixing with the resist composition overcoated on the upper part of the resist underlayer film, but it also makes it possible to remove the resist underlayer film with SPM (a mixed aqueous solution of sulfuric acid and hydrogen peroxide) after processing the lower layer, particularly after dry etching the resist underlayer film with oxygen gas. Therefore, it is possible to reduce damage to the substrate that was previously caused by dry etching with a fluorine-based gas when removing the resist underlayer film from the substrate.
In addition, in the present invention, the hydrolysis condensate having the specific organic group can be photocured, and the hydrolysis condensate is photocured to obtain a resist underlayer film (cured film).Therefore, the planarization of the organic underlayer film that may exist under the resist underlayer film, which may occur when baking at high temperature in the conventional resist underlayer film production, is not deteriorated, and a silicon-containing resist underlayer film having high planarization can be formed on the organic underlayer film having high planarization, and the resist film can be coated on the upper layer to suppress the diffuse reflection at the layer interface and the occurrence of steps after etching.

The present invention relates to a method for producing a silicon-containing resist underlayer film that can be wet-removed, particularly by an aqueous solution of sulfuric acid and hydrogen peroxide, after dry etching treatment with oxygen gas.

[Method of manufacturing silicon-containing resist underlayer film]
The silicon-containing resist underlayer film to which the present invention is applied, which can be wet-removed with an aqueous sulfuric acid/hydrogen peroxide solution after dry etching with oxygen gas, is produced by including a step of curing a coating film of a resist underlayer film-forming composition containing (A) a hydrolysis condensate of a hydrolyzable silane (polysiloxane) with ultraviolet light. That is, the silicon-containing resist underlayer film is an ultraviolet (UV)-cured film obtained by curing a coating film of the resist underlayer film-forming composition by irradiating it with ultraviolet light.
The resist underlayer film forming composition further contains (B) a crosslinkable compound, and (C) at least one of an acid and an acid generator.

[Resist Underlayer Film Forming Composition]
(A) Hydrolysis and condensation product of hydrolyzable silane (polysiloxane)
The hydrolysis condensate (A) used in the present invention is a hydrolysis condensate containing a siloxane unit containing an organic group having two or more hydroxy groups and a siloxane unit containing an organic group having an acetoxy group.

The above-mentioned (A) hydrolysis condensate can be a hydrolysis condensate of a hydrolysis silane mixture containing a hydrolysis silane containing an organic group having two or more hydroxy groups and a hydrolysis silane containing an organic group having an acetoxy group.
Alternatively, the hydrolysis condensate (A) may be a hydrolysis condensate obtained by ring-opening the epoxy group of a hydrolysis condensate (a) containing a siloxane unit containing an organic group having an epoxy group and a siloxane unit containing an organic group having an acetoxy group with an inorganic acid or a cation exchange resin. The hydrolysis condensate (a) may be a hydrolysis condensate of a hydrolysis silane mixture containing a hydrolysis silane containing an organic group having an epoxy group and a hydrolysis silane containing an organic group having an acetoxy group.
Considering not only the stability of the hydrolysis condensate (A) but also difficulties such as inhibition of reaction progress due to gelation or the like occurring during the hydrolysis condensation reaction, it is preferable that the hydrolysis condensate (A) is a hydrolysis condensate obtained via the hydrolysis condensate (a).
In the present invention, the "hydrolysis condensate" includes not only polyorganosiloxane polymers that are condensates in which condensation is completely completed, but also polyorganosiloxane polymers that are partial hydrolysis condensates in which condensation is not completely completed. Such partial hydrolysis condensates are polymers obtained by hydrolysis and condensation of hydrolyzable silane compounds, like condensates in which condensation is completely completed, but are partially hydrolyzed and not condensed, and therefore Si-OH groups remain. In addition to the hydrolysis condensate, the resist underlayer film forming composition may also contain uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and monomers (hydrolyzable silane compounds). In this specification, "hydrolyzable silane" may also be simply referred to as "silane compounds".

As described later, the hydrolyzable silane containing an organic group having an epoxy group is preferably contained in a proportion of 10 mol % to 90 mol % based on the total number of moles (100 mol %) of all hydrolyzable silanes contained in the hydrolyzable silane mixture.
By setting the ratio of hydrolyzable silane containing an organic group having an epoxy group to 10 mol % or more, it is possible to ensure intermixing resistance against the topcoat resist composition. Intermixing is an undesirable phenomenon in which the underlayer film dissolves when the composition for the upper layer is applied onto the underlayer film, causing layer mixing between the underlayer film and the composition for the upper layer.
Furthermore, by setting the ratio of hydrolyzable silane containing an organic group having an epoxy group to 90 mol % or less, optical properties and dry etching resistance can be ensured.

(a) The hydrolysis condensate can be, for example, a hydrolysis condensate of a hydrolysis silane mixture containing a hydrolysis silane containing an organic group having an epoxy group represented by the following formula (1-a) and a hydrolysis silane containing an organic group having an acetoxy group represented by the following formula (1-b).

式（１－ａ）中、
Ｒ^１ａは、ケイ素原子に結合する基であって、エポキシ基を含む有機基を表し、
Ｒ^２ａは、Ｓｉ－Ｃ結合によりケイ素原子に結合する基であって、互いに独立して、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいハロゲン化アルキル基、置換されていてもよいハロゲン化アリール基、置換されていてもよいハロゲン化アラルキル基、置換されていてもよいアルコキシアルキル基、置換されていてもよいアルコキシアリール基、置換されていてもよいアルコキシアラルキル基、若しくは置換されていてもよいアルケニル基を表すか、又はアクリロイル基、メタクリロイル基、メルカプト基、アミノ基、アミド基、アルコキシ基、スルホニル基、若しくはシアノ基を含む有機基、又はそれらの組み合わせを表し、Ｒ^３ａは、ケイ素原子に結合する基又は原子であって、互いに独立して、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アシルオキシ基又はハロゲン原子を表し、
ａ１は１を表し、ｂ１は０～２の整数を表し、４－（ａ１＋ｂ１）は１～３の整数を表す。
また式（１－ｂ）中、
Ｒ^１ｂは、ケイ素原子に結合する基であって、アセトキシ基を含む有機基を表し、
Ｒ^２ｂは、Ｓｉ－Ｃ結合によりケイ素原子に結合する基であって、互いに独立して、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいハロゲン化アルキル基、置換されていてもよいハロ
ゲン化アリール基、置換されていてもよいハロゲン化アラルキル基、置換されていてもよいアルコキシアルキル基、置換されていてもよいアルコキシアリール基、置換されていてもよいアルコキシアラルキル基、若しくは置換されていてもよいアルケニル基を表すか、又はアクリロイル基、メタクリロイル基、メルカプト基、アミノ基、アミド基、アルコキシ基、スルホニル基、若しくはシアノ基を含む有機基、又はそれらの組み合わせを表し、Ｒ^３ｂは、ケイ素原子に結合する基又は原子であって、互いに独立して、ヒドロキシ基、アルコキシ基、アラルキルオキシ基、アシルオキシ基又はハロゲン原子を表し、
ａ２は１を表し、ｂ２は０～２の整数を表し、（４－ａ２＋ｂ２）は１～３の整数を表す。

In formula (1-a),
R ^1a is a group bonded to a silicon atom and represents an organic group containing an epoxy group;
R ^2a are groups bonded to silicon atoms by Si-C bonds, each independently representing an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof; R ^3a are groups or atoms bonded to silicon atoms, each independently representing a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom;
a1 represents 1, b1 represents an integer of 0 to 2, and 4-(a1+b1) represents an integer of 1 to 3.
In addition, in formula (1-b),
R ^1b is a group bonded to a silicon atom and represents an organic group containing an acetoxy group;
R ^2b are groups bonded to silicon atoms by Si-C bonds, each independently representing an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof; R ^3b are groups or atoms bonded to silicon atoms, each independently representing a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom;
a2 represents 1, b2 represents an integer of 0 to 2, and (4−a2+b2) represents an integer of 1 to 3.

R ^1a is not particularly limited as long as it is an organic group containing an epoxy group. For example, the epoxy group itself, and organic groups in which one or more hydrogen atoms in an alkyl group or the like are substituted with an epoxy group, a glycidyl group, or a glycidyloxy group (glycidoxy group) can be mentioned.
Furthermore, R ^1b is not particularly limited so long as it is an organic group containing an acetoxy group (CH ₃ COO--), and examples thereof include organic groups in which one or more hydrogen atoms in an alkyl group or the like have been substituted with an acetoxy group.

The alkyl group whose hydrogen atom is substituted by the epoxy group or acetoxy group is not particularly limited and may be linear, branched, or cyclic, and the number of carbon atoms therein is usually 40 or less, for example 30 or less, more preferably 20 or less, or 10 or less.
Specific examples of the linear or branched alkyl group in which a hydrogen atom can be substituted by the above-mentioned epoxy group or acetoxy group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, Examples of the aryl group include, but are not limited to, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.
Specific examples of the cyclic alkyl group in which a hydrogen atom may be substituted by the above-mentioned epoxy group or acetoxy group include a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethylcyclobutyl group, a 2-ethylcyclobutyl group, a 3-ethylcyclopentyl group, a -cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-i-propyl-cyclopropyl, 2-i-propyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-
Examples of cycloalkyl groups include cyclopropyl and 2-ethyl-3-methyl-cyclopropyl groups; and bicycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl, and bicyclodecyl groups, but are not limited to these.
In addition, a hydrogen atom on an aromatic ring or a hydrogen atom on an alkyl group in an aryl group such as a phenyl group, a benzyl group, a phenylpropyl group, a methylphenyl group, an ethylphenyl group, a di(methyl)phenyl group, a di(ethyl)phenyl group, or a methylbenzyl group, or an aromatic ring-containing group such as an aralkyl group, an alkyl-substituted aryl group, or an alkyl-substituted aralkyl group, may be substituted with the above-mentioned epoxy group or acetoxy group.

Among the above, R ^1a includes, but is not limited to, an epoxy group, a glycidyl group, a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, an epoxycyclohexyl group, an epoxycyclohexylmethyl group, an epoxycyclohexylethyl group, and the like.
Examples of R ^1b include, but are not limited to, an acetoxymethyl group, an acetoxyethyl group, an acetoxypropyl group, and an acetoxybutyl group.

R ^2a in formula (1-a) and R ^2b in formula (1-b) are each a group bonded to a silicon atom by a Si—C bond, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an acryloyl group, methacryloyl group, mercapto group, amino group, amido group, alkoxy group, sulfonyl group, or cyano group, or a combination thereof.

The alkyl group may, for example, be a straight-chain or branched alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl ... -pentyl group, 3-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.
Cyclic alkyl groups can also be used. Examples of cyclic alkyl groups having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethyl ...,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 2,3- butyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-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.

Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-mercaptophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-aminophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

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

A halogenated alkyl group refers to an alkyl group substituted with a halogen atom.
The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and specific examples of the alkyl group include the same as those mentioned above.
The number of carbon atoms in the halogenated alkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.
Specific examples of halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropan-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, a perfluoropentyl group, and the like, but are not limited to these.

The halogenated aryl group is an aryl group substituted with a halogen atom, and specific examples of such aryl groups and halogen atoms are the same as those mentioned above.
The number of carbon atoms in the halogenated aryl 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 the halogenated aryl group include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,5-trifluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,3,4,5-tetrafluorophenyl group, a 2,3,4,6-tetrafluorophenyl group, and a 2,3,5,6-tetrafluorophenyl group. Examples of the fluorophenyl group include, but are not limited to, a pentafluorophenyl group, a 2-fluoro-1-naphthyl group, a 3-fluoro-1-naphthyl group, a 4-fluoro-1-naphthyl group, a 6-fluoro-1-naphthyl group, a 7-fluoro-1-naphthyl group, an 8-fluoro-1-naphthyl group, a 4,5-difluoro-1-naphthyl group, a 5,7-difluoro-1-naphthyl group, a 5,8-difluoro-1-naphthyl group, a 5,6,7,8-tetrafluoro-1-naphthyl group, a heptafluoro-1-naphthyl group, a 1-fluoro-2-naphthyl group, a 5-fluoro-2-naphthyl group, a 6-fluoro-2-naphthyl group, a 7-fluoro-2-naphthyl group, a 5,7-difluoro-2-naphthyl group, and a heptafluoro-2-naphthyl group.

The halogenated aralkyl group is an aralkyl group substituted with a halogen atom, and specific examples of such aralkyl groups and halogen atoms are the same as those mentioned above.
The number of carbon atoms in the 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, but are not limited to, 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, 2,4,5-trifluorobenzyl 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.

An alkoxyalkyl group is an alkyl group substituted with an alkoxy group. Specific examples of such alkyl groups include those mentioned above.

Examples of the alkoxy group include alkoxy groups having a straight-chain, branched or cyclic alkyl moiety having 1 to 20 carbon atoms. Examples of the straight-chain or branched alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, a n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 2-methyl-n-pentyl ... Examples of the alkyl group include a methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group. Examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3-dimethyl-cyclo butoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group, 1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group, and 2-ethyl-3-methyl-cyclopropoxy group.

The number of carbon atoms in the alkoxyalkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less.
Specific examples of alkoxyalkyl groups include lower alkyloxy-lower alkyl groups such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, and ethoxymethyl group, but are not limited to these.

The alkoxyaryl group is an aryl group substituted with an alkoxy group, and specific examples of such alkoxy groups and aryl groups include the same as those mentioned above.
The number of carbon atoms in the alkoxyaryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
Specific examples of alkoxyaryl groups include, but are not limited to, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-(1-ethoxy)phenyl group, a 3-(1-ethoxy)phenyl group, a 4-(1-ethoxy)phenyl group, a 2-(2-ethoxy)phenyl group, a 3-(2-ethoxy)phenyl group, a 4-(2-ethoxy)phenyl group, a 2-methoxynaphthalen-1-yl group, a 3-methoxynaphthalen-1-yl group, a 4-methoxynaphthalen-1-yl group, a 5-methoxynaphthalen-1-yl group, a 6-methoxynaphthalen-1-yl group, and a 7-methoxynaphthalen-1-yl group.

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

The alkenyl group includes alkenyl groups having 2 to 10 carbon atoms, such as ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5-pentenyl, 6-pentenyl, 7-pentenyl, 8-pentenyl, 9-pentenyl, 10-pentenyl, 11-pentenyl, 12-pentenyl, 13-pentenyl, 14-pentenyl, 15-pentenyl, 16-pentenyl, 17-pentenyl, 18-pentenyl, 19-pentenyl, 22-pentenyl, 23-pentenyl, 24-pentenyl, 25-pentenyl, 26-pentenyl, 27-pentenyl, 28-pentenyl, 29-pentenyl, 30-pentenyl, 31-pentenyl, 32-pentenyl, 33-pentenyl, 34-pentenyl, 35-pentenyl, 36-pentenyl, 37-pentenyl, 38-pentenyl, 39-pentenyl, 40-pentenyl, 41-pentenyl, 42-pentenyl, 43-pentenyl, 44-pentenyl, 45-pentenyl, 46-pentenyl, 47-pentenyl, 48-pentenyl, 49-pentenyl, 50-pentenyl, 51-pentenyl, nyl 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, 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, Examples of such alkenyl groups include a 2-methylene-cyclopentyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3-methyl-3-cyclopentenyl group, a 3-methyl-4-cyclopentenyl group, a 3-methyl-5-cyclopentenyl group, a 3-methylene-cyclopentyl group, a 1-cyclohexenyl group, a 2-cyclohexenyl group, and a 3-cyclohexenyl group. Examples also include bridged cyclic alkenyl groups such as a bicycloheptenyl group (norbornyl group).

