KR20130009774A - Silicon-containing resist underlayer-forming composition containing amic acid - Google Patents

Abstract

[PROBLEMS] To provide a resist underlayer film forming composition for lithography for forming a resist underlayer film that can be used as a hard mask.
[Solution] A composition comprising a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolyzate condensate thereof as a silane compound, wherein the silane compound includes an amide bond, a carboxylic acid moiety or a carboxylic acid moiety in the molecule; A resist underlayer film forming composition for lithography comprising a silane compound comprising an organic group comprising these two parts. The resist underlayer film forming composition for lithography in which the ratio of the silane compound containing the amide bond and the carboxylic acid moiety or the carboxylic acid ester moiety or the organic group including these two parts is present in the ratio of less than 5 mol% in the entire silane compound. . Formation of the resist underlayer film for lithography in which the ratio of the amide compound and the silane compound containing the carboxylic acid part or the carboxylic acid ester part or the organic group containing these two parts exists in the ratio of 0.5-4.9 mol% in the said silane compound whole. Composition.

Description

Silicon-containing resist underlayer film-forming composition containing amic acid {SILICON-CONTAINING RESIST UNDERLAYER-FORMING COMPOSITION CONTAINING AMIC ACID}

This invention relates to the composition for forming an underlayer film between the board | substrate used for manufacture of a semiconductor device, and a resist (for example, photoresist, an electron beam resist). Specifically, it relates to the resist underlayer film forming composition for lithography for forming the underlayer film used for the underlayer of a photoresist in the lithographic process of semiconductor device manufacture. Moreover, it is related with the formation method of the resist pattern using the said underlayer film forming composition.

Background Art Conventionally, in manufacturing semiconductor devices, fine processing by lithography using photoresist has been performed. The fine processing is performed by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating and developing active light such as ultraviolet rays through a mask pattern on which a pattern of a semiconductor device is drawn thereon, and developing a photoresist pattern obtained by a protective film. It is the processing method of forming the fine unevenness | corrugation corresponding to the said pattern on the surface of a board | substrate by etching a board | substrate. By the way, as the integration of semiconductor devices has increased in recent years, the active light used has also become a short wavelength from an KrF excimer laser (248 nm) to an ArF excimer laser (193 nm). Accordingly, the influence of the reflection of the actinic light from the semiconductor substrate has been a major problem.

As the underlayer film between the semiconductor substrate and the photoresist, a film known as a hard mask containing a metal element such as silicon or titanium is used (see Patent Document 1, for example). In this case, there is a big difference in the constituents between the resist and the hard mask, so the rate of removal by these dry etching greatly depends on the gas species used for the dry etching. By appropriately selecting the gas species, the hard mask can be removed by dry etching without greatly reducing the film thickness of the photoresist. As described above, in the recent manufacture of semiconductor devices, in order to achieve various effects including antireflection effects, a resist underlayer film is arranged between the semiconductor substrate and the photoresist. And although the composition of the resist underlayer film was examined until now, development of the new material for a resist underlayer film is calculated | required by the diversity of the characteristic calculated | required.

As the underlayer film between the semiconductor substrate and the photoresist, a film known as a hard mask containing a metal element such as silicon or titanium is used (see Patent Document 1, for example). In this case, there is a big difference in the constituents between the resist and the hard mask, so the rate of removal by these dry etching greatly depends on the gas species used for the dry etching. By appropriately selecting the gas species, the hard mask can be removed by dry etching without greatly reducing the film thickness of the photoresist. As described above, in the recent manufacture of semiconductor devices, in order to achieve various effects including antireflection effects, a resist underlayer film is arranged between the semiconductor substrate and the photoresist. And although the composition of the resist underlayer film was examined until now, development of the new material for a resist underlayer film is calculated | required by the diversity of the characteristic calculated | required.

A composition and a pattern formation method using the compound which has the bond of silicone and silicone are known (for example, refer patent document 2).

Moreover, the silicon containing upper surface antireflection film which has a dicarboxyimide structure is described (for example, refer patent document 3).

Japanese Patent Laid-Open No. H11-258813 Japanese Patent Application Laid-Open No. H10-209134 Japanese Patent Publication No. 2008-519297

The objective of this invention is providing the resist underlayer film forming composition for lithography which can be used for manufacture of a semiconductor device. Specifically, it is to provide a resist underlayer film forming composition for lithography for forming a resist underlayer film that can be used as a hard mask. Moreover, it is providing the resist underlayer film forming composition for lithography for forming the resist underlayer film which can be used as an antireflection film. Moreover, it is providing the resist underlayer film for lithography which does not produce intermixing with a resist, and has a large dry etching rate compared with a resist, and the resist underlayer film forming composition for forming the said underlayer film.

An object of the present invention is to provide a method of forming a resist pattern using the resist underlayer film forming composition for lithography.

In a first aspect, the present invention provides a resist underlayer film-forming composition for lithography comprising, as a silane compound, a hydrolyzable organosilane, a hydrolyzate thereof, a hydrolysis condensate thereof, or a mixture thereof. A resist underlayer film-forming composition for lithography comprising an amide compound in a molecule and a silane compound containing a carboxylic acid moiety or a carboxylic acid moiety or an organic group comprising these two moieties,

As a 2nd viewpoint, the ratio of the silane compound containing the amide bond and the carboxylic acid part, the carboxylic acid ester part, or the organic group containing these two parts in all the said silane compounds is less than 5 mol%, The description of the 1st viewpoint A resist underlayer film forming composition for lithography,

As a 3rd viewpoint, the 1st viewpoint that the ratio of the silane compound containing the amide bond and the carboxylic acid part, the carboxylic acid ester part, or the organic group containing these two parts in the said silane compound whole is 0.5-4.9 mol%. The resist underlayer film forming composition for lithography described in

As a fourth aspect, the hydrolyzable organosilane is represented by Formula (1):

[Formula 1]

(In formula, R <^3> is an organic group containing an amide bond, a carboxylic acid part, a carboxylic acid ester part, or these two parts, and shows the group couple | bonded with the silicon atom by Si-C bond. R <^1> is an alkyl group , An organic group having 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, or a cyano group, and bonded to a silicon atom by a Si-C bond. R <^2> represents an alkoxy group, an acyloxy group, or a halogen atom. An integer of 0 or 1, and b represents an integer of 1 or 2.), the composition according to any one of the first to third aspects, which is a compound represented by

As a fifth aspect, Equation (2):

[Formula 2]

(Wherein R ⁴ is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, acryloyl group, methacryloyl group, mercapto group, alkoxyaryl group, acyloxyaryl group, or cyano group) And an organic group having a group bonded to a silicon atom by a Si-C bond, R ⁵ represents an alkoxy group, an acyloxy group, or a halogen atom, and a represents an integer of 0 to 3). Organosilicon compounds,

And formula (3):

(3)

(Wherein R ⁶ represents an alkyl group, R ⁷ represents an alkoxy group, acyloxy group, or halogen atom, Y represents an alkylene group or arylene group, b represents an integer of 0 or 1, c is 0 Or at least one selected from the group consisting of organosilicon compounds represented by

The composition as described in any one of a 1st viewpoint thru | or a 4th viewpoint containing the combination of the hydrolysable organosilane represented by said formula (1), its hydrolyzate, or its hydrolysis condensate,

As a 6th viewpoint, the hydrolysis-condensation product of the hydrolyzable organosilane represented by said Formula (1), or the hydrolyzable organosilane represented by said Formula (1), and the valence of the compound represented by Formula (2) The composition according to any one of the first to fifth aspects comprising a decomposition condensate as a polymer,

As a seventh aspect, the composition according to any one of the first to sixth aspects, further comprising an acid as a hydrolysis catalyst,

As a 8th viewpoint, the composition in any one of the 1st thru | or 7th viewpoint which further contains water,

As a 9th viewpoint, the resist underlayer film obtained by apply | coating and baking the resist underlayer film forming composition in any one of a 1st viewpoint thru | or an 8th viewpoint on a semiconductor substrate,

10th viewpoint WHEREIN: The process of apply | coating the resist underlayer film forming composition in any one of a 1st viewpoint thru | or 8 viewpoint on a semiconductor substrate, baking, and forming a resist underlayer film, and the composition for resist on the said underlayer film Forming a resist film by coating a film; exposing the resist film; developing the resist film after exposure to obtain a patterned resist film; etching a resist underlayer film with the patterned resist film; and patterning A method for manufacturing a semiconductor device, comprising the step of processing a semiconductor substrate with a resist film and a resist underlayer film, and

As an 11th viewpoint, the process of forming an organic underlayer film on a semiconductor substrate, The process of apply | coating and baking the resist underlayer film forming composition in any one of a 1st viewpoint thru | or an 8th viewpoint on it, and baking it to form a resist underlayer film Applying a resist composition on the resist underlayer film to form a resist film; exposing the resist film; developing the resist film after exposure to obtain a patterned resist film; resist underlayer with the patterned resist film A method of manufacturing a semiconductor device including a step of etching a film, a step of etching an organic underlayer film by a patterned resist underlayer film, and a step of processing a semiconductor substrate by a patterned organic underlayer film.

Hydrolyzable groups, such as an alkoxy group, an acyloxy group, and a halogen atom, in a compound represented by the said Formula (1) are hydrolyzed or partially hydrolyzed, and the condensation reaction of a subsequent silanol group forms the polymer which has a polysiloxane structure as a principal chain. do. By this polysiloxane structure, the resist underlayer film containing the said polymer has a high dry etching resistance with respect to an oxygen type dry etching gas. In addition, this polymer has a carbon-nitrogen bond or a carbon-oxygen bond. With the above structure, the film containing the polymer has a high dry etching rate by the halogen-based gas, so that the upper resist pattern can be transferred to the film. According to these characteristics, the resist underlayer film formed from the resist underlayer film forming composition of this invention containing the said polymer can function as a hard mask.

