KR101524712B1 - Blocked Isocyanato Bearing Silicon Containing Composition for the Formation of Resist Undercoat - Google Patents

Abstract

(식 중, R¹은 이소시아네이트기, 블록화 이소시아네이트기 또는 이를 포함하는 유기기를 나타내며 또한 말단의 N원자 또는 C원자가 Si원자와 결합하여 Si-N결합 또는 Si-C결합을 형성하고 있는 것이며, R²는 알킬기, 아릴기, 할로겐화알킬기, 할로겐화아릴기, 알케닐기 또는 에폭시기, 아크릴로일기, 메타크릴로일기, 메르캅토기, 아미노기 혹은 시아노기를 가지는 유기기를 나타내며 또한 말단의 C원자가 Si원자와 결합하여 Si-C결합을 형성하고 있는 것이며, R³은 알콕시기, 아실옥시기 또는 할로겐원자를 나타내고, a는 1 또는 2의 정수를 나타내고, b는 0 또는 1의 정수를 나타내고, a+b는 1 또는 2의 정수를 나타낸다.)로 나타나는 것이다.There is provided a resist underlayer film forming composition for lithography for forming a resist undercoat film which can be used as a hard mask or an antireflection film.
There is provided a resist underlayer film forming composition for lithography comprising a hydrolyzable organosilane containing an isocyanate group or a blocked isocyanate group, a hydrolyzate thereof or a hydrolyzed condensate thereof. Wherein the hydrolyzable organosilane is represented by the formula (1):

Wherein R ¹ represents an isocyanate group, a blocked isocyanate group or an organic group containing the same, and the N atom or C atom at the terminal is bonded to the Si atom to form a Si-N bond or a Si-C bond, and R ² Represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, will, forming a Si-C bond, R ³ represents an alkoxy group, an acyloxy group or a halogen atom, a is an integer of 1 or 2, b is an integer of 0 or 1, a + b is 1, Or an integer of 2).

Description

[0001] The present invention relates to a silicon-containing resist underlayer film forming composition having a blocked isocyanate group,

The present invention relates to a composition for forming a lower layer film between a substrate used for manufacturing a semiconductor device and a resist (for example, a photoresist or an electron beam resist). To a resist underlayer film forming composition for lithography for forming a lower layer film used in a lower layer of a photoresist in a lithography process of semiconductor device manufacturing. The present invention also relates to a method of forming a resist pattern using the lower layer film forming composition.

BACKGROUND ART [0002] Conventionally, in the production of a semiconductor device, fine processing by lithography using a photoresist is performed. The microfabrication is performed 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 having a pattern of semiconductor devices formed thereon, developing the photoresist pattern, Thereby forming fine irregularities corresponding to the pattern on the surface of the substrate. However, in recent years, there is a tendency that an active light beam used by the progress of high integration of semiconductor devices is short-wavelengthed by an ArF excimer laser (193 nm) in a KrF excimer laser (248 nm). As a result, the influence of reflection of the active ray from the semiconductor substrate becomes a serious problem. To solve this problem, a method of providing a bottom anti-reflective coating between a photoresist and a substrate has been widely studied. As the antireflection film, many studies have been made on an organic antireflection film made of a polymer having a light absorber and the like because of ease of use and the like. For example, an acrylic resin type antireflection film having a hydroxyl group and a light absorber in the same molecule as a crosslinking reactor, a novolak-type antireflection film having a hydroxyl group as a crosslinking reactor and a light absorber in the same molecule.

The characteristics required for the antireflection film include high absorbance to light and radiation, no intermixing with the photoresist (not soluble in the photoresist solvent), high-temperature photoresist in the antireflection film during the heating and firing Diffusion of low-molecular substances of the photoresist is not caused, and a dry etching rate is higher than that of the photoresist.

In recent years, copper (copper) has been studied as a wiring material in order to solve the problem of wiring delay which becomes clear due to progress of pattern rule miniaturization of a semiconductor device. At the same time, a dual damascene process is being studied as a method of forming a wiring to a semiconductor substrate. Further, in the dual damascene process, the anti-reflection film is formed on the substrate having the large aspect ratio in which the via hole is formed. For this reason, antireflection films used in this process are required to have embedding characteristics capable of filling holes without a gap and planarization characteristics such that a flat film is formed on the substrate surface.

Further, a film known as a hard mask containing a metal element such as silicon or titanium is used as a lower layer film between a semiconductor substrate and a photoresist (see, for example, Patent Document 1). In this case, since there is a large difference between the components in the resist and the hard mask, the rate of removal by dry etching largely depends on the type of gas used for dry etching. In addition, by appropriately selecting the kind of gas, the hard mask can be removed by dry etching without accompanied by a large reduction in the film thickness of the photoresist. As described above, in recent semiconductor device fabrication, a resist underlayer film is disposed between a semiconductor substrate and a photoresist in order to achieve various effects starting from the antireflection effect. Although a composition for a resist underlayer film has been studied up to now, development of a new material for a resist underlayer film is required due to various properties required.

A composition and a pattern forming method using a compound having a bond of silicon and silicon are known (see, for example, Patent Document 2).

An anti-reflection film forming composition containing an isocyanate group or a block isocyanate group is disclosed (for example, see Patent Document 3).

A hard mask material using a resin containing polycarbosilane is disclosed (for example, Patent Document 4 and Patent Document 5).

A resist underlayer film using a silane compound having a nitrogen-containing unsaturated group has been disclosed (Patent Document 6).

Japanese Patent Application Laid-Open No. 11-258813 Japanese Patent Application Laid-Open No. 10-209134 International Publication No. 2000/01752 pamphlet Japanese Patent Application Laid-Open No. 2001-93824 Japanese Patent Application Laid-Open No. 2005-70776 International Publication No. 2006/093057 pamphlet

An object of the present invention is to provide a resist underlayer film forming composition for lithography which can be used for the production of semiconductor devices. Specifically, it is intended to provide a composition for forming a resist lower layer film for lithography for forming a resist underlayer film which can be used as a hard mask. It is another object of the present invention to provide a composition for forming a resist lower layer film for lithography for forming a resist underlayer film which can be used as an antireflection film. It is another object of the present invention to provide a resist underlayer film for lithography which has a dry etching rate higher than that of a resist without intermixing with the resist and a resist underlayer film forming composition for forming the underlayer film.

It is another object of the present invention to provide a method for forming a resist pattern using the composition for forming a resist lower layer film for lithography.

A first aspect of the present invention is a composition for forming a resist lower layer film for lithography comprising a hydrolyzable organosilane containing an isocyanate group or a blocked isocyanate group, a hydrolyzate thereof, or a hydrolyzed condensate thereof,

In a second aspect, the hydrolyzable organosilane is represented by the formula (1):

(Wherein,

R ¹ represents an isocyanate group, a blocked isocyanate group or an organic group containing the same, and the N atom or C atom at the terminal is bonded to the Si atom to form a Si-N bond or a Si-C bond,

R ² represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, Bonded to form a Si-C bond,

R ³ represents an alkoxy group, an acyloxy group or a halogen atom,

a represents an integer of 1 or 2,

b represents 0 or an integer of 1,

and a + b represents an integer of 1 or 2), wherein the resist underlayer film forming composition according to the first aspect,

In a third aspect, the isocyanate group is represented by the formula (2):

(Wherein,

And R ⁴ represents a single bond, an alkylene group, a cycloalkylene group or an arylene group), the composition for forming a resist lower layer film described in the first aspect or the second aspect,

In a fourth aspect, the blocked isocyanate group is represented by the formula (3):

(Wherein,

R ⁴ represents a single bond, an alkylene group, a cycloalkylene group or an arylene group,

And R < ⁵ > represents an active hydrogen-containing compound residue), the composition for forming a resist lower layer film described in the first aspect or the second aspect,

In a fifth aspect, the active hydrogen-containing compound residue is at least one selected from the group consisting of alcohol residue, phenol residue, phenol derivative residue, polycyclic phenol residue, amide residue, imide residue, imine residue, thiol residue, oxime residue, lactam residue, Or an active methylene-containing compound residue,

From the sixth point of view,

(Wherein,

R ⁶ represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, Bonded to form a Si-C bond,

R ⁷ represents an alkoxy group, an acyloxy group or a halogen atom,

and a represents an integer of 0 to 3) and formula (5)

(Wherein,

R ⁸ represents an alkyl group,

R ⁹ represents an alkoxy group, an acyloxy group or a halogen atom,

Y represents an alkylene group or an arylene group,

b represents 0 or an integer of 1,

and c represents an integer of 0 or 1) with a hydrolyzable organosilane of the formula (1), a hydrolyzate thereof, or a hydrolyzed condensate thereof The resist underlayer film forming composition according to any one of the second to fifth aspects,

According to a seventh aspect, there is provided a lithographic resist underlayer film comprising a compound of the formula (1) described in any one of the second to sixth aspects, or a hydrolysis-condensation product of the compound of the formula (1) and the formula (4) Forming composition,

According to an eighth aspect, there is provided a resist lower layer film forming composition according to any one of the first to seventh aspects, further comprising a curing catalyst,

A resist underlayer film obtained by coating and baking the resist underlayer film forming composition according to any one of the first to eighth aspects on a semiconductor substrate,

A step of coating and baking the resist underlayer film forming composition according to any one of the first to eighth aspects on a semiconductor substrate to form a resist underlayer film according to a tenth aspect of the present invention, A step of forming a film, a step of exposing the resist film, a step of developing the resist after exposure to obtain a resist pattern, a step of etching the resist lower layer film by a resist pattern, and a step of processing the semiconductor substrate by the patterned resist and the resist lower layer film A method of manufacturing a semiconductor device including a process, and

A step of forming an organic underlayer film on the semiconductor substrate in accordance with an eleventh aspect, a step of forming a resist underlayer film by applying and baking the resist underlayer film forming composition according to any one of the first to eighth aspects on the organic underlayer film, A step of applying a resist composition on the resist lower layer film to form a resist film, a step of exposing the resist film, a step of developing the resist after exposure to obtain a resist pattern, a step of etching the resist lower layer film by a resist pattern, A step of etching the organic undercoat film with the resist lower layer film formed on the substrate and a step of processing the semiconductor substrate with the patterned organic undercoat film.

In the present invention, a resist underlayer film is formed on a substrate by a coating method, or a resist underlayer film is formed thereon through an organic underlayer film on a substrate and a resist film (for example, a photoresist or an electron beam resist) . Then, a resist pattern is formed by exposure and development, and the resist lower layer film is dry-etched using this resist pattern to transfer the pattern. The substrate is processed by this pattern, or the organic under layer film is pattern transferred by etching, The substrate is processed by a film.

