TW201202855A - Silicon-containing resist underlayer film forming composition containing amic acid - Google Patents

Abstract

Disclosed is a lithography resist underlayer-forming composition for forming a resist underlayer that can be used as a hard mask. As the silane compound, the lithography resist underlayer-forming composition contains a hydrolyzable organosilane, a hydrolyzate thereof, or the hydrolysis condensation product thereof, wherein said silane compound includes a silane compound containing both an amide bond in the molecule and an organic group, which itself contains a carboxylate moiety, a carboxylic acid ester moiety or both. In one lithography resist underlayer-forming composition, the silane compound that contains both an amide bond and an organic group, which itself contains a carboxylate moiety, a carboxylic acid ester moiety or both, is present in a molar ratio of no greater than 5 mol% relative to the total amount of silane compound. In another lithography resist underlayer-forming composition, the silane compound that contains both an amide bond and an organic group, which itself contains a carboxylate moiety, a carboxylic acid ester moiety or both, is present in a molar ratio of between 0.5 and 4.9 mol% relative to the total amount of silane compound.

Description

201202855 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to a composition for forming an underlayer film between a substrate used in the manufacture of a semiconductor device and a resist (for example, a photoresist or an electron beam resist). Things. More specifically, it relates to a lithographic underlayer film forming composition for forming a lower film used for a lower layer of a photoresist in a lithography step of semiconductor device fabrication. Further, a method of forming a feed pattern for forming a composition using the underlayer film. [Prior Art] In the past, in the manufacture of semiconductor devices, microfabrication was performed by using lithography of photoresist. The microfabrication process forms a photoresist film on a semiconductor substrate such as a germanium wafer, and irradiates active light such as ultraviolet rays through a mask pattern of a pattern of a semiconductor device, and develops the image by using the obtained photoresist pattern. The protective film is subjected to uranium engraving treatment to form a processing method corresponding to the fine concavities and convexities of the above-described pattern on the surface of the substrate. However, in recent years, as semiconductor devices have progressed toward higher integration, there has been a short wavelength of active light from KrF excimer laser (248 nm) toward ArF excimer laser (1 93 nm). The tendency to change. The influence of the reflection of the active light rays from the semiconductor substrate becomes a big problem. In addition, a film which is known as a hard mask containing a metal element such as tantalum or titanium is used as a film between the semiconductor substrate and the photoresist (see, for example, Patent Document 1). In this case, since the resist and the hard mask are greatly different in composition, the speed at which these are removed by dry etching is largely related to the type of gas used in the etching. Therefore, by appropriately selecting the type of the gas, it is possible to remove the hard mask by dry etching without greatly reducing the thickness of the photoresist film. According to this, in the manufacture of a semiconductor device in recent years, in order to achieve various effects from the antireflection effect, a resist underlayer film is disposed between the semiconductor substrate and the photoresist. Therefore, the review of the composition for a resist underlayer film has been continued until now. However, it is desired to develop a novel material for a resist underlayer film because of the required characteristics and the like. A film which is known as a hard mask containing a metal element such as ruthenium or titanium is used as the underlayer film between the semiconductor substrate and the photoresist (see, for example, Patent Document 1). In this case, since the resist and the hard mask are greatly different in composition components, the speed at which these are removed by dry etching is largely related to the type of gas used for dry etching. Therefore, by appropriately selecting the type of gas, it is possible to remove the hard mask by dry etching without a large reduction in the thickness of the photoresist film. According to this, in the manufacture of a semiconductor device in recent years, in order to achieve various effects from the antireflection effect, a resist underlayer film is disposed between the semiconductor substrate and the photoresist. Therefore, the review of the composition for the underlayer film has been carried out so far, but it is desired to develop a novel material for the anti-tardy film because of the required diversity of properties. A composition or a pattern forming method using a compound having a bond of ruthenium and osmium is known (see, for example, Patent Document 2). Further, an antireflection film containing ruthenium having a dicarboxy quinone imine structure has been described (refer to For example, Patent Document 3).

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-258813 (Patent Document 1) Japanese Patent Publication No. Hei No. Hei 11-258813 (Patent Document No. 2) Disclosure of the Invention [Problems to be Solved by the Invention] An object of the present invention is to provide a composition for forming a lithographic underlayer film for use in the manufacture of a semiconductor device. More specifically, a composition for forming a lithographic underlayer film for forming a resist underlayer film which can be used as a hard mask is provided. Further, the present invention provides a composition for forming a lithographic underlayer film for forming a resist underlayer film which can be used as an antireflection film. Further, the present invention provides a lithographic underlayer film for lithography which does not cause intermixing with a resist, and which has a large dry etching speed with respect to a resist, and a resist underlayer film for forming the underlayer film. A composition is formed. Accordingly, it is an object of the present invention to provide a method for forming a resist pattern for forming a composition using the under-etching underlayer film for lithography. [Means for Solving the Problem] The first aspect of the present invention is a composition for forming a film for lithography, which comprises a hydrolyzable organodecane, a hydrolyzate thereof or a hydrolyzed condensate thereof or a mixture thereof. The lithography of a decane compound forms a composition using a resist underlayer film comprising an organic group-containing decane compound 201202855, the organic group comprising a guanamine bond, a carboxylic acid ester moiety or both. The second aspect is the composition for lithography described in the first aspect, wherein the entire decane compound contains a sand containing an organic group containing a carboxylic acid moiety or a carboxylate moiety or both The proportion of the substance is less than 5 mol%. The third aspect is the lower resist composition for lithography according to the first aspect, wherein the proportion of the decane containing an organic group of hydrazine and a carboxylic acid moiety or a carboxylate moiety or both of the decane compound as a whole is contained. It is 〇. 5 to 4 · 9 mol%. The fourth aspect is the object of any one of the first to third aspects, wherein the hydrolyzable organodecane is represented by the formula (1), [Chem. 1] [R1 asi (R2) 3-a 3 b R3 Formula (1) wherein R3 is a guanamine-containing bond, a carboxylic acid moiety or a carboxylic acid ester moiety or an organic group, and represents a group bonded to a ruthenium atom by a Si-C bond, and has an alkyl group and an aryl group. a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an acryloyl group, a methacryl fluorenyl group, a fluorenyl group or an aryl group, wherein the organic Si-c bond is bonded to a ruthenium atom, and R 2 represents an alkoxy group. A fluorenyloxy atom, a represents an integer of 〇 or 1, and b represents an integer of 1 or 2. The fifth aspect is any one of the first to fourth aspects, which comprises at least -8- selected from the group consisting of organic ruthenium compounds represented by the organic ruthenium compound (3) represented by the formula (2). a carboxylic acid layer or a carboxyl group-formed amide-bonding alkane-bonding film to form an amine bond, a compound of the group described above, R1 represents an epoxy group, and the halogen or the formula is the same as 201202855 with the above formula (1) a combination of hydrolyzable organodecane, a hydrolyzate or a hydrolyzed condensate thereof: R4 aSi(R5)4-a Formula (2) wherein R4 has 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 methacryl group, a fluorenyl group, an alkoxyaryl group, a decyloxy group, or an organic group of a cyano group, and The base of the Si-c bond to the ruthenium atom is bonded to the base of the ruthenium atom, Rpc, TPC, oxy or dentate atom, a, 〇 to an integer of 3, [Chemical 3] [R6cSi(R7)3-c]2Yb Formula (3) wherein R6 represents a decentral group, R7 represents an alkoxy group, a decyloxy group or a hydrazine atom, Y represents an alkylene group or an extended aryl group, and b represents an integer of 0 or ′′ Or an integer of 1). The sixth aspect is the composition according to any one of the first aspect to the fifth aspect, which comprises the hydrolysis condensate of the hydrolyzable organodecane represented by the above formula (1) or the hydrolysis represented by the above formula (1) A hydrolyzed condensate of a compound organodecane and a compound represented by the formula (2) is used as a polymer. The seventh aspect is the composition as described in the first to sixth aspects, which further contains an acid as a hydrolysis catalyst. The eighth aspect is the composition according to any one of the first to seventh aspects, which further contains water. The ninth aspect is an anti-uranium underlayer film forming composition which is coated on a semiconductor substrate and fired by the anti-uranium underlayer film forming composition as described in any one of the first aspect of the present invention. Get it. A tenth aspect is a method of manufacturing a semiconductor device, comprising the steps of: applying a resist underlayer film forming composition according to any one of the first to eighth aspects to a semiconductor substrate, and firing the same a step of forming a resist underlayer film; a step of forming a resist composition on the underlayer film to form a resist film; and exposing the resist film; and developing the resist film after exposure to obtain a pattern a step of forming a resist film; a step of etching the underlayer film by using the patterned resist film: and a step of processing the semiconductor substrate by using the patterned resist film and the underlayer film. An eleventh aspect is a method of fabricating a semiconductor device, the method comprising the steps of: forming an organic underlayer film on a semiconductor substrate; and coating thereon the anti-resistance according to any one of the first to eighth aspects a step of forming a composition by firing the underlayer film and firing to form a resist underlayer film; a step of forming a resist composition on the resist underlayer film to form a resist film; and exposing the resist film; a step of obtaining the patterned resist film by exposing the anti-uranium film after exposure; a step of etching the underlayer film by using the patterned resist film; and etching the organic film by using the patterned resist underlayer film a step of laminating the film; and a step of processing the semiconductor substrate by using the patterned organic underlayer film. [Effect of the Invention] The hydrolyzable group such as an alkoxy group, a decyloxy group or a halogen atom in the compound represented by the above formula (1) is hydrolyzed or partially hydrolyzed, followed by hydrazine.

S -10- 201202855 The condensation reaction of an alkanol group to form a polymer having a polyoxane structure as a main chain. According to the polyoxyalkylene structure, the underlayer film containing the polymer is made to have high dry etching resistance to an oxygen-based dry etching gas. Further, the polymer is a carbon-carbon bond or a carbon-oxygen bond. According to this configuration, the film containing the polymer described above is subjected to a high dry etching rate using a halogen-based gas, and the upper resist pattern can be transferred onto the film. By these characteristics, the underlayer film formed of the composition of the underlayer film of the present invention containing the polymer described above can function as a hard mask. Further, when the semiconductor device manufacturing method of the present invention is used, the upper resist pattern can be accurately transferred onto the underlying resist film as compared with the conventional resist underlayer film, so that good resist can be obtained. Graphic shape. [Embodiment] In the present invention, a resist underlayer film is formed on a substrate by a coating method, or an organic underlayer film on a substrate is formed, and a resist underlayer film is formed thereon by a coating method to form a resist underlayer film thereon. A resist film (for example, a photoresist, an electron beam resist). Next, a resist pattern is formed by exposure or development, and the resist underlayer film is dry-etched using the resist pattern and patterned, and the substrate is processed by the pattern or by etching the organic underlayer film. The transfer pattern is formed and the substrate is processed by the organic underlayer film. In terms of forming a fine pattern, there is a tendency to reduce the thickness of the resist film in order to prevent the pattern from collapsing. In order to perform dry etching of a pattern on a film existing on the lower layer by thinning of the resist, if the etching speed is higher than that of the upper film, the pattern cannot be transferred. In the present invention, the organic underlayer film on the substrate is passed through, or -11 - 201202855 is not permeable to the organic underlayer film, and the underlayer film (containing the inorganic ruthenium-oxygen compound) of the present invention is sequentially coated thereon, and subsequently thereon. A resist film (organic resist film) is coated. The film of the organic component and the film of the inorganic component are quite different in the dry uranium engraving speed depending on the selection of the etching gas, and the organic component film has a high dry etching rate with an oxygen-based gas, and the inorganic component film contains a film. The halogen gas is subjected to a high dry etching rate. For example, a resist pattern is formed, and a resist-under-layer film of the present invention existing in the lower layer is dry-etched with a halogen-containing gas to transfer the pattern onto the under-layer resist film, and transferred to the resist underlayer film. Type, the substrate is processed using a halogen-containing gas. Alternatively, the organic underlayer film is subjected to pattern transfer by dry etching the underlying organic underlayer film with an oxygen-based gas using a resist pattern underlayer film of a transfer pattern, and a halogen-containing gas is used to transfer the pattern. The organic underlayer film processes the substrate. The underlayer film of the present invention functions as a hard mask. The hydrolyzable group of the alkoxy group or the decyloxy group, the halogen atom or the like in the structure of the above formula (1) is hydrolyzed or partially hydrolyzed, followed by condensation reaction of a decyl alcohol group to form a polymer having a polysiloxane structure. The polyorganosiloxane structure has a function as a hard mask. Further, the bonding sites contained in the polyorganosiloxane have a carbon-nitrogen bond or a carbon-oxygen bond, and the dry etching rate with a halogen-based gas is higher than that of the carbon-carbon bond. It is effective when the resist pattern is transferred to the underlayer film. Therefore, the polyorganooxyalkylene structure (intermediate film) can be effectively used as an etching of an organic underlayer film present therein or a process (etching) of a substrate.

