JP2022037944A - Method for improving etching resistance of resist underlayer film by pretreatment using hydrogen gas - Google Patents

Abstract

To provide a novel method for improving resistance to halogen-containing gas etching.SOLUTION: A method for improving halogen-containing gas etching resistance of a silicon-containing film comprises a step for etching or ashing a silicon-containing film with a hydrogen gas-containing gas before the halogen-containing gas etching.SELECTED DRAWING: None

Description

The present invention relates to a method for improving the etching resistance of a resist underlayer film by pretreatment using hydrogen gas.

In the field of manufacturing semiconductor devices, a technique of forming a fine pattern on a substrate and etching according to this pattern to process the substrate is widely used.
With the progress of lithography technology, fine patterning has progressed, and KrF excimer lasers and ArF excimer lasers have been used, and exposure technologies using electron beams and EUV (extreme ultraviolet rays) have been studied.

In micromachining by lithography using photoresist, a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, and active light such as ultraviolet rays is irradiated through a mask pattern on which a pattern of a semiconductor device is drawn. By etching the substrate using the obtained photoresist pattern as a protective film, fine irregularities corresponding to the pattern are formed on the surface of the substrate. In recent years, the degree of integration of semiconductor devices has increased, and the wavelength of active light rays has tended to be shortened as described above, and the influence of reflection of active light rays from a semiconductor substrate has become a major problem. A method of providing a resist underlayer film called an antireflection film (Bottom Anti-Reflective Coating, BARC) between substrates has been widely applied.
As the resist underlayer film, for example, an underlayer film containing silicon or the like has been proposed (Patent Document 1, Patent Document 2, etc.). In this case, the rate of removal by etching depends on the gas type used for etching due to the difference in the constituent components of the resist and the underlayer film, and the desired pattern can be obtained by appropriately selecting the gas type. It is planned.

Further, as one of the pattern forming techniques, there is a pattern inversion method. In this technique, a resist pattern is first formed on a semiconductor substrate, the resist pattern is coated with a silicon-based coating liquid, the resist patterns are filled with the coating liquid, and the resist pattern is fired to form a coating film. After that, the upper part of the silicon-containing coating film is etched back to expose the upper part of the resist pattern, and then the gas is changed to remove the resist pattern by etching. The silicon-based pattern remains, and the pattern is inverted. When the silicon-based film on which this inversion pattern is formed is used as an etching mask and the lower layer or the substrate is etched, the inversion pattern is transferred and the pattern is formed on the substrate.
As a material used for forming such an inversion pattern, a composition containing polysiloxane has been proposed (Patent Documents 3 to 6).

Japanese Unexamined Patent Publication No. 2007-163846 International Title 2013/2068 International Publication No. 2017/145808 International Publication No. 2017/145809 International Publication No. 2018/066551 International Title 2018/043407

In the future, as the miniaturization of the resist pattern progresses, there will be a problem of resolution and a problem that the resist pattern will collapse after development, and it is desired to reduce the thickness of the resist. Therefore, it is difficult to obtain a resist pattern film thickness sufficient for substrate processing, and not only the resist pattern but also the resist underlayer film formed between the resist and the semiconductor substrate to be processed can function as a mask during substrate processing. The process of having it has become necessary. Unlike conventional high-etchability resist underlayers, resist underlayers for lithography, which have a selection ratio of dry etching rates close to those of resists, and dry etching rates smaller than those of resists, are selected as resist underlayers for such processes. There is an increasing demand for a resist underlayer for lithography having a selective ratio of a dry etching rate smaller than that of a resist underlayer for lithography having a ratio and a semiconductor substrate.
Further, in the method of applying the polysiloxane composition for pattern inversion on the resist pattern, it is required to improve the etching resistance when the resist pattern disappears by etching to obtain the inversion pattern, and of course, the silicon-based film is etched. When etching the lower layer or the substrate as a mask, a material having a selection ratio of a dry etching rate smaller than that of the lower layer or the substrate is required.

It is an object of the present invention to provide a new method for improving resistance to halogen-containing gas etching.

As a result of diligent studies to solve the above problems, the present inventors have performed etching or ashing treatment of the silicon-containing film with hydrogen gas-containing gas before etching the halogen-containing gas to form the film after the treatment. The present invention was completed by finding that the etching resistance to halogen-containing gas etching is improved.

（式中、Ｒ^１はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、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、もしくはシアノ基を有する有機基を示し、且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ^２はアルコキシ基、アシルオキシ基、又はハロゲン基を示し、ａは０乃至３の整数を示す。） That is, the present invention is, as a first aspect, a method for improving the halogen-containing gas etching resistance of a silicon-containing film, which comprises a step of etching or ashing the silicon-containing film with a hydrogen gas-containing gas before etching the halogen-containing gas. Including, regarding the method.
As a second aspect, the present invention relates to a method for improving the etching resistance according to the first aspect, wherein the silicon-containing film is a resist underlayer film.
As a third aspect, a step of forming a resist underlayer film from a silicon-containing resist underlayer film forming composition on a semiconductor substrate,
A step of etching or ashing the resist underlayer film with a hydrogen gas-containing gas,
A step of forming a resist film on a resist underlayer film etched or ashed with a hydrogen gas-containing gas,
A process of forming a resist pattern by irradiation and development of light or electron beam,
The present invention relates to a method for manufacturing a semiconductor device, which comprises a step of etching the resist underlayer film with a formed resist pattern and a step of processing a semiconductor substrate with a patterned resist film and a patterned resist underlayer film.
As a fourth viewpoint, a step of forming a resist film on a substrate,
A process of forming a resist pattern by irradiation and development of light or electron beam,
A step of applying a silicon-containing thin film forming composition on a resist film on which a pattern is formed during or after development and firing to form a thin film.
A step of etching or ashing the thin film with a gas containing hydrogen gas,
The process of etching and removing the patterned resist film and inverting the pattern,
The present invention relates to a method for manufacturing a semiconductor device, including the above.
The fifth aspect is a method for producing a resist underlayer film having improved halogen-containing gas etching resistance.
The step of etching or ashing the underlayer film with a hydrogen gas-containing gas is included.
The underlayer film is a cured product of a silicon-containing resist underlayer film forming composition.
Regarding the manufacturing method.
As a sixth aspect, the silicon-containing resist underlayer film forming composition is a polysiloxane composed of a hydrolyzable condensate of hydrolyzable silane, a reaction product of a silanol group and an alcohol contained in the condensate, and the silanol group as an acetal group. Containing at least one modified polysiloxane obtained by protection with the above, or a dehydration reaction product of the polysiloxane with an alcohol and an acid.
The present invention relates to the manufacturing method described in the fifth aspect.
As a seventh aspect, the production method according to the sixth aspect, wherein the polysiloxane is a hydrolyzable condensate of hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1). Regarding.

(In the formula, R ¹ is an organic group having an alkyl group, an aryl group, an alkyl halide group, an aryl halide group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group. 2 is bonded to a silicon atom by a Si—C bond, R ² represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 0 to 3).

According to the present invention, the halogen-containing gas etching resistance of the silicon-containing film can be improved by pre-etching or ashing the silicon-containing film with the hydrogen gas-containing gas.