In addition, according to the method for manufacturing a semiconductor device of the present invention, since the upper resist pattern can be transferred to the resist underlayer film more accurately than the conventional resist underlayer film, a good resist pattern shape can be obtained.

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

After forming a fine pattern, the resist film thickness tends to be thin in order to prevent pattern collapse. Dry etching for transferring a pattern to a film present in the lower layer by thinning the resist can transfer the pattern only when the etching rate is higher than that of the upper layer film. In the present invention, a resist underlayer film (containing an inorganic silicon-based compound) of the present invention is coated on the substrate without interposing an organic underlayer film or an organic underlayer film therebetween, followed by a resist film (organic resist film). Covered with Since the dry etching rate of the organic component film and the inorganic component film are greatly different depending on the selection of the etching gas, the dry etching rate of the organic component film is increased by the oxygen-based gas, and the film of the inorganic component is faster by the halogen-containing gas.

For example, a resist pattern is formed, and the resist underlayer film of this invention which exists in the lower layer is dry-etched with a halogen containing gas, the pattern is transferred to a resist underlayer film, and the halogen containing gas is carried out by the pattern transferred to the resist underlayer film. Substrate processing is carried out using. Alternatively, the organic underlayer film of the lower layer is dry-etched with an oxygen-based gas by using a pattern transferred resist underlayer film, the pattern is transferred to the organic underlayer film, and the substrate transfer is performed on the pattern transferred organic underlayer film using a halogen-containing gas. Do it.

In the present invention, the resist underlayer film functions as a hard mask.

Hydrolyzable groups, such as an alkoxy group, an acyloxy group, and a halogen atom, in the structure of said Formula (1) hydrolyze to partial hydrolysis, and form a polymer of a polysiloxane structure by condensation reaction of a silanol group after that. This polyorganosiloxane structure has sufficient function as a hard mask.

In addition, since these bonding sites included in the polyorganosiloxane have carbon-nitrogen bonds or carbon-oxygen bonds, the dry etching rate of the halogen-based gas is faster than that of the carbon-carbon bonds. It is available when transferring to the membrane.

And a polyorganosiloxane structure (intermediate film) is effective as a hard mask for the etching of the organic underlayer film which exists under it, and the process (etching) of a board | substrate. That is, it has sufficient dry etching resistance with respect to the oxygen type dry etching gas of a board | substrate process or an organic underlayer film.

The resist underlayer film of this invention is equipped with the improvement of the dry etching rate with respect to these upper layer resists, and dry etching resistance at the time of a board | substrate process.

And a favorable resist pattern shape can be formed.

The present invention provides a resist underlayer film-forming composition for lithography comprising a hydrolyzable organosilane, a hydrolyzate, or a hydrolyzed condensate thereof as a silane compound, wherein the silane compound has an amide bond, a carboxylic acid moiety or a carboxylic acid moiety in its molecule. A resist underlayer film forming composition for lithography comprising a silane compound containing a main acid ester moiety or an organic group comprising these two parts.

The hydrolyzable organosilane is described as having an amide bond in its molecule and an organic group comprising a carboxylic acid moiety or a carboxylic acid ester moiety or two parts thereof, but this is a combination of an amide bond and a carboxylic acid moiety in the silane molecule. (Amic acid structure) or an amide bond and a carboxylic acid ester moiety (amic acid ester structure), or both.

The silane compound which contains the amide bond and the carboxylic acid part, the carboxylic acid ester part, or the organic group containing these two parts in all the said silane compounds is less than 5 mol%, for example, 0.5-4.9 mol%, 0.5- 1.0 mol% or 0.5 to 0.999 mol%.

And the hydrolyzable organosilane mentioned above, its hydrolyzate, and its hydrolysis condensate can also be used as these mixture. The hydrolyzable organosilane can be hydrolyzed and the resulting hydrolyzate can be used as a condensate. When obtaining a hydrolysis condensate, the partial hydrolyzate or silane compound which hydrolysis is not fully completed may be mixed with a hydrolysis condensate, and the mixture may be used. This condensate is a polymer having a polysiloxane structure. The polysiloxane is bonded to an amide bond and an organic group comprising a carboxylic acid moiety or a carboxylic acid ester moiety or two parts thereof.

The resist underlayer film-forming composition of the present invention comprises a hydrolyzable organosilane having a amide bond, an carboxylic acid moiety, a carboxylic acid ester moiety, or an organic group comprising these two parts, a hydrolyzate thereof, or a hydrolytic condensate thereof, Contains a solvent. And as an optional component, an acid, water, alcohol, a curing catalyst, an acid generator, another organic polymer, a light absorbing compound, surfactant, etc. can be included.

Solid content in the resist underlayer film forming composition of this invention is 0.5-50 mass%, or 1-30 mass%, 1-25 mass%, for example. Here, solid content remove | excludes a solvent component from all the components of the resist underlayer film forming composition.

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

The hydrolyzable organosilane used for this invention has a structure represented by Formula (1).

R ³ represents an amide bond, an organic group comprising a carboxylic acid moiety or a carboxylic acid ester moiety, or two parts thereof, and represents a group bonded to a silicon atom by a Si—C bond. R ¹ is 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, or a cyano group and a silicon atom by a Si-C bond. Group is combined with. R ² represents an alkoxy group, acyloxy group, or halogen atom group. a represents the integer of 0 or 1, and b represents the integer of 1 or 2.

In formula (1), the alkyl group in R ¹ is a linear or branched alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl -n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group , 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n- Butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group And a 1-ethyl-2-methyl-n-propyl group.

Moreover, although an cyclic alkyl group can also be used as an alkyl group, For example, as a cyclic alkyl group of 1-10 carbon atoms, a cyclopropyl group, a cyclobutyl group, 1-methyl- cyclopropyl group, 2-methyl- cyclopropyl Group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl Group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2, 3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1- i-propyl-cyclopropyl , 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl 2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, etc. are mentioned.

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

Alkenyl groups include alkenyl groups having 2 to 10 carbon atoms, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2 -Butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-prop Phenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1 -Methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1- Butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-i-propylethenyl, 1,2-dimethyl-1-prop Phenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4 -Hexenyl group, 5-hexenyl group, 1-methyl-1-phene Neyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl -2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2- Pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4- Methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1 , 2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1 -Butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3- Dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group , 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2 -Ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-prop Phenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3- Methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3 A cyclohexenyl group etc. are mentioned.

Moreover, the organic group in which halogen atoms, such as fluorine, chlorine, bromine, or iodine, were substituted to these is mentioned.

Examples of the organic group having an epoxy group include glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group, epoxycyclohexyl group, and the like.

Examples of the organic group having an acryloyl group include acryloylmethyl group, acryloylethyl group, acryloylpropyl group, and the like.

Examples of the organic group having a methacryloyl group include methacryloylmethyl, methacryloylethyl group, methacryloylpropyl group, and the like.

As an organic group which has a mercapto group, an ethyl mercapto group, a butyl mercapto group, a hexyl mercapto group, an octyl mercapto group, etc. are mentioned.

Cyanoethyl group, cyanopropyl group, etc. are mentioned as an organic group which has a cyano group.

Examples of the alkoxy group having 1 to 20 carbon atoms in R ² of formula (1) include alkoxy groups having a straight, branched, and cyclic alkyl moiety having 1 to 20 carbon atoms, for example, a methoxy group and an ethoxy group. Period, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2 -Methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-prop Fox group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4 -Methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n- Butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl -n-propoxy, 1,2,2-trimethyl-n-propoxy, 1- Butyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, and the like, and the cyclic alkoxy group includes cyclopropoxy group, cyclobutoxy group, 1-methyl -Cyclopropoxy group, 2-methyl-cyclopropoxy group, cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl- Cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2- Methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cycloprop Period, 2-n-propyl-cyclopropoxy, 1-i-propyl-cyclopropoxy, 2-i-propyl-cyclopropoxy, 1,2,2-trimethyl-cyclopropoxy, 1, 2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-3-methyl-cyclopropoxy group, etc. are mentioned.

The acyloxy group having 1 to 20 carbon atoms in R ² of formula (1) is, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butyl Carbonyloxy group, i-butylcarbonyloxy group, s-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butyl Carbonyloxy group, 3-methyl-n-butylcarbonyloxy group, 1,1-dimethyl-n-propylcarbonyloxy group, 1,2-dimethyl-n-propylcarbonyloxy group, 2,2-dimethyl-n-propyl Carbonyloxy group, 1-ethyl-n-propylcarbonyloxy group, n-hexylcarbonyloxy group, 1-methyl-n-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n- Pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n- Butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbon Nyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propyl carbono Nyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbon And a silyloxy group and a tosylcarbonyloxy group.

Examples of the halogen atom of R ² in formula (1) include fluorine, chlorine, bromine and iodine.

The hydrolyzable organosilane represented by Formula (1) can be illustrated as follows.

[Formula 4]

[Chemical Formula 5]

[Formula 6]

Although a commercial item can be used for the hydrolysable organosilane represented by Formula (1), it can also synthesize | combine it.

For example, it can synthesize | combine by reaction of an aminosilane and an acid anhydride.

In the present invention, at least one organosilicon compound selected from the group consisting of a hydrolyzable organosilane represented by formula (1) and a compound represented by formulas (2) and (3) can be used in combination.

