WO2016080226A1 - 架橋反応性シリコン含有膜形成組成物 - Google Patents
架橋反応性シリコン含有膜形成組成物 Download PDFInfo
- Publication number
- WO2016080226A1 WO2016080226A1 PCT/JP2015/081476 JP2015081476W WO2016080226A1 WO 2016080226 A1 WO2016080226 A1 WO 2016080226A1 JP 2015081476 W JP2015081476 W JP 2015081476W WO 2016080226 A1 WO2016080226 A1 WO 2016080226A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- film
- formula
- resist
- methyl
- Prior art date
Links
- 0 *CCCc1ccc2OCCOc2c1 Chemical compound *CCCc1ccc2OCCOc2c1 0.000 description 2
- QSNNGOUNLVCFPU-UHFFFAOYSA-N CCc1ccc2OCCOc2c1 Chemical compound CCc1ccc2OCCOc2c1 QSNNGOUNLVCFPU-UHFFFAOYSA-N 0.000 description 1
- CELWCAITJAEQNL-UHFFFAOYSA-N OC1OCCCC1 Chemical compound OC1OCCCC1 CELWCAITJAEQNL-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy 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
-
- 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
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
-
- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
Definitions
- the present invention relates to a film-forming composition using a hydrolyzable silane having a crosslinking reactive group.
- siloxane materials are used for improving heat resistance, transparency, plasma resistance, flatness, and the like. These materials generally have a siloxane crosslinking method by dehydration condensation of silanol. Another method for providing cross-linking is the introduction of acrylate groups into the silicone polymer (see Patent Document 1). It has been shown that these groups can be crosslinked and cured by irradiation with UV light.
- An organosiloxane using methylol crosslinking has also been proposed (see Patent Document 2). That is, it has been proposed to crosslink an organopolysiloxane using a composition containing at least two organopolysiloxane units and a nitrogen-containing compound having a methylol group. In addition, it has been proposed to use a composition having a cross-linking material using methylol cross-linking as a resist underlayer film used in a lithography process of a semiconductor device (see Patent Document 3).
- Conventional polysiloxanes having crosslinkability have undergone a crosslinking reaction between a functional group incorporated in the side chain of the polysiloxane, such as a functional group such as a carboxyl group, a hydroxyl group, and an epoxy group, and a crosslinkable compound. .
- a functional group such as a carboxyl group, a hydroxyl group, and an epoxy group
- a crosslinkable compound such as a functional group such as a carboxyl group, a hydroxyl group, and an epoxy group.
- the present invention introduces an alkoxymethylphenyl group that causes a crosslinking reaction into the side chain of the polysiloxane, and this crosslinking group forms a crosslinked structure with each other or with other components, thereby providing a sufficiently strong crosslinked structure. It is an object of the present invention to provide a composition having excellent chemical resistance.
- the present invention includes a hydrolyzable silane, a hydrolyzate thereof, or a hydrolyzed condensate thereof as a silane
- the hydrolyzable silane is represented by the formula (1):
- R 1 is Formula (2):
- R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group
- R 5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom.
- R 6 represents an alkyl group having 1 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms
- R 6 represents an alkyl group having 1 to 10 carbon atoms
- n1 represents an integer of 0 to 10
- n2 represents 0 or 1 N3
- n4 and n5 are integers
- n3 is 1 ⁇ n3 ⁇ 5
- n4 is 0 ⁇ n4 ⁇ 4
- n5 is 0 ⁇ n5 ⁇ 4
- k1 is n1 from 1 to 10.
- R 2 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or an organic group having a cyano group, Or a combination of these and bonded to a silicon atom by a Si—C bond.
- R 3 represents an alkoxy group, an acyloxy group, or a halogen group.
- a represents an integer of 1
- b represents an integer of 0 to 2
- a + b represents an integer of 1 to 3.
- the hydrolyzable silane is a combination of a hydrolyzable silane represented by the formula (1) and another hydrolyzable silane
- the other hydrolyzable silane is represented by the formula (3):
- R 7 is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkoxyalkyl group, alkoxyaryl group, alkoxyalkoxyaryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl.