The present invention relates to a method for improving the halogen-containing gas etching resistance of a silicon-containing film, which comprises a step of etching or ashing the silicon-containing film with a hydrogen gas-containing gas.
The present invention also relates to a method for manufacturing a semiconductor device, which comprises a step of etching or ashing a resist underlayer film or a thin film with a hydrogen gas-containing gas.
Further, the present invention relates to a method for producing a resist underlayer film having improved halogen-containing gas etching resistance.
The "halogen-containing gas" intended for improving the gas etching resistance (dry etching resistance) means a gas that is a molecule containing a halogen atom (fluorine, chlorine, bromine, etc.) as a constituent atom, and is, for example, tetrafluoro. Methane (CF ₄ ), Perfluorocyclobutane (C ₄ F ₈ ), Per Fluoro Propane (C ₃ F ₈ ), Trifluoromethane (CHF ₃ ), Difluoromethane (CH ₂ F ₂ ), Sulfur hexafluoride, Trifluoride Fluorine-containing gas such as nitrogen; chlorine-containing gas such as chlorine, chlorine trifluoride, trichloroboran, and dichloroboran; bromine-containing gas such as hydrogen bromide (HBr), and the like, but are not limited thereto.
Although a technique for pre-etching an object has been proposed in order to achieve a high etching rate, there has been no proposal for a pre-etching technique for the purpose of improving etching resistance.

The gas used for the etching or ashing treatment is not particularly limited as long as it is a hydrogen gas-containing gas. Here, the "hydrogen gas-containing gas" means a gas containing hydrogen gas (H ₂ ), and is a hydrogen gas (H ₂ ) itself or, for example, a mixed gas of hydrogen (H ₂ ) and nitrogen (N ₂ ). , Hydrogen gas (H ₂ ) such as a mixed gas of hydrogen (H ₂ ) and helium (He) and a mixed gas of other gases can be mentioned.
The etching treatment can be usually carried out at 20 to 50 ° C., and the ashing treatment can be usually carried out at 20 to 320 ° C.
The total flow rate of all gases in the etching treatment or ashing treatment and the flow rate of hydrogen gas (H ₂ ) when a mixed gas is used are appropriately determined in consideration of the desired degree of halogen-containing gas etching resistance and other circumstances. Be done.
In the present invention, the degree of improvement in the etching resistance of the halogen-containing gas is the etching rate reduction rate (%) = 100-{[when the silicon-containing film after etching or ashing with the hydrogen gas-containing gas is etched with the halogen-containing gas. Etching rate] / [Etching rate when etching or ashing with a silicon-containing film with a halogen-containing gas] x 100}, and the etching rate reduction rate is usually 1% or less. In a preferred embodiment, it is 5% or less, in a more preferable embodiment, it is 10% or less, in a more preferable embodiment, it is 20% or less, and in a further preferable embodiment, it is 25% or less.
The etching rate in the present invention can be measured by, for example, a dry etching apparatus Lam 2300 manufactured by Lam Research.

<Silicone-containing film>
The silicon-containing film (resist underlayer film, thin film) to be etched / ashed to which the present invention is applied can be formed from a composition containing polysiloxane.
By etching or ashing the silicon-containing film (resist underlayer film, thin film) with the hydrogen gas-containing gas described above, the halogen-containing gas etching resistance can be improved, and the halogen-containing gas etching resistance is improved. It is possible to manufacture a silicon-containing film (resist underlayer film, thin film).

[Polysiloxane]
The polysiloxane contains a polysiloxane composed of a hydrolyzed condensate of a hydrolyzable silane, and may contain a modified polysiloxane in which a part of the silanol group of the polysiloxane composed of the hydrolyzable condensate is modified. good. Further, the polysiloxane may have a structure having any of a cage type, a ladder type, a linear type, and a branched type main chain.
The weight average molecular weight of the polysiloxane can be 1,000 to 1,000,000. For example, the preferred weight average molecular weight can be 1,000 to 100,000, or 1,000 to 50,000, 1,200 to 20,000.
As the polysiloxane, the compounds listed in the above-mentioned Patent Documents 1 to 6 can be used, and commercially available polysiloxanes can be used.

The polysiloxane usually contains a hydrolyzed condensate of hydrolyzable silane. The hydrolyzable silane can include one or more silanes.

式（１）中、Ｒ^１はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、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、もしくはシアノ基を有する有機基を示し、且つＳｉ－Ｃ結合によりケイ素原子と結合しているものであり、Ｒ^２はアルコキシ基、アシルオキシ基、又はハロゲン基を示し、ａは０乃至３の整数を示す。 Examples of the polysiloxane include hydrolyzable condensates of hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1).

In formula (1), R ¹ has an alkyl group, an aryl group, an alkyl halide group, an aryl halide group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group. It represents an organic group and is bonded to a silicon atom by a Si—C bond, R ² represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 0 to 3.

The polysiloxane is a hydrolyzed condensate of a hydrolyzable silane (ii) in which a is 1 in the formula (1), and a hydrolyzable silane (i) in which a is 0 in the formula (1). A co-hydrolyzable condensate with the hydrolyzable silane (ii) in which a in (1) is 1 can be used.
The polysiloxane can be used in the range of hydrolyzable silane (i): hydrolyzable silane (ii) in a molar ratio of 0: 100 to 50:50 or 10:90 to 50:50.

Further, as the polysiloxane (hydrolyzed condensate), hydrolyzable silane or a hydrolyzate thereof can be used as a mixture. If a partially hydrolyzed product or a silane compound whose hydrolysis is not completely completed when the hydrolyzed condensate is obtained is mixed with the hydrolyzed condensate, the mixture can also be used. This condensate is a polymer with a polysiloxane structure.

In the above formula (1), 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 and n. -Butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group , 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1- Methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-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- Examples thereof include a methyl-n-propyl group and a 1-ethyl-2-methyl-n-propyl group.

Cyclic alkyl groups can also be used. For example, as cyclic alkyl groups having 1 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 -Cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group and the like can be mentioned.

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-chlorphenyl group, and m-. Chlorphenyl group, p-chlorphenyl 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-phenanthryl group, 3-phenanthryl group , 4-Phenyltril group, 9-Phenyltril group and the like.

Examples of the alkenyl group include an alkenyl group having 2 to 10 carbon atoms, for example, an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group and a 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-cyclohexenyl group, 2- Examples thereof include a cyclohexenyl group and a 3-cyclohexenyl group.

Examples of the organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, an epoxycyclohexyl group and the like.
Examples of the organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.
Examples of the organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.
Examples of the organic group having a mercapto group include an ethyl mercapto group, a butyl mercapto group, a hexyl mercapto group, an octyl mercapto group and the like.
Examples of the organic group having a cyano group include a cyanoethyl group and a cyanopropyl group.

Examples of the alkoxy group include an alkoxy group having a linear, branched or cyclic alkyl moiety having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group and an n-butoxy. Group, i-butoxy group, s-butoxy group, t-butoxy group, 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 and the like, and cyclic alkoxy groups such as cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group and 2-methyl-cyclopropoxy group. , Cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl -Cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group , 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group , 1-i-propyl-cyclopropoxy group, 2-i- Propyl-cyclopropoxy group, 1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl- Examples thereof include a cyclopropoxy group, a 2-ethyl-1-methyl-cyclopropoxy group, a 2-ethyl-2-methyl-cyclopropoxy group and a 2-ethyl-3-methyl-cyclopropoxy group.

Examples of the acyloxy group include an acyloxy group having 1 to 20 carbon atoms, for example, a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, and an n-butylcarbonyloxy group. , I-butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butylcarbonyloxy group , 3-Methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propylcarbonyloxy group , 1-ethyl-n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 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 Group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group Group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl Examples thereof include -n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, tosylcarbonyloxy group and the like.

Examples of the halogen group include fluorine, chlorine, bromine and iodine.

