KR101847382B1

KR101847382B1 - Silicon-containing resist underlayer-forming composition containing amic acid

Info

Publication number: KR101847382B1
Application number: KR1020127023883A
Authority: KR
Inventors: 유타 칸노; 마코토 나카지마; 와타루 시바야마; 사토시 타케다
Original assignee: 닛산 가가쿠 고교 가부시키 가이샤
Priority date: 2010-02-25
Filing date: 2011-02-22
Publication date: 2018-04-10
Also published as: JPWO2011105368A1; TWI507825B; TW201202855A; JP5590354B2; WO2011105368A1; KR20130009774A

Abstract

[PROBLEMS] To provide a resist underlayer film forming composition for lithography for forming a resist undercoat film usable as a hard mask.
In a composition containing a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolyzed condensate thereof as a silane compound, the silane compound has an amide bond in the molecule and a carboxylic acid moiety or a carboxylic acid ester moiety or And a silane compound containing an organic group containing these two moieties. A composition for forming a resist for a lower layer film for lithography, wherein the ratio of the amide bond and the silane compound containing a carboxylic acid moiety or a carboxylic acid ester moiety or an organic moiety containing both these moieties is present in a proportion of less than 5 mol% . A resist underlayer film forming process in which a ratio of an amide bond and a silane compound containing a carboxylic acid moiety or a carboxylic acid ester moiety or an organic group containing both of these moieties is present in a proportion of 0.5 to 4.9 mol% Composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a silicon-containing resist underlayer film-forming composition containing amic acid,

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

Conventionally, in the manufacture of semiconductor devices, fine processing by lithography using a photoresist has been performed. The microfabrication is performed by forming a thin film of photoresist on a semiconductor substrate such as a silicon wafer, irradiating actinic rays such as ultraviolet rays through a mask pattern on which a pattern of a semiconductor device is drawn and developing the photoresist, And the substrate is subjected to an etching treatment to form fine unevenness corresponding to the pattern on the substrate surface. However, recently, with the progress of highly integrated semiconductor devices, there is a tendency that active rays used are also short-wavelengthed by an ArF excimer laser (193 nm) in a KrF excimer laser (248 nm). As a result, the influence of the reflection of the active ray from the semiconductor substrate has become a great problem.

Further, a film known as a hard mask containing a metal element such as silicon or titanium is used as a lower layer film between a semiconductor substrate and a photoresist (see, for example, Patent Document 1). In this case, since there is a large difference between the components of the resist and the hard mask, the rate of removal by the dry etching largely 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 recent semiconductor device manufacturing, a resist underlayer film is disposed between a semiconductor substrate and a photoresist in order to achieve various effects including an antireflection effect. Although a composition for a resist underlayer film has been studied up to now, development of a new material for a resist underlayer film is required due to various properties required.

As a lower layer film between a semiconductor substrate and a photoresist, a film known as a hard mask containing a metal element such as silicon or titanium is used (see, for example, Patent Document 1). In this case, since there is a large difference between the components of the resist and the hard mask, the rate of removal by the dry etching largely 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 recent semiconductor device manufacturing, a resist underlayer film is disposed between a semiconductor substrate and a photoresist in order to achieve various effects including an antireflection effect. Although a composition for a resist underlayer film has been studied up to now, development of a new material for a resist underlayer film is required due to various properties required.

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

Further, a silicon-containing top-surface antireflection film having a dicarboxyimide structure is disclosed (see, for example, Patent Document 3).

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

It is an object of the present invention to provide a resist underlayer film forming composition for lithography which can be used for the production of a semiconductor device. Specifically, the present invention is to provide a composition for forming a resist lower layer film for lithography for forming a resist lower layer film which can be used as a hard mask. It is still another object of the present invention to provide a resist underlayer film forming composition for lithography for forming a resist underlayer film which can be used as an antireflection film. Another object of the present invention is to provide a resist underlayer film for lithography that does not intermix with a resist and has a larger dry etching rate than resist, and a composition for forming a resist lower layer film for forming the underlayer film.

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

The present invention, as a first aspect, relates to a composition for forming a resist underlayer film for lithography, which comprises a hydrolyzable organosilane, a hydrolyzate thereof, a hydrolyzed condensate thereof, or a mixture thereof as a silane compound, A resist underlayer film forming composition for lithography comprising an amide bond in a molecule and a silane compound containing an organic group containing a carboxylic acid moiety or a carboxylic acid ester moiety or both of these moieties,

According to a second aspect, there is provided a process for producing a silane compound according to the first aspect wherein the ratio of the amide bond and the silane compound containing an organic group having a carboxylic acid moiety or a carboxylic acid ester moiety or both of these moieties is less than 5 mol% A resist lower layer film forming composition for lithography,

As a third aspect, it is preferable that the total amount of the silane compound is in the range of from 0.5 to 4.9 mol% of the silane compound having an amide bond and an organic group containing a carboxylic acid moiety or a carboxylic acid ester moiety or both moieties A resist underlayer film forming composition for lithography,

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

[Chemical Formula 1]

(Wherein R ³ represents an amide bond and a group which is an organic group containing a carboxylic acid moiety or a carboxylic acid ester moiety or both of these moieties and which is bonded to a silicon atom by a Si-C bond, R ¹ represents an alkyl group , An aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group or a cyano group, R ² represents an alkoxy group, an acyloxy group, or a halogen atom, a represents 0 or 1, and b represents an integer of 1 or 2), which is a compound represented by any one of the first to third aspects,

As a fifth aspect, the expression (2):

(2)

(Wherein R ⁴ represents an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an alkoxyaryl group, an acyloxyaryl group, And 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 (3):

(3)

(Wherein R ⁶ represents an alkyl group, R ⁷ represents an alkoxy group, an acyloxy group or a halogen atom, Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, c represents 0 Or an integer of 1), and at least one member selected from the group consisting of an organosilicon compound represented by the following formula

The composition according to any one of the first to fourth aspects, which comprises a combination of the hydrolyzable organosilane represented by the above formula (1), a hydrolyzate thereof, or a hydrolyzed condensate thereof,

As a sixth aspect, there is provided a hydrolysis-condensation product of a hydrolysable organosilane represented by the above formula (1), or a hydrolysable condensate of a hydrolyzable organosilane represented by the above formula (1) and a compound represented by the formula (2) The composition according to any one of the first to fifth aspects comprising a decomposition and condensation product 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 an eighth aspect, the composition according to any one of the first to seventh aspects, further comprising water,

As a ninth aspect, there is provided a resist underlayer film obtained by applying and baking the resist underlayer film forming composition described in any one of the first to eighth aspects on a semiconductor substrate,

As a tenth aspect, there is provided a method for manufacturing a resist, comprising the steps of applying a resist lower layer film forming composition described in any one of the first to eighth aspects onto a semiconductor substrate and firing to form a resist underlayer film; A step of exposing the resist film to light; a step of developing the resist film after exposure to obtain a patterned resist film; a step of etching the resist lower layer film by the patterned resist film; A step of processing a semiconductor substrate by a resist film and a resist lower layer film, and

As an eleventh aspect, there is provided a method for manufacturing a semiconductor device, comprising the steps of: forming an organic underlayer film on a semiconductor substrate; forming a resist underlayer film by applying and baking the resist underlayer film forming composition described in any one of the first to eighth aspects; A step of forming a resist film by applying a resist composition on the resist lower layer film, a step of exposing the resist film, a step of developing the resist film after exposure to obtain a patterned resist film, Etching the film, etching the organic underlayer film with the patterned resist underlayer film, and processing the semiconductor substrate with the patterned organic underlayer film.