S -12- 201202855 Hard cover. That is, it has sufficient dry etching resistance for substrate processing or organic underlayer dry etching gas. The anti-corrosion underlayer film of the present invention is provided with a dry etching resistance such as an improvement in the etching speed of the upper layer dry uranium and the substrate processing, and the like, and thus can form a favorable resist pattern shape. The underlayer film forms a composition for forming a lithographic underlayer film containing a hydrolyzable organodecane, a hydrolyzate thereof, or a hydrolyzed condensed alkane compound thereof, which is a compound including an organic group-containing decane compound in the organic molecule An organic group containing a guanamine bond, a carboxylic acid moiety or a carboxylic acid ester moiety or the hydrolyzable organodecane having a fluorinated carboxylic acid moiety or a carboxylic acid ester moiety or both in the molecule means an alkyl group a combination of a guanamine bond and a carboxylic acid moiety (either a valine or a guanamine bond and a carboxylic acid ester moiety (protonate structure). The decane compound contains a guanamine bond, a part Or the carboxylic acid ester moiety or both of the organic decane compounds 5 mol%, for example 0.5 to 4.9 mol%, 〇.5 to 〇. 〇mol. / 〇: 0.999 mol% of the proportion. Therefore, the above hydrolyzable organic The sand house, the hydrolyzate, and the compound thereof may be used in a mixture of the above. The condensate obtained by condensing the hydrolyzate into a hydrolyzate may be used, and the hydrolysis may not be obtained when the hydrolyzed condensate is obtained by mixing. A completely completed product or a decane compound, which is a mixture of a film-formed oxygen-based resist, the system of which is a decane compound, both of which are amine bonds. , a species, or a polymer having a polyoxyl-13-201202855 alkane structure partially hydrolyzed with a carboxylic acid moiety of less than 1 or 0.5 to its hydrolyzed polyorganodecane. The polyoxyalkylene group is bonded to an organic group containing a guanamine bond, a carboxylic acid moiety or a carboxylate moiety or both. The underlayer film forming composition of the present invention contains a hydrolyzable organodecane including an organic group containing a guanamine bond, a carboxylic acid moiety or a carboxylate moiety or both, a hydrolyzate thereof, or a hydrolysis condensate thereof, And solvent. Further, it may contain an acid, water, an alcohol, a curing catalyst, an acid generator, another organic polymer, a light absorbing compound, a surfactant, or the like as an optional component. The solid content in the under-layer film forming composition of the present invention is, for example, 0.5 to 50% by mass, or 1 to 30% by mass, or 1 to 25% by mass. Here, the solid component is one in which the solvent component is removed from all the components of the resist underlayer film forming composition. The ratio of the hydrolyzable organodecane, the hydrolyzate thereof, and the hydrolyzed condensate thereof in the solid component is 20% by mass or more, for example, 50 to 100% by mass, 60 to 100% by mass, and 70 to 100% by mass. The hydrolyzable organodecane used in the present invention has a structure represented by the formula (1). R3 is an organic group containing a guanamine bond, a carboxylic acid moiety or a carboxylate moiety or both, and represents a group bonded to a ruthenium atom by a Si-C bond. R1 represents an organic group having an alkyl group, an aryl group, an alkyl halide group, a halogenated aryl group, an alkenyl group, or an epoxy group, a propylene group, a methacryl group, a fluorenyl group, or a cyano group, and is represented by Si- The bond between the C bond and the deuterium atom. R2 represents an alkoxy group, a decyloxy group, or a halogen atom. a represents an integer of 0 or 1 'b represents an integer of 1 or 2. The alkyl group in R1 in the formula (1) is an alkyl group having a linear or branched carbon number of 1 to 10, and is exemplified by, for example, a methyl group, an ethyl group, and a n-propyl group.

S -14- 201202855 base, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl Base-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl' 1-ethyl-n-propyl , n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-Dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2- Trimethyl n-propyl, ethyl-1-methyl-n-propyl and 1-ethyl-2-methyl-n-propyl. Further, as the alkyl group, a cyclic alkyl group may be used, and the exemplified cyclic alkyl group having 1 to 10 carbon atoms is exemplified by a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, and a 2-methyl-ring group. Propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3- Dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl -cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-di Methyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl -cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2 -trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl 2-Ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl. -15- 201202855 The aryl group is exemplified by an aryl group having 6 to 20 carbon atoms, and is exemplified by, for example, a phenyl group, an o-methylphenyl group, a m-methylphenyl group, a p-methylphenyl group, an o-chlorobenzene group. , m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-nonylphenyl, o-methoxyphenyl, p-methoxyphenyl, p-aminophenyl, p. - cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-indenyl, 2-indenyl, 9-fluorenyl, 1 - phenanthryl, 2-phenanthryl 3-phenanthrenyl, 4-phenanthryl and 9-phenanthryl. The alkenyl group is exemplified as an alkenyl group having 2 to 10 carbon atoms, and is exemplified by, for example, a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-vinyl '1-butenyl group, and a 2-butyl group. Alkenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl 2-propenyl, pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl 2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2·methyl-2·butenyl , 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl 2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2- Cyclopentenyl, 3·cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentyl Alkenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1 -pentenyl, 2·methyl-2-pentene , 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-pentenyl, 3-methyl-1-pentenyl, 3-methyl -2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1·penta S: -16- 201202855 Alkenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2- Butenyl, 1,1, dimethyl-3-butenyl, 1,2-dimethyl-butenyl, 1,2-dimethyl-2-butenyl, 1,2-di Methyl-3-butenyl ' 1-methyl-2-ethyl-2-propenyl, 1-second butyl vinyl, 1,3-dimethyl-1-butenyl, 1,3 - dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3 - dimethyl-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3 ,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl 1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl 1,1, 2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1 -methyl-3-cyclopentenyl '2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl 4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methyl-cyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2- Cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methyl-cyclopentyl , 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, and the like. Further, an organic group in which a halogen atom such as fluorine, chlorine, bromine or iodine is substituted is used. The organic group having an epoxy group is exemplified by glycidoxymethyl group, glycidyloxyethyl group, glycidoxypropyl group, glycidoxy butyl group, -17-201202855 epoxycyclohexyl group and the like. The organic group having an acrylonitrile group is exemplified by an acryloylmethyl group, an acryloylethyl group, an acrylonitrile group or the like. The organic group having a methacryl fluorenyl group is exemplified by methacryl fluorenylmethyl group, methacryl decylethyl group, methacryl decyl propyl group or the like. The organic group having a mercapto group is exemplified by an ethyl fluorenyl group, a butyl fluorenyl group, a hexyl fluorenyl group, an octyl decyl group or the like. The organic group having a cyano group is exemplified by a cyanoethyl group, a cyanopropyl group or the like. The alkoxy group having 1 to 20 carbon atoms in R2 of the formula (1) is exemplified by an alkoxy group having a linear, branched or cyclic alkyl moiety having 1 to 20 carbon atoms, and is exemplified by, for example, methoxy. Base, ethoxy, n-propoxy, isopropoxy 'n-butoxy, isobutoxy, second butoxy, tert-butoxy, n-pentyloxy, 1-methyl-n-butyl Oxyl, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2 ,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl · n-pentyloxy, 4-methyl-n-pentyloxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl n-Butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-positive Butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1 -methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy, etc., and cyclic alkoxy is exemplified as cyclopropyl , cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentyloxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy Base, 3-methyl-cyclobutoxy, 1,2-dimethyl-

S -18 201202855 Cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl -cyclopentyloxy, 2-methyl-cyclopentyloxy, 3-methyl-cyclopentyloxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-B Cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3-dimethyl-cyclobutoxy, 2,2-dimethyl-cyclobutoxy, 2,3- Dimethyl-cyclobutoxy, 2,4-dimethyl-cyclobutoxy, 3,3-dimethyl-cyclobutoxy, 1-n-propyl-cyclopropoxy, 2-n-propyl -cyclopropoxy, 1-isopropyl-cyclopropoxy, 2·isopropyl-cyclopropoxy, 1,2,2·dimethyl-cyclopropoxy, 1,2,3 - Trimethyl-cyclopropoxy, 2,2,3-trimethyl-cyclopropoxy, 1-ethyl-2-methyl-cyclopropoxy, 2-ethyl-1.methyl·cyclo Propyloxy, 2-ethyl-2-methyl-cyclopropoxy and 2-ethyl-3-methyl-cyclopropoxy. The decyloxy group having 1 to 20 carbon atoms in R2 of the formula (1) is exemplified by, for example, methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butyl group. Carbonyloxy, isobutylcarbonyloxy, t-butylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl -n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2,2-Dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl- N-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2- Dikis-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butyl Carbocarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2- Trimethyl-n-propylcarbonyloxy, -19- 201202855 1,2,2-trimethyl-n-propylcarbonyl , 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and toluenesulfonylcarbonyloxy Wait. The halogen atom of R2 in the formula (1) is exemplified by fluorine, chlorine, bromine, iodine, etc. The hydrolyzable organodecane represented by the formula (Π) can be exemplified below.

C2H5O, ·〆 C2H50^Sl C2H5O Formula (1-1)

H3CO' / H3CO"/Si H3CO C2H50' C2H50- __ CzH5° (1-3)

Si

o C2H5OxC2H5cr C2H5O HO' Formula (1-5) ό C2H5〇' ·〆 C2H5〇"/Sl C2H5O HO Formula (1-7) O g〇 C2H5O HO Formula (1-9) O

Si

Formula (1 - 2) H3CO' 〆 H3C〇-*/Si H3CO H3CO H3CCT production 1 h3co

Cl HO' type (1-10) 6

C2H50 C2H5OT1 C2H5O

OC2H5 Si^-OCzHs OC2H5 s -20- 201202855 [Chemical 5] c2h5o, c2H5(r, Si c2h5o

0C2H5 Si-OC2H5 OC2H5

C2H5〇 C2H5OT1 C2H5O HO

〇C2H5 SirOC2H5 OC2H5 C2H5O, C2H5〇^/bl C2H6〇 (1–14)

C2H! C2H5 C2H50 sic h3co H3CO〇bl H3C0

Formula (1-17) 0 , OC2H5 Formula (1-16) 〇 o c2h5o C2H50 /1 C2H50

H〇rSS T 〇C2H5 c2 2H507 C2H50 type (1-19) c2h5o'

-21 - 201202855 [Chem. 6]

/OC2H5 SI-OC2H5, OC2H5

XI, X

/〇CH3 'S1-OCH3, OCH3 c2h5o C2H5OjSi c2h5o (1-21)

H / OC2H5 R ^ s N / Si - 〇 C2H5 OC2H5 / 〇 CH3 Si ^ - 〇 CH3 OCH3 c2h5o c2h5ct, SiC2H5O HO Formula (1-22) 0 C2H5 〇 w C2Hs 〇 C2H5O HO Formula (1-23) 0 O C2H5Q ,; C2H5O· •Si C2H5O HO (1-24) 〇

H3CO, .H3CCT, Sl H3CO HO (1-25) 0

The hydrolyzable organodecane represented by the formula (1) may be a commercially available product or a synthetic one. For example, it can be synthesized by the reaction of an amino decane with an acid anhydride. The present invention can be used in combination with at least one organic hydrazine compound selected from the group consisting of the hydrolyzable organodecane represented by the formula (1) and the compound represented by the formula (2) and the formula (3). That is, the hydrolyzable organodecane represented by the formula (1), the hydrolyzate thereof or the hydrolyzed condensate thereof, and the organic compound represented by the formula (2) may be used in combination.