The examples of groups described above are also applied to the moieties of alkyl groups, aryl groups, alkyl groups, aryl groups, alkoxy groups and halogen groups in alkoxyaryl groups.

The hydrolyzable silane represented by the above formula (1) is a tetraalkoxysilane in which a is 0 in the formula (1), a methyltrialkoxysilane, a vinyltrialkoxysilane or a vinyltrialkoxysilane in which a is 1 in the formula (1). It is preferable that it contains any one of phenyltrialkoxysilane and dimethyldialkoxysilane in which a is 2 in the formula (1).

As described above, as the polysiloxane, a modified polysiloxane in which at least a part of the silanol group is modified can be used.
The modified polysiloxane is a hydrolyzed condensate of the above-mentioned hydrolyzable silane in which a part of the silanol group contained in the condensate is reacted with an alcohol, or a dehydration reaction product of the polysiloxane with an alcohol and an acid. Further, examples thereof include those in which a part of the silanol group is protected with an acetal group.

As the alcohol, a monohydric alcohol can be used, for example, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3 -Pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3 -Pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2- Examples thereof include pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol and cyclohexanol.
Also, for example, 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy). An alkoxy group-containing alcohol such as -2-propanol) or propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used.

The reaction of the silanol group with the alcohol is such that the polysiloxane is brought into contact with the alcohol and reacted at a temperature of 110 to 160 ° C., for example, 150 ° C. for 0.1 to 48 hours, for example, 24 hours to modify the silanol group to be capped. Polysiloxane is obtained. At this time, the alcohol of the capping agent can be used as a solvent in the composition containing polysiloxane.

Further, the dehydration reaction product of polysiloxane and alcohol and acid can be produced by reacting the polysiloxane with alcohol and acid and removing the water produced by dehydration to the outside of the reaction system.
As the above-mentioned acid, an organic acid having an acid dissociation constant (pka) of -1 to 5, preferably 4 to 5, can be used. For example, the acid can be exemplified by trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid and the like, and among them, benzoic acid, isobutyric acid, acetic acid and the like.
Further, the acid can be an acid having a boiling point of 70 to 160 ° C., and examples thereof include trifluoroacetic acid, isobutyric acid, and acetic acid.
As described above, the acid preferably has either an acid dissociation constant (pka) of 4 to 5 or a boiling point of 70 to 160 ° C. That is, one having a weak acidity or one having a high acidity but a low boiling point can be used.
As the acid, any property can be used because of the acid dissociation constant and the boiling point.

式（３）中、Ｒ^１ａ、Ｒ^２ａ、及びＲ^３ａはそれぞれ水素原子、又は炭素原子数１乃至１０のアルキル基を表し、Ｒ^４ａは炭素原子数１乃至１０のアルキル基を表し、Ｒ^２ａとＲ^４ａは互いに結合して環を形成していてもよい。上記アルキル基は上述の例示を挙げることができる。

式（２）中、Ｒ^１’、Ｒ^２’、及びＲ^３’はそれぞれ水素原子、又は炭素原子数１乃至１０のアルキル基を表し、Ｒ^４’は炭素原子数１乃至１０のアルキル基を示し、Ｒ^２’とＲ^４’は互いに結合して環を形成していてもよい。式（２）において※印は隣接原子との結合を示す。隣接原子は例えばシロキサン結合の酸素原子や、シラノール基の酸素原子や、式（１）のＲ^１に由来する炭素原子が挙げられる。上記アルキル基は上述の例示を挙げることができる。 For the acetal protection of the silanol group, vinyl ether can be used, for example, vinyl ether represented by the following formula (3) can be used, and the partial structure represented by the following formula (2) is introduced into the polysiloxane by these reactions. be able to.

In formula (3), R ^1a , R ^2a , and R ^3a represent hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, respectively, and R ^4a represents alkyl groups having 1 to 10 carbon atoms, respectively, and R ^2a . And R ^4a may be coupled to each other to form a ring. The above-mentioned alkyl group can give the above-mentioned example.

In formula (2), R ¹ ', R ² ', and R ^3'represent hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, respectively, and R ^4'represents an alkyl group having 1 to 10 carbon atoms. As shown, R ^2'and R ^4'may be coupled to each other to form a ring. In formula (2), the * mark indicates a bond with an adjacent atom. Examples of the adjacent atom include an oxygen atom of a siloxane bond, an oxygen atom of a silanol group, and a carbon atom derived from ^R1 of the formula (1). The above-mentioned alkyl group can give the above-mentioned example.

Examples of the vinyl ether represented by the above formula (3) include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, and 2, Cyclic vinyl ether compounds such as 3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 2,3-dihydro-4H-pyran can be used. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran can be preferably used.

To protect the acetal of the silanol group, polysiloxane, vinyl ether, and an aprotonic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, 1,4-dioxane are used as a solvent, and pyridium paratoluene is used. It can be carried out using a catalyst such as sulfonic acid, trifluoromethanesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid and the like.

The hydrolyzed condensate of the above-mentioned hydrolyzable silane (including polysiloxane and modified product) has a weight average molecular weight of, for example, 1,000 to 1,000,000, or 1,000 to 100,000, or It can be a condensate of 1,000 to 50,000, 1,200 to 20,000. These molecular weights are the molecular weights obtained in terms of polystyrene by GPC analysis. The measurement conditions for GPC are, for example, a GPC apparatus (trade name: HLC-8220GPC, manufactured by Toso Co., Ltd.), a GPC column (trade name: TetrahydroKF803L, KF802, KF801, manufactured by Showa Denko), a column temperature of 40 ° C., an eluent (eluting solvent). Can be carried out using tetrahydrofuran, the flow rate (flow velocity) is 1.0 ml / min, and the standard sample is polystyrene (manufactured by Showa Denko KK).

For the hydrolysis of ^two -Si-R groups in the formula (1), that is, an alkoxysilyl group, an acyloxysilyl group, or a halide silyl group (hereinafter referred to as a hydrolyzable group), one of the hydrolyzable groups is used. 0.1 to 100 mol, preferably 1 to 10 mol of water per mol is used. Hydrolysis may or may not be carried out with or without a hydrolysis catalyst. When a hydrolysis catalyst is used, a hydrolysis catalyst of 0.0001 to 10 mol, preferably 0.001 to 1 mol, per mol of the hydrolyzable group can be used. The reaction temperature at the time of performing hydrolysis and condensation can be carried out in the range of usually room temperature or higher and the reflux temperature of the organic solvent used for hydrolysis at normal pressure or lower, and is, for example, 20 to 110 ° C. The hydrolysis may be complete hydrolysis, i.e. all hydrolyzable groups may be converted to silanol groups, or partially hydrolyzed, i.e. leaving unreacted hydrolyzed groups. That is, after the hydrolysis and condensation reaction, the uncondensed hydrolyzate or the monomer may remain in the hydrolyzed condensate.
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.