Hydrolyzable groups such as alkoxy groups, acyloxy groups and halogen atoms in the compound represented by the above formula (1) are hydrolyzed or partially hydrolyzed, and a polymer having a polysiloxane structure is formed as a main chain by the subsequent condensation reaction of silanol groups do. Due to the polysiloxane structure, the resist underlayer film containing the polymer has a high dry etching resistance to an oxygen-based dry etching gas. Further, the polymer has a carbon-nitrogen bond or a carbon-oxygen bond. According to the above structure, since the film containing the polymer has a high dry etching rate by the halogen-based gas, the upper layer resist pattern can be transferred to the film. Depending on these characteristics, the resist underlayer film formed from the resist underlayer film forming composition of the present invention containing the polymer can function as a hard mask.

Further, according to the manufacturing method of the semiconductor device of the present invention, since the resist pattern in the upper layer can be accurately transferred to the resist lower layer film, as compared with the case of using the conventional resist lower layer film, a good resist pattern shape can be obtained.

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

After forming a fine pattern, the thickness of the resist film tends to be thinned to prevent pattern collapse. Dry etching for transferring a pattern to a film existing in the lower layer by thinning of the resist can transfer the pattern only when the etching rate is higher than that of the film in the upper layer. In the present invention, a resist underlayer film (containing an inorganic silicon compound) of the present invention is coated on the substrate without sandwiching the organic undercoat film therebetween, or the organic undercoat film is interposed therebetween, and a resist film (organic resist film) . Since the film of the organic component and the film of the inorganic component differ greatly in dry etching rate depending on the selection of the etching gas, the film of the organic component becomes an oxygen-based gas and the dry etching rate becomes high.

For example, a resist pattern is formed, and the resist underlayer film of the present invention existing under the resist pattern is dry-etched with a halogen-containing gas to transfer the pattern to the resist underlayer film. Then, The substrate processing is performed. Alternatively, the patterned resist underlayer film is used to dry-etch the underlying organic undercoat film with an oxygen-based gas to transfer the pattern to the organic undercoat film, and then the substrate with the halogen-containing gas is processed into the patterned organic undercoat film I do.

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

The hydrolyzable group such as an alkoxy group, an acyloxy group and a halogen atom in the structure of the above formula (1) is hydrolyzed or partially hydrolyzed, and then the polymer of the polysiloxane structure is formed by the condensation reaction of the silanol group. This polyorganosiloxane structure has a sufficient function as a hard mask.

Since these bonding sites included in the polyorganosiloxane have a carbon-nitrogen bond or a carbon-oxygen bond, the dry etching rate due to the halogen-based gas is faster than the carbon-carbon bond. Therefore, This is effective when transferring to a film.

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

The resist underlayer film of the present invention has improved dry etching rate for these upper layer resist and internal dry etching property such as at the time of substrate processing.

And a good resist pattern shape can be formed.

The present invention relates to a resist underlayer film forming composition for lithography comprising a hydrolyzable organosilane, a hydrolyzate thereof, or a hydrolyzed condensate thereof as a silane compound, wherein the silane compound has an amide bond and a carboxylic acid moiety or A main ester moiety, or a silane compound containing an organic group containing both of these moieties.

It is described that the hydrolyzable organosilane has an amide bond in the molecule and an organic group containing a carboxylic acid moiety or a carboxylic acid ester moiety or both of these moieties. This is because a combination of an amide bond and a carboxylic acid moiety (Amic acid structure), or one or both of an amide bond and a carboxylic acid ester moiety (an amic acid ester structure).

The silane compound having an amide bond and an organic group containing a carboxylic acid moiety or a carboxylic acid ester moiety or both of these moieties in the entire silane compound is contained in an amount of less than 5 mol%, for example, 0.5 to 4.9 mol% 1.0 mol%, or 0.5 to 0.999 mol%.

The above-mentioned hydrolyzable organosilane, its hydrolyzate and its hydrolyzed condensate may be used as a mixture of these. The hydrolyzable organosilane can be used as a condensate obtained by hydrolyzing the hydrolyzable organosilane and condensing the obtained hydrolyzate. When the hydrolysis-condensation product is obtained, the partial hydrolyzate or the silane compound which is not completely hydrolyzed may be mixed with the hydrolysis-condensation product to use the mixture. This condensate is a polymer having a polysiloxane structure. The polysiloxane is bound to an amide bond and an organic group comprising a carboxylic acid moiety or a carboxylic acid ester moiety or both.

The resist underlayer film forming composition of the present invention is a composition for forming a resist lower layer film which comprises an amide bond and a hydrolyzable organosilane having a carboxylic acid moiety or a carboxylic acid ester moiety or an organic group containing both of these moieties, Solvent. As optional components, it may include an acid, water, an alcohol, a curing catalyst, an acid generator, another organic polymer, a light absorbing compound and a surfactant.

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

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

The hydrolyzable organosilane used in the present invention has the structure represented by the formula (1).

R ³ represents an amide bond and a group which is an organic group containing a carboxylic acid moiety or a carboxylic acid ester moiety or both of these moieties and 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, &Lt; / RTI > R ² represents an alkoxy group, an acyloxy group, or a halogen atomic group. a represents an integer of 0 or 1, and b represents an integer of 1 or 2.

The alkyl group in R ¹ in the formula (1) is a linear or branched alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, i- Butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group Methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, Butyl group, a 2,3-dimethyl-n-butyl group, a 3-dimethyl-n-butyl group, Butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl- Ethyl-2-methyl-n-propyl group and the like.

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

Examples of the aryl group include an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, A phenyl group, an o-fluorophenyl group, a p-mercaptophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, An anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group , 4-phenanthryl group and 9-phenanthryl group.

Examples of the alkenyl group include an alkenyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethynyl group, Propenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, Methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-1-butenyl group, 1-methyl-1-pentenyl group, Methyl-1-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1- Butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2- Cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, -Hexenyl group, 5-hexenyl group, 1-methyl-1-pentene Methyl-2-pentenyl group, a 1-methyl-4-pentenyl group, a 1-n-butylethenyl group, a 2- 2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, Methyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4- Methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2- Methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, Butenyl group, a 1,3-dimethyl-2-butenyl group, a 1,3-dimethyl-3-butenyl group, 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-propenyl-1-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-1-butenyl group, Ethyl-2-propenyl group, 1-t-butyl ethenyl group, 1-methyl-1-ethyl- Ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1- Cyclopentenyl group, a 2-methyl-2-cyclopentenyl group, a 2-methyl-3-cyclopentenyl group, Cyclopentenyl group, a 3-methyl-1-cyclopentenyl group, a 3-methyl-2-cyclopentenyl group, a 3- Cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3 -Cyclohexenyl group and the like.

Further, organic groups substituted with a halogen atom such as fluorine, chlorine, bromine, or iodine may be mentioned.

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

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

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

Examples of the organic group having a mercapto group include an ethylmercapto group, a butylmercapto group, a hexylmercapto group, and an octylmercapto group.

