Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
  • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
  • H10P50/282—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials
  • H10P50/283—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of inorganic materials by chemical means
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P50/00—Etching of wafers, substrates or parts of devices
  • H10P50/73—Etching of wafers, substrates or parts of devices using masks for insulating materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
  • H10P76/2042—Photolithographic processes using lasers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
  • H10P76/2043—Photolithographic processes using an anti-reflective coating
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/40—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials
  • H10P76/405—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their composition, e.g. multilayer masks

Definitions

• the present invention relates to a composition for forming a resist underlayer film, and can form a pattern with low roughness in fine patterning, and for a semiconductor substrate, a coating type organic underlayer film required in a patterning process, or a CVD film containing carbon as a main component.
• a composition for forming a silicon-containing resist underlayer film which can be easily peeled off with a peeling liquid that does not cause damage and can form a silicon-containing film capable of maintaining peelability even after dry etching.
• microfabrication by lithography using a photoresist has been performed.
• the above microfabrication is obtained by forming a photoresist thin film on a semiconductor substrate such as a silicon wafer, irradiating it with active light such as ultraviolet rays through a mask pattern on which a pattern of a semiconductor device is drawn, and developing it.
• This is a processing method for forming fine irregularities corresponding to the above pattern on the surface of the substrate by etching the substrate using the photoresist pattern as a protective film.
• a film known as a hard mask containing a metal element such as silicon or titanium is used as the underlayer film between the semiconductor substrate and the photoresist.
• the rate of removal by the dry etching of the resist and the hard mask largely depends on the gas type used for the dry etching. Then, by appropriately selecting the gas type, the hard mask can be removed by dry etching without significantly reducing the film thickness of the photoresist.
• a resist underlayer film has been arranged between a semiconductor substrate and a photoresist in order to achieve various effects including an antireflection effect.
• composition for the resist underlayer film has been studied so far, the development of a new material for the resist underlayer film is desired because of the variety of required properties.
• a coating-type BPSG (boron phosphorus glass) film-forming composition (Patent Document 1) containing a structure having a specific silicic acid as a skeleton, and a mask residue after lithography, for which a film formation capable of wet etching is an issue.
• Patent Document 2 A composition for forming a silicon-containing resist underlayer film containing a carbonyl structure, which has an object of removing a chemical solution, is disclosed.
• multi-layer processes are often used due to miniaturization of implant layers.
• transfer to the lower layer is performed by the above-mentioned dry etching, and finally substrate processing and substrate processing.
• Subsequent removal of the mask residue, for example, the resist film and the underlayer film including the resist underlayer film may also be performed by dry etching or ashing treatment.
• dry etching and ashing treatment do not cause little damage to the substrate, and improvement thereof is required.
• the present invention has been made in view of the above circumstances, and in the processing process of a semiconductor substrate or the like, not only the conventional dry etching method but also dilute phosphoric acid, buffered phosphoric acid, and alkaline chemical solution (basic chemical solution) are used.
• dilute phosphoric acid, buffered phosphoric acid, and alkaline chemical solution basic chemical solution
• alkaline chemical solution basic chemical solution
• the present inventors obtained from a composition containing a hydrolyzable condensate (polysiloxane) obtained from a hydrolyzable silane having a specific structure such as a succinic anhydride skeleton.
• the film to be obtained can be easily removed with a chemical solution such as an alkaline solution, and by controlling the structure derived from alkyltrialkoxysilane in the hydrolyzed condensate, the residue removability of the film by dry etching is enhanced.
• a chemical solution such as an alkaline solution
• the present invention is a composition for forming a resist underlayer film containing a hydrolyzable condensate of a hydrolyzable silane mixture containing a hydrolyzable silane represented by the formula (1) and an alkyltrialkoxysilane.
• the content of alkyltrialkoxysilane in the hydrolyzable silane mixture is 0 mol% or more and less than 40 mol% based on the total number of moles of total hydrolyzable silane contained in the hydrolyzable silane mixture.
• the present invention relates to a composition for forming an underlayer film.
• R 1 is a group bonded to a silicon atom and is at least one group selected from the group consisting of a succinic anhydride skeleton, an alkenyl group, an aryl group and a group represented by the following formula (1-2). Or represents an organic group containing a skeleton [In equation (1-2), X 101 represents any of the groups represented by the following formulas (1-3) to (1-5), and the carbon atom of the ketone group in the following formulas (1-4) and (1-5). Is bonded to the nitrogen atom to which R 102 in equation (1-2) is bonded.
• R 103 to R 107 are independent of each other, a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or Represents an organic group containing an epoxy group or a sulfonyl group),
• R 101 represents, independently of each other, a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy or sulfonyl group.
• R 2 is a group bonded to the silicon atoms, independently of one another, an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, or an optionally substituted alkoxyalkyl group
• R 3 is a group or atom bonded to a silicon atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom.
• R 1 is a group bonded to a silicon atom, and at least one group or skeleton selected from the group consisting of a succinic anhydride skeleton, a vinyl group, a phenyl group and an isocyanuric acid skeleton.
• the present invention relates to the composition for forming a resist underlayer film according to the first aspect, which represents an organic group containing an organic group.
• R 4 is a group bonded to a silicon atom, and independently of each other, an alkyl group which may be substituted, an alkyl halide group which may be substituted, or an alkoxyalkyl group which may be substituted.
• R 5 is a group or atom bonded to a silicon atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• c represents an integer of 0 to 3.
• the content of the compound represented by the above formula (1) in the hydrolyzable silane mixture is 5 based on the total number of moles of the total hydrolyzable silane contained in the hydrolyzable silane mixture.
• a compound represented by the formula (1) includes compounds wherein R 1 is an organic group containing a succinic anhydride skeleton, a resist underlayer film forming composition according to the fourth aspect.
• the content of the compound represented by the formula (1) in which R 1 represents an organic group containing a succinic anhydride skeleton in the hydrolyzable silane mixture is contained in the hydrolyzable silane mixture.
• the composition for forming a underlayer film of a resist according to the fifth aspect which is 1 mol% or more based on the total number of moles of the total hydrolyzable silane.
• a seventh aspect is the composition for forming a resist underlayer film according to any one of the first to fifth aspects, which is a composition having a pH of 2 to 5.
• a step of forming an organic underlayer film on a semiconductor substrate A step of applying the resist underlayer film forming composition according to any one of the first to seventh aspects on the organic underlayer film and firing the composition to form a silicon-containing resist underlayer film.
• a step of applying a resist film forming composition on the silicon-containing resist underlayer film to form a resist film The process of exposing and developing the resist film to obtain a resist pattern, A process of etching the silicon-containing resist underlayer film using a resist pattern as a mask.
• a step of etching the organic underlayer film using the patterned silicon-containing resist underlayer film as a mask is included. Regarding the pattern formation method.
• the ninth aspect is the pattern forming method according to the eighth aspect, further comprising a step of removing the silicon-containing resist underlayer film by a wet method using a chemical solution after the step of etching the organic underlayer film.
• a tenth aspect relates to the pattern forming method according to the ninth aspect, wherein the drug solution is a basic drug solution.
• water obtained by using a succinic anhydride skeleton as a hydrolyzable silane, an alkenyl group such as a vinyl group, an aryl group such as a phenyl group, or a silane compound having a specific structure containing an isocyanuric acid skeleton is used.
• the decomposition condensate as one component of the composition for forming the underlayer film of the resist, even if it is a silicon-based film, the removability by the wet method can be improved in the film formed from the composition.
• the removability by the wet method can be further enhanced. Therefore, when pattern formation using a photoresist film or the like or processing of a semiconductor substrate or the like is performed using the resist underlayer film forming composition of the present invention, removal of mask residue after processing, for example, a resist film or resist When removing the lower layer film including the lower layer film, it is possible to easily remove the lower layer film with a chemical solution, and it is possible to manufacture a semiconductor device with less damage to the substrate.
• the residue is removed by etching. It can enhance the sex.
• the pH of the composition for forming the underlayer film of the resist is adjusted, for example, nitric acid is used as a hydrolysis catalyst in the production of the hydrolysis condensate, so that the pH of the composition is within a specific range.
• the present invention targets a composition that forms a silicon-containing resist underlayer film that can be peeled off by a wet method, and is a product obtained by hydrolyzing and condensing a hydrolyzable silane mixture containing a hydrolyzable silane having a specific structure (hydration). It is characterized by containing a decomposition condensate).
• the composition for forming a resist underlayer film of the present invention contains a hydrolyzed condensate of a hydrolyzable silane mixture.
• the hydrolyzed condensate includes not only a polyorganosiloxane polymer which is a condensate whose condensation is completely completed, but also a polyorganosiloxane polymer which is a partially hydrolyzed condensate whose condensation is not completely completed. Included.
• Such a partially hydrolyzed condensate is also a polymer obtained by hydrolyzing and condensing a hydrolyzable silane compound, like the condensate in which the condensation is completely completed, but it partially stops at hydrolysis and condenses. Therefore, the Si—OH group remains.
• an uncondensed hydrolyzate completely hydrolyzed product, partially hydrolyzed product
• a monomer hydrolyzable silane compound
• the hydrolyzable silane mixture contains a hydrolyzable silane represented by the following formula (1), and if desired, other hydrolyzable substances such as tetraalkoxysilane and alkyltrialkoxysilane. It can contain silane. However, when alkyltrialkoxysilane is contained as the other silane compound, its content is less than 40 mol% based on the total number of moles (100 mol%) of the silane compound in the hydrolyzable silane mixture. That is, the proportion of alkyltrialkoxysilane in the mixture is 0 mol% or more and less than 40 mol%. The finding that the removal rate of the etching residue can be controlled by controlling the ratio of the alkyltrialkoxysilane was first discovered by the present inventors.
• the hydrolyzed condensate used in the composition for forming a resist underlayer film of the present invention can be a product of hydrolyzed condensation of a hydrolyzable silane mixture containing a silane compound represented by the following formula (1). ..
• R 1 is a group bonded to a silicon atom and is at least one selected from the group consisting of a succinic anhydride skeleton, an alkenyl group, an aryl group and a group represented by the formula (1-2) described later. Represents an organic group containing a group or skeleton.
• the organic group of R 1 is not particularly limited as long as it is an organic group containing the above skeleton or group.
• R 1 may be a group containing a plurality of types and / or a plurality of alkenyl groups, an aryl group, and a group represented by the formula (1-2), in which case the group or skeleton may be a group. It may be substituted with the above group or skeleton of the same species or another species.
• the group containing the succinic acid anhydride skeleton the alkenyl group, the aryl group and the group represented by the formula (1-2), the alkoxy group directly bonded to the silicon atom, the aralkyloxy group and the hydrogen atom in the acyloxy group are described above.