That is, it consists of the hydrolyzable organosilane represented by Formula (1), its hydrolyzate, or its hydrolyzed condensate, the organosilicon compound represented by Formula (2), and the organosilicon compound represented by Formula (3) At least one organosilicon compound selected from the group, its hydrolyzate and its hydrolyzed condensate can be used in combination.

The ratio of the hydrolyzable organosilane represented by said Formula (1), the organosilicon compound represented by Formula (2), and / or the organosilicon compound represented by Formula (3) is 1: 0-1: 200 by molar ratio. Can be used in the range of. In order to obtain a good resist shape, the ratio of the hydrolyzable organosilane represented by the formula (1) and the organosilicon compound represented by the formula (2) and / or the organosilicon compound represented by the formula (3) is 1: 1 in molar ratio. It can be used in the range of 199 to 1:19.

It is preferable to use the organosilicon compound represented by Formula (2) as the organosilicon compound selected from the group which consists of the organosilicon compound represented by Formula (2) and the organosilicon compound represented by Formula (3).

It is preferable to use these as a hydrolysis-condensation product (polymer of polyorganosiloxane), and the hydrolysis-condensation product (polyorgano) of the hydrolysable organosilane represented by Formula (1) and the organosilicon compound represented by Formula (2) Polymers of siloxanes).

In the organosilicon compound represented by formula (2) and the organosilicon compound represented by formula (3), the alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkenyl group represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ Or an alkoxy group, acyloxy group, or halogen atom contained in an organic group having an epoxy group, acryloyl group, methacryloyl group, mercapto group, or cyano group, and further a hydrolyzable group, is represented by the formula (1) What was described in can be illustrated. The organic group which has an alkoxyaryl group and an acyloxyaryl group can use the combination of the said alkoxy group, an acyloxy group, and an aryl group.

The organosilicon compound represented by Formula (2) is, for example, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetran- Butoxysilane, tetraacetoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltriamyloxysilane, Methyltriphenoxysilane, Methyltribenzyloxysilane, Methyltriphenethyloxysilane, Glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, α-Glycidoxyethyltrimethoxysilane, α- Glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltrie Oxysilane, β-glycidoxy Cipropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane , γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxy Butyl triethoxysilane, γ-glycidoxy butyl trimethoxysilane, γ-glycidoxy butyl triethoxy silane, δ-glycidoxy butyl trimethoxy silane, δ-glycidoxy butyl triethoxy silane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclo Hexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxy Cyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxy Silane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethyl Methyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldi Propoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ -Glycidoxy propyl vinyl dimethoxy silane, γ- glycidoxy propyl vinyl diethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, vinyl trimethoxy silane, vinyl trichlorosilane, vinyl triacetoxy silane, Vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, methoxyphenyltrimethoxysilane, methoxy Methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyl trichloro in Silane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltrie Methoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, iso Propoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxy Silane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t Butock Phenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxy Silane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxy Silane, ethoxynaphthyltrichlorosilane, acetoxyphenyltrimethoxysilane, acetoxyphenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriace Oxysilane, 3,3,3-trichloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β- Cyanoethyltriethoxysilane, Chloromethyl Trimethoxysilane, chloromethyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxy Silane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methyl Vinyldimethoxysilane, methyl vinyl diethoxysilane, etc. are mentioned.

The organosilicon compound represented by Formula (3) is, for example, methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane and ethylene bistria. Cetoxysilane, Propylenebistriethoxysilane, Butylenebistrimethoxysilane, Phenylenebistrimethoxysilane, Phenylenebistriethoxysilane, Phenylenebismethyldiethoxysilane, Phenylenebismethyldimethoxysilane, Naph Tylene bistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyl diethoxydisilane, bismethyldimethoxydisilane, etc. are mentioned.

As a specific example of the hydrolysis-condensation product of the hydrolyzable organosilane represented by Formula (1), and the organosilicon compound represented by Formula (2), the condensate which has the following unit structure is illustrated.

[Formula 7]

Hydrolyzed condensate (polyorganosiloxane) of hydrolyzable organosilane represented by formula (1), or organosilicon compound represented by formula (2) and / or formula (2) with hydrolyzable organosilane of formula (1) The hydrolyzed condensate (polyorganosiloxane) of the organosilicon compound represented by 3) can be obtained as a condensate having a weight average molecular weight of 1000 to 1000000 or 1000 to 100000. These molecular weights are molecular weights obtained by polystyrene conversion through GPC analysis.

The measurement conditions of GPC are, for example, a GPC device (trade name: HLC-8220GPC, manufactured by TOSOH CORPORATION), a GPC column (trade name: Shodex KF803L, KF802, KF801, manufactured by Showa Denko KK), and the column temperature is 40 ° C, eluent ( Elution solvent) can be performed using tetrahydrofuran, a flow rate (flow rate) of 1.0 ml / min, and a standard sample using polystyrene (manufactured by Showa Denko KK).

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

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

The reaction temperature at the time of performing hydrolysis and condensation is 20-80 degreeC normally.

The hydrolysis may be completely hydrolyzed or partially hydrolyzed. That is, the hydrolyzate or monomer may remain in the hydrolysis 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 is, for example, triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri-i-propoxy mono (acetyl Acetonate) titanium, tri-n-butoxy mono (acetylacetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, Diethoxy 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 (acetylacetonate) titanium, mono- n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris (acetyl Setonate) titanium, mono-n-butoxy tris (acetylacetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, Tetrakis (acetylacetonate) titanium, triethoxy mono (ethylacetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium , Tri-n-butoxy mono (ethylacetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (Ethyl aceto acetate) Titanium, di-n-propoxy bis (ethyl aceto acetate) Titanium, di-i-propoxy bis (ethyl aceto acetate) Titanium, di-n-butoxy bis (ethyl aceto acetate) Titanium, di-sec-butoxy bis (ethylacetoacetate) titanium, -t-butoxy bis (ethylacetoacetate) titanium, monoethoxy tris (ethylacetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris ( Ethylacetoacetate) titanium, mono-n-butoxytris (ethylacetoacetate) titanium, mono-sec-butoxytris (ethylacetoacetate) titanium, mono-t-butoxytris (ethylacetoacetate) titanium , Tetrakis (ethylacetoacetate) titanium, mono (acetylacetonate) tris (ethylacetoacetate) titanium, bis (acetylacetonate) bis (ethylacetoacetate) titanium, tris (acetylacetonate) mono (ethylacetoacetate) Titanium chelate compounds such as titanium; Triethoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri-i-propoxy mono (acetylacetonate) zirconium, tri-n-butoxy mono (Acetylacetonate) zirconium, tri-sec-butoxy mono (acetylacetonate) zirconium, tri-t-butoxy mono (acetylacetonate) zirconium, diethoxy bis (acetylacetonate) zirconium, di- n-propoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di-n-butoxy bis (acetylacetonate) zirconium, di-sec-butoxy Bis (acetylacetonate) zirconium, di-t-butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonate) zirconium, Mono-i-propoxy tris Cetylacetonate) zirconium, mono-n-butoxy tris (acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium , Tetrakis (acetylacetonate) zirconium, triethoxy mono (ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) Zirconium, tri-n-butoxy mono (ethylacetoacetate) zirconium, tri-sec-butoxy mono (ethylacetoacetate) zirconium, tri-t-butoxy mono (ethylacetoacetate) zirconium, diethoxy Bis (ethylacetoacetate) zirconium, di-n-propoxy bis (ethylacetoacetate) zirconium, di-i-propoxy bis (ethylacetoacetate) zirconium, di-n-butoxy bis (ethylace Acetate) zirconium, di-sec-butoxybis (ethylacetoacetate) zirconium, di-t-butoxybis (ethylacetoacetate) zirconium, monoethoxytris (ethylacetoacetate) zirconium, mono-n- Propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris ( Ethylacetoacetate) zirconium, mono-t-butoxytris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis (acetylacetonate) Zirconium chelate compounds such as bis (ethylacetoacetate) zirconium and tris (acetylacetonate) mono (ethylacetoacetate) zirconium; Aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum; And the like.

The organic acid as the hydrolysis catalyst is, for example, acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, seba Succinic acid, acetic acid, butyric acid, metic acid, arachidonic acid, succinic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloro Acetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid and the like.

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

The organic base as the hydrolysis catalyst is, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, Monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicyclo undecene, tetramethylammonium hydrooxide, etc. are mentioned. As an inorganic base, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc. are mentioned, for example. Among these catalysts, metal chelate compounds, organic acids and inorganic acids are preferable, and these may be used alone or in combination of two or more.

Examples of the organic solvent used for hydrolysis include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane and n-octane. aliphatic hydrocarbon solvents such as i-octane, cyclohexane and methylcyclohexane;

Benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amyl Aromatic hydrocarbon solvents such as naphthalene and trimethylbenzene;

Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol , sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec- tetradecyl alcohol, sec-heptadecyl alcohol, phenol, 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-2,4, 2-ethylhexanediol Polyhydric alcohol solvents such as -1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin;

Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl Ketone solvents such as ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone and phenchon;

Ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2- propylene oxide, dioxolane, 4-methyldioxolane, dioxane, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, 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- Ethylene glycol mono-n-hexyl ether, ethoxy triglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Glycol monopropyl 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, Ether solvents such as 2-methyltetrahydrofuran;

Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-acetic acid Pentyl, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate Ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, propylene glycol monoacetate Methyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, a Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, Ester solvents such as di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate;

N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, Nitrogen-containing solvents such as pyrrolidone;

And sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane and 1,3-propanesultone. These solvents may be used alone or in combination of two or more.

In particular, acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n -Hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone, phenchon (1,1,3- Ketone solvents, such as trimethyl-2- norbornene), are preferable at the point of storage stability of a solution.