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

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

Examples of the acyloxy group having 1 to 20 carbon atoms in R ² of the formula (1) include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, i-propylcarbonyloxy, Butylcarbonyloxy group, n-pentylcarbonyloxy group, 1-methyl-n-butylcarbonyloxy group, 2-methyl-n-butyl N-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-butylcarbonyloxy group, N-pentylcarbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-propylcarbonyloxy group, N-butylcarbonyloxy group, a 1,2-dimethyl-n-butylcarbonyloxy group, a 1,3-dimethyl-n-propylcarbonyloxy group, Butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n- N-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, N-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbamoyl group, A naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group,

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

The hydrolyzable organosilane represented by the formula (1) can be exemplified as follows.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The hydrolyzable organosilane represented by the formula (1) may be a commercially available product, but may also be synthesized.

For example, it can be synthesized by reacting aminosilane with an acid anhydride.

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

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

The ratio of the hydrolyzable organosilane represented by the formula (1) to the organosilicon compound represented by the formula (2) and / or the organosilicon compound represented by the formula (3) is 1: 0 to 1: 200 Of the total. In order to obtain a good resist shape, the ratio of the hydrolyzable organosilane represented by the formula (1) to the organosilicon compound represented by the formula (2) and / or the organosilicon compound represented by the formula (3) 199 to 1:19.

The organosilicon compound selected from the group consisting of the organosilicon compound represented by the formula (2) and the organosilicon compound represented by the formula (3) is preferably the organosilicon compound represented by the formula (2).

These are preferably used as the hydrolysis-condensation product (polymer of polyorganosiloxane), and the hydrolysis-condensation product of the hydrolyzable organosilane represented by the formula (1) and the organosilicon compound represented by the formula (2) Siloxane polymer) is preferably used.

The alkyl group, aryl group, halogenated alkyl group, halogenated aryl group and alkenyl group represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ in the organosilicon compound represented by formula (2) and the organosilicon compound represented by formula (3) , An alkoxy group, an acyloxy group, or a halogen atom contained in an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and further in the hydrolyzable group, Can be exemplified. The organic group having an alkoxyaryl group or an acyloxyaryl group may be a combination of the alkoxy group, acyloxy group and aryl group.

The organosilicon compound represented by the formula (2) includes, for example, tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, But are not limited to, butoxysilane, butoxysilane, tetraacetoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, But are not limited to, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? - Glycidoxyethyltriethoxysilane,? -Glycidoxyethyltrimethoxysilane,? -Glycidoxyethyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane, Ethoxy silane,? -Glycidoxine Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltripropoxysilane ,? -glycidoxypropyltributoxysilane,? -glycidoxypropyltriphenoxysilane,? -glycidoxybutyltrimethoxysilane,? -glycidoxybutyltriethoxysilane,? -glycidoxime Butyl triethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltriethoxysilane,? -Glycidoxybutyltrimethoxysilane,? -Glycidoxybutyltriethoxysilane,? -Glycidoxybutyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane,? - (3,4-epoxycyclohexyl) (3,4-epoxycyclohexyl) ethyltripropoxysilane,? - (3,4-epoxycyclohexyl) ethyltriethoxysilane, (3,4-epoxycyclohexyl) ethyltriphenoxysilane,? - (3,4-epoxycyclohexyl) propyltrimethoxysilane,? - Cyclohexyl) propyltriethoxysilane,? - (3,4-epoxycyclohexyl) butyltrimethoxysilane,? - (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxy Silane, glycidoxymethylmethyldiethoxysilane,? -Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethylmethyldiethoxysilane,? -Glycidoxyethylmethyldimethoxysilane,? -Glycidoxyethyl Methyldimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylethyldimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldi Glycidoxypropylethyldimethoxysilane, gamma -glycidoxypropylmethyldibutoxysilane, gamma -glycidoxypropylmethyldiphenoxysilane, gamma -glycidoxypropylethyldimethoxysilane, gamma -glycidoxypropylethyldiethoxysilane, gamma -glycidoxypropylethyldiethoxysilane, gamma- -Glycidoxypropyl vinyldimethoxysilane,? -Glycidoxypropyl vinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, But are not limited to, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, methoxyphenyltrimethoxysilane, meth Methoxybenzyltriethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltricycle in Silane, methoxyphenylethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltrimethoxysilane, Ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, iso-benzyltrimethoxysilane, Propoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriethoxysilane, Isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t -But Butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, t-butoxybenzyltrimethoxysilane, t- But are not limited to, silane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxy Silane, ethoxynaphthyltrichlorosilane, acetoxyphenyltrimethoxysilane, acetoxyphenyltriethoxysilane,? -Chloropropyltrimethoxysilane,? -Chloropropyltriethoxysilane,? -Chloropropyltriethacene ? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane,? -Mercaptopropyltrimethoxysilane, Cyanoethyltriethoxysilane, chloromethyl But are not limited to, trimethoxy silane, trimethoxy silane, chloromethyl triethoxy silane, dimethyl dimethoxy silane, phenyl methyl dimethoxy silane, dimethyl diethoxy silane, phenyl methyl diethoxy silane, Silane, dimethyldiacetoxysilane,? -Methacryloxypropylmethyldimethoxysilane,? -Methacryloxypropylmethyldiethoxysilane,? -Mercaptopropylmethyldimethoxysilane,? -Mercaptomethyldiethoxysilane, methyl Vinyl dimethoxysilane, methylvinyldiethoxysilane, and the like.

The organosilicon compound represented by the formula (3) includes, for example, methylenebistrimethoxysilane, methylenebistriclorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebisttrichlorosilane, Butylene bistrimethoxysilane, phenylene bistrimethoxysilane, phenylene bistriethoxysilane, phenylene bismethyldiethoxysilane, phenylene bismethyl dimethoxysilane, naphthyl bistrimethoxy silane, Bismethyldiethoxydisilane, bismethyldimethoxydisilane, and the like can be given as examples of the silane coupling agent.

Concrete examples of the hydrolysis-condensation product of the hydrolyzable organosilane represented by the formula (1) and the organosilicon compound represented by the formula (2) include condensates having the following unit structures.

(7)

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

GPC column (trade name: Shodex KF803L, KF802, KF801, manufactured by Showa Denko KK), column temperature of 40 占 폚, eluent ( (Elution solvent) is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml / min, and the standard sample is polystyrene (manufactured by Showa Denko KK).

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

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

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

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

A catalyst 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.