• Onium salt structures eg, formulas (I-1) to (I-50), formulas (II-1) to formulas (II-) listed in a group substituted with a group or a skeleton, a compound containing an onium salt described later, and the like. 30
• formulas (III-1) to see compounds listed as formulas (III-28), etc.
• groups containing an aryl group as a group containing a sulfone group or a sulfonamide group described later formula (B-1) to formulas).
• (B-36), etc.) are excluded.
• the succinic acid anhydride skeleton, the alkenyl group, the aryl group and the group represented by the formula (1-2) include not only the skeleton itself or the group itself, but also one or more hydrogen atoms in the alkyl group in particular.
• examples thereof include an organic group substituted with at least one selected from the group consisting of an acid anhydride skeleton, an alkenyl group, an aryl group and a group represented by the formula (1-2).
• the alkyl group in which the hydrogen atom is substituted by the succinic anhydride skeleton or the like is not particularly limited, and may be linear, branched chain, or cyclic, and the number of carbon atoms thereof is usually 40.
• linear or branched alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl.
• n-pentyl group 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl -N-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3- Methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2 , 2-Dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-n-
• cyclic alkyl group examples include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group and 2-methyl-cyclobutyl group.
• 3-Methyl-cyclobutyl group 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl -Cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1, 3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclo Propyl group, 2-n-propyl-cyclopropyl group
• examples of the alkenyl group in R 1 include alkenyl groups which may be substituted, and examples thereof include alkenyl groups having 2 to 10 carbon atoms. More specifically, ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl -1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3- Penthenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2- Propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-but
• Examples of the aryl group in R 1 include an aryl group which may be substituted, and examples thereof include an aryl group having 6 to 20 carbon atoms. More specifically, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorphenyl group, a p-chlorphenyl group, an o-fluorophenyl group.
• P-mercaptophenyl group o-methoxyphenyl group, p-methoxyphenyl group, p-aminophenyl group, p-cyanophenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group, o-biphenylyl group, m-biphenylyl group , P-Biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenylyl group, 2-phenylyl group, 3-phenylyl group, 4-phenanthryl group, 9-phenylyl group and the like.
• Examples of the group containing the aryl group include an optionally substituted aralkyl group, an optionally substituted aryl halide group, an optionally substituted halogenated aralkyl group, and an optionally substituted alkoxyaryl. Examples thereof include a group, an alkoxyalkyl key which may be substituted, and the like.
• the aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such an aryl group and an alkyl group include the same as those described above.
• the number of carbon atoms of the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• Specific examples of the aralkyl group include, for example, a phenylmethyl group (benzyl group), a 2-phenylethylene group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n-pentyl group, and the like.
• 6-Phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, 10-phenyl-n-decyl group and the like can be mentioned. However, it is not limited to these.
• the above-mentioned aryl group is an aryl group substituted with a halogen atom, and specific examples of such an aryl group include the same as those described above.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
• the number of carbon atoms of the aryl halide group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• aryl halide group examples include 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, and 2,5-difluorophenyl.
• the halogenated aralkyl group is an aralkyl group substituted with a halogen atom, and specific examples of such an aralkyl group and the halogen atom include the same as those described above.
• the number of carbon atoms of the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• Specific examples of the halogenated aralkyl group include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, and 2,5-difluorobenzyl group.
• alkoxyaryl group is an aryl group substituted with an alkoxy group, and specific examples of such an aryl group include the same as those described above.
• alkoxy group examples include an alkoxy group having a linear, branched, and cyclic alkyl moiety having 1 to 20 carbon atoms.
• linear or branched alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and an n-.
• Pentyroxy group 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy Group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyroxy group, 2-methyl-n-pentyroxy group, 3-methyl-n -Pentyroxy group, 4-methyl-n-pentyroxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2- Dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1 , 2-trimethyl-n-propoxy group,
• Examples of the cyclic alkoxy group include a cyclopropoxy group, a cyclobutoxy group, a 1-methyl-cyclopropoxy group, a 2-methyl-cyclopropoxy group, a cyclopentyroxy group, a 1-methyl-cyclobutoxy group, and a 2-methyl-.
• the number of carbon atoms of the alkoxyaryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• Specific examples of the alkoxyaryl group include, for example, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2- (1-ethoxy) phenyl group, 3- (1-ethoxy) phenyl group, and 4 -(1-ethoxy) phenyl group, 2- (2-ethoxy) phenyl group, 3- (2-ethoxy) phenyl group, 4- (2-ethoxy) phenyl group, 2-methoxynaphthalen-1-yl group, 3 -Methoxynaphthalen-1-yl group, 4-methoxynaphthalen-1-yl group, 5-methoxynaphthalen-1-yl group, 6-methoxynaphthalen-1-yl group, 7-methoxynaphthalen-1-y
• the alkoxyaralkyl group is an aralkyl group substituted with an alkoxy group, and specific examples of such an alkoxy group and an aralkyl group include the same as those described above.
• the number of carbon atoms of the alkoxyaralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• Specific examples of the alkoxyaralkyl group include, but are not limited to, a 3- (methoxyphenyl) benzyl group, a 4- (methoxyphenyl) benzyl group and the like.
• X 101 independently represents any of the following formulas (1-3) to (1-5), and the ketone groups in the following formulas (1-4) and (1-5).
• the carbon atom is bonded to the nitrogen atom to which R 102 in the formula (1-2) is bonded.
• R 103 to R 107 are independent of each other, a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an epoxy.
• examples thereof include the alkyl group mentioned as the alkyl group in which the hydrogen atom is substituted by the above, and the same alkenyl group as described above.
• examples of the organic group containing an epoxy group include, but are not limited to, a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, an epoxycyclohexyl group and the like.
• examples of the organic group containing a sulfonyl group include, but are not limited to, a sulfonylalkyl group and a sulfonylaryl group.
• R 101 independently contains a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group containing an epoxy group or a sulfonyl group.
• an alkyl group which may be substituted an alkenyl group which may be substituted, an epoxy group or an organic group containing an epoxy group, a suitable number of carbon atoms and the like are described above with respect to R 103 to R 107. The same thing can be mentioned.
• an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group is preferable, and specific examples thereof include an allyl group, a 2-vinylethyl group, and a 3-vinylpropyl group. 4-Vinylbutyl group and the like can be mentioned.
• the alkylene group is a divalent group derived by further removing one hydrogen atom of the alkyl group, and may be linear, branched or cyclic, and as a specific example of such an alkylene group. Can be the same as those described above.
• the number of carbon atoms of the alkylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 10 or less.
• the alkylene group of R 102 may have one or more selected from a sulfide bond, an ether bond and an ester bond at the end or in the middle, preferably in the middle.
• alkylene group examples include linear chains such as methylene group, ethylene group, trimethylene group, methylethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group and decamethylene group.
• Alkylene group 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1 , 2-Dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group and other branched chain alkylene groups, 1,2-cyclopropipandyl group, 1,2-cyclobutandyl, 1, Cyclic alkylene groups such as 3-cyclobutitanium diyl group, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, etc., -CH 2 OCH 2- , -CH 2 CH 2 OCH 2- , -CH 2 CH 2 OCH 2 CH 2- , -CH 2 CH 2 OCH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2- , -
• the hydroxyalkylene group has at least one hydrogen atom of the alkylene group replaced with a hydroxy group, and specific examples thereof include a hydroxymethylene group, a 1-hydroxyethylene group, a 2-hydroxyethylene group, and 1,2. -Dihydroxyethylene group, 1-hydroxytrimethylene group, 2-hydroxytrimethylene group, 3-hydroxytrimethylene group, 1-hydroxytetramethylene group, 2-hydroxytetramethylene group, 3-hydroxytetramethylene group, 4-hydroxy Tetramethylene group, 1,2-dihydroxytetramethylene group, 1,3-dihydroxytetramethylene group, 1,4-dihydroxytetramethylene group, 2,3-dihydroxytetramethylene group, 2,4-dihydroxytetramethylene group, 4 , 4-Dihydroxytetramethylene group and the like, but are not limited thereto.
• R 1 represents a succinic anhydride skeleton, a vinyl group, a phenyl group, and an isocyanuric acid skeleton (in the formula (1-2),
• X 101 represents a group represented by the formula (1-5). It is preferable that the group contains at least one selected from the group consisting of).
• R 2 is a group bonded to a silicon atom, which is an alkyl group which may be substituted, an alkyl group which may be substituted, or an alkyl group which may be substituted independently of each other. Also represents an alkoxyalkyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof.
• the CH 2 CH-structure contained in the acryloyl group is distinguished from the vinyl group in the definition of R 1.
• alkyl group examples include linear or branched alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and i-.
• Cyclic alkyl groups can also be used.
• cyclic alkyl groups having 3 to 10 carbon atoms cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1 -Methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2- Ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group , 1,2-dimethyl-cyclobutyl group, 1,
• the alkyl halide group refers to an alkyl group substituted with a halogen atom.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and specific examples of the alkyl group include the same as those described above.
• the number of carbon atoms of the alkyl halide group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 10 or less.
• alkyl halide group examples include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, and 2,2.
• 2-Trifluoroethyl group 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3-bromopropyl group, 2,2 , 3,3-Tetrafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 1,1,1,3,3,3-hexafluoropropane-2-yl group, 3- Examples thereof include, but are not limited to, a bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group.
• the alkoxyalkyl group refers to an alkyl group substituted with an alkoxy group. Specific examples of such an alkyl group and an alkoxy group include the same as those described above.
• the number of carbon atoms of the alkoxyalkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, still more preferably 10 or less.
• Specific examples of the alkoxyalkyl group include, but are not limited to, lower alkyloxy lower alkyl groups such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group and ethoxymethyl group. ..
• Examples of the substituent in the alkyl group, alkyl halide group, or alkoxyalkyl group include an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkoxyalkyl group, and an aryl group.
• Examples thereof include an oxy group, an alkoxyaryl group, an alkoxyaralkyl group, an alkenyl group, an alkoxy group, and an aralkyloxy group, among which an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, and a halogenated group.
• the aralkyl group, the alkoxyalkyl group, the alkoxyaryl group, the alkoxyaralkyl group, the alkenyl group, the alkoxy group, and the aralkyloxy group and the suitable number of carbon atoms thereof include the same as those described above.
• the aryloxy group mentioned in the above-mentioned substituent is a group to which the aryl group is bonded via an oxygen atom (—O—), and specific examples of such an aryl group include the same as those described above. ..
• the number of carbon atoms of the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and specific examples thereof include a phenoxy group and naphthalene. 2-Iloxy group and the like can be mentioned, but the present invention is not limited thereto. Further, when two or more substituents are present, the substituents may be bonded to each other to form a ring.
• Examples of the organic group containing the epoxy group include, but are not limited to, the above-mentioned glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group, epoxycyclohexyl group and the like.