- a hydrolyzable silane represented by formula (4) (In the formula (4), R 9 is an alkyl group and bonded to a silicon atom by a Si—C bond, R 10 represents an alkoxy group, an acyloxy group, or a halogen group, and Y represents an alkylene group or An arylene group, d is an integer of 0 or 1, and e is an integer of 0 or 1.) is at least one hydrolyzable silane selected from the group consisting of hydrolyzable silanes
- the film-forming composition according to the first aspect As a third aspect, a hydrolyzable silane hydrolysis condensate comprising a combination of a hydrolyzable silane represented by the formula (1) of the first viewpoint and a hydrolyzable silane represented by the formula (3) of the second viewpoint.
- a film-forming composition comprising as a polymer, As a fourth aspect, the film forming composition according to any one of the first aspect to the third aspect, further including a salt, As a fifth aspect, the film forming composition according to any one of the first aspect to the fourth aspect, wherein the film forming composition is a resist underlayer film forming composition used in a lithography process, As a sixth aspect, a resist underlayer film formed on a semiconductor substrate, comprising a cured product of the resist underlayer film forming composition according to the fifth aspect, As a seventh aspect, a step of applying the resist underlayer film forming composition according to the fifth aspect on a semiconductor substrate and baking to form a resist underlayer film, and applying a resist composition on the resist underlayer film to form a resist film A step of exposing the resist film, a step of developing the resist film after exposure to obtain a resist pattern, a step of etching the resist underlayer film with the resist pattern, and a patterned resist and resist underlayer film.
- a method of manufacturing a semiconductor device including a step of processing a semiconductor substrate;
- a step of forming an organic underlayer film on a semiconductor substrate, a step of applying and baking the resist underlayer film forming composition described in the fifth aspect thereon to form a resist underlayer film A step of forming a resist film by applying a resist composition thereon, a step of exposing the resist film, a step of developing the resist film after exposure to obtain a resist pattern, a step of etching the resist underlayer film with the resist pattern, a pattern
- R 6 represents an alkyl group having 1 to 10 carbon atoms having 1 to 10 alkoxy groups
- R 6 represents an alkyl group having 1 to 10 carbon atoms
- n1 represents an integer of 0 to 10
- n2 represents 0 or 1 N3
- n4 and n5 are integers
- n3 is 1 ⁇ n3 ⁇ 5
- n4 is 0 ⁇ n4 ⁇ 4
- n5 is 0 ⁇ n5 ⁇ 4
- k1 is n1 from 1 to 10.
- k2 represents a bond end with a silicon atom when n1 represents 0 and n2 represents 1, and k3 represents a bond end with n1 and n2 represents 0 Represents an end of a bond with a silicon atom.
- Si Those bonded to a silicon atom by a —C bond or Si—O bond.
- R 2 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or an organic group having a cyano group, Or a combination of these and bonded to a silicon atom by a Si—C bond.
- R 3 represents an alkoxy group, an acyloxy group, or a halogen group.
- a represents an integer of 1
- b represents an integer of 0 to 2
- a + b represents an integer of 1 to 3.
- this crosslinking group may form a crosslinking reaction with an electron-rich phenyl group. it can. Further, this alkoxymethylphenyl group can form a crosslinked structure with other hydroxyl groups, and can form a sufficiently strong crosslinked structure. Therefore, the film formed after curing of the composition of the present invention has excellent mechanical and chemical resistance.
- the film-forming composition of the present invention can form such an excellent film, it can be used as a film-forming composition for various applications.
- it can be used as a resist underlayer film forming composition for forming a resist underlayer film used in a multilayer process of semiconductor lithography by utilizing the etching resistance inherent in siloxane.
- the resist is thinned to prevent pattern collapse as the pattern is miniaturized.
- the combination of etching gas species changes the etching rate ratio of the siloxane layer and the organic layer.
- a process is performed in which the resist pattern is transferred to the silicon hard mask existing in the lower layer, further transferred to the organic lower layer film existing in the lower layer, and finally the silicon substrate is processed.
- the film forming composition of the present invention can also be used as a composition for forming a silicon hard mask (resist underlayer film) used in this process.
- the film-forming composition of the present invention is a silicon-based composition, and fills a hole in a substrate where flatness is required by adjusting the degree of curing by adjusting the temperature at which a crosslinking reaction with alkoxymethylphenyl groups occurs. It can be used as a material. That is, the film-forming composition of the present invention maintains fluidity in the temperature range below the temperature at which the crosslinking reaction by the alkoxymethylphenyl group occurs, so the composition first maintained at a temperature below the temperature at which the crosslinking reaction occurs. Is filled in fine holes on the substrate, and then the temperature is raised to cause a crosslinking reaction, thereby forming an effect of forming a highly planarized film sufficiently filled in the fine holes.