S -22- 201202855 At least one organic hydrazine compound selected from the group consisting of hydrazine compounds and organic hydrazine compounds represented by formula (3), hydrolyzates thereof and hydrolyzed condensates thereof. The ratio of the hydrolyzable organic decane represented by the above formula (1) to the organic hydrazine compound represented by the formula (2) and/or the organic hydrazine compound represented by the formula (3) may be 1:0 to 1 in molar ratio. : 200 range is used. In order to obtain a good resist shape, the ratio of the hydrolyzable organic decane represented by the formula (1) to the organic hydrazine compound represented by the formula (2) and/or the organic hydrazine compound represented by the formula (3) is in molar ratio. The meter can be used in the range of 1: 1 99 to 1: 19 . The organic ruthenium compound represented by the formula (2) is preferably used as the organic ruthenium compound selected from the group consisting of the organic ruthenium compound represented by the formula (2) and the organic ruthenium compound represented by the formula (3). These are preferably used as a hydrolysis condensate (polymer of polyorganosiloxane), and a hydrolysis condensate of the hydrolyzable organodecane represented by the formula (1) and the organic hydrazine compound represented by the formula (2) is preferably used. (Polymer of polyorganosiloxane). The organic hydrazine compound represented by the formula (2) and the organic fluorene compound represented by the formula (3) represented by R4, R5, R6 and R7 have an alkyl group, an aryl group, an alkyl halide group, or an aryl group of a halogenated group. Or an organic group of an epoxy group, an acryl fluorenyl group, a methacryl fluorenyl group, a fluorenyl group or a cyano group, and an alkoxy group, a decyloxy group or a halogen atom contained in the hydrolyzable group can be exemplified as Formula (1) narrator. The organic group having an oxyaryl group or a methoxy aryl group may be a combination of the above alkoxy group or a decyloxy group and an aryl group. The organic hydrazine compound represented by the formula (2) is exemplified by, for example, tetramethoxy-23-201202855 decane, tetrachlorodecane, tetraethoxydecane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropyl. Oxydecane, tetra-n-butoxydecane, tetraethoxydecane, methyltrimethoxydecane, methyltrichlorodecane, methyltriethoxydecane, methyltripropoxydecane, methyl Triethoxy decane, methyl tributoxy decane, methyl tripentyl decane, methyl triphenyloxy decane, methyl tribenzyloxy decane, methyl triphenyl ethoxy decane, glycidol Oxymethyltrimethoxydecane, glycidoxymethyltriethoxydecane, α-glycidoxyethyltrimethoxydecane, α-glycidoxyethyltriethoxydecane, β- Glycidoxyethyltrimethoxydecane, β-glycidoxyethyltriethoxydecane, α-glycidoxypropyltrimethoxydecane, α-glycidoxypropyltriethoxydecane , β-glycidoxypropyltrimethoxydecane, β-glycidoxypropyltriethoxy sand , γ-glycidoxypropyltrimethoxy sand 垸, γ-glycidoxypropyl triethoxy decane, γ-glycidoxypropyl tripropoxy decane, γ-glycidoxy propyl Tributoxydecane, γ-glycidoxypropyltriphenoxydecane, α-glycidoxybutyltrimethoxydecane, α-glycidoxybutyltriethoxydecane, β· Glycidoxy butyl triethoxy decane, γ-glycidoxy butyl trimethoxy decane, γ-glycidoxy butyl triethoxy decane, δ-glycidoxy butyl trimethoxy Decane, δ-glycidoxybutyl triethoxy decane, (3,4-epoxycyclohexyl)methyltrimethoxydecane, (3,4-epoxycyclohexyl)methyltriethoxy Base decane, β·(3,4-epoxycyclohexyl)ethyltrimethoxydecane, Ρ-(3,4-epoxycyclohexyl)ethyltriethoxydecane, β·(3,4 -Epoxycyclohexyl)ethyltripropoxydecane, β-(3,4-epoxy

S -24 - 201202855 Cyclohexyl)ethyl tributoxy decane, β-(3,4-epoxycyclohexyl)ethyltriphenoxydecane, γ-( 3,4-epoxycyclohexyl Propyltrimethoxydecane, γ-(3,4-epoxycyclohexyl)propyltriethoxydecane, δ_(3,4-epoxycyclohexyl)butyltrimethoxydecane, 5- (3,4-Epoxycyclohexyl)butyltriethoxydecane, glycidoxymethylmethyldimethoxydecane, glycidoxymethylmethyldiethoxydecane, α_shrinkage Glyceryloxyethylmethyldimethoxydecane, α-glycidoxyethylmethyldiethoxydecane, β-glycidoxyethylmethyldimethoxydecane, β-glycidyloxy Ethyl ethyl dimethoxy decane, α-glycidoxypropyl methyl dimethoxy decane, α-glycidoxy propyl methyl diethoxy decane, β-glycidoxy propyl Methyldimethoxydecane, β-glycidoxypropylethyldimethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ-glycidoxypropylmethyl Diethoxydecane, γ- Glycidoxypropylmethyldipropoxydecane, γ-glycidoxypropylmethyldibutoxydecane, γ-glycidoxypropylmethyldiphenoxydecane, γ-glycidol Oxypropylethyldimethoxydecane, γ-glycidoxypropylethyldiethoxydecane, γ-glycidoxypropylvinyldimethoxydecane, γ-glycidoxy Propyl vinyl diethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, vinyl trimethoxy decane, vinyl trichloro decane, vinyl triethoxy decane, vinyl three Ethoxy decane, vinyl triethoxy decane, phenyl trimethoxy decane, phenyl trichloro decane, phenyl triethoxy decane, phenyl triethoxy decane, phenyl triethoxy ox Base decane, methoxyphenyl trimethoxy decane, methoxyphenyl triethoxy decane, methoxy phenyl triethyl-25- 201202855 decyloxydecane, methoxyphenyl trichloromethane, A Oxybenzyltrimethoxydecane, methoxybenzyltriethoxydecane, methoxybenzyltriethoxydecane, Oxybenzyltrichlorodecane, methoxyphenethyltrimethoxydecane, methoxyphenethyltriethoxydecane, methoxyphenethyltriethoxydecane, methoxyphenethyl Trichlorodecane, ethoxyphenyl trimethoxy decane, ethoxyphenyl triethoxy decane, ethoxyphenyl triethoxy decane, ethoxyphenyl trichloro decane, ethoxy benzyl Trimethoxy decane, ethoxybenzyl triethoxy decane, ethoxybenzyl triethoxy decane, ethoxybenzyl trichloro decane, isopropoxy phenyl trimethoxy decane, different Propoxy phenyl triethoxy decane, isopropoxy phenyl triethoxy decane, isopropoxy phenyl trichloro decane, isopropoxy benzyl trimethoxy decane, isopropoxy benzyl Triethoxy decane, isopropoxybenzyltriethoxydecane, isopropoxybenzyltrichlorodecane, tert-butoxyphenyltrimethoxydecane, tert-butoxyphenyl three Ethoxy decane, tert-butoxyphenyl triethoxy decane, third butoxy phenyl trichloro decane, third butoxy benzyl trimethoxy decane, third butyl Benzyltriethoxydecane, tert-butoxybenzyltriethoxydecane, tert-butoxybenzyltrichlorodecane, methoxynaphthyltrimethoxydecane, methoxynaphthyltrile Ethoxy decane, methoxynaphthyltriethoxydecane, methoxynaphthyltrichlorodecane, ethoxynaphthyltrimethoxydecane, ethoxynaphthyltriethoxydecane, ethoxylate Naphthyltriethoxydecane, ethoxynaphthyltrichlorodecane, ethoxylated phenyltrimethoxydecane, ethoxylated phenyltriethoxydecane, γ-chloropropyltrimethoxydecane , γ-chloropropyltriethoxydecane, γ-chloropropyltriethoxydecane, 3,3,3-trifluoropropyltrimethoxydecane, γ-methylpropenyloxypropyl

S -26- 201202855 methoxy decane, γ-mercaptopropyltrimethoxydecane, γ-mercaptopropyloxydecane, β-cyanoethyltriethoxydecane, chloromethyltrimethoxyethane, chlorine Methyl triethoxy decane, dimethyl dimethoxy decane, phenyl dimethoxy decane, dimethyl diethoxy decane, phenyl methyl di decane, γ-chloropropyl methyl two Methoxydecane, γ-chloropropylmethyloxydecane, dimethyldiethoxydecane, γ-methylpropenyloxymethyldimethoxydecane, γ-methylpropenyloxy Propylmethyldidecane, γ-mercaptopropylmethyldimethoxydecane, γ-mercaptomethyloxydecane, methylvinyldimethoxydecane, methylvinyldimethoxydecane, and the like. The organic ruthenium compound represented by the formula (3) is exemplified by, for example, methyltrimethoxydecane, methylbistrichlorosilane, methylditrioxane, ethylditriethoxydecane, and ethyl Bis-trichlorodecane, bis-triethoxydecane, propyl bis-triethoxy decane, butyl trimethoxy decane, phenyl bis trimethoxy decane phenyl bis-tridecane Phenyl bismethyldiethoxy decane, phenyl bis methoxy decane, dinaphthyl bis trimethoxy decane, bis trimethoxy bis bis bis ethoxy dioxane, diethyl ethoxy Dioxane, bismethyloxydioxane, and the like. Specific examples of the hydrolyzable organic decane represented by the formula (1) and the hydrolysis condensate of the organic hydrazine compound represented by the formula (2) are exemplified as a condensate having the following structure. Triethyl thiol ethoxydiethyl propyl ethoxy ethoxy ethoxy bis ethoxydiethyl dimethyl dimethyl hydride , dimethyl dimethyl phthalate -27- 201202855 [Chem. 7]

^°9 ch3 一(Si〇2. 0)一一(Si〇i, 5)一一(Si〇i. 5)--(SiO!. 5)·

Equation (2 - 2)

—(Si〇2. 〇) — one (Si〇!. 5) one by one (Si〇i. 5)--(Si〇i. 5)— (2—3) ch3 is represented by the formula (1) a hydrolyzed organic decane hydrolyzed condensate (polyorganosiloxane) or a hydrolyzable organodecane of the formula (1), and an organic hydrazine compound represented by the formula (2) and/or an organic hydrazine compound represented by the formula (3) The hydrolysis condensate (polyorganosiloxane) can be obtained from a condensate having a weight average molecular weight of from 100 to 10,000, or from 1,000 to 100,000. These molecular weights were obtained by GPC analysis in terms of polystyrene. For the GPC measurement conditions, for example, a GPC apparatus (trade name: HLC_8220GPC, manufactured by TOSOH Co., Ltd.), a GPC column (trade name: Shodex KF803 L, KF8 02, KF801 'Showa Electric Co., Ltd.) can be used, and the column temperature is 40 ° C. The eluent (dissolving solvent) is tetrahydrofuran, flow rate (

S -28- 201202855 The flow rate is l.〇ml/min, and the standard sample is made of polystyrene (manufactured by Showa Denko Electric Co., Ltd.). The hydrolysis of an alkoxyalkyl group, a nonyloxyalkyl group, or a halogenated alkyl group is 〇5 to 100 moles, preferably 1 to 1 mole of water per 1 mole of the hydrolyzable group. Further, from 0 to 001 to 10 moles, preferably from 0.001 to 1 mole of the hydrolysis catalyst, per 1 mole of the hydrolyzable group. The reaction temperature at the time of hydrolysis and condensation is usually from 2 to 8 (rc. The hydrolysis can be carried out to complete hydrolysis or partial hydrolysis. That is, the hydrolyzate or the monomer can also be hydrolyzed in the hydrolysis condensate. The catalytic oxime hydrolysis catalyst can be exemplified by a metal chelate compound 'organic acid, none; H acid, organic test, inorganic base. The metal chelate compound as a hydrolysis catalyst can be exemplified by, for example, triethoxy (base • Acetylpyruvate) Titanium, Tri-n-propoxy-single (sodium acetyl-pyruvate) Titanium, Triisopropoxy-Single (Ethylpyruvylate) Titanium, Tri-n-Butoxy-Al-Single Base pyruvate) titanium, tri-tert-butoxy mono(ethenylpyruvate) titanium, tri-tert-butoxy-mono(ethylmercaptopyruvate) titanium, diethoxy bis(ethylene) Pyruvic acid) titanium, di-n-propoxy* bis(acetylthiopyruvate) titanium, diisopropoxy bis(acetylthiopyruvate) titanium, di-n-butoxy bis(acetylthiopyruvate) Titanium, di-second butoxy-bis(acetylthiopyruvate) titanium, di-t-butoxy-bis(acetylthiopyruvate) titanium, single Oxygen ginseng (ethionylpyruvate) titanium, mono-n-propoxy. ginsyl (ethionylpyruvate) titanium, monoisopropoxy ginseng (acetylthiopyruvate -29- 201202855) titanium, single n-Butoxy-paraben (acetylthiopyruvate) titanium, single second butoxy-parade (acetylthiopyruvate) titanium, mono-tert-butoxy-paraben (acetylthiopyruvate) titanium, strontium (Ethylpyruvate) Titanium, Triethoxyl Mono(ethylacetoxyacetic acid) Titanium, Tri-n-propoxy-ethoxy (monoethylideneacetic acid) Titanium, Triisopropoxy-A single ( Ethyl ethinylacetate) titanium, tri-n-butoxy. mono(ethylacetylacetic acid) titanium, tri-tert-butoxy mono(ethylacetoxyacetic acid) titanium, tri-tert-butoxy • Mono(ethylacetoxyacetic acid) titanium, diethoxy bis(ethylacetylacetic acid) titanium, di-n-propoxy-bis(ethylacetamidoacetic acid) titanium, diisopropoxy • bis(ethylacetoxyacetic acid) titanium, di-n-butoxy bis(ethylacetoxyacetic acid) titanium, two second butoxy bis(ethyl acetoxyacetic acid) titanium, two third Butoxy-bis(ethylethenyl) Acid) titanium, monoethoxy ginseng (ethyl acetoxyacetic acid) titanium, mono-n-propoxy-oxyl (ethyl ethyl acetoxyacetic acid) titanium, monoisopropoxy ginseng (ethyl ethyl fluorenyl) Acetic acid) titanium, mono-n-butoxy-parade (ethylethanoacetic acid) titanium, single second butoxy-parade (ethylethanoacetic acid) titanium, mono-tert-butoxy-para (ethyl) Ethyl mercaptoacetic acid) titanium, strontium (ethyl ethinylacetate) titanium, mono (acetyl acetonate) ginseng (ethyl ethinyl acetic acid) titanium, bis (ethyl thiopyruvate) bis (ethyl ethane Titanium chelating compounds such as thioglycolic acid, titanium, ginseng (ethylidenepyruvate), mono(ethylethanoacetic acid), titanium, etc.: triethoxyl mono(ethylmercaptopyruvate) zirconium, tri-n-propoxy • Single (acetylpyruvyl) pin, triisopropoxy mono(ethylmercaptopyruvate) zirconium, tri-n-butoxy•mono(ethylmercaptopyruvate) chromium, three second butoxy group Zirconium mono(acetylthiopyruvate), zirconium tris 3-butoxy mono(ethylmercaptopyruvate), zirconium diethoxy bis(acetylthiopyruvate), di-n-propoxy