• Examples of the organic group containing the acryloyl group include, but are not limited to, an acryloyl methyl group, an acryloyl ethyl group, and an acryloyl propyl group.
• Examples of the organic group containing a methacryloyl group include, but are not limited to, a methacryloylmethyl group, a methacryloylethyl group, a methacryloylpropyl group, and the like.
• Examples of the organic group containing the mercapto group include, but are not limited to, an ethyl mercapto group, a butyl mercapto group, a hexyl mercapto group, and an octyl mercapto group.
• Examples of the organic group containing an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group and the like.
• Examples of the organic group containing an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group. However, groups in which the alkoxy group is directly bonded to the silicon atom are excluded.
• Examples of the organic group containing a sulfonyl group include, but are not limited to, the above-mentioned sulfonylalkyl group and sulfonylaryl group.
• Examples of the organic group containing a cyano group include, but are not limited to, a cyanoethyl group and a cyanopropyl group.
• R 3 is a group or atom bonded to a silicon atom and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group or a halogen atom.
• alkoxy group and the halogen atom include the same as those described above.
• the aralkyloxy group is a group derived by removing a hydrogen atom from the hydroxy group of the aralkyl alcohol, and specific examples of such an aralkyl group include the same as those described above.
• the number of carbon atoms of the aralkyloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.
• Specific examples of the aralkyloxy group include a phenylmethyloxy group (benzyloxy group), a 2-phenylethyleneoxy group, a 3-phenyl-n-propyloxy group, a 4-phenyl-n-butyloxy group, and a 5-phenyl-n.
• the acyloxy group is a group derived by removing a hydrogen atom from the carboxylic acid group of a carboxylic acid compound, and typically removes a hydrogen atom from the carboxylic acid group of an alkylcarboxylic acid, an arylcarboxylic acid or an aralkylcarboxylic acid.
• Derived alkylcarbonyloxy groups, arylcarbonyloxy groups or aralkylcarbonyloxy groups are examples, but are not limited to these.
• Specific examples of the alkyl group, aryl group and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid and aralkylcarboxylic acid include the same as those described above.
• acyloxy group examples include an acyloxy group having 2 to 20 carbon atoms.
• a represents 1
• b represents an integer of 0 to 2
• 4- (a + b) represents an integer of 1 to 3.
• b preferably represents 0 or 1, and more preferably 0.
• the compound represented by the above formula (1) include: [(3-trimethoxysilyl) propyl] succinic acid anhydride, [(3-triethoxysilyl) propyl] succinic acid anhydride, [( Silane compounds containing a succinate anhydride skeleton such as 3-trimethoxysilyl) ethyl] succinic acid anhydride, [(3-trimethoxysilyl) butyl] succinic acid anhydride; vinyl trimethoxysilane, vinyl triethoxysilane, vinyl Trichlorosilane, vinyl triacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylace
• the silane compound in which R 1 in the formula is an organic group containing a group represented by the above formula (1-2) is a commercially available product. It may be used, and it can also be synthesized by a known method described in International Publication No. 2011/102470 and the like.
• specific examples of the silane compound containing an organic group containing a group represented by the above formula (1-2) include compounds represented by the formulas (1-2-1) to (1-2-29). However, it is not limited to these.
• examples of the silane compound represented by the above formula (1) include aryl group-containing silane compounds represented by the formulas (A-1) to (A-41).
• silane compounds hydrolyzable silane
• the silane compound represented by the above formula (1) and the silane compound represented by the following formula (2) are used.
• at least one selected from the silane compounds represented by the following formula (3) (other hydrolyzable silanes) can be used.
• the silane compound represented by the formula (2) is preferable.
• R 4 is a group bonded to the silicon atoms, independently of one another, an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, or a substituted Also represents an alkoxyalkyl group, or an organic group containing an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, an amide group, an alkoxy group, a sulfonyl group, or a cyano group, or a combination thereof.
• R 5 is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• c represents an integer of 0 to 3.
• each group in R 4 and suitable number of carbon atoms thereof may be mentioned groups and number of carbon atoms mentioned above for R 2.
• Specific examples of each group in R 5 and a suitable number of carbon atoms thereof include the above-mentioned groups and atoms and the number of carbon atoms in R 3.
• c preferably represents 0 or 1, and more preferably 0.
• R 6 is a group bonded to a silicon atom, which is an alkyl group which may be substituted, an aryl group which may be substituted, and an aralkyl group which may be substituted independently of each other.
• R 7 is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• Y is a group bonded to a silicon atom and represents an alkylene group or an arylene group independently of each other. Then, d represents an integer of 0 or 1, and e represents an integer of 0 or 1.
• each group in R 6 and a suitable number of carbon atoms thereof include the above-mentioned groups and the number of carbon atoms in R 2.
• Specific examples of each group in R 7 and a suitable number of carbon atoms thereof include the above-mentioned groups and atoms and the number of carbon atoms in R 3.
• Specific examples of the alkylene group in Y include linear chains such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group and decamethylene group.
• Alkane group 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1 , 2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-ethyltrimethylene group and other branched chain alkylene groups and other alkylene groups, methanetriyl groups, ethane-1,1,2-triyl groups, ethane -1,2,2-triyl group, ethane-2,2,2-triyl group, propane-1,1,1-triyl group, propane-1,1,2-triyl group, propane-1,2,3 -Triyl group, propane-1,2,2-triyl group, propane-1,1,3-triyl group, butane-1,1,1-triyl group, butane-1,1,2-triyl group, butane- 1,1,3-triyl group, butane-1,2,3-triy
• allylene group examples include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group; 1,5-naphthalenedyl group, 1,8-naphthalenedyl group, 2,6-.
• hydrolyzable silane represented by the formula (2) examples include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetran-propoxysilane, tetrai-propoxysilane, and tetran-butoxysilane.
• Methyltrimethoxysilane Methyltrichlorosilane, Methyltriacetoxysilane, Methyltriethoxysilane, Methyltripropoxysilane, Methyltributoxysilane, Methyltriamiloxysilane, Methyltribenzyloxysilane, Methyltriphenyloxysilane, Glyside Xymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyl Triethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycid
• silane compound represented by the formula (3) examples include methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, and butylene.
• the hydrolyzable silane mixture may contain a silane compound (hydrolyzable organosilane) having an onium group in the molecule.
• a silane compound (hydrolyzable organosilane) having an onium group in the molecule By using a silane compound (hydrolyzable organosilane) having an onium group in the molecule, the cross-linking reaction of the hydrolyzable silane can be effectively and efficiently promoted.
• hydrolyzable organosilane having such an onium group in the molecule (hydrolyzable organosilane) is represented by the formula (4).
• R 11 is a group bonded to a silicon atom and represents an onium group or an organic group containing the onium group.
• R 12 is a group bonded to a silicon atom, which is independent of each other, an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, and an substituted aralkyl group.
• R 13 is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.
• f represents 1 or 2
• g represents 0 or 1
• 1 ⁇ f + g ⁇ 2 is satisfied.
• alkyl group aryl group, aralkyl group, alkyl halide group, aryl halide group, aralkyl group halide, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, alkenyl group, and epoxy group, acryloyl group, methacryloyl group.
• the onium group examples include a cyclic ammonium group or a chain ammonium group, and a tertiary ammonium group or a quaternary ammonium group is preferable. That is, suitable specific examples of the onium group or the organic group containing the same include a cyclic ammonium group, a chain ammonium group, or an organic group containing at least one of these, and a tertiary ammonium group or a quaternary ammonium group. Alternatively, an organic group containing at least one of these is preferable.
• the onium group is a cyclic ammonium group
• the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring.
• R 11 is a group bonded to the silicon atom is a hetero-aromatic cyclic ammonium group represented by the following formula (S1).
• a 1 , A 2 , A 3 and A 4 represent groups represented by any of the following formulas (J1) to (J3) independently of each other, and A 1 to A 4 At least one of them is a group represented by the following formula (J2).
• the constituent rings exhibit aromaticity, and each of A 1 to A 4 and adjacent to each of them are adjacent to each other. It is determined whether the bond between the atoms forming the ring together is a single bond or a double bond.
• R 10 are independent of each other, single bond, hydrogen atom, alkyl group, aryl group, aralkyl group, alkyl halide group, aryl halide group, aralkyl group halide or alkenyl.
• alkyl groups, aryl groups, aralkyl groups, alkyl halide groups, aryl halide groups, halogenated aralkyl groups and alkenyl groups and suitable carbon atoms thereof include the same as those described above. Be done.
• R 14 is When two or more are present, the two R 14s may be bonded to each other to form a ring, and the ring formed by the two R 14s may have a crosslinked ring structure. In such a case, the ring may be formed.
• the cyclic ammonium group will have an adamantan ring, a norbornene ring, a spiro ring and the like.
• alkyl group an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, a halogenated aralkyl group and an alkenyl group, and suitable carbon atoms thereof include the same as described above. ..
• n 1 is an integer from 1 to 8
• m 1 is 0 or 1
• m 2 is a positive number from 0 or 1 to the maximum number that can be replaced with a monocyclic or polycyclic ring. Is an integer of.
• a (4 + n 1 ) member ring including A 1 to A 4 is formed. That is, a 5-membered ring when n 1 is 1, a 6-membered ring when n 1 is 2, a 7-membered ring when n 1 is 3, and an 8-membered ring when n 1 is 4.
• m 1 1, a condensed ring is formed in which a (4 + n 1 ) member ring containing A 1 to A 3 and a 6-member ring containing A 4 are condensed.
• a 1 to A 4 may have a hydrogen atom on the atom constituting the ring or may not have a hydrogen atom, depending on which of the formulas (J1) to (J3), but A 1 When ⁇ A 4 has a hydrogen atom on the atom constituting the ring, the hydrogen atom may be replaced with R 14. Further , R 14 may be substituted with a ring-constituting atom other than the ring-constituting atom in A 1 to A 4. Under these circumstances, as described above, m 2 is selected from 0 or 1 to the maximum number that can be replaced with a monocyclic or polycyclic integer.
• the bond of the heteroaromatic cyclic ammonium group represented by the above formula (S1) is present at any carbon atom or nitrogen atom existing in such a monocyclic or fused ring, and is directly bonded to a silicon atom.
• a linking group is bonded to form an organic group containing cyclic ammonium, which is bonded to a silicon atom. Examples of such a linking group include, but are not limited to, an alkylene group, an arylene group, an alkaneylene group and the like. Specific examples of the alkylene group and the arylene group and the suitable number of carbon atoms thereof include the same as those described above.
• the alkenylene group is a divalent group derived by further removing one hydrogen atom of the alkenyl group, and specific examples of such an alkenyl group include the same as those described above.
• the number of carbon atoms of the alkenylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples thereof include, but are not limited to, vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, 2-pentenylene group and the like.