In forming a fine pattern, the thickness of the resist film tends to be thinned to prevent pattern collapse. Dry etching for transferring a pattern to a film existing in the lower layer by thinning of the resist can not transfer the pattern unless the etching rate is higher than that of the film in the upper layer. In the present invention, the present undercoat film (containing an inorganic silicone compound) is coated on the substrate without interposing an organic undercoat film therebetween or under the organic undercoat film, and the resist film (organic resist film) is coated thereon in this order. The organic-based film and the inorganic-based film have drastically different dry etch rates depending on the selection of the etching gas, the organic-based film is an oxygen-based gas, the dry etching rate is high, and the inorganic-

For example, a resist pattern is formed and the present undercoat resist lower layer film is dry-etched with a halogen-containing gas to transfer a pattern to a resist undercoat film. Substrate processing is performed using a halogen-containing gas as a pattern transferred to the resist undercoat film I do. Alternatively, the underlayer organic film under the pattern is transferred to the organic underlayer film by dry etching with the oxygen-based gas using the patterned resist underlayer film, and the substrate is processed using the halogen-containing gas as the patterned organic underlayer film.

In the present invention, the lower resist film serves as a hard mask,

The hydrolyzable group such as an alkoxy group, an acyloxy group, or a halogen atom in the structure of the above formula (1) forms a polysiloxane structure by a condensation reaction of a silanol group after hydrolysis or partial hydrolysis. This polyorganosiloxane structure has a sufficient function as a hard mask. In addition, the isocyanate group contained in the polyorganosiloxane structure can be obtained by crosslinking the polyorganosiloxane structure by forming a triazinetrione ring by causing a cyclization reaction of three isocyanate groups using a catalyst such as trialkylphosphine have.

In addition, the polyorganosiloxane is formed by converting an isocyanate group contained in the structure into a blocked isocyanate group by a blocking agent, causing the blocked isocyanate group to be deblocked and reacting with the two molecules to form an urea structure, a buret structure, a urethane structure, an allophanate structure, Structure or the like can be formed. In the present invention, for example, a hydrolyzable organosilane having an isocyanate group may be dissolved in an alcohol to convert the isocyanate group into an alcohol-blocked blocked isocyanate. By blocking the isocyanate group, the isocyanate group can be protected during the sol-gel reaction. Among these alcohols, a polyorganosiloxane having a blocked isocyanate group in its side chain can be formed by a hydrolysis and condensation reaction by a sol-gel reaction to form a polymer. The film obtained by applying the resist underlayer film forming composition containing the blocked isocyanate group-containing polyorganosiloxane has a structure in which a blocked isocyanate group is deblocked by heating to form an isocyanate group and the isocyanate group is bonded to the triazine ring structure, Structure, an urethane structure, an allophanate structure, or the like can be formed and crosslinked in the film.

De-blocking is caused by heating, but the temperature of deblocking is different by the compound selected as a blocking agent. Therefore, when it is desired to form crosslinking by an isocyanate group formed by deblocking at a desired temperature, the blocking agent can be selected using this principle.

The blocking agent and the sol-gel solvent (the solvent in the hydrolysis and condensation reaction) may be combined, but the hydrolysable organosilane containing an isocyanate group and the blocked isocyanate group-containing hydrolyzable organosilane After the organosilane is formed, a polyorganosiloxane containing a blocked isocyanate group may be formed by hydrolysis and condensation reaction to form a polymer.

These bonding sites included in the polyorganosiloxane have a carbon-nitrogen bond or a carbon-oxygen bond, and have a higher dry etching rate due to a halogen-based gas than a carbon-carbon bond. When the upper layer resist pattern is transferred to the lower resist layer film Valid.

In addition, the polyorganosiloxane structure (intermediate film) is effective as a hard mask for etching an under organic layer film existing thereunder or for processing (etching) a substrate. That is, it has sufficient dry etching resistance to the oxygen-based dry etching gas at the time of substrate processing or the organic underlayer film.

The resist underlayer film of the present invention has improved dry etching speed for these upper layer resists and dry etching resistance such as during substrate processing.

1 is an NMR spectrum of a blocked isocyanate silane obtained by reacting 3- (triethoxysilylpropyl) -isocyanate with ethanol.
2 is an IR spectrum of a blocked isocyanate silane obtained by reacting 3- (triethoxysilylpropyl) -isocyanate with ethanol.

The composition for forming a resist lower layer film for lithography of the present invention comprises a hydrolyzable organosilane containing an isocyanate group or a blocked isocyanate group, a hydrolyzate thereof or a hydrolyzed condensate thereof. The hydrolyzable organosilane, the hydrolyzate thereof, and the hydrolyzed condensate thereof may also be used as a mixture thereof. The resist lower layer film forming composition of the present invention may be a hydrolyzate obtained by hydrolyzing a hydrolyzable organosilane, or a hydrolyzed condensate obtained by condensing a hydrolyzate obtained as a result. The composition for forming a resist lower layer film of the present invention may also be a mixture in which a partial hydrolyzate or a silane compound which has not been completely hydrolyzed is mixed with a hydrolysis-condensation product when the hydrolysis-condensation product is obtained. This condensate has a polysiloxane structure. This polysiloxane is bonded with an isocyanate group or a blocked isocyanate group or an organic group containing the isocyanate group.

The resist lower layer film-forming composition of the present invention comprises a hydrolyzable organosilane containing an isocyanate group or a blocked isocyanate group, a hydrolyzate thereof, or a hydrolysis-condensation product thereof and a solvent. The resist underlayer film forming composition of the present invention preferably contains a hydrolysis-condensation product of a hydrolysable organosilane containing an isocyanate group or a blocked isocyanate group and a solvent. The composition for forming a resist lower layer film of the present invention may contain an acid, water, alcohol, a curing catalyst, an acid generator, other organic polymer, a light absorbing compound and a surfactant as optional components.

The solid content in the resist underlayer film forming composition of the invention is, for example, 0.5 to 50 mass%, 1 to 30 mass%, or 1 to 25 mass%. Here, the solid content means that the solvent component is excluded from all components of the resist underlayer film forming composition.

The proportion of the hydrolyzable organosilane, the hydrolyzate thereof, and the hydrolyzed condensate thereof in the solid content is 20 mass% or more, for example, 50 to 100 mass%, 60 to 100 mass%, and 70 to 100 mass%.

The hydrolyzable organosilane used in the present invention has a structure represented by Formula (1). In the formula (1), R ¹ represents an isocyanate group, a blocked isocyanate group or an organic group containing the same, and is bonded to a silicon atom by a Si-N bond or a Si-C bond. R ² represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, It is combined with atoms. R ³ represents an alkoxy group, an acyloxy group or a halogen atom. a represents an integer of 1 or 2, b represents 0 or an integer of 1, and a + b represents an integer of 1 or 2.

R ¹ in the formula (1) is an isocyanate group, a blocked isocyanate group or an organic group containing the same. Blocking is a functional group conversion to protect the isocyanate group. An organic group containing an isocyanate group or a blocked isocyanate group means an organic group containing an isocyanate group or a blocked isocyanate group as well as a linking group between an isocyanate group or a blocked isocyanate group and a silicon atom present at the terminal.

The isocyanate group or the block isocyanate group of R ^{1 in} the formula (1) can be represented by the above formula (2) or (3), respectively. R ⁴ in the formulas (2) and (3) is a single bond or a linking group, and the connecting group is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms Lt; / RTI >

Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group and an octylene group. Examples of the cycloalkylene group having 3 to 10 carbon atoms include a cyclopropylene group, a cyclobutylene group, and a cyclohexene group. Examples of the arylene group having 6 to 20 carbon atoms include a phenylene group, a naphthylene group and an anthrylene group.

The hydrolyzable organosilane containing the blocked isocyanate group of the formula (3) can be obtained by reacting the hydrolyzable organosilane containing the isocyanate group of the formula (2) with a blocking agent. Commercially available hydrolysable organosilanes containing isocyanate groups are available.

The reaction of the isocyanate group of the formula (2) with the blocking agent can be carried out at 20 (room temperature) to 100 캜 for 1 to 24 hours. For example, when an alcohol is used as a solvent in a sol-gel reaction (hydrolysis and condensation reaction) of an isocyanate group-containing hydrolysable organosilane, the alcohol is a blocking agent and also a solvent in a sol-gel reaction. That is, it may be a polymer which is a condensation product (polyorganosiloxane) by hydrolysis and condensation, which is continuous with formation of a blocked isocyanate group-containing hydrolysable organosilane by blocking in an alcohol.

On the other hand, a blocked isocyanate group-containing hydrolyzable organosilane can also be obtained by reacting a hydrolyzable organosilane having an isocyanate group of the formula (2) with a blocking agent in an inert solvent. These silanes may be polymers that are condensates (polyorganosiloxanes) by continuous hydrolysis and condensation.

What is used as a blocking agent is an active hydrogen-containing compound capable of reacting with an isocyanate, for example, an alcohol, phenol, polycyclic phenol, amide, imide, imine, thiol, oxime, lactam, active hydrogen- .

Therefore, R ⁵ in the formula (3) is an active hydrogen-containing compound residue, and examples thereof include alcohol residue, phenol residue, phenol derivative residue, polycyclic phenol residue, amide residue, imide residue, imine residue, thiol residue, , A lactam residue, an active hydrogen-containing heterocyclic residue, and an active methylene-containing compound residue.

Examples of the alcohols as blocking agents include alcohols having 1 to 40 carbon atoms and include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, octanol, ethylene chlorohydrin, Propanol, t-butanol, t-pentanol, 2-ethylhexanol, cyclohexanol, lauryl alcohol, ethylene glycol, butylene glycol, trimethylol propane, glycerin, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, benzyl alcohol and the like.

Examples of the phenol as a blocking agent include phenols having 6 to 20 carbon atoms, such as phenol, chlorophenol, and nitrophenol.

Examples of the phenol derivatives as blocking agents include phenol derivatives having 6 to 20 carbon atoms, and examples thereof include para-t-butylphenol, cresol, xylenol, resorcinol and the like.

Examples of the polycyclic phenol as a blocking agent include polycyclic phenols having 10 to 20 carbon atoms, which are aromatic condensed rings having a phenolic hydroxyl group, and examples thereof include hydroxynaphthalene, hydroxyanthracene and the like.

Examples of the amide as a blocking agent include amides having 1 to 20 carbon atoms, such as acetanilide, hexanamide, octanediamide, succinamide, benzenesulfonamide, ethanediamide and the like.