S -30- 201202855 • Bis(acetylthiopyruvate) chromium, di-n-butoxyoxy•bis(ethylmercaptopyruvate) chromium, monopropoxy-paraben (acetylthiopyruvate) zirconium, single Second butoxy ginseng ((acetylthiopyruvate) • mono (ethyl ethinyl acetate) chromium, triiso-n-butoxy • mono (ethyl (ethyl ethyl decyl acetic acid) chromium, two Ethoxyethoxy bis (ethyl ethyl 'acetylacetic acid) zirconium, bis 2 -butoxy yl bis (ethyl acetoxyacetic acid) hydrazine, mono-n-isopropoxy oxyhydroxide Ethyl thioglycolic acid) zirconium, mono-tert-butyl ethyl acetoxyacetic acid) acetic acid) chromium, bis (anthracene, ginseng (ethylidene propyl hydrazine) pin, di-propoxyl group. bis (ethyl) Acetone propionate), a flute two-* —- ethoxy • ginsyl (ethionylpyruvate), monoiso-n-butoxy • ginseng (acetamyl acetonate) pin, zirconium, hafnium (Ethyl mercaptoacetic acid) pin, S n-propoxypropoxy group • Mono (ethyl ethyl acetoxyacetic acid) zirconium, Zirconium, triterpene, Butoxy group • Bis(ethyl ethyl fluorenyl fluorenyl) Acetic acid) 锗, two Iso-di-n-butoxy-bis (ethyl bis(ethylacetoxyacetic acid) acetate, monoethoxypropoxy ginseng (ethyl ethyl acetoxy) chrome, zirconium, single second butoxide · 氧基 参 参 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 乙基 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Butadiene oxy-bis(acetyl acetonate) zirconium, mono-n-propoxy-oxygen (glycolpyruvate) zirconium, single third butoxy-paraxyl) zirconium, triethoxy group, single (B) Ethyl mercaptoacetic acid) ruthenium, tris-tert-butoxy-mono-mono(ethylacetamidoacetic acid) zirconium, di-n-propoxypropoxy bis(ethyl acetoxyacetic acid) zirconium) zirconium , 2,3, 3-butoxy, ginseng (ethylethanoacetic acid), zirconium, mono-n-butoxy, ginseng (glycol (ethyl ethyl decyl ethyl acetate), zirconium (acid) ginseng (ethyl ethyl)醯Ethylethyl thioglycolate)-based acetic acid) Zirconium and other zirconium chelate-31 - 201202855 compound; aluminum chelating compound such as aluminum acetylate, ethyl acetylacetate, etc. Examples of the organic acid as the hydrolysis catalyst include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, and Diacid, azelaic acid, gallic acid, butyric acid, mellitic acid, Arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, flax Acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid And phthalic acid, fumaric acid, citric acid, tartaric acid, etc. The inorganic acid as a hydrolysis catalyst may, for example, be hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid or the like. The organic base as a hydrolysis catalyst may, for example, be pyridine, pyrrole, piperazine, piropyridine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine 'diethanolamine, dimethyl monoethanolamine, monomethyl Diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicyclononane, tetramethylammonium hydroxide, and the like. The inorganic base may, for example, be ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide or calcium hydroxide. Among these catalysts, a metal chelate compound, an organic acid, and a mineral acid are preferred, and one type or two or more types may be used. The organic solvent used for the hydrolysis may, for example, be n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane. An aliphatic hydrocarbon solvent such as an alkane, cyclohexane or methylcyclohexane; -32-

S 201202855 Benzene, toluene, xylene, ethylbenzene 'trimethylbenzene, methyl ethyl, n-propylbenzene, cumene, diethylbenzene, isobutylbenzene, triethylidene, diisopropylbenzene , aromatic hydrocarbons such as n-pentyl naphthalene, trimethylbenzene, etc. » methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol dibutanol, tert-butanol, n-pentanol, iso Pentanol, 2-methylbutanol, pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanedihexyl alcohol, 2-ethylbutanol, second heptanol , 3-heptanol, n-octanol ethylhexanol, second octanol, n-nonanol, 2,6-dimethyl-4-heptanol, alcohol, second-undecyl alcohol, trimethylhydrazine Alcohol, second-tetradecanol dipentadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5·trimethylhexanol, benzyl alcohol, phenylmethylcarbitol, a solvent such as diacetone alcohol or cresol; ethylene glycol, propylene glycol, 1,3-butanediol, pentanediol-2,4, 2-pentanediol·2,4, hexanediol-2,5, Heptanediol-2,4,2-ethylhexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol polyvalent alcohol solvent; , methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl, methyl n-hexyl ketone, two a ketone solvent such as isobutyl ketone, trimethyl fluorenone, cyclohexanone cyclohexanone, 2,4-pentanedione, acetyl ketone, diacetone alcohol, fen' ketone (Fenchone); Ether, isopropyl ether, n-butyl ether, n-hexyl ether, diethyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-phenylphenyl solvent a second alcohol, a 2-n-anthracene, a ketone, a ketone, a methyl ethyl ketone hexylmethyl-33-201202855 dioxolane, a dioxane, Dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene Alcohol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol II Ethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, Ethylene glycol mono-n-hexyl ether, ethoxy triethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, two An ether solvent such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran or 2-methyltetrahydrofuran; Ester, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, acetic acid Amyl acetate 'second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, acetic acid Methylcyclohexyl ester, n-decyl acetate, methyl acetoxyacetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl acetate Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, Acid propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetic acid glycol, methoxy triethylene glycol acetate, Ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, lactic acid

S -34- 201202855 Ester solvent such as amyl ester, diethyl malonate, dimethyl phthalate 'diethyl phthalate; N-methylformamide, N,N-dimethylformamidine Amine, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, etc. a nitrogen-containing solvent; a sulfur-containing solvent such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, cyclobutane or 1,3-propane sultone. These solvents may be used alone or in combination of two or more. In particular, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone , methyl n-hexyl ketone, diisobutyl ketone, trimethyl fluorenone, cyclohexanone, methyl cyclohexanone, 2,4 · pentanedione, acetyl ketone, diacetone alcohol, acetophenone, A ketone solvent such as anthrone (1,1,3-trimethyl-2-norbornene) is preferred in terms of storage stability of the solution. The underlayer film forming composition of the present invention may contain a hardening catalyst. The hardening catalyst functions as a curing catalyst when the coating film containing the polyorganosiloxane which is formed by the hydrolysis condensate is heat-cured. As the hardening catalyst, an ammonium salt, a phosphine, a scale salt or a phosphonium salt can be used. The ammonium salt is: a quaternary ammonium salt having a structure represented by the formula (D-1): -35- 201202855 [Chem. 8]

Illustrative (however, m represents an integer from 2 to 11, η represents an integer from 2 to 3, R11 or aryl represents an anion) has a quaternary ammonium salt of the formula (D-2): [Chem. 9] R12r13r14r15 Ν+ γ-form (D-2) 'N-independent (however, R12, R13, R14 and R15 each independently represent an alkyl or aryl group, and YA_ represents an anion, and R12, R13, R14 and R15 represents a quaternary ammonium salt having a structure represented by the formula (D-3) by a bond of a CN bond to a nitrogen atom: [Chemical 10]

Ions (However, R16 and R17 each independently represent an alkyl group or an aryl group, and YA_ represents a quaternary ammonium salt having a structure of the formula (D-4):

S -36- 201202855 [化11]

R18 Formula (D-4) (However, R18 represents an alkyl group or an aryl group, Y represents an anion), and has a quaternary ammonium salt of the formula (D-5): [Chemical 12] R20

Formula (D-5) (However, R19 and R2() each independently represent an alkyl group or an aryl group, and Υ represents an anion) > has a tertiary ammonium salt of the formula (D-6): [Chem. 13]

(CH2)n (however, m represents an integer of 2 to 11, η represents an integer of 2 to 3, Η represents a hydrogen atom, and ΥΑ_ represents an anion). Further, the onium salt is exemplified by the quaternary phosphonium salt represented by the formula (D-7): [Chem. 14] R21R22R23R24p+ γ- (D-7) -37-201202855 (However, R21, R22, R23 and R24 are each independently represented The alkyl or aryl group 'p represents a phosphorus atom, υα· represents an anion, and R21, R22, R23 and r24 are each independently bonded to a phosphorus atom by a CP bond). Further, the onium salt is exemplified by a tertiary sulfonium salt represented by the formula (D-8). [Chem. 15] R25R26R27S+ γ- (D-8) (However, R25, R2 6 and R27 each independently represent an alkyl group or an aromatic group. The base, s represents a sulfur atom, ΥΑ· represents an anion, and R25, R26 and R27 are each independently bonded to a sulfur atom by a cs bond). The compound represented by the above formula (D-1) represents a quaternary ammonium salt derived from an amine, and m represents an integer of 2 to 11, and η represents an integer of 2 to 3 'R11 of the quaternary ammonium salt represents a carbon number of 1 The alkyl group or the aryl group to 18, preferably an alkyl group of 2 to 10 or an aryl group having 6 to 18 carbon atoms is exemplified by a linear alkyl group such as an ethyl group, a propyl group, a butyl group or the like, or a benzyl group. , cyclohexyl, cyclohexylmethyl, dicyclopentadienyl and the like. Further, the anion (ΥΑ_) may be a halogen ion such as a chloride ion (cr), a bromide ion (Br_) or an iodide ion (Γ), or a carboxylate (-COO·), a sulfonate (-S〇3·) or an alcohol radical. The compound represented by the above formula (D-2) such as (-〇_) is an quaternary ammonium salt represented by R12R13R14R15N + Y. R12, R13, R14 and R15 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 compound represented by (D-2) is represented by Si. a decane compound in which a C bond is bonded to a ruthenium atom. The anion (YA_) may be a halogen ion such as a chloride ion (C1·), a bromide ion (Br_) or an iodide ion (Γ), or a carboxylate-38-