The resist underlayer film forming composition of this invention can contain a curing catalyst. The curing catalyst functions as a curing catalyst when heating and curing a coating film containing a polyorganosiloxane made of a hydrolysis condensate.

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

As an ammonium salt, Formula (D-1):

[Formula 8]

_A quaternary ammonium salt having the structure represented by formula (m is 2 to 11, n is an integer of 2 to 3, R ¹¹ is an alkyl group or an aryl group, and Y _A ^- is an anion.) 2):

[Chemical Formula 9]

(Where, R ^12, R ^13, R ¹⁴ and R ¹⁵ is an alkyl group or an aryl group, each independently, N is a nitrogen atom, Y _A ^- denotes an anion, and R ^12, R ^13, R ¹⁴ and R ¹⁵ is Quaternary ammonium salts each independently having a structure represented by a CN bond);

Formula (D-3):

[Formula 10]

(Wherein R ¹⁶ and R ¹⁷ each independently represents an alkyl group or an aryl group, Y _A ⁻ represents an anion), and a quaternary ammonium salt,

Formula (D-4):

[Formula 11]

_A quaternary ammonium salt having a structure of which R ¹⁸ represents an alkyl group or an aryl group, and Y _A ⁻ represents an anion,

Formula (D-5):

[Chemical Formula 12]

_A quaternary ammonium salt having a structure of (wherein R ¹⁹ and R ²⁰ represent an alkyl group or an aryl group, and Y _A ⁻ represents an anion),

Formula (D-6):

[Chemical Formula 13]

And tertiary ammonium salts having a structure of (m represents 2 to 11, n represents an integer of 2 to 3, H represents a hydrogen atom, and Y _A ⁻ represents an anion).

In addition, as a phosphonium salt, Formula (D-7):

[Formula 14]

(However, R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group or an aryl group, P represents a person group, Y _A ⁻ represents an anion, and R ²¹ , R ²² , R ²³ and R ^{24 respectively.} Is a quaternary phosphonium salt represented by each independently bonded to a phosphorus atom by a CP bond).

In addition, as a sulfonium salt, Formula (D-8):

[Formula 15]

(Wherein R ²⁵ , R ²⁶ and R ²⁷ each independently represent an alkyl group or an aryl group, S represents a sulfur atom, Y _A ⁻ represents an anion, and R ²⁵ , R ²⁶ and R ²⁷ each independently represent CS). And a tertiary sulfonium salt represented by) bonded to a sulfur atom by a bond).

The compound represented by said formula (D-1) shows the quaternary ammonium salt derived from an amine, m shows 2-11, n shows the integer of 2-3. R ¹¹ of this quaternary ammonium salt represents an alkyl group having 1 to 18 carbon atoms or an aryl group, preferably an alkyl group having 2 to 10 carbon atoms or an aryl group having 6 to 18 carbon atoms, for example, an ethyl group or a propyl group And linear alkyl groups such as a butyl group, or a benzyl group, a cyclohexyl group, a cyclohexylmethyl group, a dicyclopentadienyl group, and the like. Further, the anion (Y _A ^-), the chloride ions (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-), such as a halogen ion or a carboxylate (-COO ^-), sulfonate (- SO ₃ ^-), an alcoholate (-O ^- can be an acid group, etc.).

Compounds represented by the formula (D-2) ^{is, R 12 R 13 R 14 R} 15 N + Y A - is a quaternary ammonium salt represented by the following. R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ of this quaternary ammonium salt each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, or are represented by (D-2) A compound represents the silane compound couple | bonded with the silicon atom by Si-C bond. Anion (Y _A ^-) is a chloride ion (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-), such as a halogen ion or a carboxylate (-COO ^-), sulfonate (-SO ₃ ^- ), an alcoholate (-O ^-), there may be mentioned an acid group and the like. This quaternary ammonium salt can be obtained as a commercial item, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzyl ammonium chloride, triethylbenzyl ammonium chloride, trioctylmethylammonium chloride, tributylbenzyl chloride Ammonium, trimethylbenzyl ammonium chloride, etc. are illustrated.

The compound represented by the formula (D-3) represents a quaternary ammonium salt derived from 1-substituted imidazole, the number of carbon atoms of R ¹⁶ and R ¹⁷ is 1-18, and the carbon of R ¹⁶ and R ¹⁷ It is preferable that the sum total of atom number is seven or more. For example, methyl group, ethyl group, propyl group, phenyl group, benzyl group may be mentioned as R <^16> , and benzyl group, octyl group, and octadecyl group are mentioned as R <^17> . Anion (Y _A ^-), the chloride ions (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-), such as a halogen ion or a carboxylate (-COO ^-), sulfonate (-SO ₃ ^-), an alcoholate (-O ^-), there may be mentioned an acid group and the like. Although this compound can also be obtained as a commercial item, For example, imidazole type compounds, such as 1-methylimidazole and 1-benzylimidazole, and halogenated alkyl, such as benzyl bromide and methyl bromide, and a halogenated aryl are reacted. Can be prepared.

The compound represented by the formula (D-4) is a quaternary ammonium salt derived from pyridine, and R ¹⁸ is an alkyl group having 1 to 18 carbon atoms, preferably an alkyl group having 4 to 18 carbon atoms or 6 to 6 carbon atoms. The aryl group of 18 is shown and a butyl group, an octyl group, a benzyl group, and a lauryl group can be illustrated, for example. Anion (Y _A ^-), the chloride ions (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-), such as a halogen ion or a carboxylate (-COO ^-), sulfonate (-SO ₃ ^-), an alcoholate (-O ^-), there may be mentioned an acid group and the like. This compound can also be obtained as a commercial item, for example, can be manufactured by making pyridine, halogenated alkyl, such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, and octyl bromide, or aryl halide react. This compound can illustrate, for example, N-laurylpyridinium chloride, N-benzylpyridinium bromide, and the like.

The compound represented by the above formula (D-5) is a quaternary ammonium salt derived from substituted pyridine represented by picoline and the like, and R ¹⁹ is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms or carbon. An aryl group having 6 to 18 atoms is represented, and examples thereof include methyl group, octyl group, lauryl group, benzyl group and the like. R ²⁰ represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, for example, when quaternary ammonium derived from picoline, R ²⁰ represents a methyl group. Anion (Y _A ^-), the chloride ions (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-), such as a halogen ion or a carboxylate (-COO ^-), sulfonate (-SO ₃ ^-), an alcoholate (-O ^-), there may be mentioned an acid group and the like. This compound can be obtained as a commercial item, and can be prepared by, for example, reacting a substituted pyridine such as picoline with a halogenated alkyl such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride or benzyl bromide, or an aryl halide. Can be. This compound can illustrate N-benzyl picolinium chloride, N-benzyl picolinium bromide, N-lauryl picolinium chloride, etc., for example.

The compound represented by the formula (D-6) is a tertiary ammonium salt derived from an amine, m is 2 to 11 and n represents an integer of 2 to 3. Further, the anion (Y _A ^-), the chloride ions (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-), such as a halogen ion or a carboxylate (-COO ^-), sulfonate (- SO ₃ ^-), an alcoholate (-O ^- can be an acid group, etc.). The compound represented by a formula (D-6) can be manufactured by reaction of an amine and weak acids, such as carboxylic acid and a phenol. If represents the (HCOO-), with acetic acid, the ^{anion-carboxylic} acid in the case of using formic acid can be exemplified by formic acid or acetic acid, the anion (Y _{A) (A} Y ^-) is (CH ₃ COO ^- ). In addition, when using the phenol anion represents a (Y _A ^{- -)} is (C ₆ H ₅ O).

Compounds represented by the formula (D-7) ^{is, R 21 R 22 R 23 R} 24 P + Y A - is a quaternary phosphonium salt having a structure represented by. R ²¹ , R ²² , R ²³ and R ²⁴ represent a silane compound bonded to a silicon atom by an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms or a Si-C bond, Preferably, three out of four substituents of R ²¹ to R ²⁴ represent a phenyl group or a substituted phenyl group, and as these three substituents, for example, a phenyl group or a tolyl group can be exemplified, and the remaining one substituent is carbon. It is a silyl group couple | bonded with the silicon atom by the C1-C18 alkyl group, the C6-C18 aryl group, or Si-C bond. Further, the anion (Y _A ^-), the chloride ions (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-), such as a halogen ion or a carboxylate (-COO ^-), sulfonate (- SO ₃ ^-), an alcoholate (-O ^- can be an acid group, etc.). This compound can be obtained as a commercial item, For example, Halogenated trialkyl benzyl phosphide, such as halogenated tetraalkyl phosphonium, such as a halogenated tetran- butyl phosphonium, a halogenated tetra n-propyl phosphonium, and a halogenated triethylbenzyl phosphonium Halogenated triphenyl monoalkyl phosphonium, halogenated triphenylbenzyl phosphonium, halogenated tetraphenyl phosphonium, halogenated tritolyl monoaryl phosphonium, or halogenated triphenyl, such as phosphium, halogenated triphenylmethyl phosphonium, and halogenated triphenylethyl phosphonium Tolyl monoalkyl phosphonium (The halogen atom is a chlorine atom or a bromine atom) is mentioned. In particular, halogenated triphenyl monoalkyl phosphonium, such as halogenated triphenylmethyl phosphonium and halogenated triphenyl ethyl phosphonium, halogenated triphenyl monoaryl phosphonium, such as halogenated triphenyl benzyl phosphonium, halogenated tritolyl monophenyl phosphonium, etc. The halogenated tritolyl monoalkyl phosphonium (halogen atom is a chlorine atom or a bromine atom), such as a halogenated tritolyl monoaryl phosphonium and a halogenated tritolyl monomethyl phosphonium, is preferable.

