JP2021189314A - Manufacturing method of silicone-containing resist underlay film - Google Patents

Abstract

To provide a manufacturing method of a silicone-containing resist underlay film, which is a resist underlay film usable for manufacture of a semiconductor device, capable of removing by a wet method using a chemical liquid, in particular, SPM (mixed aqueous solution of sulfuric acid and hydrogen peroxide water) can be applied, even after an oxygen gas etching was applied.SOLUTION: A method of manufacturing a silicon-containing resist underlayer film capable of being removed by an aqueous sulfuric acid hydrogen peroxide solution after dry etching with oxygen gas comprises a step of curing, with ultraviolet ray, a coating film of a resist underlay film formation composition containing (A) a hydrolysis condensate 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.SELECTED DRAWING: None

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 a photoresist has been performed. The above microfabrication is obtained by forming a photoresist thin film on a semiconductor substrate such as a silicon wafer, irradiating it with active light such as ultraviolet rays through a mask pattern on which a pattern of a semiconductor device is drawn, and developing it. This is a processing method for forming fine irregularities corresponding to the above pattern on the surface of the substrate by etching the substrate using the photoresist pattern as a protective film.
In recent years, the degree of integration of semiconductor devices has been increasing, and the wavelength of active light rays used has tended to be shortened from KrF excimer laser (248 nm) to ArF excimer laser (193 nm). With the shortening of the wavelength of the active light, the influence of the reflection of the active light from the semiconductor substrate becomes a big problem. A resist underlayer film called an antireflection film (Bottom Anti-Reflective Coating, BARC) between the photoresist and the substrate to be processed. The method of providing the above has become widely applied.

As the underlayer film between the semiconductor substrate and the photoresist, a film known as a hard mask containing a metal element such as silicon or titanium is used. In this case, since there is a large difference in the constituent components between the resist and the hard mask, the rate of removal by dry etching thereof largely depends on the gas type used for the dry etching. Then, by appropriately selecting the gas type, the hard mask can be removed by dry etching and pattern processing can be performed without significantly reducing the film thickness of the photoresist. As described above, in the recent manufacture of semiconductor devices, a resist underlayer film has come to be arranged between a semiconductor substrate and a photoresist in order to achieve various effects including an antireflection effect.

In recent years, due to the miniaturization of state-of-the-art semiconductor devices, a three-layer process in which a resist underlayer film of an organic film, a resist underlayer film containing silicon on the substrate, and a resist layer on the resist layer is used has been used. Since damage to the substrate due to dry etching can be considered in a normal three-layer process, a step of removing the silicon-containing resist underlayer film by a wet method is desired.
For example, it has been proposed that an antireflection film material containing a titanium siloxane resin having a crosslinkable organic group is used to remove the film obtained from the material by a wet strip (Patent Document 1 and the like).
Further, in the manufacture of a semiconductor element, ion implantation is adopted in which, for example, an impurity ion that imparts an n-type or p-type conductive type to a semiconductor substrate is introduced into a semiconductor substrate using a photoresist pattern as a mask. In this case, the impurity ions are implanted directly into the semiconductor substrate or through a thin film formed on the surface of the semiconductor substrate by using an ion implantation device (ion doping device). After that, 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 wetly removing the silicon-containing resist underlayer film is also desired. It is rare.

Further, since the depth of focus decreases as the exposure wavelength becomes shorter, it is necessary to improve the flatness of the film formed on the substrate. In order to manufacture a semiconductor device that requires a finer design, a flattening technique on a substrate is important. For example, a method of forming a resist underlayer film formed under a resist by photocuring is disclosed. ing.
For example, a resist underlayer film forming composition containing a silicon-based compound having a cationically polymerizable reactive group such as an epoxy group or a vinyl group, a photocationic polymerization initiator, and a photoradical polymerization initiator is disclosed (Patent). See Document 2).

Japanese Unexamined Patent Publication No. 2007-163846 International Publication No. 2007/066597

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

As a result of diligent studies to solve the above problems, the present inventors can obtain a polysiloxane 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. We have found that the photocured film can be removed by a wet method using a chemical solution even after the oxygen gas etching treatment, and completed the present invention.

That is, the present invention is, as a first aspect, a method for producing a silicon-containing resist underlayer film that can be removed by an aqueous solution of hydrogen peroxide after dry etching with oxygen gas.
(A) A resist underlayer film forming composition containing a hydrolysis condensate of hydrolyzable silane, which comprises 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 present invention relates to a method for producing a silicon-containing resist underlayer film, which comprises a step of curing a coating film of an object with ultraviolet rays.
As a second aspect, the resist underlayer film forming composition is
The present invention relates to the method for producing a silicon-containing resist underlayer film according to the first aspect, which comprises (B) a crosslinkable compound and (C) at least one of an acid and an acid generator.
As a third aspect, according to the first aspect or the second aspect, the aqueous hydrogen peroxide solution contains sulfuric acid and hydrogen peroxide in a ratio of sulfuric acid / hydrogen peroxide = 85-95 wt% / 1-10 wt%. The present invention relates to a method for producing a silicon-containing resist underlayer film.

According to the present invention, the resist underlayer film to be produced by the present invention has a siloxane unit containing an organic group having two or more hydroxy groups and an organic having an acetoxy group as a hydrolyzable condensate of hydrolyzable silane. It is formed from a composition containing a hydrolyzed condensate containing a siloxane unit containing a group, and further containing a crosslinkable compound and an acid or the like.
Conventionally, a co-hydrolysis condensate (polysiloxane) of a tetrafunctional silane such as tetraethoxysilane and a trifunctional silane used for a silicon-containing resist underlayer film is mainly produced by forming a crosslinked structure between silanol groups. Although the resist underlayer film has the advantage of not intermixing with the resist composition overcoated on top, it is subsequently processed with a chemical solution such as SPM (mixed aqueous solution of sulfuric acid and hydrogen peroxide solution) after processing the underlayer or substrate. ) Was difficult to remove.
In the present invention, by using the above-mentioned hydrolysis condensate having two or more hydroxy groups and acetoxy groups in the production of the underlayer film of the resist, the hydroxy groups can be used with each other, or between the hydroxy groups and the silanol groups, or with the hydroxyl groups. It forms a crosslinked structure with a crosslinkable compound. Therefore, not only does intermixing with the resist composition overcoated on the upper part of the resist underlayer film not occur, but also after the lower layer is processed, especially after the resist underlayer film is dry-etched with oxygen gas. , SPM (mixed aqueous solution of sulfuric acid and hydrogen peroxide solution) can be used for removal. Therefore, it is possible to reduce the damage to the substrate caused by dry etching with a fluorine-based gas when the resist underlayer film is conventionally removed from the substrate.
Further, in the present invention, it is possible to photo-cure the hydrolyzed condensate having the above-mentioned specific organic group, and the hydrolyzed condensate is photo-cured to form a resist underlayer film (cured film). ). Therefore, conventionally, the flattening of the organic underlayer film that may exist in the lower layer of the resist underlayer film, which may occur when the resist underlayer film is manufactured at a high temperature, is not deteriorated, and the flattening property is on the organic underlayer film. By forming a highly flattening silicon-containing resist underlayer film and coating the resist film on the upper layer, it is possible to suppress diffused reflection at the layer interface and suppress the generation 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 can be removed by an aqueous solution of hydrogen peroxide after dry etching with oxygen gas.

[Manufacturing method of silicon-containing resist underlayer film]
After the dry etching treatment with oxygen gas to which the present invention is applied, the silicon-containing resist underlayer film that can be wet-removed with an aqueous solution of hydrogen peroxide is (A) a hydrolyzed condensate of hydrolyzable silane (polysiloxane). The coating film of the resist underlayer film forming composition containing the above-mentioned material is produced by including a step of curing with ultraviolet rays. That is, the silicon-containing resist underlayer film is an ultraviolet (UV) cured film obtained by curing the coating film of the resist underlayer film forming composition by ultraviolet irradiation.
The resist underlayer film forming composition further contains at least one of (B) a crosslinkable compound, (C) an acid and an acid generator.

[Resist Underlayer Film Forming Composition]
(A) Hydrolyzed condensate of hydrolyzable silane (polysiloxane)
The (A) hydrolyzed condensate used in the present invention is a hydrolyzed 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 hydrolyzed condensate (A) is a hydrolyzable silane mixture containing a hydrolyzable silane containing an organic group having two or more hydroxy groups and a hydrolyzable silane containing an organic group having an acetoxy group. It can be a hydrolyzed condensate.
Alternatively, (A) the hydrolyzed condensate is an inorganic acid or cation exchange of the hydrolyzed condensate (a) containing an organic group having an epoxy group and a siloxane unit containing an organic group having an acetoxy group. The resin can be used as a hydrolyzed condensate obtained by opening the ring of the epoxy group. The hydrolyzed condensate (a) is a hydrolyzed condensate of a hydrolyzable silane mixture containing a hydrolyzable silane containing an organic group having an epoxy group and a hydrolyzable silane containing an organic group having an acetoxy group. Can be.
In addition to the stability of the (A) hydrolyzed condensate, the (A) hydrolyzed condensate is a hydrolyzed condensate (A), considering the drawbacks such as inhibition of the progress of the reaction due to gelation during the hydrolyzed condensation reaction. It is preferably a hydrolyzed condensate obtained through a).
In the present invention, the "hydrolyzed condensate" includes not only a polyorganosiloxane polymer which is a condensate whose condensation is completely completed but also a polyorganosiloxane polymer which is a partially hydrolyzed condensate whose condensation is not completely completed. Will be done. Such a partially hydrolyzed condensate is also a polymer obtained by hydrolysis and condensation of a hydrolyzable silane compound, like the condensate in which condensation is completely completed, but it partially stops at hydrolysis and condenses. Therefore, the Si—OH group remains. Further, in the resist underlayer film forming composition, in addition to the above-mentioned hydrolyzed condensate, an uncondensed hydrolyzate (completely hydrolyzed product, partially hydrolyzed product) and a monomer (hydrolyzable silane compound) remain. May be. In the present specification, "hydrolyzable silane" may be simply referred to as "silane compound".

Further, as described later, the hydrolyzable silane containing an organic group having an epoxy group is 10 mol% based on the total number of moles (100 mol%) of the total hydrolyzable silane contained in the hydrolyzed silane mixture. It is preferably contained in a proportion of ~ 90 mol%.
By setting the proportion of the hydrolyzable silane containing an organic group having an epoxy group to 10 mol% or more, intermixing resistance to the topcoat resist composition can be ensured. Intermixing is an unfavorable phenomenon because when the upper layer composition is applied onto the lower layer film, the lower layer film dissolves and the lower layer film and the upper layer composition cause layer mixing.
Further, by setting the ratio of the hydrolyzable silane containing an organic group having an epoxy group to 90 mol% or less, optical physical characteristics and dry etching resistance can be ensured.

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

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 equation (1-a),
R ^1a is a group bonded to a silicon atom and represents an organic group containing an epoxy group.
R ^2a is a group that is bonded to a silicon atom by a Si—C bond, and is an alkyl group that may be substituted, an aryl group that may be substituted, or an aralkyl group that may be substituted independently of each other. , A optionally substituted alkyl halide group, an optionally substituted aryl halide group, an optionally substituted aralkyl halide group, an optionally substituted alkoxyalkyl group, optionally substituted. Represents an alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, a sulfonyl group, or Representing an organic group containing a cyano group or a combination thereof, R ^3a is a group or atom bonded to a silicon atom, and independently of each other, a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom. Represents
a1 represents 1 and b1 represents an integer of 0 to 2, and 4- (a1 + b1) represents an integer of 1 to 3.
Also, in equation (1-b),
R ^1b is a group bonded to a silicon atom and represents an organic group containing an acetoxy group.
R ^2b is a group bonded to a silicon atom by a Si—C bond, and is an alkyl group which may be substituted independently of each other, an aryl group which may be substituted, and an aralkyl group which may be substituted. , A optionally substituted alkyl halide group, an optionally substituted aryl halide group, an optionally substituted aralkyl halide group, an optionally substituted alkoxyalkyl group, optionally substituted. Represents an alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, a sulfonyl group, or Representing an organic group containing a cyano group or a combination thereof, R ^3b is a group or atom bonded to a silicon atom, and independently of each other, a hydroxy group, an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom. Represents
a2 represents 1 and 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, an organic group in which one or more hydrogen atoms in the epoxy group itself, particularly in an alkyl group or the like, is substituted with an epoxy group, a glycidyl group, or a glycidyloxy group (glycidoxy group) can be mentioned.
Further, R ^1b is not particularly limited as long as it is an organic group containing an acetoxy group (CH ₃ COO−), and examples thereof include an organic group in which one or more hydrogen atoms in an alkyl group or the like are substituted with an acetoxy group.

The alkyl group in which the 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 thereof is usually 40 or less. For example, it can be 30 or less, more for example, 20 or less, and 10 or less.
Specific examples of the linear or branched alkyl group in which the hydrogen atom can be replaced by the above epoxy group or acetoxy group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and i. -Butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1- Dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group , 2-Methyl-n-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 , 1-ethyl-2-methyl-n-propyl group and the like, but are not limited thereto.
Specific examples of the cyclic alkyl group in which the hydrogen atom can be replaced by the above-mentioned epoxy group or acetoxy group include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group and cyclopentyl group. 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2 -Ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group Group, 1,2-dimethyl-cyclobutyl 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-
Cycloalkyl group such as cyclopropyl, 2-ethyl-3-methyl-cyclopropyl group, bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, bicyclodecyl group and the like Examples thereof include, but are not limited to, alkyl groups.
Further, 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 and a methylbenzyl group, an aralkyl group and an alkyl-substituted aryl group. , The hydrogen atom on the aromatic ring or the hydrogen atom on the alkyl group in the aromatic ring-containing group such as the alkyl-substituted aralkyl group may be substituted with the epoxy group or the acetoxy group.

Among the above, R ^1a includes an epoxy group, a glycidyl group, a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, an epoxycyclohexyl group, an epoxycyclohexylmethyl group, and an epoxycyclohexyl. Examples thereof include, but are not limited to, ethyl groups.
Further, ^{examples of R 1b} include, but are not limited to, an acetoxymethyl group, an acetoxyethyl group, an acetoxypropyl group, an acetoxybutyl group, and the like.