Examples of the metal chelate compound as the hydrolysis catalyst include triethoxy mono (acetylacetonate) titanium, tri-n-propoxy mono (acetylacetonate) titanium, tri- (Acetyl acetonate) titanium, tri-sec-butoxy mono (acetylacetonate) titanium, tri-t-butoxy mono (acetylacetonate) titanium, Bis (acetylacetonate) titanium, di-n-propoxy bis (acetylacetonate) titanium, di-i-propoxy bis (acetylacetonate) titanium, di- (Acetylacetonate) titanium, di-sec-butoxy bis (acetylacetonate) titanium, di-t-butoxy bis (acetylacetonate) titanium, monoethoxy tris n-propoxy tris (acetylacetonate) titanium, mono-i-propoxy tris (acetyl Butoxy tris (acetyl acetonate) titanium, mono-sec-butoxy tris (acetylacetonate) titanium, mono-t-butoxy tris (acetylacetonate) titanium, (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethylacetoacetate) titanium, tri-i-propoxy mono (ethylacetoacetate) titanium (Ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethylacetoacetate) titanium, tri-t-butoxy mono (ethylacetoacetate) titanium, diethoxy bis (Ethyl acetoacetate) titanium, di-n-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (ethylacetoacetate) titanium, Titanium, di-sec-butoxy-bis (ethylacetoacetate) titanium, (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethylacetoacetate) titanium, mono-i-propoxy tris Butoxy tris (ethyl acetoacetate) titanium, mono-sec-butoxy tris (ethylacetoacetate) titanium, mono-t-butoxy tris (ethylacetoacetate) titanium (Ethyl acetoacetate) titanium, bis (acetylacetonate) titanium, tris (acetylacetonate) mono (acetylacetonate) titanium, bis Titanium chelate compounds such as titanium; Tri-n-butoxy mono (acetylacetonate) zirconium, tri-n-propoxy mono (acetylacetonate) zirconium, tri- (Acetylacetonate) zirconium, diethoxy bis (acetylacetonate) zirconium, di-tert-butoxy mono (acetylacetonate) zirconium, n-butoxy bis (acetylacetonate) zirconium, di-i-propoxy bis (acetylacetonate) zirconium, di- (Acetylacetonate) zirconium, di-t-butoxy bis (acetylacetonate) zirconium, monoethoxy tris (acetylacetonate) zirconium, mono-n-propoxy tris Mono-i-propoxy tris (Acetylacetonate) zirconium, mono-sec-butoxy tris (acetylacetonate) zirconium, mono-t-butoxy tris (acetylacetonate) zirconium (Ethylacetoacetate) zirconium, tri-n-propoxy mono (ethylacetoacetate) zirconium, tri-i-propoxy mono (ethylacetoacetate) (Ethyl acetoacetate) 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 Acetate) zirconium, di-sec-butoxy bis (ethylacetoacetate) zirconium, di-t-butoxy bis (ethylacetoacetate) zirconium, monoethoxy tris (ethylacetoacetate) zirconium, Propoxy tris (ethylacetoacetate) zirconium, mono-i-propoxy tris (ethylacetoacetate) zirconium, mono-n-butoxy tris (ethylacetoacetate) zirconium, mono-sec-butoxy tris Ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, mono (acetylacetonate) tris (ethylacetoacetate) zirconium, bis 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.

Examples of the organic acid as the hydrolysis catalyst include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, But are not limited to, acetic acid, succinic acid, tartaric acid, tartaric acid, tartaric acid, tartaric acid, tartaric acid, tartaric acid, tartaric acid, 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.

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

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

Examples of the solvent include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, Aromatic hydrocarbon solvents such as naphthalene and trimethylbenzene;

Propanol, n-butanol, i-butanol, sec-butanol, t-butanol, Butanol, 2-ethylhexanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol n-decanol, sec-undecyl alcohol, trimethyl nonyl 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- Polyhydric alcohol solvents such as diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and glycerin;

But are not limited to, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, Ketone solvents such as ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone and fenchone;

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, 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, tetrahydrofuran, Ether solvents such as 2-methyltetrahydrofuran;

Propyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-butyl acetate, n-butyl acetate, Propyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate , Ethyl acetoacetate, acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, acetic acid diethylene glycol mono-n-butyl ether, acetic acid propylene glycol mono Methyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid glycol, 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;

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.

Particularly preferred are ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, -Butyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone, Trimethyl-2-norbornene) are preferred from the viewpoint of the storage stability of the solution.

The resist underlayer film forming composition of the present invention may contain a curing catalyst. The curing catalyst functions as a curing catalyst when curing a coating film containing a polyorganosiloxane composed of a hydrolyzed condensate.

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

As the ammonium salt, a compound represented by the formula (D-1):

[Chemical Formula 8]

(Wherein m is an integer of 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), a quaternary ammonium salt represented by the formula (D- 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 Each of which is bonded to the nitrogen atom by a CN bond), a quaternary ammonium salt having a structure represented by the formula

Formula (D-3):

[Chemical formula 10]

(Provided that R ¹⁶ and R ¹⁷ each independently represent an alkyl group or an aryl group, and Y _A ^- represents an anion), a quaternary ammonium salt,

Formula (D-4):

(11)

(Wherein R ¹⁸ represents an alkyl group or an aryl group, and Y _A ^- represents an anion)

Formula (D-5):

[Chemical Formula 12]

(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]

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

As the phosphonium salt, a compound represented by the formula (D-7):

[Chemical Formula 14]

(Wherein R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent an alkyl group or an aryl group, P represents a phosphorus atom, Y _A ^- represents an anion, and R ²¹ , R ²² , R ²³ and R ²⁴ Are each independently bonded to a phosphorus atom by CP bonding).

As the sulfonium salt, a compound represented by the formula (D-8):

[Chemical Formula 15]

(Wherein R ²⁵ , R ²⁶ and R ²⁷ each independently represents 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 is bonded to the sulfur atom by a bond).

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

The compound represented by the formula (D-2) is a quaternary ammonium salt represented by R ¹² R ¹³ R ¹⁴ R ¹⁵ N ⁺ Y _A ^- . R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ of the 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 a group represented by the formula (D-2) The compound represents a silane compound bonded to a silicon atom by a 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. The quaternary ammonium salt is commercially available, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzyl chloride Ammonium, trimethylbenzylammonium chloride, and the like.

The compound represented by the above formula (D-3) represents a quaternary ammonium salt derived from a 1-substituted imidazole, the number of carbon atoms of R ¹⁶ and R ¹⁷ is 1 to 18, the carbon of R ¹⁶ and R ¹⁷ The total number of atoms is preferably 7 or more. Examples of R ¹⁶ include a methyl group, an ethyl group, a propyl group, a phenyl group, and a benzyl group; and R ¹⁷ is a benzyl group, an octyl group, and an octadecyl 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 also be obtained as a commercially available product. For example, an imidazole compound such as 1-methylimidazole or 1-benzylimidazole is reacted with a halogenated alkyl such as benzyl bromide, methyl bromide, or halogenated aryl .

The compound represented by the above 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 4 to 18 carbon atoms, An aryl group having 1 to 18 carbon atoms, and examples thereof include a butyl group, an octyl group, a benzyl group and a lauryl 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 also be obtained as a commercial product, for example, by reacting pyridine with a halogenated alkyl such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or halogenated aryl. This compound can be exemplified by, 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 pyridines 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 and includes, for example, methyl, octyl, lauryl, benzyl 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 and, for example, 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 also be obtained as a commercial product, for example, by reacting a substituted pyridine such as picoline with a halogenated alkyl such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or halogenated aryl . This compound can be exemplified by, for example, N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-laurylpicolinium chloride and the like.