Metal chelating compounds as a hydrolysis catalyst include, for example, 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-propoxy bis (acetylacetone) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (acetylacetonate) titanium, di-sec-butoxy bis (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 (ethylacetate acetate) titanium, trit-butoxy mono (ethylacetacetate) titanium, diethoxy bis (ethylacetacetate) titanium, z-n-propoxybis (ethylacetacetate) titanium, di-i- Propoxy bis (ethyl acetoacetate) titanium, z-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis (ethyl acetoacetate) Titanium, Monoethoxytris (Ethylacetacetate) Titanium, Mono-n-Propoxy Tris (Ethylacetacetate) Titanium, Mono-i-Propoxy Tris (Ethylacetacetate) Titanium, Mono-n-Butoxy Tris (Ethyl) Acetacetate) Titanium, Mono-sec-Butoxytris (Ethylacetacetate) Titanium, Mono-t-Butoxytris (Ethylacetacetate) Titanium, Tetrakiss (Ethylacetacetate) Titanium, Mono (Acetylacetonate) Tris (Ethyl) Titanium chelate compounds such as acetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) titanium; triethoxy mono (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 (acetylacetonato) zirconium, mono- n-butoxytris (acetylacetonate) zirconium, mono-sec-butoxytris (acetylacetonate) zirconium, mono-t-butoxytris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy. Mono (ethylacetate acetate) zirconium, tri-n-propoxy mono (ethylacetone acetate) zirconium, tri-i-propoxy mono (ethylacetate acetate) zirconium, tri-n-butoxy mono (ethylacetate acetate) zirconium, Tri-sec-butoxy mono (ethylacetone acetate) zirconium, tri-t-butoxy mono (ethylacetone acetate) zirconium, diethoxy bis (ethylacetone acetate) zirconium, di-n-propoxy bis (ethylacetate acetate) Zirconium, di-i-propoxy bis (ethylacetone acetate) zirconium, di-n-butoxy bis (ethylacetate acetate) zirconium, di-sec-butoxy bis (ethylacetate acetate) zirconium, dit-butoxy. Bis (ethylacetate acetate) zirconium, monoethoxytris (ethylacetoneacetate) zirconium, mono-n-propoxytris (ethylacetate acetate) zirconium, mono-i-propoxytris (ethylacetate acetate) zirconium, mono-n -Butoxy-tris (ethylacetate) zirconium, mono-sec-butoxy-tris (ethylacetate) zirconium, mono-t-butoxy-tris (ethylacetate) zirconium, tetrakis (ethylacetate) zirconium, mono (acetyl) Zyrosine chelating compounds such as acetonate) tris (ethylacetoneacetate) zirconium, bis (acetylacetonet) bis (ethylacetoneacetate) zirconium, tris (acetylacetonate) mono (ethylacetoneacetate) zirconium; tris (acetylacetonate) ) Aluminum chelate compounds such as aluminum, tris (ethylacetate acetate) aluminum; and the like.

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, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid , Benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartrate acid and the like.
Examples of the inorganic acid as a hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.

Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrol, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diah. Examples thereof include zabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.

Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferable, and one or more of these may be used at the same time.

Examples of the organic solvent used for hydrolysis include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-. Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbensen, i-propylbensen, diethylbenzene, i-butylbenzene, triethylbenzene, di -Aromatic hydrocarbon solvents such as i-propylbensen, n-amylnaphthalene, trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec -Heptanol, Heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec -Monoalcohol solvents such as tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol; Ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4,2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4,2-ethylhexanediol- Polyhydric alcohol solvents such as 1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i -Butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcy Ketone solvents such as clohexanone, 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-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n -Hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl 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, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, Ether-based solvents such as dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetra; diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone , Γ-Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate , 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl acetate Ether, acetic acid Diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol acetate Monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-lactate Ester solvents such as butyl, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc .; N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, Nitrogen-containing solvents such as N, N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, sulfolane, and 1,3-propanesulton. Examples include system solvents and the like. These solvents can be used alone or in combination of two or more.

Hydrolyzable silane is hydrolyzed and condensed in a solvent using a catalyst, and the obtained hydrolyzed condensate (polymer) simultaneously removes by-products alcohol, the hydrolyzed catalyst used, and water by vacuum distillation or the like. can do. In addition, the acid and base catalyst used for hydrolysis can be removed by neutralization or ion exchange.

The hydrolyzed condensate (polysiloxane) thus obtained is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and this can be used as it is as a composition containing polysiloxane. 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 reaction of the hydrolyzable silane. The diluting solvent is not particularly limited, and either one type or two or more types can be arbitrarily selected and used.

[Composition containing polysiloxane]
The composition containing polysiloxane includes the above-mentioned hydrolyzable silane, a hydrolyzate thereof, a hydrolyzed condensate thereof (including polysiloxane and a modified product), and a solvent. Here, the solid content in the composition is, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, 0.5 to 20.0% by mass, or 1.0 to 1.0 to It is 10.0% by mass. The solid content refers to the ratio of all the components of the composition excluding the solvent component.
The ratio of the hydrolyzable silane, its hydrolyzate, and its hydrolyzed condensate (including polysiloxane and modified product) to the solid content is 20% by mass or more, for example, 50 to 100% by mass. It is 60 to 100% by mass, 70 to 100% by mass, 80 to 100% by mass, and 80 to 99% by mass.
The concentration of the hydrolyzable silane, its hydrolyzate, and its hydrolyzed condensate (including polysiloxane and modified product) in the composition is 0.5 to 20.0% by mass.

The hydrolyzable silane, its hydrolyzate, its hydrolyzed condensate, and its modified product have a resin component different from that of a resist or the like. As a result, a new pattern is formed by the hydrolyzed condensate (polysiloxane) in which the resist or the like is selectively dry-etched and filled by selecting the gas type in the dry etching step.

The solvent can be used without particular limitation as long as it can dissolve the solid content contained in the composition, and the organic solvent used for the hydrolysis reaction of the hydrolyzable silane and the silanol described above can be used. Alcohols used for group modification (capping) can be used.
Examples of the above-mentioned solvent include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monoether. Ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, Ethylene glycol monomethyl ether, 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 lactic acid, 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, butyrate Chill, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3 -Methyl 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-methoxybutylbutyrate, Methyl acetoacetate, Toluene, Xylene, Methylethylketone, Methylpropylketone, Methylbutylketone, 2-Heptanone, 3-Heptanone, 4-Heptanone, Cyclohexanone, N, N -Dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, γ-butyrolactone and the like can be mentioned. These solvents can be used alone or in combination of two or more.

Various additives can be added to the above 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.), a cross-linking agent, a cross-linking catalyst, a stabilizer (organic acid, water, alcohol, etc.), and an organic substance. Polymer compounds, photoacid generators (onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, etc.), surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants) , Fluorine-based surfactants, UV-curable surfactants, etc.), rheology adjusters, adhesion aids, etc., various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, antireflection films, and pattern inversion films. Examples thereof include known additives to be blended in the material (composition) forming the above.
Various additives are exemplified below, but the present invention is not limited thereto.

As the curing catalyst, ammonium salts, phosphines, phosphonium salts and sulfonium salts can be used.

（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. R21 of this quaternary ammonium salt represents an alkyl group or an aryl group having 1 to ¹⁸ carbon atoms, preferably 2 to 10 carbon atoms, and for example, a linear alkyl group such as an ethyl group, a propyl group or a butyl group, or a benzyl group. Examples thereof include a group, a cyclohexyl group, a cyclohexylmethyl group, a dicyclopentadienyl group and the like. The anions (Y-) include halide ions such as chloride ion ( ^{Cl- )} , bromine ion (Br- ⁾ , ^and iodine ion (I-), carboxylate (-COO- ⁾ , and sulfonate (-SO _3- ⁾ . ), Alcolate ( ^-O- ) and other acid groups can be mentioned.

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 ⁻ . R ²² , R ²³ , R ²⁴ and R ²⁵ of this quaternary ammonium salt are alkyl groups or aryl groups having 1 to 18 carbon atoms. Anions (Y-) include halide ions such as chloride ion ( ^{Cl- )} , bromine ion (Br- ⁾ , ^and iodine ion (I-), carboxylate (-COO- ⁾ , and sulfonate (-SO _3- ⁾ . , Alcolate ( ^-O- ) and other acid groups can be mentioned. 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.