- FIG. 1 shows a cross-sectional view of the stepped substrate used in the hole-filling evaluation test.
- the present invention is a film-forming composition
- a hydrolyzable silane as a silane, a hydrolyzate thereof, or a hydrolysis condensate thereof wherein the hydrolyzable silane includes a hydrolyzable silane represented by the formula (1).
- the film-forming composition of the present invention contains a hydrolyzable silane represented by formula (1), a hydrolyzate thereof, or a hydrolyzed condensate thereof, and a solvent.
- acid, water, alcohol, curing catalyst, acid generator, other organic polymer, light-absorbing compound, surfactant and the like can be included.
- the solid content in the film-forming composition of the present invention is, for example, 0.1 to 50% by mass, or 0.1 to 30% by mass, or 0.1 to 25% by mass.
- the solid content is obtained by removing the solvent component from all components of the film-forming composition.
- the ratio of the hydrolyzable silane, its hydrolyzate, and its hydrolysis condensate in the solid content is 20% by mass or more, for example, 50 to 100% by mass, 60 to 99% by mass, 70 to 99% by mass. It is.
- hydrolyzable silane, its hydrolyzate, and its hydrolysis condensate can also be used as a mixture thereof. It can be used as a condensate obtained by hydrolyzing a hydrolyzable silane and condensing the obtained hydrolyzate.
- a hydrolysis condensate it is also possible to use a mixture obtained by mixing a hydrolysis product with a partially hydrolyzed product or a silane compound in which hydrolysis is not completely completed.
- This condensate is a polymer having a polysiloxane structure.
- the polysiloxane includes a hydrolyzable silane represented by the formula (1), or a hydrolyzable silane represented by the formula (1) and other hydrolyzable silanes (for example, a hydrolyzable silane represented by the formula (3)). And a hydrolytic condensate. Also, a hydrolyzable silane represented by formula (1) or a hydrolyzate of hydrolyzable silane comprising a combination of hydrolyzable represented by formula (1) and hydrolyzable silane represented by formula (3) From the mixture of the hydrolyzable silane represented by the formula (1) or the hydrolyzable silane represented by the formula (3) and the hydrolyzable silane represented by the formula (3) A hydrolyzable silane can be added.
- R 1 is an organic group represented by the formula (2) and is bonded to a silicon atom by a Si—C bond or a Si—O bond.
- R 2 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or an organic group having a cyano group, Or a combination of these and bonded to a silicon atom by a Si—C bond.
- R 3 represents an alkoxy group, an acyloxy group, or a halogen group.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group
- R 5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 1 carbon atoms.
- R 6 represents an alkyl group having 1 to 10 carbon atoms having 10 alkoxy groups
- R 6 represents an alkyl group having 1 to 10 carbon atoms
- n1 represents an integer of 0 to 10
- n2 represents an integer of 0 or 1 N3
- n4 and n5 are integers
- n3 is 1 ⁇ n3 ⁇ 5
- n4 is 0 ⁇ n4 ⁇ 4
- n5 is 0 ⁇ n5 ⁇ 4.
- a k1, a k2, or a k3 part represents a bonding end with a silicon atom
- k1 represents a bonding end with a silicon atom when n1 represents 1 to 10
- k2 represents n1 represents 0, and n2 represents 1 represents a bond end with a silicon atom
- k3 represents a bond end with a silicon atom when n1 and n2 represent 0.
- couples with a silicon atom in k1 part can be selected.
- the alkyl group is an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, or an s-butyl group.
- T-butyl group cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3- Methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclyl Ropropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-penty
- the aryl group is an aryl group having 6 to 40 carbon atoms, for example, a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, p -Chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl 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-phenanthryl group, 2-phenanthryl group, 3-phenanthryl
- the alkenyl group is, for example, an alkenyl group having 2 to 10 carbon atoms, and includes an ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3- Butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2 -Pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-buten
- the acyl group is, for example, an acyl group having 2 to 10 carbon atoms, such as methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, i-propylcarbonyl group, cyclopropylcarbonyl group, n-butylcarbonyl group, i- Butylcarbonyl group, s-butylcarbonyl group, t-butylcarbonyl group, cyclobutylcarbonyl group, 1-methyl-cyclopropylcarbonyl group, 2-methyl-cyclopropylcarbonyl group, n-pentylcarbonyl group, 1-methyl-n -Butylcarbonyl group, 2-methyl-n-butylcarbonyl group, 3-methyl-n-butylcarbonyl group, 1,1-dimethyl-n-propylcarbonyl group, 1,2-dimethyl-n-propylcarbonyl group, 2 , 2-Dimethyl-n-propy
- Examples of the organic group having an epoxy group include glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, and epoxycyclohexyl.