Moreover, as phosphines, 1st phosphines, such as methyl phosphine, ethyl phosphine, propyl phosphine, isopropyl phosphine, isobutyl phosphine, and phenyl phosphine, dimethyl phosphine, diethyl phosphine, diiso Third phosphines such as propyl phosphine, diisoamyl phosphine, diphenyl phosphine, triphosphophosphine, triethyl phosphine, triphenyl phosphine, methyl diphenyl phosphine, dimethyl phenyl phosphine A pin.

Compounds represented by the formula (D-8) ^{is, R 25 R 26 R 27 S} + Y A - is a tertiary sulfonium salt having a structure represented by. R ²⁵ , R ²⁶ and R ²⁷ represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, or a group bonded to a silicon atom by a Si-C bond, preferably R ²⁵ to Of the four substituents of R ²⁷ , three are phenyl groups or substituted phenyl groups, and examples of the three substituents may include, for example, a phenyl group and a tolyl group, and the remaining one substituent may be an alkyl group having 1 to 18 carbon atoms. Or an aryl group having 6 to 18 carbon atoms. These alkyl groups and aryl groups can illustrate the functional group of the said carbon atom number of the above-mentioned illustration. Further, the anion (Y _A ^-), the chloride ions (Cl ^-), bromide ion (Br ^-), iodide ion (I ^-), such as a halogen ion or a carboxylate (-COO ^-), sulfonate (- SO ₃ ^-), an alcoholate (-O ^- can be an acid group, etc.). This compound can be obtained as a commercial item, for example, halogenated trialkylbenzyl sulfide, such as halogenated tetraalkyl phosphonium, such as a halogenated trin-butyl sulfonium, a halogenated trin-propyl sulfonium, and a halogenated diethyl benzyl sulfonium. Halogenated diphenyl monoalkylsulfonium, halogenated triphenylsulfonium, such as phonium, a halogenated diphenyl methyl sulfonium, and a halogenated diphenyl ethyl sulfonium, (halogen atom is a chlorine atom or a bromine atom), trin- butylsulfonium carboxyl Trialkylbenzylsulfonium carboxylates, such as the tetraalkyl phosphonium carboxylates, such as the rate and a trin- propylsulfonium carboxylate, diethylbenzylsulfonium carboxylate, diphenylmethylsulfonium carboxylate, di Diphenyl monoalkyl sulfonium carboxylates, such as phenyl ethyl sulfonium carboxylate, and a triphenyl sulfonium carboxylate are mentioned. In particular, halogenated triphenylsulfonium and triphenylsulfonium carboxylate are preferable.

The quantity of a curing catalyst is 0.01-10 mass parts, 0.01-5 mass parts, or 0.01-3 mass parts with respect to 100 mass parts of polyorganosiloxane.

The hydrolyzable organosilane is condensed by hydrolysis using a catalyst in a solvent, and the obtained hydrolysis condensate (polymer) is subjected to distillation under reduced pressure or the like to simultaneously produce an alcohol, a hydrolysis catalyst and water used as a byproduct. Can be removed In addition, the acid and base catalyst used for hydrolysis can be removed by neutralization or ion exchange. And in the resist underlayer film forming composition for lithography of this invention, organic acid, water, alcohol, or these combination can be added for stabilization of the resist underlayer film forming composition containing this hydrolysis-condensation product.

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, salicylic acid, and the like. Especially, oxalic acid and a maleic acid are preferable. The organic acid to add is 0.5-5.0 mass parts with respect to 100 mass parts of condensates (polyorganosiloxane). In addition, pure water, ultrapure water, ion-exchange water, etc. can be used for the water to add, The addition amount can be 1-20 mass parts with respect to 100 mass parts of resist underlayer film forming compositions.

Moreover, as alcohol to add, what is easy to scatter by heating after application | coating is preferable, For example, methanol, ethanol, propanol, isopropanol, butanol, etc. are mentioned. The alcohol to add can be 1-20 mass parts with respect to 100 mass parts of resist underlayer film forming compositions.

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

By using the organic polymer compound, the dry etching rate (reduced amount of film thickness per unit time), attenuation coefficient and refractive index of the resist underlayer film formed from the underlayer film forming composition for lithography of the present invention can be adjusted.

Although there is no restriction | limiting in particular as an organic polymer compound, Various organic polymers can be used. A polycondensation polymer, an addition polymerization polymer, etc. can be used. Addition polymers and polycondensation polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacryl polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, polycarbonate and the like can be used. Organic polymers having an aromatic ring structure, such as a benzene ring, naphthalene ring, anthracene ring, triazine ring, quinoline ring and quinoxaline ring, which function as light absorption sites, are preferably used.

As such an organic polymer compound, for example, benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxy styrene, benzyl Addition polymers containing addition polymerizable monomers such as 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. An addition polymerizable monomer is used for manufacture of an addition polymerization polymer. Such addition polymerizable monomers include acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride and acrylonitrile. Etc. can be mentioned.

As an acrylate ester compound, methyl acrylate, ethyl acrylate, normal hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthryl methyl acrylate, 2-hydroxyethyl acrylate , 3-chloro-2-hydroxypropylacrylate, 2-hydroxypropylacrylate, 2,2,2-trifluoroethylacrylate, 2,2,2-trichloroethylacrylate, 2-bromo Ethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxy Norbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, glycidyl acrylate, and the like.

As methacrylic acid ester compound, methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthryl methyl methacrylate Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2- Bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryl Royloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl Methacrylate and bromophenyl meth There may be mentioned acrylate and the like.

As acrylamide compound, acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-benzyl acrylamide, N-phenyl acrylamide, N, N- dimethyl acrylamide, N- anthryl acrylamide, etc. are mentioned. Can be.

 Methacrylamide compounds, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N, N-dimethylmethacrylamide and N-anthryl Acrylamide etc. are mentioned.

 As a vinyl compound, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl Ether, vinyl naphthalene, vinyl anthracene and the like.

Examples of the styrene compound include styrene, hydroxy styrene, chlorostyrene, bromostyrene, methoxy styrene, cyano styrene, acetyl styrene and the like.

As a maleimide compound, maleimide, N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-hydroxyethyl maleimide, etc. are mentioned.

When a polycondensation polymer is used as a polymer, such a polymer is, for example, a polycondensation polymer of a glycol compound and a dicarboxylic acid compound. Diethylene glycol, hexamethylene glycol, butylene glycol etc. are mentioned as a glycol compound. Succinic acid, adipic acid, terephthalic acid, maleic anhydride etc. are mentioned as a dicarboxylic acid compound. Moreover, polyester, such as polypyromelitimide, poly (p-phenylene terephthalamide), polybutylene terephthalate, polyethylene terephthalate, polyamide, polyimide is mentioned, for example.

When the hydroxyl group is contained in the organic polymer compound, the hydroxyl group can form a crosslinking reaction with the polyorganosiloxane.

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

Only 1 type can be used for an organic polymer compound, or can be used for it in combination of 2 or more type.

When the organic polymer compound is used, the ratio is 1 to 200 parts by mass, 5 to 100 parts by mass, or 10 to 50 parts by mass, or 20 to 30 parts by mass based on 100 parts by mass of the condensate (polyorganosiloxane). It is a mass part.

The resist underlayer film forming composition of this invention can contain an acid generator.

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

The photoacid generator generates an acid upon exposure of the resist. This makes it possible to adjust the acidity of the underlayer film. This is one of the methods for matching the acidity of the lower layer film with the acidity of the upper layer resist. In addition, by adjusting the acidity of the lower layer film, the pattern shape of the resist formed on the upper layer can be adjusted.

An onium salt compound, a sulfonimide compound, a disulfonyl diazomethane compound, etc. are mentioned as a photo-acid generator contained in the resist underlayer film forming composition of this invention.

As onium salt compound, diphenyl iodonium hexafluorophosphate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium nonafluoro normal butane sulfonate, diphenyl iodonium perfluoro normal octane Iodo such as sulfonate, diphenyl iodonium camphor sulfonate, bis (4-tert-butylphenyl) iodonium camphor sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate Nium salt compounds and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro normal butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate Can be mentioned.

Examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonnafluoronormalbutanesulfonyloxy) succinimide, and N- (camphorsulfonyloxy). Succinimide, N- (trifluoromethanesulfonyloxy) naphthalimide, etc. are mentioned.

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

Only 1 type can be used for a photo-acid generator, or can be used for it in combination of 2 or more type.

When a photo-acid generator is used, the ratio is 0.01-5 mass parts, 0.1-3 mass parts, or 0.5-1 mass part with respect to 100 mass parts of condensates (polyorganosiloxane).

The surfactant is effective for suppressing the occurrence of pinholes and striation after applying the resist underlayer film-forming composition for lithography of the present invention to a substrate.

As surfactant contained in the resist underlayer film forming composition of this invention, For example, polyoxy, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc. Polyoxyethylene alkyl allyl ethers such as ethylene alkyl ethers, polyoxyethylene octyl phenol ethers and polyoxyethylene nonyl phenol ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurates and sorbitan monopalmi Sorbitan fatty acid esters such as tate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate , Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene Nonionic surfactants, such as polyoxyethylene sorbitan fatty acid esters, such as a sorbitan tristearate, brand names EFTOP EF301, EF303, EF352 (made by Tohkem products Corporation), brand names MEGAFAC F171, F173, R-08, R-30 (Dainippon Ink and Chemicals, Inc.), FLUORAD FC430, FC431 (manufactured by Sumitomo 3M Limited), trade names ASAHI GUARD AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd And fluorine-based surfactants and the like, and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more thereof. When surfactant is used, it is 0.0001-5 mass parts, 0.001-1 mass part, or 0.01-0.5 mass part with respect to 100 mass parts of condensates (polyorganosiloxane) as the ratio.