The compound of the above formula (D-3) is a quaternary ammonium salt derived from the 1-substituted imidazole, and R ²⁶ and R ²⁷ have 1 to 18 carbon atoms, and the carbon of R ²⁶ and R ²⁷ is carbon. It is preferable that the total number of atoms is 7 or more. For example, ^R26 can be exemplified with a methyl group, an ethyl group, a propyl group, a phenyl group and a benzyl group, and ^R27 can be exemplified with a benzyl group, an octyl group and an octadecyl group. Anions (Y-) include halide ions such as chloride ion ( ^{Cl- )} , bromine ion (Br- ⁾ , ^and iodine ion (I-), carboxylate (-COO- ⁾ , and sulfonate (-SO _3- ⁾ . , Alcolate ( ^-O- ) and other acid groups can be mentioned. 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 ^R28 is an alkyl group or an aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Yes, for example, a butyl group, an octyl group, a benzyl group, and a lauryl group can be exemplified. Anions (Y-) include halide ions such as chloride ion ( ^{Cl- )} , bromine ion (Br- ⁾ , ^and iodine ion (I-), carboxylate (-COO- ⁾ , and sulfonate (-SO _3- ⁾ . , Alcolate ( ^-O- ) and other acid groups can be mentioned. This compound can also be obtained as a commercial 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. It is an alkyl group or an aryl group of, for example, a methyl group, an octyl group, a lauryl group, a benzyl group and the like can be exemplified. R ³⁰ is an alkyl group or an aryl group having 1 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 chloride ion ( ^{Cl- )} , bromine ion (Br- ⁾ , ^and iodine ion (I-), carboxylate (-COO- ⁾ , and sulfonate (-SO _3- ⁾ . , Alcolate ( ^-O- ) and other acid groups can be mentioned. 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 anions (Y-) include halide ions such as chloride ion ( ^{Cl- )} , bromine ion (Br- ⁾ , ^and iodine ion (I-), carboxylate (-COO- ⁾ , and sulfonate (-SO _3- ⁾ . ), Alcolate ( ^-O- ) and other acid groups can be mentioned. 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 or aryl groups having 1 to 18 carbon atoms, preferably three of the four substituents R ³¹ to R ³⁴ are phenyl or substituted. For example, a phenyl group or a tolyl group can be exemplified, and the remaining one is an alkyl group or an aryl group having 1 to 18 carbon atoms. The anions (Y-) include halide ions such as chloride ion ( ^{Cl- )} , bromine ion (Br- ⁾ , ^and iodine ion (I-), carboxylate (-COO- ⁾ , and sulfonate (-SO _3- ⁾ . ), Alcolate ( ^-O- ) and other acid groups can be mentioned. 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 triphenylmonoalkylphosphonium such as phosphonium, halogenated triphenylmethylphosphonium, halogenated triphenylethylphosphonium, halogenated triphenylbenzylphosphonium, halogenated tetraphenylphosphonium, halogenated tritrylmonoarylphosphonium, or halogenated tritrylmono Examples thereof include alkylphosphonium (halogen atom is chlorine atom or 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 or aryl groups having 1 to 18 carbon atoms, preferably two of the three substituents R ³⁵ to R ³⁷ are phenyl or substituted phenyl groups. For example, a phenyl group or a tolyl group can be exemplified, and the remaining one is an alkyl group or an aryl group having 1 to 18 carbon atoms. The anions (Y-) include halide ions such as chloride ion ( ^{Cl- )} , bromine ion (Br- ^{) and} iodine ion (I-), carboxylate (-COO- ⁾ , and sulfonate (-SO _3- ⁾ . ), Alcolate ( ^-O- ), maleate anion, nitrate anion and other acid groups. 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. , Diphenyl Methyl Sulfonium Halide, Diphenyl Monoalkyl Sulfonium Haldenized such as Diphenyl Ethyl Sulfonium Halide, Triphenyl Sulfonium Halide, (Halogen atom is chlorine atom or bromine atom), Tri n-butyl sulfonium carboxylate, Tri n-propyl Trialkyl sulfonium carboxylates such as sulfonium carboxylates, dialkylbenzyl sulfonium carboxylates such as diethylbenzyl sulfonium carboxylates, diphenyl monoalkyl sulfonium carboxylates such as diphenylmethyl sulfonium carboxylates and diphenyl ethyl sulfonium carboxylates, and triphenyl sulfonium carboxylates 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, it is 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. ..

Organic acids, water, alcohols, or combinations thereof can be added as the stabilizer.
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, maleic acid and the like are preferable. When an organic acid is added, the amount added is 0.1 part by mass to 5.0 parts by mass with respect to 100 parts by mass of polysiloxane.
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 composition containing polysiloxane. can do.
The alcohol is preferably one that is easily scattered by heating after coating, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol and the like. When alcohol is added, the amount thereof may be 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the composition containing polysiloxane.

By adding the organic polymer compound to the composition, the dry etching rate (decrease in film thickness per unit time) of the silicon-containing film (resist underlayer film, thin film) formed from the composition, and also. The attenuation coefficient, refractive index, etc. can be adjusted.
The organic polymer compound is not particularly limited, and various organic polymers can be used, and a polycondensation polymer, an addition polymerization polymer and the like can be used. For example, addition polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolak, polyether, polyamide, polycarbonate and the like, and polypolymers can be used.
When an organic polymer compound is used, the amount to be added is 1 part by mass to 200 parts by mass, 5 parts by mass to 100 parts by mass, or 10 parts by mass to 50 parts by mass, or 10 parts by mass, or the amount added to 100 parts by mass of polysiloxane. It is 20 parts by mass to 30 parts by mass.

Examples of the photoacid generator include onium salt compounds, sulfoneimide compounds, disulfonyldiazomethane compounds and the like.

Examples of onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butane sulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphor sulfonate, and bis (4-tert-butylphenyl) iodonium camphor sulfonate. , Iodium salt compounds such as bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butane sulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate. Such as sulfonium salt compounds and the like can be mentioned.

Examples of the sulfoneimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormalbutanesulfonyloxy) succinimide, N- (kanfersulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide. Can be mentioned.

Examples of the disulfonyl diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzenesulfonyl). ) Diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane and the like.

Only one type of photoacid generator can be used, or two or more types can be used in combination.
When a photoacid generator is used, the amount added thereof is 0.01 part by mass to 30 parts by mass, 0.01 part by mass to 15 parts by mass, or 0.1 part by mass with respect to 100 parts by mass of polysiloxane. To 10 parts by mass.

The surfactant is effective in suppressing the occurrence of pinholes, stirries, and the like when the 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 alkyl allyl 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 names EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade names Megafuck F171, F173, R-08, R-30, R-30N , R-40LM (manufactured by DIC Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade name Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass (Asahi Glass) Fluorosurfactants such as (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) can be mentioned. These surfactants may be used alone or in combination of two or more.
When a surfactant is used, the amount added thereof is 0.0001 parts by mass to 5 parts by mass, 0.001 parts by mass to 1 part by mass, or 0.01 parts by mass to 100 parts by mass of polysiloxane. It is 1 part by mass.