[0043] Examples of the substituent in the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group 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 and suitable numbers of carbon atoms for these groups are the same as those described above or below.
The aryloxy group is a group in which an aryl group is bonded via an oxygen atom (-O-), and specific examples of such aryl groups include those mentioned above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less, and specific examples thereof include, but are not limited to, a phenoxy group, a naphthalene-2-yloxy group, and the like.
When two or more substituents are present, the substituents may be bonded to each other to form a ring.

Examples of the organic group containing an acryloyl group include, but are not limited to, an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.
Examples of the organic group containing a methacryloyl group include, but are not limited to, a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.
Examples of the organic group containing a mercapto group include, but are not limited to, an ethyl mercapto group, a butyl mercapto group, a hexyl mercapto group, and an octyl mercapto group.
Examples of organic groups containing an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group.
An example of an organic group containing an amino group or an amide group is a cyanuric acid derivative.
Examples of the organic group containing a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group.
Examples of the organic group containing a cyano group include, but are not limited to, a cyanoethyl group and a cyanopropyl group.

R ^3a in formula (1-a) and R ^3b in formula (1-b) each represent a group or atom bonded to a silicon atom, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. Examples of the alkoxy group and halogen atom include the same as those mentioned above.

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

The acyloxy group is a group derived by removing a hydrogen atom from the carboxylic acid group of a carboxylic acid compound, and typically includes, but is not limited to, an alkylcarbonyloxy group, an arylcarbonyloxy group, or an aralkylcarbonyloxy group derived by removing a hydrogen atom from the carboxylic acid group of an alkylcarboxylic acid, an arylcarboxylic acid, or an aralkylcarboxylic acid. Specific examples of the alkyl group, aryl group, and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid, and aralkylcarboxylic acid are the same as those mentioned above.
Specific examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms. For example, a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 3-methyl-n-pentylcarbonyloxy group, Examples of the aryloxy group include, but are not limited to, a 4-methyl-n-pentylcarbonyloxy group, a 1,1-dimethyl-n-butylcarbonyloxy group, a 1,2-dimethyl-n-butylcarbonyloxy group, a 1,3-dimethyl-n-butylcarbonyloxy group, a 2,2-dimethyl-n-butylcarbonyloxy group, a 2,3-dimethyl-n-butylcarbonyloxy group, a 3,3-dimethyl-n-butylcarbonyloxy group, a 1-ethyl-n-butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxy group, a 1,1,2-trimethyl-n-propylcarbonyloxy group, a 1,2,2-trimethyl-n-propylcarbonyloxy group, a 1-ethyl-1-methyl-n-propylcarbonyloxy group, a 1-ethyl-2-methyl-n-propylcarbonyloxy group, a phenylcarbonyloxy group, and a tosylcarbonyloxy group.

In the above formula (1-a), a1 represents 1, b1 represents an integer of 0 to 2, and 4-(a1+b1) represents an integer of 1 to 3. b1 preferably represents 0 or 1, and more preferably 0.
In the above formula (1-b), a2 represents 1, b2 represents an integer of 0 to 2, and 4-(a2+b2) represents an integer of 1 to 3. b2 preferably represents 0 or 1, and more preferably 0.

Specific examples of hydrolyzable silanes represented by formula (1-a) include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, -glycidoxypropyltributoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclo hexyl)ethyl tripropoxysilane, β-(3,4-epoxycyclohexyl)ethyl tributoxysilane, γ-(3,4-epoxycyclohexyl)propyl trimethoxysilane, γ-(3,4-epoxycyclohexyl)propyl triethoxysilane, δ-(3,4-epoxycyclohexyl)butyl trimethoxysilane, δ-(3,4-epoxycyclohexyl)butyl triethoxysilane, glycidoxymethyl methyl dimethoxysilane, glycidoxymethyl methyl diethoxysilane, α-glycidoxyethyl methyl dimethoxysilane, α-glycidoxyethyl methyl diethoxysilane, β-glycidoxyethyl methyl dimethoxysilane, β-glycidoxyethyl ethyl Examples include dimethoxysilane, α-glycidoxypropyl methyl dimethoxysilane, α-glycidoxypropyl methyl diethoxysilane, β-glycidoxypropyl methyl dimethoxysilane, β-glycidoxypropyl ethyl dimethoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-glycidoxypropyl methyl diethoxysilane, γ-glycidoxypropyl methyl dipropoxysilane, γ-glycidoxypropyl methyl dibutoxysilane, γ-glycidoxypropyl ethyl dimethoxysilane, γ-glycidoxypropyl ethyl diethoxysilane, γ-glycidoxypropyl vinyl dimethoxysilane, and γ-glycidoxypropyl vinyl diethoxysilane.

Specific examples of the hydrolyzable silane represented by formula (1-b) include acetoxymethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxyethyltrimethoxysilane, acetoxyethyltriethoxysilane, acetoxypropyltrimethoxysilane, acetoxypropyltriethoxysilane, acetoxybutyltrimethoxysilane, acetoxybutyltriethoxysilane, acetoxypentyltrimethoxysilane, acetoxypentyltriethoxysilane, acetoxyphenyltrimethoxysilane, acetoxyphenyltriethoxysilane, acetoxybenzyltrimethoxysilane, acetoxybenzyltriethoxysilane, and acetoxyphenyltrimethoxysilane. Examples of such silane include acetoxyphenylpropyl trimethoxysilane, acetoxyphenylpropyl triethoxysilane, acetoxymethylphenyl trimethoxysilane, acetoxymethylphenyl triethoxysilane, acetoxyethylphenyl trimethoxysilane, acetoxyethylphenyl triethoxysilane, acetoxymethylbenzyl trimethoxysilane, acetoxymethylbenzyl trimethoxysilane, di(acetoxymethyl)phenyltrimethoxysilane, di(acetoxymethyl)phenyltriethoxysilane, di(acetoxyethyl)phenyltrimethoxysilane, and di(acetoxyethyl)phenyltriethoxysilane.

[Other silane compounds (hydrolyzable silanes)]
In the present invention, in the above hydrolyzable silane mixture, hydrolyzable silanes other than those of the above formulas can be used in addition to the hydrolyzable silanes represented by the above formula (1-a) and (1-b). Note that in the examples of compounds shown below, hydrolyzable silanes containing an organic group having an epoxy group and hydrolyzable silanes containing an organic group having an acetoxy group may be exemplified, but these compounds can be used as hydrolyzable silanes containing an organic group having an epoxy group and hydrolyzable silanes containing an organic group having an acetoxy group, respectively.

For example, for the purpose of adjusting the film properties such as the film density, at least one hydrolyzable silane (other hydrolyzable silane) selected from the hydrolyzable silane represented by the following formula (2) and the hydrolyzable silane represented by the following formula (3) can be used. Among these other hydrolyzable silanes, the hydrolyzable silane represented by formula (2) is preferred.

式（２）中、Ｒ^４は、Ｓｉ－Ｃ結合によりケイ素原子に結合する基であって、互いに独立して、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいハロゲン化アルキル基、置換されていてもよいハロゲン化アリール基、置換されていてもよいハロゲン化アラルキル基、置換されていてもよいアルコキシアルキル基、置換されていてもよいアルコキシアリール基、置換されていてもよいアルコキシアラルキル基、若しくは置換されていてもよいアルケニル基を表すか、又はアクリロイル基、メタクリロイル基、メルカプト基、アミノ基、アミド基、アルコキシ基、スルホニル基、若しくはシアノ基を含む有機基、又はそれらの組み合わせを表す。
またＲ^５は、ケイ素原子に結合する基又は原子であって、互いに独立して、アルコキシ基、アラルキルオキシ基、アシルオキシ基、又はハロゲン原子を表す。
そしてｃは、０～３の整数を表す。

In formula (2), R ⁴ is a group bonded to a silicon atom by a Si-C bond, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group containing an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof.
^R5 is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
and c represents an integer of 0 to 3.

Specific examples of each group in ^R4 and their suitable numbers of carbon atoms include the groups described above, for example, the groups and numbers of carbon atoms described above for ^R2a and ^R2b .
Specific examples of each group in ^R5 and their suitable numbers of carbon atoms include the groups, atoms and numbers of carbon atoms described above for the groups, ^R3a and ^R3b .
Furthermore, c preferably represents 0 or 1, and more preferably 0.

式（３）中、Ｒ^６は、Ｓｉ－Ｃ結合によりケイ素原子に結合する基であって、互いに独立して、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいハロゲン化アルキル基、置換されていてもよいハロゲン化アリール基、置換されていてもよいハロゲン化アラルキル基、置換されていてもよいアルコキシアルキル基、置換されていてもよいアルコキシアリール基、置換されていてもよいアルコキシアラルキル基、若しくは置換されていてもよいアルケニル基を表すか、又はアクリロイル基、メタクリロイル基、メルカプト基、アミノ基、アミド基、アルコキシ基、スルホニル基、若しくはシアノ基を含む有機基、又はそれらの組み合わせを表す。
またＲ^７は、ケイ素原子に結合する基又は原子であって、互いに独立して、アルコキシ基、アラルキルオキシ基、アシルオキシ基、又はハロゲン原子を表す。
Ｙは、Ｓｉ－Ｃ結合によりケイ素原子に結合する基であって、互いに独立して、アルキレン基又はアリーレン基を表す。
そして、ｄは０又は１を表し、ｅは０又は１を表す。

In formula (3), R ⁶ is a group bonded to a silicon atom by a Si-C bond, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group containing an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amido group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof.
^R7 is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
Y's are groups bonded to the silicon atom by a Si--C bond and each independently represent an alkylene group or an arylene group.
And, d represents 0 or 1, and e represents 0 or 1.

Specific examples of each group in ^R6 and ^R7 and their suitable numbers of carbon atoms include the groups and numbers of carbon atoms described above.
Specific examples of each group in R ⁶ and their suitable numbers of carbon atoms include the groups described above, for example, the groups and numbers of carbon atoms described above for R ^2a and R ^2b .
Specific examples of each group in ^R7 and their suitable numbers of carbon atoms include the groups, atoms and numbers of carbon atoms described above for ^R3a and ^R3b .
Specific examples of the alkylene group for Y include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; and alkylene groups such as methanetriyl, ethane-1,1,2-triyl, ethane-1,2,2-triyl, and ethane-2,2,2-triyl. alkane triyl groups such as, butane-1,1,1-triyl group, propane-1,1,2-triyl group, propane-1,2,3-triyl group, propane-1,2,2-triyl group, propane-1,1,3-triyl group, butane-1,1,1-triyl group, butane-1,1,2-triyl group, butane-1,1,3-triyl group, butane-1,2,3-triyl group, butane-1,2,4-triyl group, butane-1,2,2-triyl group, butane-2,2,3-triyl group, 2-methylpropane-1,1,1-triyl group, 2-methylpropane-1,1,2-triyl group, 2-methylpropane-1,1,3-triyl group, and 2-methylpropane-1,1,1-triyl group.
Specific examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group; a 1,5-naphthalenediyl group, a 1,8-naphthalenediyl group, a 2,6-naphthalenediyl group, a 2,7-naphthalenediyl group, a 1,2-anthracenediyl group, a 1,3-anthracenediyl group, a 1,4-anthracenediyl group, a 1,5-anthracenediyl group, a 1,6-anthracenediyl group, a 1,7-anthracenediyl group, a 1,8
Examples of such condensed ring aromatic hydrocarbon compounds include groups derived by removing two hydrogen atoms on an aromatic ring of a condensed ring aromatic hydrocarbon compound, such as a condensed ring anthracenediyl group, a 2,3-anthracenediyl group, a 2,6-anthracenediyl group, a 2,7-anthracenediyl group, a 2,9-anthracenediyl group, a 2,10-anthracenediyl group, or a 9,10-anthracenediyl group; and groups derived by removing two hydrogen atoms on an aromatic ring of a ring-linked aromatic hydrocarbon compound, such as a 4,4'-biphenyldiyl group or a 4,4"-para-terphenyldiyl group, but are not limited to these.
Furthermore, d preferably represents 0 or 1, and more preferably 0.
Further, e is preferably 1.

Specific examples of hydrolyzable silanes represented by formula (2) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, and methoxybenzyltrimethoxysilane. phenyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, i-propoxyphenyltrimethoxysilane, i-propoxyphenyltriethoxysilane, i-propoxyphenyltriacetoxysilane, i-propoxyphenyltrichlorosilane, i-propoxybenzyltrimethoxysilane, i-propoxybenzyltriethoxysilane, i-propoxybenzyltriacetoxysilane t-Butoxysilane, i-propoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane , methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoro ... Silane, γ-methacryloxypropyl trimethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl triethoxysilane, β-cyanoethyl triethoxysilane, chloromethyl trimethoxysilane, chloromethyl triethoxysilane, triethoxysilylpropyl diallyl isocyanurate, bicyclo(2,2,1)heptenyl triethoxysilane, benzenesulfonylpropyl triethoxysilane, benzenesulfonamidopropyl triethoxysilane, dimethylaminopropyl trimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-
Examples of the silane compound include, but are not limited to, mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and silane compounds represented by the following formulas (A-1) to (A-41).

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

Among these, from the viewpoints of improving the crosslink density of the film obtained from the composition, suppressing the diffusion of components of the resist film into the obtained film, and maintaining and improving the resist properties of the resist film, it is preferable to use methoxybenzyltrimethoxysilane, triethoxysilylpropyldiallylisocyanurate, methyltriethoxysilane, etc.

In the present invention, the hydrolyzable silane mixture may contain a silane compound having an onium group in the molecule (hydrolyzable organosilane). By using a silane compound having an onium group in the molecule (hydrolyzable organosilane), the crosslinking reaction of the hydrolyzable silane can be effectively and efficiently promoted.

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

式（４）中、Ｒ^１１は、ケイ素原子に結合する基であって、オニウム基又はそれを含む有機基を表す。
Ｒ^１２は、ケイ素原子に結合する基であって、互いに独立して、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいハロゲン化アルキル基、置換されていてもよいハロゲン化アリール基、置換されていてもよいハロゲン化アラルキル基、置換されていてもよいアルコキシアルキル基、置換されていてもよいアルコキシアリール基、置換されていてもよいアルコキシアラルキル基、若しくは置換されていてもよいアルケニル基を表すか、又はアクリロイル基、メタクリロイル基、メルカプト基、アミノ基、若しくはシアノ基を含む有機基、又はそれらの組み合わせを表す。
Ｒ^１３は、ケイ素原子に結合する基又は原子であって、互いに独立して、アルコキシ基、アラルキルオキシ基、アシルオキシ基、又はハロゲン原子を表す。
ｆは１又は２を表し、ｇは０又は１を表し、１≦ｆ＋ｇ≦２を満たす。

In formula (4), R ¹¹ is a group bonded to a silicon atom and represents an onium group or an organic group containing an onium group.
R ¹² is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an organic group containing an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, or a combination thereof.
R ¹³ is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
f represents 1 or 2, g represents 0 or 1, and 1≦f+g≦2 is satisfied.