A quaternary ammonium salt such as S 201202855 (-COO·), sulfonate (-S03-), or an alcohol (-〇') may be commercially available, and is exemplified by, for example, tetramethylammonium and tetrabutylammonium acetate. Salt, triethylbenzylammonium chloride, triethylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, quaternary ammonium chloride, and the like. The compound represented by the above formula (D-3) represents a quaternary ammonium salt derived from azole, and the total number of carbon atoms of R16 and R17 is from 1 to 18, and the total number of carbon atoms of R17 is 7 or more. For example, R16 is exemplified by an ethyl group, a propyl group or a phenyl 'benzyl group, and R17 is exemplified by a benzyl group and an octadecyl group. The anion (ΥΑ·) may be a halogen ion such as a chloride ion (cr) (Bf) or an iodide ion (Γ), or an acid group such as a carboxylate ( ), a sulfonate (-S03·) or an alcohol (-CT). . This is commercially available, and may be produced, for example, by using 1-methylimidazole or a 1-benzylimidazole-based compound, or a halogenated alkane such as benzyl bromide or methyl bromide or halogenated aromatic. The compound represented by the above formula (D-4) is a quaternary ammonium salt derived from pyridine, and R18 represents an alkyl group having 1 to 18 carbon atoms, preferably a carbon atom of g 18 or an aryl group having 6 to 18 carbon atoms. It can be exemplified by a butyl group, a benzyl group, and a lauryl group. Examples of the anion (Y) include a halogen ion such as a chloride ion, a bromide ion (ΒΓ), or an iodide ion (Γ), or a (-COO·), a sulfonate group (-S〇3_), an alcohol group (-〇·), or the like. A compound such as an acid is commercially available, but for example, pyridine can be produced by reacting a halogenated alkane such as benzyl, benzyl chloride, benzyl bromide, methyl bromide or octyl bromide or a halogen. An example of the compound is exemplified by N-lauric acid chloride. The acetate-based benzyltrimethyl-substituted methoxide, preferably methyl octyl, bromine: -COO, carbazole, and the like, is reacted to form a number of 4 to octyl (cr) carboxylate groups. The cinnabar is chlorinated aromatic pyridinium-39-201202855, N-benzylpyridyl bromide, and the like. The compound represented by the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by methylpyridine, and R1 9 represents an alkyl group having 1 to 18, preferably 4 to 18 carbon atoms. Or an aryl group having 6 to 18 carbon atoms may, for example, be a methyl group, an octyl group, a lauryl group, a benzyl group or the like. R2() represents an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. For example, when quaternary ammonium is derived from methylpyridine, R2() represents a methyl group. The anion (YA_) can be exemplified by a chloride ion (Cl_), a bromide ion (B〇, an iodide ion (Γ), or the like, or a carboxylate (-cocr), a sulfonate (-sor), or an alcohol (-〇-). Such acid groups are commercially available, but may, for example, be substituted pyridyl chloride with methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide or the like. The compound is produced by an aromatic reaction. Examples of the compound include N-benzylmethylpyridine chloride, N-benzylmethylpyridinium bromide, N-laurylmethylpyridine chloride, and the like. The compound represented by the above formula (D_6) is an amine-derived tertiary ammonium salt 'm represents an integer of 2 to 11, and n represents an integer of 2 to 3. Further, an anion (Υ,) can be exemplified as chloride ion (C1·). a halogen ion such as a bromide ion (Br_) or an iodide ion (factory), or an acid group such as a carboxylate group (-C00·), a sulfonate group (-S03·) or an alcohol group (-〇-). The compound represented by the formula can be produced by reacting an amine with a weak acid such as a carboxylic acid or a phenol. The carboxylic acid is exemplified by formic acid or acetic acid, and when formic acid is used, the anion (ΥΑ·) is expressed by (HC0CT). In the case of acetic acid, the anion (ΥΑ·) represents (ch3coo·). When phenol is used, the anion (Y,) represents (c6h5ct). The compound represented by the above formula (D-7) has the structure of r21r22r23r24p+ γΑ·s -40- 201202855 represents a quaternary money salt of the structure R21, R22, R23 and an alkyl group of 1 to 18 or an aryl group having 6 to 18 carbon atoms, or a decane compound bonded to a ruthenium atom, but preferably R21 to R24 Three of them represent a phenyl group or a substituted phenyl group, and the three are represented by a phenyl group or a tolyl group, and the remaining one is an alkyl group of the group, an aryl group having 6 to 18 carbon atoms, or by Si. Bonded decyl group, and anion () can be listed as C1·), bromide (Br_), iodide (Γ) and other halides (-C Ο 0 _ ), sulfonate (-S Ο Γ ), alcohol Root I. The compound is commercially available, and examples thereof include a halogenated tetraalkyl scale such as a halogen or a tetra-n-propyl halide, a trialkylbenzylphosphonium halide or the like, a triphenylmethylethylethylphosphonium halide or the like. The triphenylmonoalkylphosphonium halide, the tetraphenylphosphonium triphenyl halide, the trimethylphenyl monoaryl scale, or the haloalkyl iron (the halogen atom is a chlorine atom or a bromine atom). a halogenated triphenylmonoaryl scale such as a phenylene methyl iron or a triphenylethyl halide, such as a triphenylbenzyl sulfonium halide, a triphenyl monoaryl scale such as a monophenyl scale, or the like. Or a halogenated trimethylphenyl monoalkyl scale (halogen atom) such as a halogenated hydrazine is preferred. Further, the phosphines are exemplified by primary phosphines such as methyl phosphine, ethyl phosphine, propionylphosphine, isobutylphosphine, and phenylphosphine, dimethylphosphine diisopropylphosphine, diisopentylphosphine, diphenylphosphine, and the like. Secondary, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and two represent a carbon atom by a Si-C bond and four substituent substituents thereof may be an atomic number of 1 to 18 -C bond And the ruthenium atom is an acid-based tetra-n-butyl iron triethyl benzyl sulphate such as a chlorinated ion (or a carboxylic acid [- 〇 )), a triphenyl benzyl fluoride, a trimethyl sulfonium group, With a halogenated trisyl monoalkyl scale, a trimethylphenyltrimethylphosphonium monomethyl group is a chlorine atom or a bromophosphine, an isopropyl group, a diethylphosphine, a phosphine, a trimethylphosphine methylphenylphosphine, etc. -41 - 201202855 Tertiary phosphine. The compound represented by the above formula (D-8) is a tertiary sulfonium salt having a structure represented by r25r26R27S + YA_. R25, R26 and R27 represent a aryl group having from 1 to 18 carbon atoms or an aryl group having from 6 to 18 carbon atoms, or a group bonded to a ruthenium atom by a Si-C bond, but preferably four of R25 to R27 Three of the substituents represent a phenyl group or a substituted phenyl group, and the three substituents may be exemplified as a phenyl group or a tolyl group, and the remaining one substituent is an alkyl group having 1 to 18 carbon atoms or carbon. An aryl group having 6 to 18 atoms. The alkyl group or the aryl group can be exemplified by the functional group of the carbon number of the above-exemplified product. Further, the anion (ΥΑ·) may be a halogen ion such as chloride ion (Cl·), bromide ion (ΒΓ), or iodide ion (factory), or a carboxylate (-COO_), a sulfonate (-S03_), or an alcohol (- CT) and other acid groups. The compound is commercially available, and is exemplified by a tetraalkylphosphonium halide such as tri-n-butylphosphonium halide or tri-n-propylphosphonium halide; a trialkylbenzylphosphonium halide such as diethylbenzylphosphonium halide; a diphenylmonoalkylphosphonium halide such as phenylmethylhydrazine or diphenylethylphosphonium halide; a triphenylphosphonium halide (a halogen atom is a chlorine atom or a bromine atom), a tri-n-butyl phosphonium residue, and a tri-n-butyl group. a tetraalkylphosphonium carboxylate such as a propyl phosphonium carboxylate; a trialkylbenzylphosphonium carboxylate such as diethylbenzylphosphonium carboxylate; a diphenylmethylphosphonium carboxylate or a diphenylethyl a diphenylmonoalkylphosphonium carboxylate such as a hydrazine carboxylate; a triphenylphosphonium carboxylate. Most preferred are triphenylphosphonium halide and triphenylsulfonium carboxylate. The amount of the hardening 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, per 100 parts by mass of the polyorganosiloxane. The hydrolyzable organodecane is hydrolyzed and condensed by using a catalyst in a solvent, and the obtained hydrolysis condensate (polymer) can be simultaneously removed by distillation under reduced pressure.

S -42- 201202855 Alcohol as a by-product or a hydrolysis catalyst or water used. Further, the acid or base catalyst used for the hydrolysis can be removed by neutralization or ion exchange. Further, in the lithographic underlayer film forming composition of the present invention, an organic acid, water, alcohol, or a combination thereof for neutralizing the resist underlayer film forming composition containing the hydrolyzed condensate may be added. The above organic acid is exemplified by, for example, oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid 'malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid, salicylic acid, etc. . Among them, oxalic acid, maleic acid and the like are preferred. 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). Further, 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 1 part by mass of the composition of the underlayer film forming composition. Further, the alcohol to be added is preferably one which is easily volatilized by heating after coating, and is exemplified by methanol, ethanol, propanol, isopropanol, butanol or the like. The added alcohol may be 1 to 20 parts by mass relative to the resist underlayer film forming composition 10 parts by mass. The underlayer film forming composition for lithography of the present invention may contain, in addition to the above components, an organic polymer compound, a photoacid generator, a surfactant, and the like, as needed. By using the organic polymer compound, the dry uranium engraving speed (reduction in film thickness per unit time), the attenuation coefficient, and the refractive index of the underlayer film formed by the composition film for forming a lithography film of the present invention can be adjusted. Wait. The organic polymer compound is not particularly limited, and various organic polymers can be used. A polycondensation polymer, an addition polymerization polymer, or the like can be used. Can use -43- 201202855 polyester, polystyrene, polyimine, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac resin, naphthol novolac resin, polyether, polyamine Addition polymerized polymers such as polycarbonate, and polycondensation polymers. An organic polymer having an aromatic ring structure such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a porphyrin ring or a quinone ring which functions as a light absorbing site is preferably used. The organic polymer compounds are exemplified by, for example, benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, decyl methacrylate, decyl methyl methacrylate styrene, hydroxystyrene, benzyl. An addition polymerizable monomer such as a vinyl ether and an N-phenylmaleamide is used as a polymerization polymer of a structural unit thereof, or a polycondensation polymer such as a phenol novolak resin or a naphthol novolak resin. When an addition polymerized polymer is used as the organic polymer compound, the polymer compound may be a homopolymer or a copolymer. The addition polymerization polymer is produced by using an addition polymerizable monomer. The addition polymerizable monomer is exemplified by acrylic acid, methacrylic acid, acrylate compound, methacrylate compound, acrylamide compound, methacrylamide compound, vinyl compound, styrene compound, and maleimide compound. , maleic anhydride, acrylonitrile, etc. The acrylate compound is exemplified by methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, decyl methyl acrylate, 2-hydroxyethyl acrylate, acrylic acid 3 -Chloro-2-hydroxypropyl ester, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, C-44-

S 201202855 ester hail original hydrogen hydroxy acid 6 ene-propyl ester ethyl oxymethane 2 acid acrylic acid, ester ester alkane gold - 2 I butyl methyl 2-hydroxy acid 4-enoic acid propylene, oxy decene丙t日日" 6 octanoic acid carboxylic acid ester oil condensate-2. Acid ene ene plate and alkanoyl oxy ethoxypropyl oxy decyl propyl methacrylate compound are listed as methyl methacrylate, Ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, decyl methyl methacrylate, methacrylic acid 2 -hydroxyethyl ester, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate 4, hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methyl propylene oxime 6-hydroxynorbornene-2-carboxylic acid-6-lactone, 3-methylpropenyloxypropyltriethoxydecane, methacrylic acid Water glyceride, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate and bromophenyl methacrylate. The acrylamide compound is exemplified by acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-benzyl acrylamide, N-phenyl acrylamide, hydrazine, hydrazine-dimethyl propylene. Guanamine and N-mercaptopropenylamine. The methacrylamide compound is exemplified by methacrylamide, Ν-methylmethacrylamide, Ν-ethyl methacrylamide, Ν-benzyl methacrylamide, Ν-phenylmethyl Acrylamide, hydrazine, hydrazine-dimethyl methacrylamide and fluorenyl-mercaptomethyl decylamine. The vinyl compounds are exemplified by vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyl-45-201202855 trimethoxydecane, 2-chloroethyl Vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene and vinyl anthracene. The styrene compound is exemplified by styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and ethyl styrene styrene. Maleimide compounds are listed as maleimide, methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaline Amine and N-hydroxyethyl maleimide and the like. When a polycondensation polymer is used as the polymer, the polymers are exemplified by a polycondensation polymer of a diol compound and a dicarboxylic acid compound. The diol compound is exemplified by diethylene glycol, hexamethylene glycol, butylene glycol and the like. The dicarboxylic acid compound is exemplified by succinic acid, adipic acid, terephthalic acid, maleic anhydride or the like. Further, it is exemplified by polyesters such as polypyrenetetramine, poly(p-phenylene terephthalamide), polybutylene terephthalate, polyethylene terephthalate, and polyamine. , polyimine. When the organic polymer compound contains a hydroxyl group, the hydroxyl group can form a crosslinking reaction with the polyorganosiloxane. The organic polymer compound may use a polymer compound having a weight average molecular weight of, for example, 1,000 to 1,000,000, or 3,000 to 300,000, or 5,000 to 200,000, or 1,000,000 to 100,000. The organic polymer compound may be used singly or in combination of two or more. When the organic polymer compound is used, the ratio thereof is from 1 to 200 parts by mass, or from 5 to 100% by mass based on 100 parts by mass of the condensate (polyorganosiloxane).

