JP2023027108A - Production method of polysiloxane having excellent storage stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound for capping a silanol group of hydrogenated polysiloxane having high heat resistance, insulation properties, and etching resistance.

SOLUTION: Provided is a compound for capping a silanol group of polysiloxane, having a structure represented by the formula (1) (R¹ is an alkyl group or an aryl group; R² is an alkoxy group; a is an integer of 1 or 2). The polysiloxane is one used for a composition for forming a flattening film used for flattening of a substrate having a level difference or the polysiloxane is one used for a composition for forming an interlayer used as a hard mask between a resist and an organic film in a lithography process by a multilayer resist method.

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

The present invention relates to a method for producing hydrogenated polysiloxane excellent in storage stability and used in the lithography process of semiconductor production.

2. Description of the Related Art Microfabrication by lithography using a photoresist has been conventionally performed in the manufacture of semiconductor devices. The fine processing is obtained by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating actinic rays such as ultraviolet rays through a mask pattern on which a semiconductor device pattern is drawn, and developing. This is a processing method in which fine irregularities corresponding to the pattern are formed on the surface of the substrate by etching the substrate using the photoresist pattern as a protective film. In recent years, however, the degree of integration of semiconductor devices has advanced, and the wavelength of actinic rays used has tended to be shortened from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). Along with this, the influence of reflection of actinic rays from semiconductor substrates has become a serious problem.

Also, a film known as a hard mask containing metal elements such as silicon and titanium is used as an underlayer film between the semiconductor substrate and the photoresist. In this case, since the resist and the hard mask have a large difference in their constituent components, their removal rate by dry etching greatly depends on the type of gas used for dry etching. By appropriately selecting the gas species, the hard mask can be removed by dry etching without significantly reducing the film thickness of the photoresist. As described above, in the recent manufacture of semiconductor devices, a resist underlayer film has been placed between the semiconductor substrate and the photoresist in order to achieve various effects including an antireflection effect. Compositions for resist underlayer films have been studied so far, but the development of new materials for resist underlayer films is desired due to the diversity of properties required thereof.

In order to improve dry etching resistance, it is considered to increase the silicon content in polysiloxane. Complete polysiloxane containing no organic component has problems in coating physical properties and the like, so polysiloxane containing an organic group is used. By using hydrogenated polysiloxane in which some or all of the organic groups in the polysiloxane are replaced with hydrogen atoms, the silicon content in the polysiloxane can be improved.

Regarding hydrogenated polysiloxane, Patent Documents 1 to 6 can be mentioned.

A method of protecting the hydroxyl groups of an organic compound containing polysiloxane with a ketalizing agent is exemplified (see Patent Document 7).

JP-A-7-097548 JP-A-9-137121 JP-A-11-251310 JP 2001-131479 JP 2005-187657 JP 2010-151923 International publication WO2012/165235 pamphlet

The present invention provides a method for producing a hydrogenated polysiloxane having high heat resistance, insulating properties, and etching resistance with improved storage stability. It is an object of the present invention to provide a hydrogenated polysiloxane composition having improved properties.

（式（１）中、Ｒ^１はアルキル基、又はアリール基を示し、Ｒ^２はアルコキシ基を示し、ａは１～２の整数を示す。）で表される構造を有する上記化合物、 A first aspect of the present invention is a compound for capping silanol groups of polysiloxane, which has the formula (1):

(in formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkoxy group, and a represents an integer of 1 to 2).

As a second aspect, a first step of obtaining a hydrolytic condensate of a hydrolyzable silane, and capping silanol groups in the hydrolytic condensate using the compound represented by formula (1) described in the first aspect. A method for producing polysiloxane, comprising a second step of

（式（２）中、Ｒ^３は水素原子を示し、且つＳｉ－Ｈ結合によりケイ素原子と結合しているものを示し、Ｒ^４はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、ｂは１～２の整数を示す。）で表される加水分解性シランを含む第２観点に記載のポリシロキサンの製造方法、 As a third aspect, the hydrolyzable silane used in the first step has the following formula (2):

(In formula (2), R ³ represents a hydrogen atom and is bonded to a silicon atom via a Si—H bond, R ⁴ represents an alkoxy group, an acyloxy group, or a halogen atom, and b is 1 The method for producing the polysiloxane according to the second aspect, which contains a hydrolyzable silane represented by ),

（式（３）中、Ｒ^５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を示し、Ｒ^６はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、ｃは１～２の整数を示す。）で表される加水分解性シラン、及び
式（４）：

（式（４）中、Ｒ^７はアルキル基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものを示し、Ｒ^８はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、Ｙはアルキレン基又はアリーレン基を示し、ｄは０又は１の整数を示し、ｅは０又は１の整数を示す。）で表される加水分解性シランからなる群より選ばれた少なくとも１種の加水分解性シランであり、
上記式（２）で表される加水分解性シランとその他の加水分解性シランが１００：０～９０：１０のモル比で存在する第２観点又は第３観点に記載のポリシロキサンの製造方法、 As a fourth aspect, the hydrolyzable silane used in the first step is a combination of the hydrolyzable silane represented by the above formula (2) and another hydrolyzable silane, and the other hydrolyzable silane is represented by the formula (3):

(wherein R ⁵ represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group; and is bonded to a silicon atom via a Si—C bond, R ⁶ represents an alkoxy group, an acyloxy group, or a halogen atom, and c represents an integer of 1 to 2.) Hydrolyzable silanes represented, and formula (4):

(In formula (4), R ⁷ represents an alkyl group and is bonded to a silicon atom via a Si—C bond, R ⁸ represents an alkoxy group, an acyloxy group, or a halogen atom, and Y represents an alkylene group or an arylene group, d is an integer of 0 or 1, and e is an integer of 0 or 1.) at least one hydrolyzable silane selected from the group consisting of hydrolyzable silanes represented by can be,
The method for producing polysiloxane according to the second aspect or the third aspect, wherein the hydrolyzable silane represented by the above formula (2) and the other hydrolyzable silane are present in a molar ratio of 100:0 to 90:10,

As a fifth aspect, in the first step, the hydrolyzable silane represented by the formula (2) or the hydrolyzable silane represented by the formula (2) and other hydrolyzable silanes are hydrolyzed with an acid catalyst, The method for producing polysiloxane according to any one of the second to fourth aspects, in which a decomposition condensate is obtained;

As a sixth aspect, in the first step, the hydrolyzable silane represented by the formula (2) or the hydrolyzable silane represented by the formula (2) and other hydrolyzable silanes are hydrolyzed to produce a hydrolyzed condensate. obtained, and in the second step, the silanol groups in the hydrolyzed condensate are capped with the compound of formula (1) described in the first aspect in the presence of an acid catalyst. A method for producing a polysiloxane of

As a seventh aspect, in the first step, the hydrolyzable silane represented by the formula (2) or the hydrolyzable silane represented by the formula (2) and other hydrolyzable silanes are hydrolyzed with an acid, In the first aspect, the decomposition product is condensed to obtain a solution of the hydrolytic condensate, and in the second step, the acid remaining in the solution of the hydrolytic condensate is used as a catalyst to remove the silanol groups in the hydrolytic condensate. The method for producing polysiloxane according to any one of the second to fifth aspects, wherein capping is performed with the compound of formula (1) of

As an eighth aspect, any one of the second aspect to the seventh aspect, wherein the polysiloxane is a polysiloxane used in a composition for forming a planarizing film used to planarize a substrate including steps. A method for producing the polysiloxane described, and

As a ninth aspect, the polysiloxane is a polysiloxane used in a composition for forming an intermediate film used as a hard mask between a resist and an organic film in a lithography process using a multilayer resist method. A method for producing polysiloxane according to any one of the seven aspects.