- Examples of the organic group having an acryloyl group include acryloylmethyl, acryloylethyl, acryloylpropyl, and the like.
- Examples of the organic group having a methacryloyl group include methacryloylmethyl, methacryloylethyl, methacryloylpropyl, and the like.
- Examples of the organic group having a mercapto group include ethyl mercapto, butyl mercapto, hexyl mercapto, octyl mercapto and the like.
- Examples of the organic group having an amino group include an amino group, an aminomethyl group, and an aminoethyl group.
- Examples of the organic group having a cyano group include cyanoethyl and cyanopropyl.
- alkoxy group having 1 to 20 carbon atoms or the alkoxy group having 1 to 10 carbon atoms include alkoxy groups having a linear, branched or cyclic alkyl moiety having 1 to 20 carbon atoms, such as a methoxy group and an ethoxy group.
- Examples of the acyloxy group having 2 to 20 carbon atoms and 1 to 10 carbon atoms include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, and an n-butylcarbonyloxy group.
- halogen group examples include fluorine, chlorine, bromine and iodine.
- the hydrolyzable silane can be used as a combination of the hydrolyzable silane represented by the formula (1) and other hydrolyzable silanes.
- R 7 is an alkyl group, aryl group, halogenated alkyl group, halogenated aryl group, alkoxyalkyl group, alkoxyaryl group, alkoxyalkoxyaryl group, alkenyl group, or epoxy group, acryloyl group, methacryloyl group.
- R 9 is an alkyl group and bonded to a silicon atom by a Si—C bond
- R 10 represents an alkoxy group, an acyloxy group, or a halogen group
- Y represents an alkylene group or an arylene group Represents a group
- d represents an integer of 0 or 1
- e represents an integer of 0 or 1.
- the organic group having a cyano group, an alkoxy group, an acyloxy group, and a halogen group the above-mentioned examples can be used.
- An alkoxyalkyl group is an alkyl group substituted by an alkoxy group, and examples thereof include a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, and an ethoxymethyl group.
- An alkoxyaryl group is an aryl group substituted by an alkoxy group, and examples thereof include a methoxyphenyl group and an ethoxyphenyl group.
- the alkoxyalkoxyaryl group is an aryl group substituted by an organic group in which an alkoxy group is substituted with an alkoxy group, and examples thereof include a methoxymethoxyphenyl group, a methoxyethoxyphenyl group, an ethoxymethoxyphenyl group, and an ethoxyethoxyphenyl group.
- the film-forming composition can contain, as a polymer, a hydrolysis condensate of a hydrolyzable silane composed of a combination of a hydrolyzable silane represented by the formula (1) and a hydrolyzable silane represented by the formula (3).
- Examples of the hydrolyzable silane represented by the formula (1) are as follows. Me represents a methyl group, and Et represents an ethyl group. Hereinafter, these abbreviations may be used in the present specification.
- the hydrolyzable silane is a combination of the hydrolyzable silane represented by the formula (1) and other hydrolyzable silanes, and the other hydrolyzable silanes are derived from the formulas (3) and (4). At least one hydrolyzable silane selected from the group can be used.
- Examples of the silicon-containing compound represented by the formula (3) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, and methyltrimethoxysilane.
- Methyltrichlorosilane methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane Glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane ⁇ -glycidoxyethyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysi
- hydrolyzable silanes can also be used.
- Examples of the silicon-containing compound represented by the formula (4) include methylene bistrimethoxysilane, methylene bistrichlorosilane, methylene bistriacetoxysilane, ethylene bistriethoxysilane, ethylene bistrichlorosilane, ethylene bistriacetoxysilane, propylene bistriethoxysilane, and butylene bistrimethoxysilane.
- a silane having a sulfone group or a silane having a sulfonamide group can be used as the hydrolyzable silane, and examples thereof include the following.
- hydrolysis-condensation product polysiloxane
- the hydrolyzable condensate (polyorganosiloxane) of the hydrolyzable silane can obtain a condensate having a weight average molecular weight of 1,000 to 1,000,000, or 1,000 to 100,000. These molecular weights are molecular weights obtained in terms of polystyrene by GPC analysis.