• silane compound (hydrolyzable organosilane) represented by the formula (4) having a heteroaromatic cyclic ammonium group represented by the above formula (S1) are the following formulas (I-1) to (I). Examples thereof include, but are not limited to, silane represented by -50).
• R 11 which is a group bonded to a silicon atom in the above formula (4) can be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).
• a 5 , A 6 , A 7 and A 8 represent groups represented by any of the following formulas (J4) to (J6) independently of each other, and A 5 to A 8 At least one of them is a group represented by the following formula (J5).
• R 10 are independent of each other, single bond, hydrogen atom, alkyl group, aryl group, aralkyl group, alkyl halide group, aryl halide group, aralkyl group halide or alkenyl.
• the specific examples of the alkyl group, the aryl group, the aralkyl group, the alkyl halide group, the aryl halide group, the halogenated aralkyl group and the alkenyl group and their suitable carbon atoms are the same as those described above. Can be mentioned.
• R 15 independently of one another, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, halogenated aryl group, a halogenated aralkyl group, an alkenyl group or a hydroxy group
• R 15 is When two or more are present, the two R 15s may be bonded to each other to form a ring, and the ring formed by the two R 15s may have a crosslinked ring structure. In such a case, the ring may be formed.
• the cyclic ammonium group will have an adamantan ring, a norbornene ring, a spiro ring and the like.
• alkyl group aryl group, aralkyl group, alkyl halide group, aryl halide group, halogenated aralkyl group and alkenyl group and suitable carbon atoms thereof
• alkyl group aryl group, aralkyl group, alkyl halide group, aryl halide group, halogenated aralkyl group and alkenyl group and suitable carbon atoms thereof.
• n 2 is an integer from 1 to 8
• m 3 is 0 or 1
• m 4 is a positive number from 0 or 1 to the maximum number that can be replaced with a monocyclic or polycyclic ring. Is an integer of.
• m 3 is 0, a (4 + n 2 ) member ring including A 5 to A 8 is formed. That is, a 5-membered ring when n 2 is 1, a 6-membered ring when n 2 is 2, a 7-membered ring when n 2 is 3, and an 8-membered ring when n 2 is 4.
• a condensed ring is formed by condensing a (4 + n 2 ) member ring containing A 5 to A 7 and a 6-member ring containing A 8.
• a 5 to A 8 may have a hydrogen atom on the atom constituting the ring or may not have a hydrogen atom, depending on which of the formulas (J4) to (J6), but A 5 When ⁇ A 8 has a hydrogen atom on the atom constituting the ring, the hydrogen atom may be replaced with R 15.
• ring-constituting atom other than the ring member atoms in the A 5 ⁇ A 8, R 15 may be substituted.
• m 4 is selected from 0 or 1 to the maximum number that can be replaced with a monocyclic or polycyclic integer.
• the bond of the heteroaliphatic cyclic ammonium group represented by the above formula (S2) is present at any carbon atom or nitrogen atom present in such a monocyclic or fused ring, and is directly bonded to a silicon atom.
• a linking group is bonded to form an organic group containing cyclic ammonium, which is bonded to a silicon atom. Examples of such a linking group include an alkylene group, an arylene group or an alkaneylene group, and specific examples of the alkylene group, the arylene group and the alkaneylene group and suitable carbon atoms thereof include the same as described above.
• silane compound (hydrolyzable organosilane) represented by the formula (4) having a heteroaliphatic cyclic ammonium group represented by the above formula (S2) are the following formulas (II-1) to (II). Examples thereof include, but are not limited to, silane represented by -30).
• R 11 which is a group bonded to a silicon atom in the above formula (4) can be a chain ammonium group represented by the following formula (S3).
• R 10 independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group or an alkenyl group, and the alkyl group
• Specific examples of the aryl group, the aralkyl group, the alkyl halide group, the aryl halide group, the halide aralkyl group and the alkenyl group, and suitable carbon atoms thereof include the same as those described above.
• the chain ammonium group represented by the formula (S3) is directly bonded to the silicon atom, or the linking group is bonded to form an organic group containing the chain ammonium group, which is bonded to the silicon atom.
• Examples of such a linking group include an alkylene group, an arylene group or an alkaneylene group, and specific examples of the alkylene group, the arylene group and the alkaneylene group include the same as described above.
• silane compound (hydrolyzable organosilane) represented by the formula (4) having a chain ammonium group represented by the above formula (S3) are the following formulas (III-1) to (III-28). ), But not limited to these.
• composition for forming a resist underlayer film of the present invention may further contain a silane compound having a sulfone group and a silane compound having a sulfonamide group in the hydrolyzable silane mixture. Specific examples thereof will be given below, but the present invention is not limited thereto.
• Me represents a methyl group
• Et represents an ethyl group.
• hydrolyzable silane mixture may contain other silane compounds (hydrolyzable silanes) other than the above examples as long as the effects of the present invention are not impaired.
• the composition for forming a resist underlayer film of the present invention contains a hydrolyzed condensate of the hydrolyzable silane mixture.
• the composition for forming a resist underlayer film of the present invention contains at least a hydrolyzed condensate of the above hydrolyzable silane mixture.
• the hydrolyzable condensate contained in the composition for forming a resist underlayer film of the present invention is a hydrolyzable silane represented by the formula (2) in addition to the silane represented by the formula (1).
• optionally other hydrolyzable condensates obtained with at least other hydrolyzable silanes is optionally other hydrolyzable condensates obtained with at least other hydrolyzable silanes.
• the hydrolyzed condensate contains the silane compound represented by the formula (1) in an amount of, for example, 5 mol% or more, preferably 10 mol, based on the total amount of the silane compound contained in the hydrolyzable silane mixture. It can be a hydrolyzed condensate of a hydrolyzable silane mixture containing% or more. In a more preferred embodiment, the hydrolyzed condensate is the hydrolysis of a hydrolyzable silane mixture containing, as a compound represented by the formula (1), a compound in which R 1 represents an organic group containing a succinic acid anhydride skeleton as an essential compound.
• It can be a condensate, in which case the compound represented by the formula (1) in which R 1 represents an organic group containing a succinic anhydride skeleton is added to the total amount of the silane compound contained in the hydrolyzable silane mixture.
• it can be a hydrolyzed condensate of a hydrolyzable silane mixture containing, for example, in a proportion of 1 mol% or more, preferably in a proportion of 5 mol% or more.
• the amount of the silane compound represented by the formula (1) charged is the hydrolyzable silane. It can be, for example, 5 mol% or more, preferably 10 mol% or more, based on the charged amount (100 mol%) of all the silane compounds (hydrolytable silane) contained in the mixture. From the viewpoint of obtaining the above-mentioned effects of the present invention with good reproducibility, it is particularly preferable to use a compound represented by the formula (1) in which R 1 represents an organic group containing a succinic acid anhydride skeleton as essential, and this is hydrolyzable.
• the silane compound contained in the silane mixture for example, usually 0.1 mol% or more, preferably 0.5 mol% or more, more preferably 1 mol% or more, even more preferably.
• the ratio more preferably 5.5 mol% or less, can be used.
• the amount of all silane compounds (hydrolyzable silanes) contained in the degradable silane mixture can be usually 60 mol% to 90 mol%, but as described above, the condensate of the mixture. From the viewpoint of improving the residue removability by etching when the film formed from the composition containing the above is dry-etched, the amount of alkyltrialkoxysilane charged is less than 40 mol%, that is, 0 mol% or more and less than 40 mol%. Is.
• the amount of the organosilane charged is all silane compounds (hydrolyzable silane). It is usually 0.01 mol% or more, preferably 0.1 mol% or more, and usually 30 mol% or less, preferably 10 mol% or less, based on the charged amount of.
• the hydrolyzed condensate of the above hydrolyzable silane mixture can have a weight average molecular weight of, for example, 500 to 1,000,000.
• the weight average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, still more preferably 100,000 or less. It can be preferably 700 or more, more preferably 1,000 or more, from the viewpoint of achieving both storage stability and coatability.
• the weight average molecular weight is a molecular weight obtained in terms of polystyrene by GPC analysis.
• a GPC apparatus (trade name: HLC-8220GPC, manufactured by Toso Co., Ltd.) and a GPC column (trade name: Shodex® KF803L, KF802, KF801, manufactured by Showa Denko KK) are used to determine the column temperature. It can be carried out at 40 ° C., using tetrahydrofuran as the eluent (eluting solvent), setting the flow rate (flow velocity) to 1.0 mL / min, and using polystyrene (manufactured by Showa Denko KK) as a standard sample.
• the hydrolyzed condensate of the hydrolyzable silane mixture is obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane).
• the silane compound (hydrolyzable silane) contains an alkoxy group, an aralkyloxy group, an acyloxy group, and a halogen atom that are directly bonded to a silicon atom, that is, an alkoxysilyl group, an aralkyloxysilyl group, and an acyloxysilyl that are hydrolyzable groups. Includes groups, silyl halide groups.
• hydrolysis catalyst for the hydrolysis of these hydrolyzable groups, usually 0.5 to 100 mol, preferably 1 to 10 mol of water is used per 1 mol of the hydrolyzable group.
• a hydrolysis catalyst may be used for the purpose of accelerating the reaction, or hydrolysis and condensation may be carried out without using the hydrolysis catalyst.
• a hydrolysis catalyst of usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, can be used per mol of the hydrolyzable group.
• the reaction temperature for hydrolysis and condensation is usually in the range of room temperature or higher and the reflux temperature of an organic solvent that can be used for hydrolysis at normal pressure, for example, 20 to 110 ° C., or 20 to 80 ° C.
• the hydrolysis can be complete hydrolysis, i.e. all hydrolyzable groups may be converted to silanol groups, or partially hydrolyzed, i.e. leaving unreacted hydrolyzable groups. good.
• the hydrolysis catalyst that can be used for hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
• Metal chelate compounds as hydrolysis catalysts include, for example, triethoxy mono (acetylacetonet) titanium, tri-n-propoxymono (acetylacetonate) titanium, tri-i-propoxymono (acetylacetonate) titanium, and tri.
• Organic acids as hydrolysis catalysts include, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacin.
• Examples of the inorganic acid as a hydrolysis catalyst include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, phosphoric acid and the like.
• Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrol, piperazine, pyrrolidine, piperidine, picolin, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diah.
• the inorganic base as the hydrolysis catalyst include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like.
• metal chelate compounds organic acids, and inorganic acids are preferable, and these may be used alone or in combination of two or more.
• nitric acid can be preferably used as the hydrolysis catalyst.
• the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, the change in the molecular weight of the hydrolysis condensate can be suppressed.
• the stability of the hydrolyzed condensate in liquid has been found to depend on the pH of the solution. As a result of diligent studies, it was found that the pH of the solution became a stable range by using an appropriate amount of nitric acid.