^{R 2a} in the formula (1-a), ^{R 2b} in the formula (1-b), respectively, a group bonded to the silicon atom by Si-C bond, independently of one another, be substituted A good alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkyl halide group, an optionally substituted aryl halide group, optionally substituted. Represents a 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 acryloyl. Represents a group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, a sulfonyl group, an organic group containing a cyano group, or a combination thereof.

Examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-. Butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl -N-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group , 2-Methyl-n-pentyl group, 3-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 and the like.
Cyclic alkyl groups can also be used. For example, as cyclic alkyl groups having 3 to 10 carbon atoms, cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1 -Methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2- Ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group , 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 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 Examples thereof include -cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclopropyl group.

Examples of the aryl group include an aryl group having 6 to 20 carbon atoms, for example, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, and the like. p-chlorophenyl group, o-fluorophenyl group, p-mercaptophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-aminophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group , O-Biphenylyl group, m-Biphenylyl group, p-Biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthril group, 3-phenylentril group, 4-phenylentril group And 9-Phenyltril group and the like.

The aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such an aryl group and an alkyl group include the same as those described above.
The number of carbon atoms of 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, for example, 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, and the like. 6-Phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, 10-phenyl-n-decyl group and the like can be mentioned. However, it is not limited to these.

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

The aryl halide group is an aryl group substituted with a halogen atom, and specific examples of such an aryl group and a halogen atom include the same as those described above.
The number of carbon atoms of the aryl halide group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
Specific examples of the aryl halide group include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, and 2,5-difluorophenyl. Group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,5-trifluorophenyl group, 2, 3,6-trifluorophenyl group, 2,4,5-trifluorophenyl group, 2,4,6-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,4,5- Tetrafluorophenyl group, 2,3,4,6-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, pentafluorophenyl group, 2-fluoro-1-naphthyl group, 3-fluoro-1 -Naphthyl group, 4-fluoro-1-naphthyl group, 6-fluoro-1-naphthyl group, 7-fluoro-1-naphthyl group, 8-fluoro-1-naphthyl group, 4,5-difluoro-1-naphthyl group , 5,7-Difluoro-1-naphthyl group, 5,8-difluoro-1-naphthyl group, 5,6,7,8-tetrafluoro-1-naphthyl group, heptafluoro-1-naphthyl group, 1-fluoro -2-naphthyl group, 5-fluoro-2-naphthyl group, 6-fluoro-2-naphthyl group, 7-fluoro-2-naphthyl group, 5,7-difluoro-2-naphthyl group, heptafluoro-2-naphthyl Examples include, but are not limited to, these.

The halogenated aralkyl group is an aralkyl group substituted with a halogen atom, and specific examples of such an aralkyl group and the halogen atom include the same as those described above.
The number of carbon atoms of 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 the halogenated aralkyl group include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, and 2,5-difluorobenzyl group. 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 Examples thereof include, but are not limited to, a 6-tetrafluorobenzyl group, a 2,3,5,6-tetrafluorobenzyl group, a 2,3,4,5,6-pentafluorobenzyl group.

The alkoxyalkyl group refers to an alkyl group substituted with an alkoxy group. Specific examples of such an alkyl group include the same as those described above.

Examples of the alkoxy group include an alkoxy group having a linear, branched, and cyclic alkyl moiety having 1 to 20 carbon atoms. Examples of the linear 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 and an n-. Pentyroxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy Group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyroxy group, 2-methyl-n-pentyroxy group, 3-methyl-n -Pentyroxy group, 4-methyl-n-pentyroxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2- Dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1 , 2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, etc. Can be mentioned. Examples of the cyclic alkoxy group include a cyclopropoxy group, a cyclobutoxy group, a 1-methyl-cyclopropoxy group, a 2-methyl-cyclopropoxy group, a cyclopentyroxy group, a 1-methyl-cyclobutoxy group and a 2-methyl-. Cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy Group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclo Butoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclo Butoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclo Propoxy 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, 2-ethyl-3-methyl-cyclopropoxy group and the like, but are not limited thereto. ..

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

The alkoxyaryl group is an aryl group substituted with an alkoxy group, and specific examples of such an alkoxy group and an aryl group include the same as those described above.
The number of carbon atoms of 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 the alkoxyaryl group include, for example, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2- (1-ethoxy) phenyl group, 3- (1-ethoxy) phenyl group, and 4 -(1-ethoxy) phenyl group, 2- (2-ethoxy) phenyl group, 3- (2-ethoxy) phenyl group, 4- (2-ethoxy) phenyl group, 2-methoxynaphthalene-1-yl group, 3 -Methoxynaphthalen-1-yl group, 4-methoxynaphthalen-1-yl group, 5-methoxynaphthalen-1-yl group, 6-methoxynaphthalen-1-yl group, 7-methoxynaphthalen-1-yl group, etc. However, but not limited to these.

The alkoxyaralkyl group is an alcoholyl group substituted with an alkoxy group, and specific examples of such an alkoxy group and an alcoholyl group include the same as those described above.
The number of carbon atoms of 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.

Examples of the alkenyl group include an alkenyl group having 2 to 10 carbon atoms, for example, an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, and the like. 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group , 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1- Methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl Group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group , 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2- Methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1 -Pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4 -Methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1, 2-Dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group , 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl Group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3- Dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl -2-Propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t- Butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1- Propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2- Cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group , 3-Methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1- Examples thereof include a cyclohexenyl group, a 2-cyclohexenyl group, a 3-cyclohexenyl group and the like, and a crosslinked cyclic alkenyl group such as a bicycloheptenyl group (norbornyl group) can also be mentioned.

Examples of the substituent in the above-mentioned alkyl group, aryl group, aralkyl group, alkyl halide group, aryl halide group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group include an alkyl group and the like. Examples thereof include an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkoxyalkyl group, an aryloxy group, an alkoxyaryl group, an alkoxyaralkyl group, an alkenyl group, an alkoxy group and an aralkyloxy group. , Specific examples thereof and suitable number of carbon atoms thereof include the same as those described above or described below.
Further, the aryloxy group is a group to which an aryl group is bonded via an oxygen atom (−O−), and specific examples of such an aryl group include the same as those described above. The number of carbon atoms of the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and specific examples thereof include a phenoxy group and naphthalene. 2-Iloxy group and the like can be mentioned, but the present invention is not limited thereto.
Further, 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 the acryloyl group include, but are not limited to, an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.
Examples of the organic group containing the methacryloyl group include, but are not limited to, a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.
Examples of the organic group containing the 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 the organic group containing an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group and the like.
Examples of the organic group containing an amino group and an amide group include 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 the formula (1-a), ^{R 3b} in the formula (1-b), respectively, a group or atom bonded to the silicon atoms, independently of one another, alkoxy groups, aralkyloxy groups, acyloxy Represents a group or halogen atom. Examples of the alkoxy group and the halogen atom include the same as those described above.

The aralkyloxy group is a group derived by removing a hydrogen atom from the hydroxy group of the aralkyl alcohol, and specific examples of such an aralkyl group include the same as those described above.
The number of carbon atoms of 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 the aralkyloxy group include phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group, and 5-phenyl-n. -Pentyloxy group, 6-Phenyl-n-hexyloxy group, 7-Phenyl-n-Heptyloxy group, 8-Phenyl-n-octyloxy group, 9-Phenyl-n-nonyloxy group, 10-Phenyl-n- Examples thereof include, but are not limited to, decyloxy groups.

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

In the above equation (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.
Further, in the above equation (1-b), a2 represents 1 and 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, more preferably 0.

Specific examples of the hydrolyzable silane represented by the formula (1-a) include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, and α-glycid. Xiethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycid Xipropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycid Xipropyltributoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycid Xibutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β-( 3,4-Epoxycyclohexyl) ethyltributoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxy) Cyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α -Glysidoxyethyl methyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethyl ethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane , Β-glycidoxypropylmethyldimethoxysilane, β -Glysidoxypropyl ethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxy Examples thereof include silane, γ-glycidoxypropyl ethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane.

Specific examples of the hydrolyzable silane represented by the formula (1-b) include acetoxymethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxyethyltrimethoxysilane, acetoxyethyltriethoxysilane, and acetoxypropyltrimethoxylan. , Acetoxypropyltriethoxylan, Acetoxybutyltrimethoxylan, Acetoxybutyltriethoxylan, Acetoxypentyl Trimethoxylan, Acetoxypentyl Triethoxylan, Acetoxyphenyl Trimethoxysilane, Acetoxyphenyl Triethoxysilane Acetoxybenzyl Trimethoxysilane, Acetoxybenzyl Triethoxysilane, Acetoxyphenylpropyltrimethoxysilane, Acetoxyphenylpropyltriethoxysilane, Acetoxymethylphenyltrimethoxysilane, Acetoxymethylphenyltriethoxysilane, Acetoxyethylphenyltrimethoxysilane, Acetoxyethylphenyltriethoxysilane, Acetoxymethylbenzyltrimethoxysilane , Acetoxymethylbenzyltrimethoxysilane, di (acetoxymethyl) phenyltrimethoxysilane, di (acetoxymethyl) phenyltriethoxysilane, di (acetoxyethyl) phenyltrimethoxysilane, di (acetoxyethyl) phenyltriethoxysilane, etc. Be done.

[Other silane compounds (hydrolyzable silane)]
In the present invention, in the hydrolyzable silane mixture, the hydrolyzable silane represented by the above formula (1-a), the hydrolyzable silane represented by the formula (1-b), and water other than the above formula are added. Degradable silane can be used. In the examples of the compounds shown below, a hydrolyzable silane containing an organic group having an epoxy group and a hydrolyzable silane containing an organic group having an acetoxy group may be exemplified, but these compounds are each epoxy. It can be used as a hydrolyzable silane containing an organic group having a group and a hydrolyzable silane containing an organic group having an acetoxy group.

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

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 the formula (2), R ⁴ is a group bonded to the silicon atom by Si-C bond, independently of one another, an optionally substituted alkyl group, an aryl group which may be substituted, it is substituted Aralkyl group which may be substituted, alkyl halide group which may be substituted, aryl halide group which may be substituted, aralkyl group which may be substituted, alkoxyalkyl group which may be substituted, Represents a optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an acrylloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy. Represents a group, a sulfonyl group, an organic group containing a cyano group, or a combination thereof.
The R ⁵ is a group or atom attached to silicon atoms, each independently represent 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 represented by R ^4, and as their preferred number of carbon atoms, may be mentioned the groups described above, for example, the R ^2a and groups and number of carbon atoms mentioned above for R ^2b.
The above specific examples of each group in R ^5, and as their preferred number of carbon atoms, the above groups, may be mentioned groups and atoms and number of carbon atoms mentioned above for R ^3a and R ^3b.
Further, 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 is an alkyl group which may be substituted independently of each other, an aryl group which may be substituted, and a substituted group. Aralkyl group which may be substituted, alkyl halide group which may be substituted, aryl halide group which may be substituted, aralkyl group which may be substituted, alkoxyalkyl group which may be substituted, Represents a optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or an acrylloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy. Represents a group, a sulfonyl group, an organic group containing a cyano group, or a combination thereof.
Further, R ⁷ is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
Y is a group bonded to a silicon atom by a Si—C bond and represents an alkylene group or an arylene group independently of each other.
And d represents 0 or 1, and e represents 0 or 1.

Specific examples of each group in R ⁶ and R ⁷ and a suitable number of carbon atoms thereof include the above-mentioned groups and the number of carbon atoms.
Specific examples of each group represented by R ^6, and as their preferred number of carbon atoms, may be mentioned the groups described above, for example, the R ^2a and groups and number of carbon atoms mentioned above for R ^2b.
The above specific examples of each group in R ^7, and as their preferred number of carbon atoms, may be mentioned the above-mentioned groups, such as R ^3a and groups described above and atoms and number of carbon atoms for R ^3b.
Specific examples of the alkylene group in Y include linear chains such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, and decamethylene group. Alkane group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1 , 2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, alkylene group such as branched alkylene group such as 1-ethyltrimethylene group, methanetriyl group, ethane-1,1,2-triyl group, ethane -1,2,2-triyl group, etan-2,2,2-triyl group, propane-1,1,1-triyl group, propane-1,1,2-triyl group, propane-1,2,3 -Triyl group, propane-1,2,2-triyl group, propane-1,1,3-triyl group, butane-1,1,1-triyl group, butane-1,1,2-triyl group, butane- 1,1,3-triyl group, butane-1,2,3-triyl group, butane-1,2,4-triyl group, butane-1,2,2-triyl group, butane-2,2,3- Triyl group, 2-methylpropane-1,1,1-triyl group, 2-methylpropane-1,1,2-triyl group, 2-methylpropane-1,1,3-triyl group, 2-methylpropane- Examples thereof include, but are not limited to, an alkanetriyl group having a 1,1,1-triyl group.
Specific examples of the arylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group; 1,5-naphthalenediyl group, 1,8-naphthalenediyl group, 2,6-. Naphthalenediyl group, 2,7-naphthalenediyl group, 1,2-anthracendiyl group, 1,3-anthracendiyl group, 1,4-anthrasendiyl group, 1,5-anthracendiyl group, 1,6-anthrasendil Group, 1,7-anthrassendiyl group, 1,8
-Anthracene Group, 2,3-Anthracene Group, 2,6-Anthracene Group, 2,7-Anthracene Group, 2,9-Anthracene Group, 2,10-Anthracene Group, 9,10-Anthracene A group derived by removing two hydrogen atoms on the aromatic ring of a fused ring aromatic hydrocarbon compound such as a diyl group; a ring linkage of 4,4'-biphenyldiyl group and 4,4 "-paratelphenyldiyl group. Examples thereof include, but are not limited to, a group derived by removing two hydrogen atoms on the aromatic ring of the aromatic hydrocarbon compound.
Further, d preferably represents 0 or 1, and more preferably 0.
Further, e is preferably 1.