- GPC measurement conditions are, for example, GPC apparatus (trade name HLC-8220 GPC, manufactured by Tosoh Corporation), GPC column (trade names Shodex KF803L, KF802, KF801, Showa Denko), column temperature is 40 ° C., and eluent (elution solvent) Is tetrahydrofuran, the flow rate (flow rate) is 1.0 ml / min, and the standard sample is polystyrene (made by Showa Denko KK).
- hydrolysis of the alkoxysilyl group, acyloxysilyl group, or halogenated silyl group 0.5 to 100 mol, preferably 1 to 10 mol of water is used per mol of the hydrolyzable group. Further, 0.001 to 10 mol, preferably 0.001 to 1 mol of hydrolysis catalyst can be used per mol of the hydrolyzable group.
- the reaction temperature during the hydrolysis and condensation is usually 20 to 80 ° C.
- Hydrolysis may be performed completely or partially. That is, a hydrolyzate or a monomer may remain in the hydrolysis condensate.
- a catalyst can be used in the hydrolysis and condensation. Examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.
- Examples of the metal chelate compound as the hydrolysis catalyst include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri -N-Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxy bis (acetylacetonato) titanium , Di-n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (Acetylacetonate) titanium, di-t Butoxy bis (acetylacetonato) titanium, monoethoxy tris (acetylacetonato) titanium
- Organic acids as hydrolysis catalysts are, 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 Acid, gallic acid, butyric acid, merit acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthal
- Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and the like.
- Organic bases as hydrolysis catalysts include, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazine.
- the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and the like. Of these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.
- organic solvent used in the hydrolysis examples include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i- Aliphatic hydrocarbon solvents such as octane, cyclohexane and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethylbenzene, i-butylbenzene, triethylbenzene, di -Aromatic hydrocarbon solvents such as i-propyl benzene, n-amyl naphthalene, trimethylbenzene; methanol, ethanol, ethanol
- acetone methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di- Ketone solvents such as i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchon are preferred from the viewpoint of storage stability of the solution.
- bisphenol S or a bisphenol S derivative can be added as an additive.
- Bisphenol S or a bisphenol S derivative is 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyorganosiloxane.
- Preferred bisphenol S or bisphenol S derivatives are exemplified below.
- the film-forming composition of the present invention can contain a curing catalyst.
- the curing catalyst functions as a curing catalyst when a coating film containing polyorganosiloxane composed of a hydrolysis condensate is heated and cured.
- ammonium salts, phosphines, phosphonium salts, and sulfonium salts can be used.
- the formula (D-1) (Wherein m is an integer of 2 to 11, n is an integer of 2 to 3, R 21 is an alkyl group or an aryl group, and Y A ⁇ is an anion.)
- the formula (D-7) (However, R 31 , R 32 , R 33 , and R 34 represent an alkyl group or an aryl group, P represents a phosphorus atom, Y A ⁇ represents an anion, and R 31 , R 32 , R 33 , and R 34 are each linked to a phosphorus atom by a CP bond).
- the formula (D-8) (However, R 35 , R 36 , and R 37 represent an alkyl group or an aryl group, S represents a sulfur atom, Y A ⁇ represents an anion, and R 35 , R 36 , and R 37 represent C—S, respectively. And a tertiary sulfonium salt which is bonded to a sulfur atom by a bond).
- the compound represented by the formula (D-1) is a quaternary ammonium salt derived from an amine, m represents an integer of 2 to 11, and n represents an integer of 2 to 3.
- R 21 of this quaternary ammonium salt represents an alkyl group or aryl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as a linear alkyl group such as an ethyl group, a propyl group or a butyl group, or a benzyl group. Cyclohexyl group, cyclohexylmethyl group, dicyclopentadienyl group and the like.
- Anions (Y A ⁇ ) include halogen ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 ⁇ ). And acid groups such as alcoholate (—O ⁇ ).
- R 22 R 23 R 24 R 25 N + Y A - is a quaternary ammonium salt represented by.
- R 22 , R 23 , R 24 and R 25 are an alkyl group or aryl group having 1 to 18 carbon atoms, or a silane compound bonded to a silicon atom by a Si—C bond.
- Anions (Y A ⁇ ) are halogen ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 ⁇ ).
- This quaternary ammonium salt can be obtained commercially, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzyl chloride. Examples include ammonium and trimethylbenzylammonium chloride.