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

The compound represented by the above formula (D-7) is a quaternary phosphonium salt having a structure represented by R ²¹ R ²² R ²³ R ²⁴ P ⁺ Y _A ^- . R ²¹ , R ²² , R ²³ and R ²⁴ represent an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms or a silane compound bonded to a silicon atom by a Si-C bond, Preferably three of the four substituents R ²¹ to R ²⁴ represent a phenyl group or a substituted phenyl group, and examples of the three substituents include a phenyl group or a tolyl group, and the remaining one substituent is carbon An alkyl group having 1 to 18 atoms, an aryl group having 6 to 18 carbon atoms, or a silyl group bonded to a silicon atom by a Si-C bond. Examples of the anion (Y _A ^- ) include halogen ions such as chloride ion (Cl ^- ), bromine ion (Br ^- ) and iodide ion (I ^- ), carboxylate (-COO ^- ), sulfonate SO ₃ ^-), an alcoholate (-O ^- can be an acid group, etc.). This compound is commercially available, and examples thereof include halogenated tetraalkylphosphonium halides such as tetra n-butylphosphonium halide and halogenated tetra-n-propylphosphonium, halogenated trialkylbenzylphosphones such as halogenated triethylbenzylphosphonium and the like Halogenated triphenylmethylalkylphosphonium, halogenated triphenylmethylphosphonium, halogenated triphenylmethylphosphonium, halogenated triphenylmethylphosphonium, halogenated triphenylmethylphosphonium, halogenated triphenylmethylphosphonium, halogenated triphenylmethylphosphonium, halogenated tetraphenylphosphonium, halogenated tritolylmonoarylphosphonium, or halogenated tri Tolylmonoalkylphosphonium (halogen atom is chlorine atom or bromine atom). Particularly, halogenated triphenylmethylphosphonium such as halogenated triphenylmethylphosphonium and halogenated triphenylethylphosphonium, halogenated triphenylmonoarylphosphonium such as halogenated triphenylbenzylphosphonium, halogenated triphenylmonophenylphosphonium and the like And halogenated tritolylmonoalkylphosphonium (halogen atom is chlorine atom or bromine atom) such as halogenated tritolylmonoarylphosphonium and halogenated tritolylmonomethylphosphonium.

Examples of the phosphine include methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and primary phosphines such as phenylphosphine, dimethylphosphine, diethylphosphine, diisobutylphosphine, A second phosphine such as propylphosphine, propylphosphine, diisoamylphosphine and diphenylphosphine, a third force such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine and dimethylphenylphosphine, Pins.

The compound represented by the above formula (D-8) is a tertiary sulfonium salt having a structure represented by R ²⁵ R ²⁶ R ²⁷ S ⁺ Y _A ^- . R ^25, R ²⁶ and R ²⁷ can denote a group which is by an aryl group of carbon atoms from 1 to 18 alkyl group, or a 6 to 18 carbon atoms, or Si-C bonds is combined with a silicon atom, and preferably R ²⁵ to And three of the four substituents of R ²⁷ are a phenyl group or a substituted phenyl group. Examples of the three substituents include a phenyl group and a tolyl group, and the remaining one substituent is 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 be exemplified by the functional groups of the corresponding carbon atoms in the above-mentioned examples. Examples of the anion (Y _A ^- ) include halogen ions such as chloride ion (Cl ^- ), bromine ion (Br ^- ) and iodide ion (I ^- ), carboxylate (-COO ^- ), sulfonate SO ₃ ^-), an alcoholate (-O ^- can be an acid group, etc.). These compounds are commercially available, and examples thereof include halogenated tetraalkylphosphonium halides such as tri-n-butylsulfonium halide and halogenated tri-n-propylsulfonium, halogenated trialkylbenzyl sulfides such as halogenated diethylbenzylsulfonium, Halogenated diphenylmethylsulfonium, halogenated diphenylmethylsulfonium, halogenated diphenylmethylsulfonium and halogenated diphenylethylsulfonium, halogenated triphenylsulfonium (the halogen atom is chlorine atom or bromine atom), tri-n-butylsulfonium carboxyl Triethylbenzylsulfonium carboxylate such as tetraalkylphosphonium carboxylate and diethylbenzylsulfonium carboxylate, diphenylmethylsulfonium carboxylate, diphenylmethylsulfonium carboxylate, di Diphenyl monoalkylsulfonium carboxylates such as phenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. Particularly preferred are halogenated triphenylsulfonium and triphenylsulfonium carboxylate.

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

The hydrolysis-condensation product (polymer) is subjected to a condensation reaction in the presence of a catalyst such as alcohol, a by-product hydrolysis catalyst and water Can be removed. Further, the acid or base catalyst used for hydrolysis can be removed by neutralization or ion exchange. In the composition for forming a resist lower layer film for lithography of the present invention, an organic acid, water, an alcohol, or a combination thereof may be added to stabilize the resist lower layer film forming composition containing the 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 and salicylic acid. Of these, oxalic acid and maleic acid are preferable. The organic acid to be added is 0.5 to 5.0 parts by mass based on 100 parts by mass of the condensate (polyorganosiloxane). The water to be added may be pure water, ultrapure water, ion-exchanged water or the like, and the amount thereof may be 1 to 20 parts by mass based on 100 parts by mass of the composition for forming a resist lower layer film.

The alcohol to be added is preferably one which tends to be scattered by heating after application, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol and the like. The alcohol to be added may be 1 to 20 parts by mass based on 100 parts by mass of the resist underlayer film forming composition.

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

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

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

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

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

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

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2- Methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloxypropyl methacrylate, Acryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl-3-methacryloxypropyltrimethoxysilane, Methacrylate and bromophenylmethacrylate There may be mentioned acrylate and the like.

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

Methacrylamide compounds, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N, N-dimethylmethacrylamide and N- Acrylamide, and the like.

Examples of the vinyl compound include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, Ether, vinylnaphthalene, vinyl anthracene, and the like.

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

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

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

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

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

The organic polymer compound may be used alone or in combination of two or more.

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

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

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

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

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

Examples of the onium salt compounds include diphenyl iodonium hexafluorophosphate, diphenyl iodonium trifluoromethane sulfonate, diphenyl iodonium nonafluoro nobutane sulfonate, diphenyl iodonium perfluorononoctane (4-tert-butylphenyl) iodonium camphor sulfonate, and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, such as diphenyl iodonium camphor sulfonate, bis And sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate, etc. .

Examples of sulfone imide compounds include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoroaromatic butanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) Succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide, and the like.

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

Only one photoacid generator may be used, or two or more photoacid generators may be used in combination.

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

The surfactant is effective in suppressing occurrence of pinholes, striations, etc. after the composition for forming a resist lower layer film for lithography of the present invention is applied to a substrate.

Examples of the surfactant contained in the resist underlayer film forming composition of the present invention include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc., Polyoxyethylene alkylaryl ethers such as ethylene alkyl ethers, polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmate, Sorbitan fatty acid esters such as sorbitol monostearate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate , Polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene (Trade names: EFTOP EF301, EF303 and EF352 (manufactured by Tohkem products Corporation), trade names MEGAFAC F171, F173, R-08 and R-30 (trade names, manufactured by Tohkem products Corporation), and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan fatty acid esters (Manufactured by Dainippon Ink and Chemicals, Inc.), FLUORAD FC430, FC431 (manufactured by Sumitomo 3M Limited), trade name ASAHI GUARD AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 , And organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more. When a surfactant is used, the ratio thereof is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass based on 100 parts by mass of the condensate (polyorganosiloxane).

In addition, a rheology modifier, 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. The adhesion assisting agent is effective for improving the adhesion between the semiconductor substrate or the resist and the underlayer film.

Examples of the rheology adjusting agent include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate and butyl isodecyl phthalate, dynomal butyl adipate, diisobutyl adipate, diisooctyl Adipic acid derivatives such as adipate and octyldecyl adipate, maleic acid derivatives such as dinomalbutyl maleate, diethyl maleate and dinonyl maleate, methyl oleate, butyl oleate, and tetrahydrofurfuryl alcohol Oleic acid derivatives, and stearic acid derivatives such as normal butyl stearate and glyceryl stearate. These rheology modifiers are usually compounded at a ratio of less than 30% by mass based on 100% by mass of the total composition of the resist underlayer film forming composition.