Specific examples of the hydrolyzable silane represented by the formula (2) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetran-propoxysilane, tetrai-propoxysilane, and tetran-butoxysilane. Methyltrimethoxysilane, Methyltrichlorosilane, Methyltriacetoxysilane, Methyltriethoxysilane, Methyltripropoxysilane, Methyltributoxysilane, Methyltriamiloxysilane, Methyltribenzyloxysilane, Methyltriphenethyloxysilane, Ethyltrimethoxy Silane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxy Benzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenetiltrimethoxysilane, methoxyphenetiltilriethoxysilane, methoxyphenetilitriactoxysilane, methoxyphenetiltichlorosilane, ethoxyphenyltrimethoxysilane , Ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, i-propoxyphenyltrimethoxysilane, i -Propoxyphenyltriethoxysilane, i-propoxyphenyltriacetoxysilane, i-propoxyphenyltrichlorosilane, i-propoxybenzyltrimethoxysilane, i-propoxybenzyltriethoxysilane, i-propoxybenzyltriacetoxysilane, i-propoxybenzyl Trichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxycybenzyltri Chlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltrichlorosilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthylliactoxysilane, ethoxynaphthyltrichlorosilane, γ- Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Silane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo (2,2,1) heptenyltriethoxysilane , Benzenesulfonylpropyltriethoxysilane, benzenesulfonamidepropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane , Γ-Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-
Examples thereof include mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and silane compounds represented by the following formulas (A-1) to (A-41). However, it is not limited to these.

Specific examples of the silane compound represented by the formula (3) include methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, and butylene. Bistrimethoxysilane, phenylene bistrimethoxysilane, phenylene bistriethoxysilane, phenylene bismethyldiethoxysilane, phenylene bismethyldimethoxysilane, naphthylene bistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, bismethyldimethoxy Examples thereof include, but are not limited to, disilane.

Among these, from the viewpoint of improving the cross-linking density of the film obtained from the above composition, suppressing the diffusion of the components of the resist film into the obtained film, and maintaining / improving the resist characteristics of the resist film. , Methoxybenzyltrimethoxysilane, triethoxysilylpropyldialyl isocyanurate, methyltriethoxysilane and the like are preferably used.

In the present invention, the hydrolyzable silane mixture may contain a silane compound (hydrolyzable organosilane) having an onium group in the molecule. By using a silane compound (hydrolyzable organosilane) having an onium group in the molecule, the cross-linking 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 the 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 the formula (4), R ¹¹ is a group bonded to a silicon atom and represents an onium group or an organic group containing the onium group.
R ¹² is a group bonded to a silicon atom, which is an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, and a substituent which may be substituted. May be an alkyl halide group, an optionally substituted aryl halide group, an optionally substituted aralkyl halide group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, substituted. Represents an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, 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 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.

The above alkyl group, aryl group, aralkyl group, alkyl halide group, aryl halide group, aralkyl group halide, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, and acryloyl group, methacryloyl group, mercapto. Specific examples of a group, an organic group containing an amino group or a cyano group, an alkoxy group, an aralkyloxy group, an acyloxy group, a halogen atom, and an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, and a halogenated group. those aralkyl group, an alkoxyalkyl group, specific examples of the substituents of alkoxy aryl group, alkoxy aralkyl and alkenyl groups, and as their preferred number of carbon atoms, for R ¹² is, for example, described above with respect to R ^2a and R ^2b For R ¹³ , for example, the above-mentioned ones ^{for R 3a} and R ^{3b can be mentioned, respectively.}

More specifically, specific examples of the onium group include a cyclic ammonium group or a chain ammonium group, and a tertiary ammonium group or a quaternary ammonium group is preferable.
That is, suitable specific examples of the onium group or the organic group containing the same include a cyclic ammonium group, a chain ammonium group, or an organic group containing at least one of these, and a tertiary ammonium group or a quaternary ammonium group. Alternatively, an organic group containing at least one of these is preferable.
When the onium group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. At this time, when 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 directly or divalently linking groups. It may be connected via.

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

In formula (S1), A ¹ , A ² , A ³ and A ⁴ represent groups represented by any of the following formulas (J1) to (J3) independently of each other, but A ^{1 to} A ⁴ At least one of them is a group represented by the following formula (J2). ^{Depending on which of A 1 to} A ⁴ the silicon atom in the above formula (4) ^{is bonded to, A 1 to} A ^{4 and} each of them are adjacent to each other so that the constituent rings exhibit aromaticity. It is determined whether the bond between the atoms forming the ring together is a single bond or a double bond.

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 are independent of each other, single bond, hydrogen atom, alkyl group, aryl group, aralkyl group, alkyl halide group, aryl halide group, aralkyl group halide or alkenyl. Specific examples of the alkyl group, the aryl group, the aralkyl group, the alkyl halide group, the aryl halide group, the halogenated aralkyl group and the alkenyl group and the suitable number of carbon atoms thereof include the same as those described above. Will be.

Wherein (S1), R ^14, independently of one another, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, halogenated aryl group, a halogenated aralkyl group, an alkenyl group or a hydroxy group, R ¹⁴ is When two or more are present, the two R ^14s may be coupled to each other to form a ring, or the ring formed by the two R ^14s may have a crosslinked ring structure, in such cases. , The cyclic ammonium group will have an adamantan ring, a norbornen ring, a spiro ring and the like.
Specific examples of such an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, a halogenated aralkyl group and an alkenyl group, and suitable carbon atoms thereof include the same as described above. ..

In equation (S1), n ¹ is an integer from ^{1 to 8, m 1} is 0 or 1, and m ² is a positive number from 0 or 1 to the maximum number that can be replaced with a monocyclic or polycyclic ring. Is an integer of.
When m ¹ is 0, a (4 + n ¹ ) member ring ^{containing A 1 to} A ^{4 is configured.} That is, a 5-membered ring when ^{n 1} is 1, a 6-membered ring when ^{n 1} is 2, a 7-membered ring when ^{n 1} is 3, and an 8-membered ring when ^{n 1 is 4.} A 9-membered ring when ^{n 1} is 5, a 10-membered ring when ^{n 1} is 6, an 11-membered ring when ^{n 1} is 7, and a 12-membered ring when ^{n 1 is 8.} It is composed.
When m ¹ is 1, a condensed ring is formed by condensing a (4 + n ¹ ) -membered ring ^{containing A 1 to} A ^{3 and a 6-membered ring containing A 4.}
Depending on which of the formulas (J1) to (J3), A ^{1 to} A ⁴ may have a hydrogen atom on the atom constituting the ring or may not have a hydrogen atom, but A ¹ When ~ A ⁴ has a hydrogen atom on an atom constituting a ring, the hydrogen atom may be replaced with ^{R 14.} Further ^{, R 14} may be substituted with a ring-constituting atom other than the ring-constituting atom in ^{A 1 to} A ^4. Under these circumstances, as described above, m ² is selected from 0 or 1 to the maximum number that can be replaced with a monocyclic or polycyclic integer.

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

Further, the alkenylene group is a divalent group derived by further removing one hydrogen atom of the alkenyl group, and specific examples of such an alkenyl group include the same as those described above. The number of carbon atoms of 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, 2-pentenylene group and the like.

Specific examples of the silane compound (hydrolyzable organosilane) represented by the formula (4) having a heteroaromatic cyclic ammonium group represented by the above formula (S1) are given 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 the formula (S2), A ⁵ , A ⁶ , A ⁷ and A ⁸ are independent of each other and have the following formulas (J4) to (J).
Represents a group represented by any one of 6), at least one of A ⁵ to A ⁸ is a group represented by the following formula (J5). Silicon atoms in the above formula (4) depending on whether bound with any A ⁵ to A ^8, as the ring is constructed showing the non-aromatic, and A ⁵ to A ⁸ each, adjacent to their respective It is determined whether the bond with the atom constituting the ring is a single bond or a double bond.

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 is independent of each other and has a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl group halide or an alkenyl. Specific examples of an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group and an alkenyl group and their suitable carbon atoms are the same as those described above. Can be mentioned.

Wherein (S2), R ^15, independently of one another, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, halogenated aryl group, a halogenated aralkyl group, an alkenyl group or a hydroxy group, R ¹⁵ is When two or more are present, the two R ^15s may be coupled to each other to form a ring, or the ring formed by the two R ^15s may have a crosslinked ring structure, in such cases. , The cyclic ammonium group will have an adamantan ring, a norbornen ring, a spiro ring and the like.
Specific examples of the alkyl group, aryl group, aralkyl group, alkyl halide group, aryl halide group, halogenated aralkyl group and alkenyl group and suitable carbon atoms thereof include the same as those described above.

In the formula (S2), n ² is an integer of 1 to 8, m ³ is 0 or 1, and m ⁴ is a positive number from 0 or 1 to the maximum number that can be replaced with a monocyclic or polycyclic ring. Is an integer of.
When m ³ is 0, a (4 + n ² ) member ring ^{containing A 5 to} A ^{8 is configured.} That is, a 5-membered ring when ^{n 2} is 1, a 6-membered ring when ^{n 2} is 2, a 7-membered ring when ^{n 2} is 3, and an 8-membered ring when ^{n 2 is 4.} When n ² is 5, there is a 9-membered ring, when n ² is 6, there is a 10-membered ring, when n ² is 7, there is an 11-membered ring, and when n ² is 8, there is a 12-membered ring. It is composed.
When m ³ is 1, a condensed ring is formed by condensing a (4 + n ² ) member ring ^{containing A 5 to} A ^{7 and a 6 member ring containing A 8.}
Depending on which of the formulas (J4) to (J6), A ^{5 to} A ⁸ may have a hydrogen atom on the atom constituting the ring or may not have a hydrogen atom, but A ⁵ When ~ A ⁸ has a hydrogen atom on the atom constituting the ring, the hydrogen atom may be replaced with ^{R 15. Further,} the ring-constituting atom other than the ring member atoms in the A 5 ~A ^{8, R 15} may be substituted.
Under such circumstances, as described above, m ⁴ is selected from an integer from 0 or 1 to a maximum number that can be substituted in the monocyclic or polycyclic.

The bond of the heteroaliphatic cyclic ammonium group represented by the above formula (S2) is present at any carbon atom or nitrogen atom present in such a monocyclic or fused ring, and is directly bonded to a silicon atom. Alternatively, a linking group is bonded 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, and specific examples of the alkylene group, the arylene group and the alkenylene group and suitable carbon atoms thereof include the same as described above.

Specific examples of the silane compound (hydrolyzable organosilane) represented by the formula (4) having a heteroaliphatic cyclic ammonium group represented by the above formula (S2) are given 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 the formula (S3), R ¹⁰ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group or an alkenyl group independently of each other, and the alkyl group, Specific examples of the aryl group, the aralkyl group, the alkyl halide group, the aryl halide group, the halogenated aralkyl group and the alkenyl group, and suitable carbon atoms thereof include the same ones as described above.

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

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

Further, the hydrolyzable silane mixture may further contain a hydrolyzable silane having a sulfone group and a hydrolyzable silane having a sulfonamide group. Specific examples thereof will be given below, but the present invention is not limited thereto.
In the following formula, Me represents a methyl group and Et represents an ethyl group.

Further, in the present invention, the hydrolyzable silane mixture may contain a silane compound (hydrolyzable organosilane) having a cyclic urea skeleton in the molecule, and specific examples thereof are not limited to this. However, a silane compound (hydrolyzable organosilane) represented by the following formula (5-1) can be mentioned.

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), ^R501 is a group bonded to a silicon atom and represents a group represented by formula (5-2) independently of each other.
R ⁵⁰² is a group bonded to a silicon atom, which is an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, and a substituent which may be substituted. May be an alkyl halide group, an optionally substituted aryl halide group, an optionally substituted aralkyl halide group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, substituted. Represents an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, 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 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.

Alkyl group of the R ^502, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, a halogenated aralkyl group, an alkoxyalkyl group, an alkoxyaryl group, alkoxy aralkyl group, an alkenyl group, and an epoxy group, an acryloyl group specific examples of the organic group containing a methacryloyl group, a mercapto group, or a cyano group, and specific examples of alkoxy groups, aralkyloxy, specific examples of the acyloxy group and a halogen atom, and the substituents of R ^503, preferred carbon As for the number of atoms and the like, for example, for R ⁵⁰² , the above-mentioned ones for R ^2a and R ^2b can be mentioned, ^{and for R 503} , for example ^{, those mentioned above for R 3a} and R ^{3b can be mentioned.}

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 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, independently of each other. ..
R ⁵⁰⁵ 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 of R ⁵⁰⁴ , the specific examples of the organic group containing the optionally substituted alkenyl group and the epoxy group, the suitable number of carbon atoms and the like are the same as those described above. However, in addition to these, as the alkyl group even if substituted, an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group is preferable, and specific examples thereof include an allyl group, a 2-vinylethyl group, and a 3-vinylpropyl group. Groups, 4-vinylbutyl groups and the like can be mentioned.

The organic group containing a sulfonyl group is not particularly limited as long as it contains a sulfonyl group, and may be substituted alkylsulfonyl group, optionally substituted arylsulfonyl, or optionally substituted aralkylsulfonyl group. , An optionally substituted alkyl halide sulfonyl group, an optionally substituted aryl halide sulfonyl group, an optionally substituted aralkyl sulfonyl halide group, an optionally substituted alkoxyalkylsulfonyl group, substituted. Examples thereof include an alkoxyarylsulfonyl group which may be present, an alkoxyaralkylsulfonyl group which may be substituted, an alkenylsulfonyl group which may be substituted, and the alkyl group, the aryl group, and the aralkyl group in these groups.
Specific examples of the alkyl halide group, the aryl halide group, the aralkyl halide group, the alkoxyalkyl group, the alkoxyaryl group, the alkoxyaralkyl group and the alkenyl group and their substituents, the suitable number of carbon atoms and the like are as described above. The same can be mentioned.

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

Further, the alkylene group may have one or more selected from a sulfide bond, an ether bond and an ester bond at the terminal or in the middle, preferably in the middle.
Specific examples of the alkylene group include a straight chain such as a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group. Alkylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1 , 2-Dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group and other branched chain alkylene groups, 1,2-cyclopropipandyl group, 1,2-cyclobutandyl, 1, Cyclic alkylene such as 3-cyclobutitaniumdiyl group, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, etc., -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 CH ₂ −, −CH Examples thereof include, but are not limited to, alkylene groups containing ether groups such as ₂ CH ₂ CH ₂ SCH ₂ CH ₂ CH ₂ −, −CH ₂ OCH ₂ CH ₂ SCH _{2 −.}

The hydroxyalkylene group has at least one hydrogen atom of the alkylene group replaced with a hydroxy group, and specific examples thereof include a hydroxymethylene group, a 1-hydroxyethylene group, a 2-hydroxyethylene group, and 1,2. -Dihydroxyethylene group, 1-hydroxytrimethylene group, 2-hydroxytrimethylene group, 3-hydroxytrimethylene group, 1-hydroxytetramethylene group, 2-hydroxytetramethylene group, 3-hydroxytetramethylene group, 4-hydroxy Tetramethylene group, 1,2-dihydroxytetramethylene group, 1,3-dihydroxytetramethylene group, 1,4-dihydroxytetramethylene group, 2,3-dihydroxytetramethylene group, 2,4-dihydroxytetramethylene group, 4 , 4-Dihydroxytetramethylene group and the like, but are not limited thereto.