The rheology adjuster mainly improves the fluidity of the composition, particularly improves the film thickness uniformity of the silicon-containing film (resist underlayer film, thin film) formed in the baking step, and the composition inside the hole. It is added for the purpose of improving the filling property of. Specific examples include phthalic acid derivatives such as dimethylphthalate, diethylphthalate, diisobutylphthalate, dihexylphthalate and butylisodecylphthalate, adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate and octyldecyl adipate, and didi. Examples include maleic acid derivatives such as normal butylmalate, diethylmalate, and dinonylmalate, oleic acid derivatives such as methyl olate, butyl olate, and tetrahydrofurfuryl oleate, and stearic acid derivatives such as normal butyl stearate and glyceryl stearate. can.
When these rheology adjusters are used, the amount added is usually less than 30% by weight based on the total solid content of the composition.

The above-mentioned adhesive aid is mainly intended to improve the adhesion between the substrate or the resist and the silicon-containing film (resist underlayer film, thin film) formed from the composition, and particularly to prevent the resist from peeling off during development. Is added at. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxy. Alkicsilanes such as silane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silanes such as trimethylsilylimidazole, vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltri Silanes such as ethoxysilane, γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercapto Examples thereof include heterocyclic compounds such as imidazole and mercaptopyrimidine, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds.
When these adhesive aids are used, the amount added is usually less than 5% by weight, preferably less than 2% by weight, based on the total solid content of the composition.

In order to form a silicon-containing film from the composition containing polysiloxane, the composition may be applied to a substrate and then fired if necessary.
The coating method of the above composition is arbitrary, and for example, a spin coating method, a dip method, a flow coating method, an inkjet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, etc. Methods such as brush coating, blade coating method, and air knife coating method can be adopted.
The base material includes silicon, glass on which indium tin oxide (ITO) is formed, glass on which indium zinc oxide (IZO) is formed, polyethylene terephthalate (PET), plastic, glass, quartz, and ceramics. Examples thereof include a base material made of the above, and a flexible base material having flexibility can also be used.
The above composition can be filtered before use, and is not particularly limited in the effective filtration area and material of the filter material, and may be filtered according to the target product.

After applying the above composition to the substrate, firing can be performed for the purpose of evaporating the solvent. The firing temperature is not particularly limited, and the firing temperature can be, for example, 40 to 400 ° C. In the firing, the temperature may be changed in two or more steps for the purpose of exhibiting high uniformity without bias in the distribution of the film thickness and promoting the reaction of the cross-linking agent or the like on the substrate.
The firing method is not particularly limited, and for example, the solvent may be evaporated using a hot plate or an oven under an atmosphere, an inert gas such as nitrogen, or an appropriate atmosphere such as in a vacuum.

<Manufacturing method of semiconductor devices>
Hereinafter, a method for manufacturing a semiconductor device using the above composition as a resist underlayer film forming composition will be described.

First, substrates used in the manufacture of semiconductor devices (eg, silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low dielectric constant materials (low-k materials)). A resist underlayer film forming composition is applied onto a coated substrate or the like by an appropriate coating method such as a spinner or a coater, and then fired to form a resist underlayer film.
The firing conditions are appropriately selected from a firing temperature of 40 ° C. to 400 ° C., or 80 ° C. to 250 ° C., and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150 ° C. to 500 ° C. and the firing time is 0.5 to 2 minutes.
Here, the film thickness of the resist underlayer film formed is, for example, 10 to 1000 nm, 20 to 500 nm, 50 to 300 nm, 100 to 200 nm, or 10 to 100 nm. ..

An organic underlayer film may be formed on the substrate, and the resist underlayer film may be formed on the organic underlayer film. 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.

After forming the resist underlayer film, a step of etching or ashing the underlayer film with a hydrogen gas-containing gas is carried out.
The gas used for the etching or ashing treatment and the etching treatment or ashing treatment conditions are as described above.

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 solution onto a resist underlayer film and firing.
The film thickness of the resist film is, for example, 50 to 10000 nm, 100 to 2000 nm, or 200 to 1000 nm, or 30 to 200 nm.

The photoresist used for the resist film formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure. Both negative photoresists and positive photoresists can be used. A positive photoresist consisting of a novolak resin and a 1,2-naphthoquinone diazidosulfonic 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, and an acid. A chemically amplified photoresist consisting of a low molecular weight compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate. There are chemically amplified photoresists composed of low molecular weight compounds and photoacid generators that decompose with an acid to increase the alkali dissolution rate of the photoresist. For example, the product name APEX-E manufactured by Shipley Co., Ltd., the product name PAR710 manufactured by Sumitomo Chemical Co., Ltd., the product name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd., and the like can be mentioned. 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 photoresists as described in 3999,365-374 (2000) can be mentioned.

Next, exposure is performed through a predetermined mask. For the exposure, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm) and the like can be used. After exposure, if necessary, post-exposure heating (post)
It is also possible to perform an exposure break). 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 to 10 minutes.

Further, as the resist film formed on the resist underlayer film, a resist for electron beam lithography or an EUV resist can be used instead of the photoresist. As the electron beam resist, either a negative type or a positive type can be used. A chemically amplified resist consisting of an acid generator and a binder having a group that decomposes with an acid to change the alkali dissolution rate, and a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist. A chemically amplified resist composed of an acid generator, a binder having a group that decomposes with an acid to change the alkali dissolution rate, and a chemically amplified resist composed of a low molecular weight compound that decomposes with an acid and changes the alkali dissolution rate of the resist. There are non-chemically amplified resists made of a binder having a group that is decomposed by an electron beam to change the alkali dissolution rate, and non-chemically amplified resists made of a binder that is cut by an electron beam and has a site that changes the alkali dissolution rate. Even when these electron beam resists are used, a resist pattern can be formed in the same manner as when a photoresist is used with the irradiation source as an electron beam.
Further, as the EUV resist, a methacrylate resin-based resist can be used.

Then, development is performed with a developer. As a result, for example, when a positive photoresist is used, the photoresist in the exposed portion is removed and a resist pattern is formed.

The 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, ethanolamine and propylamine. An alkaline aqueous solution such as an amine aqueous solution such as 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 to 600 seconds.

Then, the resist underlayer film is removed by using the pattern of the resist film thus formed as a protective film. Removal of the underlayer of the resist is performed by dry etching, and tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, carbon monoxide, argon, oxygen. , Nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane and the like can be used.

When an organic underlayer film is provided between the substrate and the resist underlayer film, the organic underlayer film can be removed by using the film composed of the patterned resist film and the patterned resist underlayer film as a protective film. Will be done. The organic underlayer film is preferably performed by dry etching with an oxygen-based gas.

Next, the semiconductor substrate is processed using a film composed of a patterned resist film and a patterned resist underlayer film (optionally patterned organic underlayer film) as a protective film. The processing of the semiconductor substrate is preferably performed by dry etching with a fluorine-based gas.
Examples of the fluorine-based gas include tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, and difluoromethane (CH ₂ F ₂ ). Can be mentioned.

Next, a method for manufacturing a semiconductor device using the above composition as a reverse material (pattern inversion material) (silicon-containing thin film forming composition) will be described.

First, a resist film is formed on the above-mentioned substrate by the above-mentioned method, exposed through a predetermined mask, and developed to form a resist pattern. As the substrate used here, various resists related to the formation of the resist film, the light source used for exposure, the developing solution, and the resist film forming conditions and the exposure / development conditions, the above-mentioned ones can be adopted.
Further, as the resist pattern, a pattern formed by nanoimprint can be used.