Specific examples of the above alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, and organic groups containing an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, an alkoxy group, an aralkyloxy group, an acyloxy group, and a halogen atom, as well as specific examples of the substituents of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group, and their suitable numbers of carbon atoms, for R ¹² , include those described above for R ^2a and R ^2b , and for R ¹³ , those described above for R ^3a and R ^3b .

More specifically, specific examples of the onium group include a cyclic ammonium group or a chain ammonium group, with a tertiary ammonium group or a quaternary ammonium group being preferred.
That is, specific examples of suitable onium groups or organic groups containing the onium group include cyclic ammonium groups or chain ammonium groups, or organic groups containing at least one of these, and tertiary ammonium groups or quaternary ammonium groups, or organic groups containing at least one of these, are preferred.
In addition, when the onium group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. In this case, the nitrogen atom constituting the ring and the silicon atom are bonded directly or via a divalent linking group, and the carbon atom constituting the ring and the silicon atom are bonded directly or via a divalent linking group.

In one preferred embodiment of the present invention, R ¹¹ , which is a group bonded to a silicon atom, is a heteroaromatic cyclic ammonium group represented by the following formula (S1).

In formula (S1), A ¹ , A ² , A ³ and A ⁴ each independently represent a group represented by any one of the following formulae (J1) to (J3), with at least one of A ¹ to A ⁴ being a group represented by the following formula (J2): Depending on which of A ¹ to A ⁴ the silicon atom in formula (4) is bonded to, whether the bond between each of A ¹ to A ⁴ and the adjacent atom constituting the ring together therewith is a single bond or a double bond is determined so that the constituted ring exhibits aromaticity.

式（Ｊ１）～（Ｊ３）中、Ｒ^１０は、互いに独立して、単結合、水素原子、アルキル基、アリール基、アラルキル基、ハロゲン化アルキル基、ハロゲン化アリール基、ハロゲン化アラルキル基又はアルケニル基を表し、アルキル基、アリール基、アラルキル基、ハロゲン化アルキル基、ハロゲン化アリール基、ハロゲン化アラルキル基及びアルケニル基の具体例及びそれらの好適な炭素原子数としては、上述と同じものが挙げられる。

In formulas (J1) to (J3), R ¹⁰ each independently represent a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, or an alkenyl group. Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, and alkenyl group and suitable numbers of carbon atoms thereof are the same as those described above.

In formula (S1), R ^14s each independently represent an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, or a hydroxy group. When two or more R ^14s are present, the two R ^14s may be bonded to each other to form a ring, or the ring formed by the two R ^14s may be a bridged ring structure. In such a case, the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, or the like.
Specific examples of such alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups and alkenyl groups and suitable numbers of carbon atoms therefor are the same as those mentioned above.

In formula (S1), ⁿ¹ is an integer of 1 to 8, ^m1 is 0 or 1, and ^m2 is a positive integer of 0 or 1 to the maximum number that can be substituted on a monocyclic or polycyclic ring.
When ^m1 is 0, a (4+ ⁿ¹ )-membered ring including ^A1 to ^A4 is formed. That is, when ⁿ¹ is 1, a 5-membered ring is formed, when ⁿ¹ is 2, a 6-membered ring is formed, when ⁿ¹ is 3, a 7-membered ring is formed, when ⁿ¹ is 4, an 8-membered ring is formed, when ⁿ¹ is 5, a 9-membered ring is formed, when ⁿ¹ is 6, a 10-membered ring is formed, when ⁿ¹ is 7, an 11-membered ring is formed, and when ⁿ¹ is 8, a 12-membered ring is formed.
When ^m1 is 1, a (4+ ⁿ¹ )-membered ring including ^A1 to ^A3 is fused with a 6-membered ring including ^A4 to form a fused ring.
Depending on which of formulas (J1) to (J3) A ¹ to A ⁴ are, they may or may not have a hydrogen atom on an atom constituting the ring, but when A ¹ to A ⁴ have a hydrogen atom on an atom constituting the ring, the hydrogen atom may be replaced with R ^14. In addition, a ring-constituting atom other than the ring-constituting atoms in A ¹ to A ⁴ may be substituted with R ^14. In view of these circumstances, as described above, m ² is selected from an integer of 0 or 1 to the maximum number that can be substituted on a monocyclic or polycyclic ring.

The bond of the heteroaromatic cyclic ammonium group represented by the above formula (S1) is present on any carbon atom or nitrogen atom present in such a single ring or condensed ring, and is directly bonded to a silicon atom, or is bonded to a linking group to form an organic group containing cyclic ammonium, which is bonded to a silicon atom.
Examples of such linking groups include, but are not limited to, alkylene groups, arylene groups, alkenylene groups, and the like.
Specific examples of the alkylene group and arylene group and suitable numbers of carbon atoms therefor are the same as those mentioned above.

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

Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (4) having a heteroaromatic cyclic ammonium group represented by formula (S1) above are listed below, but are not limited thereto.

式（Ｓ２）中、Ａ^５、Ａ^６、Ａ^７及びＡ^８は、互いに独立して、下記式（Ｊ４）～（Ｊ
６）のいずれかで表される基を表すが、Ａ^５～Ａ^８のうち少なくとも１つは、下記式（Ｊ５）で表される基である。上記式（４）におけるケイ素原子がＡ^５～Ａ^８のいずれと結合するかに応じて、構成される環が非芳香族性を示すように、Ａ^５～Ａ^８それぞれと、それら各々に隣接し共に環を構成する原子との結合が、単結合であるか、二重結合であるかが定まる。 In another example, R ¹¹ which is a group bonded to a silicon atom in the above formula (4) can be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).

In formula (S2), A ⁵ , A ⁶ , A ⁷ and A ⁸ each independently represent any one of the following formulae (J4) to (J
Each of A ^{5 to A 8 represents a group represented by any one of the following formula (6), and at least one of A 5} to A ⁸ is a group represented by the following formula (J5). Depending on which of A ⁵ to A ⁸ the silicon atom in formula (4) is bonded to, whether the bond between each of A ⁵ to A ⁸ and the adjacent atom that together constitutes the ring is a single bond or a double bond is determined so that the constituted ring exhibits non-aromaticity.

式（Ｊ４）～（Ｊ６）中、Ｒ^１０は、互いに独立して、単結合、水素原子、アルキル基、アリール基、アラルキル基、ハロゲン化アルキル基、ハロゲン化アリール基、ハロゲン化アラルキル基又はアルケニル基を表し、アルキル基、アリール基、アラルキル基、ハロゲン化アルキル基、ハロゲン化アリール基、ハロゲン化アラルキル基及びアルケニル基の具体例及びそれらの好適な炭素原子数としては、上述したものと同じものが挙げられる。

In formulas (J4) to (J6), R ¹⁰ each independently represent a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, or an alkenyl group. Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, and alkenyl group and suitable numbers of carbon atoms thereof are the same as those described above.

In formula (S2), R ¹⁵ each independently represents an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, or a hydroxy group. When two or more R ¹⁵ are present, the two R ¹⁵ may be bonded to each other to form a ring, or the ring formed by the two R ¹⁵ may be a bridged ring structure. In such a case, the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, or the like.
Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group and alkenyl group and suitable numbers of carbon atoms thereof are the same as those mentioned above.

In formula (S2), ⁿ² is an integer of 1 to 8, ^m3 is 0 or 1, and ^m4 is a positive integer ranging from 0 or 1 to the maximum number that can be substituted on a monocyclic or polycyclic ring.
When ^m3 is 0, a (4+ ⁿ² )-membered ring including ^A5 to ^A8 is formed. That is, when ⁿ² is 1, a 5-membered ring is formed, when ⁿ² is 2, a 6-membered ring is formed, when ⁿ² is 3, a 7-membered ring is formed, when ⁿ² is 4, an 8-membered ring is formed, when ⁿ² is 5, a 9-membered ring is formed, when ⁿ² is 6, a 10-membered ring is formed, when ⁿ² is 7, an 11-membered ring is formed, and when ⁿ² is 8, a 12-membered ring is formed.
When ^m3 is 1, a (4+n ² )-membered ring including A ⁵ to A ⁷ is fused with a 6-membered ring including A ⁸ to form a fused ring.
Depending on which of formulas (J4) to (J6) A ⁵ to A ⁸ are, they may or may not have a hydrogen atom on an atom constituting the ring, but when A ⁵ to A ⁸ have a hydrogen atom on an atom constituting the ring, the hydrogen atom may be replaced by R ^15. In addition, a ring-constituting atom other than the ring-constituting atom in A ⁵ to A ⁸ may be substituted by R ¹⁵ .
In view of this, as described above, ^m4 is selected from integers of 0 or 1 to the maximum number that can be substituted on a monocyclic or polycyclic ring.

The bond of the heteroaliphatic cyclic ammonium group represented by the above formula (S2) is present on any carbon atom or nitrogen atom present in such a single ring or condensed ring, and is directly bonded to a silicon atom, or is bonded to a linking group to form an organic group containing cyclic ammonium, which is bonded to a silicon atom.
Examples of such a linking group include an alkylene group, an arylene group, or an alkenylene group. Specific examples of the alkylene group, the arylene group, and the alkenylene group and suitable numbers of carbon atoms therefor are the same as those described above.

Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (4) having the heteroaliphatic cyclic ammonium group represented by formula (S2) above are listed below, but are not limited thereto.

式（Ｓ３）中、Ｒ^１０は、互いに独立して、水素原子、アルキル基、アリール基、アラルキル基、ハロゲン化アルキル基、ハロゲン化アリール基、ハロゲン化アラルキル基又はアルケニル基を表し、アルキル基、アリール基、アラルキル基、ハロゲン化アルキル基、ハロゲン化アリール基、ハロゲン化アラルキル基及びアルケニル基の具体例及びそれらの好適な炭素原子数としては、上述したものと同じものが挙げられる。 In still another example, R ¹¹ which is a group bonded to a silicon atom in the above formula (4) can be a chain ammonium group represented by the following formula (S3).

In formula (S3), R ¹⁰ each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, or an alkenyl group. Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, and alkenyl group and suitable numbers of carbon atoms thereof are the same as those described above.

The chain ammonium group represented by formula (S3) is directly bonded to a silicon atom, or a linking group is bonded to form an organic group containing the chain ammonium group, which is bonded to a silicon atom.
Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group. Specific examples of the alkylene group, the arylene group, and the alkenylene group are the same as those mentioned above.

Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (4) having a chain ammonium group represented by formula (S3) above are listed below, but are not limited thereto.

The hydrolyzable silane mixture may further contain a hydrolyzable silane having a sulfone group or a hydrolyzable silane having a sulfonamide group. Specific examples thereof are given below, but are not limited to these.
In the following formula, Me represents a methyl group and Et represents an ethyl group.

Furthermore, in the present invention, the hydrolyzable silane mixture may contain a silane compound (hydrolyzable organosilane) having a cyclic urea skeleton in the molecule. A specific example, but not limited to, is a silane compound (hydrolyzable organosilane) represented by the following formula (5-1):

式（５－１）中、Ｒ^５０１は、ケイ素原子に結合する基であって、互いに独立して、式
（５－２）で表される基を表す。
Ｒ^５０２は、ケイ素原子に結合する基であって、互いに独立して、置換されていてもよいアルキル基、置換されていてもよいアリール基、置換されていてもよいアラルキル基、置換されていてもよいハロゲン化アルキル基、置換されていてもよいハロゲン化アリール基、置換されていてもよいハロゲン化アラルキル基、置換されていてもよいアルコキシアルキル基、置換されていてもよいアルコキシアリール基、置換されていてもよいアルコキシアラルキル基、若しくは置換されていてもよいアルケニル基を表すか、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、若しくはシアノ基を含む有機基、又はそれらの組み合わせを表す。
Ｒ^５０３は、ケイ素原子に結合する基又は原子であって、互いに独立して、アルコキシ基、アラルキルオキシ基、アシルオキシ基、又はハロゲン原子を表す。
ｘは１又は２を表し、ｙは０又は１を表し、ｘ＋ｙ≦２を満たす。

In formula (5-1), R ⁵⁰¹ is a group bonded to a silicon atom and each independently represents a group represented by formula (5-2).
R ⁵⁰² is a group bonded to a silicon atom, and each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, or a combination thereof.
R ⁵⁰³ is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
x represents 1 or 2, y represents 0 or 1, and x+y≦2 is satisfied.

Specific examples of the ^{organic group} including an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkoxyalkyl group, an alkoxyaryl group, an alkoxyaralkyl group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group for R ^{502, and specific examples of the alkoxy group, an aralkyloxy group, an acyloxy group, and a halogen atom for R 503} , as well as specific examples of the substituents thereof, and the preferred number of carbon atoms, etc., for R ⁵⁰² are those described above for R ^2a and R ^2b , and for R ⁵⁰³ are those described above for R ^3a and R ^3b .

式（５－２）中、Ｒ^５０４は、互いに独立して、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、又はエポキシ基若しくはスルホニル基を含む有機基を表す。
Ｒ^５０５は、互いに独立して、アルキレン基、ヒドロキシアルキレン基、スルフィド結合（－Ｓ－）、エーテル結合（－Ｏ－）又はエステル結合（－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－）を表す。
なお、Ｒ^５０４の置換されていてもよいアルキル基、置換されていてもよいアルケニル基及びエポキシ基を含む有機基の具体例、好適な炭素原子数等は、上述したものと同じものが挙げられるが、これらの他、置換されていてもアルキル基としては、末端の水素原子がビニル基で置換されたアルキル基が好ましく、その具体例としては、アリル基、２－ビニルエチル基、３－ビニルプロピル基、４－ビニルブチル基等が挙げられる。

In formula (5-2), R ⁵⁰⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy group or a sulfonyl group.
R ⁵⁰⁵ each independently represents an alkylene group, a hydroxyalkylene group, a sulfide bond (--S--), an ether bond (--O--) or an ester bond (--CO--O-- or --O--CO--).
Specific examples of the optionally substituted alkyl group, optionally substituted alkenyl group and organic group containing an epoxy group for R ⁵⁰⁴ , and suitable numbers of carbon atoms, etc., are the same as those described above. In addition, as the alkyl group, even if substituted, an alkyl group in which a terminal hydrogen atom is substituted with a vinyl group is preferable, and specific examples thereof include an allyl group, a 2-vinylethyl group, a 3-vinylpropyl group, a 4-vinylbutyl group, etc.

The organic group containing a sulfonyl group is not particularly limited as long as it contains a sulfonyl group, and examples thereof include an optionally substituted alkylsulfonyl group, an optionally substituted arylsulfonyl group, an optionally substituted aralkylsulfonyl group, an optionally substituted halogenated alkylsulfonyl group, an optionally substituted halogenated arylsulfonyl group, an optionally substituted halogenated aralkylsulfonyl group, an optionally substituted alkoxyalkylsulfonyl group, an optionally substituted alkoxyarylsulfonyl group, an optionally substituted alkoxyaralkylsulfonyl group, an optionally substituted alkenylsulfonyl group, and the like. In these groups, the alkyl group, the aryl group, the aralkyl group,
Specific examples of the halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group and alkenyl group, as well as the substituents thereof, and suitable numbers of carbon atoms and the like, are the same as those described above.