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 the formula (5-2), X ₅₀₁ represents a group represented by the following formulas (5-3) to (5-5) independently of the following formulas (5-4) and (5). The carbon atom of the ketone group (-C (= O)-) in −5) is bonded to the nitrogen atom to which ^{R505 is bonded in the formula (5-2).}

In formulas (5-3) to (5-5), R ^{506 to} R ⁵¹⁰ are independent of each other, a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, and an epoxy. Representing an organic group containing a group, a sulfonyl group or any of them, a specific example of an organic group containing a optionally substituted alkyl group, an optionally substituted alkenyl group and an epoxy group, a suitable number of carbon atoms, etc. Can be the same as those described above for R ^2a and R ^2b.
Above all, from the viewpoint of realizing excellent lithography characteristics with good reproducibility, X ₅₀₁ is preferably a group represented by the formula (5-5).

From the viewpoint of achieving excellent lithography characteristics with good reproducibility, ^{it is preferable that at least one of R 504} and R ^{506 to} R ⁵¹⁰ is 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 described in International Publication No. 2011/102470 or the like.

Hereinafter, specific examples of the hydrolyzable organosilane represented by the formula (5-1) will be given, but the present invention is not limited thereto.

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

The hydrolyzed condensate (a) of the above-mentioned hydrolyzed silane mixture is obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane).
The above-mentioned silane compound (hydrolyzable silane) has an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom directly bonded to a silicon atom, that is, an alkoxysilyl group, an aralkyloxysilyl group, or an acyloxysilyl which is a hydrolyzable group. Includes groups and silyl halide groups.
For the hydrolysis of these hydrolyzable groups, usually 0.5 to 100 mol, preferably 1 to 10 mol of water is used per 1 mol of the hydrolyzable group.
At the time of hydrolysis and condensation, a hydrolysis catalyst may be used for the purpose of accelerating the reaction, or hydrolysis and condensation may be carried out without using the hydrolysis catalyst. When a hydrolysis catalyst is used, a hydrolysis catalyst of usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, can be used per mol of the hydrolyzable group.
The reaction temperature for hydrolysis and condensation is usually in the range of room temperature or higher, reflux temperature or less at normal pressure of an organic solvent that can be used for hydrolysis, and normal pressure of an organic solvent that can be used for hydrolysis. Hydrolysis can be carried out in the range below the reflux temperature in, eg 20-110 ° C., and for example 20-80 ° C., is completely hydrolyzed, i.e. all hydrolyzable groups are silanol groups. Or may be partially hydrolyzed, i.e. leaving unreacted hydrolyzable groups.
Examples of the hydrolysis catalyst that can be used for 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 (acetylacetonate) titanium, tri-n-propoxymono (acetylacetonate) titanium, tri-i-propoxymono (acetylacetonate) titanium, and tri. -N-Butoxy mono (acetylacetonet) titanium, tri-sec-butoxymono (acetylacetonate) titanium, trit-butoxymono (acetylacetonate) titanium, diethoxybis (acetylacetonate) titanium , Di-n-propoxybis (acetylacetonate) titanium, di-i-propoxybis (acetylacetonate) titanium, di-n-butoxybis (acetylacetonate) titanium, di-sec-butoxybis (Acetylacetonate) Titanium, Di-t-butoxy-bis (Acetylacetonet) Titanium, Monoethoxytris (Acetylacetonet) Titanium, Mono-n-Propoxytris (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, Tetrakiss (Acetylacetonet) Titanium, Triethoxy Mono (Ethylacetone Acetate) Titanium, Tri-n-Propoxy Mono (Ethylacetone Acetate) Titanium, Tri-i-Propoxy Mono (Ethylacetone Acetate) Titanium, Tri- n-butoxy mono (ethylacetone acetate) titanium, tri-sec-butoxy mono (ethylacetone acetate) titanium, trit-butoxy mono (ethylacetone acetate) titanium, diethoxy bis (ethylacetone acetate) titanium, Di-n-propoxybis (ethylacetone acetate) titanium, di-i-propoxybis (ethylacetoneacetate) titanium, di-n-butoxybis (ethylacetoneacetate) titanium, di-sec-butoxybis ( Ethylacetacetate) Titanium, Di-t-butoxy-bis (ethylacetoneacetate) titanium, Monoethoxytris (ethylacetoneacetate) titanium, Mono-n-propoxytris (ethylacetoneacetate) titanium, Mono-i-propoxy・ Tris (ethylacetone acetate) titanium, mono-n-butoxy tris (d) Chilacetacetate) Titanium, Mono-sec-Butoxytris (Ethylacetacetate) Titanium, Mono-t-Butoxytris (Ethylacetacetate) Titanium, Tetrakiss (Ethylacetacetate) Titanium, Mono (Acetylacetonate) Tris ( Titanium chelate compounds such as ethylacetacetate) titanium, bis (acetylacetonate) bis (ethylacetonate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxymono (acetylacetonate) zirconium, tri -N-propoxymono (acetylacetonate) zirconium, tri-i-propoxymono (acetylacetonate) zirconium, tri-n-butoxymono (acetylacetonate) zirconium, tri-sec-butoxymono (acetyl) Acetonate) Zirconium, Trit-butoxy mono (acetylacetonate) zirconium, Diethoxybis (acetylacetonate) zirconium, di-n-propoxybis (acetylacetonate) zirconium, di-i-propoxybis (Acetylacetonate) Zirconium, di-n-butoxy-bis (acetylacetonate) zirconium, di-sec-butoxy-bis (acetylacetonate) zirconium, di-t-butoxy-bis (acetylacetonato) zirconium, mono Ethoxytris (acetylacetonate) zirconium, mono-n-propoxytris (acetylacetonate) zirconium, mono-i-propoxytris (acetylacetonate) zirconium, mono-n-butoxytris (acetylacetonate) Zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxytris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri- n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethyl acetoacetate) zirconium, tri-sec-butoxy mono (ethyl aceto) Acetate) Zirconium, Trit-butoxy Mono (Ethylacet Acetate) Zirconium, Diethoxybis (D) Tyracetoacetate) Zirconium, di-n-propoxybis (ethylacetate) zirconium, di-i-propoxybis (ethylacetate) zirconium, di-n-butoxybis (ethylacetate) zirconium, di- sec-butoxy bis (ethyl acetoacetate) zirconium, dit-butoxy bis (ethyl acetoacetate) zirconium, monoethoxy tris (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) zirconium , Mono-i-propoxytris (ethylacetate) zirconium, mono-n-butoxytris (ethylacetacetate) zirconium, mono-sec-butoxytris (ethylacetacetate) zirconium, mono-t-butoxytris (Ethylacetacetate) Zirconium, Tetrakiss (Ethylacetacetate) Zirconium, Mono (Acetylacetonate) Tris (Ethylacetacetate) Zirconium, Bis (Acetylacetonate) Bis (Ethylacetacetate) Zirconium, Tris (Acetylacetonate) Mono (Ethylacetacetate) Zirconium chelating compounds such as zirconium; aluminum chelating compounds such as tris (acetylacetonate) aluminum and tris (ethylacetacetate) aluminum can be mentioned, but are not limited thereto.

Organic acids as hydrolysis catalysts include, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptonic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacin. Acid, gallic acid, butyric acid, merit acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfon Examples thereof include, but are not limited to, acids, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartrate acid and the like.

Examples of the inorganic acid as a hydrolysis catalyst include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphoric acid and the like.

Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrol, piperazine, pyrrolidine, piperidine, picolin, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diah. Zabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide Etc., but are not limited to these.
Examples of the inorganic base as the hydrolysis catalyst include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Among these hydrolysis catalysts, during the hydrolysis condensation reaction of the hydrolysis condensate (a), hydrolysis proceeds for each hydrolyzable silane molecule, that is, it is present in one hydrolyzable silane (molecule). In the silane compound in which at least one hydrolyzable group is hydrolyzed, it is preferable to use an organic base or an inorganic base from the viewpoint of promoting the hydrolysis of another hydrolyzable group in the same molecule. One type may be used alone, or two or more types may be used in combination. For example, an aqueous solution of these (alkaline substances) can be used. In the present invention, an alkaline substance aqueous solution is present at the time of hydrolysis condensation of hydrolyzable silane, priority is given to the formation of silanol groups to obtain a hydrolysis condensate (a), and then an inorganic acid is added or cations are used as described later. The exchange resin can be used to change the epoxy group to a dihydroxy group to obtain a hydrolyzed condensate (A) containing an organic group having a dihydroxy group.
When the ring-opening reaction of the epoxy group occurs during the hydrolysis-condensation reaction, the hydrolysis-condensation reaction and the side reaction (dehydration condensation) of the silanol group of the hydrolyzable silane and the hydroxy group generated by the ring-opening occur at the same time. It can proceed, in which case the resulting hydrolyzed condensate can gel and form a gel-like structure, which is not preferred.

When hydrolyzing, an organic solvent may be used as a solvent, and specific examples thereof include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2. , 4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbon solvents; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbensen, i-propylbensen , Diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbensen, n-amylnaphthalene, trimethylbenzene and other aromatic hydrocarbon solvents; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpen Tanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol , N-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenyl Monoalcoholic solvents such as methylcarbinol, diacetone alcohol, cresol; ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5 -Polyhydric alcohol solvents such as hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl -N-propylketone, methyl-n-butylketone, diethylketone, methyl-i-butylketone, methyl-n-pentylketone, ethyl-n-butylketone, methyl-n-hexylketone, di-i-ve Ketone solvents such as tylketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentandione, acetonylacetone, diacetone alcohol, acetophenone, fenchon; ethyl ether, i-propyl ether, n-butyl ether, n- Hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolan, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n -Butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl 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-methyltetra ether-based solvent; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i acetate -Propyl, 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, Ethylene glycol monoethyl ether acetate, Diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, Diethylene glycol monoethyl acetate -Butyl ether, 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, methoxy acetate Triglycol, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate , Ether-based solvents such as dimethyl phthalate, diethyl phthalate; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methyl Nitrogen-containing solvents such as propionamide, N-methyl-2-pyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, sulfolane, 1,3- Sulfur-containing solvents such as propane sultone can be mentioned, but the present invention is not limited thereto. These solvents can be used alone or in combination of two or more.

The hydrolyzed condensate thus obtained is a hydrolyzed 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.
The hydrolyzable condensate (a) is a hydrolyzable silane containing an organic group having an epoxy group (for example, a compound represented by the formula (1-a)) contained in a hydrolyzable silane mixture. Based on the total amount of silane (total number of moles: 100 mol%), for example, in a hydrolyzable silane containing an organic group having an acetoxy group (eg, formula (1-b)) containing 10 mol% to 90 mol%. The compound represented) is hydrolyzed, for example, in a proportion of 10 mol% to 90 mol% based on the total amount of hydrolyzable silane contained in the hydrolyzable silane mixture (total number of moles: 100 mol%). It can be a hydrolyzed condensate of a sex silane mixture.

In a hydrolyzable silane mixture, a hydrolyzable silane containing an organic group having an epoxy group (for example, a compound represented by the formula (1-a)) and a hydrolyzable silane containing an organic group having an acetoxy group (for example, a formula (for example) When a hydrolyzable silane other than the compound represented by 1-b) is used, the amount of the hydrolyzable silane containing an organic group having an epoxy group (for example, the compound represented by the formula (1-a)) is charged. , For example, 10 mol% to 90 mol% can be set with respect to the charged amount (100 mol%) of all the hydrolyzable silanes contained in the hydrolyzable silane mixture. The amount of the hydrolyzable silane (for example, the compound represented by the formula (1-b)) containing an organic group having an acetoxy group can be 10 mol% to 90 mol%. From the viewpoint of obtaining the above-mentioned effects of the present invention with good reproducibility, preferably, the compound represented by the formula (1-a) is contained in an amount of 15 mol% to 85 mol%, 15 mol% to 80 mol%, or 20 mol% to 60. 15 mol% to 85 mol% or 15 mol% to the compound represented by the formula (1-b) in a charge amount of mol%, 20 mol% to 40 mol%, or 15 mol% to 45 mol%. The charging amount can be 80 mol%, or 20 mol% to 60 mol%, or 20 mol% to 40 mol%, or 15 mol% to 45 mol%, and these can be appropriately prepared depending on the compound used.
When a silane compound represented by the formula (2) or a silane compound represented by the formula (3) is used in the hydrolyzable silane mixture, the amount of these silane compounds charged is all contained in the hydrolyzable silane mixture. The amount of the hydrolyzable silane charged is usually 10 mol% to 90 mol%, for example, 10 mol% to 80 mol%, 10 mol% to 70 mol%, 20 mol% to 60 mol%, or the like. Can be done.
When a hydrolyzable organosilane having an onium group represented by the formula (4) in the molecule is used in the hydrolyzable silane mixture, the amount of the organosilane charged is all silane compounds (hydrolyzable silane). It is usually 0.01 mol% or more, preferably 0.1 mol% or more, and usually 30 mol% or less, preferably 10 mol% or less, with respect to the charged amount of.
When the hydrolyzable organosilane represented by the formula (5-1) is used in the hydrolyzable silane mixture, the amount of the organosilane charged is usually 0.1 among all the silane compounds (hydrolyzable silane). It is mol% or more, preferably 0.3 mol% or more, usually 50 mol% or less, preferably 30 mol% or less.

In the above (a) hydrolyzed condensate, the epoxy group in the condensate becomes a dihydroxy group by opening the ring, thereby having a siloxane unit containing an organic group having two or more hydroxy groups and an acetoxy group. A hydrolysis condensate (A) containing a siloxane unit containing an organic group is obtained.
After the hydrolysis and condensation reactions are completed, the reaction solution may be directly subjected to the ring-opening reaction of the epoxy group. Further, the hydrolysis catalyst such as acid or base used for hydrolysis and condensation can be removed by treating the reaction solution as it is, by diluting or concentrating it and neutralizing it, or by treating it with an ion exchange resin. Further, before or after such treatment, by vacuum distillation or the like, alcohol or water as a by-product, the hydrolyzed catalyst used, etc. could be removed from the reaction solution, and these operations were performed. It may be subjected to a ring-opening reaction later.