Examples of imides as blocking agents include imides having 6 to 20 carbon atoms, and examples thereof include cyclohexane dicarboxyimide, cyclohexane dicarboxyimide, benzene dicarboxyimide, cyclobutane dicarboxyimide and carbodiimide. do.

Examples of the imine as the blocking agent include imines having 1 to 20 carbon atoms, such as hexane-1-imine, 2-propaneimine, ethane-1,2-imine and the like.

Examples of the thiol as a blocking agent include thiol having 1 to 20 carbon atoms, and examples thereof include ethanethiol, butanethiol, thiophenol, 2,3-butanedithiol, and the like.

The oxime as a blocking agent is, for example, an oxime having 1 to 20 carbon atoms, and examples thereof include acetoxime, methyl ethyl ketoxime, cyclohexanone oxime, dimethyl ketoxime, methyl isobutyl ketoxime, methyl amyl ketoxime, Acetylacetonium, diacetylmonooxime, benzophenone oxime, cyclohexanoxime and the like.

The lactam as a blocking agent is, for example, a lactam having 4 to 20 carbon atoms, and examples thereof include? -Caprolactam,? -Valerolactam,? -Butyrolactam,? -Propyllactam,? -Pyrrolidone and lauryllactam .

The active hydrogen-containing heterocyclic compound as a blocking agent is, for example, an active hydrogen-containing heterocyclic compound having 3 to 30 carbon atoms and is a pyrrole, imidazole, pyrazole, piperidine, piperazine, morpholine, pyridine, indole, Indazole, purine, carbazole, and the like.

Examples of active methylene-containing compounds as blocking agents include active methylene-containing compounds having 3 to 20 carbon atoms, such as dimethyl malonate, diethyl malonate, methyl acetate, ethyl acetate, and acetylacetone.

In R ² in the formula (1), the alkyl group includes a cyclic or straight chain alkyl group.

Examples of the straight chain alkyl group having 1 to 10 carbon atoms include straight chain or branched alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, butyl group, a 1-methyl-n-butyl group, a 1-methyl-n-propyl group, a 1-methyl- N-propyl group, a 2-dimethyl-n-propyl group, a 1-ethyl- Dimethyl-n-butyl group, 1, 2-dimethyl-n-butyl group, 1, 3-dimethyl-n-pentyl group, Butyl group, a 2-ethyl-n-butyl group, a 2-ethyl-n-butyl group, n-propyl group, 1-ethyl-1-methyl-n-propyl group and 1-ethyl- Methyl-n-propyl group and the like.

Examples of the cyclic alkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, Dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a 2-methyl-cyclopropyl group, Cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclohexyl group, Dimethyl-cyclohexyl group, 2,3-dimethyl-cyclohexyl group, 2,4-dimethyl-cyclohexyl group, 2,2- Cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, Cyclopropyl group, 1,2,2-trimethyl-cycloprop Methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl- 2-ethyl-2-methyl-cyclopropyl group and 2-ethyl-3-methyl-cyclopropyl group.

The aryl group in R ² is preferably a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o- chlorophenyl group, an m- chlorophenyl group, a p- chlorophenyl group, n-pentyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, o-methoxyphenyl group, p- Anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group and 9- have.

Examples of the halogenated alkyl group or halogenated aryl group in R ² of the formula (1) include an organic group in which the above-mentioned alkyl group or aryl group is substituted by a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom .

In R ² in the formula (1), the alkenyl group is an alkenyl group having 2 to 10 carbon atoms such as an ethenyl (vinyl) group, a 1-propenyl group, a 2-propenyl group, Methyl-1-propenyl group, 2-methyl-1-propenyl group, 1-methylbutyl group, 1-methyl-1-butenyl, 1-methyl-1-butenyl, 1-methyl-1-butenyl, 1-methylpropyl, Propyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group 1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1- Propenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl- Methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group Propyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl- Methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dipentenylmethyl- Butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2- Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3- A butenyl group, a 1-i-butylethenyl group, a 2,2-dimethyl-3-butenyl group, a 2,3-dimethyl-1-butenyl group, a 2,3- Butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-1-butenyl group, 3-butenyl group, 1-n-propyl-1- Ethyl-1-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2- Propyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl- , 1-i-propyl-1-propenyl group and 1-i-propyl-2-propenyl group.

Examples of the organic group having an epoxy group in R ² of the formula (1) include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.

Examples of the organic group having an acryloyl group in R ² of the formula (1) include an acryloylmethyl group, an acryloylethyl group and an acryloylpropyl group.

In R ² of the formula (1), examples of the organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.

Examples of the organic group having a mercapto group in R ² of the formula (1) include an ethylmercapto group, a butylmercapto group, a hexylmercapto group, and an octylmercapto group.

Examples of the organic group having an amino group in R ² of the formula (1) include an aminoethyl group and an aminopropyl group.

In R ² of the formula (1), examples of the organic group having a cyano group include a cyanoethyl group and a cyanopropyl group.

Examples of the alkoxy group having 1 to 20 carbon atoms in R ³ in the formula (1) include an alkoxy group having a straight-chain, branched or cyclic alkyl moiety having 1 to 20 carbon atoms. Examples of the alkoxy group include a methoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t- n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2- N-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group N-butoxy group, 1-ethyl-n-butoxy group, 1,1,2-trimethyl-n Propoxy group, 1,2,2-trimethyl-n-propoxy group, 1- 1-methyl-n-propoxy group and 1-ethyl-2-methyl-n-propoxy group, and cyclic alkoxy groups include cyclopropoxy group, cyclobutoxy group, Cyclobutyl group, 2-methyl-cyclopropoxy group, cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl- Cyclopentyloxy group, a 2-methyl-cyclopentyloxy group, a 2-methyl-cyclopentyloxy group, a 2-methyl-cyclopentyloxy group, Cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl- Dimethyl-cyclobutoxy group, 2-dimethyl-cyclobutoxy group, 2-dimethyl-cyclobutoxy group, -Cyclopropoxy group, 2-n- 1-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group, 1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl- Ethyl-2-methyl-cyclopropoxy group, a 2-ethyl-1-methyl-cyclopropoxy group, a 2-ethyl- Methyl-cyclopropoxy group and 2-ethyl-3-methyl-cyclopropoxy group.

In R ³ in the formula (1), examples of the acyloxy group include an acyloxy group having 1 to 20 carbon atoms such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, Butylcarbonyloxy group, an i-butylcarbonyloxy group, a s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n Butylcarbonyloxy group, a 1-methyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentyl group, N-pentylcarbonyloxy group, a 4-methyl-n-pentylcarbonyloxy group, a 1,1-dimethyl-n-butyl Dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butyl N-butylcarbonyloxy group, a 3,3-dimethyl-n-butylcarbonyloxy group, a 1-ethyl-n-butylcarbonyloxy group, butylcarbonyloxy group, a 2-ethyl-n-butylcarbonyloxy group, a 1,1,2-trimethyl-n-propylcarbonyloxy group, a 1,2,2-trimethyl- Ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group and tosylcarbonyloxy group .

In R ³ in the formula (1), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the hydrolyzable organosilane represented by the formula (1) are exemplified, for example, in the following.

The hydrolysis-condensation product of the hydrolysable organosilane of the formula (1) is exemplified, for example, in the following.

In the present invention, the hydrolyzable organosilane represented by the formula (1) may be used in combination with at least one silicon-containing compound selected from the group represented by the formulas (4) and (5).

That is, the hydrolyzable organosilane represented by the formula (1), the hydrolyzate thereof, or the hydrolyzed condensate thereof and at least one silicon-containing compound selected from the group represented by the formulas (4) and (5) Decomposition products, or hydrolysis-condensation products can be used in combination.

The ratio of the hydrolysable organosilane of the formula (1) to the silicon-containing compound of the formula (4) and / or the formula (5) can be used in a molar ratio of 1: 0 to 1: 200. The silicon-containing compound selected from the group consisting of the formulas (4) and (5) is preferably the silicon-containing compound represented by the formula (4).

These are preferably used as hydrolysis-condensation products (polymers of polyorganosiloxanes), and hydrolysis-condensation products of a hydrolyzable organosilane represented by the formula (1) and a silicon-containing compound represented by the formula (4) Siloxane polymer) is preferably used.

An alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group or an epoxy group represented by R ⁶ , R ⁷ , R ⁸ and R ⁹ in the silicon-containing compound represented by the formula (4) An alkoxy group, an acyloxy group or a halogen atom contained in an organic group having a methacryloyl group, a mercapto group, an amino group or a cyano group, and the hydrolyzable group can be exemplified by the above-mentioned formula (1).

The silicon-containing compound represented by the formula (4) is, for example, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxy But are not limited to, silane, tetraacetoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltri Amyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenetyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,? -Glycidoxyethyltrimethoxy Silane,? -Glycidoxyethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, Doxi Profile Trietalk Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane, Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltriethoxysilane, ,? -glycidoxybutyltriethoxysilane,? -glycidoxybutyltrimethoxysilane,? -glycidoxybutyltriethoxysilane,? -glycidoxybutyltrimethoxysilane,? -glycidoxime (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltriethoxysilane,? - (3,4-epoxycyclohexyl) ethyltripropoxysilane, ? - (3,4-epoxycyclohexyl) ethyltributoxysilane,? - (3,4-epoxycyclohexyl) ethyltriphenoxysilane,? - (3,4-epoxycyclohexyl) propyltriethoxysilane,? - (3,4-epoxycyclohexyl) butyltrimethoxysilane,? - Silane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane,? -Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethylmethyldiethoxysilane,? -Glycidoxyethylmethyldimetate Glycidoxyethyldimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane, Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ- Glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyl Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, gamma -chloropropyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, ? -Chloropropyltriethoxysilane,? - chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? - methacryloxypropyltrimethoxysilane,? - mercapto propyl (Meth) acrylate, methoxysilane,? -Mercaptopropyltriethoxysilane,? -Cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N- Aminopropyltrimethoxysilane, N- (? -Aminoethyl)? -Aminopropyltriethoxysilane,? - aminopropyltrimethoxysilane,? - aminopropyltrimethoxysilane, Aminopropyltrimethoxysilane, N- (? -Aminoethyl)? -Aminopropylmethyldiethoxysilane, N- (? -Aminoethyl)? -Aminopropylmethyldichlorosilane, N- (? -aminoethyl)? -aminopropylmethyldiacetoxysilane,? -aminopropylmethyldimethoxysilane,? -aminopropylmethyldichlorosilane, N- (? -aminoethyl)? -aminopropyltriethoxysilane, N- (? -Aminoethyl)? -Aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyl Dimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane,? -Chloropropylmethyldimethoxysilane,? -Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane,? -Methacryloxypropylmethyldimethoxysilane,? -Methacryloxypropylmethyldimethoxysilane, and? -methacryloxypropylmethyldiethoxysilane,? -mercaptopropylmethyldimethoxysilane,? -mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and the like.