When silanol groups remain in the polysiloxane material, condensation occurs between the silanol groups, increasing the molecular weight and lowering the stability. By capping the silanol groups of polysiloxane, condensation between silanol groups can prevent an increase in molecular weight and destabilization.

However, when alcohol is used as a capping material for silanol groups, water is generated by capping, and the capped portions may return to silanol groups.

The capping agent of the present invention caps silanol groups by using a capping agent having a plurality of (for example, 2 to 3) alkoxy groups in the molecule such as 2,2-dimethoxypropane or trimethyl orthoacetate. When this is done, the products are polysiloxanes containing capped silanol groups, ketones and esters, and alcohols, and no water is by-produced. Therefore, capped moieties do not revert to silanol groups.

A method for producing hydrogenated polysiloxane having high heat resistance, insulating properties, and etching resistance with improved storage stability, and the obtained polysiloxane has excellent storage stability, so the molecular weight of the polymer does not change. Therefore, even if it is used as a component of a coating composition for flattening a substrate having unevenness, the change in the molecular weight of the polymer is small, so that a coating composition with high flattening properties can be obtained.

The present invention is a compound for capping silanol groups of polysiloxane, which compound has a structure represented by formula (1).

Then, a first step of obtaining a hydrolytic condensate of a hydrolyzable silane, and a second step of capping the silanol groups in the hydrolytic condensate using a compound represented by formula (1). A method for producing a polysiloxane comprising Here, polysiloxane is obtained by capping some or all of the silanol groups of a hydrolysis condensate using a compound represented by formula (1). Capping forms an alkoxysilane structure (Si—OR ² ) with the alkoxy group derived from R ² in formula (1).

The capping rate can be, for example, 10 to 100 mol %, 30 to 100 mol %, 50 to 90 mol %, or 50 to 80 mol % with respect to the generated silanol groups.

The capping of the silanol groups of the polysiloxane and the compound represented by formula (1) is carried out in a solvent in the presence of an acid catalyst. For example, the solvent used for hydrolysis and condensation of the hydrolyzable silane is used for capping with the compound represented by formula (1), and the acid catalyst used for hydrolysis at that time is used as the acid catalyst for capping. can do. Capping can be performed at a temperature between room temperature and 100°C, such as between room temperature and 80°C, or between 50 and 70°C.

In formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkoxy group, and a represents an integer of 1-2. The alkoxy group for ^R2 is particularly preferably a methoxy group, an ethoxy group, or the like.

The hydrolyzable silane used in the first step can contain hydrolyzable silane represented by the following formula (2).

In formula (2), R ³ represents a hydrogen atom and is bonded to a silicon atom via a Si—H bond, R ⁴ represents an alkoxy group, an acyloxy group, or a halogen atom, and b represents 1 to Indicates an integer of 2.

Further, the hydrolyzable silane used in the first step is a combination of the hydrolyzable silane represented by the above formula (2) and another hydrolyzable silane, and the other hydrolyzable silane is represented by formula (3). and at least one hydrolyzable silane selected from the group consisting of a hydrolyzable silane represented by the formula (4), and a hydrolyzable silane represented by the above formula (2). Degradable silanes and other hydrolyzable silanes can be present in molar ratios of 100:0 to 90:10.

式（３）中、Ｒ^５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を示し、Ｒ^６はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、ｃは１～２の整数を示す。

In formula (3), R ⁵ has an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, 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 via a Si—C bond, R ⁶ represents an alkoxy group, an acyloxy group, or a halogen atom, and c represents an integer of 1-2.

式（４）中、Ｒ^７はアルキル基で且つＳｉ－Ｃ結合によりケイ素原子と結合しているものを示し、Ｒ^８はアルコキシ基、アシルオキシ基、又はハロゲン原子を示し、Ｙはアルキレン基又はアリーレン基を示し、ｄは０又は１の整数を示し、ｅは０又は１の整数を示す。

In formula (4), R ⁷ represents an alkyl group and is bonded to a silicon atom via a Si—C bond, R ⁸ represents an alkoxy group, an acyloxy group, or a halogen atom, and Y represents an alkylene group or arylene. group, d is an integer of 0 or 1, and e is an integer of 0 or 1;

The alkyl group used in formula (1), formula (2), formula (3), and formula (4) is a linear or branched alkyl group having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl- n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl -n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1- dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group , 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl -n-propyl group, 1-ethyl-1-methyl-n-propyl group and 1-ethyl-2-methyl-n-propyl group.

Cyclic alkyl groups can also be used. Examples of cyclic alkyl groups having 1 to 10 carbon atoms include cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 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- Examples include methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclopropyl group. Bicyclo groups can also be used.

The alkenyl group is an alkenyl group having 2 to 10 carbon atoms, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl and 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-cyclohexenyl group, 3-cyclohexenyl group and the like.

Examples of aryl groups include aryl groups having 6 to 40 carbon atoms, such as phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl group, o-fluorophenyl group, p-mercaptophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-aminophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl and 9-phenanthryl groups.

Organic groups having an epoxy group include glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, epoxycyclohexyl and the like.

Organic groups having an acryloyl group include acryloylmethyl, acryloylethyl, acryloylpropyl and the like.

Organic groups having a methacryloyl group include methacryloylmethyl, methacryloylethyl, and methacryloylpropyl.

Organic groups having a mercapto group include ethylmercapto, butylmercapto, hexylmercapto, octylmercapto and the like.

Examples of the organic group having an amino group include an amino group, an aminomethyl group, and an aminoethyl group.

Examples of organic groups having a cyano group include cyanoethyl and cyanopropyl.

An alkoxyalkyl group is an alkyl group substituted with an alkoxy group, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group and an ethoxyethyl group.

Examples of the alkoxy group include alkoxy groups having straight, branched, and cyclic alkyl moieties having 1 to 20 carbon atoms, such as methoxy, ethoxy, n-propoxy, i-propoxy, and n-butoxy. , i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy 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 -pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n- butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl -n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n -propoxy group, 1-ethyl-2-methyl-n-propoxy group and the like, and cyclic alkoxy groups such as cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1 -ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl- cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-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-propoxy le-cyclopropoxy group, 1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl- Cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group and 2-ethyl-3-methyl-cyclopropoxy group, and the like.

Examples of the acyloxy group include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, i-propylcarbonyloxy, n-butylcarbonyloxy, i-butylcarbonyloxy and s-butylcarbonyloxy. , 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, 2,2-dimethyl-n-butylcarbonyloxy group , 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1 , 1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2- methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, tosylcarbonyloxy group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The compound of formula (1) can be exemplified below.

Hydrolyzable silanes of formula (2) can be exemplified below, for example.

Hydrolyzable silanes of formula (3) are, for example, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, Methyltrichlorosilane, Methyltriacetoxysilane, Methyltripropoxysilane, Methyltriacetoxysilane, Methyltributoxysilane, Methyltriamyloxysilane, Methyltriphenoxysilane, Methyltribenzyloxysilane, Methyltriphenethyloxysilane, Glycides xymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyl triethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane,
β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltri Methoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3 ,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl) ) propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane , glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β - glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyl Gife Noxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyl triethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane Silane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyl triethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane silane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxy benzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane,
γ-Chloropropyltrimethoxysilane, γ-Chloropropyltriethoxysilane, γ-Chloropropyltriacetoxysilane, 3,3,3-Trifluoropropyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane, γ-Mercaptopropyl trimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane , γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane and the like.