Examples of the adhesion assisting agent include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, Alkoxysilanes such as dimethylvinylethoxysilane, diphenyldimethoxysilane and phenyltriethoxysilane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimide Silane residues such as sol, vinyl trichlorosilane,? -Chloropropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and the like, benzotriazole, benzimide Mercaptobenzothiazole, 2-mercaptobenzoxazole, ureasol, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc., and the like. Heterocyclic , Urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds. The adhesion promoter is usually blended at a ratio of less than 5 mass%, preferably less than 2 mass%, based on 100 mass% of the total composition of the resist underlayer film forming composition.

The solvent used in the resist lower layer film forming composition of the present invention may be any solvent that can dissolve the above solid components without any particular limitation. Such solvents include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol Propylene glycol monomethyl 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 Ethylene glycol monopropyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl 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 Propyl formate, isopropyl formate, isobutyl formate, isobutyl formate, amyl formate, isoamyl formate, isoamyl formate, isopropyl formate, isopropyl formate, isopropyl formate, And isopropyl acetate, ethyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl 2-hydroxypropionate, isobutyrate, isobutyl butyrate, ethyl hydroxyacetate, , Ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, Acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, N, N-dimethylacetamide, N, N-dimethylacetamide, N, N-dimethylacetamide, N, N-dimethylacetamide, N, N-dimethylacetamide, N, -Methylpyrrolidone and? -Butyrolactone, and the like. These solvents may be used alone or in combination of two or more.

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

(E.g., a silicon wafer substrate, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a glass substrate, an ITO substrate, a polyimide substrate, and a low dielectric constant material A substrate or the like) is coated with a resist underlayer film forming composition of the present invention by a suitable coating method such as a spinner or a coater and then fired to form a resist underlayer film. The firing conditions are appropriately selected at a firing temperature of 80 to 250 DEG C and a firing time of 0.3 to 60 minutes. Preferably, the baking temperature is 150 deg. C to 250 deg. C and the baking time is 0.5 to 2 minutes. Here, the film thickness of the lower layer film to be formed is, for example, 10 to 1000 nm, or 20 to 500 nm, or 50 to 300 nm, or 100 to 200 nm.

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

In the present invention, it is possible to deposit the organic undercoat film on the substrate, form the undercoat resist film of the present invention thereon, and coat the photoresist thereon. As a result, the pattern width of the photoresist becomes narrow, so that even when the photoresist is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, a fluorine-based gas having a sufficiently high etching rate with respect to the photoresist can be used as an etching gas to form a resist lower layer film of the present invention. Further, It is possible to process an organic underlayer film using a gas as an etching gas and further to process the substrate with a fluorine-based gas having a sufficiently high etching rate with respect to the organic underlayer film as an etching gas.

There is no particular limitation on the photoresist formed on the resist underlayer film of the present invention as long as it is photosensitive with light used for exposure. Both negative photoresists and positive photoresists can be used. A positive type photoresist comprising a novolac resin and a 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist comprising a binder having a group which is decomposed by an acid and has a group for raising an alkali dissolution rate, and a photoacid generator, A chemical amplification type photoresist composed of an alkali soluble binder and a photo acid generator, and a binder having a group which is decomposed by an acid and has a group for increasing the alkali dissolution rate, A chemically amplified photoresist composed of a low molecular weight compound that increases the alkali dissolution rate of the resist and a photo acid generator, and the like. Examples thereof include trade name APEX-E available from Shipley Company, trade name PAR710 available from Sumitomo Chemical Company, and SEPR430 available from Shin-Etsu Chemical Co., Also, for example, Proc. SPIE, Vol.3999, 330-334 (2000), Proc. SPIE, Vol.3999, 357-364 (2000) or Proc. SPIE, Vol. 3999, 365-374 (2000), and fluorine atom polymeric photoresists.

Then, exposure is performed through a predetermined mask. For the exposure, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), and an F ₂ excimer laser (wavelength: 157 nm) After the exposure, post exposure bake may be carried out if necessary. Post-exposure baking is carried out under the conditions appropriately selected at a heating temperature of 70 ° C to 150 ° C and a heating time of 0.3 to 10 minutes.

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

Subsequently, development is carried out by the developer. Thus, for example, when a positive photoresist is used, the photoresist of the exposed portion is removed, and a pattern of photoresist is formed.

Examples of the developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline hydroxide; and aqueous amine solutions such as ethanolamine, propylamine and ethylenediamine For example, an aqueous alkaline solution. In addition, a surfactant or the like may be added to these developers. Conditions for the development are appropriately selected at a temperature of 5 to 50 캜 and a time of 10 to 600 seconds.

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

First, the resist lower layer film (intermediate layer) of the present invention where the photoresist is removed is removed by dry etching to expose the semiconductor substrate. For the dry etching of the resist lower layer film of the present invention, tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, Gases such as oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used. A halogen-based gas is preferably used for dry etching of the resist lower layer film. In dry etching with a halogen-based gas, a photoresist made of an organic material is basically not removed well. On the other hand, the resist underlayer film of the present invention containing a large amount of silicon atoms is quickly removed by the halogen-based gas. Thus, it is possible to suppress the reduction of the film thickness of the photoresist due to the dry etching of the resist lower layer film. As a result, the photoresist can be used as a thin film. Resist lower layer film is dry-etched preferably by fluorine-based gas and fluorine-based gas, for example, tetrafluoromethane (CF _4), perfluoro-cyclobutane (C ₄ F _8), perfluoro-propane (C ₃ to F ₈ ), trifluoromethane and difluoromethane (CH ₂ F ₂ ).

Thereafter, the organic undercoat layer is removed using the patterned photoresist and the resist underlayer film of the present invention as a protective film. It is preferable that the organic underlayer film (lower layer) is formed by dry etching with an oxygen-based gas. This is because the resist underlayer film of the present invention containing a large amount of silicon atoms can not be removed well by dry etching with an oxygen-based gas.

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

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

An organic antireflection film can be formed on the upper layer of the resist underlayer film of the present invention before forming the photoresist. The antireflection film composition to be used here is not particularly limited, but it can be arbitrarily selected from those conventionally used in the lithography process. Further, it is also possible to use a commonly used method, for example, a spinner, The antireflection film can be formed.

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

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

Further, the resist underlayer film formed from the resist underlayer film forming composition can be used as a buried material capable of filling holes without gaps, by being applied to a substrate having a via hole used in a dual damascene process. It may also be used as a flat fire for planarizing the surface of the semiconductor substrate having the unevenness.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

Example

First, a hydrolyzable silane represented by the formula (1) used as a raw material was synthesized. 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 frequency: 32 times, reference sample: tetramethylsilane (TMS).

(Synthesis of Compound 1)

20.00 g of aminopropyltriethoxysilane was placed in a 200 ml three-necked flask equipped with a mechanical stirrer and 9.04 g of powdered succinic anhydride was added to the flask while cooling in a water bath, Lt; / RTI > Thereafter, the resulting crude product was purified by hexane to obtain Compound 1 as a target product. The compound 1 thus obtained corresponded to the compound represented by the formula (1-1).