- the compound represented by the above formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole
- R 26 and R 27 are an alkyl group or an aryl group having 1 to 18 carbon atoms
- the total number of carbon atoms of R 26 and R 27 is preferably 7 or more.
- R 26 can be exemplified by methyl group, ethyl group, propyl group, phenyl group and benzyl group
- R 27 can be exemplified by benzyl group, octyl group and octadecyl group.
- Anions (Y A ⁇ ) are halogen ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 ⁇ ). And acid groups such as alcoholate (—O ⁇ ).
- This compound can be obtained as a commercial product.
- imidazole compounds such as 1-methylimidazole and 1-benzylimidazole are reacted with alkyl halides and aryl halides such as benzyl bromide and methyl bromide. Can be manufactured.
- the compound represented by the above formula (D-4) is a quaternary ammonium salt derived from pyridine, and R 28 is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms.
- R 28 is an alkyl or aryl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms.
- Anions (Y A ⁇ ) are halogen ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 ⁇ ).
- this compound can be obtained as a commercial product, it is produced, for example, by reacting pyridine with an alkyl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or an aryl halide. I can do it. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.
- the compound represented by the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by picoline or the like, and R 29 is an alkyl having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms. Group or aryl group, for example, methyl group, octyl group, lauryl group, benzyl group and the like.
- R 30 is an alkyl group or aryl group having 1 to 18 carbon atoms. For example, in the case of quaternary ammonium derived from picoline, R 30 is a methyl group.
- Anions (Y A ⁇ ) are halogen ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 ⁇ ). And acid groups such as alcoholate (—O ⁇ ).
- This compound can also be obtained as a commercial product. 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 represented by the above formula (D-6) is a tertiary ammonium salt derived from an amine, m represents an integer of 2 to 11, and n represents an integer of 2 to 3.
- Anions (Y A ⁇ ) include halogen ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 ⁇ ). And acid groups such as alcoholate (—O ⁇ ). It can be produced by reacting an amine with a weak acid such as carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid.
- the anion (Y A ⁇ ) When formic acid is used, the anion (Y A ⁇ ) is (HCOO ⁇ ), and when acetic acid is used, the anion (Y A ⁇ ) is (CH 3 COO ⁇ ). When phenol is used, the anion (Y A ⁇ ) is (C 6 H 5 O ⁇ ).
- the compound represented by the above formula (D-7) is a quaternary phosphonium salt having a structure represented by R 31 R 32 R 33 R 34 P + Y A — .
- R 31 , R 32 , R 33 , and R 34 are an alkyl group or aryl group having 1 to 18 carbon atoms, or a silane compound bonded to a silicon atom by a Si—C bond, preferably R 31 to R 34 of the four substituents of 34 are a phenyl group or a substituted phenyl group, and examples thereof include a phenyl group and a tolyl group, and the remaining one is an alkyl group having 1 to 18 carbon atoms, A silane compound bonded to a silicon atom by an aryl group or Si—C bond.
- Anions (Y A ⁇ ) include halogen ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 ⁇ ). And acid groups such as alcoholate (—O ⁇ ).
- This compound can be obtained as a commercial product, for example, a halogenated tetraalkylphosphonium such as tetra-n-butylphosphonium halide, tetra-n-propylphosphonium halide, or a trialkylbenzyl halide such as triethylbenzylphosphonium halide.
- Triphenylmonoalkylphosphonium halides such as phosphonium, triphenylmethylphosphonium halide, triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritolylmonoarylphosphonium halide, or tritolyl monohalogenate Examples thereof include alkylphosphonium (the halogen atom is a chlorine atom or a bromine atom).
- halogens such as triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide, triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, and halogens such as tritolylmonophenylphosphonium halide.
- Preferred is a tolylyl monoarylphosphonium halide, or a tolyl monoalkylphosphonium halide such as a tolyl monomethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).
- the phosphines include methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, phenylphosphine and the like first phosphine, dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, diphenylphosphine and the like.
- tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.
- the compound represented by the above formula (D-8) is a tertiary sulfonium salt having a structure represented by R 35 R 36 R 37 S + Y A — .
- R 35 , R 36 , and R 37 are alkyl or aryl groups having 1 to 18 carbon atoms, or a silane compound bonded to a silicon atom through a Si—C bond, preferably 4 of R 35 to R 37 .
- Three of the substituents are phenyl groups or substituted phenyl groups, and examples thereof include phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group. It is.