Hydrolyzable silanes of formula (4) are, for example, methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, butylenebistrimethoxysilane, phenylenebistrimethoxysilane, phenylenebistriethoxysilane, phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane, naphthylenebistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, bismethyldimethoxydisilane, and the like. be done.

Specific examples of the hydrolytic condensate (polysiloxane) used in the present invention are shown below.

A condensate having a weight average molecular weight of 1,000 to 1,000,000 or 1,000 to 100,000 can be obtained from the hydrolytic condensate (polyorganosiloxane) of the hydrolyzable silane. These molecular weights are molecular weights obtained in terms of polystyrene by GPC analysis.

GPC measurement conditions are, for example, GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC column (trade name Shodex KF803L, KF802, KF801, manufactured by Showa Denko), column temperature 40 ° C., eluent (elution solvent). is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml/min, and the standard sample is polystyrene (manufactured by Showa Denko KK).

For hydrolysis of an alkoxysilyl group, acyloxysilyl group or silyl halide group, 0.5 to 100 mol, preferably 1 to 10 mol of water is used per 1 mol of hydrolyzable group.

In addition, 0.001 to 10 mol, preferably 0.001 to 1 mol of hydrolysis catalyst can be used per 1 mol of hydrolyzable group.

The reaction temperature for hydrolysis and condensation is usually 20 to 80°C.

The hydrolysis may be a complete hydrolysis or a partial hydrolysis. That is, the hydrolyzate and the monomer may remain in the hydrolyzed condensate.

A catalyst can be used during the hydrolysis and condensation.

An acid can be used as the hydrolysis catalyst.

Organic acids as hydrolysis catalysts are, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacine. Acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone acids, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like.

Inorganic acids as hydrolysis catalysts include, for example, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of organic solvents used for hydrolysis include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Octane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbon solvents; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, - Aromatic hydrocarbon solvents such as i-propylbenzene, n-amylnaphthalene, and trimethylbenzene; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl- n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, Ketone solvents such as Fenchon; diethyl ether, di-i-propyl ether, di-n-butyl ether, di-n-hexyl ether, diisoamyl 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-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, Tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc. Solvent; 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 acetate glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, Ester solvents such as di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate; N-methylformamide, N,N- Nitrogen-containing solvents such as dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydro Sulfur-containing solvents such as thiophene, dimethylsulfoxide, sulfolane, and 1,3-propanesultone can be used. These solvents can be used singly or in combination of two or more.

Ether solvents such as diisoamyl ether and dibutyl ether are particularly preferred.

Compositions containing polysiloxanes obtained by the present invention may contain curing catalysts.

Ammonium salts, phosphines, phosphonium salts, and sulfonium salts can be used as curing catalysts.

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

（但し、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^－は陰イオンを示し、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）で示される構造を有する第４級アンモニウム塩、
式（Ｄ－３）：

（但し、Ｒ^２６及びＲ^２７はアルキル基又はアリール基を、Ｙ^－は陰イオンを示す）の構造を有する第４級アンモニウム塩、
式（Ｄ－４）：

（但し、Ｒ^２８はアルキル基又はアリール基を、Ｙ^－は陰イオンを示す）の構造を有する第４級アンモニウム塩、
式（Ｄ－５）：

（但し、Ｒ^２９及びＲ^３０はアルキル基又はアリール基を、Ｙ^－は陰イオンを示す）の構造を有する第４級アンモニウム塩、
式（Ｄ－６）：

（但し、ｍは２～１１、ｎは２～３の整数を、Ｈは水素原子を、Ｙ^－は陰イオンを示す）の構造を有する第３級アンモニウム塩が上げられる。 As an ammonium salt, formula (D-1):

(provided that m is an integer of 2 to 11, n is an integer of 2 to 3, R ²¹ is an alkyl group or an aryl group, and Y is an anion), a quaternary ammonium salt having a structure represented by
Formula (D-2):

(wherein R ²² , R ²³ , R ²⁴ and R ²⁵ represent an alkyl group or an aryl group, N represents a nitrogen atom, Y ^- represents an anion, and R ²² , R ²³ , R ²⁴ and R ²⁵ each attached to the nitrogen atom by a C—N bond), a quaternary ammonium salt having the structure
Formula (D-3):

(provided that R ²⁶ and R ²⁷ represent an alkyl group or an aryl group, and ^Y- represents an anion), a quaternary ammonium salt having a structure of
Formula (D-4):

(provided that R ²⁸ represents an alkyl group or an aryl group, and ^Y- represents an anion), a quaternary ammonium salt having a structure of
Formula (D-5):

(provided that R ²⁹ and R ³⁰ represent an alkyl group or an aryl group, and ^Y- represents an anion), a quaternary ammonium salt having a structure of
Formula (D-6):

(However, m is an integer of 2 to 11, n is an integer of 2 to 3, H is a hydrogen atom, and Y ^{2 -} is an anion).

（但し、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^－は陰イオンを示し、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）で示される第４級ホスホニウム塩が上げられる。 Further, as the phosphonium salt, the formula (D-7):

(where R ³¹ , R ³² , R ³³ and R ³⁴ represent an alkyl group or an aryl group, P represents a phosphorus atom, ^Y- represents an anion, and R ³¹ , R ³² , R ³³ and R ³⁴ are each bonded to the phosphorus atom via a CP bond).

（但し、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^－は陰イオンを示し、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）で示される第３級スルホニウム塩が上げられる。 Further, as the sulfonium salt, the formula (D-8):

(where 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 each represent a C—S bond). and a tertiary sulfonium salt represented by the following.

The compound of formula (D-1) above is a quaternary ammonium salt derived from an amine, where m is an integer of 2-11 and n is an integer of 2-3. R ²¹ 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 examples thereof include linear alkyl groups such as ethyl, propyl, and butyl, and benzyl. , cyclohexyl group, cyclohexylmethyl group, dicyclopentadienyl group and the like. The anion (Y ⁻ ) includes halogen ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ). , alcoholate ( ^-O-
) and other acid groups can be mentioned.

The compound of formula (D-2) above 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, or silane compounds bonded to silicon atoms via Si—C bonds. Anions (Y ⁻ ) include halogen ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), Acid groups such as alcoholate ( ^-O- ) can be mentioned. The quaternary ammonium salts are commercially 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 formula (D-3) above is a quaternary ammonium salt derived from 1-substituted imidazole, R ²⁶ and R ²⁷ have 1 to 18 carbon atoms, and R ²⁶ and R ²⁷ have 1 to 18 carbon atoms. is preferably 7 or more. For example, ^R26 can be exemplified by methyl group, ethyl group, propyl group, phenyl group and benzyl group, and ^R27 can be exemplified by benzyl group, octyl group and octadecyl group. Anions (Y ⁻ ) include halogen ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), Acid groups such as alcoholate ( ^-O- ) can be mentioned. Although this compound can be obtained as a commercial product, for example, imidazole compounds such as 1-methylimidazole and 1-benzylimidazole are reacted with alkyl and aryl halides such as benzyl bromide and methyl bromide. can be manufactured by

The compound of formula (D-4) above is a quaternary ammonium salt derived from pyridine, R ²⁸ is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, Examples include butyl group, octyl group, benzyl group and lauryl group. Anions (Y ⁻ ) include halogen ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), Acid groups such as alcoholate ( ^-O- ) can be mentioned. This compound can be obtained as a commercial product, but for example, it is produced by reacting 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 and N-benzylpyridinium bromide.