• an organic solvent may be used as a solvent, and specific examples thereof include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, and 2 , 2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbon solvents; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i- Aromatic hydrocarbon solvents such as propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene; methanol
• Ether 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n- Butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether , Diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl
• sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethylsulfoxide, sulfolane, 1,3-propanesulton and the like. , Not limited to these. These solvents can be used alone or in combination of two or more.
• the reaction solution is used as it is or diluted or concentrated, neutralized, and treated with an ion exchange resin to hydrolyze the acids and bases used for the hydrolysis and condensation.
• the catalyst can be removed. Further, before or after such treatment, alcohol or water as a by-product, the hydrolysis catalyst used, or the like can be removed from the reaction solution by vacuum distillation or the like.
• the hydrolyzed condensate thus obtained (hereinafter, also referred to as polysiloxane) is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and this is used as it is as a composition for forming a resist underlayer film, which will be described later. Can be used as.
• the obtained polysiloxane varnish may be solvent-substituted, or may be appropriately diluted with a solvent.
• the obtained polysiloxane varnish may have a solid content concentration of 100% by distilling off an organic solvent as long as its storage stability is not poor.
• the organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane mixture.
• the dilution solvent is not particularly limited, and either one type or two or more types can be arbitrarily selected and used.
• composition for forming a resist underlayer film contains a hydrolyzable condensate (polysiloxane) of the hydrolyzable silane mixture and a solvent, and may further contain other components described later.
• the solid content concentration in the resist underlayer film forming composition is, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, 0 with respect to the total mass of the composition. It can be 5.5 to 20.0% by mass.
• the solid content refers to a component obtained by removing the solvent component from all the components of the composition.
• the content of the hydrolyzed condensate of the hydrolyzable silane mixture in the solid content is usually 20% by mass to 100% by mass, but from the viewpoint of obtaining the above-mentioned effect of the present invention with good reproducibility, the lower limit value thereof. Is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, still more preferably 80% by mass, and the upper limit thereof is preferably 99% by mass. Can be used as an additive.
• the content of the hydrolyzed condensate of the hydrolyzable silane mixture in the composition can be, for example, 0.5 to 20.0% by mass.
• the resist underlayer film forming composition preferably has a pH of 2 to 5, and more preferably has a pH of 3 to 4.
• the composition for forming a resist underlayer film can be produced by mixing a hydrolyzed condensate of the above-mentioned hydrolyzable silane mixture, a solvent, and, if desired, other components, if desired.
• a solution containing a hydrolyzed condensate or the like may be prepared in advance, and this solution may be mixed with a solvent or other components.
• the mixing order is not particularly limited.
• a solvent may be added to a solution containing a hydrolyzed condensate or the like and mixed, and other components may be added to the mixture.
• the solution containing the hydrolyzed condensate or the like, the solvent and other components may be mixed at the same time. You may.
• additional solvent may be added at the end, or some components that are relatively soluble in the solvent may be left unincluded in the mixture and added at the end, but agglomeration of the components.
• the hydrolyzed condensate and the like may aggregate or precipitate when they are mixed, depending on the type and amount of the solvent to be mixed together, the amount and properties of other components, and the like.
• the hydrolyzed condensate or the like is prepared so that the amount of the hydrolyzed condensate or the like in the finally obtained composition is a desired amount. Also keep in mind that it is necessary to determine the concentration of the solution and the amount used. In the preparation of the composition, heating may be appropriately performed as long as the components are not decomposed or deteriorated.
• the present invention may be filtered using a filter on the order of submicrometer or the like at the stage of producing the composition for forming the resist underlayer film or after mixing all the components.
• the resist underlayer film forming composition of the present invention can be suitably used as a resist underlayer film forming composition used in the lithography process.
• the solvent used in the composition for forming a resist underlayer film of the present invention can be used without particular limitation as long as it is a solvent capable of dissolving the solid content.
• a solvent is not limited as long as it dissolves the hydrolyzed condensate of the hydrolyzable silane mixture and other components.
• methyl cellosolve acetate ethyl cellosolve acetate
• propylene glycol propylene glycol monomethyl ether (1-methoxy-2-propanol)
• propylene glycol monoethyl ether 1,3-bis(trimethoxy-2-propanol)
• methyl isobutyl carbinol methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and methyl isobutyl carbinol.
• composition for forming a resist underlayer film of the present invention may contain water as a solvent.
• water When water is contained as the solvent, the content thereof may be, for example, 30% by mass or less, preferably 20% by mass or less, and even more preferably 15% by mass or less, based on the total mass of the solvent contained in the composition. can.
• additives can be added to the resist underlayer film forming composition of the present invention depending on the use of the composition.
• the additive include a curing catalyst (ammonium salt, phosphine, phosphonium salt, sulfonium salt, nitrogen-containing silane compound, etc.), a cross-linking agent, a cross-linking catalyst, a stabilizer (organic acid, water, alcohol, etc.), and an organic substance.
• Polymer compounds acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), It is blended in materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as pH adjusters, rheology adjusters, adhesive aids, resist underlayer films, antireflection films, and pattern inversion films.
• surfactants nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.
• materials compositions that form various films that can be used in the manufacture of semiconductor devices, such as pH adjusters, rheology adjusters, adhesive aids, resist underlayer films, antireflection films, and pattern inversion films.
• Known additives can be mentioned.
• Various additives are exemplified below, but the present invention is not limited
• ⁇ Curing catalyst> ammonium salts, phosphines, phosphonium salts, sulfonium salts and the like can be used.
• the following salts described as curing catalysts may be added in the form of salts, or those that form a salt in the above composition (the one that is added as a separate compound at the time of addition and forms a salt in the system). ) May be used.
• the ammonium salt has the formula (D-1): (In the formula, m represents an integer of 2 to 11, n represents an integer of 2 to 3, R 21 represents an alkyl group or an aryl group, and Y ⁇ represents an anion.)
• Equation (D-2) (In the formula, R 22 , R 23 , R 24 and R 25 represent an alkyl or aryl group, N represents a nitrogen atom, Y ⁇ represents an anion, and R 22 , R 23 , R 24 , and R 25.
• Equation (D-3) A quaternary ammonium salt having a structure represented by (in the formula, R 26 and R 27 represent an alkyl group or an aryl group, N represents a nitrogen atom, and Y ⁇ represents an anion).
• Equation (D-4) A quaternary ammonium salt having a structure represented by (in the formula, R 28 represents an alkyl group or an aryl group, N represents a nitrogen atom, and Y ⁇ represents an anion).
• the formula (D-7) (In the formula, R 31 , R 32 , R 33 , and R 34 represent an alkyl or aryl group, P represents a phosphorus atom, Y ⁇ represents an anion, and R 31 , R 32 , R 33 , and R. Each of 34 is bonded to a phosphorus atom by a CP bond), and a quaternary phosphonium salt can be mentioned.
• the formula (D-8) (In the formula, R 35 , R 36 , and R 37 represent an alkyl or aryl group, S represents a sulfur atom, Y ⁇ represents an anion, and R 35 , R 36 , and R 37 are CS, respectively.
• a tertiary sulfonium salt represented by (which is bonded to a sulfur atom by a bond) can be mentioned.
• the compound of the above formula (D-1) is a quaternary ammonium salt derived from an amine, and m represents an integer of 2 to 11 and n represents an integer of 2 to 3.
• the compound of the above formula (D-2) is a quaternary ammonium salt represented by R 22 R 23 R 24 R 25 N + Y ⁇ .
• R 22 , R 23 , R 24 and R 25 of this quaternary ammonium salt are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms.
• Anion (Y -), chlorine ion (Cl -), bromine ion (Br -) - or a halide ion such as, carboxylate (-COO -), iodide ion (I), sulfonato (-SO 3 -) , alcoholates - can be exemplified an acid group such as (-O).
• This quaternary ammonium salt is commercially available and is available, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzyl chloride. Ammonium, trimethylbenzylammonium chloride and the like are exemplified.
• the compound of the above formula (D-3) is a quaternary ammonium salt derived from the 1-substituted imidazole, and R 26 and R 27 have 1 to 18 carbon atoms, and are of R 26 and R 27 .
• the total number of carbon atoms is preferably 7 or more.
• R 26 can be exemplified as a methyl group, an ethyl group, a propyl group, a phenyl group or a benzyl group
• R 27 can be exemplified by a benzyl group, an octyl group or an octadecyl group.
• Anion (Y -), chlorine ion (Cl -), bromine ion (Br -) - or a halide ion such as, carboxylate (-COO -), iodide ion (I), sulfonato (-SO 3 -) , alcoholates - can be exemplified an acid group such as (-O).
• This compound can be obtained as a commercially available product, but for example, an imidazole compound such as 1-methylimidazole or 1-benzylimidazole is reacted with an alkyl halide such as benzyl bromide or methyl bromide or an aryl halide. Can be manufactured.
• the compound of the above formula (D-4) is a quaternary ammonium salt derived from pyridine, and R 28 is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or a carbon atom.
• the aryl group is number 6 to 18, and examples thereof include a butyl group, an octyl group, a benzyl group, and a lauryl group.
• Anion (Y -), chlorine ion (Cl -), bromine ion (Br -) - or a halide ion such as, carboxylate (-COO -), iodide ion (I), sulfonato (-SO 3 -) , alcoholates - can be exemplified an acid group such as (-O).
• This compound can be obtained as a commercially available product, but is produced by reacting, for example, pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide, or an aryl halide. can do. Examples of this compound include N-lauryl pyridinium chloride, N-benzyl pyridinium bromide, and the like.
• the compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline or the like, and R 29 has 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms. , Or an aryl group having 6 to 18 carbon atoms, and examples thereof include a methyl group, an octyl group, a lauryl group, and a benzyl group.
• R 30 is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, for example, when it is a quaternary ammonium derived from picoline, R 30 is a methyl group.
• Anion (Y -), chlorine ion (Cl -), bromine ion (Br -) - or a halide ion such as, carboxylate (-COO -), iodide ion (I), sulfonato (-SO 3 -) , alcoholates - can be exemplified an acid group such as (-O).
• This compound can be obtained as a commercial product, but for example, a substituted pyridine such as picoline is reacted with an alkyl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide, or an aryl halide. Can be manufactured. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, N-laurylpicolinium chloride and the like.
• the compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, where m represents an integer of 2 to 11 and n represents an integer of 2 to 3.
• the anion (Y -), chlorine ion (Cl -), bromine ion (Br -) - or a halide ion such as, carboxylate (-COO -), iodide ion (I), sulfonato (-SO 3 - ), alcoholates (-O - can be given) acid groups and the like.
• This compound can be produced by reacting an amine with a weak acid such as a carboxylic acid or phenol.