The silicon-containing compound represented by the formula (5) includes, for example, methylenebistrimethoxysilane, methylenebistriclorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistriclorosilane, ethylenebistriacetoxy Silane, propylene bistriethoxy silane, butylene bistrimethoxy silane, phenylene bistrimethoxy silane, phenylene bistriethoxy silane, phenylene bismethyl diethoxy silane, phenylene bismethyl dimethoxy silane, naphthylene bis Trimethoxysilane, trimethoxysilane, trimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, and bismethyldimethoxydisilane.

Specific examples of the hydrolysis-condensation product of the hydrolysable organosilane represented by the formula (1) and the silicon-containing compound represented by the formula (4) are illustrated below.

The hydrolyzable condensation product (polyorganosiloxane) of the hydrolyzable organosilane of the formula (1) or the hydrolyzable organosilane of the formula (1) and the silicon-containing compound of the formula (4) and / or the formula (5) (Polyorganosiloxane) having a weight average molecular weight of 1000 to 1000000 or 1000 to 100000 can be obtained. These molecular weights are the molecular weights obtained in terms of polystyrene by GPC analysis.

The measurement conditions of GPC were measured using a GPC apparatus (trade name: HLC-8220GPC, manufactured by TOSOH CORPORATION) and a GPC column (trade names: Shodex KF803L, KF802, KF801, SHOWA DENKO KK) ), Tetrahydrofuran at a flow rate (flow rate) of 1.0 mL / min, and standard samples of polystyrene (manufactured by SHOWA DENKO KK).

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

The hydrolysis catalyst may be used in an amount of 0.001 to 10 mol, preferably 0.001 to 1 mol, per mol of the hydrolyzable group.

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

The hydrolysis may be completely hydrolyzed or partially hydrolyzed. That is, the hydrolyzate and the monomer may remain in the hydrolyzed condensate.

A catalyst may be used for hydrolysis and condensation.

Examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases and inorganic bases.

The metal chelate compound as the hydrolysis catalyst includes, for example, triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono ) Titanium, tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, Diacetate) bis (acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di-n-butoxy bis (Acetylacetonate) titanium, di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris Propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris Butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethylacetate) titanium, tri-i-propoxy mono (ethylacetate) titanium (Ethylacetate) titanium, tri-sec-butoxy mono (ethylacetate) titanium, tri-t-butoxy mono (ethylacetate) titanium, diethoxy bis (Ethyl acetoacetate) titanium, di-n-propoxy bis (ethylacetate) titanium, di-i-propoxy bis (ethylacetate) titanium, Titanium, di-sec-butoxy-bis (ethylacetate) titanium, di-t -Butoxy bis (ethylacetate) titanium, monoethoxy tris (ethylacetate) titanium, mono-n-propoxy tris (ethylacetate) titanium, mono-i-propoxy tris Butoxy tris (ethylacetate) titanium, mono-sec-butoxy tris (ethylacetate) titanium, mono-t-butoxy tris (ethylacetate) (Ethyl acetoacetate) titanium, bis (acetylacetonate) titanium, tris (acetylacetonate) titanium, mono (acetylacetonate) Titanium chelate compounds such as triethoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri-i-propoxy mono (Acetylacetonate) zirconium, tri-tert-butoxy mono (acetylacetonate) zirconium, tri-sec-butoxy mono Bis (acetylacetonate) zirconium, di-n-propoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (Acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, di-tert-butoxy bis (acetylacetonate) zirconium, di- Mono-sec-butoxy tris (acetylacetonate) zirconium, mono-i-propoxy tris (acetylacetonate) zirconium, mono-n-butoxy tris (Acetylacetonate) zirconium , Mono-t-butoxy tris (acetylacetonate) zirconium, tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetate) zirconium, tri- (Ethyl acetoacetate) zirconium, tri-n-butoxy mono (ethylacetate) zirconium, tri-sec-butoxy mono (Ethylacetate) zirconium, diethoxy bis (ethylacetate) zirconium, di-n-propoxy bis (ethylacetate) zirconium, di-i-propoxy bis ) Zirconium, di-n-butoxy bis (ethylacetate) zirconium, di-sec-butoxy bis (ethylacetate) zirconium, di- Talk Mono-n-propoxy tris (ethyl acetoacetate) zirconium, mono-i-propoxy tris (ethylacetate) zirconium, mono-n-butoxy tris Mono-sec-butoxy tris (ethylacetate) zirconium, mono-t-butoxy tris (ethylacetate) zirconium, tetrakis (ethylacetate) zirconium, mono (acetylacetonate) zirconium, Zirconium chelate compounds such as tris (ethylacetate) zirconium, bis (acetylacetonate) bis (ethylacetate) zirconium, and tris (acetylacetonate) mono (ethylacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetate) aluminum; And the like.

Examples of the organic acid as the hydrolysis catalyst include organic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, Benzenesulfonic acid, benzenesulfonic acid, monosubstituted benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, benzenesulfonic acid, Acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid and tartaric acid.

Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

The organic base as the hydrolysis catalyst may be, for example, pyridine, pyrrole, piperidine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, Diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclo-nonane, diazabicyclo-undecene, tetramethylammonium hydroxide, and the like. Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. In these catalysts, a metal chelate compound, an organic acid, and an inorganic acid are preferable, and one or two or more of them may be used at the same time.

Examples of the organic solvent used for the hydrolysis include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, Aliphatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene , Aromatic hydrocarbon solvents such as triethylbenzene, di-i-propylbenzene, n-amylnaphthalene and trimethylbenzene; Propanol, n-butanol, i-butanol, sec-butanol, t-butanol, Butanol, sec-butanol, heptanol-3, n-octanol, 2-ethylhexanol sec-octadecyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, n-octyl alcohol, Monoalcohol solvents such as cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol and cresol; Ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol- Polyhydric alcohol solvents such as diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and glycerin; ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, di Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone , 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone, and fenchone; Ethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, Ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 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- , Diethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, Ethers such as diethyl carbonate, methyl acetate, ethyl acetate,? -Butyrolactone,? -Valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, Methylcyclohexyl, n-nonyl acetate, methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol acetate 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 acetate Butyl ether, propyleneglycol diethyl ether, di-n-butyl oxalate, methyl lactate, ethyl lactate, ethyl lactate, diethylene glycol monoethyl ether acetate, Ester solvents such as n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; organic solvents such as N-methylformamide, N, N-dimethylformamide, Amide, N-methyl acetamide, N, N-dimethylacetamide, N-methyl propionamide and N-methyl pyrrolidone; And a sulfur-containing solvent such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, sulfolane, and 1,3-propanesultone. These solvents may be used alone or in combination of two or more.

Particularly preferred are propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , And propylene glycol monopropyl ether acetate are preferable from the viewpoint of the storage stability of the solution.

The resist underlayer film forming composition of the present invention may contain a curing catalyst. The curing catalyst is obtained by heating a coating film containing a polyorganosiloxane composed of a hydrolysis-condensation product to form a crosslinking catalyst when the polyorganosiloxane forms a crosslink in the silanol period, the isocyanate period, or the silanol group and the isocyanate period .

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

Examples of the ammonium salt include a compound represented by the formula (D-1):

(Wherein m represents an integer of 2 to 11, n represents an integer of 2 to 3, R ¹ represents an alkyl group or an aryl group, and Y ^- represents an anion) ,

Formula (D-2):

(Wherein R ² , R ³ , R ⁴ and R ⁵ represent an alkyl group or an aryl group, N represents a nitrogen atom, Y ^- represents an anion, and R ² , R ³ , R ⁴ and R ⁵ represent CN bond to a nitrogen atom), a quaternary ammonium salt having a structure represented by the following formula

Formula (D-3):

(Wherein R ⁶ and R ⁷ represent an alkyl group or an aryl group, and Y ^- represents an anion)

Formula (D-4):

(Wherein R ⁸ represents an alkyl group or an aryl group, and Y ^- represents an anion), a quaternary ammonium salt having a structure represented by the following formula

Formula (D-5):

(Wherein R ⁹ and R ¹⁰ represent an alkyl group or an aryl group, and Y ^- represents an anion), a quaternary ammonium salt,

Formula (D-6):

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

The phosphonium salt may be a compound represented by the formula (D-7):

^{(Wherein, R 11, R 12, R} 13 and R ¹⁴ represents an alkyl group or an aryl group, P represents cut personnel, Y ^- represents the anion also R ^11, R ^12, R ¹³ and R ¹⁴ are CP each coupled , And the quaternary phosphonium salt represented by the following formula (I).

The compound of the formula (D-1) is a quaternary ammonium salt derived from an amine, m represents an integer of 2 to 11, and n represents an integer of 2 to 3. R ¹ of the 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 a straight chain alkyl group such as an ethyl group, a propyl group and a butyl group, a benzyl group, Cyclohexylmethyl group, dicyclopentadienyl group, and the like. Further, the anion (Y ^-) is a chloride ion (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-) a halogen ion or a carboxylate (-COO ^-), such as, sulfonate (-SO ₃ ^-) , alcoholate (-O ^-) may be an acid group, such as.

The compound of the above formula (D-2) is a quaternary ammonium salt represented by R ² R ³ R ⁴ R ⁵ N ⁺ Y ^- . R ² , R ³ , R ⁴ and R ⁵ of the quaternary ammonium salt are an alkyl group or an aryl group having 1 to 18 carbon atoms. Anion (Y ^-) is a chloride ion (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-) a halogen ion or a carboxylate (-COO ^-), such as, sulfonate (-SO ₃ ^-), alcohol And a rate (-O < ^- >). These quaternary ammonium salts are commercially available and include, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, Trimethylbenzylammonium, and the like.

The compound of the above formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, R ⁶ and R ⁷ are each a carbon number of 1 to 18, and the total number of carbon atoms of R ⁶ and R ⁷ is 7 Or more. For example, R ⁶ may be a methyl group, an ethyl group, a propyl group, a phenyl group or a benzyl group, and R ⁷ may be a benzyl group, an octyl group or an octadecyl group. Anion (Y-) is a chlorine ion (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-) a halogen ion or a carboxylate (-COO ^-), such as, sulfonate (-SO ₃ ^-), alcohol And a rate (-O < ^- >). This compound can be obtained commercially, for example, by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with a halogenated alkyl such as benzyl bromide or methyl bromide or a halogenated aryl have.

The compound of the formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ⁸ is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, such as butyl, An octyl group, a benzyl group, and a lauryl group. Anion (Y ^-) is a chloride ion (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-) a halogen ion or a carboxylate (-COO ^-), such as, sulfonate (-SO ₃ ^-), alcohol And a rate (-O < ^- >).