Next, the silicon-containing thin film forming composition is applied onto the resist film on which the pattern is formed during or after development, and a fired thin film is formed. This firing condition is as described above. By this step, the silicon-containing thin film-forming composition is embedded in the formed resist pattern.

Then, a step of etching or ashing the thin film with a hydrogen gas-containing gas is carried out.
The gas used for the etching or ashing treatment and the etching treatment or ashing treatment conditions are as described above.

Subsequently, the patterned resist film (resist pattern) is removed by etching to invert the pattern. The resist film is removed by dry etching, and tetrafluoromethane, perfluorocyclobutane (C ₄ F ₈ ), and perfluoro propane (C ₃ F ₈ ).
, Trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride and the like can be used.
In addition, before this step, a step of etching back the surface of the thin film formed from the above-mentioned silicon-containing thin film forming composition to expose the surface of the resist pattern can be included. As a result, in a later step, the surface of the resist pattern and the surface of the thin film match, and due to the difference in the gas etching rate between the resist pattern and the thin film, only the resist component is removed, and the component formed from the silicon-containing thin film forming composition is obtained. It remains, resulting in pattern inversion. Etchback can be carried out with a gas capable of removing the thin film (the gas used for removing the resist underlayer film described above). Further, after this etchback step, a step of etching or ashing the surface of the thin film with a hydrogen gas-containing gas may be performed, and then a step of etching and removing the patterned resist film to invert the pattern may be performed.

As a result, the initial resist pattern is removed, and a reverse pattern by polysiloxane (polymer for pattern inversion formation) contained in the silicon-containing thin film forming composition is formed on the substrate, and the reverse pattern is used to form a semiconductor substrate. Is processed.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
In the examples, the equipment and conditions used for the analysis of the physical properties of the sample are as follows.
(1) Molecular weight measurement HLC-8320 manufactured by Tosoh Corporation
(2) Film thickness measurement SCREEN, RE-3100

(Example 1)
53.9 g of tetraethoxysilane (containing 50 mol% in total silane), 46.1 g of methyltriethoxysilane (containing 50 mol% in total silane) and 100 g of acetone were placed in a flask. A dropping funnel containing 32.6 g of an aqueous hydrochloric acid solution (0.01 mol / liter) prepared by attaching a cooling tube was set in this flask, and the aqueous hydrochloric acid solution was slowly added dropwise at room temperature and stirred for several minutes. Then, the reaction was carried out in an oil bath at 85 ° C. for 4 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool, then set in an evaporator, and ethanol generated during the reaction was removed to obtain a reaction product (polysiloxane of Example 1) (formula (1-) described later). Polymer corresponding to 1)). In addition, acetone was replaced with propylene glycol monoethyl ether using an evaporator. The solid content in the obtained reaction product was 13% by mass as a result of measurement by the firing method. The molecular weight (Mw) of the obtained product (solid content) was 3,700.

(Example 2)
82.5 g of vinyltrimethoxysilane (containing 100 mol% in total silane) and 123 g of acetone were placed in a flask. A dropping funnel containing 30.0 g of an aqueous hydrochloric acid solution (0.01 mol / liter) prepared by attaching a cooling tube was set in this flask, and the aqueous hydrochloric acid solution was slowly added dropwise at room temperature and stirred for several minutes. Then, the reaction was carried out in an oil bath at 95 ° C. for 12 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool, then set in an evaporator, and ethanol generated during the reaction was removed to obtain a reaction product (polysiloxane of Example 2) (formula (1-) described later). Polymer corresponding to 2)). Further, 20 g of the prepared polymer solution was placed in a two-necked flask and reacted at 95 ° C. for 12 hours in an oil bath. The solid content in the obtained reaction product was 30.0% by mass as a result of measurement by the firing method. The molecular weight (Mw) of the obtained product (solid content) was 10,000.

(Example 3)
116.52 g of tetraethoxysilane (75 mol% in total silane), 33.24 g of methyltriethoxysilane (25 mol% in total silane) and 99.84 g of acetone were placed in a flask. A dropping funnel containing 50.36 g of an aqueous hydrochloric acid solution (0.01 mol / liter) prepared by attaching a cooling tube was set in this flask, and the aqueous hydrochloric acid solution was slowly added dropwise at room temperature and stirred for several minutes. Then, the reaction was carried out in an oil bath at 85 ° C. for 4 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool, then set in an evaporator, and ethanol generated during the reaction was removed to obtain a reaction product (polysiloxane) (formula (1-1) described later). Equivalent polymer). In addition, acetone was replaced with propylene glycol monomethyl ether using an evaporator. The solid content in the obtained reaction product was 21.12% by mass as a result of measurement by the firing method. The molecular weight (Mw) of the obtained product (solid content) was 2430.
60.01 g of the obtained polysiloxane, 40.10 g of propylene glycol monoethyl ether, and 0.120 g of maleic acid were placed in a flask. A cooling tube was attached to this flask and reacted at 60 ° C. for 15 hours in an oil bath to synthesize a modified polysiloxane (polysiloxane of Example 3) in which the silanol group of polysiloxane was capped with an ethoxyisopropyl group (formula (1) described later. -3) Polymer). The solid content in the obtained reaction product was 12.12% by mass as a result of measurement by the firing method. The molecular weight (Mw) of the obtained product (solid content) was 2,300.

(Example 4)
22.2 g of tetraethoxysilane (containing 30 mol% in all silanes), 44.4 g of methyltriethoxysilane (containing 70 mol% in all silanes) and 100 g of acetone were placed in a 500 ml flask and placed in the flask. While stirring the mixed solution with a magnetic stirrer, 21.2 g of 0.01 mol / L silane was added dropwise to the mixed solution. After the dropping, the flask was transferred to an oil bath adjusted to 85 ° C. and reacted under warm reflux for 4 hours. Then, the reaction solution is cooled to room temperature, 100 g of 4-methyl-2-pentanol (methylisobutylcarbinol) is added to the reaction solution, and acetone, water and hydrochloric acid, and ethanol, which is a reaction by-product, are depressurized from the reaction solution. The mixture was distilled off and concentrated to obtain a methylisobutylcarbinol solution of a co-hydrolyzed condensate (polysiloxane). The solid content concentration was adjusted to be 13% by mass in terms of solid residue at 140 ° C.
20 mg of acetic acid was added to 15 g of the prepared polymer solution. A modified polysiloxane in which the silanol group of the polysiloxane was capped with 4-methyl-2-pentanol, which was transferred to an oil bath adjusted to 150 ° C. and reacted under warm reflux for 48 hours (polysiloxane of Example 4). ) Was synthesized (a polymer corresponding to the formula (1-4) described later). The weight average molecular weight Mw of the obtained product (solid content) by GPC was 5,300 in terms of polystyrene. The obtained polysiloxane was a polysiloxane in which a part of the silanol group was capped with 4-methyl-2-pentanol.