In addition, a rheology modifier, an adhesion aid, and the like 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. An adhesion aid is effective in improving the adhesiveness of a semiconductor substrate or a resist and an underlayer film.

As a rheology regulator, For example, phthalic acid derivatives, such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate, dinormal butyl adipate, diisobutyl adipate, and diisooctyl Adipic acid derivatives such as adipate and octyldecyl adipate, maleic acid derivatives such as dinomal butyl maleate, diethyl maleate and dinonyl maleate, methyl oleate, butyl oleate and tetrahydrofurfuryl oleate Oleic acid derivatives or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. These rheology modifiers are mix | blended normally with the ratio of less than 30 mass% with respect to 100 mass% of all compositions of a resist underlayer film forming composition.

As the adhesion aid, for example, chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, Alkoxysilanes such as dimethylvinylethoxysilane, diphenyldimethoxysilane and phenyltriethoxysilane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimida Silanes such as sol, silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane, benzotriazole and benzimi Dazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urasol, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc. Heterocyclicization Urea or thiourea compounds, such as a compound, 1, 1- dimethyl urea and 1, 3- dimethyl urea, are mentioned. An adhesive aid is normally mix | blended in the ratio of less than 5 mass%, Preferably it is less than 2 mass% with respect to 100 mass% of all compositions of a resist underlayer film forming composition.

As a solvent used for the resist underlayer film forming composition of this invention, if the solvent which can melt | dissolve the said solid content can be used without a restriction | limiting in particular. Examples of such a solvent include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, and propylene. Glycol Monomethyl Ether Acetate, Propylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monopropyl Ether Acetate, Propylene Glycol Monobutyl Ether Acetate, Toluene, Xylene, Methyl Ethyl Ketone, Cyclopentanone, Cyclohexanone, Ethyl 2-hydroxypropionate , Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol Nomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene Glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoam formate, Methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate and isopropyl propyl butyrate Butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate Ethyl ethoxyacetate, 3-methoxy methyl propionate, 3-ethoxy propionate ethyl, 3-methoxy ethylpropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl Acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, toluene, xylene, methylethylketone, Methylpropyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N -Methylpyrrolidone, gamma -butyrolactone, etc. are mentioned. These solvents can be used individually or in combination of 2 or more types.

Hereinafter, use of the resist underlayer film forming composition of this invention is demonstrated.

Substrates (eg, silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low dielectric constant materials (low-k materials) coatings used in the manufacture of semiconductor devices The resist underlayer film forming composition of this invention is apply | coated by suitable coating methods, such as a spinner and a coater, on a board | substrate etc.) and after that, a resist underlayer film is formed by baking. As conditions for baking, it selects from the baking temperature of 80 degreeC-250 degreeC, and baking time 0.3-60 minutes suitably. Preferably, the baking temperature is 150 ° C to 250 ° C and the baking time is 0.5 to 2 minutes. Here, as a film thickness of the underlayer film formed, it is 10-1000 nm, 20-500 nm, 50-300 nm, or 100-200 nm, for example.

Then, for example, a layer of photoresist is formed on the resist underlayer film. Formation of the layer of a photoresist can be performed by a well-known method, ie, application | coating and baking on the underlayer film of a photoresist composition solution. As a film thickness of a photoresist, it is 50-10000 nm, 100-2000 nm, or 200-1000 nm, for example.

In this invention, after forming an organic underlayer film on a board | substrate, the resist underlayer film of this invention can be formed on it, and a photoresist can be coat | covered on it again. As a result, the pattern width of the photoresist becomes narrow, and even when the photoresist is thinly coated to prevent the pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, an oxygen-based gas that can be processed into a resist underlayer film of the present invention using a fluorine-based gas that has a sufficiently fast etching rate with respect to a photoresist as an etching gas, and that has a sufficiently fast etching rate with respect to a resist underlayer film of the present invention. The organic underlayer film can be processed by using the gas as an etching gas, and further, the substrate can be processed by using a fluorine-based gas that has a sufficiently fast etching rate with respect to the organic underlayer film as the etching gas.

The photoresist formed on the resist underlayer film of the present invention is not particularly limited as long as it is photosensitive to light used for exposure. Both negative photoresist and positive photoresist can be used. Positive photoresist consisting of a novolak resin and 1,2-naphthoquinonediazidesulfonic acid ester, chemically amplified photoresist composed of a binder having a group which is decomposed by acid to increase the alkali dissolution rate, and a photoacid generator, It is decomposed by a low molecular weight compound to increase the alkali dissolution rate of the photoresist, a chemically amplified photoresist consisting of an alkali-soluble binder and a photoacid generator, and an acid to decompose by a binder and an acid having a group to increase the alkali dissolution rate. And chemically amplified photoresists comprising low molecular weight compounds and photoacid generators that increase the alkali dissolution rate of the resist. For example, the brand name APEX-E by Shipley Company Inc., the brand name PAR710 by Sumitomo Chemical Company, and the brand name SEPR430 by Shin-Etsu Chemical Co., Ltd. etc. are mentioned. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000) or Proc. And fluorine-containing polymer-based photoresists, as described in 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), an F ₂ excimer laser (wavelength 157 nm), etc. can be used for exposure. After exposure, it is also possible to perform post exposure bake if necessary. Post-exposure heating is performed on conditions suitably selected at the heating temperature of 70 degreeC-150 degreeC, and 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 negative and positive types can be used. A chemically amplified resist consisting of a binder having a group which is decomposed by an acid generator and an acid to change an alkali dissolution rate, an alkali-soluble binder and a low molecular compound which is decomposed by an acid generator and an acid to change an alkali dissolution rate of a resist Chemically amplified resist, a chemically amplified resist composed of a binder having a group which is decomposed by an acid generator and an acid to change the alkali dissolution rate, and a low molecular compound which is decomposed by an acid to change the alkali dissolution rate of the resist. And a non-chemically amplified resist composed of a binder having a group for changing the alkali dissolution rate, a non-chemically amplified resist composed of a binder having a site that is cleaved by an electron beam to change the alkali dissolution rate. Even when these electron beam resists are used, a resist pattern can be formed similarly to the case where a photoresist is used with an irradiation source as an electron beam.

Then, image development is performed with a developing solution. Thus, for example, when a positive photoresist is used, the photoresist of the exposed portion is removed, thereby forming a pattern of the photoresist.

As a developing solution, aqueous solution of alkali metal hydroxides, such as potassium hydroxide and sodium hydroxide, aqueous solution of quaternary ammonium hydroxides, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, amine aqueous solution, such as ethanolamine, propylamine, and ethylenediamine, etc. An alkaline aqueous solution of is mentioned. Furthermore, surfactant etc. can also be added to these developing solutions. As conditions for image development, it selects from the temperature of 5-50 degreeC, and time 10-600 second suitably.

Then, the resist underlayer film (middle layer) of the present invention is removed 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 (middle layer) of the present invention is removed. As a protective film, the organic underlayer film (lower layer) is removed. Finally, the semiconductor substrate is processed using the patterned resist underlayer film (middle layer) and the organic underlayer film (lower layer) of the present invention as protective films.

First, the resist underlayer film (middle layer) of this invention in the part from which the photoresist was removed is removed by dry etching, and a semiconductor substrate is exposed. Dry etching of the resist underlayer film of the present invention includes tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, carbon monoxide, argon, Gases such as oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used. It is preferable to use a halogen gas for the dry etching of the resist underlayer film. In dry etching with a halogen-based gas, a photoresist basically made of an organic material is hardly removed. In contrast, the resist underlayer film of the present invention containing a large amount of silicon atoms is quickly removed by a halogen gas. Thereby, the reduction of the film thickness of the photoresist by the dry etching of the resist underlayer film can be suppressed. As a result, the photoresist can be used as a thin film. Dry etching of the resist underlayer film is preferably made of fluorine-based gas, and examples of the fluorine-based gas include tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), and perfluoropropane (C _3). F ₈ ), trifluoromethane, difluoromethane (CH ₂ F ₂ ), and the like.

Thereafter, the organic underlayer film is removed by using the patterned photoresist and the resist underlayer film of the present invention as a protective film. It is preferable that an organic underlayer film (lower layer) is formed by dry etching with an oxygen-based gas. It is because the resist underlayer film of this invention which contains many silicon atoms is hard to remove by the dry etching by oxygen type gas.

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

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

In addition, an organic antireflection film can be formed on the upper layer of the resist underlayer film of the present invention before the photoresist is formed. The anti-reflective coating composition used herein is not particularly limited, but may be arbitrarily selected and used from those conventionally used in the lithography process, and furthermore, coating and firing by conventional methods such as spinners and coaters Through the anti-reflection film can be formed.

The substrate on which the resist underlayer film forming composition of the present invention is applied may have an organic or inorganic antireflective 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 underlayer film formed from the resist underlayer film forming composition of this invention may have absorption with respect to the light further, depending on the wavelength of the light used by a lithographic process. In this case, it can function as an antireflection film having an effect of preventing the reflected light from the substrate. And the underlayer film of this invention has a function which prevents the bad effect to the board | substrate of the layer which prevents interaction between a board | substrate and a photoresist, the material used for a photoresist, or the substance produced at the time of exposure to a photoresist. It can also be used as a layer, a layer having a function of preventing the diffusion of a material generated from the substrate into the upper photoresist upon heating and baking, 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 from the resist underlayer film forming composition is applied to the substrate on which the via hole used in the dual damascene process is formed, and can be used as a buried material which can fill the hole without gaps. Moreover, it can also be used as a planarization material for planarizing the surface of the uneven semiconductor substrate.