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

The alkylene group may have one or more bonds selected from a sulfide bond, an ether bond and an ester bond at its terminal or in the middle, preferably in the middle.
Specific examples of the alkylene group include linear alkylene groups such as methylene, ethylene, trimethylene, methylethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkylene groups such as 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl; and -CH ₂ OCH ₂ -, -CH ₂ CH ₂ OCH ₂ -, -CH 2 _{CH 2} OCH ₂ CH ₂ -, -CH 2 _{CH 2} CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ OCH ₂ CH 2 CH ₂ -, -CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -, -CH ₂ SCH ₂ -, -CH ₂ CH ₂ SCH ₂ -, _{-CH 2} CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ SCH ₂ CH ₂ -, -CH ₂ CH ₂ SCH ₂ CH 2 C H ₂ -, -CH ₂ CH ₂ CH ₂ SCH _{2 CH 2} CH ₂ -, -CH ₂ OCH Examples include, but are not limited to, alkylene groups containing ether groups such as ₂ CH ₂ SCH ₂ —.

The hydroxyalkylene group is an alkylene group in which at least one of the hydrogen atoms has been replaced with a hydroxy group. Specific examples include, but are not limited to, a hydroxymethylene group, a 1-hydroxyethylene group, a 2-hydroxyethylene group, a 1,2-dihydroxyethylene group, a 1-hydroxytrimethylene group, a 2-hydroxytrimethylene group, a 3-hydroxytrimethylene group, a 1-hydroxytetramethylene group, a 2-hydroxytetramethylene group, a 3-hydroxytetramethylene group, a 4-hydroxytetramethylene group, a 1,2-dihydroxytetramethylene group, a 1,3-dihydroxytetramethylene group, a 1,4-dihydroxytetramethylene group, a 2,3-dihydroxytetramethylene group, a 2,4-dihydroxytetramethylene group, and a 4,4-dihydroxytetramethylene group.

式（５－３）乃至式（５－５）中、Ｒ^５０６乃至Ｒ^５１０は、互いに独立して、水素原子、又は置換されていてもよいアルキル基、置換されていてもよいアルケニル基、エポキシ基、スルホニル基若しくはそれらのいずれかを含む有機基を表し、置換されていてもよいアルキル基、置換されていてもよいアルケニル基及びエポキシ基を含む有機基の具体例及び好適な炭素原子数等は、Ｒ^２ａ及びＲ^２ｂに関し上述したものと同じものが挙げられる。
中でも、優れたリソグラフィー特性を再現性よく実現する観点から、Ｘ_５０１は式（５－５）で表される基が好ましい。 In formula (5-2), X ₅₀₁ each independently represents a group represented by the following formula (5-3) to formula (5-5), and the carbon atom of the ketone group (-C(=O)-) in formula (5-4) and formula (5-5) below is bonded to the nitrogen atom to which R ⁵⁰⁵ in formula (5-2) is bonded.

In formula (5-3) to formula (5-5), R ⁵⁰⁶ to R ⁵¹⁰ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an epoxy group, a sulfonyl group, or an organic group containing any of them. Specific examples of the optionally substituted alkyl group, the optionally substituted alkenyl group, and the organic group containing an epoxy group, and the suitable number of carbon atoms, etc., are the same as those described above for R ^2a and R ^2b .
Among these, from the viewpoint of realizing excellent lithography properties with good reproducibility, X ₅₀₁ is preferably a group represented by formula (5-5).

From the viewpoint of realizing excellent lithography properties with good reproducibility, at least one of R ⁵⁰⁴ and R ⁵⁰⁶ to R ⁵¹⁰ is preferably an alkyl group in which a terminal hydrogen atom is substituted with a vinyl group.

The silane compound (hydrolyzable organosilane) represented by the above formula (5-1) may be a commercially available product, or may be synthesized by a known method such as that described in International Publication No. WO 2011/102470.

Specific examples of the hydrolyzable organosilane represented by formula (5-1) are listed below, but the present invention is not limited to these.

In addition to the above examples, the hydrolyzable silane mixture may contain other hydrolyzable silanes other than those listed above, as long as the effects of the present invention are not impaired.

The hydrolysis condensate (a) of the hydrolyzed silane mixture can be obtained by hydrolysis and condensation of the above-mentioned silane compound (hydrolyzable silane).
The silane compound (hydrolyzable silane) contains an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom that is directly bonded to a silicon atom, that is, an alkoxysilyl group, an aralkyloxysilyl group, an acyloxysilyl group, or a halogenated silyl group that is a hydrolyzable group.
For the hydrolysis of these hydrolyzable groups, usually 0.5 to 100 mol, preferably 1 to 10 mol, of water is used per mol of the hydrolyzable group.
In the hydrolysis and condensation, a hydrolysis catalyst may be used or may not be used for the purpose of promoting the reaction, etc. When a hydrolysis catalyst is used, the amount of the hydrolysis catalyst that can be used is usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, per mol of the hydrolyzable group.
The reaction temperature during hydrolysis and condensation is usually in the range of from room temperature to the reflux temperature at normal pressure of the organic solvent that can be used for the hydrolysis, and can be in the range of not more than 20 to 110° C., or not more than 20 to 80° C. The hydrolysis can be complete, i.e., all hydrolyzable groups are converted to silanol groups, or can be partial, i.e., some hydrolyzable groups remain unreacted.
Examples of hydrolysis catalysts that can be used in the hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

Examples of the metal chelate compound as a hydrolysis catalyst include triethoxy mono(acetylacetonato)titanium, tri-n-propoxy mono(acetylacetonato)titanium, tri-i-propoxy mono(acetylacetonato)titanium, tri-n-butoxy mono(acetylacetonato)titanium, tri-sec-butoxy mono(acetylacetonato)titanium, tri-t-butoxy mono(acetylacetonato)titanium, diethoxy bis(acetylacetonato)titanium, di-n-propoxy bis(acetylacetonato)titanium, di-i-propoxy bis(acetylacetonato)titanium, di-n-butoxy bis(acetylacetonato)titanium, di-sec-butoxy bis(acetylacetonato)titanium, 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, 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(ethoxy) ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethylacetoacetate) titanium, di-n-propoxy bis(ethylacetoacetate) titanium, di-i-propoxy bis(ethylacetoacetate) titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethylacetoacetate) titanium, mono-n-propoxy tris(ethylacetoacetate) titanium, mono-i-propoxy tris(ethylacetoacetate titanium chelate compounds such as mono-n-butoxy tris(ethylacetoacetate) titanium, mono-sec-butoxy tris(ethylacetoacetate) titanium, mono-t-butoxy tris(ethylacetoacetate) titanium, tetrakis(ethylacetoacetate) titanium, mono(acetylacetonato) tris(ethylacetoacetate) titanium, bis(acetylacetonato) bis(ethylacetoacetate) titanium, and tris(acetylacetonato) mono(ethylacetoacetate) titanium; triethoxy mono(acetylacetonato) zirconium, tri-n-propoxy mono(acetylacetonato) zirconium, tri-i-propoxy mono(acetylacetonato) 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(acetylacetonate)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 tetrakis(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(ethylacetoacetate)zirconium, diethoxy bis(ethylacetoacetate)zirconium, di-n-propoxy bis(ethylacetoacetate)zirconium, di-i-propoxy bis(ethylacetoacetate)zirconium, di-n-butoxy bis(ethylacetoacetate)zirconium, di-sec-butoxy bis(ethylacetoacetate)zirconium, di-t-butoxy bis(ethylacetoacetate)zirconium, monoethoxy tris(ethylacetoacetate)zirconium, mono-n-propoxy tris(ethylacetoacetate)zirconium, mono-i-propoxy tris(ethylacetoacetate)zirconium, mono-n-butoxy zirconium chelate compounds such as tris(ethylacetoacetate)zirconium, mono-sec-butoxy-tris(ethylacetoacetate)zirconium, mono-t-butoxy-tris(ethylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, mono(acetylacetonato)tris(ethylacetoacetate)zirconium, bis(acetylacetonato)bis(ethylacetoacetate)zirconium, and tris(acetylacetonato)mono(ethylacetoacetate)zirconium; aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethylacetoacetate)aluminum, but are not limited to these.

Examples of organic acids that can be 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, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

Examples of inorganic acids that can be used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of organic bases 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.
Examples of inorganic bases as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like.

Among these hydrolysis catalysts, in the hydrolysis condensation reaction of the hydrolysis condensate (a), hydrolysis proceeds for each hydrolyzable silane molecule, that is, in a silane compound in which at least one hydrolyzable group present in one hydrolyzable silane (molecule) is hydrolyzed, hydrolysis of another hydrolyzable group in the same molecule is promoted. From this viewpoint, it is preferable to use an organic base or an inorganic base, and these may be used alone or in combination of two or more. For example, an aqueous solution of these (alkaline substances) can be used. In the present invention, an aqueous alkaline substance solution is present during the hydrolysis condensation of the hydrolyzable silane, and the hydrolysis condensate (a) is obtained by giving priority to the formation of silanol groups, and then, as described below, an inorganic acid is added or a cation exchange resin is used to convert the epoxy group into a dihydroxy group, and the hydrolysis condensate (A) containing an organic group having a dihydroxy group can be obtained.
In addition, if a ring-opening reaction of the epoxy group occurs during the hydrolysis and condensation reaction, the hydrolysis and condensation reaction and a side reaction (dehydration condensation) of the silanol group of the hydrolyzable silane and the hydroxy group generated by the ring-opening may proceed simultaneously. In this case, the obtained hydrolysis and condensation product may gel and have a gel-like structure, which is not preferable.

In carrying out the hydrolysis, an organic solvent may be used as a solvent. Specific examples of the organic solvent 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; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, and trimethylbenzene; 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-methylbutanol, 4-methylbutanol, 5-methylbutanol, 6-methylbutanol, 7-methylbutanol, 8-methylbutanol, 9-methylbutanol, 10-methylbutanol, 11-methylbutanol, 12-methylbutanol, 13-methylbutanol, 14-methylbutanol, 15-methylbutanol, 16-methylbutanol, 17-methylbutanol, 18-methylbutanol, 19-methylbutanol, 20-methylbutanol, 21-methylbutanol, 22-methylbutanol, 23-methylbutanol, 24-methylbutanol, 25-methylbutanol, 26-methylbutanol, 27-methylbutanol, 28-methylbutanol, 29-methylbutanol, 30-methylbutanol, 31-methylbutanol, 32-methylbutanol, 3 monoalcohol solvents such as butyl butanol, n-hexanol, 2-methyl pentanol, sec-hexanol, 2-ethyl butanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethyl hexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethyl nonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, phenyl methyl carbinol, diacetone alcohol, and cresol; ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, Polyhydric alcohol solvents such as hexanediol, 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 fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, and dimethyl Dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, 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 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 acetate Cholesterol monoethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate Examples of suitable solvents include, but are not limited to, ester-based solvents such as ethyl, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more.

The hydrolysis-condensation product thus obtained is a hydrolysis-condensation product (a) containing siloxane units containing an organic group having an epoxy group and siloxane units containing an organic group having an acetoxy group.
The hydrolyzed condensate (a) may be a hydrolyzed condensate of a hydrolyzable silane mixture that contains a hydrolyzable silane containing an organic group having an epoxy group (e.g., a compound represented by formula (1-a)) in a ratio of, for example, 10 mol % to 90 mol % based on the total amount of hydrolyzable silanes contained in the hydrolyzable silane mixture (total number of moles: 100 mol %), and contains a hydrolyzable silane containing an organic group having an acetoxy group (e.g., a compound represented by formula (1-b)) in a ratio of, for example, 10 mol % to 90 mol % based on the total amount of hydrolyzable silanes contained in the hydrolyzable silane mixture (total number of moles: 100 mol %).

In the hydrolyzable silane mixture, when a hydrolyzable silane other than a hydrolyzable silane containing an organic group having an epoxy group (e.g., a compound represented by formula (1-a)) and a hydrolyzable silane containing an organic group having an acetoxy group (e.g., a compound represented by formula (1-b)) is used, the amount of the hydrolyzable silane containing an organic group having an epoxy group (e.g., a compound represented by formula (1-a)) to be charged can be, for example, 10 mol% to 90 mol% relative to the amount (100 mol%) of all the hydrolyzable silanes contained in the hydrolyzable silane mixture. The amount of the hydrolyzable silane containing an organic group having an acetoxy group (e.g., a compound represented by formula (1-b)) to be charged can be, for example, 10 mol% to 90 mol%. From the viewpoint of reproducibly obtaining the above-mentioned effects of the present invention, preferably, the compound represented by formula (1-a) is charged in an amount of 15 mol% to 85 mol%, or 15 mol% to 80 mol%, or 20 mol% to 60 mol%, or 20 mol% to 40 mol%, or 15 mol% to 45 mol%, and the compound represented by formula (1-b) is charged in an amount of 15 mol% to 85 mol%, or 15 mol% to 80 mol%, or 20 mol% to 60 mol%, or 20 mol% to 40 mol%, or 15 mol% to 45 mol%, which can be appropriately adjusted depending on the compounds used.
When the silane compound represented by formula (2) or the silane compound represented by formula (3) is used in the hydrolyzable silane mixture, the amount of these silane compounds charged can be medium, usually 10 mol % to 90 mol %, for example 10 mol % to 80 mol %, 10 mol % to 70 mol %, 20 mol % to 60 mol %, based on the amount of all hydrolyzable silanes contained in the hydrolyzable silane mixture.
Furthermore, when a hydrolyzable organosilane having an onium group represented by formula (4) in the molecule is used in the hydrolyzable silane mixture, the amount of the organosilane charged is usually 0.01 mol % or more, preferably 0.1 mol % or more, and usually 30 mol % or less, preferably 10 mol % or less, based on the amount of all silane compounds (hydrolyzable silanes) charged.
When the hydrolyzable organosilane represented by formula (5-1) is used in the hydrolyzable silane mixture, the amount of the organosilane charged is usually 0.1 mol % or more, preferably 0.3 mol % or more, and usually 50 mol % or less, preferably 30 mol % or less, of all the silane compounds (hydrolyzable silanes).

In the above hydrolysis condensation product (a), the epoxy groups in the condensation product are ring-opened to form dihydroxy groups, thereby obtaining a hydrolysis condensation product (A) containing siloxane units containing an organic group having two or more hydroxy groups and siloxane units containing an organic group having an acetoxy group.
After the hydrolysis and condensation reactions are completed, the reaction solution may be directly subjected to the ring-opening reaction of the epoxy group. Alternatively, the reaction solution may be used as it is or after dilution or concentration, and then neutralized or treated with an ion exchange resin to remove the hydrolysis catalyst such as an acid or base used in the hydrolysis and condensation. Furthermore, before or after such treatment, the reaction solution may be subjected to the ring-opening reaction to remove by-products such as alcohol and water, and the hydrolysis catalyst used, by vacuum distillation or the like.