The ring-opening reaction of the epoxy group in the hydrolyzed condensate (a) can be carried out with an inorganic acid or a cation exchange resin.
The above-mentioned inorganic acid can be added as an aqueous solution of an inorganic acid. The concentration of the inorganic acid aqueous solution can be used, for example, at a concentration of about 0.01 M to 10 M. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.
Examples of the cation exchange resin include a strongly acidic cation resin (for example, a sulfonic acid type ion exchange resin) and a weakly acidic cation resin (for example, a carboxylic acid type ion exchange resin).
When an organic acid is used, in the reaction between the epoxy group and the organic acid, the organic acid residue undergoes an addition reaction during the ring opening reaction of the epoxy group, and a dihydroxy structure cannot be formed.

The protons of the inorganic acid and the cation exchange resin function as catalysts in the ring-opening reaction of the epoxy group. In the present invention, when the above-mentioned hydrolysis with an aqueous solution of an alkaline substance and a condensation reaction are carried out and an inorganic acid or a cation exchange resin is added to a reaction system containing a hydrolysis condensate, the inorganic acid or the cation exchange resin is a residual alkaline substance. May be consumed for neutralization. The above-mentioned protons used in the ring-opening reaction of an epoxy group generate a dihydroxy group by adding a proton at a ratio of 0.01 to 100 mol% with respect to the epoxy group, but the amount consumed in neutralizing an alkaline substance. Also, it can be added in a ratio of 0.01 to 1000 mol%, or 0.01 to 500 mol%, 0.01 to 300 mol%, 0.01 to 100 mol%.

Further, after adding the inorganic acid or the cation exchange resin, the anion exchange resin can be used to remove the anion. As the anion exchange resin, a strongly basic anion exchange resin (for example, a quaternary ammonium type ion exchange resin) and a weakly basic anion exchange resin (for example, a polyamine type ion exchange resin) can be added.
The cation exchange resin and the anion exchange resin can be easily removed from the reaction system by filtration.

The hydrolyzed 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 is used as it is for forming a resist underlayer film, which will be described later. It can be used in the production of compositions. The obtained polysiloxane varnish may be solvent-substituted or diluted with a solvent as appropriate. The obtained polysiloxane varnish may have a solid content concentration of 100% by distilling off an organic solvent as long as its storage stability is not poor.
The organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane mixture. The diluting solvent is not particularly limited, and either one type or two or more types can be arbitrarily selected and used.

Further, the hydrolyzed condensate (A) of the above-mentioned hydrolyzable silane mixture and the hydrolyzed condensate (a) which is a precursor thereof can have a weight average molecular weight of, for example, 500 to 1,000,000. .. From the viewpoint of suppressing the precipitation of the hydrolyzed condensate in the resist underlayer film forming composition, the weight average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, still more preferably 100,000 or less. From the viewpoint of achieving both storage stability and coatability, the concentration is preferably 700 or more, more preferably 1,000 or more.
The weight average molecular weight is a molecular weight obtained in terms of polystyrene by GPC analysis. For GPC analysis, for example, a GPC apparatus (trade name: HLC-8220GPC, manufactured by Toso Co., Ltd.) and a GPC column (trade name: Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko KK) are used to determine the column temperature. It can be carried out at 40 ° C., using tetrahydrofuran as the eluent (eluting solvent), setting the flow rate (flow rate) to 1.0 mL / min, and using polystyrene (manufactured by Showa Denko KK) as a standard sample.

(B) Crosslinkable compound (crosslinking agent)
Examples of the crosslinkable compound (B) used in the present invention include a crosslinkable compound having 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.

Examples of the crosslinkable compound include melamine-based compounds, substituted urea-based compounds, and polymer-based compounds thereof. A cross-linking agent having at least two cross-linking substituents, preferably methoxymethylated glycol uryl, butoxymethylated glycol uril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, methoxy. It is a compound such as methylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Further, a condensate of these compounds can also be used. Tetramethoxymethyl glycol uryl is available from Mitsui Cytec Co., Ltd. as Powder Link 1174 (PL-LI).

Further, as the cross-linking agent, a cross-linking agent having high heat resistance can be used. As the cross-linking agent having high heat resistance, a compound containing a cross-linking substituent having an aromatic ring (for example, a benzene ring or 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。 Examples of this compound include a compound having a partial structure represented by the following formula (6) and a polymer or oligomer having a repeating unit represented by the following formula (7).

In formula (6), R ⁴¹ and R ⁴² are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, or aryl groups having 6 to 20 carbon atoms, respectively, and n ⁴¹ is an integer of 1 to 4. n ⁴² is an integer of 1 to (5-n ⁴¹ ), and n ⁴¹ + n ⁴² is 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, and n ⁴³ is an integer of 1 to 4. n ⁴⁴ is 0 to (4-n ⁴³ ), and n ⁴³ + n ⁴⁴ represents an integer of 1 to 4.
Oligomers and polymers can be used in the range of 2-100 or 2-50 repeating unit structures. Examples of these alkyl groups and aryl groups can be mentioned above.
The structure other than the partial structure represented by the above formula (6) and the structure other than the repeating unit represented by the formula (7) are not particularly limited, and for example, the benzene ring in the formula (6) and the formula (7) is used. It may be substituted with any substituent.

The compound containing the partial structure represented by the above formula (6), the polymer having the repeating unit represented by the formula (7), and the oligomer are exemplified below.

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

The amount of the (B) crosslinkable compound added varies depending on the solvent used, the underlying substrate used, the required solution viscosity, the required film shape, and the like, but with respect to the total solid content of the resist underlayer film forming composition. It is 0.001 to 80% by mass, preferably 0.01 to 50% by mass, and more preferably 0.05 to 40% by mass. These cross-linking agents may cause a cross-linking reaction by self-condensation, but if cross-linking substituents are present in the hydrolyzed condensate (A), they can cause a cross-linking reaction with those cross-linking substituents. ..

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

The acid (acidic compound) may have an action of promoting a cross-linking reaction, for example, camphor sulfonic acid, citric acid, p-toluene sulfonic acid, pyridinium-p-toluene sulfonic acid, trifluoromethane sulfonic acid, salicyl 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 Acids, 1-naphthalene sulfonic acid, pyridinium-1-naphthalene sulfonic acid and the like can be mentioned. Only one of these acids can be used, or two or more of these acids can be used in combination.
The acid (acidic compound) is 0.01 to 10% by mass, or 0.05 to 8% by mass, or 0.1 to 8% by mass, or 0. It can be used in an amount of 3 to 8% by mass, or 0.5 to 5% by mass.

Further, examples of the acid generator include a thermal acid generator and a photoacid generator.
Among them, the photoacid generator generates acid when the resist is exposed and can adjust the acidity of the lower layer film, so that it is useful as a method for adjusting the acidity of the lower layer film to the acidity of the upper layer resist. Therefore, it can be preferably used. Further, since the pattern shape of the resist formed on the upper layer can be adjusted by adjusting the acidity of the lower layer film, the use of a photoacid generator is preferred from this viewpoint as well.
Further, the thermal acid generator promotes organic cross-linking between the hydrolyzed condensate (A) and the cross-linking compound (B) by generating an acid.

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

Specific examples of the onium salt compound include diphenyliodonium hexafluorosulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butane sulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphor sulfonate, and bis (4-t-butyl). Iodonium salt compounds such as phenyl) iodonium camphor sulfonate, bis (4-t-butylphenyl) iodonium trifluoromethane sulfonate, triphenyl sulfonium hexafluoroantimonate, triphenyl sulfonium nonafluoronormal butane sulfonate, triphenyl sulfonium camphor sulfonate, triphenyl Examples thereof include, but are not limited to, sulfonium salt compounds such as sulfonium trifluoromethane sulfonate, triphenyl sulfonium nitrate, triphenyl sulfonium trifluoro acetate, triphenyl sulfonium maleate, and triphenyl sulfonium chloride.

Specific examples of the sulfoneimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormalbutanesulfonyloxy) succinimide, N- (kanfersulfonyloxy) succinimide, and N- (trifluoromethanesulfonyloxy) naphthalimide. Etc., but are not limited to these.

Specific examples of the disulfonyl diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzene). Sulfonyl) Diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane and the like, but are not limited thereto.

The amount of the acid generator added cannot be unconditionally specified because it is appropriately determined in consideration of the type of the acid generator and the like, but is usually 0.01 to 10% by mass with respect to the mass of the hydrolyzed condensate (A). The range is preferably 8% by mass or less, more preferably 5% by mass or less from the viewpoint of suppressing precipitation of the acid generator in the composition, and preferably from the viewpoint of sufficiently obtaining the effect. Is 0.1% by mass or more, more preferably 0.5% by mass or more.
The acid generator may be used alone or in combination of two or more, or a photoacid generator and a thermoacid generator may be used in combination.

The resist underlayer film forming composition contains at least one of (A) a hydrolyzable condensate of hydrolyzable silane (polysiloxane), (B) a crosslinkable compound, (C) an acid and an acid generator. Further, it may contain a solvent and other components described later.
The concentration of the solid content in the resist underlayer film forming composition is, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, 0. It can be 5 to 20.0% by mass. The solid content refers to a component obtained by removing a solvent component from all the components of the composition.
The content of the hydrolyzed condensate (A) in the solid content is usually 20% by mass to 100% by mass, but the lower limit thereof is preferable from the viewpoint of obtaining the above-mentioned effect of the present invention with good reproducibility. Is 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, still more preferably 80% by mass, the upper limit thereof is preferably 99% by mass, and the remainder is the additive described below. Can be.
The content of the hydrolyzed condensate (A) in the composition can be, for example, 0.5 to 20.0% by mass.

The resist underlayer film forming composition can be produced by mixing the above-mentioned components (A) to (C) and, if desired, other components described later. At this time, a solvent is added to the (A) hydrolyzed condensate, a solution containing the (A) hydrolyzed condensate is prepared in advance, and this solution is mixed with the (B) component, the (C) component, and other components. You may.
The mixing order is not particularly limited. For example, the component (B) and the component (C) may be added in order to a solution containing the (A) hydrolyzed condensate and mixed, and other components may be added to the mixture to obtain the (A) hydrolyzed condensate. The containing solution may be mixed with the component (B), the component (C), and other components at the same time.
If necessary, an additional solvent may be added at the end, or some components that are relatively soluble in the solvent may be left unincluded in the mixture and added at the end, but the agglomeration of the components may be added. From the viewpoint of suppressing the separation and preparing a composition having excellent uniformity with good reproducibility, it is preferable to prepare a solution in which the hydrolysis condensate is well dissolved and prepare the composition using the solution. It should be noted that the hydrolyzed condensate may aggregate or precipitate when these are mixed, depending on the type and amount of the solvent to be mixed together, the amount and properties of other components, and the like. Further, when the composition is prepared using the solution in which the hydrolyzed condensate is dissolved, the concentration of the solution of the hydrolyzed condensate so that the amount of the hydrolyzed condensate in the finally obtained composition is a desired amount. Also keep in mind that it is necessary to determine the amount used.
In the preparation of the composition, heating may be appropriately performed as long as the components are not decomposed or deteriorated.

In the present invention, filtration may be performed using a filter on the order of submicrometers or the like at the stage of producing the resist underlayer film forming composition or after mixing all the components.

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

<Solvent>
The solvent that can be used for 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) hydrolyzable condensate, (B) crosslinkable compound, (C) acid and acid generator, and other components. ..

Specific examples thereof 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), and methyl isobutyl carbinol. , Propropylene 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, cyclo Pentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene Glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate , Isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate , Butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxy-2-methylpropion Methyl acid, 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 , Methylbutyl Ketone, 2-Heptanone, 3-Heptanone, 4-Heptanone, Cyclohexanone, N, N-Dimethylformamide, N-Methylacetamide, N, N-dimethylacetamide, N-Methyl-2-pyrrolidone, 4-Methyl- Examples thereof include 2-pentanol, γ-butyrolactone, and the solvent can be used alone or in combination of two or more.

Further, the resist underlayer film forming composition may contain water as a solvent. When water is contained as the solvent, the content thereof may 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 solvent contained in the composition. can.

<Other additives>
Various additives can be added to the resist underlayer film forming composition depending on the use of the composition.
Examples of the additive include a curing catalyst (ammonium salt, phosphine, phosphonium salt, sulfonium salt, nitrogen-containing silane compound, etc.), stabilizer (organic acid, water, alcohol, etc.), organic polymer compound, and surfactant. (Nonion-based surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorosurfactants, UV-curable surfactants, etc.), pH adjusters, rhology adjusters, adhesion aids Examples thereof include known additives to be blended in materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as agents, resist underlayer films, antireflection films, and pattern inversion films.
Various additives are exemplified below, but the present invention is not limited thereto.

<Curing catalyst>
As the curing catalyst, ammonium salts, phosphines, phosphonium salts, sulfonium salts and the like can be used. The following salts described as curing catalysts may be added in the form of salts, or those that form a salt in the above composition (at the time of addition, those that are added as a separate compound to form a salt in the system). ) May be any of them.

（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 has the formula (D-1) :.

(In the formula, m represents an integer of 2 to 11, n represents an integer of 2 to 3, R ²¹ represents an alkyl group or an aryl group, and Y ⁻ represents an anion.) A quaternary ammonium salt having a structure represented by the above. ,
Equation (D-2):

(In the formula, R ²² , R ²³ , R ²⁴ and R ²⁵ represent an alkyl or aryl group, N represents a nitrogen atom, Y ⁻ represents an anion, and R ²² , R ²³ , R ²⁴ , and R ^25. Are quaternary ammonium salts having a structure represented by (each of which is bonded to a nitrogen atom by a CN bond).
Equation (D-3):

A quaternary ammonium salt having a structure represented by (in the formula, R ²⁶ and R ²⁷ represent an alkyl group or an aryl group, N represents a nitrogen atom, and Y ^{− represents an anion).}
Equation (D-4):

A quaternary ammonium salt having a structure represented by (in the formula, R ²⁸ represents an alkyl group or an aryl group, N represents a nitrogen atom, and Y ^{− represents an anion).}
Equation (D-5):

A quaternary ammonium salt having a structure represented by (in the formula, R ²⁹ and R ³⁰ represent an alkyl group or an aryl group, N represents a nitrogen atom, and Y ^{− represents an anion).}
Equation (D-6):

(In the formula, m is an integer of 2 to 11, n is an integer of 2 to 3, H is a hydrogen atom, N is a nitrogen atom, and Y ⁻ is an anion). You can mention salt.