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited by this.

Example

First, the hydrolyzable silane represented by Formula (1) used as a raw material was synthesize | combined. The obtained compound was identified by ¹ H-NMR measurement. Sample tube: 5 mm, solvent: deuterated chloroform, measurement temperature: room temperature, pulse interval: 5 seconds, integration count: 32 times, reference sample: tetramethylsilane (TMS).

(Synthesis of Compound 1)

Into a 200 ml three-necked flask equipped with a mechanical stirrer, 20.00 g of aminopropyltriethoxysilane was added and 9.04 g of powdered succinic anhydride was added while cooling in a water bath. Stirred. Then, the obtained crude product was refine | purified with hexane and the compound 1 which is a target object was obtained. Obtained compound 1 was corresponded to the compound represented by Formula (1-1).

¹ H-NMR (400 MHz): 0.64 ppm (t, 2H), 1.23 ppm (t, 9H), 1.63 ppm (quint, 2H), 2.51 ppm (t, 2H), 2.68 ppm (t, 2H), 3.24 ppm (q, 2H), 3.82 ppm (q, 6H), 6.42 ppm (s, 1H).

(Synthesis of Compound 2)

Into a 200 ml three-necked flask equipped with a mechanical stirrer, 20.00 g of aminopropyltriethoxysilane was added, 8.86 g of powdered maleic anhydride was added while cooling in a water bath, followed by stirring at room temperature for one day. Then, the obtained crude product was refine | purified with hexane and the compound 2 which is a target object was obtained. Obtained compound 2 was corresponded to the compound represented by Formula (1-5).

¹ H-NMR (400 MHz): 0.68 ppm (t, 2H), 1.23 ppm (t, 9H), 1.74 ppm (quint, 2H), 3.38 ppm (q, 2H), 3.82 ppm (q, 6H), 6.29- 6.47 ppm (dd, 2H), 8.22 ppm (s, 1H).

(Synthesis of Compound 3)

20.00 g of aminopropyltriethoxysilane, 11.43 g of triethylamine, and 30.00 g of tetrahydrofuran were added to a 200 ml three-necked flask, and a mixed solution of 14.87 g of ethyl succinate chloride and 20.00 g of tetrahydrofuran was added dropwise while cooling in a water bath. After stirring at 0 degreeC for 1 hour, it stirred at room temperature for 6 hours. After the reaction, the solution was filtered, and tetrahydrofuran was removed under reduced pressure with an evaporator. 100 ml of dichloroethane was added and washed several times with water. Thereafter, the mixture was dried over magnesium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a crude product of compound 3 as a target product. After distillation under reduced pressure, Compound 3 was obtained as a target. Obtained compound 3 was corresponded to the compound represented by Formula (1-3).

¹ H-NMR (400 MHz): 0.59 ppm (t, 2H), 1.16-1.24 ppm (m, 12H), 1.60 ppm (quint, 2H), 2.40-2.67 ppm (dt, 4H), 3.22 ppm (q, 2H) ), 3.78 ppm (q, 6H), 4.11 ppm (q, 2H), 6.00 ppm (s, 1H).

(Synthesis Example 1)

0.32 g of compound 1, 14.58 g of tetraethoxysilane (TEOS), 0.99 g of phenyltrimethoxysilane (PhTMOS), 4.28 g of methyltriethoxysilane (MeTEOS), and 30.26 g of acetone were added to a 100 mL flask. It put and melt | dissolved, the obtained mixed solution was heated while stirring with a magnetic stirrer, and it refluxed. Then, 6.67 g of 0.01 M aqueous hydrochloric acid solution 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, ethanol, water, and hydrochloric acid as reaction by-products were distilled off under reduced pressure to obtain a hydrolysis condensate solution. Thereafter, propylene glycol diethyl ether was added to the hydrolysis condensate solution to finally obtain a 15% hydrolysis condensate solution. The weight average molecular weight by GPC of the obtained polymer was Mw 1600 in polystyrene conversion. The obtained polymer was corresponded to the polymer which has a unit structure represented by Formula (2-1).

The compound 2 was used instead of the compound 1 used by the synthesis example 1, and the synthesis example 2 was obtained through the same operation. The compound 3 was used instead of the compound 1 used by the synthesis example 1, and the synthesis example 3 was obtained through the same operation. In addition, Comparative Synthesis Examples 1-2 were obtained through the same operation without using the compound corresponding to Compound 1 used in Synthesis Example 1. Table 1 shows the compounding ratios of the silane compounds in the compositions of Synthesis Examples 1-3 and Comparative Synthesis Examples 1-2.

In Synthesis Example 2, the obtained polymer was equivalent to a polymer having a unit structure represented by Formula (2-2), and in Synthesis Example 3, the obtained polymer was equivalent to a polymer having a unit structure represented by Formula (2-3).

In addition, the polymer obtained from the comparative synthesis examples 1-2 was corresponded to the polymer which has a unit structure represented by following formula (3-1).

[Chemical Formula 16]

[Table 1]

(Example 1)

To 20.00 g of the polymer solution (15.00 mass% solids) obtained in Synthesis Example 1, 0.03 g of maleic acid, 19.36 g of ultrapure water, 0.01 g of benzyltriethylammonium chloride, 7.02 g of propylene glycol monomethyl ether acetate, and 14.89 g of propylene glycol monomethyl ether And 90.64 g of propylene glycol monoethyl ether were added to prepare a resist underlayer film material.

(Example 2)

A resist underlayer film material was prepared in the same manner as in Example 1 except that the polymer solution (solid content of 15.00% by mass) obtained in Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1.

(Example 3)

A resist underlayer film material was prepared in the same manner as in Example 1 except that the polymer solution (solid content of 15.00% by mass) obtained in Synthesis Example 3 was used instead of the polymer obtained in Synthesis Example 1.

(Example 4)

To 20.00 g of the polymer solution (15.00 mass% solids) obtained in Synthesis Example 1, 0.03 g of maleic acid, 19.36 g of ultrapure water, 0.01 g of triphenylsulfonium chloride, 7.02 g of propylene glycol monomethyl ether acetate, and 14.89 g of propylene glycol monomethyl ether And 90.64 g of propylene glycol monoethyl ether were added to prepare a resist underlayer film material.

(Example 5)

To 20.00 g of the polymer solution (15.00 mass% solids) obtained in Synthesis Example 1, 0.03 g of maleic acid, 19.36 g of ultrapure water, 0.01 g of triphenylsulfonium maleate, 7.02 g of propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether 14.89 g and propylene glycol monoethyl ether 90.64 g were added to prepare a resist underlayer film material.

(Example 6)

To 20.00 g of the polymer solution (15.00 mass% solids) obtained in Synthesis Example 1, 0.03 g of maleic acid, 19.36 g of ultrapure water, 0.01 g of N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, and propylene 7.02 g of glycol monomethyl ether acetate, 14.89 g of propylene glycol monomethyl ether, and 90.64 g of propylene glycol monoethyl ether were added to prepare a resist underlayer film material.

(Comparative Example 1)

A resist underlayer film material was prepared in the same manner as in Example 1 except that the polymer solution (solid content of 15.00% by mass) obtained in Comparative Synthesis Example 1 was used instead of the polymer obtained in Synthesis Example 1.

(Comparative Example 2)

A resist underlayer film material was prepared in the same manner as in Example 1 except that the polymer solution (solid content of 15.00% by mass) obtained in Comparative Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1.

(Solvent resistance test)

The resist underlayer film-forming composition was applied onto the silicon wafer by spin coating, respectively, and baked on a hot plate at 140 ° C. for 1 minute to form a resist underlayer film. Subsequently, it is immersed in propylene glycol monomethyl ether acetate used for the solvent of the top coat resist composition for 1 minute, and when the change of the film thickness of the resist underlayer film is 1 nm or less before and after immersion, it is judged as "good" and displays "○", When the change in the film thickness was more than that, it was judged as "defective" and "x" was displayed. The results are shown in Table 2.

Hereinafter, the resist underlayer film obtained from the resist underlayer film forming composition of Examples 1-6 is shown as Example resist underlayer film 1-6. The resist underlayer film obtained from the resist underlayer film forming composition of Comparative Examples 1-2 was shown as Comparative Example resist underlayer film 1-2.

[Table 2]

(Optical constant measurement)

The resist underlayer film forming composition was apply | coated on a silicon wafer using the spinner, respectively. It heated at 240 degreeC on the hotplate for 1 minute, and formed the resist underlayer film (film thickness 0.09 micrometer). The resist underlayer films were also referred to as refractive index (n value) and optical absorption coefficient (k value, attenuation coefficient) at a wavelength of 193 nm using a spectroscopic ellipsometer (JAWoollam Co., Inc., VUV-VASE VU-302). ) Was measured. The results are shown in Table 3.

[Table 3]

(Measurement of dry etching rate)

The etchant and etching gas used for the measurement of a dry etching rate are as follows.

Etcher was used ES401 (trade name, Nippon Scientific Co., Ltd. agent), it was subjected to etching with a CF ₄ gas.

Further, etcher was used for RIE-10NR (trade name, SAMCO International Inc. agent), it was subjected to etching with O ₂ gas.

The solutions of the resist underlayer film forming compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were each applied onto a silicon wafer using a spinner. It heated at 240 degreeC on the hotplate for 1 minute, the resist underlayer film was formed, and the etching rate was measured using each etching gas. The etching rate was measured using CF ₄ gas as an etching gas at the film thickness of the resist underlayer film, and the etching rate was measured using an O ₂ gas as the etching gas at a film thickness of 0.08 μm of the resist underlayer film.