This compound can be obtained commercially, for example, by reacting pyridine with a halogenated alkyl such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl octane, or halogenated aryl. These compounds include, for example, N-laurylpyridinium chloride, N-benzylpyridinium bromide, and the like.

The compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline or the like, R ⁹ is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, For example, a methyl group, an octyl group, a lauryl group, a benzyl group and the like. R ¹⁰ is an alkyl group or an aryl group having 1 to 18 carbon atoms and is, for example, quaternary ammonium derived from picoline, R ¹⁰ is a methyl group. Anion (Y ^-) is a chloride ion (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-) a halogen ion or a carboxylate (-COO ^-), such as, sulfonate (-SO ₃ ^-), alcohol And a rate (-O < ^- >). This compound can be obtained commercially, for example, by reacting a substituted pyridine such as picoline with a halogenated alkyl such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or halogenated aryl. This compound can be exemplified by, for example, N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-lauryl picolinium chloride and the like.

The compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, m represents an integer of 2 to 11, and n represents an integer of 2 to 3. Further, the anion (Y ^-) is a chloride ion (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-) a halogen ion or a carboxylate (-COO ^-), such as, sulfonate (-SO ₃ ^-) , alcoholate (-O ^-) may be an acid group, such as. Or by reacting an amine with a weak acid such as carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. The anion (Y ^- ) is (HCOO ^- ) when formic acid is used and the anion (Y ^- ) is (CH ₃ COO ^- ) when acetic acid is used. In addition, when phenol is used, the anion (Y ^- ) is (C ₆ H ₅ O ^- ).

A quaternary phosphonium salt having the structure of the ^compounds of the formula (D-7) is ^{R 11 R 12 R 13 R 14} P + Y. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are alkyl groups or aryl groups having 1 to 18 carbon atoms, but preferably three of the four substituents R ¹¹ to R ¹⁴ are phenyl groups or substituted phenyl groups, A tolyl group, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group. In addition, the anion (Y ^-) is a chloride ion (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-) a halogen ion or a carboxylate (-COO ^-), such as, sulfonate (-SO ₃ ^-), there may be mentioned an acid group, such ^{as-alcoholate} (-O). These compounds are commercially available and include, for example, halogenated tetraalkylphosphonium halides such as tetra n-butylphosphonium halide and tetra-n-propylphosphonium halide, halogenated trialkylbenzylphosphonium halides such as halogenated triethylbenzylphosphonium , Halogenated triphenylmethylphosphonium halide such as triphenylmethylphosphonium and halogenated triphenylmethylphosphonium, halogenated triphenylbenzylphosphonium, halogenated tetraphenylphosphonium, halogenated tritolylmonoarylphosphonium, or halogenated tritolylmono Alkylphosphonium (the halogen atom is a chlorine atom or a bromine atom). Particularly, halogenated triphenylmethylphosphonium such as halogenated triphenylmethylphosphonium and halogenated triphenylethylphosphonium, halogenated triphenylmonoarylphosphonium such as halogenated triphenylbenzylphosphonium, halogenated triphenylmonophenylphosphonium and the like Halogenated tristyrylmonoalkylphosphonium (halogen atom is chlorine atom or bromine atom) such as halogenated tritolylmonoarylphosphonium or halogenated tritolylmonomethylphosphonium is preferable.

Examples of the phosphines include first phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine and phenylphosphine, dimethylphosphine, diethylphosphine, diisopropylphosphine, A second phosphine such as phosphine, diisooamylphosphine and diphenylphosphine, a third phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine and dimethylphenylphosphine, .

The curing catalyst is 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass based on 100 parts by mass of the condensate (polyorganosiloxane).

The hydrolysis-condensation product (polymer) obtained by hydrolyzing and condensing the hydrolysable organosilane in a solvent in the presence of a catalyst can simultaneously remove alcohol as a by-product or a used hydrolysis catalyst or water by vacuum distillation or the like. Further, the acid or base catalyst used for hydrolysis can be removed by neutralization or ion exchange. In the composition for forming a resist lower layer film for lithography of the present invention, an organic acid, water, an alcohol, or a combination thereof may be added to stabilize the resist underlayer film forming composition containing the hydrolyzed condensate thereof.

Examples of the organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid and salicylic acid. Of these, preferred are hydrochloric acid and maleic acid. The added organic acid is 0.5 to 1.0 part by mass based on 100 parts by mass of the condensate (polyorganosiloxane). Water to be added may be pure water, ultrapure water, ion-exchanged water or the like, and the amount thereof may be 1 to 20 parts by mass based on 100 parts by mass of the composition for forming a resist lower layer film.

The alcohol to be added is preferably easily scattered by heating after application, and examples thereof include methanol, ethanol, propanol, isopropanol and butanol. The alcohol to be added may be 1 to 20 parts by mass based on 100 parts by mass of the composition for forming a resist lower layer film.

The composition for forming a lower layer film for lithography of the present invention may contain an organic polymer compound, a photoacid generator, a surfactant, and the like in addition to the above components, if necessary.

By using the organic polymer compound, it is possible to adjust the dry etching rate (reduction amount of the film thickness per unit time), the attenuation coefficient, the refractive index, etc. of the resist lower layer film formed of the composition for forming a lower layer film for lithography of the present invention.

The organic polymer compound is not particularly limited and various kinds of organic polymers can be used. A condensation polymer and an addition polymer may be used. Addition polymerized polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide and polycarbonate and polycondensation polymers can be used. An organic polymer having an aromatic ring structure such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, and a quinoxaline ring which function as a light absorbing site is preferably used.

Examples of such organic polymer compounds include benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthrylmethyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether And N-phenylmaleimide as structural units, and polycondensation polymers such as phenol novolak and naphthol novolak.

When an addition polymer is used as the organic polymer compound, the polymer compound may be a homopolymer or a copolymer. Addition polymerization monomers are used in the production of the addition polymerization polymer. Examples of the addition-polymerizable monomer include acrylic acid, methacrylic acid, acrylic ester compound, methacrylic acid ester compound, acrylamide compound, methacrylamide compound, vinyl compound, styrene compound, maleimide compound, maleic anhydride, acrylonitrile And the like.

Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, Acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy- N-2-carboxy-6-lactone, 3-acryloxypropyltriethoxysilane and glycidyl acrylate.

Examples of the methacrylic ester compound include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate Methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2- Methyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-anamantyl methacrylate, 5-methacryloyloxy 2-carboxy-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate And bromophenyl methacrylate It can be a bit like.

Examples of the acrylamide compound include acrylamide, N-methylacrylamide, N-ethyl acrylamide, N-benzyl acrylamide, N-phenyl acrylamide, N, N-dimethylacrylamide and N-anthryl acrylamide have.

Examples of the methacrylamide compound include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N, N-dimethylmethacrylamide, Acrylamide and trityl acrylamide.

Examples of the vinyl compound include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether , Vinyl naphthalene, vinyl anthracene, and the like.

Examples of the styrene compound include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene and acetylstyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and N-hydroxyethylmaleimide.

When a polycondensation polymer is used as the polymer, examples of such a polymer include a polycondensation polymer of a glycol compound and a dicarboxylic acid compound. Examples of the glycol compound include diethylene glycol, hexamethylene glycol, and butylene glycol. Examples of the dicarboxylic acid compound include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Further, examples thereof include polyesters, polyamides and polyimides such as poly (pyromellitimide), poly (p-phenylene terephthalamide), polybutylene terephthalate and polyethylene terephthalate.

When the organic polymer compound contains a hydroxyl group, the hydroxyl group may form a crosslinking reaction with the polyorganosiloxane.

As the organic polymer compound, a polymer compound having a weight average molecular weight of, for example, 1000 to 1000000, or 3000 to 300000, or 5000 to 200000, or 10000 to 100000 may be used.

Only one kind of organic polymer compound may be used, or two or more kinds may be used in combination.

When the organic polymer compound is used, the proportion thereof is 1 to 200 parts by mass, or 5 to 100 parts by mass, or 10 to 50 parts by mass, or 20 to 30 parts by mass, relative to 100 parts by mass of the condensate (polyorganosiloxane) Wealth.

The resist lower layer film forming composition of the present invention may contain an acid generator.

Examples of the acid generator include a thermal acid generator and a photo acid generator.

The photoacid generator generates an acid upon exposure of the resist. Therefore, it is possible to adjust the acidity of the lower layer film. This is one way to match the acidity of the underlayer film to the acidity of the upper layer resist. Further, the shape of the resist pattern formed on the upper layer can be adjusted by adjusting the acidity of the lower layer film.

Examples of the photoacid generator contained in the resist lower layer film forming composition of the present invention include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound.

Examples of the onium salt compounds include diphenyl iodonium hexafluorophosphate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium nonafluoro non-n-butanesulfonate, diphenyl iodonium perfluorononoctane Iodonium salts such as sulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate. And sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate, And the like.

Examples of the sulfone imide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoroarnobutane sulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide And N- (trifluoromethanesulfonyloxy) naphthalimide, and the like.

Examples of the disulfonyldiazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis Sulfonyl) diazomethane, bis (2,4-dimethylbenzenesulfonyl) diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

The photoacid generators may be used alone or in combination of two or more.

When a photoacid generator is used, the proportion thereof is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.5 to 1 part by mass based on 100 parts by mass of the condensate (polyorganosiloxane).

The surfactant is effective for suppressing the occurrence of pinholes, strains, and the like when the resist underlayer film forming composition for lithography of the present invention is applied to a substrate.

Examples of the surfactant contained in the resist underlayer film forming composition of the present invention include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, Sorbitan fatty acid esters such as sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, poly Oxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbate (Trade names, manufactured by ToChem Products), trade names MEGAFAC F171, F173, R-08, R (trade name) manufactured by Tohoku Kasei K.K.), and polyoxyethylene sorbitan fatty acid esters (Product of Dai Nippon Ink Chemical Industry Co., Ltd.), FLUORAD FC430 and FC431 (manufactured by Sumitomo 3M Ltd.), trade names Asahi Guard AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Manufactured by Shin-Etsu Chemical 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 mass, 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass based on 100 parts by mass of the condensate (polyorganosiloxane).

In addition, a rheology modifier and an adhesion aid may be added to the resist lower layer film forming composition of the present invention. The rheology modifier is effective for improving the fluidity of the underlayer film forming composition. The adhesion auxiliary agent is effective for improving the adhesion between the semiconductor substrate or the resist and the underlayer film.