• the carboxylic acid include formic acid and acetic acid
• the anion (Y -) - in the case of using formic acid, the anion (Y -) -, and the case of using acetic acid, the anion (HCOO) (Y -) is (CH 3 COO - ).
• the anion (Y ⁇ ) is (C 6 H 5 O ⁇ ).
• the compound of the above formula (D-7) is a quaternary phosphonium salt having a structure of R 31 R 32 R 33 R 34 P + Y ⁇ .
• R 31 , R 32 , R 33 , and R 34 are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms, preferably among the four substituents R 31 to R 34.
• Three are phenyl groups or substituted phenyl groups, for example, a phenyl group or a tolyl group can be exemplified, and the remaining one is an alkyl group having 1 to 18 carbon atoms and 6 to 18 carbon atoms. It is an aryl group.
• This compound is available as a commercial product, for example, tetraalkylphosphonium halides such as tetran-butylphosphonium halides and tetran-propylphosphonium halides, and trialkylbenzyl halides such as triethylbenzylphosphonium halides.
• Triphenyl monoalkyl phosphonium halides such as phosphonium, triphenyl methyl phosphonium halogenated, triphenyl ethyl phosphonium halogenated, triphenyl benzyl phosphonium halogenated, tetraphenyl phosphonium halogenated, tritril monoaryl phosphonium halogenated, or tritril mono halide
• alkylphosphonium the halogen atom is a chlorine atom or a bromine atom.
• halogenated triphenylmonoalkylphosphoniums such as triphenylmethylphosphonium halides and triphenylethylphosphonium halides
• triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halides
• halogens such as tritrilmonophenylphosphonium halogenated.
• Halogenated tritryl monoalkylphosphonium halogen atom is chlorine atom or bromine atom
• tritryl monoarylphosphonium halide or tritril monomethyl phosphonium halogenated is preferable.
• phosphines include primary phosphine such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine and phenylphosphine, and second phosphine such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine and diphenylphosphine. , Trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine and the like.
• the compound of the above formula (D-8) is a tertiary sulfonium salt having a structure of R 35 R 36 R 37 S + Y ⁇ .
• R 35 , R 36 , and R 37 are alkyl groups having 1 to 18 carbon atoms or aryl groups having 6 to 18 carbon atoms, preferably two of the three substituents R 35 to R 37 are phenyl.
• a group or substituted phenyl group, for example, a phenyl group or a tolyl group can be exemplified, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. be.
• the anion (Y -), chlorine ion (Cl -), bromine ion (Br -) - or a halide ion such as, carboxylate (-COO -), iodide ion (I), sulfonato (-SO 3 - ), alcoholates (-O -), maleic acid anion include an acid group such as a nitrate anion.
• This compound is available as a commercial product, for example, trialkyl sulfonium halides such as tri n-butyl sulfonium halide and tri n-propyl sulfonium halide, and dialkyl benzyl sulfonium halides such as diethyl benzyl sulfonium halide.
• trialkyl sulfonium halides such as tri n-butyl sulfonium halide and tri n-propyl sulfonium halide
• dialkyl benzyl sulfonium halides such as diethyl benzyl sulfonium halide.
• a nitrogen-containing silane compound can be added as a curing catalyst.
• the nitrogen-containing silane compound include an imidazole ring-containing silane compound such as N- (3-triethoxysiripropyl) -4,5-dihydroimidazole.
• a curing catalyst When a curing catalyst is used, it is 0.01 parts by mass to 10 parts by mass, 0.01 parts by mass to 5 parts by mass, or 0.01 parts by mass to 3 parts by mass with respect to 100 parts by mass of polysiloxane. ..
• the stabilizer may be added for the purpose of stabilizing the hydrolyzed condensate of the hydrolyzable silane mixture, and as a specific example thereof, an organic acid, water, alcohol, or a combination thereof may be added.
• an organic acid include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, salicylic acid and the like. Of these, oxalic acid and maleic acid are preferable.
• the amount added is 0.1 to 5.0% by mass with respect to the mass of the hydrolyzed condensate of the hydrolyzable silane mixture.
• These organic acids can also act as pH regulators.
• As the water pure water, ultrapure water, ion-exchanged water, or the like can be used, and when used, the amount added is 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resist underlayer film forming composition.
• the alcohol is preferably one that easily scatters (volatilizes) by heating after coating, and examples thereof include methanol, ethanol, propanol, i-propanol, butanol and the like.
• the amount of alcohol added can be 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the resist underlayer film forming composition.
• Organic polymer By adding the organic polymer compound to the composition for forming a resist underlayer film, the dry etching rate (amount of decrease in film thickness per unit time) of the film (resist underlayer film) formed from the composition and the amount of decrease in the film thickness per unit time can be determined. Moreover, the attenuation coefficient, the refractive index, and the like can be adjusted.
• the organic polymer compound is not particularly limited, and is appropriately selected from various organic polymers (condensation polymer and addition polymer) according to the purpose of addition thereof.
• an organic polymer containing an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, a quinoxaline ring, or a heteroaromatic ring that functions as an absorption site also needs such a function.
• an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, a quinoxaline ring, or a heteroaromatic ring that functions as an absorption site also needs such a function.
• organic polymer compounds include addition polymerizable properties such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether and N-phenylmaleimide.
• addition-polymerized polymers containing a monomer as a structural unit thereof and depolymerized polymers such as phenol novolac and naphthol novolac.
• the polymer compound may be either a homopolymer or a copolymer.
• Addition-polymerizable monomers are used in the production of addition-polymerizable polymers, and specific examples of such addition-polymerizable monomers include acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, and methacrylic acids. Examples thereof include, but are not limited to, amide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic acid anhydrides, and acrylonitrile.
• acrylic acid ester compound examples include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthryl methyl acrylate, 2-hydroxyethyl acrylate, and 3-chloro-2.
• methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate and 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-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc. However, it is not limited to these.
• acrylamide compound examples include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N, N-dimethylacrylamide, N-anthrylacrylamide and the like. Not limited.
• methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N, N-dimethylmethacrylamide, and N-anthrylmethacrylamide. Etc., but are not limited to these.
• vinyl compounds include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene and vinyl. Anthracene and the like can be mentioned, but the present invention is not limited to these.
• styrene compound examples include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene and the like.
• maleimide compound examples include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-hydroxyethylmaleimide and the like.
• such a polymer includes, for example, a polycondensation polymer of a glycol compound and a dicarboxylic acid compound.
• the glycol compound include diethylene glycol, hexamethylene glycol, butylene glycol and the like.
• the dicarboxylic acid compound include succinic acid, adipic acid, terephthalic acid, maleic anhydride and the like.
• polyesters such as polypyrromeritimide, poly (p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, polyamides, and polyimides can be mentioned, but are not limited thereto.
• the organic polymer compound contains a hydroxy group, the hydroxy group can undergo a cross-linking reaction with a hydrolyzed condensate or the like.
• the weight average molecular weight of the organic polymer compound is usually 1,000 to 1,000,000.
• the weight average molecular weight thereof is, for example, 3,000 to 300,000, or 5,000, from the viewpoint of suppressing precipitation in the composition while sufficiently obtaining the effect of the function as a polymer. It can be from 300,000, 10,000 to 200,000, and the like.
• Such an organic polymer compound may be used alone or in combination of two or more.
• the composition for forming a resist underlayer film of the present invention contains an organic polymer compound
• its content cannot be unconditionally determined because it is appropriately determined in consideration of the function of the organic polymer compound and the like, but usually, the above-mentioned hydrolyzable silane It can be in the range of 1 to 200% by mass with respect to the mass of the hydrolyzed condensate of the mixture, and from the viewpoint of suppressing precipitation in the composition, for example, 100% by mass or less, preferably 50% by mass or less. , More preferably 30% by mass or less, and from the viewpoint of sufficiently obtaining the effect, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more.
• thermoacid generator examples include a thermoacid generator and a photoacid generator, and a photoacid generator can be preferably used.
• photoacid generator examples include, but are not limited to, onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds and the like.
• thermoacid generator examples include, but are not limited to, tetramethylammonium nitrate.
• the onium salt compound examples include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butane sulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphor sulfonate, and bis (4-t-butylphenyl).
• Iodonium salt compounds such as iodonium camphor sulfonate, bis (4-t-butylphenyl) iodonium trifluoromethane sulfonate, triphenyl sulfonium hexafluoroantimonate, triphenyl sulfonium nonafluoronormal butane sulfonate, triphenyl sulfonium camphor sulfonate, triphenyl sulfonium Examples thereof include, but are not limited to, trifluoromethanesulfonate, triphenylsulfonium nitrate (nitrate), triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and sulfonium salt compounds such as triphenylsulfonium chloride.
• sulfoneimide compound examples include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormal butanesulfonyloxy) succinimide, N- (kanfersulfonyloxy) succinimide, and N- (trifluoromethanesulfonyloxy) naphthalimide. Etc., but are not limited to these.
• disulfonyldiazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzene).
• Sulfonyl) Diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane and the like can be mentioned, but are not limited thereto.
• the content thereof cannot be unconditionally determined because it is appropriately determined in consideration of the type of the acid generator and the like, but usually, the hydrolyzable silane mixture is described above. It is in the range of 0.01 to 5% by mass with respect to the mass of the hydrolyzed condensate of the above, and is preferably 3% by mass or less, more preferably 3% by mass or less, from the viewpoint of suppressing the precipitation of the acid generator in the composition. It is 1% by mass or less, preferably 0.1% by mass or more, and more preferably 0.5% by mass or more from the viewpoint of sufficiently obtaining the effect.
• the acid generator may be used alone or in combination of two or more, and the photoacid generator and the thermoacid generator may be used in combination.
• the surfactant is effective in suppressing the occurrence of pinholes, stirrers, etc. when the composition for forming a resist underlayer film is applied to a substrate.
• the above-mentioned surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants and the like. More specifically, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol.
• Polyoxyethylene alkylaryl ethers such as ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurates, sorbitan monopalmitates, sorbitan monostearates, sorbitan monooleates, sorbitan trioleates, sorbitan tristearates.
• Solbitan fatty acid esters such as, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene such as polyoxyethylene sorbitan tristearate.
• Nonionic surfactants such as sorbitan fatty acid esters, trade names EF301, EF303, EF352 (manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd. (formerly Tochem Products Co., Ltd.)), trade name Megafuck ( Registered trademarks) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Co., Ltd.), Florard FC430, FC431 (manufactured by 3M Japan Co., Ltd.), trade name Asahi Guard (registered trademark) ) Fluorine surfactants such as AG710 (manufactured by AGC Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane. Polyethylene-KP341 (manufactured by Shin-Etsu Chemical Industry Co.