S -46 - 201202855 parts, or 10 to 50 parts by mass, or 20 to 30 parts by mass. The acid generating agent which may be contained in the under-layer film forming composition of the present invention is exemplified by a thermal acid generating agent or a photoacid generating photoacid generating agent which generates an acid upon exposure of the resist. Due to the acidity of the film. This is a method for conforming the acidity of the underlayer film to the acidity of the underlayer film. Further, by adjusting, the pattern shape of the resist formed on the upper layer can be adjusted. The anti-corrosion underlayer film forming composition of the present invention is exemplified by a key salt compound, a sulfonimide compound, a disulfonate compound and the like. The onium salt compound is exemplified by diphenylphosphonium hexafluorophosphate fluoromethanesulfonate, diphenyliodonium nonafluorobutane sulfonate fluoro-n-octane sulfonate, diphenyl camphorsulfonate, diphenyl Base) camphor sulfonate and bismuth (4-tert-butylphenyl sulfonate, etc., and triphenylsulfonium hexafluoroantimony nonafluorobutane sulfonate, triphenyl camphor An sulfonium salt compound such as a sulfonate fluoromethanesulfonate or the like. The sulfonimide compound is exemplified by, for example, N-(trifluoromethylammonium imine 'N-(nonafluoro-n-butane sulfonyloxy) succinate (camphor Sulfomethoxy) succinimide and N-(trifluoromethylnaphthalene imine, etc. Disulfonyldiazomethane compounds are exemplified by, for example, biguanide) Diazomethane, bis(cyclohexylsulfonyl) a diazosulfonyl)diazomethane or a bis(p-toluenesulfonyl) acid generator. This is a photoacid generator which can adjust the acidity of the lower resist layer film. Nitromethane, monophenylphosphonium tris, diphenyliodonium (4-tert-butyl) iodine trifluoromethane, triphenyl and dibenzyl sulfonium oxyalkylene) N-alkylsulfonyloxy) (di-methyl methyl, methane, bis(phenyl)diazomethane, -47- 201202855 bis(2,4-dimethylphenylsulfonyl)diazomethane, and methyltoluene Sulfhydryl diazomethane, etc. The photoacid generator may be used alone or in combination with two photoacid generators in a ratio of 0.01 to 5 parts by mass, or 0.13 to 0.5 to 1 part by weight based on 100 parts by mass of the condensed oxane. Parts by mass. When the surfactant for lithography of the present invention is applied to a substrate, the surfactant can effectively suppress pinholes and strips formed in the underlayer film forming composition of the present invention, for example, polyoxyethylene Polyoxyl such as lauryl ether, polyoxyethylene ethyl hard methyl ethyl cetyl ether, polyoxyethyl ether oleyl ether, polyoxyethylene ethyl octyl phenol ether, polyoxyethylene ethyl decyl ether Alkyl aryl ethers, polyoxyethylene ethyl • polyoxygen propylene sorbate monosorbate, sorbitan monostearate monostearate, sorbitan monooleate Sorbose such as ester trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyalcoholic monopalmitate, polyoxyethylene sorbitol Polyoxyethylene-ethyl sorbitan fatty acid sub-system surfactant such as polyoxyethylene-ethyl sorbitan trioleate or polyoxyethylene tristearate, trade name EF Τ Ο PEF 3 0 1 ,

(Manufactured by TOKEMU PRODUCTS), 商商F F171, F173, R-〇8, R-30 (made by Dainippon Ink Chemicals), FLUORAD FC430, FC431 (Sumitomo 3M sulfonyl-based, etc.) (Polyorganic 矽g 3 parts by mass, or underlayer film formation, etc.. Interfacial surfactants such as aliphatic ether, polyoxyalkylene ether ether phenol ether, etc. Mountain, sorbitan alcoholic anhydride fatty acid ester oxygen exoethyl sorbate monostearate, sorbitan ester, etc. non-ion EF303, EF3 52 S MEGAFAC industrial (stock) system (stock) manufacturing)

S-48 - 201202855, trade name ASAHI GUARD AG710, SURFLON S-382, SC101, SC 1 02 'SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, and organic siloxane polymerization KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and so on. These surfactants may be used singly or in combination of two or more. When the surfactant is used, the ratio thereof is 0.000 1 to 5 parts by mass, or 0.001 to 1 part by mass, or 〇.〇1 to 〇.5 parts by mass relative to 100 parts by mass of the condensate (polyorganosiloxane). Further, a rheology adjusting agent and an auxiliary agent may be added to the underlayer film forming composition of the present invention. The rheology modifier can effectively increase the fluidity of the underlying film forming composition. The adjuvant can then effectively improve the adhesion of the semiconductor substrate or the resist to the underlying film. Examples of the rheology modifier include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and isobutyl phthalate. , di-n-butyl adipate, di-isobutyl adipate, diisooctyl adipate, octyl phthalate adipate and other adipate derivatives, di-n-butyl maleate, maleic acid An oleic acid derivative such as ethyl oleate or diterpene maleate derivative, such as methyl oleate, butyl oleate or tetrahydrofurfuryl oleate, or n-butyl stearate or glyceryl stearate. A stearic acid derivative such as an ester. The rheology modifier is usually less than 30% by mass based on 100% by mass of the total composition of the underlayer film forming composition. /. Proportional allocation. Next, the adjuvant may, for example, be a chlorodecane-trimethylmethoxy decane such as trimethylchlorodecane, dimethylvinylchlorodecane, methyldiphenylchlorodecane or chloromethyldimethylchloromethane. Alkoxy decane alkane, such as dimethyldiethoxy decane, methyl-49-201202855 dimethoxy decane, dimethylvinyl ethoxy decyl decane, phenyl triethoxy decane,矽'-bis(trimethyldecyl)urea, dialkylamine, trimethyldecyl imidazole and the like decazane, γ-chloropropyltrimethoxydecane, γ-aminopropyltriethylene glycerol a decane such as oxypropyltrimethoxydecane, a heterocyclic ring such as imidazole, oxazole, imidazole, 2-mercaptobenzimidazole, 2-2-mercaptobenzoxazole, urezo, thiouracil or fluorenyl a compound of the formula, 1,1-dimethylurea, 1,3-dithiourea compound. Then, the auxiliary agent is usually formulated in an amount of not more than 5% by mass, based on 100% by mass of the entire composition of the undercoat layer. The solvent for dissolving the solid component in the composition for forming a resist underlayer film of the present invention may be, for example, methyl cellosolve acetate, ethyl propylene glycol, propylene glycol monomethyl ether or propylene glycol monoethyl bromide. Carbitol, propylene glycol monobutyl ether, propylene glycol monomethyl alcohol monoethyl ether acetate, propylene glycol monopropyl ether acetate acetate, toluene, xylene, methyl ethyl ketone, 2- Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutylpropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxyethoxypropionate, methyl pyruvate, ethyl ether pyruvate, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diphenyl dimethoxy, hexamethyl Urea or film forming composition of dimercaptomethyltrimethyldecalenyl trichlorodecane, oxyindole, γ-benzotriazole, benzoxylbenzothiazole, imidazole, mercaptopyrimidine methyl urea A solvent which is preferably less than 2 masses is used as long as it is usable. These lyophilized cellulose acetate, ether, methyl isobutyl styrene acetate, propylene glycol, propylene glycol monobutyl, cyclopentanone, cyclohexyl ethyl ester, methyl ethoxyacetate, 3-methoxy Ethyl propionate, 3-vinegar, ethylene glycol monomethyl, ethylene glycol monobutyl

S -50- 201202855 Ether, ethylene glycol monomethyl ether acetate 'ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate , diethylene glycol dimethyl ether, diethylene glycol diethyl ether 'diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol diethyl ether, propylene glycol Dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, Butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, C Acid propyl ester, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, butyric acid Butyl ester, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropanoate, methyl 2-hydroxy-3-methylbutanoate, A Ethyl oxyacetate, B Ethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxy acetate Propyl propyl ester, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3·methyl-3·methoxybutyl butyrate, B Methyl thioglycolate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N, N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N.methylpyrrolidone, and γ-butyrolactone. These solvents may be used singly or in combination of two or more. The use of the underlayer film forming composition of the present invention will be described below. -51 - 201202855 Substrates used in the manufacture of semiconductor devices (for example, wafer substrate 'sand/sand oxide coated substrate, nitrided substrate, glass substrate, ZT 0 substrate, polyimide substrate, and low dielectric The resist material underlayer film forming composition of the present invention is applied onto a rate material (low-k material) substrate or the like by a suitable coating method such as a spin coater or an applicator, and then formed by firing. Resist the underlayer film. The firing conditions can be appropriately selected from the firing temperature of 80 to 250 ° C and the firing time of 0.3 to 60 minutes. Preferably, the firing temperature is from 150 to 260 ° C and the firing time is from 0.5 to 2 minutes. Here, the film thickness of the underlayer film is, for example, 10 to 10 nm, or 20 to 500 nm, or 50 to 300 nm, or 100 to 200 nm. A photoresist layer is then formed on the underlayer film. The formation of the photoresist layer can be carried out by a conventional method in which a photoresist composition solution is applied onto the underlayer film and fired. The film thickness of the photoresist is, for example, 50 to 1 000 nm, or 100 to 2000 nm, or 200 to 100 nm. In the present invention, after the organic underlayer film is formed on the substrate, the underlayer film of the present invention is formed thereon, and then the photoresist is coated thereon. Accordingly, even in order to narrow the width of the photoresist pattern and prevent the pattern from collapsing and to coat the photoresist thinly, it is possible to perform substrate processing by selecting an appropriate etching gas. For example, the anti-corrosion underlayer film of the present invention can be processed by using a fluorine-based gas having a fast etching rate for the photoresist as an etching gas, and an oxygen-based gas having a sufficiently fast etching rate for the under-layer film of the present invention can be used as the etching gas. The etching gas is processed on the organic underlayer film, and the fluorine-based gas having a sufficiently fast etching rate to the organic underlayer film can be used as an etching gas to process the substrate.

S-52-201202855 The photoresist formed on the resist underlayer film of the present invention is not particularly limited as long as it is photosensitive to light used for exposure. Any of a negative photoresist and a positive photoresist can be used. The photoresists include a positive photoresist composed of a novolac resin and 1,2-naphthoquinone azide sulfonate, and a binder and a photoacid generator having a base for increasing the alkali dissolution rate by acid decomposition. a chemically amplified photoresist composed of a low molecular compound and an alkali soluble binder and a photoacid generator which increase the alkali dissolution rate of the photoresist by acid decomposition, and has a A chemically amplified photoresist composed of a low molecular compound and a photoacid generator which are capable of increasing the rate of alkali dissolution by decomposition of an acid and a base which dissolves by a decomposition of an acid. For example, the trade name APEX-E manufactured by CHYPRE, the trade name PAR710 manufactured by Sumitomo Chemical Industries Co., Ltd., and the trade name SEPR43 0 manufactured by Shin-Etsu Chemical Co., Ltd. Further, it can be cited, for example, as Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), or Proc. SPIE, Vol. 3 999, 3 65 - Fluorinated atomic polymer system photoresist as described in 3 74 (2000). Next, exposure is performed through a specific mask. The exposure can use KrF quasi-molecular laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and F2 excimer laser (wavelength 157 nm). After exposure, post exposure bake can be performed as needed. The post-exposure heating can be appropriately selected by heating at a temperature of 70 ° C to 150 ° C for a heating time of 3 3 to 10 minutes. Further, the present invention can replace the light as a photoresist with a resist by electron beam lithography. Resistance. The electron beam anti-uranium agent can be either a negative type or a positive type. -53- 201202855 The uranium-resistant agent has a chemically amplified anti-caries agent composed of an acid generator and a binder having a base for changing the alkali dissolution rate by acid decomposition, an alkali-soluble binder and an acid generator, and A chemically amplified resist composed of a low molecular compound which changes the alkali dissolution rate of the resist by decomposition of an acid. a chemically amplified resist composed of an acid generator and a binder having a base which changes the rate of alkali dissolution by acid decomposition and a low molecular compound which changes the alkali dissolution rate of the resist by acid decomposition, A non-chemically amplified resist composed of a binder which changes the base dissolution rate by electron beam decomposition, and is a non-chemically amplified type composed of a binder having a portion which changes the alkali dissolution rate by electron beam cutting. Resist, etc. When such an electron beam resist is used, an anti-hungry pattern similar to the case where a light source of an electron beam is used as an electron beam can be formed. Next, development is carried out by a developing solution. Accordingly, when a positive photoresist is used, for example, the photoresist of the exposed portion is removed to form a photoresist pattern. As the developing solution, an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, or a tetrabasic ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline may be mentioned. An aqueous solution of an aqueous solution such as an aqueous solution of an amine such as ethanolamine, propylamine or ethylenediamine. Further, a surfactant may be added to the developing solutions. The conditions for development are appropriately selected from the temperature of 5 to 5 (TC, time 10 to 600 seconds. Next, the resist underlayer film (intermediate layer) of the present invention is carried out using the pattern of the photoresist (upper layer) thus formed as a protective film. After removal, the film formed by the patterned photoresist and the underlayer film (intermediate layer) of the present invention is used as a protective film to remove the organic underlayer film (lower layer). Finally,