The solvent used in the resist lower layer film forming composition of the present invention is not particularly limited as long as it is a solvent capable of dissolving the solid content. Examples of the solvent include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono ether ether acetate, propylene glycol monomethyl ether acetate, Glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy- Ethyl propionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 2-hydroxypropionate, Ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono 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 diethyl ether, Diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, iso-lactate Propyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, formate isoylmethyl acetate, ethyl acetate, amyl acetate, Wheat, acetic acid panting , Methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, butyric isobutyl, Methyl 2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, Methyl-3-methoxybutyl butyrate, methyl acetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N , N-dimethylformamide , There may be mentioned N- methyl acetamide, N, N- dimethylacetamide and the like, N- lactone-methylpyrrolidone, γ- and butynyl. These solvents may be used alone or in combination of two or more.

Hereinafter, the use of the resist lower layer film forming composition of the present invention will be described.

(E.g., a silicon wafer substrate, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, and a low dielectric constant material Etc.) is coated with a composition for forming a resist lower layer film of the present invention by an appropriate application 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 to 250 DEG C and a firing time of 0.3 to 60 minutes. The baking temperature is preferably 150 to 250 DEG C, and the baking time is 0.5 to 2 minutes. The film thickness of the lower layer film formed here is, for example, 10 to 1000 nm, or 20 to 500 nm, or 50 to 300 nm, or 100 to 200 nm.

Then, for example, a photoresist layer is formed on the lower resist film. The photoresist layer can be formed by a well-known method, that is, coating and firing of the photoresist composition solution onto the lower layer film. The film thickness of the photoresist is, for example, 50 to 10000 nm, or 100 to 2000 nm, or 200 to 1000 nm.

The photoresist to be formed on the resist underlayer film of the present invention is not particularly limited as long as it can be sensitized to light used for exposure. Both negative photoresists and positive photoresists can be used. A positive photoresist comprising novolac resin and 1,2-naphthoquinone diazidesulfonic acid ester, a chemically amplified photoresist comprising a binder having a group which is decomposed by an acid and which increases the alkali dissolution rate and a photoacid generator, A chemically amplified photoresist composed of a low molecular weight compound decomposed and increasing the alkali dissolution rate of the photoresist, an alkali soluble binder and a photoacid generator, and a binder having a group capable of decomposing by an acid to increase the alkali dissolution rate, A chemically amplified photoresist composed of a low molecular weight compound for increasing the alkali dissolution rate of the resist and a photoacid generator. For example, trade name APEX-E, manufactured by Shipley, PAR710, manufactured by Sumitomo Chemical Co., Ltd., and SEPR430, manufactured by Shin-Etsu Chemical Co., Also, for example, Proc. SPIE, Vol.3999, 330-334 (2000), Proc. SPIE, Vol.3999, 357-364 (2000) or Proc. SPIE, Vol. 3999, 365-374 (2000).

Then, exposure is performed through a predetermined mask. A KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), and an F2 excimer laser (wavelength: 157 nm) can be used for exposure. After exposure, a post exposure bake may be performed if necessary. The post-exposure baking is carried out under the conditions appropriately selected at a heating temperature of 70 ° C to 150 ° C and a heating time of 0.3 to 10 minutes.

In the present invention, a resist for electron beam lithography can be used instead of a photoresist as a resist. As the electron beam resist, both of a negative type and a positive type can be used. A chemically amplified resist comprising a binder having a group capable of decomposing alkali by decomposition by an acid generator and an acid, an alkali-soluble binder, an acid generator, and a low-molecular compound decomposing by an acid to change the alkali dissolution rate of the resist A chemically amplified resist, a chemically amplified resist comprising a photoacid generator and a binder having a group decomposed by an acid and changing the alkali dissolution rate and a low molecular compound decomposed by an acid to change the alkali dissolution rate of the resist, A non-chemically amplified resist comprising a binder having a group capable of changing an alkali dissolution rate, and a non-chemically amplified resist comprising a binder having a site cut by an electron beam and changing an alkali dissolution rate. Even when these electron beam resists are used, a resist pattern can be formed as in the case of using a photoresist with an electron beam as a radiation beam.

Next, development is carried out with a developing solution. Thus, for example, when a positive type photoresist is used, the photoresist of the exposed portion is removed to form a photoresist pattern.

Examples of the developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; and amine aqueous solutions such as ethanolamine, propylamine and ethylenediamine Alkaline aqueous solutions. Surfactants and the like may also be added to these developers. The development conditions are suitably selected at a temperature of 5 to 50 DEG C and a time of 10 to 600 seconds.

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

First, the resist lower layer film (intermediate layer) of the present invention where the photoresist is removed is removed by dry etching to expose the semiconductor substrate. For the dry etching of the resist lower layer film of the present invention, tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, Gases such as oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used. A halogen-based gas is preferably used for dry etching of the resist lower layer film. The dry etching using a halogen-based gas is basically difficult to remove the photoresist made of an organic material. On the other hand, the resist underlayer film of the present invention containing a large amount of silicon atoms is quickly removed by the halogen-based gas. Therefore, the film thickness reduction of the photoresist due to the dry etching of the resist lower layer film can be suppressed. As a result, it becomes possible to use a photoresist as a thin film. Resist lower layer film is dry-etched preferably by fluorine-based gas and fluorine-based gas, for example, tetrafluoromethane (CF _4), perfluoro-cyclobutane (C ₄ F _8), perfluoro-propane (C ₃ F ₈ ), trifluoromethane, and difluoromethane (CH ₂ F ₂ ).

Thereafter, the organic undercoat film is removed using the patterned photoresist and the resist undercoat film of the present invention as a protective film. It is preferable that the organic underlayer film (lower layer) is formed by dry etching with an oxygen-based gas. This is because the resist underlayer film of the present invention containing a large amount of silicon atoms is hardly removed by dry etching with an oxygen-based gas.

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

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

An organic antireflection film can be formed on the upper layer of the resist lower layer film of the present invention before forming the photoresist. The antireflection film composition used herein is not particularly limited and may be arbitrarily selected from those conventionally used in the lithography process. In addition, the antireflection film composition may be applied by a conventional method, for example, Can be formed.

In the present invention, it is possible to deposit an organic undercoat film on a substrate, to form a resist undercoat film of the present invention thereon, and to coat the photoresist thereon. As a result, the pattern width of the photoresist is narrowed. Even when the photoresist is thinly coated to prevent the pattern collapse, it is possible to process the substrate by selecting an appropriate etching gas. For example, it is possible to process the resist underlayer film of the present invention by using a fluorine-based gas having a sufficiently high etching rate with respect to the photoresist as an etching gas. Further, an oxygen-based gas having a sufficiently high etching rate for the resist underlayer film of the present invention It is possible to process an organic underlayer film by using it as an etching gas and to process the substrate by using a fluorine-based gas which has a sufficiently high etching rate with respect to the organic underlayer film as an etching gas.

The substrate to which the resist underlayer film forming composition of the present invention is applied may have an organic or inorganic antireflection film formed on the surface thereof by CVD or the like, and the underlayer film of the present invention may be formed thereon.

The resist undercoat film formed with the resist underlayer film forming composition of the present invention also has absorption of light depending on the wavelength of light used in the lithography process. In such a case, the under-resist film of the present invention can function as an antireflection film having an effect of preventing reflected light from the substrate. Further, the underlayer film of the present invention has a function of preventing the substrate from reacting with the substrate, the material used for the photoresist, or the substance generated during exposure to the photoresist, A layer having a function of preventing the diffusion of substances generated in the substrate to the upper layer photoresist during the heating and firing and a barrier layer for reducing the poisoning effect of the photoresist layer by the semiconductor substrate dielectric layer .

In addition, the resist underlayer film formed of the resist underlayer film forming composition of the present invention is applied to a substrate having via holes used in a dual damascene process, and can be used as a filling material capable of filling a hole without a gap. The lower resist film of the present invention can also be used as a flat fire for planarizing the surface of a semiconductor substrate having concave and convex portions.

Hereinafter, the present invention will be described more specifically by way of examples. The present invention is not limited thereto.

Example

(Analysis of Reaction Products of Isocyanate and Blocking Agent)

10 g of 3- (triethoxysilylpropyl) -isocyanate and 10 g of ethanol were placed in a 200 mL flask and refluxed for 2 hours. Thereafter, excess ethanol was distilled off to obtain a blocked isocyanate silane corresponding to the formula (A-50). This blocked isocyanate silane was measured to be a blocked isocyanate silane corresponding to the formula (A-50) by measuring the spectrum of NMR (nuclear magnetic resonance) and FT-IR (infrared absorption) shown below.

The results of NMR spectra are shown in Fig. NMR was measured at room temperature in a heavy DMSO solvent using ¹ H-NMR of 500 MHz (ECP500, manufactured by Nihon Denshi Co., Ltd.). The peak corresponding to (a) in the following structure has a broad peak near 5.0 ppm, the peak corresponding to (b) has a quadruple at 4.0 to 4.2 ppm, the peak corresponding to (c) A quartz line exists at 3.85 ppm, a peak corresponding to (d) has a quadruple at 3.1 to 3.2 ppm, a peak corresponding to (e) has a quintet at 1.55 to 1.62 ppm, And the peak corresponding to (g) had a triple line at 1.15 to 1.30 ppm, and the peak corresponding to (h) had a triple line at 0.60 to 0.65 ppm.

The FT-IR spectrum was measured by the ATR method. Device name using Nicolet6700 (Thermo FISHER SCIENTIFIC Co., Ltd.) and measuring apparatus is a wave number 4000 to 650cm ^-1 and the scan number is 32 times, the resolution was carried out by 8cm ^-1. The measurement spectrum of the IR spectrum is shown in Fig.

Peaks corresponding to the NH stretching vibration peak is present in 3340cm ^-1 and corresponding to the CH stretching vibrations of the CH ₃ peak is present in 2975cm ^-1 and corresponding to the CH stretching vibrations of the CH ₂ is 2929cm ^-1, 2887cm ^- present in ^1, and C = O stretching vibration peak corresponding to the (amide I) is present in 1700cm ^-1, amide NH byeongak vibration peak corresponding to the (amide II) is present in the 1533cm ^-1, and CH ₂ CH The peak corresponding to the gentle vibration exists at 1444 cm ^-1 , the CH speckle vibration of CH ₃ exists at 1390 cm ^-1 , the CO inverse symmetric stretching vibration exists at 1247 cm ^-1 , the Si-OC skeletal vibration is at 1102 cm ^-1 , 1066 cm < ^-1 >, and the Si-C rutting vibration was at 775 cm < ^{-1 &} gt ;.