• the content thereof is usually 0.0001 to 5% by mass with respect to the mass of the hydrolyzed condensate of the hydrolyzable silane mixture. , It can be preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass.
• the rheology adjuster mainly improves the fluidity of the composition for forming a resist underlayer film, particularly in the baking step, improves the film thickness uniformity of the film to be formed, and improves the filling property of the composition inside the hole. Added for the purpose of enhancing. Specific examples include phthalate derivatives such as dimethylphthalate, diethylphthalate, dii-butylphthalate, dihexylphthalate, and butyl i-decylphthalate, dinormal butyl adipate, di-i-butyl adipate, and di-i-octyl adipate.
• Adiponic acid derivatives such as octyldecyl adipate, maleic acid derivatives such as dinormal butylmalate, diethyl malate, dinonyl malate, oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate, or normal butyl stealate, glyceryl steer Examples thereof include phthalates and other stearic acid derivatives. When these rheology modifiers are used, the amount added is usually less than 30% by mass based on the total solid content of the resist underlayer film forming composition.
• the adhesive auxiliary mainly improves the adhesion between the substrate or the resist and the film formed from the composition for forming the resist underlayer film (resist underlayer film), and suppresses / prevents the peeling of the resist particularly during development. It is added for the purpose.
• Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane, and hexamethyl.
• Silazans such as disilazan, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, ⁇ -chloropropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane
• silanes such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urasol, thiouracil, mercaptoimidazole, mercaptopyrimidine and other heterocyclic compounds.
• ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds can be mentioned.
• the amount added thereof is usually less than 5% by mass, preferably less than 2% by mass, based on the total solid content of the resist underlayer film forming composition.
• a bisphenol S or a bisphenol S derivative can be added in addition to the acid having one or two or more carboxylic acid groups such as the organic acid mentioned above as the ⁇ stabilizer>.
• the bisphenol S or bisphenol S derivative is 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 0.01 to 100 parts by mass with respect to 100 parts by mass of the hydrolyzed condensate of the hydrolyzable silane mixture. 5 parts by mass.
• a substrate used for manufacturing a precision integrated circuit element for example, a semiconductor substrate such as a silicon oxide film, a silicon nitride film or a silicon wafer coated with a silicon nitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (none). Includes alkali glass, low alkali glass, and crystallized glass), glass substrates on which ITO (indium tin oxide) films and IZO (indium zinc oxide) films are formed, plastic (polyimide, PET, etc.) substrates, low dielectrics.
• a semiconductor substrate such as a silicon oxide film, a silicon nitride film or a silicon wafer coated with a silicon nitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (none). Includes alkali glass, low alkali glass, and crystallized glass), glass substrates on which ITO (indium tin oxide) films and IZO (indium zinc oxide) films
• the composition for forming a resist underlayer film of the present invention is applied onto a rate material (low-k material) coated substrate, flexible substrate, etc.] by an appropriate coating method such as a spinner or a coater, and then a hot plate or the like is used.
• the composition is cured by firing using a heating means to form a resist underlayer film.
• the resist underlayer film means a film formed from the resist underlayer film forming composition of the present invention.
• the firing conditions are appropriately selected from a firing temperature of 40 ° C. to 400 ° C., or 80 ° C. to 250 ° C., and a firing time of 0.3 minutes to 60 minutes.
• the firing temperature is 150 ° C. to 250 ° C.
• the film thickness of the resist underlayer film formed here is, for example, 10 nm to 1,000 nm, 20 nm to 500 nm, 50 nm to 300 nm, or 100 nm to 200 nm, or 10 to 150 nm.
• the organic underlayer film is formed on the substrate, and then the resist underlayer film is formed on the organic underlayer film.
• the organic underlayer film may not be provided.
• the organic underlayer film used here is not particularly limited, and can be arbitrarily selected and used from those conventionally used in the lithography process.
• the resist underlayer film of the present invention can be processed by using a fluorine-based gas having a sufficiently fast etching rate for the photoresist film as the etching gas, and the resist underlayer film of the present invention can be sufficiently processed.
• An oxygen-based gas having a high etching rate can be used as an etching gas to process an organic underlayer film, and a fluorine-based gas having a sufficiently fast etching rate with respect to the organic underlayer film can be used as an etching gas to form a substrate.
• the substrate and coating method that can be used at this time include the same as those described above.
• a layer of a photoresist material is formed on the resist underlayer film.
• the resist film can be formed by a well-known method, that is, by applying a coating-type resist material (for example, a composition for forming a photoresist film) on a resist underlayer film and firing it.
• the film thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.
• the photoresist material used for the resist film formed on the resist underlayer film is particularly limited as long as it is sensitive to light used for exposure (for example, KrF excimer laser, ArF excimer laser, etc.).
• both negative photoresist materials and positive photoresist materials can be used.
• a positive photoresist material consisting of novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester
• a chemically amplified photoresist consisting of a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator.
• Chemically amplified photoresist material consisting of a low molecular weight compound, an alkali-soluble binder and a photoacid generator, which decomposes with a material and an acid to increase the alkali dissolution rate of the photoresist material, and decomposes with an acid to increase the alkali dissolution rate.
• chemically amplified photoresist materials composed of a low molecular weight compound that decomposes with a binder having a group to cause the photoresist and an acid to increase the alkali dissolution rate of the photoresist material, and a photoacid generator.
• Specific examples available as commercial products include chypre product name APEX-E, Sumitomo Chemical Co., Ltd.
• the resist film formed on the resist underlayer film is a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film) instead of the resist film.
• the composition for forming a resist underlayer film containing silicon of the present invention can be used for forming a resist underlayer film for electron beam lithography or for forming a resist underlayer film for EUV lithography.
• it is suitable as a composition for forming a resist underlayer film for EUV lithography.
• the electron beam resist material either a negative type material or a positive type material can be used.
• Specific examples thereof include a chemically amplified resist material composed of an acid generator and a binder having a group that decomposes with an acid to change the alkali dissolution rate, and an alkali-soluble binder, an acid generator and an acid decomposed with an acid to make the alkali of the resist material.
• a chemically amplified resist material composed of a low molecular weight compound that changes the dissolution rate, a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, and an acid that decomposes with an acid to change the alkali dissolution rate of the resist material.
• It has a chemically amplified resist material composed of a low molecular weight compound, a non-chemically amplified resist material composed of a binder having a group that decomposes with an electron beam and changes the alkali dissolution rate, and a site that is cut by an electron beam to change the alkali dissolution rate.
• a non-chemically amplified resist material made of binders. Even when these electron beam resist materials are used, a resist film pattern can be formed in the same manner as when a photoresist material is used with the irradiation source as an electron beam.
• a methacrylate resin-based resist material can be used as the EUV resist material.
• the resist film formed on the upper layer of the resist lower layer film is exposed through a predetermined mask (rectyl).
• a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), an EUV (wavelength 13.5 nm), an electron beam or the like can be used.
• post-exposure heating (post exposure break) can be performed if necessary. Post-exposure heating is performed under appropriately selected conditions from a heating temperature of 70 ° C. to 150 ° C. and a heating time of 0.3 minutes to 10 minutes.
• the developing solution includes an aqueous solution of an alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and ethanol.
• alkaline aqueous solution such as an amine aqueous solution such as amine, propylamine, or ethylenediamine can be mentioned as an example. Further, a surfactant or the like can be added to these developers.
• the development conditions are appropriately selected from a temperature of 5 to 50 ° C. and a time of 10 seconds to 600 seconds.
• an organic solvent can be used as the developing solution, and development is performed with the developing solution (solvent) after exposure.
• the developing solution solvent
• the photoresist film in the unexposed portion is removed, and a pattern of the photoresist film is formed.
• Examples of the developing solution include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy acetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like.
• the resist lower layer film (intermediate layer) is removed, and then the patterned photoresist film and the patterned resist lower layer film (intermediate layer) are removed.
• the substrate is processed using the organic underlayer film (lower layer) as a protective film.
• Removal of the resist lower layer film (intermediate layer) performed using the pattern of the resist film (upper layer) as a protective film is performed by dry etching, and tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), and perfluoropropane.
• gases such as (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane and dichloroborane. can do. It is preferable to use a halogen-based gas for dry etching of the resist underlayer film.
• the photoresist film In dry etching with a halogen-based gas, it is difficult to remove a resist film (photoresist film) basically composed of an organic substance. On the other hand, the silicon-containing resist underlayer film containing a large amount of silicon atoms is rapidly removed by the halogen-based gas. Therefore, it is possible to suppress a decrease in the film thickness of the photoresist film due to dry etching of the resist underlayer film. As a result, the photoresist film can be used as a thin film.
• the dry etching of the resist underlayer film is preferably performed by a fluorine-based gas
• a fluorine-based gas examples include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), and perfluoro propane (C 3 F). 8 ), trifluoromethane, difluoromethane (CH 2 F 2 ) and the like, but are not limited thereto.
• the removal of the organic lower layer film (lower layer) performed by using the film as a protective film is preferably performed by dry etching with an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.). This is because the resist underlayer film of the present invention containing a large amount of silicon atoms is difficult to be removed by dry etching with an oxygen-based gas.
• oxygen-based gas oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.
• the processing of the (semiconductor) substrate using the patterned resist underlayer film (intermediate layer) and the optionally patterned organic underlayer film (lower layer) as the protective film is performed by dry etching with a fluorine-based gas.
• a fluorine-based gas examples include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, and difluoromethane (CH 2 F 2 ).
• the resist underlayer film it is possible to remove the resist underlayer film with a chemical solution after the step of etching (removing) the organic underlayer film.
• the resist underlayer film can be removed with the chemical solution after the substrate is processed with the patterned organic underlayer film.
• a structure derived from a silane compound containing the above-mentioned succinic anhydride skeleton and the like is incorporated into a hydrolyzed condensate (polysiloxane), whereby a film formed from the condensate is formed under alkaline conditions. Solubility can be increased. For example, it is soluble in alkaline solutions such as aqueous solutions containing ammonia and hydrogen peroxide.
• the chemical solution includes dilute hydrofluoric acid, buffered fluorophore, an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 chemical solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM chemical solution), and fluoroacid and hydrogen peroxide.
• alkaline solutions such as aqueous solutions (FPM chemicals) and aqueous solutions containing ammonia and hydrogen peroxide (SC-1 chemicals), and it is preferable to use alkaline chemicals (basic chemicals) from the viewpoint of reducing the effect on the substrate.
• alkaline chemicals basic chemicals
• examples of the alkaline solution include ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, as well as the above-mentioned ammonia superwater (SC-1 chemical solution) obtained by mixing ammonia, hydrogen peroxide solution and water.
• an organic antireflection film can be formed on the upper layer of the resist lower layer film before the resist film is formed.