The compound of formula (D-5) above is a quaternary ammonium salt derived from a substituted pyridine typified by picoline and the like, and R ²⁹ is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or It is an aryl group, and examples thereof include a methyl group, an octyl group, a lauryl group, and a benzyl group. R ³⁰ is an alkyl group having 1 to 18 carbon atoms or an aryl group. For example, in the case of a quaternary ammonium derived from picoline, R ³⁰ is a methyl group. Anions (Y ⁻ ) include halogen ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ), Acid groups such as alcoholate ( ^-O- ) can be mentioned. This compound can be obtained as a commercial product. 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. It is possible to manufacture Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-laurylpicolinium chloride and the like.

The compound of formula (D-6) above is a tertiary ammonium salt derived from an amine, where m is an integer of 2-11 and n is an integer of 2-3. The anion (Y ⁻ ) includes halogen ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ). , alcoholate (—O ⁻ ) and other acid groups. It can be produced by reacting an amine with a weak acid such as carboxylic acid or phenol. Carboxylic acids 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 ^- ). Also, when phenol is used, the anion (Y ⁻ ) is (C ₆ H ₅ O ⁻ ).

The compound of formula (D-7) above 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, or silane compounds bonded to silicon atoms via Si—C bonds, preferably R ³¹ to R 3 of the 4 substituents of ³⁴ are phenyl groups or substituted phenyl groups, for example, phenyl group and tolyl group can be exemplified, and the remaining one is an alkyl group having 1 to 18 carbon atoms, An aryl group or a silane compound bonded to a silicon atom through a Si—C bond. The anion (Y ⁻ ) includes halogen ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ). , alcoholate (—O ⁻ ) and other acid groups. This compound can be obtained as a commercial product, and examples thereof include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, and trialkylbenzyl halides such as triethylbenzylphosphonium halide. Phosphonium, triphenylmethylphosphonium halide, triphenylmonoalkylphosphonium halide such as triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritolylmonoarylphosphonium halide, or tritolylmonohalide Alkylphosphonium (halogen atom is chlorine atom or bromine atom) can be mentioned. In particular, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, and halogens such as tritolylmonophenylphosphonium halide Tritolylmonoalkylphosphonium halides (halogen atoms are chlorine atoms or bromine atoms) such as tritolylmonoarylphosphonium halides and tritolylmonomethylphosphonium halides are preferable.

Phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine and phenylphosphine, and secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine and diphenylphosphine. , trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine and dimethylphenylphosphine.

The compound of formula (D-8) above is a tertiary sulfonium salt having a structure of R ³⁵ R ³⁶ R ³⁷ S ⁺ Y ^- . R ³⁵ , R ³⁶ and R ³⁷ are alkyl groups or aryl groups having 1 to 18 carbon atoms, or silane compounds bonded to silicon atoms via Si—C bonds, but preferably 4 of R ³⁵ to R ³⁷ Three of the four substituents are phenyl groups or substituted phenyl groups, examples of which include phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group. is. The anion (Y ⁻ ) includes halogen ions such as chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodine ion (I ⁻ ), carboxylate (—COO ⁻ ), sulfonate (—SO ₃ ⁻ ). , alcoholate (—O ⁻ ), maleate anion, nitrate anion and the like. This compound can be obtained as a commercial product, for example, tetraalkylsulfonium halides such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, and trialkylbenzyl halides such as diethylbenzylsulfonium halide. sulfonium, diphenylmethylsulfonium halide, diphenylethylsulfonium halide and other diphenylmonoalkylsulfonium halides, triphenylsulfonium halide, (halogen atom is chlorine atom or bromine atom), tri-n-butylsulfonium carboxylate, tri-n- tetraalkylphosphonium carboxylates such as propylsulfonium carboxylate, trialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenyl monoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate, diphenylethylsulfonium carboxylate, triphenyl Sulfonium carboxylate. Also, triphenylsulfonium halides and triphenylsulfonium carboxylates can be preferably used.

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

The curing catalyst is 0.01 to 10 parts by weight, or 0.01 to 5 parts by weight, or 0.01 to 3 parts by weight with respect to 100 parts by weight of polyorganosiloxane.

The hydrolyzable silane is hydrolyzed and condensed in a solvent using a catalyst, and the resulting hydrolyzed condensate (polymer) is subjected to vacuum distillation or the like to simultaneously remove the by-product alcohol, the used hydrolysis catalyst, and water. be able to. Moreover, the acid used for hydrolysis can be removed by neutralization or ion exchange. In the coating composition containing the polysiloxane of the present invention, an organic acid can be added for stabilization of the coating composition containing the hydrolytic condensate (polysiloxane).

Examples of the organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid and salicylic acid. Among them, oxalic acid, maleic acid and the like are preferable. The organic acid to be added is 0.1 to 5.0 parts by weight per 100 parts by weight of the condensate (polyorganosiloxane).

In the present invention, the obtained polysiloxane can be used to obtain a composition containing polysiloxane. A composition containing polysiloxane may contain one or more selected from the group consisting of water, acid, and a curing catalyst.

The composition containing the polysiloxane of the present invention can contain, if necessary, an organic polymer compound, a photoacid generator, a surfactant, and the like, in addition to the above components.

By using the organic polymer compound, the dry etching rate (decrease in film thickness per unit time), attenuation coefficient, refractive index, etc. of the resist underlayer film formed from the composition containing the polysiloxane of the present invention can be adjusted. be able to.

When a photoacid generator is used, the ratio is 0.01 to 30 parts by weight, 0.01 to 15 parts by weight, or 0.1 to 100 parts by weight with respect to 100 parts by weight of the condensate (polyorganosiloxane) 10 parts by mass.

Surfactants are effective in suppressing the occurrence of pinholes, striations, etc. when the composition containing the polysiloxane of the present invention is applied to a substrate.

Examples of surfactants contained in the composition containing polysiloxane of the present invention include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether. polyoxyethylene alkylallyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate , sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, trade names F-top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), trade name Megafac F171 , F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), trade names Asahiguard AG710, Surflon S-382, Fluorinated surfactants such as SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more. When a surfactant is used, the ratio is 0.0001 to 5 parts by weight, or 0.001 to 1 part by weight, or 0.01 to 1 part by weight per 100 parts by weight of the condensate (polyorganosiloxane) part by mass.

Moreover, a rheology modifier, an adhesion aid, and the like can be added to the composition containing the polysiloxane of the present invention. Rheology modifiers are effective in improving the fluidity of the Underlayer film-forming composition. Adhesion aids are effective in improving the adhesion between the semiconductor substrate or resist and the underlying film.

The solvent used in the composition containing the polysiloxane of the present invention is not particularly limited as long as it can dissolve the above-mentioned solid content. Examples of such solvents include diethyl ether, di-i-propyl ether, di-n-butyl ether, di-n-hexyl ether, diisoamyl 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-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol , tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 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, propylene glycol monoether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-hydroxy ethyl propionate, 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, pyruvic acid Methyl, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol Monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate , isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, propion Methyl acid, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, 2-hydroxy-2 -ethyl methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3 -ethyl methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate , methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-hept Thanone, 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. Ether solvents such as di-n-butyl ether and diisoamyl ether can be preferably used. These solvents can be used alone or in combination of two or more.

The use of the polysiloxane-containing composition of the present invention as a composition for forming a resist underlayer film will be described below.