(Example 5)
10.09 g of tetraethoxysilane (containing 85 mol% in total silane), 15.08 g of methyltriethoxysilane (containing 15 mol% in total silane) and 172.52 g of acetone were placed in a flask. A dropping funnel containing 30.37 g of an aqueous hydrochloric acid solution (0.01 mol / liter) prepared by attaching a cooling tube was set in this flask, and the aqueous hydrochloric acid solution was slowly added dropwise at room temperature and stirred for several minutes. Then, the reaction was carried out in an oil bath at 85 ° C. for 4 hours. After completion of the reaction, the flask containing the reaction solution was allowed to cool, then set in an evaporator, and ethanol generated during the reaction was removed to obtain a reaction product (polysiloxane) (formula (1-1) described later). Equivalent polymer). In addition, acetone was replaced with propylene glycol monomethyl ether using an evaporator. The solid content in the obtained reaction product was 19.7% by mass as a result of measurement by the firing method. The molecular weight (Mw) of the obtained product (solid content) was 2,004.
51.07 g of the obtained polysiloxane, 50.00 g of propylene glycol monomethyl ether acetate, 500.0 mg of pyridium paratoluene sulfonate, and 10.02 g of ethyl vinyl ether were placed in a flask. This flask was reacted at room temperature for 2 days to synthesize a modified polysiloxane (polysiloxane of Example 5) in which the silanol group of the polysiloxane was capped with an ethoxyethyl group (a polymer corresponding to the formula (1-5) described later). After completion of the reaction, 150 mL of propylene glycol monomethyl ether acetate, 50 mL of methyl isobutyl ketone and 150 mL of an aqueous acetic acid solution (0.01 mol / liter) were added and extracted. The solvent of the organic layer was removed using an evaporator and further replaced with methylisobutylcarbinol to obtain 43.33 g of a reaction product (polysiloxane). The solid content in the obtained reaction product was 19.6% by mass as a result of measurement by the firing method. The molecular weight (Mw) of the obtained product (solid content) was 5,457.
Protection rate: acetal group / (acetal group + SiOH group) x 100 = 50.7 mol%

(Example 6)
As the polysiloxane of Example 6, a cage-type methylsilsesquioxane (manufactured by Konishi Chemical Industry Co., Ltd., trade name: SR-13) was used (a polymer corresponding to the formula (1-6) described later).

[Preparation Example 1-6: Preparation of Polysiloxane-Containing Composition]
The polysiloxanes of Examples 1 to 6 and the curing catalyst and solvent are mixed at the ratios shown in Table 1 below, and then filtered through a 0.1 μm fluororesin filter to obtain the poly of Preparation Example 1-6. A siloxane-containing composition was prepared. The addition ratio of the polymer in Table 1 below indicates the addition amount of the polymer itself, not the addition amount of the polymer solution.

The meanings of the abbreviations used in Table 1 below are as follows.
MA: Maleic acid IMIDTEOS: N- (3-triethoxypropyl) -4,5-dihydroimidazole TPS-NO ₃ : Triphenylsulfonium nitrate PGMEA: Propylene glycol monomethyl ether acetate PGEE: Propylene glycol monoethyl ether PGME: Propylene glycol monomethyl Ether MIBC: Methyl Isobutyl Carbinol DIW: Pure Water

The polysiloxane-containing composition prepared in Preparation Examples 1 to 6 was applied onto a silicon wafer using a spinner. On a hot plate, each of them was heated for 1 minute under the conditions shown in Table 2 to obtain cured films (Si-containing composition films) 1 to 6. The film thickness of each of the obtained cured films is also shown in Table 2.
Then, _each cured film was subjected to H2 / _N2 etching or H2 / He ashing under the conditions shown in Table ₃ and the following conditions related to the apparatus and the like.

For the film subjected to the etching treatment or the ashing treatment, the Cl ₂ dry etching rate was measured under the following conditions related to the apparatus and the like (Example 1-1 to Example 1-6: H ₂ / N ₂ ). Cl ₂ dry etching rate for the etched film, Examples 2-1 to 2-6: Cl ₂ dry etching rate for the H ₂ / He ashing film).
Further, for the films not subjected to H ₂ / N ₂ etching or H ₂ / He ashing (etching / ashing untreated film), the Cl ₂ dry etching rate was measured in the same manner (Reference Example 1 to Reference Example 7: Not yet). Cl ₂ dry etching rate for the treated film).
The results obtained are shown in Table 4. Table 4 also shows the rate of decrease in the Cl ₂ dry etching rate of the etching / ashing treated film with respect to the Cl ₂ dry etching rate of the etching / ashing untreated film.

<Etching / ashing conditions with hydrogen gas-containing gas>
Telius SCCM manufactured by Tokyo Electron Limited
H ₂ / N ₂ etching: 25 ° C, H ₂ (150 sccm) / N ₂ (200 sccm)
H ₂ / He Ashing: 300 ° C, H ₂ (500 sccm) / He (6500 sccm)
)

<Measurement of dry etching rate>
The following etchers and etching gases were used to measure the dry etching rate.
Lam Research dry etching equipment Lam2300: Cl ₂

As shown in Table 4, it was confirmed that the etching rate of the halogen-containing gas was reduced by 5% or more and the halogen-containing gas etching resistance was significantly improved by the etching / ashing treatment with the hydrogen gas-containing gas. In the cured film 5 using the polysiloxane of Example 5, the etching resistance of the H ₂ / He treated film was improved as compared with the H ₂ / N ₂ treated film, but all of the other cured films were H ₂ /. The result was that the etching resistance of the _N2 treated film was further improved.

Assuming that the organic group bonded to the siloxane skeleton was modified to a hydroxy group, a tentative correlation was observed between the Si content of the modified polymer and the halogen-containing gas etching rate. Therefore, although it is not clear, the etching / ashing treatment with the hydrogen gas-containing gas caused some chemical / physical structural change in the silicon-containing film (polysiloxane), which improved the etching resistance of the halogen-containing gas. It is presumed to be one of the reasons.

Claims (7)

A method for improving the halogen-containing gas etching resistance of a silicon-containing film.
A method comprising etching or ashing a silicon-containing film with a hydrogen gas-containing gas prior to halogen-containing gas etching. The method for improving etching resistance according to claim 1, wherein the silicon-containing film is a resist underlayer film. A step of forming a resist underlayer film from a silicon-containing resist underlayer film forming composition on a semiconductor substrate,
A step of etching or ashing the resist underlayer film with a hydrogen gas-containing gas,
A step of forming a resist film on a resist underlayer film etched or ashed with a hydrogen gas-containing gas,
A process of forming a resist pattern by irradiation and development of light or electron beam,
A method for manufacturing a semiconductor device, comprising a step of etching the resist underlayer film with a formed resist pattern and a step of processing a semiconductor substrate with a patterned resist film and a patterned resist underlayer film. The process of forming a resist film on a substrate,
A process of forming a resist pattern by irradiation and development of light or electron beam,
A step of applying a silicon-containing thin film forming composition on a resist film on which a pattern is formed during or after development and firing to form a thin film.
A step of etching or ashing the thin film with a gas containing hydrogen gas,
The process of etching and removing the patterned resist film and inverting the pattern,
A method for manufacturing a semiconductor device, including. A method for producing a resist underlayer film having improved halogen-containing gas etching resistance.
The step of etching or ashing the underlayer film with a hydrogen gas-containing gas is included.
The underlayer film is a cured product of a silicon-containing resist underlayer film forming composition.
Production method. The silicon-containing resist underlayer film forming composition is obtained by protecting a polysiloxane composed of a hydrolyzed condensate of hydrolyzable silane, a reaction product of a silanol group and an alcohol contained in the condensate, and the silanol group with an acetal group. Containing at least one modified polysiloxane or a dehydration reaction product of the polysiloxane with an alcohol and an acid.
The manufacturing method according to claim 5. The production method according to claim 6, wherein the polysiloxane is a hydrolyzed condensate of hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1).

(In the formula, R ¹ is an organic group having an alkyl group, an aryl group, an alkyl halide group, an aryl halide group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group. 2 is bonded to a silicon atom by a Si—C bond, R ² represents an alkoxy group, an acyloxy group, or a halogen group, and a represents an integer of 0 to 3).