（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。 Further, as the phosphonium salt, the formula (D-7):

(In the formula, R ³¹ , R ³² , R ³³ , and R ³⁴ represent an alkyl or aryl group, P represents a phosphorus atom, Y ⁻ represents an anion, and R ³¹ , R ³² , R ³³ , and R. ^{Each of 34} is bonded to a phosphorus atom by a CP bond), and a quaternary phosphonium salt can be mentioned.

（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。 Further, as the sulfonium salt, the formula (D-8):

(In the formula, 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 represent CS, respectively. A tertiary sulfonium salt represented by (which is bonded to a sulfur atom by a bond) can be mentioned.

The compound of the above formula (D-1) is a quaternary ammonium salt derived from an amine, and m represents an integer of 2 to 11 and n represents an integer of 2 to 3. The quaternary R ²¹ ammonium salt 1 to 18 carbon atoms, preferably an 2-10 alkyl group, or an aryl group having a carbon number of 6 to 18, for example, an ethyl group, a propyl group, a butyl group Examples thereof include a linear alkyl group, a benzyl group, a cyclohexyl group, a cyclohexylmethyl group, a dicyclopentadienyl group and the like. The anion (Y ⁻ ) includes halide ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), and iodine ion (I ⁻ ), carboxylate (−COO ⁻ ), and sulfonate (−SO ₃ ^−). ), alcoholates (-O ^- can be given) acid groups and the like.

The compound of the above formula (D-2) is a quaternary ammonium salt ^{represented by R 22} R ²³ R ²⁴ R ²⁵ N ⁺ Y ^−. The quaternary ammonium salts R ²² , R ²³ , R ²⁴ and R ²⁵ are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms. Anions (Y ⁻ ) include halide ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), and iodine ion (I ⁻ ), carboxylate (−COO ⁻ ), and sulfonate (−SO ₃ ⁻ ). , alcoholates ^- can be exemplified an acid group such as (-O). This quaternary ammonium salt is commercially available and is available, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzyl chloride. Ammonium, trimethylbenzylammonium chloride and the like are exemplified.

Compounds of formula (D-3) above is a quaternary ammonium salt derived from 1-substituted ^imidazole, carbon atoms ^{R 26} and ^{R 27} is 1 to ^18, of ^{R 26} and ^{R 27} It is preferable that the total number of carbon atoms is 7 or more. For example R ²⁶ is a methyl group, an ethyl group, a propyl group, a phenyl group, a benzyl group, R ²⁷ can be exemplified benzyl group, octyl group, octadecyl group. Anions (Y ⁻ ) include halide ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), and iodine ion (I ⁻ ), carboxylate (−COO ⁻ ), and sulfonate (−SO ₃ ⁻ ). , alcoholates ^- can be exemplified an acid group such as (-O). This compound can also be obtained as a commercially available product, but for example, an imidazole compound such as 1-methylimidazole or 1-benzylimidazole is reacted with an alkyl halide such as benzyl bromide or methyl bromide or an aryl halide. Can be manufactured.

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 an alkyl group having 4 to 18 carbon atoms, or a carbon atom. The number is 6 to 18, and examples thereof include a butyl group, an octyl group, a benzyl group, and a lauryl group. Anions (Y ⁻ ) include halide ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), and iodine ion (I ⁻ ), carboxylate (−COO ⁻ ), and sulfonate (−SO ₃ ⁻ ). , alcoholates ^- can be exemplified an acid group such as (-O). This compound can also be obtained as a commercially available product, but is produced by reacting, for example, pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or an aryl halide. can do. Examples of this compound include N-laurylpyridinium chloride, N-benzylpyridinium bromide, and the like.

The compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline or the like, and R ²⁹ has 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms. , Or an aryl group having 6 to 18 carbon atoms, and examples thereof include a methyl group, an octyl group, a lauryl group, and 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 quaternary ammonium derived from picoline, for example, R ³⁰ is a methyl group. Anions (Y ⁻ ) include halide ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), and iodine ion (I ⁻ ), carboxylate (−COO ⁻ ), and sulfonate (−SO ₃ ⁻ ). , alcoholates ^- can be exemplified an acid group such as (-O). This compound can also be obtained as a commercial product, but for example, a substituted pyridine such as picoline is reacted with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or an aryl halide. Can be manufactured. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-laurylpicolinium chloride and the like.

The compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, where m represents an integer of 2 to 11 and n represents an integer of 2 to 3. The anion (Y ⁻ ) includes halide ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), and iodine ion (I ⁻ ), carboxylate (−COO ⁻ ), and sulfonate (−SO ₃ ^−). ), alcoholates (-O ^- can be given) acid groups and the like. 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, preferably among the four substituents ^{R 31 to} R ^34. Three are phenyl groups or substituted phenyl groups, for example, a phenyl group or a trill group can be exemplified, and the remaining one is an alkyl group having 1 to 18 carbon atoms and 6 to 18 carbon atoms. It is an aryl group. The anion (Y ⁻ ) includes halide ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), and iodine ion (I ⁻ ), carboxylate (−COO ⁻ ), and sulfonate (−SO ₃ ^−). ), alcoholates (-O ^- can be given) acid groups and the like. This compound is available as a commercial product, for example, tetraalkylphosphonium halides such as tetra n-butylphosphonium halides and tetra n-propylphosphonium halides, and trialkylbenzyl halides such as triethylbenzylphosphonium halides. Halogenated triphenyl monoalkylphosphonium, halogenated triphenylbenzylphosphonium, such as phosphonium, halogenated triphenylmethylphosphonium, halogenated triphenylethylphosphonium, etc.
Examples thereof include tetraphenylphosphonium halide, tritrylmonoarylphosphonium halide, and tritryl monoalkylphosphonium halide (henceforth, the halogen atom is a chlorine atom or a bromine atom). In particular, halogenated triphenylmonoalkylphosphoniums such as triphenylmethylphosphonium halides and triphenylethylphosphonium halides, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halides, and halogens such as tritrylmonophenylphosphonium halides. Halogenated tritryl monoalkylphosphonium (halogen atom is chlorine atom or bromine atom) such as tritryl monoarylphosphonium halide or tritryl monomethyl phosphonium halide is preferable.

Examples of phosphines include primary phosphine such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine and phenylphosphine, and second phosphine such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine and diphenylphosphine. , Trith phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine and the like.

The compound of the above formula (D-8) 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, preferably two of the three substituents ^{R 35 to} R ^{37 are phenyl.} A group or substituted phenyl group, for example a phenyl group or a trill group can be exemplified, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. Is. The anion (Y ⁻ ) includes halide ions such as chlorine ion (Cl ⁻ ), bromine ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (−COO ⁻ ), and sulfonate (−SO ₃ ^−). ), alcoholates (-O ^-), maleic acid anion include an acid group such as a nitrate anion. This compound is available as a commercial product, for example, trialkylsulfonium halides such as tri-n-butyl sulfonium halides and tri-n-propyl sulfonium halides, and dialkyl benzyl sulfonium halides such as diethyl benzyl sulfonium halides. , Diphenylmethylsulfonium halide, diphenylmonoalkylsulfonium halide such as diphenylethylsulfonium halide, triphenylsulfonium halide (above, halogen atom is chlorine atom or bromine atom), tri n-butyl sulfonium carboxylate, tri n- Trialkyl sulfonium carboxylate such as propyl sulfonium carboxylate, dialkyl benzyl sulfonium carboxylate such as diethyl benzyl sulfonium carboxylate, diphenyl monoalkyl sulfonium carboxylate such as diphenylmethyl sulfonium carboxylate, diphenyl ethyl sulfonium carboxylate, triphenyl sulfonium carboxylate Can be mentioned. Further, halogenated triphenyl sulfonium and triphenyl sulfonium carboxylate can be preferably used.

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

When a curing catalyst is used, (A) 0.01 parts by mass to 10 parts by mass, 0.01 parts by mass to 5 parts by mass, or 0.01 parts by mass to 3 parts by mass with respect to 100 parts by mass of polysiloxane. It is a department.

<Stabilizer>
The stabilizer can be added for the purpose of stabilizing the hydrolyzed condensate and the like, and as a specific example thereof, an organic acid, water, alcohol, or a combination thereof can be added.
Examples of the organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartrate acid, phthalic acid, citric acid, glutaric acid, lactic acid, salicylic acid and the like. Of these, oxalic acid and maleic acid are preferable. When an organic acid is added, the amount of the organic acid added is 0.1 to 5.0% by mass with respect to the mass of the hydrolyzed condensate (A). These organic acids can also act as pH regulators.
As the water, pure water, ultrapure water, ion-exchanged water, or the like can be used, and when used, the amount added is 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resist underlayer film forming composition. Can be.
The alcohol is preferably one that easily scatters by heating after coating, and examples thereof include methanol, ethanol, propanol, i-propanol, butanol and the like. When alcohol is added, the amount thereof 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>
By adding the organic polymer compound to the resist underlayer film forming composition, the dry etching rate (decrease in film thickness per unit time) of the film (resist underlayer film) formed from the composition, and the amount of decrease in the film thickness per unit time, and also. The attenuation coefficient, refractive index, etc. can be adjusted. The organic polymer compound is not particularly limited, and is appropriately selected from various organic polymers (condensation polymer and addition polymer) according to the purpose of addition thereof.
Specific examples thereof include addition-polymerized polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolak, polyether, polyamide and polycarbonate, and polypolymerized polymers.
In the present invention, an organic polymer containing an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, a quinoxaline ring, or a heteroaromatic ring that functions as an absorption site also has such a function. Can be suitably used. Specific examples of such organic polymer compounds include addition polymerizable properties such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether and N-phenylmaleimide. Examples thereof include, but are not limited to, addition-polymerized polymers containing a monomer as a structural unit thereof, and condensed-polymerized polymers such as phenol novolac and naphthol novolak.

When an addition polymerization polymer is used as the organic polymer compound, the polymer compound may be either a homopolymer or a copolymer.
Addition-polymerizable monomers are used in the production of addition-polymerizable polymers, and specific examples of such addition-polymerizable monomers include acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, and methacryl. Examples thereof include, but are not limited to, amide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic acid anhydrides, and acrylonitrile.

Specific examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate, 2-hydroxyethyl acrylate, and 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, Examples thereof include tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate. Not limited to these.

Specific examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate and 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 -Adamantil methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidylmethacrylate, 2-phenylethylmethacrylate, hydroxyphenylmethacrylate, bromophenylmethacrylate, etc. However, but not limited to these.

Specific examples of the acrylamide compound include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N, N-dimethylacrylamide, N-anthrylacrylamide and the like. Not limited.

Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N, N-dimethylmethacrylamide, N-anthrylacrylamide and the like. However, it is not limited to these.

Specific examples of the vinyl compound include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene and vinyl. Examples include, but are not limited to, anthracene.

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

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

When a polycondensation polymer is used as the polymer, such a polymer includes, for example, a polycondensation polymer of a glycol compound and a dicarboxylic acid compound. Examples of the glycol compound include diethylene glycol, hexamethylene glycol, butylene glycol and the like. Examples of the dicarboxylic acid compound include succinic acid, adipic acid, terephthalic acid, maleic anhydride and the like. Further, examples thereof include, but are not limited to, polyesters such as polypyrro meritimide, poly (p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, polyamides, and polyimides.
When the organic polymer compound contains a hydroxy group, the hydroxy group can undergo a cross-linking reaction with a hydrolyzed condensate or the like.

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

When the resist underlayer film forming composition contains an organic polymer compound, the content thereof cannot be unconditionally determined because it is appropriately determined in consideration of the function of the organic polymer compound and the like, but usually, the hydrolysis condensate (A) It can be in the range of 1 to 200% by mass with respect to the mass of the above, and from the viewpoint of suppressing precipitation in the composition, for example, 100% by mass or less, preferably 50% by mass or less, more preferably 30% by mass. % Or less, and from the viewpoint of sufficiently obtaining the effect, for example, it can be 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

<Surfactant>
The surfactant is effective in suppressing the occurrence of pinholes, stirries, 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-based surfactants, fluorine-based surfactants, UV-curable surfactants and the like. More specifically, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol. Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurates, sorbitan monopalmitates, sorbitan monostearates, sorbitan monooleates, sorbitan trioleates, sorbitan tristearates. Solbitan fatty acid esters such as, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene such as polyoxyethylene sorbitan tristearate. Nonionic surfactants such as sorbitan fatty acid esters, trade name Ftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Material Denshi Kasei Co., Ltd. (formerly Tochem Products Co., Ltd.)), trade name Megafuck ( Registered trademarks) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Co., Ltd.), Florard FC430, FC431 (manufactured by 3M Japan Co., Ltd.), trade name Asahi Guard (registered trademark) ) Fluorosurfactants such as AG710 (manufactured by AGC Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxanes. Polyethylene-KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned, but the present invention is not limited thereto.
The surfactant 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 with respect to the mass of the hydrolyzed condensate (A), or It can be 0.01 to 1% by mass, or 0.01 to 1% by mass.

<Rheology adjuster>
The rheology adjuster mainly improves the fluidity of the resist underlayer film forming composition, particularly in the baking step, improves the film thickness uniformity of the formed film, and enhances the filling property of the composition into the hole. Added for the purpose. Specific examples include phthalate derivatives such as dimethylphthalate, diethylphthalate, dii-butylphthalate, dihexylphthalate, and butyl i-decylphthalate, dinormal butyl adipate, di-i-butyl adipate, and di-i-octyl adipate. Adipic acid derivatives such as octyldecyl adipate, maleic acid derivatives such as dinormal butyl malate, diethyl malate, dinonyl malate, oleic acid derivatives such as methyl oleate, butyl olate, tetrahydrofurfuryl oleate, or normal butyl stearate, glyceryl steer. Examples thereof include phthalates and the like stearic acid derivatives.
When these rheology adjusters are used, the amount added thereof is usually less than 30% by mass with respect to the total solid content of the resist underlayer film forming composition.