Substrates used in the manufacture of semiconductor devices, such as silicon wafer substrates, silicon/silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low-k material coated substrates etc.), the resist underlayer film-forming composition of the present invention is applied by an appropriate coating method such as a spinner or a coater, and then baked to form a resist underlayer film. The firing conditions are appropriately selected from a firing temperature of 80° C. to 250° C. and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150° C. to 250° C. and the firing time is 0.5 to 2 minutes. Here, the film thickness of the underlayer film to be formed is, for example, 5 to 1000 nm, 20 to 500 nm, 50 to 300 nm, or 50 to 200 nm.

A layer of, for example, photoresist is then formed on the resist underlayer film. The formation of the photoresist layer can be carried out by a well-known method, ie, applying a solution of the photoresist composition onto the underlying film and baking. The film thickness of the photoresist is, for example, 50 to 10000 nm, 50 to 2000 nm, or 50 to 1000 nm.

In the present invention, after forming an organic underlayer film on a substrate, the resist underlayer film of the present invention can be formed thereon, and a photoresist can be further coated thereon. As a result, the pattern width of the photoresist is narrowed, and even if the photoresist is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, the resist underlayer film of the present invention can be processed by using a fluorine-based gas that provides a sufficiently high etching rate for the photoresist as an etching gas, and the resist underlayer film of the present invention can be etched at a sufficiently high etching rate. The organic underlayer film can be processed by using the following oxygen-based gas as an etching gas, and the substrate can be processed by using a fluorine-based gas, which has a sufficiently high etching rate for the organic underlayer film, as an etching gas.

The photoresist to be formed on the resist underlayer film of the present invention is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. positive photoresist composed of novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester; A chemically amplified photoresist comprising a low-molecular 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 is a chemically amplified photoresist composed of a low-molecular-weight compound and a photoacid generator, which are decomposed by acid to increase the rate of alkali dissolution of the photoresist. Examples thereof include APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

Next, exposure is performed through a predetermined mask. KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), EUV, etc. can be used for exposure. After exposure, a post exposure bake can be performed if necessary. The post-exposure heating is performed under conditions appropriately selected from a heating temperature of 70° C. to 150° C. and a heating time of 0.3 to 10 minutes.

Further, in the present invention, a resist for electron beam lithography or a resist for EUV lithography can be used in place of the photoresist as the resist. Both negative type and positive type electron beam resists can be used. A chemically amplified resist consisting of an acid generator and a binder having a group that is decomposed by an acid to change the alkali dissolution rate, and an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that is decomposed by an acid to change the alkali dissolution rate of the resist. a chemically amplified resist consisting of an acid generator, a binder having a group that is decomposed by an acid to change the alkali dissolution rate, and a low-molecular-weight compound that is decomposed by the acid to change the alkali dissolution rate of the resist, There are non-chemically amplified resists composed of a binder having a group that is decomposed by an electron beam to change the alkali dissolution rate, and non-chemically amplified resists composed of a binder having a site that is cut by an electron beam and 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 an electron beam as an irradiation source.

As the EUV resist, a methacrylate resin resist, a methacrylate-polyhydroxystyrene hybrid resin resist, and a polyhydroxystyrene resin resist can be used. Either a negative type or a positive type can be used as the EUV resist. A chemically amplified resist consisting of an acid generator and a binder having a group that is decomposed by an acid to change the alkali dissolution rate, and an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that is decomposed by an acid to change the alkali dissolution rate of the resist. a chemically amplified resist consisting of an acid generator, a binder having a group that is decomposed by an acid to change the alkali dissolution rate, and a low-molecular-weight compound that is decomposed by the acid to change the alkali dissolution rate of the resist, There are non-chemically amplified resists composed of binders having groups that are decomposed by EUV light to change the alkali dissolution rate, and non-chemically amplified resists composed of binders that are cleaved by EUV light and have sites that change the alkali dissolution rate.

Development is then carried out with a developer (for example, an alkaline developer). This removes the exposed portions of the photoresist and forms a pattern of the photoresist, for example, if a positive photoresist is used.

Examples of the developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium hydroxides such as choline, ethanolamine, propylamine, Examples include aqueous alkaline solutions such as aqueous solutions of amines such as ethylenediamine. Furthermore, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

Also, in the present invention, an organic solvent can be used as the developer. After exposure, development is performed with a developer (solvent). This removes the unexposed portions of the photoresist and forms a pattern of the photoresist, for example, if a positive photoresist is used.

Examples of the developer include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monopropyl. ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3- Methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate , propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, propionate isopropyl acid, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate Examples include pionates and the like. Furthermore, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

Then, using the pattern of the photoresist (upper layer) thus formed as a protective film, the resist underlayer film (intermediate layer) of the present invention is removed, and then the patterned photoresist and the resist underlayer film of the present invention are removed. The organic underlayer film (lower layer) is removed by using the film composed of the (intermediate layer) as a protective film. Finally, the semiconductor substrate is processed using the patterned resist underlayer film (intermediate layer) and the organic underlayer film (lower layer) of the present invention as protective films.

First, the portion of the resist underlayer film (intermediate layer) of the present invention where the photoresist has been removed is removed by dry etching to expose the semiconductor substrate. For dry etching of the resist underlayer film of the present invention, tetrafluoromethane (CF ₄ ), trifluoromethane (CHF ₃ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, Gases such as carbon oxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used. It is preferable to use a halogen-based gas for the dry etching of the resist underlayer film. In dry etching with a halogen-based gas, the photoresist basically made of an organic substance is difficult to remove. In contrast, the resist underlayer film of the present invention containing a large amount of silicon atoms is quickly removed by a halogen-based gas. Therefore, reduction in the thickness of the photoresist accompanying dry etching of the resist underlayer film can be suppressed. And, as a result, it becomes possible to use the photoresist in a thin film. The dry etching of _the resist underlayer _film is preferably performed using a fluorine- _based gas _. Propane (C ₃ F ₈ ), trifluoromethane, difluoromethane (CH ₂ F ₂ ), and the like.

After that, the organic underlayer film is removed by using a film composed of the patterned photoresist and the resist underlayer film of the present invention as a protective film. The organic underlayer film (lower layer) is preferably dry-etched using an oxygen-based gas. This is because the resist underlayer film of the present invention containing a large amount of silicon atoms is difficult to remove by dry etching using an oxygen-based gas.

Finally, processing of the semiconductor substrate is performed. The semiconductor substrate is preferably processed by dry etching using a fluorine-based gas.

Examples of fluorine-based gases include tetrafluoromethane (CF ₄ ), trifluoromethane (CHF ₃ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, and difluoromethane ( CH ₂ F ₂ ) and the like.

In addition, an organic antireflection film can be formed on the resist underlayer film of the present invention before forming the photoresist. The antireflection coating composition used there is not particularly limited, and can be used by arbitrarily selecting from those commonly used in the lithography process. The antireflection film can be formed by coating with a coater and baking.

The substrate to which the composition for forming a resist underlayer film of the present invention is applied may have an organic or inorganic antireflection film formed on its surface by a CVD method or the like. Inventive underlayer films can also be formed.

Depending on the wavelength of the light used in the lithography process, the resist underlayer film formed from the resist underlayer film-forming composition of the present invention may also absorb light. In such a case, it can function as an antireflection film having an effect of preventing reflected light from the substrate. Furthermore, the underlayer film of the present invention is a layer for preventing interaction between the substrate and the photoresist, and has a function of preventing adverse effects on the substrate of materials used for the photoresist or substances generated when the photoresist is exposed to light. layer, a layer having a function of preventing diffusion of substances generated from the substrate during heating and baking into the upper photoresist layer, and a barrier layer for reducing the poisoning effect of the photoresist layer by the dielectric layer of the semiconductor substrate. is also possible.