Synthesis Example 1 (Synthesis of ICY70)

64.64 g of 3- (triethoxysilylpropyl) -isocyanate (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), 23.33 g of tetraethoxysilane (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), 87.98 g of ethanol, And dissolved. The resulting mixed solution was warmed and refluxed while stirring with a magnetic stirrer.

At this point, an ethanol solution containing a mixture of formula (A-50) and tetraethoxysilane was produced with a hydrolyzable organosilane containing blocked isocyanate groups.

Next, an aqueous solution prepared by dissolving 1.36 g of hydrochloric acid in 22.19 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-15). The obtained polymer contained about 70 mol% of the repeating unit derived from the formula (1).

The weight-average molecular weight of the obtained polymer by GPC was Mw 2200 in terms of polystyrene.

Synthesis Example 2 (Synthesis of ICY50)

47.25 g of 3- (triethoxysilylpropyl) -isocyanate, 39.79 g of tetraethoxysilane, and 87.04 g of ethanol were placed in a 300 mL flask and dissolved. The resulting mixture was warmed and refluxed with stirring on a magnetic stirrer. At this point, an ethanol solution containing a mixture of formula (A-50) and tetraethoxysilane was produced with a hydrolyzable organosilane containing blocked isocyanate groups.

Next, an aqueous solution in which 1.39 g of hydrochloric acid was dissolved in 24.08 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-15). The obtained polymer contained about 50 mol% of the repeating units derived from the formula (1). The weight-average molecular weight of the obtained polymer by GPC was Mw 2600 in terms of polystyrene.

Synthesis Example 3 (Synthesis of ICY30)

29.15 g of 3- (triethoxysilylpropyl) -isocyanate, 57.29 g of tetraethoxysilane, and 86.44 g of ethanol were placed in a 300 mL flask and dissolved. The resulting mixture was warmed and refluxed with stirring on a magnetic stirrer. At this point, an ethanol solution containing a mixture of formula (A-50) and tetraethoxysilane was produced with a hydrolyzable organosilane containing blocked isocyanate groups. Next, an aqueous solution prepared by dissolving 1.43 g of hydrochloric acid in 26.18 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-15). The obtained polymer contained about 30 mol% of the repeating unit derived from the formula (1). The weight average molecular weight of the obtained polymer by GPC was Mw 3100 in terms of polystyrene.

Synthesis Example 4 (Synthesis of ICY10)

9.95 g of 3- (triethoxysilylpropyl) -isocyanate, 75.42 g of tetraethoxysilane, and 87.04 g of ethanol were placed in a 300 mL flask and dissolved. The resulting mixture was warmed and refluxed with stirring on a magnetic stirrer. At this point, an ethanol solution containing a mixture of formula (A-50) and tetraethoxysilane was produced with a hydrolyzable organosilane containing blocked isocyanate groups. Next, an aqueous solution in which 1.47 g of hydrochloric acid was dissolved in 28.25 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-15). The obtained polymer contained about 10 mol% of the repeating unit derived from the formula (1). The weight average molecular weight of the obtained polymer by GPC was Mw 6500 in terms of polystyrene.

Synthesis Example 5 (Synthesis in MeOH)

5.26 g of 3- (triethoxysilylpropyl) -isocyanate, 51.20 g of tetraethoxysilane, 22.77 g of methyltriethoxysilane (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), Phenyltrimethoxysilane (manufactured by TOKYO CHEMICAL INDUSTRY CO , LTD.) And 85.45 g of methanol were placed in a 300 mL flask and dissolved. The resulting mixture was warmed and refluxed with stirring on a magnetic stirrer. At this point, a methanol solution containing a mixture of (A-49), tetraethoxysilane, methyltriethoxysilane and phenyltrimethoxysilane was produced with a hydrolyzable organosilane containing a blocked isocyanate group.

Next, an aqueous solution prepared by dissolving 1.55 g of hydrochloric acid in 27.59 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-24). The obtained polymer contained about 5 mol% of the repeating units derived from the formula (1). The weight average molecular weight of the obtained polymer by GPC was Mw 8000 in terms of polystyrene.

Synthesis Example 6 (Synthesis in EtOH)

A mixture obtained by dissolving 5.26 g of 3- (triethoxysilylpropyl) -isocyanate, 51.20 g of tetraethoxysilane, 22.77 g of methyltriethoxysilane, 4.22 g of phenyltrimethoxysilane and 85.45 g of ethanol into a 300 mL flask and mixing The solution was warmed and refluxed with stirring on a magnetic stirrer. At this point, an ethanol solution containing a mixture of (A-50), tetraethoxysilane, methyltriethoxysilane and phenyltrimethoxysilane was produced with a hydrolyzable organosilane containing a blocked isocyanate group.

Next, an aqueous solution prepared by dissolving 1.55 g of hydrochloric acid in 27.59 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-25). The obtained polymer contained about 5 mol% of the repeating units derived from the formula (1). The weight-average molecular weight of the obtained polymer by GPC was Mw 6300 in terms of polystyrene.

Synthesis Example 7 (Synthesis in 1-BuOH)

5.26 g of 3- (triethoxysilylpropyl) -isocyanate, 51.20 g of tetraethoxysilane, 22.77 g of methyltriethoxysilane, 4.22 g of phenyltrimethoxysilane and 85.45 g of 1-butanol were dissolved in a 300 mL flask The obtained mixed solution was warmed and refluxed while stirring with a magnetic stirrer. At this point, a 1-butanol solution containing a mixture of (A-51), tetraethoxysilane, methyltriethoxysilane and phenyltrimethoxysilane was produced with a hydrolyzable organosilane containing blocked isocyanate groups. Next, an aqueous solution prepared by dissolving 1.55 g of hydrochloric acid in 27.59 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-26). The obtained polymer contained about 5 mol% of the repeating units derived from the formula (1). The weight-average molecular weight of the obtained polymer by GPC was 21,000 in terms of polystyrene.

Synthesis Example 8 (Synthesis in 2-BuOH)

5.26 g of 3- (triethoxysilylpropyl) -isocyanate, 51.20 g of tetraethoxysilane, 22.77 g of methyltriethoxysilane, 4.22 g of phenyltrimethoxysilane and 85.45 g of 2-butanol were dissolved in a 300 mL flask The resulting mixed solution was warmed and refluxed while stirring with a magnetic stirrer. At this point, a 2-butanol solution containing a mixture of (A-52), tetraethoxysilane, methyltriethoxysilane and phenyltrimethoxysilane was produced with a hydrolyzable organosilane containing blocked isocyanate groups. Next, an aqueous solution prepared by dissolving 1.55 g of hydrochloric acid in 27.59 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-27). The obtained polymer contained about 5 mol% of the repeating units derived from the formula (1). The weight-average molecular weight of the obtained polymer by GPC was Mw 10500 in terms of polystyrene.

Synthesis Example 9 (Synthesis in t-BuOH)

5.26 g of 3- (triethoxysilylpropyl) -isocyanate, 51.20 g of tetraethoxysilane, 22.77 g of methyltriethoxysilane, 4.22 g of phenyltrimethoxysilane and 85.45 g of t-butanol were dissolved in a 300 mL flask The resulting mixed solution was warmed and refluxed while stirring with a magnetic stirrer. At this point, a 2-butanol solution containing a mixture of (A-53), tetraethoxysilane, methyltriethoxysilane and phenyltrimethoxysilane was produced as the hydrolyzable organosilane containing the blocked isocyanate group. Next, an aqueous solution prepared by dissolving 1.55 g of hydrochloric acid in 27.59 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The resulting polymer has a partial structure corresponding to the formula (C-28). The obtained polymer contained about 5 mol% of the repeating units derived from the formula (1). The weight-average molecular weight of the obtained polymer by GPC was Mw 8300 in terms of polystyrene.

Synthesis Example 10

6.68 g of N- [5- (trimethoxysilyl) -2-aza-oxo-pentyl] caprolactam (formula (A-83), manufactured by AZmax Co. Ltd.), 52.50 g of tetraethoxysilane, 22.47 g of triethoxysilane, 4.16 g of phenyltrimethoxysilane, and 85.82 g of acetone were placed in a 300 mL flask and dissolved. The resulting mixture was warmed and refluxed with stirring on a magnetic stirrer.

Next, an aqueous solution prepared by dissolving 1.53 g of hydrochloric acid in 27.23 g of ion-exchanged water was added to the mixed solution. After reacting for 120 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. It can be considered that the obtained polymer has a partial structure corresponding to the formula (C-30). The obtained polymer contained about 5 mol% of the repeating units derived from the formula (1). The weight-average molecular weight of the obtained polymer by GPC was Mw5000 in terms of polystyrene.

Synthesis Example 11

To a solution of 6.78 g of 9-fluorenylmethyl chloroformate dissolved in 150 mL of tetrahydrofuran, 5.80 g of 3-aminopropyltriethoxysilane dissolved in 70 mL of tetrahydrofuran and 2.98 g of triethylamine were stirred in an ice bath . After completion of the dropwise addition, the reaction solution was allowed to stand at room temperature and stirred for 40 minutes. Then, triethylamine hydrochloride was filtered off and the filtrate was subjected to solvent removal to obtain a white solid. The resulting solid was recrystallized from hexane to obtain the desired compound (A-89).

The obtained compound (A-89) was confirmed by 1 H-NMR measurement.

The measurement was carried out using a sample tube (5 mm), a solvent (deuterated chloroform), a measurement temperature (room temperature), a pulse interval (5 seconds), the number of times of integration (16 times) and a reference sample (tetramethylsilane: TMS).

(Q, 2H), 3.22 ppm (q, 2H), 3.82 ppm (q, 3.82H), 1.27 ppm (t, , 4.22 ppm (t, 1H), 4.39 ppm (d, 2H), 5.06 ppm (s, 1H), 7.30 to 7.42 ppm (m, 4H) and 7.59 to 7.77 ppm (m, 4H).

Next, 2.00 g of the compound (A-89), 0.89 g of phenyltrimethoxysilane, 11.25 g of tetraethoxysilane, 4.81 g of methyltriethoxysilane and 28.43 g of acetone were put into a 100 mL three-necked flask The mixed solution obtained by dissolving was warmed and refluxed while stirring with a magnetic stirrer. Next, an aqueous solution obtained by dissolving 0.01 g of hydrochloric acid in 5.83 g of ion-exchanged water was added to the mixed solution. After reacting for 240 minutes, the obtained reaction solution was cooled to room temperature. Thereafter, 20.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and methanol, ethanol, microcrystalline, and hydrochloric acid, which are by-products, were removed by decantation to obtain a hydrolyzed condensate solution.

The obtained polymer is considered to have a partial structure of formula (C-31).