The ring-opening reaction of the epoxy group in the hydrolysis condensate (a) can be carried out with an inorganic acid or a cation exchange resin.
The inorganic acid can be added as an aqueous solution of inorganic acid. The concentration of the aqueous solution of inorganic acid can be, for example, about 0.01 M to 10 M. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
Examples of the cation exchange resin include strong acid cation resins (such as sulfonic acid type ion exchange resins) and weak acid cation resins (such as carboxylate type ion exchange resins).
In addition, when an organic acid is used, an addition reaction occurs during the ring-opening reaction of the epoxy group, and a dihydroxy structure cannot be formed.

The inorganic acid and the protons of the cation exchange resin function as catalysts in the ring-opening reaction of the epoxy group. In the present invention, when hydrolysis and condensation reactions are performed using the above-mentioned aqueous alkaline substance solution and an inorganic acid or a cation exchange resin is added to the reaction system containing the hydrolysis condensate, the inorganic acid or the cation exchange resin may be consumed in neutralizing the remaining alkaline substance. The above-mentioned protons used in the ring-opening reaction of the epoxy group generate dihydroxy groups by adding the protons at a ratio of 0.01 to 100 mol % relative to the epoxy group, but taking into account the amount consumed in neutralizing the alkaline substance, they can be added at a ratio of 0.01 to 1000 mol %, 0.01 to 500 mol %, 0.01 to 300 mol %, or 0.01 to 100 mol %.

After the inorganic acid or cation exchange resin is added, an anion exchange resin can be used to remove the anions. As the anion exchange resin, a strongly basic anion exchange resin (e.g., a quaternary ammonium type ion exchange resin) or a weakly basic anion exchange resin (e.g., a polyamine type ion exchange resin) can be added.
The cation exchange resin and anion exchange resin can be easily removed from the reaction system by filtration.

The hydrolysis condensate (A) (hereinafter also referred to as polysiloxane) thus obtained is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, which can be used as is for the manufacture of a resist underlayer film-forming composition described below. The obtained polysiloxane varnish may be solvent-substituted or may be diluted with a suitable solvent. If the obtained polysiloxane varnish has good storage stability, the organic solvent may be distilled off to make the solid content concentration 100%.
The organic solvent used for the solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane mixture. The dilution solvent is not particularly limited, and one or more kinds may be arbitrarily selected and used.

The hydrolysis condensate (A) of the hydrolyzable silane mixture and the hydrolysis condensate (a) which is its precursor can have a weight average molecular weight of, for example, 500 to 1,000,000. From the viewpoint of suppressing precipitation of the hydrolysis condensate in the resist underlayer film-forming composition, the weight average molecular weight can be preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less, and from the viewpoint of achieving both storage stability and coatability, the weight average molecular weight can be preferably 700 or more, more preferably 1,000 or more.
The weight average molecular weight is a molecular weight obtained by GPC analysis in terms of polystyrene. The GPC analysis can be performed, for example, using a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation) and a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), setting the column temperature at 40° C., using tetrahydrofuran as an eluent (elution solvent), setting the flow rate (flow velocity) at 1.0 mL/min, and using polystyrene (manufactured by Showa Denko K.K.) as a standard sample.

(B) Crosslinkable compound (crosslinking agent)
The crosslinkable compound (B) used in the present invention may be a crosslinkable compound containing a ring structure having an alkoxymethyl group or a hydroxymethyl group, or a crosslinkable compound having a blocked isocyanate group.
As the alkoxymethyl group, a methoxymethyl group can be preferably used.

The crosslinking compound may be a melamine-based compound, a substituted urea-based compound, or a polymer thereof. A crosslinking agent having at least two crosslink-forming substituents is preferred, and is a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds may also be used. Tetramethoxymethylglycoluril is available as Powder Link 1174 (PL-LI) from Mitsui Cytec Co., Ltd.

Furthermore, a crosslinking agent having high heat resistance can be used as the crosslinking agent. As a crosslinking agent having high heat resistance, a compound containing a crosslinking-forming substituent having an aromatic ring (e.g., a benzene ring, a naphthalene ring) in the molecule can be preferably used.

式（６）中、Ｒ^４１及びＲ^４２はそれぞれ水素原子、炭素原子数１～１０のアルキル基、又は炭素原子数６～２０のアリール基であり、ｎ^４１は１～４の整数であり、ｎ^４２は１～（５－ｎ^４１）の整数であり、ｎ^４１＋ｎ^４２は２～５の整数を示す。
式（７）中、Ｒ^４３は水素原子又は炭素原子数１～１０のアルキル基であり、Ｒ^４４は炭素原子数１～１０のアルキル基であり、ｎ^４３は１～４の整数であり、ｎ^４４は０～（４－ｎ^４３）であり、ｎ^４３＋ｎ^４４は１～４の整数を示す。
オリゴマー及びポリマーは繰り返し単位構造の数が２～１００、又は２～５０の範囲で用いることができる。これらのアルキル基やアリール基は上述の例示を挙げることができる。
なお上記式（６）で表される部分構造以外の構造や式（７）で表される繰り返し単位以外の構造は特に限定されず、例えば式（６）及び式（７）中のベンゼン環は任意の置換基で置換されていてもよい。 The compound may be a compound having a partial structure represented by the following formula (6), or a polymer or oligomer having a repeating unit represented by the following formula (7).

In formula (6), R ⁴¹ and R ⁴² each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; n ⁴¹ represents an integer of 1 to 4; n ⁴² represents an integer of 1 to (5−n ⁴¹ ); and n ⁴¹ +n ⁴² represents an integer of 2 to 5.
In formula (7), R ⁴³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁴⁴ is an alkyl group having 1 to 10 carbon atoms, n ⁴³ is an integer of 1 to 4, n ⁴⁴ is an integer of 0 to (4−n ⁴³ ), and n ⁴³ +n ⁴⁴ is an integer of 1 to 4.
The number of repeating structural units of the oligomers and polymers can be in the range of 2 to 100, or 2 to 50. Examples of the alkyl groups and aryl groups include those mentioned above.
The structures other than the partial structure represented by the above formula (6) and the structures other than the repeating unit represented by the formula (7) are not particularly limited, and for example, the benzene rings in the formulas (6) and (7) may be substituted with any substituent.

Examples of compounds containing the partial structure represented by formula (6) and polymers and oligomers having a repeating unit represented by formula (7) are shown below.

Compounds containing the partial structure represented by formula (6) above, and polymers and oligomers having a repeating unit represented by formula (7) are available as products from Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd.
For example, they can be obtained under the trade names 26DMPC (compound of formula (6-7)), 46DMOC, DM-BIPC-F (compound of formula (6-3)), DM-BIOC-F (compound of formula (6-4)), and TM-BIP-A (compound of formula (6-21)) manufactured by Asahi Organic Chemicals Co., Ltd.; and under the trade names T-MOM-PTBP (compound of formula (6-23)) and TMOM-BP (compound of formula (6-22)) manufactured by Honshu Chemical Industry Co., Ltd.

The amount of the crosslinking compound (B) added varies depending on the solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80 mass %, preferably 0.01 to 50 mass %, and more preferably 0.05 to 40 mass %, based on the total solids content of the resist underlayer film-forming composition. These crosslinking agents may cause a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the hydrolysis condensate (A), they can cause a crosslinking reaction with those crosslinkable substituents.

(C) Acid and Acid Generator Furthermore, in the present invention, (C) at least one of an acid and an acid generator is used.

The above-mentioned acids (acidic compounds) can have the effect of promoting the crosslinking reaction, and examples thereof include camphorsulfonic acid, citric acid, p-toluenesulfonic acid, pyridinium-p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, sulfosalicylic acid, pyridinium-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, pyridinium-4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, pyridinium-4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, pyridinium-benzenedisulfonic acid, benzoic acid, hydroxybenzoic acid, 1-naphthalenesulfonic acid, and pyridinium-1-naphthalenesulfonic acid. These acids can be used alone or in combination of two or more.
The acid (acidic compound) can be used in an amount of 0.01 to 10 mass%, or 0.05 to 8 mass%, or 0.1 to 8 mass%, or 0.3 to 8 mass%, or 0.5 to 5 mass%, relative to the mass of the hydrolysis-condensation product (A).

Examples of the acid generator include a thermal acid generator and a photoacid generator.
Among them, a photoacid generator is preferably used because it generates acid when the resist is exposed to light and can adjust the acidity of the underlayer film, which is useful as a method for matching the acidity of the underlayer film to that of the upper layer resist. In addition, the pattern shape of the resist formed in the upper layer can be adjusted by adjusting the acidity of the underlayer film, so the use of a photoacid generator is preferred from this viewpoint as well.
The thermal acid generator also promotes organic crosslinking between the hydrolysis condensate (A) and the crosslinkable compound (B) by generating an acid.

Examples of the photoacid generator include, but are not limited to, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
Examples of the thermal acid generator include, but are not limited to, tetramethylammonium nitrate and quaternary ammonium salts of trifluoromethanesulfonic acid.

Specific examples of onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride, but are not limited to these.

Specific examples of sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

Specific examples of disulfonyldiazomethane 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, methylsulfonyl-p-toluenesulfonyldiazomethane, etc.

The amount of the acid generator to be added cannot be generally specified since it is appropriately determined taking into consideration the type of the acid generator and the like. However, it is usually in the range of 0.01 to 10 mass % relative to the mass of the hydrolysis-condensation product (A). From the viewpoint of suppressing precipitation of the acid generator in the composition, etc., it is preferably 8 mass % or less, more preferably 5 mass % or less, and from the viewpoint of fully obtaining the effect thereof, it is preferably 0.1 mass % or more, more preferably 0.5 mass % or more.
The acid generators may be used alone or in combination of two or more kinds. A photoacid generator and a thermal acid generator may be used in combination.

The resist underlayer film-forming composition contains at least one of the above-mentioned (A) hydrolysis condensate of hydrolyzable silane (polysiloxane), (B) crosslinking compound, and (C) acid and acid generator, and may further contain a solvent and other components described later.
The solid content in the resist underlayer film-forming composition may be, for example, 0.1 to 50 mass%, 0.1 to 30 mass%, 0.1 to 25 mass%, or 0.5 to 20.0 mass%, relative to the total mass of the composition. The solid content refers to all components of the composition excluding the solvent component.
The content of the hydrolysis-condensation product (A) in the solid content is usually 20% by mass to 100% by mass. From the viewpoint of reproducibly obtaining the above-mentioned effects of the present invention, 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 additive described below.
The content of the hydrolysis-condensation product (A) in the composition may be, for example, 0.5 to 20.0% by mass.

The resist underlayer film-forming composition can be produced by mixing the above components (A) to (C) and, if desired, other components described below. In this case, a solvent may be added to the hydrolysis-condensation product (A) to prepare a solution containing the hydrolysis-condensation product (A) in advance, and this solution may be mixed with the component (B), the component (C), and the other components.
The order of mixing is not particularly limited. For example, the (B) component and the (C) component may be added in this order to a solution containing the (A) hydrolysis-condensation product and mixed, and other components may be added to the mixture, or the (A) hydrolysis-condensation product solution may be mixed with the (B) component, the (C) component, and other components at the same time.
If necessary, a solvent may be added at the end, or some components that are relatively soluble in the solvent may be left out of the mixture and added at the end. However, from the viewpoint of suppressing aggregation or separation of the components and reproducibly preparing a composition with excellent uniformity, it is preferable to prepare a solution in which the hydrolysis condensate is well dissolved in advance and use this to prepare the composition. Note that the hydrolysis condensate may aggregate or precipitate when mixed with other components depending on the type and amount of the solvent to be mixed with them, the amount and properties of other components, etc. In addition, when preparing a composition using a solution in which the hydrolysis condensate is dissolved, it is also necessary to determine the concentration of the solution of the hydrolysis condensate and the amount used so that the hydrolysis condensate in the final composition is the desired amount.
In preparing the composition, heating may be performed appropriately within a range that does not cause decomposition or deterioration of the components.

In the present invention, the resist underlayer film forming composition may be filtered using a sub-micrometer filter or the like during the production process or after all components are mixed.

The above resist underlayer film forming composition can be suitably used as a composition for forming a resist underlayer film used in a lithography process.

<Solvent>
The solvent that can be used in the resist underlayer film forming composition is not particularly limited as long as it is a solvent that can dissolve the solid content.
Such a solvent is not limited as long as it dissolves at least one of the above-mentioned (A) hydrolysis condensation product, (B) crosslinking compound, (C) acid and acid generator, and other components.

Specific examples include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether propylene glycol monomethyl ether ter, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, 2-hydroxy -3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 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, γ-butyrolactone, etc. can be mentioned, and the solvent can be used alone or in combination of two or more.

The resist underlayer film forming composition may also contain water as a solvent. When water is contained as a solvent, the content of water can be, for example, 30% by mass or less, preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total mass of the solvents contained in the composition.

<Other additives>
The resist underlayer film-forming composition may contain various additives depending on the intended use of the composition.
Examples of the additives include curing catalysts (ammonium salts, phosphines, phosphonium salts, sulfonium salts, nitrogen-containing silane compounds, etc.), stabilizers (organic acids, water, alcohols, etc.), organic polymer compounds, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, rheology adjusters, adhesion aids, and other known additives that are blended 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.
Various additives are exemplified below, but are not limited to these.

<Curing catalyst>
As the curing catalyst, ammonium salts, phosphines, phosphonium salts, sulfonium salts, etc. The following salts described as curing catalysts may be added in the form of a salt, or may form a salt in the composition (added as a separate compound and forming a salt in the system).

（式中、ｍは２乃至１１、ｎは２乃至３の整数を、Ｒ^２１はアルキル基又はアリール基を、Ｙ^－は陰イオンを表す。）で表される構造を有する第４級アンモニウム塩、
式（Ｄ－２）：

（式中、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＲ^２５はアルキル基又はアリール基を、Ｎは窒素原子を、Ｙ^－は陰イオンを表し、且つＲ^２２、Ｒ^２３、Ｒ^２４、及びＲ^２５はそれぞれＣ－Ｎ結合により窒素原子と結合されているものである）で表される構造を有する第４級アンモニウム塩、
式（Ｄ－３）：

（式中、Ｒ^２６及びＲ^２７はアルキル基又はアリール基を、Ｎは窒素原子を、Ｙ^－は陰イオンを表す）で表される構造を有する第４級アンモニウム塩、
式（Ｄ－４）：

（式中、Ｒ^２８はアルキル基又はアリール基を、Ｎは窒素原子を、Ｙ^－は陰イオンを表す）で表される構造を有する第４級アンモニウム塩、
式（Ｄ－５）：

（式中、Ｒ^２９及びＲ^３０はアルキル基又はアリール基を、Ｎは窒素原子を、Ｙ^－は陰イオンを表す）で表される構造を有する第４級アンモニウム塩、
式（Ｄ－６）：

（式中、ｍは２乃至１１、ｎは２乃至３の整数を、Ｈは水素原子を、Ｎは窒素原子を、Ｙ^－は陰イオンを表す）で表される構造を有する第３級アンモニウム塩を挙げることができる。 The ammonium salt may be represented by the formula (D-1):

(wherein m is an integer of 2 to 11, n is an integer of 2 or 3, R ²¹ is an alkyl group or an aryl group, and Y 1 ⁻ is an anion),
Formula (D-2):

(wherein R ²² , R ²³ , R ²⁴ and R ²⁵ represent an alkyl group or an aryl group, N represents a nitrogen atom, Y ⁻ represents an anion, and R ²² , R ²³ , R ²⁴ and R ²⁵ are each bonded to the nitrogen atom via a C—N bond),
Formula (D-3):

(wherein R ²⁶ and R ²⁷ represent an alkyl group or an aryl group, N represents a nitrogen atom, and Y 1 ^- represents an anion),
Formula (D-4):

(wherein R ²⁸ represents an alkyl group or an aryl group, N represents a nitrogen atom, and Y 1 ⁻ represents an anion),
Formula (D-5):

(wherein R ²⁹ and R ³⁰ represent an alkyl group or an aryl group, N represents a nitrogen atom, and Y 1 ^- represents an anion),
Formula (D-6):

(wherein m is an integer of 2 to 11, n is an integer of 2 or 3, H is a hydrogen atom, N is a nitrogen atom, and ^Y- is an anion).