In addition, the resist underlayer film formed from the resist underlayer film-forming composition can be applied to a substrate in which via holes used in a dual damascene process are formed, and can be used as a filling material capable of filling the holes without gaps. It can also be used as a planarizing material for planarizing the uneven surface of a semiconductor substrate.

In addition to the function as a hard mask, the underlayer film of the EUV resist can also be used for the following purposes. Without intermixing with the EUV resist, EUV that can prevent unfavorable exposure light (wavelength 13.5 nm), such as the above-mentioned UV and DUV (ArF light, KrF light), from being reflected from the substrate or interface. The composition for forming a resist underlayer film can be used as a resist underlayer antireflection film. Reflections can be effectively prevented under the EUV resist. When used as an EUV resist underlayer film, the process can be performed in the same manner as for the photoresist underlayer film.

A composition containing polysiloxane obtained in the present invention can be used as a reverse material. Step (1) of applying a resist onto a substrate, step (2) of exposing and developing the resist, and step (3) of applying a composition containing the polysiloxane obtained by the present invention to the resist pattern during or after development. ), and a step (4) of removing the resist pattern by etching to reverse the pattern.

The above composition is coated on a resist pattern having coarse and fine layouts.

A resist pattern formed by nanoimprint before being coated with the above composition can be used.

As the photoresist used in step (1), the above resists can be used.

After the resist solution is applied, it is baked at a temperature of 70 to 150° C. for a time of 0.5 to 5 minutes to obtain a resist film thickness in the range of 10 to 1000 nm. The resist solution, the developer, and the coating materials described below can be applied by spin coating, dipping, spraying, or the like, with spin coating being particularly preferred. Exposure of the resist is performed through a predetermined mask. A KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), EUV light (wavelength: 13.5 nm), an electron beam, or the like can be used for exposure. After exposure, post-exposure baking (PEB: Post Exposure Bake) can be performed as necessary. Post-exposure heating is appropriately selected from a heating temperature of 70° C. to 150° C. and a heating time of 0.3 to 10 minutes.

A step (1-1) of forming a resist underlayer film on the substrate can be included before step (1). The resist underlayer film has antireflection and organic hard mask functions.

The formation of the resist in the step (1) can be replaced by the step (1-1) of forming a resist underlayer film on the semiconductor substrate and forming the resist thereon.

Further, step (1-1) can form a resist underlayer film on the semiconductor substrate, form a silicon hard mask thereon, and form a resist thereon.

The resist lower layer film used in the above step (1-1) is intended to prevent irregular reflection of the upper layer resist during exposure, and is used for the purpose of improving adhesion to the resist. A novolac resin can be used. The resist underlayer film can be formed as a film with a film thickness of 1 to 1000 nm on the semiconductor substrate.

The resist underlayer film used in the above step (1-1) is a hard mask using an organic resin, and a material with a high carbon content and a low hydrogen content is used. Examples thereof include polyvinylnaphthalene-based resins, carbazole novolak resins, phenol novolac resins, naphthol novolak resins, and the like. These can form a film with a film thickness of 5 to 1000 nm on a semiconductor substrate.

Polysiloxane obtained by hydrolyzing a hydrolyzable silane can be used as the silicon hard mask used in the step (1-1). Examples include polysiloxanes obtained by hydrolyzing tetraethoxysilane, methyltrimethoxysilane, and phenyltriethoxysilane. These can form a film with a thickness of 5 to 200 nm on the resist underlayer film.

In step (2), exposure is performed through a predetermined mask. KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EUV (wavelength 13.5 nm), or the like can be used for exposure. After exposure, a post exposure bake can be performed if necessary. The post-exposure heating is performed under conditions appropriately selected from a heating temperature of 70° C. to 150° C. and a heating time of 0.3 to 10 minutes.

Development is then performed with a developer. This removes the exposed portions of the photoresist and forms a pattern of the photoresist, for example, if a positive photoresist is used.

As the developer, the above-described alkaline developer or organic solvent developer can be used.

Furthermore, a surfactant or the like can be added to the developer. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

As step (3), the coating composition of the present application is applied to the resist during or after development. It can be formed by heating the coating composition in step (3). Heating is performed at a firing temperature of 50 to 180° C. for 0.5 to 5 minutes.

Further, the present application can include a step (3-1) of etching back the coating film surface to expose the resist pattern surface after the step (3). As a result, in the subsequent step (4), the surface of the resist pattern and the surface of the coating composition match, and due to the difference in gas etching rate between the resist pattern and the coating composition, only the resist component is removed, and the component by the coating composition is removed. remains, resulting in pattern reversal. Etching back is performed by exposing the resist pattern with a gas (for example, a fluorine-based gas) that can remove the coating composition.

In step (4), the resist pattern is removed by etching to reverse the pattern. process (4
), dry etching is performed with tetrafluoromethane, perfluorocyclobutane ( _C4F8 ), perfluoropropane ( _C3F8 ), trifluoromethane, carbon _monoxide , argon, oxygen, nitrogen, sulfur _hexafluoride , difluoromethane , nitrogen trifluoride and chlorine trifluoride. In particular, dry etching is preferably performed using an oxygen-based gas.

As a result, the original resist pattern is removed, and a reverse pattern is formed by the pattern reversal forming polysiloxane contained in the coating composition.

(Synthesis example 1)
HTEOS: MTEOS = 95 mol%: The silanol groups of the polysiloxane prepared from 5 mol% are capped with methoxy groups.

49.28 g of triethoxysilane (HTEOS) (containing 95 mol % of all silanes), 2.82 g of methyltriethoxysilane (MTEOS) (containing 5 mol % of all silanes) and 104.20 g of acetone were placed in a flask. I put it in. A dropping funnel containing a mixture of 8.53 mg of acetic acid, 8.53 g of water and 104.20 g of acetone was placed in the flask, and the mixture was slowly added dropwise while maintaining the temperature at 30°C or lower. After that, the mixture was reacted at room temperature for 65 hours. After that, 62.82 g of 2,2-dimethoxypropane (capping agent) was added and reacted at 65° C. for 1 hour. After completion of the reaction, 77.30 g of diisoamyl ether was charged and set in an evaporator to remove low boiling point components generated during the reaction to obtain 97.32 g of polysiloxane solution (corresponding to formula (5-1)). The solid content in the obtained reaction product was 18.2% by mass as a result of measurement by a calcination method.

¹ H-NMR (500 MHz, CD ₃ COCD ₃ ): δ=6.901 (br, 0.08H), 4.337 (br, 1.06H), 3.880 (br, 0.09H), 3. 280 (br, 0.38H), 1.095 (br, 0.11H), 0.264 (br, 0.15H)
* Assuming that the integral value of Si-Me is 0.15H Capping rate:
(Methoxy group + ethoxy group) / (methoxy group + ethoxy group + SiOH group) x 100 = 69.2 mol%

Calculation of the capping ratio was performed by capping the unhydrolyzed ethoxy groups (Si—OC ₂ H ₅ ) and the hydrolyzed silanol groups of the starting silane with methoxy groups (Si—OCH ₃ ). The capping rate was calculated from
GPC (converted to polystyrene): Mw = 7325

Thereafter, the polysiloxane obtained as described above was diluted at the ratio shown in the table below and filtered through a filter with a pore size of 0.1 μm to obtain a polysiloxane composition.