S-54-201202855 The patterned underlayer film (middle and lower layer) of the present invention is patterned as a protective film, and the semiconductor substrate is first removed by dry etching to remove the underlayer film (intermediate layer) to dry the semiconductor underlayer film. For the etching, a gas such as tetrafluoromethane < c4F8), perfluoropropane (C3F8), trifluoro 'oxygen, nitrogen, sulfur hexafluoride, difluoromethane, chlorine, trichloroborane or dichloroborane can be used. It is good to use a halogen gas. The photoresist consisting of organic substances is removed by a halogen gas. The resist underlayer film of the present invention of the phase can be halogen-reducing, thereby suppressing dry etching of the underlayer film. Therefore, as a result, the dry uranium using the film in the form of a film is preferably subjected to a fluorine-based gas such as tetrafluoromethane (cf4), perfluorocyclobutene (C3F8) 'trifluoromethane and difluoromethane (subsequently The patterned photoresist and the formed film are used as a protective film to perform the lower layer of the organic underlayer film.) It is preferably removed by dry etching using an oxygen-based gas under the resist of the present invention containing a plurality of germanium atoms. Finally, the semiconductor substrate is processed by a dry etching of a fluorine-based gas by a fluorine-based gas, for example, a tetrafluoro-transpyrene layer, and an organic underlayer film (the processing of the sheet. The resist of the present invention is exposed. The dry etching of the present invention: CF4), perfluorocyclobutane (a compound, carbon monoxide, argon nitrogen trifluoride and chlorine trifluoride, dry etching of the underlayer film is substantially difficult for dry etching) The gas containing a large amount of ruthenium-based gas is rapidly removed. The light-resistance of the photoresist film is reduced. Under the resist, the fluorine-based gas is exemplified by an alkane (c4F8) or a perfluoropropane ch2f2). Removal of the underlayer film of the present invention. The organic underlayer film is subjected to dry etching. This is difficult to carry out by the oxide film by the oxygen film. E (CF4), perfluorocyclobutane-55-201202855 (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc. Further, on the upper layer of the underlayer film of the present invention, an organic anti-reflection film can be formed before the formation of the photoresist. The material is not particularly limited and can be arbitrarily selected from among those conventionally used in the lithography process, and can be applied by a conventional method such as coating and firing by a spin coater or an applicator. Further, the substrate on which the composition for forming a resist underlayer film of the present invention is applied may have an organic or inorganic antireflection film formed by a CVD method or the like on the surface thereof, or The underlayer film of the present invention is formed thereon. The underlayer film formed by forming the composition of the underlayer film of the present invention also has absorption of light of a wavelength of light used in the lithography process. Therefore, in this case, As having prevention The function of the antireflection film from the effect of reflecting light from the substrate. Moreover, the underlayer film of the present invention can also serve as a layer for preventing interaction between the substrate and the photoresist, and has a material for preventing photoresist or a substance generated when exposed to a photoresist. A layer that functions as a function of adverse effects of the substrate, has a function of preventing diffusion of a substance generated from the substrate toward the upper layer resist during heating and firing, and serves as a poisoning layer for reducing a photoresist layer caused by the dielectric layer of the semiconductor substrate. Further, the barrier underlayer formed of the underlayer film forming composition can be used as a substrate for forming a via hole in a dual damascene process without gaps. It is used as a buried material. In addition, a flattening material for flattening the surface of the uneven semiconductor substrate can be used.

S-56-201202855 Hereinafter, the present invention will be more specifically described by way of examples, but the invention is not limited thereto. EXAMPLES First, the synthesis of the hydrolyzable decane represented by the formula (1) used in the raw material was carried out. The obtained compound was identified by 1 H-NMR measurement. Using a sample tube: 5 mm, solvent: deuterated chloroform, measuring temperature·room temperature, pulse interval: 5 seconds, cumulative number··3 2 times, standard sample: tetramethyl decane (TMS). (Synthesis of Compound 1) Into a 200 ml three-necked flask equipped with a mechanical stirrer, 20.00 g of aminopropyltriethoxydecane was poured in. While cooling with a water bath, 9.04 g of powdered succinic anhydride was poured and stirred at room temperature for one day. . Subsequently, the obtained crude product was purified with hexane to give Compound 1 of the subject. The obtained Compound 1 is equivalent to the compound represented by the formula (1-1). 1H-NMR (400MHz): 0.64ppm (t, 2H), 1.23ppm (t, 9H), 1.63ppm (quint, 2H), 2.51ppm (t, 2H), 2.68 ppm (t, 2H), 3.24ppm ( q, 2H), 3.82 ppm (q, 6H), 6.42 ppm (s, 1H). (Synthesis of Compound 2) Into a 200 ml three-necked flask equipped with a mechanical stirrer, 20-00 g of aminopropyltriethoxydecane was poured, and 886 g of powdery succinic anhydride was poured while cooling with a water bath, and stirred at room temperature for one day. Subsequently, the obtained crude product was purified as hexane-57-201202855 to obtain Compound 2 as the subject. The obtained Compound 2 is a compound represented by the formula (1-5). 1 H-NMR (400 MHz) 0.68 ppm (t, 2H), 1 -23 ppm (t, 9H) 1.74 ppm (quint, 2H), 3 .3 8 ppm (q, 2H), 3.82 ppm (q, 6H) 6.2 9 - 6.4 7 p pm (dd, 2H), 8.22 ppm(s, 1H) ° (Synthesis of Compound 3) Injecting Aminopropyltriethoxy Sands into a 200ml three-necked furnace 2 〇· 0 〇g 'Triethylamine> 3,300 g of 1.43 g of tetrahydrofuran, and a mixed solution of 14.87 g of ethyl amber ruthenium chloride and 20.00 g of tetrahydrofuran was added dropwise while cooling in a water bath, and stirred at 〇 ° C for one hour at room temperature. Stir for 6 hours. After the reaction, the solution was filtered, and tetrahydrofuran was distilled off under reduced pressure using an evaporator. Add 100 ml of dichloroethane, and wash it several times with water. Subsequently, it was dried over magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure to give the crude product of Compound 3 of the subject. After purification by reduced pressure distillation, the title compound 3 was obtained. The obtained Compound 3 is equivalent to the compound represented by the formula (1-3). 1H-NMR (400MHz): 59.59ppm(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) 〇 (Synthesis Example 1) 32.32g of compound 1, 14.58g of tetraethoxy decane (TEOS) 〇.99g of phenyltrimethoxydecane (PhTMOS), 4.28g of methyltriethoxydecane (MeTEOS), 30.26g of acetone and 100ml of calcined-58-

S 201202855 The bottle was dissolved and heated while stirring with a magnetic stirrer and refluxed. Next, 6.67 g of a 0.01 M aqueous hydrochloric acid solution was added to the mixed solution. After reacting for 240 minutes, the resulting reaction solution was cooled to room temperature. Subsequently, 20.00 g of propylene glycol monomethyl ether acetate was added to the reaction solution. The ethanol, water, and hydrochloric acid of the reaction by-product were distilled off under reduced pressure to obtain a hydrolysis condensate solution. Subsequently, propylene glycol diethyl ether was added to the hydrolysis condensate solution to finally obtain a 15% hydrolysis condensate solution. The weight average molecular weight of the obtained polymer as measured by GPC was 1600 in terms of polystyrene. The obtained polymer is equivalent to a polymer having a unit structure represented by the formula (2-1). Synthesis Example 2 was obtained in the same manner by using Compound 2 instead of the compound used in Synthesis Example 1. Synthesis Example 3 was obtained in the same manner by using Compound 3 instead of Compound 1 used in Synthesis Example 1. Further, the same operation as in Comparative Example 1 using Compound 1 was carried out, and Comparative Synthesis Examples 1 to 2 were obtained. The blending ratios of the decane compounds in the compositions of Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 2 are shown in Table 1. The polymer obtained in Synthesis Example 2 corresponds to a polymer having a unit structure represented by the formula (2-2), and the polymer obtained in Synthesis Example 3 corresponds to a polymer having a unit structure represented by the formula (2-3). The polymer obtained in Comparative Synthesis Examples 1 to 2 is equivalent to a polymer having a unit structure represented by the following formula (3-1). -59- 201202855 [Chem. 16]

—(Si02.

9 ch3 ο)--(Si〇!. 5)--(Si〇i. 5)

Formula (3 - 1) [Table 1] TEOS Table PhTMOS 1 MeTEOS Formula (1) decane molar % Mohr % Mohr % Mohr % Synthesis Example 1 70 5.003 24 0-997 (Compound 1) Synthesis Example 2 70 10.003 19 0.997 (Compound 2) Synthesis Example 3 70 10.003 19 0.997 (Compound 3) Comparative Synthesis Example 1 70 5 25 Comparative Synthesis Example 2 70 10 20 (Example 1) Polymer solution obtained in Synthesis Example 1 (solid content) 15.00% by mass) 0.03 g of maleic acid, 19.36 g of ultrapure water, benzyltriethylammonium chloride O.Olg, propylene glycol monomethyl ether acetate 7.02 g, and propylene glycol monomethyl ether 14.89 g were added to 20.00 g. And propylene glycol monoethyl ether 90.64g, to prepare a resist underlayer film material. (Example 2) A resist underlayer film material was prepared as in Example 1 except that the polymer solution obtained in Synthesis Example 2 (solid content: 15.00% by mass) was used instead of the polymer obtained in Synthesis Example 1.

S-60-201202855 (Example 3) A resist was prepared as in Example 1 except that the polymer solution obtained in Synthesis Example 3 (solid content: 15.00% by mass) was used instead of the polymer obtained in Synthesis Example 1. Lower film material. (Example 4) The polymer solution obtained in Synthesis Example 1 (solid content: 15.00% by mass) was added to 20.00 g of ruthenium maleate, ruthenium 3 g, ultrapure water of 19.36 g, and triphenyl sulfonium O.Olg. Propylene glycol monomethyl ether acetate 7.02 g, propylene glycol monomethyl ether 14.89 g, and propylene glycol monoethyl ether 90.64 g were used to prepare a resist underlayer film material. (Example 5) The polymer solution obtained in Synthesis Example 1 (solid content: 15.00 mass 〇 / 〇 > 20.00 g was added with 0.03 g of maleic acid, 19.36 g of ultrapure water, and triphenyl sulfonium maleate O .Olg, propylene glycol monomethyl ether acetate 7.02 g, propylene glycol monomethyl ether 14.89 g, and propylene glycol monoethyl ether 90.64 g, and a resist underlayer film material was prepared. (Example 6) Polymer obtained in Synthesis Example 1. Solution (solid content: 15.00 mass/〇) 20.00 g of maleic acid 0.03 g, ultrapure water 19.36 g 'N-(3-^ethoxydecylpropyl)-4,5-dihydroimidazolium 〇1§' Propylene glycol monomethyl-61 - 201202855 base ether acetate 7.02g, propylene glycol monomethyl ether 14.89g, propylene glycol monoethyl ether 90.64g, to prepare a resist underlayer film material (Comparative Example 1) The polymer solution obtained in Synthesis Example 1 (solid content: 15.00% by mass) was used in the same manner as in Example 1 except that the polymer obtained in Synthesis Example 1 was used, and the underlayer film material was prepared. (Comparative Example 2) The polymer solution obtained in Synthesis Example 2 (solid content: 15.00% by mass) was used instead of the polymerization obtained in Synthesis Example 1. The resist underlayer film material was prepared as in Example 1. (Solvent resistance test) The underlayer film forming composition was applied onto a germanium wafer by a spin coating method at 140 ° C. The plate was fired for 1 minute to form a resist underlayer film, and then immersed in propylene glycol monomethyl ether acetate used for the solvent for applying the resist composition for one minute, and the film thickness of the underlayer film before and after the immersion was performed. When the change was 1 nm or less, it was judged as "good", and when the film thickness was changed to 1 nm or more, it was judged as "poor" and indicated by "X". The results are shown in Table 2 » Hereinafter, Example 1 The underlayer film obtained by the composition of the underlayer film forming composition of 6 is shown as the resist underlayer films 1 to 6. The resist underlayer film obtained by forming the composition of the underlayer film of Comparative Examples 1 to 2 is represented as ratio

S -62- 201202855 Comparative example anti-uranium underlayer film 1 to 2. [Table 2] _ Table 2 ____ Example of the underlayer film 1 〇 Example of the underlayer film 2 〇 Example of the underlayer film 3 〇 Example of the underlayer film 4 〇 Example of the underlayer film 5 〇 Example resistance Underlayer film 6 〇 Comparative example underlayer film 1 〇 Comparative example underlayer film 2 〇 (measurement of optical constant) The uranium-underlying film forming composition was applied onto a germanium wafer by a spin coater. The film was heated at 240 ° C for 1 minute on a hot plate to form a resist underlayer film (film thickness: 0·09 μm). Then, using a spectroscopic ellipsometer (manufactured by JA Woollam Co., Ltd., VUV-VASE VU-302), the refractive index (η値) of the underlayer film at a wavelength of 193 nm and the optical absorption coefficient (k値, also referred to as an attenuation coefficient) were measured. ). The results are shown in Table 3. -63-201202855 [Table 3] Table 3 Refractive index η Optical absorption coefficient k (wavelength 193 nm) (wavelength 193 nm) Example resist underlayer film 1 1.61 0.12 Example Resist underlayer film 2 1.68 0.19 Example Resist underlayer film 3 1.68 0.19 Example Resist Underlayer Film 4.60 0.14 Example Resist Underlayer Film 5 1.60 0.14 Example Resist Underlayer Film ό 1.61 0.12 Comparative Example Resist Underlayer Film 1.60 0.14 Comparative Example Underlayer Film 2 1.67 0.19 (Dry Etching) Measurement of Velocity) The following uses the etchant and etching gas system used for the measurement of the dry etching rate. The etchant was etched with CF4 gas using ES401 (trade name, manufactured by SCIENTIFIC, Japan). Further, the etchant was etched with 〇2 gas using RIE-10NR (trade name, manufactured by SAMCO). The resist underlayer films prepared in Examples 1 to 6 and Comparative Examples 1 to 2 were formed using a spin coater. A solution of the composition is applied to the tantalum wafer, respectively. The film was heated at 240 ° C for 1 minute on a hot plate to form a resist underlayer film, and the etching rate was measured using each etching gas. The underlayer film was measured for an etching rate using a CF4 gas as an etching gas at a film thickness of 0.20 μm, and the etching rate was measured using a 02 gas as an etching gas in a film thickness of 0.08 μηι.