The weight-average molecular weight of the obtained polymer by GPC was Mw2100 in terms of polystyrene.

Comparative Synthesis Example 1 (Synthesis of ICY0 (TEOS100)

84.63 g of tetraethoxysilane and 84.63 g of ethanol were placed in a 300 ml flask and dissolved. The resulting mixture was warmed and refluxed with stirring on a magnetic stirrer. Next, an aqueous solution prepared by dissolving 1.48 g of hydrochloric acid in 29.26 g of ion-exchanged water was added to the mixed solution. After reacting for 60 minutes, the obtained reaction solution was cooled to room temperature. Then, 200 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-products, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. The weight-average molecular weight of the obtained polymer by GPC was Mw 6200 in terms of polystyrene.

Example 1

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 1 to prepare a composition for forming a resist lower layer film.

Example 2

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 2 to prepare a composition for forming a resist lower layer film.

Example 3

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 3 to prepare a composition for forming a resist lower layer film.

Example 4

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 4 to prepare a composition for forming a resist lower layer film.

Example 5

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 5 to prepare a composition for forming a resist lower layer film.

Example 6

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 6 to prepare a composition for forming a resist lower layer film.

Example 7

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 7 to prepare a composition for forming a resist lower layer film.

Example 8

To 5.0 g of a solution containing the polymer obtained in Synthesis Example 8 (polymer concentration: 15 mass%), 25.0 g of propylene glycol monomethyl ether acetate was added to prepare a composition for forming a resist lower layer film.

Example 9

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 9 to prepare a composition for forming a resist lower layer film.

Example 10

25.0 g of propylene glycol monomethyl ether was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 10 to prepare a composition for forming a resist lower layer film.

Example 11

25.0 g of propylene glycol monomethyl ether was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Synthesis Example 11 to prepare a composition for forming a resist lower layer film.

Comparative Example 1

25.0 g of propylene glycol monomethyl ether acetate was added to 5.0 g of a solution (polymer concentration: 15 mass%) containing the polymer obtained in Comparative Synthesis Example 1 to prepare a composition for forming a resist lower layer film.

(Solvent resistance test)

The composition for forming a resist lower layer film was applied on a silicon wafer by a spin coating method and fired on a hot plate at 240 캜 for 1 minute to form a resist lower layer film. Thereafter, the film was immersed in propylene glycol monomethyl ether acetate used for the overcoat resist composition solvent for one minute. When the change in film thickness of the resist underlayer film before and after immersion was 2 nm or less, it was judged to be good and indicated by the symbol " O ". The results are shown in Table 1.

(Optical constant)

The resist underlayer film forming composition was applied on a silicon wafer using a spinner. And heated on a hot plate at 240 DEG C for 1 minute to form a resist lower layer film (film thickness 0.09 mu m). The refractive index (n value) and the optical absorption coefficient (also referred to as a damping coefficient) of the resist underlayer film at a wavelength of 193 nm were measured using a spectroscopic ellipsometer (VUV-VASE VU-302, manufactured by JA Woollam) . The results are shown in Table 1.

(Measurement of dry etching rate)

Etching and etching gases used for measuring the dry etching rate were as follows.

ES401 (Nippon Scientific Co., Ltd. No.): CF ₄

RIE-10NR (made by SAMCO Inc.): O ₂

The solutions of the resist lower layer film forming compositions prepared in Examples 1 to 11 and Comparative Example 1 were each coated on a silicon wafer using a spinner. By heating 240 ℃, 1 minutes in a hot plate to form a resist underlayer film and using each of the CF ₄ gas, O ₂ gas as an etching gas to measure the etching rate.

In the same manner, a photoresist solution (trade name UV113, manufactured by Shipley) was applied to a silicon wafer using a spinner to form resist films each having a thickness of 0.20 mu m. The dry etching rate was measured using CF ₄ gas and O ₂ gas as the etching gas, respectively. Then, the dry etching rate between the lower resist film and the resist film was compared. The results are shown in Table 1. The etching rate ratio is the dry etching rate ratio of (resist underlayer film) / (resist).

Solvent resistance
Refractive index n
(Wavelength: 193 nm)
Optical absorption coefficient k
(Wavelength: 193 nm) Etching rate ratio CF ₄ O ₂ Example 1 ○ 1.68 0.04 2.30 0.06 Example 2 ○ 1.68 0.03 2.15 0.05 Example 3 ○ 1.56 0.03 2.11 0.04 Example 4 ○ 1.46 0.03 1.79 0.02 Comparative Example 1 ○ 1.48 0.00 1.32 0.01

As shown in Table 1, it was found that the CF ₄ dry etching rate was improved as the amount of isocyanate groups blocked with ethanol in the polymer was increased.

(Minimum curing temperature)

On each of the silicon wafers, the resist underlayer film forming compositions of Examples 5 to 11 were applied to the respective substrates by spin coating and baked on a hot plate at 20 占 폚 for 1 minute from 100 占 폚 to 300 占 폚. Thereafter, the substrate was immersed in propylene glycol monomethyl ether acetate used for the solvent of the overcoat resist composition for 1 minute, and the temperature at which the change in film thickness of the resist underlayer film before and after immersion was 2 nm or less was defined as the lowest curing temperature (Table 2).

Minimum curing temperature
Refractive index n
(Wavelength: 193 nm)
Optical absorption coefficient k
(Wavelength: 193 nm)
Etching rate ratio CF ₄ O ₂ Example 5 180 DEG C 1.60 0.11 1.83 0.02 Example 6 160 ° C 1.61 0.12 1.77 0.02 Example 7 260 ℃ 1.61 0.11 1.94 0.03 Example 8 160 ° C 1.61 0.10 1.91 0.02 Example 9 100 ℃ 1.61 0.10 1.92 0.02 Example 10 160 ° C 1.59 0.11 2.00 0.02 Example 11 140 ° C 1.60 0.16 1.89 0.02

By changing the kind of the blocking agent of the block isocyanate, the deblocking temperature is changed, and thus the temperature at which the crosslinking occurs is controlled, so that the curability can be controlled.

The resist undercoat film obtained from the resist underlayer film forming composition according to the present invention has a sufficiently high dry etching rate with respect to the photoresist film.

The obtained hydrolysis-condensation product is a polymer, and it may contain a repeating unit derived from the formula (1) in a proportion of 1 mol% to 100 mol% in all the repeating units of the polymer. As shown in the examples, the polymer can be provided with solvent resistance by containing 5 mol% or more of the repeating units derived from the formula (1). Including 80 mol% of the repeating unit derived from the formula (1) in the polymer can also provide a film with an improved etching rate.

The deblocking temperature differs depending on the kind of the deblocking agent, and the curing temperature can be determined by selecting an appropriate deblocking agent. One type of de-blocking agent may be used, or a mixture of various types may be used.

The resist underlayer film obtained from the resist underlayer film forming composition according to the present invention has a high dry etching rate. Therefore, even if the thickness of the resist film is reduced to prevent pattern collapse due to miniaturization of the pattern size, the resist underlayer film has a sufficiently high etching rate, and therefore, the resist pattern can be transferred to the lower layer.

Claims (11)

A hydrolyzable organosilane containing a blocked isocyanate group, a hydrolyzate thereof or a hydrolyzed condensate thereof,
Wherein the hydrolyzable organosilane is represented by the formula (1):
[Chemical Formula 1]

(Wherein,
R ¹ represents an isocyanate group, a blocked isocyanate group or an organic group containing the same, and the N atom or C atom at the terminal is bonded to the Si atom to form a Si-N bond or a Si-C bond,
R ² represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, Bonded to form a Si-C bond,
R ³ represents an alkoxy group, an acyloxy group or a halogen atom,
a represents an integer of 1 or 2,
b represents 0 or an integer of 1,
and a + b represents an integer of 1 or 2)
Wherein the blocked isocyanate group is represented by the formula (3):
(3)

(Wherein,
R ⁴ represents a single bond, an alkylene group, a cycloalkylene group or an arylene group,
And R < ⁵ > represents an active hydrogen-containing compound residue)
A resist lower layer film forming composition for lithography.
delete delete delete The method according to claim 1,
Wherein the active hydrogen containing compound residue is selected from the group consisting of alcohol residues, phenol residues, phenol derivative residues, polycyclic phenol residues, amide residues, imide residues, imine residues, thiol residues, oxime residues, lactam residues, A composition for forming a resist lower layer film which is a compound residue.
6. The method according to claim 1 or 5,
Equation (4)
[Chemical Formula 4]

(Wherein,
R ⁶ represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, Bonded to form a Si-C bond,
R ⁷ represents an alkoxy group, an acyloxy group or a halogen atom,
and a represents an integer of 0 to 3) and formula (5)
[Chemical Formula 5]

(Wherein,
R ⁸ represents an alkyl group,
R ⁹ represents an alkoxy group, an acyloxy group or a halogen atom,
Y represents an alkylene group or an arylene group,
b represents 0 or an integer of 1,
and c represents an integer of 0 or 1) with a hydrolyzable organosilane of the formula (1), a hydrolyzate thereof, or a hydrolyzed condensate thereof A resist underlayer film forming composition.
A compound of formula (1) as defined in any one of claims 1 to 5, or a compound of formula (1) and
Equation (4)
[Chemical Formula 4]

(Wherein,
R ⁶ represents an organic group having an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group or a cyano group, Bonded to form a Si-C bond,
R ⁷ represents an alkoxy group, an acyloxy group or a halogen atom,
and a represents an integer of 0 to 3.)
As a polymer, a hydrolysis-condensation product of a compound of the formula
6. The method according to claim 1 or 5,
Further comprising a curing catalyst.
A resist underlayer film obtained by applying the resist lower layer film forming composition according to any one of claims 1 to 5 on a semiconductor substrate and firing the same.
A process for forming a resist underlayer film by applying and firing a composition for forming a resist lower layer film as set forth in any one of claims 1 to 5 on a semiconductor substrate, a step for applying a resist composition onto the underlayer film, A step of exposing the film, a step of developing the resist after exposure to obtain a resist pattern, a step of etching the resist lower layer film by the resist pattern, and a step of processing the semiconductor substrate by the patterned resist and the resist lower layer film ≪ / RTI >
A step of forming an organic undercoat film on a semiconductor substrate, a step of applying a resist underlayer film forming composition according to claim 1 or 5 onto the organic undercoat film and firing to form a resist undercoat film, A step of forming a resist film by applying a resist composition, a step of exposing the resist film, a step of developing the resist after exposure to obtain a resist pattern, a step of etching the resist lower layer film by a resist pattern, A step of etching the organic underlayer film; and a step of processing the semiconductor substrate by the patterned organic underlayer film.

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