（式中、Ｒ^３１、Ｒ^３２、Ｒ^３３、及びＲ^３４はアルキル基又はアリール基を、Ｐはリン原子を、Ｙ^－は陰イオンを表し、且つＲ^３１、Ｒ^３２、Ｒ^３３、及びＲ^３４はそれぞれＣ－Ｐ結合によりリン原子と結合されているものである）で表される第４級ホスホニウム塩を挙げることができる。 The phosphonium salt may also be represented by the formula (D-7):

(in the formula, R ³¹ , R ³² , R ³³ , and R ³⁴ represent an alkyl group or an aryl group, P represents a phosphorus atom, Y ⁻ represents an anion, and R ³¹ , R ³² , R ³³ , and R ³⁴ are each bonded to the phosphorus atom via a C—P bond).

（式中、Ｒ^３５、Ｒ^３６、及びＲ^３７はアルキル基又はアリール基を、Ｓは硫黄原子を、Ｙ^－は陰イオンを表し、且つＲ^３５、Ｒ^３６、及びＲ^３７はそれぞれＣ－Ｓ結合により硫黄原子と結合されているものである）で表される第３級スルホニウム塩を挙げることができる。 The sulfonium salt may also be represented by the formula (D-8):

(wherein R ³⁵ , R ³⁶ , and R ³⁷ represent an alkyl group or an aryl group, S represents a sulfur atom, Y ⁻ represents an anion, and R ³⁵ , R ³⁶ , and R ³⁷ are each bonded to the sulfur atom via a C—S bond).

The compound of formula (D-1) above is a quaternary ammonium salt derived from an amine, where m is an integer from 2 to 11 and n is an integer from 2 to 3. R ²¹ of this quaternary ammonium salt represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples of such groups include linear alkyl groups such as ethyl, propyl, and butyl, benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. Examples of the anion (Y ⁻ ) include halide ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), and iodine ion (I ⁻ ), and acid groups such as carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), and alcoholate (—O ⁻ ).

The compound of formula (D-2) above is a quaternary ammonium salt represented by R ²² R ²³ R ²⁴ R ²⁵ N ⁺ Y ^- . In this quaternary ammonium salt, R ²² , R 23 , R ²⁴ and R ²⁵ are an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. Examples of the ^anion (Y ^- ) include halide ions such as chloride ion (Cl ^- ), bromide ion (Br ^- ) and iodine ion (I ^- ), and acid groups such as carboxylate (-COO ^- ), sulfonate (-SO ₃ ^- ) and alcoholate (-O ^- ). This quaternary ammonium salt is commercially available, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

The compound of formula (D-3) above is a quaternary ammonium salt derived from 1-substituted imidazole, and R ²⁶ and R ²⁷ each have 1 to 18 carbon atoms, and it is preferable that the sum of the carbon atoms of R ²⁶ and R ²⁷ is 7 or more. For example, R ²⁶ can be methyl, ethyl, propyl, phenyl, or benzyl, and R ²⁷ can be benzyl, octyl, or octadecyl. Examples of the anion (Y ^- ) include halide ions such as chloride ion (Cl ^- ), bromide ion (Br ^- ), or iodine ion (I ^- ), and acid groups such as carboxylate (-COO ^- ), sulfonate (-SO ₃ ^- ), or alcoholate (-O ^- ). This compound is commercially available, but can also be produced by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with an alkyl halide or aryl halide such as benzyl bromide or methyl bromide.

The compound of the above formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ²⁸ is 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, such as a butyl group, an octyl group, a benzyl group, or a lauryl group. The anion (Y ⁻ ) can be a halide ion such as a chloride ion (Cl ⁻ ), a bromide ion (Br ⁻ ), or an iodide ion (I ⁻ ), or an acid group such as a carboxylate (—COO ⁻ ), a sulfonate (—SO ₃ ⁻ ), or an alcoholate (—O ⁻ ). This compound can be obtained as a commercial product, but can also be produced by reacting pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide, or an aryl halide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

The compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline, and R ²⁹ is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, such as a methyl group, an octyl group, a lauryl group, or a benzyl group. R ³⁰ is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and in the case of a quaternary ammonium derived from picoline, R ³⁰ is a methyl group. Examples of the anion (Y ⁻ ) include halide ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), and iodine ion (I ⁻ ), and acid groups such as carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), and alcoholate (—O ⁻ ). This compound is commercially available, but can also be produced by reacting, for example, a substituted pyridine such as picoline with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or an aryl halide, etc. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

The compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, where m is an integer from 2 to 11 and n is an integer from 2 to 3. Examples of the anion (Y ⁻ ) include halide ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), and iodide ion (I ⁻ ), and acid groups such as carboxylate (-COO ⁻ ), sulfonate (-SO ₃ ⁻ ), and alcoholate (-O ⁻ ). This compound can be produced by reacting an amine with a weak acid such as a carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. When formic acid is used, the anion (Y ⁻ ) is (HCOO ⁻ ), and when acetic acid is used, the anion (Y ⁻ ) is (CH ₃ COO ⁻ ). When phenol is used, the anion (Y ⁻ ) is (C ₆ H ₅ O ⁻ ).

The compound of the above formula (D-7) is a quaternary phosphonium salt having a structure of R ³¹ R ³² R ³³ R ³⁴ P ⁺ Y ^-. R ³¹ , R ³² , R ³³ , and R ³⁴ are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms, and preferably three of the four substituents of R ³¹ to R ³⁴ are phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. Examples of the anion (Y ^- ) include halide ions such as chloride ion (Cl ^- ), bromide ion (Br ^- ), and iodine ion (I ^- ), and acid groups such as carboxylate (-COO ^- ), sulfonate (-SO ₃ ^- ), and alcoholate (-O ^- ). This compound is available as a commercially available product, and examples of the compound 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 halides,
Examples of the halogenated tetraphenylphosphonium include halogenated triphenylmonoarylphosphonium, halogenated triphenylmonoalkylphosphonium, and halogenated triphenylmethylphosphonium, and halogenated triphenylethylphosphonium (wherein the halogen atom is a chlorine atom or a bromine atom). In particular, halogenated triphenylmonoalkylphosphonium such as halogenated triphenylmethylphosphonium and halogenated triphenylethylphosphonium, halogenated triphenylmonoarylphosphonium such as halogenated triphenylbenzylphosphonium, halogenated tritolylmonoarylphosphonium such as halogenated tritolylmonophenylphosphonium, and halogenated tritolylmonoalkylphosphonium such as halogenated tritolylmonomethylphosphonium (wherein the halogen atom is a chlorine atom or a bromine atom) are preferred.

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.

The compound of formula (D-8) above is a tertiary sulfonium salt having a structure of R ³⁵ R ³⁶ R ³⁷ S ⁺ Y ^- . R ³⁵ , R ³⁶ , and R ³⁷ are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms, and preferably two of the three substituents of R ³⁵ to R ³⁷ are phenyl groups or substituted phenyl groups, for example, phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. Examples of the anion (Y ^- ) include halide ions such as chloride ion (Cl ^- ), bromide ion (Br ^- ), and iodine ion (I ^- ), and acid groups such as carboxylate (-COO ^- ), sulfonate (-SO ₃ ^- ), alcoholate (-O ^- ), maleic acid anion, and nitrate anion. This compound is commercially available, and examples thereof include trialkylsulfonium halides such as tri-n-butylsulfonium halides and tri-n-propylsulfonium halides, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halides, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halides and diphenylethylsulfonium halides, triphenylsulfonium halides (wherein 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 halides and triphenylsulfonium carboxylates can be preferably used.

In addition, in the present invention, a nitrogen-containing silane compound can be added as a curing catalyst. Examples of the nitrogen-containing silane compound include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

When a curing catalyst is used, it is used in an amount of 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight, or 0.01 to 3 parts by weight, per 100 parts by weight of (A) polysiloxane.

<Stabilizer>
The stabilizer may be added for the purpose of stabilizing the hydrolysis-condensation product, and specific examples thereof include an organic acid, water, an alcohol, or a combination thereof.
Examples of the organic acid 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 an organic acid is added, the amount of the organic acid added is 0.1 to 5.0% by mass based on the mass of the hydrolysis-condensation product (A). These organic acids can also function as pH adjusters.
As the water, pure water, ultrapure water, ion-exchanged water, etc. can be used. When used, the amount of water added can be 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resist underlayer film-forming composition.
The alcohol is preferably one that is easily dispersed by heating after application, and examples thereof include methanol, ethanol, propanol, i-propanol, butanol, etc. When an alcohol is added, the amount added can be 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resist underlayer film forming composition.

<Organic Polymer>
The organic polymer compound can be added to the resist underlayer film-forming composition to adjust the dry etching rate (amount of film thickness reduction per unit time) of the film (resist underlayer film) formed from the composition, as well as the attenuation coefficient, refractive index, etc. The organic polymer compound is not particularly limited and is appropriately selected from various organic polymers (condensation polymerization polymers and addition polymerization polymers) depending on the purpose of its addition.
Specific examples thereof include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymers, methacrylic polymers, 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 moieties can also be suitably used when such a function is required. Specific examples of such organic polymer compounds include addition polymerization polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as structural units, and condensation polymerization polymers such as phenol novolac and naphthol novolac, but are not limited to these.

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

Specific examples of the acrylic acid ester compound include, but are not limited to, methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthryl 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.

Specific examples of methacrylic acid ester compounds include, but are not limited to, methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthryl 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.

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-anthrylacrylamide.

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-anthrylacrylamide.

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 acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, and the like.

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

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

When a condensation polymerization polymer is used as the polymer, such a polymer may be, for example, a condensation polymerization polymer of a glycol compound and a dicarboxylic acid compound. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, butylene glycol, etc. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, maleic anhydride, etc. Examples of polyesters, polyamides, and polyimides such as polypyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, but are not limited to these.
When the organic polymer compound contains a hydroxy group, this hydroxy group can undergo a crosslinking reaction with a hydrolysis condensation product or the like.

The weight average molecular weight of the organic polymer compound can usually be 1,000 to 1,000,000. When an organic polymer compound is blended, from the viewpoint of suppressing precipitation in the composition while fully obtaining the effect of its function as a polymer, the weight average molecular weight can be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000.
Such organic polymer compounds may be used alone or in combination of two or more.

When the resist underlayer film forming composition contains an organic polymer compound, its content cannot be generally defined because it is appropriately determined in consideration of the function of the organic polymer compound, but it can usually be in the range of 1 to 200% by mass relative to the mass of the hydrolysis condensate (A). From the viewpoint of suppressing precipitation in the composition, it can be, for example, 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less, and from the viewpoint of fully obtaining the effect, it can be, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

<Surfactant>
The surfactant is effective in suppressing the occurrence of pinholes, striations, etc., when the resist underlayer film forming composition is applied to a substrate. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicon surfactants, fluorine surfactants, UV-curable surfactants, etc. 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 polyoxyethylene sorbitan fatty acid esters such as oleate and polyoxyethylene sorbitan tristearate, trade names EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.)), trade names MEGAFAC (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), and Fluorad F Examples of suitable surfactants include, but are not limited to, fluorine-based surfactants such as C430, FC431 (manufactured by 3M Japan Ltd.), trade name Asahi Guard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
The surfactants can be used alone or in combination of two or more.

When the resist underlayer film forming composition contains a surfactant, the content thereof can be in the range of 0.0001 to 5% by mass, or 0.01 to 1% by mass, or 0.01 to 1% by mass, relative to the mass of the hydrolysis condensate (A).

<Rheology Modifier>
The rheology control agent is added mainly for the purpose of improving the fluidity of the resist underlayer film forming composition, and improving the film thickness uniformity of the film formed, particularly in the baking step, and enhancing the filling property of the composition into the inside of the hole.Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate, adipic acid derivatives such as di-n-butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyl decyl adipate, maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate, oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate, and stearic acid derivatives such as normal butyl stearate and glyceryl stearate.
When these rheology control agents are used, the amount added is usually less than 30 mass % based on the total solid content of the resist underlayer film forming composition.

<Adhesive assistant agent>
The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or resist and the film (resist underlayer film) formed from the resist underlayer film-forming composition, and particularly for the purpose of suppressing or preventing peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane, silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole, and vinyltrichlorosilane. , other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc.; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc.; and ureas such as 1,1-dimethylurea, 1,3-dimethylurea, etc., or thiourea compounds.
When these adhesion aids are used, the amount added is usually less than 5 mass %, and preferably less than 2 mass %, based on the total solid content of the resist underlayer film-forming composition.

<pH Adjuster>
In addition to the acids having one or more carboxylic acid groups such as the organic acids listed above as the <stabilizers>, bisphenol S or bisphenol S derivatives can be added as pH adjusters. The amount of bisphenol S or bisphenol S derivative is 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 the hydrolysis-condensation product (A).

Specific examples of bisphenol S and bisphenol S derivatives are given below, but the invention is not limited thereto.

As described above, the present invention provides a method for producing a silicon-containing resist underlayer film, comprising the steps of applying the resist underlayer film-forming composition described above to obtain a coating film and curing the coating film with ultraviolet light, and the silicon-containing resist underlayer film is removable with an aqueous sulfuric acid/hydrogen peroxide solution after a dry etching treatment with oxygen gas.
Hereinafter, specific examples of the method for producing a resist underlayer film using the resist underlayer film forming composition will be described in conjunction with, for example, steps before and after the application of the resist underlayer film to a semiconductor device, and wet removal of the resist underlayer film after production.