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

(Synthesis of Compound 2)

In a 200 ml three-necked flask equipped with a mechanical stirrer, 20.00 g of aminopropyltriethoxysilane was added, and 8.86 g of maleic anhydride powder was added while cooling in a water bath, followed by stirring at room temperature for one day. Thereafter, the crude product thus obtained was purified by hexane to obtain Compound 2 as a target product. The compound 2 thus obtained corresponded to the compound represented by the formula (1-5).

^{1 H-NMR (400MHz):} 0.68ppm (t, 2H), 1.23ppm (t, 9H), 1.74ppm (quint, 2H), 3.38ppm (q, 2H), 3.82ppm (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 placed in a 200 ml three-necked flask, and a mixed solution of 14.87 g of ethyl succinic acid chloride and 20.00 g of tetrahydrofuran was added dropwise while cooling in a water bath , And the mixture was stirred at 0 ° C for 1 hour and then at room temperature for 6 hours. After the reaction, the solution was filtered, and the tetrahydrofuran was removed under reduced pressure using an evaporator. 100 ml of dichloroethane was added, and the mixture was washed several times with water. Thereafter, the reaction product was dried with magnesium sulfate, filtered, and the solvent was removed under reduced pressure to obtain a crude product of Compound 3 as a target product. After purification by distillation under reduced pressure, Compound 3 as a target product was obtained. The obtained compound 3 corresponds to the compound represented by the formula (1-3).

^{1 H-NMR (400MHz):} 0.59ppm (t, 2H), 1.16 ~ 1.24ppm (m, 12H), 1.60ppm (quint, 2H), 2.40 ~ 2.67ppm (dt, 4H), 3.22ppm (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 in a 100 mL flask And the resulting mixed solution was warmed while stirring with a magnetic stirrer and refluxed. Then, 6.67 g of 0.01 M aqueous hydrochloric acid solution was added to the mixed solution. After reaction for 240 minutes, the obtained reaction solution was cooled to room temperature. Thereafter, 20.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution, and the reaction by-product, ethanol, water and hydrochloric acid were vacuum-distilled off to obtain a hydrolyzed condensate solution. Thereafter, propylene glycol diethyl ether was added to the hydrolyzed condensate solution to finally obtain a 15% hydrolyzed condensate solution. The weight-average molecular weight of the obtained polymer by GPC was Mw 1600 in terms of polystyrene. The resulting polymer corresponds to a polymer having a unit structure represented by the formula (2-1).

Using Compound 2 instead of Compound 1 used in Synthesis Example 1, Synthesis Example 2 was obtained through the same procedure. Using Compound 3 instead of Compound 1 used in Synthesis Example 1, Synthesis Example 3 was obtained through the same procedure. In addition, Comparative Synthesis Examples 1 and 2 were obtained through the same procedure without using a compound corresponding to Compound 1 used in Synthesis Example 1. The mixing ratios of the silane compounds in the compositions of Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 2 are shown in Table 1.

In Synthesis Example 2, the resulting polymer corresponds to a polymer having a unit structure represented by Formula (2-2). In Synthesis Example 3, the obtained polymer corresponds to a polymer having a unit structure represented by Formula (2-3).

In addition, the polymer obtained from Comparative Synthesis Examples 1 and 2 corresponded to a polymer having a unit structure represented by the following formula (3-1).

[Chemical Formula 16]

[Table 1]

(Example 1)

To 20.00 g of the polymer solution (solid content 15.00 mass%) 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, 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 15.00 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 15.00 mass%) obtained in Synthesis Example 3 was used instead of the polymer obtained in Synthesis Example 1.

(Example 4)

0.039 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 were added to 20.00 g of the polymer solution (solid content 15.00% by mass) obtained in Synthesis Example 1 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 (solid content 15.00 mass%) 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 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 6)

0.03 g of maleic acid, 19.36 g of ultrapure water, 0.01 g of N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, 20 g of 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 obtained in Comparative Synthesis Example 1 (solid content 15.00 mass%) 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 15.00 mass%) obtained in Comparative Synthesis Example 2 was used instead of the polymer obtained in Synthesis Example 1.

(Solvent resistance test)

The composition for forming a resist lower layer film was coated on a silicon wafer by a spin coating method, and fired on a hot plate at 140 캜 for 1 minute to form a resist lower layer film. Thereafter, the film was immersed in propylene glycol monomethyl ether acetate used for the solvent of the upper resist composition for 1 minute. When the change in the film thickness of the resist lower layer film before and after the immersion was 1 nm or less, "good" was judged to be " When the change in the film thickness was more than this, it was judged to be " defective ", and " x " The results are shown in Table 2.

Hereinafter, the resist underlayer films obtained from the resist underlayer film forming compositions of Examples 1 to 6 are shown as the resist underlayer films 1 to 6 of the examples. The resist underlayer films obtained from the resist underlayer film forming compositions of Comparative Examples 1 and 2 are shown as Comparative Example resist underlayer films 1 to 2.

[Table 2]

(Optical constant measurement)

The resist lower layer film forming composition was coated on a silicon wafer using a spinner. And heated on a hot plate at 240 DEG C for 1 minute to form a resist lower layer film (film thickness 0.09 mu m). The refractive index (n value) and the optical absorption coefficient (k value, also referred to as a damping coefficient) at a wavelength of 193 nm are measured using a spectroscopic ellipsometer (JAWoollam Co., Inc., VUV-VASE VU-302) ) Were measured. The results are shown in Table 3.

[Table 3]

(Measurement of dry etching rate)

Etchers and etching gases used for measuring the dry etching rate are as follows.

The etcher was ES401 (trade name, manufactured by Nippon Scientific Co., Ltd.), and etching was performed with CF ₄ gas.

In addition, RIE-10NR (trade name, manufactured by SAMCO International Inc.) was used as the etcher, and etching was performed with O ₂ gas.

The solutions of the resist lower layer film forming compositions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were each coated on a silicon wafer using a spinner. Heated on a hot plate at 240 DEG C for 1 minute to form a resist undercoat film, and the etching rate was measured using each etching gas. The etching rate was measured using a CF ₄ gas as an etching gas at a film thickness of 0.20 탆 for the resist lower layer film and the etching rate was measured using O ₂ gas as an etching gas at a film thickness of 0.08 탆 for the resist lower layer film.

Likewise, a 0.20 占 퐉 resist film was formed on a silicon wafer using a photoresist solution (Shipley Company Inc., trade name UV113) using a spinner. The dry etching rate was measured using CF ₄ gas and O ₂ gas as the etching gas. Then, the dry etching rates of the lower resist film and the resist film were compared. The results are shown in Table 4. The speed ratio is the dry etching rate ratio of (resist underlayer film) / (resist).

[Table 4]

(Preparation of organic underlayer film)

16.5 g of acenaphthylene, 1.5 g of 4-hydroxystyrene and 60 g of 1,2-dichloroethane as a solvent were added to a 200-mL flask. 1 g of trifluoroboron was added as a polymerization initiator, the temperature was raised to 60 캜, and the reaction was carried out for 24 hours. 1 liter of methanol and 500 g of water were added to this solution to perform reprecipitation purification, and the resulting white solid was filtered and dried to obtain 11 g of a white polymer.

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

The weight average molecular weight Mw was 6,000, the weight average molecular weight Mw / number average molecular weight Mn was 1.5.