- Anions (Y A ⁇ ) include halogen ions such as chlorine ions (Cl ⁇ ), bromine ions (Br ⁇ ), iodine ions (I ⁇ ), carboxylates (—COO ⁇ ), sulfonates (—SO 3 ⁇ ). ), Alcoholate (—O ⁇ ), maleate anion, nitrate anion and the like. This compound is available as a commercial product.
- halogenated tetraalkylsulfonium such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide
- trialkylbenzyl halide such as diethylbenzylsulfonium halide.
- Halogenated diphenylmonoalkylsulfonium such as sulfonium, halogenated diphenylmethylsulfonium, halogenated diphenylethylsulfonium, halogenated triphenylsulfonium, (halogen atom is chlorine or bromine atom), tri-n-butylsulfonium carboxylate, tri-n- Tetraalkylphosphonium carboxylates such as propylsulfonium carboxylate and trialkylbenzines such as diethylbenzylsulfonium carboxylate Sulfonium carboxylate, diphenylmethyl sulfonium carboxylate, diphenyl monoalkyl sulfonium carboxylate, triphenylsulfonium carboxylate such as diphenylethyl sulfonium carboxylate. Further, triphenylsulfonium halide and triphenylsulfonium carboxylate can
- a nitrogen-containing silane compound can be added as a curing catalyst.
- the nitrogen-containing silane compound include imidazole ring-containing silane compounds such as N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole.
- the curing catalyst is 0.01 to 10 parts by mass, 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyorganosiloxane.
- Hydrolyzable silane is hydrolyzed using a catalyst in a solvent to condense, and the resulting hydrolyzed condensate (polymer) simultaneously removes by-product alcohol, used hydrolysis catalyst, and water by distillation under reduced pressure. be able to.
- the acid and base catalyst used for hydrolysis can be removed by neutralization or ion exchange.
- the organic acid, water, alcohol, or those combination can be added to the film formation composition of this invention for stabilization of the film formation composition containing the hydrolysis-condensation product.
- organic acid examples include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid, and salicylic acid. Of these, oxalic acid and maleic acid are preferred.
- the organic acid to be added is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the condensate (polyorganosiloxane).
- pure water, ultrapure water, ion exchange water, etc. can be used for the water to add, The addition amount can be 1 thru
- alcohol to add what is easy to be scattered by the heating after application
- coating is preferable, for example, methanol, ethanol, propanol, isopropanol, a butanol etc. are mentioned.
- the added alcohol can be 1 to 20 parts by mass with respect to 100 parts by mass of the film-forming composition.
- the film-forming composition of the present invention can contain an organic polymer compound, a photoacid generator, a surfactant and the like as necessary in addition to the above-described components.
- the organic polymer compound is not particularly limited, and various organic polymers can be used. Polycondensation polymers and addition polymerization polymers can be used. Addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolak, naphthol novolak, polyether, polyamide, and polycarbonate can be used.
- An organic polymer having an aromatic ring structure such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, and a quinoxaline ring that functions as a light absorption site is preferably used.
- organic polymer compounds include addition polymerizable monomers 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 as a structural unit, and polycondensation polymers such as phenol novolac and naphthol novolak.
- the polymer compound When an addition polymerization polymer is used as the organic polymer compound, the polymer compound may be a homopolymer or a copolymer.
- An addition polymerizable monomer is used for the production of the addition polymerization polymer.
- examples of such addition polymerizable monomers include acrylic acid, methacrylic acid, acrylic ester compounds, methacrylic ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile and the like. It is done.
- acrylic ester compounds include methyl acrylate, ethyl acrylate, normal hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthryl methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-Methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy Examples thereof include silic-6-lactone, 3-acryloxypropyltriethoxysilane, and glycidyl acryl
- Methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthryl methyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2, 2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5 -Methacryloyloxy-6-hydroxynorbornene-2-carboxyl Examples include ku-6-lactone, 3-methacryloxypropyltriethoxysilane,
- acrylamide compound examples include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N, N-dimethylacrylamide and N-anthrylacrylamide.
- methacrylamide compounds include methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-benzyl methacrylamide, N-phenyl methacrylamide, N, N-dimethyl methacrylamide and N-anthryl acrylamide. .
- vinyl compounds include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene. Can be mentioned.
- styrene compound examples include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.
- maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and N-hydroxyethylmaleimide.
- examples of such a polymer include a polycondensation polymer of a glycol compound and a dicarboxylic acid compound.