<Adhesive aid>
The above-mentioned adhesive auxiliary mainly has the purpose of improving the adhesion between the substrate or the resist and the film formed from the resist underlayer film forming composition (resist underlayer film), and particularly for suppressing / preventing the peeling of the resist during development. Is added at. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxy. Alkoxysilanes such as silane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silanes such as trimethylsilylimidazole, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyl Other silanes such as triethoxysilane, γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, Examples thereof include heterocyclic compounds such as thiouracil, mercaptoimidazole and mercaptopyrimidine, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds.
When these adhesive aids are used, the amount added thereof is usually less than 5% by mass, preferably less than 2% by mass, based on the total solid content of the resist underlayer film forming composition.

<pH adjuster>
Further, as the pH adjuster, a bisphenol S or a bisphenol S derivative can be added in addition to an acid having 1 or 2 or more carboxylic acid groups such as the organic acid mentioned above as the <stabilizer>. The bisphenol S or the 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 with respect to 100 parts by mass of the hydrolyzed condensate (A). be.

Hereinafter, specific examples of bisphenol S and bisphenol S derivatives will be given, but the present invention is not limited thereto.

As described above, the present invention is a method for producing a silicon-containing resist underlayer film, which comprises a step of applying the above-mentioned resist underlayer film forming composition to obtain a coating film and curing the coating film with ultraviolet rays, wherein the silicon-containing resist underlayer film is produced. The resist underlayer film can be removed by a hydrogen sulfate aqueous solution after a dry etching treatment with oxygen gas.
Hereinafter, specific examples of a method for producing a resist underlayer film using the resist underlayer film forming composition will be described in the steps before and after the resist underlayer film is applied in a semiconductor device, and the wet removal of the resist underlayer film after production. I will explain it together with.

Substrate used for manufacturing precision integrated circuit elements [For example, semiconductor substrate such as silicon oxide film, silicon nitride film or silicon wafer coated with silicon oxide film, silicon nitride substrate, quartz substrate, glass substrate (alkali-free glass) , Low alkaline glass, including crystallized glass), glass substrate on which ITO (indium tin oxide) film or IZO (indium zinc oxide) film is formed, plastic (polyimide, PET, etc.) substrate, low dielectric constant material (Low-k material) coated substrate, flexible substrate, etc.] is coated with the resist underlayer film forming composition by an appropriate coating method such as a spinner, a coater, etc., and if necessary, the solvent is removed, and the coating film is applied. To get. The solvent can be removed by reducing the pressure or heating. As the heating conditions, it is preferable that the solvent can be removed and the conditions are milder. By adopting such conditions, excellent wet removal properties can be realized with good reproducibility. The heating conditions are appropriately determined from a heating temperature range of 30 to 140 ° C. and a heating time of 5 seconds to 2 minutes in consideration of the boiling point of the solvent, the reactivity of the solid content, the concentration of the solid content, the desired film thickness, and the like. Will be done.
The coating film is exposed to form a resist underlayer film. Hereinafter, in the present specification, the resist underlayer film means a film formed from the resist underlayer film forming composition.

Next, the obtained coating film is exposed.
Ultraviolet light (wavelength 10 nm to 400 nm) can be used for exposure, and light having a wavelength of 150 nm to 330 nm, preferably 150 nm to 248 nm can be used, for example, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm). ), Xe excimer laser (wavelength 172 nm), F2 excimer laser (wavelength 157 nm) and the like can be used. Above all, the use of light having a wavelength of 172 nm is preferable.
The amount of exposure may be 10 mJ / cm ² to 3000 mJ / cm ^2.
The exposure step may be performed in an inert gas atmosphere in which oxygen and / or water vapor (water) is present. As the inert gas, nitrogen gas can be particularly preferably used.

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

As will be described later, the resist underlayer film photo-cured by ultraviolet irradiation is dry-etched with oxygen gas. The resist underlayer film after the dry etching treatment can be removed by an aqueous solution of hydrogen peroxide sulfate, as will be described later.

It is also possible to form the resist underlayer film after forming the organic underlayer film on the substrate, and in the present invention, it is preferable to provide the organic underlayer film. Hereinafter, as an embodiment in which the organic underlayer film is provided, a step after the resist underlayer film forming step will be described.
The organic underlayer film used here is not particularly limited, and can be arbitrarily selected and used from those conventionally used in the lithography process.
By providing an organic underlayer film, a resist underlayer film on the substrate, and a resist film described later on the substrate, the pattern width of the photoresist film is narrowed, and the photoresist is prevented from collapsing. Even when the film is thinly coated, the substrate can be processed by selecting an appropriate etching gas described later.
For example, a fluorogas having a sufficiently fast etching rate for a photoresist film can be used as an etching gas to process a resist underlayer film, and an oxygen-based gas having a sufficiently fast etching rate for the resist underlayer film can be processed. The organic underlayer can be processed by using the gas as the etching gas, and the substrate can be processed by using the fluorogas having a sufficiently high etching rate with respect to the organic underlayer as the etching gas. ..

Next, for example, a photoresist layer (resist film) is formed on the resist underlayer film. The resist film can be formed by a well-known method, that is, by applying a resist composition (for example, a photoresist) on a resist underlayer film and firing it.
The film thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2
It is 000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

The photoresist material used for the resist film formed on the resist underlayer film is particularly limited as long as it is sensitive to light used for exposure (for example, KrF excimer laser, ArF excimer laser, etc.). However, both negative photoresist materials and positive photoresist materials can be used. For example, a positive photoresist material consisting of novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist consisting of a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator. A chemically amplified photoresist material consisting of a low molecular weight compound, an alkali-soluble binder, and a photoacid generator that decomposes with a material and an acid to increase the alkali dissolution rate of the photoresist material, and decomposes with an acid to increase the alkali dissolution rate. There are chemically amplified photoresist materials composed of a low molecular weight compound that decomposes with an acid and a binder having a group to increase the alkali dissolution rate of the photoresist material, and a photoacid generator.
Specific examples available as commercial products include chypre product name APEX-E, Sumitomo Chemical Co., Ltd. product name PAR710, JSR Corporation product name; product name AR2772JN, and Shin-Etsu Chemical Co., Ltd. product name. SEPR430 and the like can be mentioned, but the present invention is not limited thereto. Also, for example, Proc. SPIE, Vol. 3999,330-334 (2000), Proc. SPIE, Vol. 3999,357-364 (2000), and Proc. SPIE, Vol. Fluorine-containing atomic polymer-based photoresist materials as described in 3999,365-374 (2000) can be mentioned.

Further, the resist film formed on the resist underlayer film is 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) instead of the photoresist film. Can be used.
As the electron beam resist material, either a negative type material or a positive type 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 alkali dissolution rate, an alkali-soluble binder, an acid generator, and an alkali of the resist material decomposed with an acid. A chemically amplified resist material composed of a low molecular weight compound that changes the dissolution rate, a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, and an acid that decomposes with an acid to change the alkali dissolution rate of the resist material. It has a chemically amplified resist material made of a low molecular weight compound, a non-chemically amplified resist material made of a binder having a group that decomposes with an electron beam and changes the alkali dissolution rate, and a site that is cut by an electron beam to change the alkali dissolution rate. There are non-chemically amplified resist materials made of binders. Even when these electron beam resist materials are used, a resist film pattern can be formed in the same manner as when a photoresist material is used with the irradiation source as an electron beam.
Further, 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 lower layer film is exposed through a predetermined mask (rectyl). 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, if necessary, post-exposure heating (post exposure break) can be performed. Post-exposure heating is performed under appropriately selected conditions from a heating temperature of 70 ° C. to 150 ° C. and a heating time of 0.3 minutes to 10 minutes.

Then, development is performed with a developer (for example, an alkaline developer). As a result, for example, when a positive photoresist film is used, the photoresist film in the exposed portion is removed, and a pattern of the photoresist film is formed.
The developing solution (alkali developing solution) includes an aqueous solution of an alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and ethanol. An alkaline aqueous solution (alkaline developing solution) such as an amine aqueous solution such as amine, propylamine, or ethylenediamine can be mentioned as an example. Further, 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 seconds to 600 seconds.

Further, in the present invention, an organic solvent can be used as the developing solution, and development is performed with the developing solution (solvent) after exposure. As a result, for example, when a positive photoresist film is used, the photoresist film in the unexposed portion is removed, and a pattern of the photoresist film is formed.
Examples of the developing solution (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, and 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 mono Ethyl 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, formate Butyl, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate , Ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxy Examples thereof include propionate and propyl-3-methoxypropionate. Further, a surfactant or the like can be added to these developers. As the development conditions, the temperature is appropriately selected from 5 ° C. to 50 ° C. and the time is appropriately selected from 10 seconds to 600 seconds.

Using the pattern of the photoresist film (upper layer) thus formed as a protective film, the resist lower layer film (intermediate layer) is removed, and then the patterned photoresist film and the patterned resist lower layer film (intermediate layer) are removed. ) Is used as a protective film to remove the organic underlayer film (lower layer), and the substrate in the portion where the organic underlayer film has been removed is processed by injecting ions (impurities) or the like, and then the resist underlayer film is formed. Removal is done.

The removal of the resist lower layer film (intermediate layer) performed using the resist film (upper layer) pattern as a protective film is performed by dry etching, and tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), and perfluoropropane. (C ₃ F ₈ ), trifluoromethane,
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. Dry etching with a halogen-based gas basically makes it difficult to remove a resist film (photoresist film) made of an organic substance. On the other hand, the silicon-containing resist underlayer film containing a large amount of silicon atoms is rapidly removed by the halogen-based gas. Therefore, it is possible to suppress a decrease in the film thickness of the photoresist film due to dry etching of the resist underlayer film. As a result, the photoresist film can be used as a thin film. Therefore, dry etching of the resist underlayer film is preferably performed by a fluorine-based gas, and examples of the fluorine-based gas include tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), and perfluoro propane (C ₃ F). ₈ ), trifluoromethane, difluoromethane (CH ₂ F ₂ ) and the like, but are not limited thereto.

When an organic underlayer film is provided between the substrate and the resist underlayer film, an organic film composed of a patterned resist film (upper layer) and a patterned resist underlayer film (intermediate layer) is used as a protective film. The removal of the lower film (lower layer) is preferably performed by dry etching with an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.). This is because the resist underlayer film containing a large amount of silicon atoms is difficult to be removed by dry etching with an oxygen-based gas.

Subsequently, ion implantation can be performed as processing of the (semiconductor) substrate.
Ion implantation is performed, for example, by implanting impurity ions into the substrate using a known ion implantation device or ion doping device. As the ion implantation conditions, for example, an appropriate condition is selected from the range of acceleration voltage: 500 eV to 10 MeV, dose amount: 1 × 10 ¹⁰ / cm ^{2 to} 1 × 10 ¹⁸ / cm ^2.

Finally, the resist underlayer film is removed. Generally, dry etching or wet etching is performed to remove the resist underlayer film.
Dry etching of the resist underlayer film (intermediate layer) is carried out, for example, with a fluorine-based gas, for example, tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoro propane (C ₃ F ₈ ), trifluo. Examples thereof include lomethane and difluoromethane (CH ₂ F _2).
Wet etching of the resist underlayer film (intermediate layer) is performed, for example, by dilute hydrofluoric acid, buffered hydrofluoric acid, an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), and an aqueous solution containing sulfuric acid and hydrogen peroxide (sulfuric acid excess). It is carried out with a chemical solution such as an aqueous solution containing hydrogen oxide (SPM chemical solution), an aqueous solution containing fluoride and hydrogen peroxide (FPM chemical solution), and 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 the dry etching treatment with oxygen gas.
When the substrate is a silicon oxide film, or when ion implantation is performed as a processing of the substrate, when dry etching with a conventionally used fluorine-based gas is performed to remove the resist underlayer film, the silicon oxide film or ion implantation is performed. There is a risk that the board will be damaged.
According to the present invention, the coating film of the resist underlayer film forming composition is photocured to produce a resist underlayer film, whereby the resist underlayer film after the oxygen gas etching treatment is removed with a hydrogen sulfate aqueous solution. Compared to dry etching with a fluorine-based gas, damage to the substrate can be suppressed.

Further, an organic antireflection film can be formed on the upper layer of the resist lower layer film before the resist film is formed. The antireflection film composition used therefor is not particularly limited, and for example, it can be arbitrarily selected and used from those conventionally used in a lithography process, and a commonly used method, for example, is used. The antireflection film can be formed by coating and firing with a spinner and a coater.

Further, the substrate on which the resist underlayer film forming composition is applied may have an organic or inorganic antireflection film formed on the surface thereof by a CVD method or the like, and the resist underlayer film may be formed on the substrate. Can also be formed.

The resist underlayer film formed from the resist underlayer film forming composition may also have absorption to the light depending on the wavelength of the light used in the lithography process. Then, in such a case, it can function as an antireflection film having an effect of preventing the reflected light from the substrate.
Further, the resist underlayer film has an adverse effect on the substrate as a layer for preventing interaction between the substrate and the resist film (photoresist film, etc.), a material used for the resist film, or a substance generated during exposure to the resist film. As a layer having a function of preventing the resist film, a layer having a function of preventing the diffusion of substances generated from the substrate during heating and firing into the upper resist film, and a barrier layer for reducing the poisoning effect of the resist film by the dielectric layer of the semiconductor substrate. It is also possible to use it.

The resist underlayer film can be applied to a substrate on which via holes are formed, which is used in the dual damascene process, and can be used as a hole filling material (filling material) capable of filling holes without gaps. It can also be used as a flattening material for flattening the surface of a semiconductor substrate having irregularities.
Further, the resist underlayer film is not only a function as a hard mask as an EUV resist film underlayer film, but also does not intermix with, for example, an EUV resist film, and is not preferable for exposure light such as EUV exposure (wavelength 13.5 nm). It can be used as a lower antireflection film of an EUV resist film that can prevent reflection of UV (ultraviolet) light or DUV (deep ultraviolet) light (: ArF light, KrF light) from the substrate or interface. That is, reflection can be efficiently prevented in the lower layer of the EUV resist film. When used as an EUV resist underlayer, the process can be performed in the same manner as a photoresist underlayer.