The resist underlayer film-forming composition is applied onto a substrate used in the manufacture of precision integrated circuit elements (e.g., a semiconductor substrate such as a silicon wafer coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (including alkali-free glass, low-alkali glass, and crystallized glass), a glass substrate on which an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film is formed, a plastic (polyimide, PET, etc.) substrate, a substrate coated with a low dielectric constant material (low-k material), a flexible substrate, etc.) by a suitable application method such as a spinner or coater, and the solvent is removed as necessary to obtain a coating film. The solvent can be removed by reducing pressure or heating. Heating conditions that can remove the solvent and are milder are preferable, and by adopting such conditions, excellent wet removability can be realized with good reproducibility. The heating conditions are appropriately determined, taking into consideration the boiling point of the solvent, the reactivity of the solids, the concentration of the solids, the desired film thickness, etc., usually within the ranges of a heating temperature of 30 to 140° C. and a heating time of 5 seconds to 2 minutes.
The coating film is exposed to light to form a resist underlayer film. Hereinafter, in this specification, the term "resist underlayer film" refers to a film formed from the resist underlayer film-forming composition.

Next, the resulting coating film is exposed to light.
For the exposure, ultraviolet light (wavelength 10 nm to 400 nm) can be used, and light having a wavelength of 150 nm to 330 nm, preferably 150 nm to 248 nm can be used, such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), Xe excimer laser (wavelength 172 nm), and F2 excimer laser (wavelength 157 nm), etc. Among them, the use of light having a wavelength of 172 nm is preferred.
The exposure light amount can be set to 10 mJ/cm ² to 3000 mJ/cm ² .
The exposure step may be carried out in an inert gas atmosphere in which oxygen and/or water vapor (water) is present. As the inert gas, nitrogen gas is particularly preferred.

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

As described below, the resist underlayer film photocured by ultraviolet irradiation is dry etched with oxygen gas. After the dry etching process, the resist underlayer film can be removed with an aqueous solution of sulfuric acid and hydrogen peroxide, as described below.

In addition, the resist underlayer film may be formed on the organic underlayer film formed on the substrate, and the present invention preferably has an organic underlayer film formed thereon. Hereinafter, the embodiment in which the organic underlayer film is formed will be described, including the steps following the resist underlayer film forming step.
The organic underlayer film used here is not particularly limited, and any film that has been conventionally used in the lithography process can be selected and used.
By providing an organic underlayer film on a substrate, a resist underlayer film thereon, and a resist film, which will be described later, on top of that, the pattern width of the photoresist film becomes narrower. Even if the photoresist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas, which will be described later.
For example, a resist underlayer film can be processed by using, as an etching gas, a fluorine-based gas having a sufficiently fast etching rate for a photoresist film, and an organic underlayer film can be processed by using, as an etching gas, an oxygen-based gas having a sufficiently fast etching rate for the resist underlayer film, and further, a substrate can be processed by using, as an etching gas, a fluorine-based gas having a sufficiently fast etching rate for the organic underlayer film.

Next, for example, a photoresist layer (resist film) is formed on the resist underlayer film. The resist film can be formed by a known method, that is, by applying a resist composition (for example, a photoresist) on the resist underlayer film and baking 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.

The photoresist material used in the resist film formed on the 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 photoresist materials and positive photoresist materials can be used. For example, there are positive photoresist materials consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresist materials consisting of a binder having a group that decomposes with acid to increase the alkaline dissolution rate and a photoacid generator, chemically amplified photoresist materials consisting of a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresist materials consisting of a binder having a group that decomposes with acid to increase the alkaline dissolution rate, a low molecular compound that decomposes with acid to increase the alkaline dissolution rate of the photoresist material, and a photoacid generator.
Specific examples of commercially available products include, but are not limited to, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., AR2772JN (trade name) manufactured by JSR Corporation, and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. In addition, examples of fluorine-containing polymer photoresist materials include 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).

In addition, for the resist film formed on the resist underlayer film, a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film) can be used instead of a photoresist film.
As the electron beam resist material, either a negative material or a positive material can be used. Specific examples thereof include a chemically amplified resist material consisting of an acid generator and a binder having a group that decomposes with an acid to change the alkaline dissolution rate, a chemically amplified resist material consisting of an alkali-soluble binder, an acid generator, and a low molecular weight compound that decomposes with an acid to change the alkaline dissolution rate of the resist material, a chemically amplified resist material consisting of an acid generator, a binder having a group that decomposes with an acid to change the alkaline dissolution rate, and a low molecular weight compound that decomposes with an acid to change the alkaline dissolution rate of the resist material, a non-chemically amplified resist material consisting of a binder having a group that decomposes with an electron beam to change the alkaline dissolution rate, and a non-chemically amplified resist material consisting of a binder having a site that is cut by an electron beam to change the alkaline dissolution rate. When these electron beam resist materials are used, a resist film pattern can be formed in the same way as when a photoresist material is used with an electron beam as the irradiation source.
As the EUV resist material, a methacrylate resin-based resist material can be used.

Next, the resist film formed on the upper layer of the resist underlayer film is exposed through a predetermined mask (reticle). For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), an EUV (wavelength 13.5 nm), an electron beam, or the like can be used.
After the exposure, a post-exposure bake may be carried out as necessary, at a heating temperature of 70° C. to 150° C. for a heating time of 0.3 to 10 minutes.

Next, development is carried out with a developer (e.g., an alkaline developer), whereby, when a positive photoresist film is used, the photoresist film in the exposed portion is removed, and a photoresist film pattern is formed.
Examples of the developer (alkaline developer) include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline, and an aqueous solution of an amine such as ethanolamine, propylamine or ethylenediamine. Furthermore, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

In the present invention, an organic solvent can be used as a developer, and development is carried out with the developer (solvent) after exposure. In this way, when a positive photoresist film is used, the photoresist film in the unexposed portion is removed, and a photoresist film pattern is formed.
Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate Examples of the developing solution include ethyl, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Furthermore, a surfactant or the like can be added to these developing solutions. The development conditions are appropriately selected from a temperature of 5° C. to 50° C. and a development time of 10 seconds to 600 seconds.

The pattern of the photoresist film (upper layer) thus formed is used as a protective film to remove the resist underlayer film (middle layer), then the film consisting of the patterned photoresist film and the patterned resist underlayer film (middle layer) is used as a protective film to remove the organic underlayer film (lower layer), and the substrate in the portion from which the organic underlayer film has been removed is subjected to processing such as ion (impurity) implantation, after which the resist underlayer film is removed.

The _resist underlayer film ( _middle layer) is removed by _dry etching using the pattern of the resist film ( _{upper layer} ) as a protective film.
Gases such as carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used.
It is preferable to use a halogen-based gas for dry etching of the resist underlayer film. In dry etching with a halogen-based gas, a resist film (photoresist film) made of an organic material is basically difficult to remove. In contrast, a silicon-containing resist underlayer film containing a large amount of silicon atoms is quickly removed by a halogen-based gas. Therefore, the decrease in the thickness of the photoresist film caused by dry etching of the resist underlayer film can be suppressed. As a result, the photoresist film can be used as a thin film. Therefore, it is preferable to use a fluorine-based gas for dry etching of the resist underlayer film, and examples of the fluorine-based gas include, but are not limited to, tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, difluoromethane (CH ₂ F ₂ ), etc.

When an organic underlayer film is present between the substrate and the resist underlayer film, the organic underlayer film (lower layer) is then removed using the patterned resist film (upper layer) and the patterned resist underlayer film (middle layer) as a protective film, and is preferably removed by dry etching with an oxygen-based gas (oxygen gas, oxygen/carbonyl sulfide (COS) mixed gas, etc.). This is because the resist underlayer film contains a large amount of silicon atoms and is difficult to remove by dry etching with an oxygen-based gas.

Subsequently, ion implantation can be performed as processing of the (semiconductor) substrate.
The ion implantation is performed by, for example, using a known ion implantation device or ion doping device to inject impurity ions into the substrate. The ion implantation conditions are appropriately selected from the following ranges: acceleration voltage: 500 eV to 10 MeV, dose: 1×10 ¹⁰ /cm ² to 1×10 ¹⁸ /cm ² .

Finally, the resist underlayer film is removed, which is generally performed by dry etching or wet etching.
Dry etching of the resist underlayer film (intermediate layer) is carried out, for example, with a fluorine-based gas, such as tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, and difluoromethane (CH ₂ F ₂ ).
In addition, the wet etching of the resist underlayer film (intermediate layer) is performed using a chemical solution such as dilute hydrofluoric acid, buffered hydrofluoric acid, an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (sulfuric acid-hydrogen peroxide aqueous solution) (SPM chemical solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM chemical solution), or an aqueous solution containing ammonia and hydrogen peroxide (SC-1 chemical solution).
The ratio of sulfuric acid to hydrogen peroxide in the SPM chemical solution is, for example, sulfuric acid/hydrogen peroxide=85-95 wt %/1-10 wt %.

In the present invention, the resist underlayer film obtained by the manufacturing method using the silicon-containing resist underlayer film can be wet-removed after dry etching with oxygen gas.
When the substrate is a silicon oxide film or when ion implantation is performed as a process for the substrate, there is a risk that the silicon oxide film or the ion-implanted substrate may be damaged if dry etching using a fluorine-based gas, which has been conventionally used, is performed to remove the resist underlayer film.
According to the present invention, a resist underlayer film is produced by photocuring a coating film of the resist underlayer film-forming composition, and the resist underlayer film after oxygen gas etching treatment can be removed by an aqueous sulfuric acid/hydrogen peroxide solution, and damage to the substrate can be suppressed compared to dry etching using a fluorine-based gas.

An organic anti-reflective film can be formed on the upper layer of the resist underlayer film before the formation of the resist film. There are no particular limitations on the anti-reflective film composition used therein, and any composition that has been conventionally used in lithography processes can be selected and used. The anti-reflective film can be formed by a conventional method, such as coating with a spinner or coater and baking.

The substrate to which the resist underlayer film-forming composition is applied may have an organic or inorganic anti-reflective film formed on its surface by a CVD method or the like, and a resist underlayer film may be formed thereon.

The resist underlayer film formed from the resist underlayer film forming composition may also absorb light depending on the wavelength of light used in the lithography process, and in such a case, can function as an antireflection film having an effect of preventing light reflected from the substrate.
Furthermore, the resist underlayer film can also be used as a layer for preventing interaction between the substrate and a resist film (such as a photoresist film), a layer having a function of preventing adverse effects on the substrate of materials used in the resist film or substances generated during exposure of the resist film, a layer having a function of preventing diffusion of substances generated from the substrate during heating and baking into the upper resist film, and a barrier layer for reducing the poisoning effect of the resist film due to the dielectric layer of the semiconductor substrate.

The resist underlayer film can be applied to a substrate having via holes formed therein for use in a dual damascene process, and can be used as a hole filling material (embedding material) capable of filling the holes without gaps. It can also be used as a planarizing material for planarizing the surface of a semiconductor substrate having irregularities.
In addition to its function as a hard mask, the resist underlayer film can be used as an underlayer anti-reflection film of an EUV resist film, which can prevent the reflection of undesirable exposure light, such as UV (ultraviolet) light or DUV (deep ultraviolet) light (ArF light, KrF light), from a substrate or interface during EUV exposure (wavelength 13.5 nm) without intermixing with the EUV resist film. That is, it can efficiently prevent reflection at the underlayer of the EUV resist film. When used as an EUV resist underlayer film, the process can be carried out in the same manner as for a photoresist underlayer film.

The present invention will be described in more detail below with reference to Synthesis Examples and Examples, but the present invention is not limited to the following.
The weight average molecular weight of the polymer (hydrolysis condensation product) prepared below was measured using the following GPC measuring device and measuring conditions.
GPC device Product name: HLC-8220GPC (manufactured by Tosoh Corporation)
GPC column Product name: Shodex (registered trademark KF803L, KF802, KF801 (manufactured by Showa Denko K.K.)
Column temperature: 40°C
Eluent (elution solvent): tetrahydrofuran Flow rate (flow rate): 1.0 mL/min
・Standard material: Polystyrene (Showa Denko K.K.)

[1] Preparation of polymer (hydrolysis condensation product) (Synthesis Example 1)
0.74 g of an aqueous solution of tetraethylammonium hydroxide (concentration: 35% by mass), 1.18 g of water, 22.15 g of isopropyl alcohol, and 44.30 g of methyl isobutyl ketone
While stirring the resulting solution with a magnetic stirrer, a mixture of 2.34 g of methoxybenzyltrimethoxysilane, 5.46 g of triethoxysilylpropyl diallyl isocyanurate, 2.20 g of methyltriethoxysilane, 4.33 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 7.82 g of acetoxypropyltrimethoxysilane was added dropwise thereto. After the addition, the flask was transferred to an oil bath adjusted to 40° C., and the reaction was carried out for 240 minutes.
Thereafter, 43.98 g of an aqueous nitric acid solution (concentration: 1 mol/L) was dropped into the reaction solution to ring-open the epoxy groups and form a hydrolysis condensate having dihydroxy groups, and the reaction was further carried out at 40° C. for 4 hours.
Thereafter, the reaction solution was cooled to room temperature, and the reaction solution was subjected to liquid separation treatment using 132.91 g of methyl isobutyl ketone and 66.45 g of water, and the organic layer was recovered. 66.45 g of propylene glycol monomethyl ether was added to the recovered organic layer, and methyl isobutyl ketone, methanol, ethanol and water were distilled off under reduced pressure to obtain a concentrated solution of a hydrolysis condensate (polymer) with propylene glycol monomethyl ether as a solvent. The solid content concentration of the obtained concentrated solution was more than 13 mass% in terms of solid residue when heated at 140 ° C.
Next, propylene glycol monoethyl ether was added to the obtained concentrated solution, and the concentration was adjusted to 13% by mass in terms of solid residue when heated at 140° C., to obtain a solution of a hydrolysis condensation product (polymer) in which propylene glycol monoethyl ether was used as a solvent (solid content concentration: 13% by mass). The obtained polymer contained a structure represented by formula (X-1), and its weight average molecular weight (Mw) was Mw2,500 in terms of polystyrene by GPC. In addition, the epoxy value was 0 as a result of measurement according to the method according to the JIS standard (JIS K 7236).

(Synthesis Example 2)
0.85 g of an aqueous solution of tetraethylammonium hydroxide (concentration: 35% by mass), 1.35 g of water, 24.80 g of isopropyl alcohol, and 49.59 g of methyl isobutyl ketone were placed in a 300 mL flask and stirred, and the resulting solution was stirred with a magnetic stirrer while a mixture of 3.04 g of methoxybenzyltrimethoxysilane, 6.23 g of triethoxysilylpropyl diallyl isocyanurate, 5.82 g of methyltriethoxysilane, 4.95 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 4.75 g of acetoxymethyltrimethoxysilane was added dropwise thereto. After the addition, the flask was transferred to an oil bath adjusted to 40° C., and the reaction was allowed to proceed for 240 minutes.
Thereafter, in order to ring-open the epoxy groups to form a hydrolysis condensation product having dihydroxy groups, 50.29 g of an aqueous nitric acid solution (concentration: 1 mol/L) was dropped into the reaction solution, and the reaction was further carried out at 40° C. for 4 hours.
Thereafter, the reaction solution was cooled to room temperature, and the reaction solution was subjected to a liquid separation treatment using 148.77 g of methyl isobutyl ketone and 74.39 g of water, and the organic layer was recovered. 74.39 g of propylene glycol monomethyl ether was added to the recovered organic layer, and methyl isobutyl ketone, methanol, ethanol and water were distilled off under reduced pressure to obtain a concentrated solution of a hydrolysis condensate (polymer) with propylene glycol monomethyl ether as a solvent. The solid content concentration of the obtained concentrated solution was more than 13 mass% in terms of solid residue when heated at 140 ° C.
Next, propylene glycol monoethyl ether was added to the obtained concentrated solution, and the concentration was adjusted to 13% by mass in terms of solid residue when heated at 140° C., to obtain a solution of a hydrolysis condensation product (polymer) in which propylene glycol monoethyl ether was used as a solvent (solid content concentration: 13% by mass). The obtained polymer contained a structure represented by formula (X-2), and its weight average molecular weight (Mw) was Mw2,700 in terms of polystyrene by GPC. In addition, the epoxy value was 0 as a result of measurement according to the method according to the JIS standard (JIS K 7236).