• the antireflection film composition used therefor is not particularly limited, and for example, it can be arbitrarily selected and used from those conventionally used in the lithography process, and a commonly used method, for example, is used.
• the antireflection film can be formed by coating and firing with a spinner or coater.
• 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 on its surface by a CVD method or the like, and may be on the substrate. It is also possible to form a resist underlayer film.
• the substrate to be used is an organic or inorganic antireflection film formed on the surface thereof by a CVD method or the like. It may have.
• the resist underlayer film formed from the resist underlayer film forming composition of the present invention may also have absorption to the light depending on the wavelength of the light used in the lithography process. Then, in such a case, it can function as an antireflection film having an effect of preventing the reflected light from the substrate.
• the resist underlayer film is a layer for preventing interaction between the substrate and the resist film (photoresist film, etc.), a material used for the resist film, or a substance generated during exposure to the resist film, which has an adverse effect on the substrate.
• a layer having a function of preventing the resist film As a layer having a function of preventing the resist film, a layer having a function of preventing diffusion of substances generated from the substrate during heating and firing into the upper resist film, and a barrier layer for reducing the poisoning effect of the resist film by the dielectric layer of the semiconductor substrate. It is also possible to use it.
• the resist underlayer film can be applied to a substrate on which via holes are formed, which is used in the dual damascene process, and can be used as a hole filling material (embedding material) capable of filling the holes without gaps. It can also be used as a flattening material for flattening the surface of a semiconductor substrate having irregularities.
• the resist underlayer film serves as an underlayer film of the EUV resist film, and has a function as a hard mask. It can be used as an underlayer antireflection film of an EUV resist film that can prevent reflection of UV (ultraviolet) light or DUV (deep ultraviolet) light (: ArF light, KrF light) from the substrate or interface. That is, reflection can be efficiently prevented as a lower layer of the EUV resist film.
• the process can be performed in the same manner as the photoresist underlayer film.
• the semiconductor substrate can be suitably processed. Further, as described above, a step of forming an organic underlayer film, a step of forming a silicon-containing resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition of the present invention, and the above-mentioned According to the method for manufacturing a semiconductor device, which includes a step of forming a resist film on a silicon-containing resist underlayer film, highly accurate processing of a semiconductor substrate can be realized with good reproducibility, so that stable manufacturing of the semiconductor device can be achieved. You can expect it.
• hydrolyzable condensate of the above-mentioned hydrolyzable silane polyorganosiloxane
• a condensate having a weight average molecular weight of 1,000 to 1,000,000 or 1,000 to 100,000 can be obtained.
• These molecular weights are the molecular weights obtained in terms of polystyrene by GPC analysis.
• the measurement conditions for GPC are, for example, a GPC apparatus (trade name HLC-8220 GPC, manufactured by Toso Co., Ltd.), a GPC column (trade name Shodex® KF803L, KF802, KF801, manufactured by Showa Denko KK), and a column temperature of 40.
• the temperature can be adjusted by using tetrahydrofuran as the eluent (eluting solvent), 1.0 mL / min as the flow rate (flow velocity), and polystyrene (manufactured by Showa Denko KK) as the standard sample.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,700 in terms of polystyrene.
• Mw weight average molecular weight
• the number attached next to the siloxane unit represents the molar ratio (total 100).
• ⁇ Synthesis example 2> A 100 mL flask containing 29.2 g of tetraethoxysilane, 7.7 g of methyltriethoxysilane, 5.1 g of phenyltrimethoxysilane, 2.7 g of 3- (triethoxysilylpropyl) diallyl isocyanurate, and 67 g of 1-ethoxy-2-propanol. The obtained solution was stirred with a magnetic stirrer, and 28 g of a 0.2 mol / L nitrate aqueous solution was added dropwise thereto. After the dropping, the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and the reaction by-products methanol and ethanol are distilled off under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using -ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,900 in terms of polystyrene.
• the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours. Then, the reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and the reaction by-products methanol and ethanol are distilled off under reduced pressure. A concentrated solution of a hydrolyzed condensate (polymer) using -ethoxy-2-propanol as a solvent was obtained. The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C. The obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,600 in terms of polystyrene.
• Mw weight average molecular weight
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and the reaction by-products methanol and ethanol are distilled off under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using -ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,800 in terms of polystyrene.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and the reaction by-products methanol and ethanol are distilled off under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using -ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,700 in terms of polystyrene.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and the reaction by-products methanol and ethanol are distilled off under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using -ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,000 in terms of polystyrene.
• ⁇ Synthesis example 7> A 100 mL flask containing 14.6 g of tetraethoxysilane, 3.8 g of methyltriethoxysilane, 2.1 g of phenyltrimethoxysilane, 2.2 g of 3- (triethoxysilylpropyl) diallyl isocyanurate and 34 g of 1-ethoxy-2-propanol.
• the obtained solution was stirred with a magnetic stirrer, and 14 g of a 0.2 mol / L nitrate aqueous solution was added dropwise thereto. After the dropping, the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and the reaction by-products methanol and ethanol are distilled off under reduced pressure to obtain 1-.
• a concentrated solution of a hydrolyzed condensate (polymer) using ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,800 in terms of polystyrene.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,100 in terms of polystyrene.
• ⁇ Synthesis example 9 > 31.2 g of tetraethoxysilane, 6.4 g of vinyltrimethoxysilane, 4.3 g of phenyltrimethoxysilane, 0.7 g of [(3-triethoxysilyl) propyl] succinic anhydride and 64 g of 1-ethoxy-2-propanol.
• the mixture was placed in a 100 mL flask and stirred, and 28 g of a 0.2 mol / L nitrate aqueous solution was added dropwise thereto while stirring the obtained solution with a magnetic stirrer. After the dropping, the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,900 in terms of polystyrene.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and the reaction by-products methanol and ethanol are distilled off under reduced pressure to obtain 1-.
• a concentrated solution of a hydrolyzed condensate (polymer) using ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,000 in terms of polystyrene.
• the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours. Then, the reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and the reaction by-products methanol and ethanol are distilled off under reduced pressure to obtain 1-.
• a concentrated solution of a hydrolyzed condensate (polymer) using ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,300 in terms of polystyrene.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,100 in terms of polystyrene.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,100 in terms of polystyrene.
• the mixture was placed in a 100 mL flask and stirred, and 20 g of a 0.2 mol / L nitrate aqueous solution was added dropwise thereto while stirring the obtained solution with a magnetic stirrer. After the dropping, the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,300 in terms of polystyrene.
• the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours. Then, the reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,500 in terms of polystyrene.
• the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours. Then, the reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,300 in terms of polystyrene.
• the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours. Then, the reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,200 in terms of polystyrene.
• the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours. Then, the reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,000 in terms of polystyrene.
• the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours. Then, the reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,000 in terms of polystyrene.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and ethanol, which is a reaction by-product, are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,300 in terms of polystyrene.
• the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours. Then, the reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,800 in terms of polystyrene.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate, and the reaction by-products methanol and ethanol are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent The solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 1,900 in terms of polystyrene.
• ⁇ Reference synthesis example> 20.8 g of tetraethoxysilane, 7.6 g of methyltriethoxysilane and 42 g of 1-ethoxy-2-propanol were placed in a 100 mL flask and stirred, and the obtained solution was stirred with a magnetic stirrer to 0. . 19 g of a 2 mol / L nitric acid aqueous solution was added dropwise. After the dropping, the flask was transferred to an oil bath adjusted to 65 ° C. and reacted for 16 hours.
• reaction solution is cooled to room temperature, 100 g of 1-ethoxy-2-propanol is added to the reaction solution, and water and nitrate and ethanol, which is a reaction by-product, are distilled off from the reaction solution under reduced pressure.
• a concentrated solution of a hydrolyzed condensate (polymer) using 1-ethoxy-2-propanol as a solvent was obtained.
• the solid content concentration of the obtained concentrated liquid exceeded 20% by mass in terms of solid residue when heated at 150 ° C.
• the obtained polysiloxane corresponded to the following formula, and the weight average molecular weight (Mw) by GPC was 2,700 in terms of polystyrene.
• Examples 20 to 38 and Comparative Examples 2 to 4 Preparation of composition (coating liquid) for forming a silicon-containing resist underlayer film The hydrolyzed condensate obtained in Synthesis Examples 1 to 19 and Comparative Synthesis Examples 1 to 3. Various additives and solvents shown in Table 2 are mixed with the concentrated solution of (polymer) at the ratio shown in Table 2, and each mixture obtained is filtered through a fluororesin filter having a pore size of 0.1 ⁇ m to prepare a coating solution. Obtained. Each addition amount in Table 2 is shown by mass.
• the addition ratio of the hydrolyzed condensate (polymer) in Table 2 shows the addition amount of the polymer itself, not the addition amount of the concentrated solution of the hydrolyzed condensate (polymer).
• PGEE is 1-ethoxy-2-propanol (propylene glycol monoethyl ether)
• PGMEA is 1-methoxy-2-propanol monoacetate (propylene glycol monomethyl ether acetate)
• PGME is 1-methoxy-2.
• -Propanol (propylene glycol monomethyl ether) means each.
• MA means maleic acid
• IMID means N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole
• TPSNO3 means triphenylsulfonium nitrate.
• composition for forming an organic underlayer film Carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0. 040 mol, manufactured by Tokyo Chemical Industry Co., Ltd. and paratoluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and 1,4-dioxane (6.69 g) is added thereto. , Kanto Chemical Co., Ltd. was added and stirred, and then the mixture was heated to 100 ° C. to dissolve the solid and initiate polymerization.
• a resist film 120 nm
• the NSR-S307E scanner manufactured by Nikon Co., Ltd. (wavelength: 193 nm, NA: 0.85, ⁇ : 0.85 / 0.93) was used to develop the photoresist line width and between the lines after the following development.
• the mixture was heated after the exposure (110 ° C.
• resist patterns were formed using the coating liquids obtained in Examples 21 to 38 and Comparative Examples 2 to 4, respectively.
• the obtained photoresist pattern was evaluated by confirming the pattern shape by observing the pattern cross section, and those in which pattern collapse (significant pattern peeling, undercut, and line bottom thickening (footing)) did not occur were "good". , The one in which the pattern collapse occurred was evaluated as "defective”.
• Table 3 the example number of the resist underlayer film forming composition used will also be treated as an example number of various evaluations performed using the composition.
• Example 20 Evaluation of siloxane Bond Strength Ratio by FT-IR
• the coating liquid obtained in Example 20 was spin-coated on a silicon wafer and heated on a hot plate at 215 ° C. for 1 minute to form a silicon-containing resist underlayer.
• a film (B layer) 120 nm was formed.
• the silicon-containing resist underlayer film was formed by using the coating liquids obtained in Examples 21 to 38 and Comparative Example 2, respectively.

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