[Chemical Formula 17]

1.0 g of tetramethoxymethyl glycoluril (trade name POWDERLINK 1174, manufactured by Mitsui Cytec Ltd.), 0.01 g of para-toluenesulfonic acid as a crosslinking catalyst, and 0.1 g of MEGAFAC R-3 as a surfactant were added to 10 g of the obtained polymer (formula (3-2) 30 (Dainippon Ink and Chemicals, Inc., trade name) was added, and dissolved in 101.57 g of propylene glycol monomethyl ether acetate and 25.39 g of propylene glycol monomethyl ether. Thereafter, the solution was filtered using a microfilter made of polyethylene having a pore diameter of 0.10 탆, and filtered again using a microfilter made of polyethylene having a pore diameter of 0.05 탆 to prepare a solution of the organic lower layer film forming composition used in the lithography process by the multi- Lt; / RTI >

(Resist patterning evaluation)

A composition for forming an organic underlayer film (A layer) containing the polymer (formula (3-2)) was applied on a silicon wafer and heated on a hot plate at 240 캜 for 1 minute to form an organic underlayer film A Layer). The composition of the Si-containing resist underlayer film (B layer) obtained in Examples 1 to 6 and Comparative Examples 1 to 2 was coated thereon and heated on a hot plate at 240 占 폚 for 1 minute to form a Si Containing layer (B layer) was obtained. A commercial photoresist solution (manufactured by Sumitomo Chemical Company, trade name PAR 855) was applied thereon using a spinner and heated on a hot plate at 100 ° C for 1 minute to form a photoresist film (C layer) having a film thickness of 150 nm Respectively. The patterning of the resist was performed using ASML's liquid immersion exposure apparatus 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 the number of lines was 15 after the development, that is, a so-called line-and-space line width of 0.05 탆 and a line width of the photoresist. Thereafter, the wafer was baked on a hot plate at 105 DEG C for 60 seconds, cooled and then developed with a 2.38% tetramethylammonium hydroxide developer in a 60 second single paddle process of the industry standard.

[Table 5]

The footing is a hemming bottom phenomenon under the pattern in the resist pattern shape and the undercut is a thin phenomenon under the pattern in the resist pattern shape and is not preferable because it does not show a rectangular pattern shape in both cases.

The resist underlayer film obtained from the resist underlayer film forming composition having an amic acid or an amic acid ester structure according to the present invention contains a large amount of hetero elements and thus has a sufficiently high dry etching rate for the photoresist film. In Examples 1 to 6, since the etching rate by the fluorine-based gas is improved as compared with Comparative Examples 1 and 2, the resist pattern in the upper layer of the resist lower layer film of the present invention can be accurately transferred to the resist lower layer film of the present invention.

The resist underlayer films obtained from the resist underlayer film forming compositions of Examples 1 to 6 were superior to the resist underlayer films obtained from the resist underlayer film compositions of Comparative Examples 1 and 2 in etching resistance due to oxygen gas, It has a sufficiently high function as a hard mask for processing an underlying organic film or substrate lower than the lower resist film of the invention.

In the case of resist patterning of 0.08 占 퐉, the refractive index n and the optical extinction coefficient k are the same value (the resist undercoat film having a low optical absorption coefficient k) in Examples 1, 4 to 6 and Comparative Example 1, It can be seen that Examples 1 and 4 to 6, in which the terminal carboxylic acid moiety is not ring-closed at the time of hydrolysis, are effective in reducing the hemming bottom of the resist.

On the other hand, in comparison between Examples 2 and 3 and Comparative Example 2, although the refractive index n and the optical absorption coefficient k are the same value (the resist underlayer film having a high optical absorption coefficient k), the terminal carboxylic acid is closed during film formation, In Example 2, which is the amide carboxylic acid ester, exhibits good phosphorus properties (adhesion), and thus it is effective in improving the adhesion with the resist.

The resist underlayer film forming composition having an amic acid or an amic acid ester structure according to the present invention can control the resist shape depending on whether the structure is changed during film formation.

Claims

As a silane compound, a composition for forming a resist underlayer film for a lithography, which comprises a hydrolyzable organosilane, a hydrolyzate thereof, a hydrolyzate thereof, a hydrolyzate thereof, or a mixture thereof, wherein the silane compound has an amide bond and a carboxylic acid moiety A carboxylic acid ester moiety or an organic group containing both of these moieties, wherein the hydrolyzable organosilane is represented by the following formula (1):

(Wherein R ³ represents an amide bond and a group which is an organic group containing a carboxylic acid moiety or a carboxylic acid ester moiety or both of these moieties and which is bonded to a silicon atom by a Si-C bond, R ¹ represents an alkyl group , An aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, R ² represents an alkoxy group, an acyloxy group, or a halogen atom, and a represents a hydrogen atom or an alkyl group, 0 or 1, and b represents an integer of 1 or 2.). &Lt; / RTI >

The method according to claim 1,
Wherein the ratio of the amide bond to the silane compound containing a carboxylic acid moiety or a carboxylic acid ester moiety or an organic group containing both of these moieties is less than 5 mol% in the entire silane compound.

The method according to claim 1,
Wherein the ratio of the amide bond to the silane compound having a carboxylic acid moiety or a carboxylic acid ester moiety or an organic group containing both of these moieties is 0.5 to 4.9 mol% in the whole silane compound.

delete

4. The method according to any one of claims 1 to 3,
Equation (2):

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

(Wherein R ⁶ represents an alkyl group, R ⁷ represents an alkoxy group, an acyloxy group or a halogen atom, Y represents an alkylene group or an arylene group, b represents an integer of 0 or 1, c represents 0 Or an integer of 1), and at least one member selected from the group consisting of an organosilicon compound represented by the following formula
A composition for forming a resist lower layer film for lithography, which comprises a combination of a hydrolyzable organosilane represented by the above formula (1), a hydrolyzate thereof, or a hydrolyzed condensate thereof.

4. The method according to any one of claims 1 to 3,
The hydrolyzed condensate of the hydrolyzable organosilane represented by the above formula (1) or the hydrolyzable organosilane represented by the above formula (1) and the hydrolyzable organosilane represented by the following formula (2):

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

4. The method according to any one of claims 1 to 3,
A composition for forming a resist lower layer film for lithography, which further comprises an acid as a hydrolysis catalyst.

4. The method according to any one of claims 1 to 3,
A water-based photoresist composition for lithography, comprising: water;

A resist underlayer film obtained by applying the resist lower layer film forming composition according to any one of claims 1 to 3 on a semiconductor substrate and firing the same.

A process for forming a resist underlayer film by applying the resist underlayer film forming composition described in any one of claims 1 to 3 on a semiconductor substrate and firing the resist underlayer film composition, a step of applying a resist composition on the underlayer film to form a resist film A step of exposing the resist film to light; a step of developing the resist film after exposure to obtain a patterned resist film; a step of etching the resist lower layer film by the patterned resist film; And a step of processing the semiconductor substrate.

A step of forming an organic underlayer film on a semiconductor substrate, a step of applying and baking the resist underlayer film forming composition described in any one of claims 1 to 3 to form a resist underlayer film, A step of forming a resist film by applying the composition, a step of exposing the resist film, a step of developing the resist film after exposure to obtain a patterned resist film, a step of etching the resist lower layer film by the patterned resist film, A step of etching the organic underlying film by the resist underlayer film; and a step of processing the semiconductor substrate by the patterned organic underlying film.