(Synthesis example 2)
HTEOS: MTEOS = 95 mol%: The silanol groups of the polysiloxane prepared from 5 mol% are capped with methoxy groups.

32.86 g of triethoxysilane (HTEOS) (containing 95 mol % of all silanes), 1.88 g of methyltriethoxysilane (MTEOS) (containing 5 mol % of all silanes) and 46.31 g of acetone were placed in a flask. I put it in. A dropping funnel containing a mixture of 5.68 mg of acetic acid, 5.68 g of water, and 34.73 g of acetone was added to the flask, and the mixture was slowly added dropwise while maintaining the temperature below 30°C. After that, the mixture was reacted at room temperature for 41 hours. After that, 41.88 g of 2,2-dimethoxypropane (capping agent) was added and reacted at 65° C. for 1 hour. After completion of the reaction, 60.66 g of diisoamyl ether was charged and set in an evaporator to remove low boiling point components generated during the reaction to obtain 73.95 g of polysiloxane solution (corresponding to formula (5-1)). The solid content in the obtained reaction product was 15.68% by mass as a result of measurement by a calcination method.

¹ H-NMR (500 MHz, CD ₃ COCD ₃ ): δ=6.941 (br, 0.11 H), 4.345 (br, 0.87 H), 3.849 (br, 0.09 H), 3. 306 (br, 0.31H), 1.286 (br, 0.20H), 0.258 (br, 0.15H)
* Assuming that the integral value of Si-Me is 0.15H Capping rate:
(Methoxy group + ethoxy group) / (methoxy group + ethoxy group + SiOH group) x 100 = 56.9 mol%

Calculation of the capping ratio was performed by capping the unhydrolyzed ethoxy groups (Si—OC ₂ H ₅ ) and the hydrolyzed silanol groups of the starting silane with methoxy groups (Si—OCH ₃ ). The capping rate was calculated from
GPC (converted to polystyrene): Mw = 17251

Thereafter, the polysiloxane obtained as described above was diluted at the ratio shown in the table below and filtered through a filter with a pore size of 0.1 μm to obtain a polysiloxane composition.

(Comparative Synthesis Example 1)
Preparation of polysiloxane solution prepared from HTEOS:MTEOS = 95 mol%:5 mol%.

49.28 g of triethoxysilane (HTEOS) (containing 95 mol % of all silanes), 2.82 g of methyltriethoxysilane (MTEOS) (containing 5 mol % of all silanes) and 104.20 g of acetone were placed in a flask. I put it in. A dropping funnel containing a mixture of 8.53 mg of acetic acid, 8.53 g of water and 104.20 g of acetone was placed in the flask, and the mixture was slowly added dropwise while maintaining the temperature at 30°C or lower. After that, the mixture was reacted at room temperature for 65 hours. After completion of the reaction, 82.61 g of diisoamyl ether was charged and set in an evaporator to remove low boiling point components generated during the reaction to obtain 102.17 g of polysiloxane solution (corresponding to formula (5-1)). The solid content in the obtained reaction product was 17.66% by mass as a result of measurement by a calcination method.

¹ H-NMR (500 MHz, CD ₃ COCD ₃ ): δ=6.849 (br, 0.19H), 4.355 (br, 0.98H), 3.848 (br, 0.02H), 1. 217 (br, 0.05H), 0.262 (br, 0.15H)
* Assuming that the integral value of Si-Me is 0.15H Capping rate:
(Methoxy group + ethoxy group) / (methoxy group + ethoxy group + SiOH group) x 100 = 0.0 mol%
GPC (converted to polystyrene): Mw = 8196

Thereafter, the polysiloxane obtained as described above was diluted at the ratio shown in the table below and filtered through a filter with a pore size of 0.1 μm to obtain a polysiloxane composition.

(Comparative Synthesis Example 2)
Preparation of polysiloxane solution prepared from HTEOS:MTEOS = 95 mol%:5 mol%.

32.86 g of triethoxysilane (HTEOS) (containing 95 mol % of all silanes), 1.88 g of methyltriethoxysilane (MTEOS) (containing 5 mol % of all silanes) and 46.31 g of acetone were placed in a flask. I put it in. A dropping funnel containing a mixture of 5.68 mg of acetic acid, 5.68 g of water, and 34.73 g of acetone was added to the flask, and the mixture was slowly added dropwise while maintaining the temperature below 30°C. After that, the mixture was reacted at room temperature for 41 hours. After completion of the reaction, 58.07 g of diisoamyl ether was charged and set in an evaporator to remove low-boiling components generated during the reaction to obtain 72.66 g of polysiloxane solution (corresponding to formula (5-1)). The solid content in the obtained reaction product was 15.69% by mass as a result of measurement by a calcination method.

¹ H-NMR (500 MHz, CD ₃ COCD ₃ ): δ = 6.925 (br, 0.23H), 4.320 (br, 0.88H), 0.254 (br, 0.15H)
* Assuming that the integral value of Si-Me is 0.15H Capping rate:
(Methoxy group + ethoxy group) / (methoxy group + ethoxy group + SiOH group) x 100 = 0.0 mol%
GPC (converted to polystyrene): Mw = 20181

Thereafter, the polysiloxane obtained as described above was diluted at the ratio shown in the table below and filtered through a filter with a pore size of 0.1 μm to obtain a polysiloxane composition.

(Comparative Synthesis Example 3)
A flask was charged with 53.9 g of tetraethoxysilane (containing 50 mol % of the total silane), 46.1 g of methyltriethoxysilane (containing 50 mol % of the total silane) and 100 g of acetone. A dropping funnel containing 32.6 g of a prepared hydrochloric acid aqueous solution (0.01 mol/liter) fitted with a cooling tube was set in this flask, and the hydrochloric acid aqueous solution was slowly dropped at room temperature and stirred for several minutes. After that, the mixture was reacted at 85° C. for 4 hours in an oil bath. After completion of the reaction, the flask containing the reaction solution was allowed to cool, then set in an evaporator to remove the ethanol produced during the reaction to obtain a reaction product (polysiloxane) (corresponding to formula (6-1)). . Furthermore, 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 a calcination method.
GPC (converted to polystyrene): Mw = 3700

Thereafter, the polysiloxane obtained as described above was diluted at the ratio shown in the table below and filtered through a filter with a pore size of 0.1 μm to obtain a polysiloxane composition.

(Adjustment of polysiloxane composition)
The polysiloxanes obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Examples 1, 2 and 3 and the solvent were mixed in the proportions shown in Tables 1 and 2, and filtered through a 0.1 μm fluororesin filter. , a solution of the polysiloxane composition was prepared, respectively. The addition ratio of the polymer in the table below indicates the addition amount of the polymer itself, not the addition amount of the polymer solution.

In the table below, diisoamyl ether is DIAE, maleic acid as a curing catalyst is MA, N-(3-triethoxypropyl)-4,5-dihydroimidazole as a curing catalyst is IMITTEOS, propylene glycol monomethyl ether acetate as a solvent is PGMEA, Propylene glycol monoethyl ether as a solvent is abbreviated as PGEE, and propylene glycol monomethyl ether as a solvent is abbreviated as PGME. Each addition amount is shown in parts by mass.