In addition, the same use of a spin coater to make a photoresist solution (CHYPRE

S-64-201202855, manufactured by the company, under the trade name UV113), forms a 0.20μηι resist film on the tantalum wafer. The dry etching rate was measured using CF4 gas and 02 gas as etching gases. Next, a comparison of the dry etching rate of the underlayer film and the resist film is performed. The results are shown in Table 4. The speed ratio is the dry etching speed ratio of (resist underlayer film) / (resist film). [Table 4] Table 4 Dry etching speed ratio C F4 gas 〇 2 gas Example Resist underlayer film 1 1.78 0.02 Example Resist underlayer film 2 1.75 0.02 Example Resist underlayer film 3 1.80 0.02 Example Resist underlayer film 4 1.78 0.02 Example Corrosion Underlayer Film 5.79 0.02 Example Resist Underlayer Film 6 1.80 0.02 Comparative Example Resist Underlayer Film 1.65 0.02 Comparative Example Underlayer Film 2 1.68 0.02 (Manufacture of Organic Underlayer Film) In a 200 mL Flask 16.5 g of acenaPhthylene, 1.5 g of 4-hydroxystyrene, and 0 g of solvent were added as a solvent, 2-dichloroethane. After adding 1 g of trifluoroboron as a polymerization initiator, the temperature was raised to 60 ° C and the reaction was carried out for several hours. To the solution, 1 L of methanol and 50 μg of water were added for reprecipitation purification, and the obtained white solid was filtered, and then dried to give a white polymer (1 g). The obtained polymerized product (formula (3-2)) was determined by 13C, 1H.NMR & GPC to determine the molar ratio of the olefinic acid: 4-hydroxystyrene to 86: 14° -65 - 201202855, the weight average molecular weight was 6000, and the weight was The average molecular weight M w / number average molecular weight Μη = 1.5. [Chem. 17]

Add tetramethoxymethylglycol urea to the obtained polymer (formula (3-2)) (manufactured by Mitsui ScienTech Co., Ltd., trade name Powering 1174) l.Og, O.Olg MEGAFAC R-30 (manufactured by Otsuka Ink Chemicals Co., Ltd., trade name) of p-toluenesulfonic acid and ruthenium ruthenium 3g as a surfactant, dissolved in propylene glycol monomethyl ether acetate 101.57g , propylene glycol monomethyl ether 2 5.3 9g. Subsequently, it was filtered using a polyethylene microfilter having a pore size of Ο.ΙΟηηι, and then filtered using a polyethylene microfilter having a pore size of 〇·〇5 μηι to prepare an organic underlayer film for use in a lithography process using a multilayer film. A solution of the composition is formed. (Resist pattern evaluation) The organic underlayer film (ruthenium layer) containing the above polymer (formula (3-2)) was formed on a tantalum wafer and heated on a hot plate at 240 ° C. One minute, an organic underlayer film (layer A) having a film thickness of 250 nm was obtained. The Si-containing underlayer film (layer B) obtained in Examples 1 to 6 and Comparative Examples 1 to 2 was applied thereon, and heated on a hot plate at 240 ° C for 1 minute to obtain a film. A 35 nm thick underlayer film (layer B) containing Si. Using a spin coater, separately coated with a commercially available photoresist solution (Sumitomo Chemical Industry Co., Ltd. -66 -

S 201202855 Manufactured under the trade name PAR855), heated on a hot plate at 10 (TC for 1 minute to form a photoresist film (C layer) with a film thickness of 15 nm. The pattern of the photoresist is immersed in ASML. Exposure machine TWINSCAN XT: 1900Gi scanner (wavelength 193nm, ΝΑ, σ:1·20, 0.94/0.74 (C-quad) liquid immersion liquid: water). The photoresist line width after the target is developed and its line The width is 0·05μηη, which is a so-called line and space (dense line), and is exposed by a mask that is set to form 15 lines. Then, it is baked on a hot plate at 1〇5 °C for 60 seconds. After cooling, it was developed with a 2.3 8% tetramethylammonium hydroxide aqueous solution by an industrial standard 60 second single blade step. [Table 5] Table 5 Resist Shape Evaluation Example Anti-uranium Underlayer Film 1 resist tail shape good example resist underlayer film 2 good example resist underlayer film 3 good (partial side cut) embodiment resist underlayer film 4 good example resist underlayer film 5 good example resist underlayer Membrane 6 good comparative example underlayer film 1 appears in the foot comparative example underlayer film 2 side The footing phenomenon is the tailing phenomenon of the lower part of the pattern in the shape of the resist pattern, and the side cut is a thin phenomenon of the lower part of the pattern in the shape of the resist pattern, and it is not preferable to display the rectangular shape at the same time. The anti-corrosion underlayer obtained by the film-forming composition of the present invention having a phthalic acid or glutamate structure-67-201202855 has a sufficiently high dry etching rate for the photoresist film because it contains a large amount of hetero elements. Compared with Comparative Examples 1 to 2, in Examples 1 to 6, since the etching rate using the fluorine-based gas can be improved, the resist pattern of the upper layer of the anti-hungry film of the present invention can be correctly transferred to the present invention. On the resist underlayer film, the resist underlayer film obtained by forming the composition of the resist underlayer film of Examples 1 to 6, and the resist obtained by forming the composition of the resist underlayer film of Comparative Examples 1 to 2 Since the underlying film has the same etching resistance by oxygen gas, it has a sufficiently high function as a hard mask for processing the underlying film or substrate of the underlayer of the resist underlayer film of the present invention. 8μη! resist pattern In the case of the comparison of Examples 1, 4 to 6 and Comparative Example 1, it is understood that the refractive index η and the optical absorption coefficient k are equivalent enthalpy (the underlayer film having a low optical absorption coefficient k), but at the time of film formation In Examples 1 and 4 to 6 in which the terminal carboxylic acid moiety was not closed, there was an effect of reducing the drag of the photoresist. On the other hand, when Comparative Examples 2 to 3 and Comparative Example 2 were compared, it was found that the refractive index η and the optical absorption coefficient k were It is an equivalent enthalpy (resist underlayer film having a high optical absorption coefficient k), but in Example 3 in which the terminal carboxylic acid is ring-closed at the time of film formation, and the quinone imine structure was formed, Example 3 showed good The lithographic property (adhesion) has the effect of improving the adhesion to the photoresist. The underlayer film forming composition having a lysine or glutamate structure according to the present invention can control the shape of the antibacterial agent depending on whether or not the structure is formed at the time of film formation.

S-68-

Claims (1)

201202855 VII. Application for Patent Park: 1. A composition for forming a lithographic underlayer film, which comprises a hydrolyzable organic sand pot, a hydrolyzate thereof or a hydrolyzed condensate thereof or a mixture thereof as a sand compound The lithography forms a composition using a resist underlayer film comprising a decane compound containing an organic group containing a guanamine bond, a carboxylic acid moiety or a carboxylic acid ester moiety or both thereof in a molecule thereof 0 2 · The composition for forming a lithographic underlayer film for lithography according to the scope of the patent application, wherein the entire decane compound contains a guanamine bond, a residual acid moiety or a carboxylic acid ester moiety or both The proportion of the organic decane compound is less than 5 mol%. 3. The composition for forming a lithographic underlayer film for lithography according to the first aspect of the patent application, wherein the entire decane compound contains an organic amine or a carboxylic acid moiety or a carboxylic acid ester moiety or both. The proportion of the decane compound is from 0.5 to 4.9 mol%. 4. The composition according to any one of claims 1 to 3, wherein the hydrolyzable organodecane is a compound represented by the formula (1), [Chemical Formula 1] [Rl a S i (R2) 3_a]b R3 Formula (1) (β Φ R3 is an organic group containing a guanamine bond, a carboxylic acid moiety or a carboxylate moiety or both) and represents a group bonded to a ruthenium atom by a Si_c bond, and R1 represents a fen-based group An aryl group, a halogenated alkyl 'halogenated aryl group, an alkenyl group, or an epoxy group, an acrylonitrile group, a methacryl fluorenyl 'fluorenyl group or an organic group of a cyano group, and bonded to a ruthenium atom by a Si-C bond The group represents an alkoxy group, a decyloxy group or a halogen-69-201202855 atom, a represents an integer of 0 or 1, and b represents an integer of 1 or 2. 5. The composition according to any one of claims 1 to 4, which comprises at least one selected from the group consisting of an organic phosphonium compound represented by the formula (2) and an organic phosphonium compound represented by the formula (3). a combination with the hydrolyzable organodecane represented by the above formula (1), the hydrolyzate or the hydrolysis condensate; [Chem. 2] R aSi(R )4-a (2) (wherein R4 Is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an epoxy group, a propylene group, a methacryl fluorenyl group, a fluorenyl group, an alkoxy aryl group, a decyloxy group, or An organic group of a cyano group, and a group in which a Si-C bond is bonded to a ruthenium atom, R5 represents an alkoxy group, a decyloxy group or a halogen atom, and a represents an integer of 〇 to 3), [Chemical 3] [R6 cSi ( R7)3-c]2Yb Formula (3) wherein R6 represents an alkyl group, R7 represents an alkoxy group, a decyloxy group or a halogen atom, Y represents an alkylene group or an extended aryl group, and b represents an integer of 0 or 1. c represents 〇 or an integer of 1). 6. The composition according to any one of claims 1 to 5, which comprises the hydrolyzed condensate of the hydrolyzable organodecane represented by the above formula (1) or the hydrolyzable organic compound represented by the above formula (1) A hydrolyzed condensate of decane and a compound represented by the formula (2) is used as a polymer. 7. If the composition of any one of the scopes 6-1 to 6 is applied, it is contained in S-70-201202855 and contains acid as a hydrolysis catalyst. 8. The composition of any one of the items 1 to 7 of the patent application, which further contains water. A resist underlayer film which is obtained by applying a resist underlayer film forming composition according to any one of claims 1 to 8 to a semiconductor substrate and firing it. 10. A method of manufacturing a semiconductor device, comprising the steps of: coating a resist underlayer film forming composition according to any one of claims 1 to 8 on a semiconductor substrate, and firing to form an anti- a step of etching the underlayer film; a step of forming a resist composition on the underlayer film to form a resist film; a step of exposing the resist film; and developing the resist film after exposure to obtain a pattern a step of etching a resist film; a step of etching the underlayer film by using the patterned resist film; and a step of processing the semiconductor substrate by using the patterned resist film and the underlayer film. A method of manufacturing a semiconductor device, comprising the steps of: forming an organic underlayer film on a semiconductor substrate; and coating thereon a resist underlayer film formed according to any one of claims 1 to 8. a step of forming a resist underlayer film by firing; forming a resist film on the resist underlayer film to form a resist film; and exposing the resist film to a step of exposing a step of obtaining a patterned resist film by using a resist film: a step of etching a resist underlayer film by using the patterned resist film; and a step of etching the organic underlayer film by using a patterned resist underlayer film And a step of processing the semiconductor substrate by using the patterned organic underlayer film. -71 - 201202855 IV. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the symbol of the representative figure is simple: 201202855 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. : -4-, S.