Similarly, a photoresist solution (Shipley Company Inc., trade name UV113) was formed using a spinner to form a resist film of 0.20 mu m on the silicon wafer. Dry etching rate was measured using CF ₄ gas and O ₂ gas as etching gas. And the dry etching rate of the resist underlayer film and the resist film was compared. The results are shown in Table 4. The speed ratio is a dry etching speed ratio of (resist underlayer film) / (resist).

[Table 4]

(Manufacture of organic underlayer film)

Into a 200 mL flask was added 16.5 g of acenaphthylene, 1.5 g of 4-hydroxystyrene and 60 g of 1,2-dichloroethane as a solvent. 1 g of trifluoroboron was added as a polymerization initiator, and it heated up to 60 degreeC, and made it react for 24 hours. Methanol 1L and water 500g were added to this solution, reprecipitation purification was carried out, and the obtained white solid was filtered and dried to obtain 11 g of a white polymer.

When the obtained polymer (formula (3-2)) was measured by ¹³ C, ¹ H-NMR and GPC, the molar ratio of acenaphthylene: 4-hydroxystyrene was 86:14.

The weight average molecular weight Mw was 6000 and the weight average molecular weight Mw / number average molecular weight Mn = 1.5.

[Chemical Formula 17]

1.0 g of tetramethoxymethylglycoluril (manufactured by Mitsui Cytec Ltd., trade name POWDERLINK 1174) to the obtained 10 g polymer (formula (3-2)), 0.01 g of paratoluenesulfonic acid as a crosslinking catalyst, and MEGAFAC R- as a surfactant. 0.03g of 30 (Dainippon Ink and Chemicals, Inc., brand name) was added, and it dissolved in 101.57g of propylene glycol monomethyl ether acetates and 25.39g of propylene glycol monomethyl ethers. Thereafter, the resultant was filtered using a polyethylene microfilter having a pore diameter of 0.10 mu m, and again filtered using a polyethylene micro filter having a pore diameter of 0.05 mu m, and a solution of the organic underlayer film forming composition used in the lithography process by a multilayer film. It prepared.

(Resist patterning evaluation)

The organic underlayer film (A layer) forming composition containing the polymer (formula (3-2)) was applied onto a silicon wafer, heated at 240 ° C. on a hot plate for 1 minute, and an organic underlayer film (A) having a film thickness of 250 nm. Layer). The Si-containing resist underlayer film (B layer) compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were respectively applied thereon, and heated at 240 ° C. on a hot plate for 1 minute to form a Si having a thickness of 35 nm. A containing resist underlayer film (B layer) was obtained. Commercially available photoresist solution (trade name PAR 855, manufactured by Sumitomo Chemical Company) was applied thereon using a spinner, and heated at 100 ° C. on a hot plate for 1 minute to form a photoresist film (C layer) having a thickness of 150 nm. It was. The resist was patterned using an ASML immersion exposure machine TWIN SCAN XT: 1900Gi scanner (wavelength 193 nm, NA, sigma: 1.20, 0.94 / 0.74 (C-quad) immersion liquid: water). The target was exposed through a mask set so that 15 lines were formed in so-called dense lines, in which the line width of the photoresist and the line-to-line width thereof were 0.05 µm after development. Thereafter, the plate was baked at 105 DEG C on a hot plate for 60 seconds, and after cooling, developed with a 2.38% tetramethylammonium hydroxide developer in an industrial standard 60 second single paddle process.

[Table 5]

Footing is a hemming bottom phenomenon at the bottom of the pattern in the resist pattern shape, and undercut is a thin phenomenon at the bottom of the pattern in the resist pattern shape, and both are undesirable because they do not exhibit a rectangular pattern shape.

Since the resist underlayer film obtained from the amic acid or the resist underlayer film forming composition which has an amic acid ester structure contains many hetero elements, it has a sufficiently high dry etching rate with respect to a photoresist film. In Examples 1-6, since the etching rate by a fluorine-type gas improves compared with Comparative Examples 1-2, the resist pattern of the upper layer of the resist underlayer film of this invention can be correctly transferred to the resist underlayer film of this invention.

In addition, since the resist underlayer film obtained from the resist underlayer film forming composition of Examples 1-6 is the same as the etching resistance by oxygen gas compared with the resist underlayer film obtained from the resist underlayer film forming composition of Comparative Examples 1-2, It has a sufficiently high function as a hard mask at the time of processing the organic underlayer film and board | substrate which are the lower layer of the resist underlayer film of this invention.

In the case of resist patterning of 0.08 mu m, when Examples 1, 4 to 6 and Comparative Example 1 were compared, the refractive index n and the optical absorption coefficient k were equal values (resist underlayer film having a low optical absorption coefficient k). In Examples 1, 4 to 6, in which the terminal carboxylic acid moiety is not closed, it is found that it is effective in reducing the hemming bottom of the resist.

On the other hand, when Examples 2 to 3 and Comparative Example 2 are compared, although the refractive index n and the optical absorption coefficient k are equal values (resist underlayer film having a high optical absorption coefficient k), the terminal carboxylic acid is closed during the film formation and the imide In Example 2 which forms a structure, and Example 3 which is an amide carboxylic acid ester, since the favorable phosphorus characteristic (adhesiveness) is shown, it turns out that it is effective in improving adhesiveness with a resist.

The resist underlayer film forming composition having the amic acid or the amic acid ester structure according to the present invention can control the resist shape depending on whether or not the structure is changed during film formation.

Claims (11)

In the resist underlayer film forming composition for lithography containing a hydrolyzable organosilane, its hydrolyzate, its hydrolysis condensate, or a mixture thereof as a silane compound, the said silane compound contains an amide bond, a carboxylic acid moiety or A resist underlayer film forming composition for lithography comprising a silane compound comprising a carboxylic acid ester moiety or an organic group comprising these two moieties.
The method of claim 1,
The resist underlayer film forming composition for lithography in which the ratio of the silane compound and the silane compound which contains an amide bond and an organic group containing a carboxylic acid part, a carboxylic acid ester part, or these two parts in all the said silane compounds is less than 5 mol%.
The method of claim 1,
The resist underlayer film forming composition for lithography in which the ratio of the silane compound and the silane compound containing the carboxylic acid moiety, the carboxylic acid ester moiety, or the organic group containing these two parts in the whole silane compound is 0.5-4.9 mol%.
4. The method according to any one of claims 1 to 3,
The hydrolyzable organosilane is of formula (1):
[Formula 1]

(In formula, R <^3> is an organic group containing an amide bond, a carboxylic acid part, a carboxylic acid ester part, or these two parts, and shows the group couple | bonded with the silicon atom by Si-C bond. R <^1> is an alkyl group , An organic group having 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, or a cyano group, and bonded to a silicon atom by a Si-C bond. R <^2> represents an alkoxy group, an acyloxy group, or a halogen atom. The resist underlayer film forming composition for lithography which is a compound represented by the integer of 0 or 1, and b represents the integer of 1 or 2.
5. The method according to any one of claims 1 to 4,
Equation (2):
(2)

(Wherein R ⁴ is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, acryloyl group, methacryloyl group, mercapto group, alkoxyaryl group, acyloxyaryl group, or cyano group) And an organic group having a group bonded to a silicon atom by a Si-C bond, R ⁵ represents an alkoxy group, an acyloxy group, or a halogen atom, and a represents an integer of 0 to 3). Organosilicon compounds,
And formula (3):
(3)

(Wherein R ⁶ represents an alkyl group, R ⁷ represents an alkoxy group, acyloxy group, or halogen atom, Y represents an alkylene group or arylene group, b represents an integer of 0 or 1, c is 0 Or at least one selected from the group consisting of organosilicon compounds represented by
The resist underlayer film forming composition for lithography containing the combination of hydrolysable organosilane represented by said Formula (1), its hydrolyzate, or its hydrolysis condensate.
The method according to any one of claims 1 to 5,
Hydrolysis-condensation product of the hydrolyzable organosilane represented by said Formula (1), or hydrolysis-condensation product of the hydrolyzable organosilane represented by said Formula (1), and the compound represented by Formula (2) as a polymer A resist underlayer film forming composition for lithography.
7. The method according to any one of claims 1 to 6,
A resist underlayer film forming composition for lithography, further comprising an acid as a hydrolysis catalyst.
8. The method according to any one of claims 1 to 7,
The resist underlayer film forming composition for lithography which further contains water.
The resist underlayer film obtained by apply | coating and baking the resist underlayer film forming composition in any one of Claims 1-8 on a semiconductor substrate.
The process of apply | coating the resist underlayer film forming composition in any one of Claims 1-8 on a semiconductor substrate, baking, and forming a resist underlayer film, The process of apply | coating a resist composition on the said underlayer film, and forming a resist film. Exposing the resist film; developing the resist film after exposure to obtain a patterned resist film; etching the resist underlayer film with the patterned resist film; and patterning the resist film and resist underlayer film The manufacturing method of a semiconductor device including the process of processing a semiconductor substrate.
A process of forming an organic underlayer film on a semiconductor substrate, The process of apply | coating and baking the resist underlayer film forming composition of any one of Claims 1-8 on it, and forming a resist underlayer film on the said resist underlayer film for resists Applying a composition to form a resist film, exposing the resist film, developing the resist film after exposure to obtain a patterned resist film, etching the resist underlayer film with the patterned resist film, patterning A method of manufacturing a semiconductor device, comprising a step of etching an organic underlayer film by a resist underlayer film, and a step of processing a semiconductor substrate by a patterned organic underlayer film.