Hereinafter, the present invention will be described in more detail with reference to synthetic examples and examples, but the present invention is not limited to the following.
The weight average molecular weight of the polymer (hydrolyzed condensate) prepared below was measured by the following GPC measuring device and measurement conditions.
・ GPC device Product name: HLC-8220GPC (manufactured by Tosoh Corporation)
-GPC column Product name: Shodex (registered trademarks KF803L, KF802, KF801 (manufactured by Showa Denko KK)
-Column temperature: 40 ° C
-Eluent (eluting solvent): Tetrahydrofuran-Flow rate (flow rate): 1.0 mL / min
・ Standard substance: Polystyrene (manufactured by Showa Denko KK)

[1] Preparation of polymer (hydrolyzed condensate) (Synthesis Example 1)
Tetraethylammonium hydroxide aqueous solution (concentration: 35% by mass) 0.74 g, water 1.18 g, isopropyl alcohol 22.15 g and methyl isobutyl ketone 44.30
G was placed in a 300 mL flask and stirred, and the obtained solution was stirred with a magnetic stirrer to 2.34 g of methoxybenzyltrimethoxysilane, 5.46 g of triethoxysilylpropyldiallyl isocyanurate, and methyltriethoxy. A mixture of 2.20 g of silane, 4.33 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 7.82 g of acetoxypropyltrimethoxysilane was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 40 ° C. and reacted for 240 minutes.
Then, in order to open the ring of the epoxy group to obtain a hydrolyzed condensate having a dihydroxy group, 43.98 g of an aqueous nitrate solution (concentration: 1 mol / L) was added dropwise to the reaction solution, and the reaction was further carried out at 40 ° C. for 4 hours. I let you.
Then, 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 to recover the organic layer. A hydrolysis condensate (polymer) using propylene glycol monomethyl ether as a solvent by adding 66.45 g of propylene glycol monomethyl ether to the recovered organic layer and distilling off methyl isobutyl ketone, methanol, ethanol and water under reduced pressure. Concentrate was obtained. The solid content concentration of the obtained concentrated liquid exceeded 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, the concentration was adjusted so as to be 13% by mass in terms of solid residue when heated at 140 ° C., and propylene glycol monoethyl ether was used as a solvent. A solution of the hydrolysis condensate (polymer) (solid content concentration 13% by mass) was obtained. The obtained polymer contained a structure represented by the formula (X-1), and its weight average molecular weight (Mw) was Mw2,500 in terms of polystyrene by GPC. Further, as a result of measurement by a method according to JIS standard (JISK 7236), the epoxy value was 0.

(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 obtained solution was magnetic. While stirring with a stirrer, 3.04 g of methoxybenzyltrimethoxysilane, 6.23 g of triethoxysilylpropyldialyl isocyanurate, 5.82 g of methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy. A mixture of 4.95 g of silane and 4.75 g of acetoxymethyltrimethoxysilane was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 40 ° C. and reacted for 240 minutes.
Then, 50.29 g of an aqueous nitrate solution (concentration: 1 mol / L) was added dropwise to the reaction solution in order to open the ring of the epoxy group to obtain a hydrolyzed condensate having a dihydroxy group, and the reaction was further carried out at 40 ° C. for 4 hours. I let you.
Then, the reaction solution was cooled to room temperature, and the reaction solution was subjected to liquid separation treatment using 148.77 g of methyl isobutyl ketone and 74.39 g of water to recover the organic layer. A hydrolysis condensate (polymer) using propylene glycol monomethyl ether as a solvent by adding 74.39 g of propylene glycol monomethyl ether to the recovered organic layer and distilling off methyl isobutyl ketone, methanol, ethanol and water under reduced pressure. Concentrate was obtained. The solid content concentration of the obtained concentrated liquid exceeded 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, the concentration was adjusted so as to be 13% by mass in terms of solid residue when heated at 140 ° C., and propylene glycol monoethyl ether was used as a solvent. A solution of the hydrolysis condensate (polymer) (solid content concentration 13% by mass) was obtained. The obtained polymer contained a structure represented by the formula (X-2), and its weight average molecular weight (Mw) was Mw2,700 in terms of polystyrene by GPC. Further, as a result of measurement by a method according to JIS standard (JISK 7236), the epoxy value was 0.

(Comparative synthesis example 1)
25.4 g of tetraethoxysilane, 1.73 g of phenyltrimethoxysilane, 7.36 g of methyltriethoxysilane, 0.72 g of triethoxysilylpropyldiallyl isocyanurate and 53.02 g of acetone were placed in a 300 mL flask and stirred to obtain the obtained product. While stirring the solution with a magnetic stirrer, 11.63 g of an aqueous hydrochloric acid solution (concentration 0.01 mol / L) was added dropwise thereto. After the dropping, 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 is added, and acetone, methanol, ethanol, hydrochloric acid and water are distilled off under reduced pressure to concentrate a hydrolyzed condensate (polymer) using propylene glycol monomethyl ether acetate as a solvent. Got The solid content concentration of the obtained concentrated liquid exceeded 13% by mass in terms of solid residue when heated at 140 ° C.
Next, propylene glycol monoethyl ether was added to the obtained concentrate, and the concentration was adjusted so as to be 13% by mass in terms of solid residue when heated at 140 ° C., and propylene glycol monomethyl ether acetate and propylene glycol mono A solution (solid content concentration: 13% by mass) of an aqueous decomposition condensate (polymer) using a mixed solvent of ethyl ether (20/80 (V / V)) as a solvent was obtained. The obtained polymer contained a structure represented by the formula (X-3), and its weight average molecular weight (Mw) was Mw2,100 in terms of polystyrene by GPC. Further, as a result of measurement by a method according to JIS standard (JISK 7236), the epoxy value was 0.

[2] Examples 1 and 2, Comparative Example 1: Preparation of Silicon-Containing Resist Underlayer Film Forming Composition The hydrolysis condensate (Si polymer), acid and the acid obtained in the above Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 An acid generator, a crosslinkable compound, a solvent, etc. are mixed at the ratios (parts by mass) shown in Tables 1 and 2, and filtered through a fluororesin filter having a pore size of 0.1 μm to form a silicon-containing resist underlayer film formation composition. Each thing was prepared.
The addition ratio of the polymer (polysiloxane) in Tables 1 and 2 indicates the addition amount of the polymer itself, not the addition amount of the polymer solution.
The abbreviations used in Tables 1 and 2 below are as follows.
PPTS: Pyridinium-p-toluenesulfonic acid TAG-2689: Tertiary ammonium salt of trifluoromethanesulfonic acid (heat acid generator manufactured by King Industries)
PL-LI: Tetramethoxymethylglycoluryl (manufactured by Mitsui Cytec Co., Ltd., trade name: Powder Link 1174)
MA: IMID-TEOS maleate: N- (3-triethoxypropyl) -4,5-dihydroimidazole PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate PGE: 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, product name: EHPE-3150 (2,2-bis (hydroxymethyl) -1-butanol). 1,2-Epoxy-4- (2-oxylanyl) cyclohexane adduct, manufactured by Daicel Co., Ltd.) 5.00 g, 9-anthracenecarboxylic acid 3.11 g, benzoic acid 2.09 g and ethyltriphenylphosphonium bromide 0.62 g Was added, and the mixture was heated and refluxed for 13 hours under a nitrogen atmosphere.
After cooling the reaction mixture to room temperature, 16 g of cation exchange resin (product name: Amberlist [registered trademark] 15JWET, manufactured by Organo Co., Ltd.) and anion exchange resin (product name: Dawex [registered trademark] MONOSPHERE [Registered trademark] 550A, manufactured by Muromachi Chemical Co., Ltd., 16 g was added, and the mixture was stirred at 25 ° C to 30 ° C for 4 hours. Then, the resin was removed by filtration to obtain a solution containing a polymer as a reaction product.
GPC analysis of the obtained reaction product revealed that the weight average molecular weight was 4,700 in terms of standard polystyrene. The obtained reaction product is presumed to be a copolymer having a structural unit represented by the following formula (Y).

In 5 g of the obtained solution containing the polymer (polymer concentration: 16% by mass), 0.2 g of tetraethoxymethyl glycol uryl, 0.03 g of pyridinium-p-toluenesulfonate, and the product name Megafuck [registered trademark] R-30. 0.0008 g (manufactured by DIC Co., Ltd.), 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. Then, it was further filtered with 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, respectively. Then, the film thickness of each obtained film was measured.
Then, a mixed solvent (7/3 (V / V)) of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate was applied onto each membrane, and spin-dried. Then, the film thickness after drying was measured, and the presence or absence of a change in the film thickness before and after the application of the mixed solvent was evaluated. Based on the film thickness before coating with the mixed solvent, those having a film thickness change of 10% or less after coating were evaluated as "good", and those having a film thickness change of less than 10% were evaluated as "not cured". The results obtained 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 various evaluations carried out using the composition.

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

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

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

[6] Resist pattern evaluation by ArF immersion exposure (resist patterning evaluation: evaluation via PTD process for 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).
Each of the silicon-containing resist underlayer film forming compositions prepared in Examples 1 and 2 and Comparative Example 1 is applied onto the A layer using a spinner, and heated on a hot plate at 100 ° C. for 1 minute to form a coating film. Then, under a nitrogen atmosphere, a light irradiation device (SUS867 manufactured by Ushio Denki Co., Ltd.) was used to irradiate the entire surface of each film with ^{light having a wavelength of 172 nm under the condition of about 100 mJ / cm 2.} A silicon-containing resist underlayer film (B layer) (thickness: 40 nm) was formed. Further, the same operation was performed under ^{the conditions of about 300 mJ / cm 2} or about 500 mJ / cm ² to form a silicon-containing resist underlayer film (B layer) (film thickness 40 nm).
A commercially available resist solution for immersion in ArF is 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) (thickness 90 nm). After forming, using a scanner (wavelength 193 nm, NA: 1.35, 0.98 / 0.75), after development, the line width of the photoresist and the width between the lines are 0.040 μm, that is, a line of 0.040 μm. Exposure was performed through a mask set so that a dense line of and space (L / S) = 1/1 was formed.
After the exposure, the mixture was heated after the exposure (110 ° C. for 1 minute), cooled to room temperature on a cooling plate, developed with an alkaline aqueous solution having a concentration of 38% by mass for 60 seconds, rinsed, and a resist pattern was formed.
The obtained resist patterns were evaluated as "good" if they did not cause large pattern peeling, undercut, or thickening (footing) at the bottom of the line, and as "pattern collapse" if they had collapse. The results obtained are shown in Table 5.

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

[7] Evaluation of SPM Removability of Photocurable Resist Underlayer Film The silicon-containing resist underlayer film forming composition prepared in Examples 1 and 2 and Comparative Example 1 was applied onto a silicon wafer using a spinner, respectively, and a hot plate was applied. The film was formed by heating at 100 ° C. for 1 minute, respectively, and then, using a light irradiation device (SUS867 manufactured by Ushio Denki Co., Ltd.) under a nitrogen atmosphere, light having a wavelength of 172 nm was set to a condition of ^{about 100 mJ / cm 2.} Then, the entire surface of each film was irradiated to form a photocurable film. Further, the same operation was performed under ^{the conditions of about 300 mJ / cm 2} or about 500 mJ / cm ² to form a photocurable film. Then, the film thickness of each of the obtained photocurable films was measured.
On the other hand, the silicon-containing resist underlayer film forming compositions prepared in Examples 1 and 2 and Comparative Example 1 were applied onto a silicon wafer using a spinner, respectively, and heated on a hot plate at 180 ° C. for 60 seconds to obtain a thermosetting film. Was formed, and the film thickness of each obtained thermosetting film was measured.
On each of the obtained photo-cured films or each thermo-cured film, a resist stripping agent RS-30 (sulfuric acid / hydrogen peroxide mixed water (sulfuric acid / hydrogen peroxide = 85-95 wt% / 1-) manufactured by Lhasa Industry Co., Ltd. 10 wt%): SPM chemical solution) was applied, rinsed with water, and dried by blowing air on the substrate. Then, the film thickness of each film after drying was measured, and the presence or absence of change in the film thickness before and after the application of the mixed solvent was evaluated. Based on the film thickness before applying the SPM chemical solution, those having a film thickness change of 70% or more after application were evaluated as "good", and those having a film thickness change of less than 70% were 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 results obtained are shown in Table 6.

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

[8] Evaluation of SPM Removability of Resist Underlayer Film After Dry Etching Using the silicon-containing resist underlayer film forming compositions prepared in Examples 1 and 2 and Comparative Example 1, light was used in the same manner as described above. A cured film or a thermosetting film was obtained, and the thickness of each of the obtained photo-cured film and the thermosetting film was measured.
_{For each of the obtained photo-cured films or each thermo-cured film, an O 2} dry etching process (etching conditions: N ₂ / O ₂ ) was performed using a parallel plate type reactive ion etching apparatus RIE-10NR (manufactured by SAMCO Corporation). = 150/50 (sccm / sccm), time: 30 seconds, pressure: 8Pa, 100W).
After that, a resist stripping agent RS-30 (sulfuric acid / hydrogen peroxide mixed water: SPM chemical solution) manufactured by Lhasa Kogyo Co., Ltd. is applied on each photo-cured film or each thermosetting film that has been etched, and rinsed with water. , It was dried by blowing air on the substrate. Then, the film thickness of each film after drying was measured, and the presence or absence of change in the film thickness before and after the application of the mixed solvent was evaluated. Based on the film thickness before SPM chemical solution application (before etching treatment), those with a film thickness change of 70% or more after application are evaluated as "good", and those with a film thickness change of less than 70% are evaluated as "not dissolved". did. 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 results obtained are shown in Table 7.

As shown in Table 7, the film obtained by photo-curing each of the silicon-containing resist underlayer film forming compositions of Examples 1 and ₂ has good removability with an SPM chemical solution even after O 2 etching. confirmed.

Claims (3)

A method for producing a silicon-containing resist underlayer film that can be removed by an aqueous solution of hydrogen peroxide after dry etching with oxygen gas.
(A) A resist underlayer film forming composition containing a hydrolysis condensate of hydrolyzable silane, which comprises 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, which comprises a step of curing a coating film of an object with ultraviolet rays. The resist underlayer film forming composition is
The method for producing a silicon-containing resist underlayer film according to claim 1, which contains (B) a crosslinkable compound and (C) at least one of an acid and an acid generator. The silicon-containing resist underlayer film according to claim 1 or 2, wherein the aqueous 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%. Manufacturing method.