[Table 1]
Table 1
-------------------------------------------------- ----------------
polymer solvent
-------------------------------------------------- ----------------
Example 1 Synthesis Example 1 DIAE
(Parts by mass) 15.00 85.00
Example 2 Synthesis Example 2 DIAE
(Parts by mass) 15.00 85.00
Comparative Example 1 Comparative Synthesis Example 1 DIAE
(Parts by mass) 15.00 85.00
Comparative Example 2 Comparative Synthesis Example 2 DIAE
(Parts by mass) 15.00 85.00
-------------------------------------------------- ----------------

[Table 2]
Table 2
-------------------------------------------------- ------------------------------
Polymer Curing catalyst 1 Curing catalyst 2 Solvent
-------------------------------------------------- ---------------------------------Comparative Example 3 Comparative Synthesis Example 3 MA IMIDTEOS PGME PGMEA PGEE Water (parts by mass) 6.9 0.01 0.01 4.6 9.2 67.2 11.1
-------------------------------------------------- ------------------------------

(Storage stability of polysiloxane)
The capping polysiloxane solutions of Synthesis Examples 1 and 2 and the polysiloxane solutions of Comparative Synthesis Examples 1 and 2 were stored at 40° C. and −20° C., and Mw (weight average molecular weight) was compared by GPC. The evaluation results are shown in Tables 3 and 4.

[Table 3]
Table 3
-------------------------------------------------- -----------------------
Example 1 Example 1 Example 2 Example 2
-------------------------------------------------- -----------------------
Polymer Synthesis example 1 Synthesis example 1 Synthesis example 2 Synthesis example 2
Temperature -20°C 40°C -20°C 40°C
Time 1 week 1 week 1 week 1 week
-------------------------------------------------- -----------------------
Mw 8596 18938 18314 22032
-------------------------------------------------- -----------------------

[Table 4]
Table 4
-------------------------------------------------- -----------------------
Comparative Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 2
-------------------------------------------------- -----------------------
Polymer Comparative Synthesis Example 1 Comparative Synthesis Example 1 Comparative Synthesis Example 2 Comparative Synthesis Example 2
Temperature -20°C 40°C -20°C 40°C
Time 1 week 1 week 1 week 1 week
-------------------------------------------------- -----------------------
Mw 33313 gelled 103127 gelled
-------------------------------------------------- -----------------------

As shown in the above table, the polysiloxane solution with the silanol groups protected has a smaller increase in Mw (weight average molecular weight) than the polysiloxane solution with the unprotected silanol groups, and gelation is less likely to occur. It can be seen that it is superior in quality.

(Evaluation of flatness on Si substrate)
The polysiloxane compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated for planarization as follows. Table 5 shows the evaluation results.

On a stepped substrate with a groove depth of 200 nm and a width of 800 nm, using a spin coater, the polysiloxane composition of Example 1 was applied at a rotation speed of 1500 rpm for 60 seconds, and then baked at 100 ° C. for 1 minute. bottom. Similarly, the polysiloxane compositions of Example 2 and Comparative Examples 1 and 2 were applied and heated on a hot plate at 100° C. for 1 minute to form polysiloxane composition films (prepared to have a film thickness of 180 nm). Next, the shape of the cross section of the obtained polysiloxane composition film was observed by cross-sectional SEM to evaluate the planarization property. Observe a groove pattern with a depth of 200 nm and a width of 800 nm, measure the film thickness at the lowest film thickness and the highest film thickness with reference to the groove bottom, calculate the film thickness difference, and find that the film thickness difference is small. It was evaluated that the flattening property was good as much as possible.

[Table 5]
Table 5
----------------------------------------
Film thickness difference
----------------------------------------
Example 1 35.8 nm
Example 2 57.5 nm
Comparative Example 1 89.3 nm
Comparative Example 2 99.2 nm
----------------------------------------

As shown in the above table, the siloxane coating film formed using the composition of the present invention exhibited good planarization properties as compared with the comparative example.

(Evaluation of dry etching rate)
The solutions of the polysiloxane-containing compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were applied onto the wafer using a spin coater at a rotation speed of 1500 rpm for 60 seconds, and then baked at 100° C. for 1 minute. Then, a polysiloxane composition film (prepared to have a film thickness of 180 nm) was formed.

These coating films were dry-etched, and the chlorine gas etching rate (etching rate: nm/min) was measured.

For measurement of the dry etching rate, LAM-2300 (manufactured by Lam Research) was used as an etcher.

[Table 6]
Table 6
--------------------------------------------
Etching rate by chlorine gas
--------------------------------------------
Example 1 4.9
Example 2 5.6
Comparative Example 1 3.6
Comparative Example 2 4.0
--------------------------------------------

As shown in the above table, the siloxane coating film formed using the composition of the present invention exhibited good etching resistance comparable to that of the comparative example. When used as a coating composition or a resist composition, it exhibits good etching resistance when the pattern formed is used to process a substrate.

(electrical insulation evaluation)
A solution of the composition containing the polysiloxane of Example 1 was applied onto the wafer using a spin coater at a rotation speed of 1000 rpm for 60 seconds, and then baked at 110° C. for 1 minute to form a polysiloxane composition film. formed. Similarly, the solution of Comparative Example 3 was applied at 1000 rpm for 60 seconds and then baked at 205° C. for 1 minute to form a polysiloxane composition film. Regarding the electrical insulation of the obtained resin film, the leakage current density A/cm ² was measured when an electric field strength of 1 MV/cm and 3 MV/cm was applied to the resin film using a mercury prober (manufactured by Four Dimensions, CVmap92A). . The results are shown in Table 7.

[Table 7]
Table 7
-------------------------------------------------- ------------------
Film thickness 1MV/cm 3MV/cm
-------------------------------------------------- ------------------
Example 1 273 nm 3.78E-09 2.03E-07
Comparative Example 3 177 nm 2.63E-07 6.02E-06
-------------------------------------------------- ------------------

As shown in the table above, the siloxane coating film formed using the composition of the present invention exhibited excellent insulating properties.

(Heat resistance evaluation)
A solution of the composition containing polysiloxane of Example 1 was applied onto the wafer using a spin coater at a rotation speed of 1500 rpm for 60 seconds, and then baked at 110° C. for 1 minute to form a polysiloxane composition film. formed. The obtained resin film was scraped off with a scraper, and the heat resistance of the obtained sample was measured by TG-DTA (TG/DTA2010SR manufactured by NETZSCH). Nitrogen was used as the gas, and the sample was heated to 500°C at a rate of 10°C/min and then held at 500°C for 1 hour to evaluate the weight loss. Table 8 shows the measurement results.

[Table 8]
Table 8
-------------------------------------------------- ------------------
Room temperature to 500°C Hold at 500°C for 1 hour
Weight loss when weight loss to
-------------------------------------------------- ------------------
Example 1 -4.8% 0.4%
Comparative Example 3 7.2% 1.6%
-------------------------------------------------- ------------------

As shown in the table above, the siloxane coating film formed by using the composition of the present invention had a small weight loss at 500° C. and exhibited excellent heat resistance.

A method of manufacturing hydrogenated polysiloxane with high heat resistance, insulation, and etching resistance with improved storage stability, and hydrogenation with improved storage stability and improved planarization as a coating film. This is the polysiloxane composition part.

Claims (1)

A compound for capping silanol groups of polysiloxanes, the compound having formula (1):

(in formula (1), R ¹ represents an alkyl group or an aryl group, R ² represents an alkoxy group, and a represents an integer of 1 to 2) .
The polysiloxane is a polysiloxane used in a composition for forming a planarizing film used for planarizing a substrate including steps, or a hard mask between a resist and an organic film in a lithography process using a multilayer resist method. The above compound, which is a polysiloxane used in a composition for forming an intermediate film used as a .