Comparative Synthesis Example 1
25.4 g of tetraethoxysilane, 1.73 g of phenyltrimethoxysilane, 7.36 g of methyltriethoxysilane, 0.72 g of triethoxysilylpropyl diallyl isocyanurate, and 53.02 g of acetone were placed in a 300 mL flask and stirred, and 11.63 g of an aqueous hydrochloric acid solution (concentration: 0.01 mol/L) was added dropwise to the resulting solution while stirring it with a magnetic stirrer. After the addition, the flask was transferred to an oil bath adjusted to 85° C. and refluxed for 240 minutes.
Then, 70 g of propylene glycol monomethyl ether acetate was added, and acetone, methanol, ethanol, hydrochloric acid, and water were distilled off under reduced pressure to obtain a concentrated solution of a hydrolysis condensate (polymer) with propylene glycol monomethyl ether acetate as a solvent. The solid content of the obtained concentrated solution was more than 13% by mass in terms of solid residue when heated at 140°C.
Next, propylene glycol monoethyl ether was added to the obtained concentrated solution, and the concentration was adjusted to 13% by mass in terms of solid residue when heated at 140° C., to obtain a solution of a hydrolysis condensate (polymer) (solid content concentration 13% by mass) in a mixed solvent (20/80 (V/V)) of propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether. The obtained polymer contained a structure represented by formula (X-3), and its weight average molecular weight (Mw) was Mw2,100 in terms of polystyrene by GPC. In addition, the epoxy value was 0 as a result of measurement according to the method according to the JIS standard (JIS K 7236).

[2] Examples 1 and 2, Comparative Example 1: Preparation of silicon-containing resist underlayer film-forming compositions The hydrolysis-condensation products (Si polymers), acids and acid generators, crosslinking compounds, solvents, etc. obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 above were mixed in the ratios (parts by mass) shown in Tables 1 and 2, and the mixture was filtered through a fluororesin filter having a pore size of 0.1 μm to prepare silicon-containing resist underlayer film-forming compositions.
The proportion of polymer (polysiloxane) added in Tables 1 and 2 indicates the amount of polymer itself added, not the amount of polymer solution added.
In addition, the abbreviations used in Tables 1 and 2 below are as follows.
PPTS: Pyridinium-p-toluenesulfonic acid TAG-2689: Quaternary ammonium salt of trifluoromethanesulfonic acid (thermal acid generator manufactured by King Industries)
PL-LI: Tetramethoxymethylglycoluril (manufactured by Mitsui Cytec Co., Ltd., product name Powder Link 1174)
MA: Maleic acid IMID-TEOS: N-(3-triethoxypropyl)-4,5-dihydroimidazole PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate PGEE: Propylene glycol monoethyl ether

得られたポリマーを含む溶液５ｇ（ポリマーの濃度：１６質量％）に、テトラエトキシメチルグリコールウリル０．２ｇ、ピリジニウム－ｐ－トルエンスルホナート０．０３ｇ及び製品名 メガファック［商標登録］Ｒ－３０（ＤＩＣ（株）製）０．０００８ｇ、プロピレングリコールモノメチルエーテル６．４ｇ及びプロピレングリコールモノメチルエーテルアセテート４．５ｇを加えて混合し、得られた溶液を孔径０．１０μｍのポリエチレン製ミクロフィルターで濾過した後、孔径０．０５μｍのポリエチレン製ミクロフィルターで更に濾過し、有機下層膜形成組成物を得た。 [3] Preparation of Organic Underlayer Film-Forming Composition To 7.57 g of propylene glycol monomethyl ether, 17.67 g of propylene glycol monomethyl ether acetate, 5.00 g of product name: EHPE-3150 (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, manufactured by Daicel Corporation), 3.11 g of 9-anthracenecarboxylic acid, 2.09 g of benzoic acid, and 0.62 g of ethyltriphenylphosphonium bromide were added, and the mixture was heated to reflux for 13 hours under a nitrogen atmosphere.
After the reaction mixture was cooled to room temperature, 16 g of a cation exchange resin (product name: Amberlyst [registered trademark] 15JWET, manufactured by Organo Corporation) and 16 g of an anion exchange resin (product name: Dowex [registered trademark] MONOSPHERE [registered trademark] 550A, manufactured by Muromachi Chemical Co., Ltd.) were added thereto, and the mixture was stirred for 4 hours at 25° C. to 30° C. Then, the resin was removed by filtration, and a solution containing a polymer, which was the reaction product, was obtained.
The reaction product obtained was subjected to GPC analysis, and the weight average molecular weight, calculated based on standard polystyrene, was found to be 4,700. The reaction product obtained is presumed to be a copolymer (polymer) having a structural unit represented by the following formula (Y).

To 5 g of the obtained solution containing the polymer (polymer concentration: 16% by mass), 0.2 g of tetraethoxymethylglycoluril, 0.03 g of pyridinium-p-toluenesulfonate, 0.0008 g of product name Megafac [registered trademark] R-30 (manufactured by DIC Corporation), 6.4 g of propylene glycol monomethyl ether, and 4.5 g of propylene glycol monomethyl ether acetate were added and mixed, and the obtained solution was filtered through a polyethylene microfilter having a pore size of 0.10 μm and then further filtered through a polyethylene microfilter having a pore size of 0.05 μm, to obtain an organic underlayer film-forming composition.

[4] Thermosetting test (100°C, 1 minute)
Each of the silicon-containing resist underlayer film forming compositions prepared in Examples 1 and 2 and Comparative Example 1 was applied onto a silicon wafer using a spinner, and heated on a hot plate at 100° C. for 1 minute to form a film, and the film thickness of each of the obtained films was measured.
Thereafter, a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (7/3 (V/V)) was applied onto each film, and spin-dried. The film thickness of the dried film was then measured, and the presence or absence of a change in film thickness before and after application of the mixed solvent was evaluated. Based on the film thickness before application of the mixed solvent, a film with a film thickness change of 10% or less after application was evaluated as "good", and a film with a film thickness change of less than 10% was evaluated as "not cured". The results are shown in Table 3. In the following description, the example number of the resist underlayer film-forming composition used will also be treated as the example number of the various evaluations performed using the composition.

As shown in Table 3, it was confirmed that under the above heating conditions, the films formed using the silicon-containing resist underlayer film-forming compositions of Examples 1 and 2 and Comparative Example 1 did not exhibit sufficient solvent resistance.

[5] Photocurability test Each of the silicon-containing resist underlayer film forming compositions prepared in Examples 1 and 2 and Comparative Example 1 was applied onto a silicon wafer using a spinner, heated on a hot plate at 100°C for 1 minute to form a film, and then irradiated the entire surface of each film with light having a wavelength of 172 nm at about 300 mJ/ ^cm2 or about 500 mJ/ ^cm2 under a nitrogen atmosphere using a light irradiation device (SUS867 manufactured by Ushio Inc.). Then, the film thickness of each film after irradiation was measured.
Thereafter, a mixed solvent of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (=7/3 (V/V)) was applied onto each film, spun and dried. The film thickness of each film after drying was then measured, and the presence or absence of change in film thickness before and after application of the mixed solvent was evaluated. Using the film thickness before application of the mixed solvent as the standard, films with a film thickness change of 10% or less after application were evaluated as "good", and films with a film thickness change of less than 10% were evaluated as "not cured". The results are shown in Table 4.

As shown in Table 4, it was confirmed that the films formed using the silicon-containing resist underlayer film-forming compositions of Examples 1 and 2 exhibited photocurability.

[6] Evaluation of resist pattern by ArF immersion exposure (resist patterning evaluation: evaluation via PTD process involving alkaline development)
The organic underlayer film-forming composition was applied onto a silicon wafer using a spinner, and heated on a hot plate at 240° C. for 1 minute to form an organic underlayer film (layer A).
Film thickness: 200 nm.
On the A layer, each of the silicon-containing resist underlayer film forming compositions prepared in Examples 1 to 2 and Comparative Example 1 was applied using a spinner, and heated on a hot plate at 100°C for 1 minute to form a coating film, and then, under a nitrogen atmosphere, the entire surface of each film was irradiated with light having a wavelength of 172 nm at about 100 mJ/ ^cm2 using a light irradiation device (SUS867 manufactured by Ushio Inc.) to form a silicon-containing resist underlayer film (B layer) (film thickness 40 nm). The same operation was also carried out under conditions of about 300 mJ/ ^cm2 or about 500 mJ/ ^cm2 to form a silicon-containing resist underlayer film (B layer) (film thickness 40 nm).
A commercially available ArF immersion resist solution was further applied onto the B layer using a spinner, and heated on a hot plate at 110° C. for 1 minute to form a photoresist film (C layer) (film thickness 90 nm). After that, exposure was performed using a scanner (wavelength 193 nm, NA: 1.35, 0.98/0.75) through a mask set so that after development, the photoresist line width and the width between the lines would be 0.040 μm, i.e., a dense line with a line and space (L/S) of 0.040 μm (L/S) = 1/1).
After exposure, post-exposure baking (110° C. for 1 minute) was performed, followed by cooling to room temperature on a cooling plate, and developing for 60 seconds using an alkaline aqueous solution with a concentration of 38% by mass, followed by rinsing treatment to form a resist pattern.
The resist patterns obtained were evaluated as "good" if no significant pattern peeling, undercut, or thickening of the line bottom (footing) occurred, and as "pattern collapse" if collapsed. The results are shown in Table 5.

As shown in Table 5, it was confirmed that the films formed using the silicon-containing resist underlayer film forming compositions of Examples 1 and 2 exhibited good lithography properties.

[7] Evaluation of SPM Removability of Photocured Resist Underlayer Film Each of the silicon-containing resist underlayer film forming compositions prepared in Examples 1 and 2 and Comparative Example 1 was applied onto a silicon wafer using a spinner, and heated on a hot plate at 100°C for 1 minute to form a film. Next, in a nitrogen atmosphere, the entire surface of each film was irradiated with light having a wavelength of 172 nm at about 100 mJ/ ^cm2 using a light irradiation device (SUS867 manufactured by Ushio Inc.) to form a photocured film. The same operation was also performed under conditions of about 300 mJ/ ^cm2 or about 500 mJ/ ^cm2 to form a photocured film. The film thickness of each of the obtained photocured films was then measured.
On the other hand, each of the silicon-containing resist underlayer film forming compositions prepared in Examples 1 and 2 and Comparative Example 1 was applied onto a silicon wafer using a spinner, and heated on a hot plate at 180° C. for 60 seconds to form a thermocured film, and the film thickness of each of the obtained thermocured films was measured.
On each of the photocured or thermocured films obtained, resist remover RS-30 manufactured by Rasa Kogyo Co., Ltd. (mixed water of sulfuric acid and hydrogen peroxide (sulfuric acid/hydrogen peroxide = 85-95 wt %/1-10 wt %): SPM chemical solution) was applied, rinsed with water, and dried by blowing air onto the substrate. The film thickness of each film after drying was then measured, and the presence or absence of change in film thickness before and after application of the mixed solvent was evaluated. Using the film thickness before application of the SPM chemical solution as the standard, a film with a film thickness change of 70% or more after application was evaluated as "good", and a film with a film thickness change of less than 70% was evaluated as "not dissolved". From the viewpoint of confirming the removal performance by the SPM chemical solution, the evaluation of "not dissolved" in this case is not preferable in the present invention. The obtained results are shown in Table 6.

As shown in Table 6, it was confirmed that the films photocured and thermally cured using each of the silicon-containing resist underlayer film-forming compositions of Examples 1 and 2 all had good removability with an SPM chemical solution.

[8] Evaluation of SPM removability of resist underlayer film after dry etching Using each of the silicon-containing resist underlayer film-forming compositions prepared in Examples 1 and 2 and Comparative Example 1, a photocured film or a thermocured film was obtained in the same manner as described above, and the film thickness of each of the obtained photocured films and thermocured films was measured.
Each of the photocured films or thermocured films obtained was subjected to _O2 dry etching treatment (etching conditions: _N2 / _O2 =150/50 (sccm/sccm), time: 30 seconds, pressure: 8 Pa, 100 W) using a parallel plate reactive ion etcher RIE-10NR (manufactured by Samco Corporation).
Then, on each photocured film or each thermocured film that had been etched, a resist remover RS-30 (mixed water of sulfuric acid and hydrogen peroxide: SPM chemical solution) manufactured by Rasa Kogyo Co., Ltd. was applied, rinsed with water, and dried by blowing air onto the substrate. Then, the film thickness of each film after drying was measured, and the presence or absence of a change in film thickness before and after application of the mixed solvent was evaluated. Based on the film thickness before application of the SPM chemical solution (before etching), a film with a film thickness change of 70% or more after application was evaluated as "good", and a film with a film thickness change of less than 70% was evaluated as "not dissolved". From the viewpoint of confirming the removal performance by the SPM chemical solution, the evaluation of "not dissolved" in this case is not preferable in the present invention. The obtained results are shown in Table 7.

As shown in Table 7, it was confirmed that the films obtained by photocuring each of the silicon-containing resist underlayer film-forming compositions of Examples 1 and 2 had good removability by the SPM chemical solution even after _O2 etching.

Claims (2)

(A) A hydrolysis condensate of a hydrolyzable silane, comprising a siloxane unit containing an organic group having two or more hydroxy groups and a siloxane unit containing an organic group having an acetoxy group.
A method for producing a silicon-containing resist underlayer film, comprising: curing a coating film of a resist underlayer film-forming composition containing the compound with ultraviolet light,
The silicon-containing resist underlayer film is
A treatment process is applied that includes a step of removing the film using a sulfuric acid/hydrogen peroxide aqueous solution after dry etching using oxygen gas,
the dry etching treatment using oxygen gas is treatment using at least one gas selected from the group consisting of oxygen gas, oxygen/carbonyl sulfide (COS) mixed gas, and oxygen/nitrogen mixed gas;
The method for producing a silicon-containing resist underlayer film, wherein the aqueous sulfuric acid/hydrogen peroxide solution contains sulfuric acid and hydrogen peroxide in a ratio of sulfuric acid/hydrogen peroxide=85-95 wt %/1-10 wt %. The resist underlayer film forming composition,
2. The method for producing a silicon-containing resist underlayer film according to claim 1, comprising: (B) a crosslinkable compound; and (C) at least one of an acid and an acid generator.