- examples of the glycol compound include diethylene glycol, hexamethylene glycol, butylene glycol and the like.
- examples of the dicarboxylic acid compound include succinic acid, adipic acid, terephthalic acid, maleic anhydride and the like.
- examples thereof include polyesters such as polypyromellitimide, poly (p-phenylene terephthalamide), polybutylene terephthalate, polyethylene terephthalate, polyamide, and polyimide.
- the organic polymer compound contains a hydroxyl group
- the hydroxyl group can form a crosslinking reaction with the polyorganosiloxane.
- the organic polymer compound a polymer compound having a weight average molecular weight of, for example, 1,000 to 1,000,000, 3,000 to 300,000, 5,000 to 200,000, or 10,000 to 100,000 can be used. Only one organic polymer compound can be used, or two or more organic polymer compounds can be used in combination. When the organic polymer compound is used, the proportion thereof is 1 to 200 parts by mass, 5 to 100 parts by mass, or 10 to 50 parts by mass, or 20 with respect to 100 parts by mass of the condensate (polyorganosiloxane). Thru
- the film forming composition of the present invention may contain an acid generator.
- the acid generator include a thermal acid generator and a photoacid generator.
- the photoacid generator contained in the film-forming composition of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.
- onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormalbutanesulfonate, diphenyliodonium perfluoronormaloctanesulfonate, diphenyliodoniumcamphorsulfonate, bis (4-tert-butylphenyl) iodoniumcamphor.
- Iodonium salt compounds such as sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenyls Sulfonium salt compounds such as phosphonium trifluoromethanesulfonate, and the like.
- sulfonimide compounds include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormalbutanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide. Can be mentioned.
- disulfonyldiazomethane compound examples include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and bis (2,4-dimethylbenzenesulfonyl). And diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.
- a photo-acid generator can use only 1 type, or can be used in combination of 2 or more type.
- the proportion thereof is 0.01 to 5 parts by mass, 0.1 to 3 parts by mass, or 0.5 with respect to 100 parts by mass of the condensate (polyorganosiloxane). Thru
- the surfactant is effective in suppressing the occurrence of pinholes and installations when the film-forming composition of the present invention is applied to a substrate as a resist underlayer film-forming composition for lithography.
- the surfactant contained in the film-forming composition of the present invention include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, Polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan Sorbitan fatty acid esters such as monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monora Nonionic surfactants such as polyoxy
- surfactants may be used alone or in combination of two or more.
- the ratio is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 1 with respect to 100 parts by mass of the condensate (polyorganosiloxane). Part by mass.
- a rheology adjusting agent, an adhesion aid and the like can be added to the film forming composition of the present invention.
- the rheology modifier is effective in improving the fluidity of the film-forming composition.
- the adhesion aid is effective for improving the adhesion between the semiconductor substrate or resist and the lower layer film.
- any solvent can be used without particular limitation as long as it can dissolve the solid content.
- solvents include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate , Ethyl
- the film forming composition can be used as a resist underlayer film forming composition used in a lithography process.
- a resist underlayer film-forming composition comprising the film-forming composition of the present invention is applied by an appropriate coating method such as a spinner or a coater, and then baked to form a resist underlayer film.
- the conditions for firing are appropriately selected from firing temperatures of 80 ° C. to 250 ° C. and firing times of 0.3 to 60 minutes.
- the firing temperature is 150 ° C. to 250 ° C.
- the firing time is 0.5 to 2 minutes.
- the film thickness of the resist underlayer film of the present invention to be formed is, for example, 10 to 1000 nm, 20 to 500 nm, 50 to 300 nm, or 100 to 200 nm.
- a photoresist layer is formed on the resist underlayer film. Formation of the photoresist layer can be performed by a well-known method, that is, by applying a photoresist composition solution onto the lower layer film and baking.
- the film thickness of the photoresist is, for example, 50 to 10,000 nm, 100 to 2000 nm, or 200 to 1000 nm.
- the resist underlayer film of the present invention can be formed thereon, and a photoresist can be further coated thereon.
- the substrate can be processed by selecting an appropriate etching gas.
- an appropriate etching gas For example, it is possible to process the resist underlayer film of the present invention using a fluorine-based gas that has a sufficiently high etching rate for photoresist as an etching gas, and a sufficiently high etching rate for the resist underlayer film of the present invention.
- the organic underlayer film can be processed using an oxygen-based gas as an etching gas, and the substrate can be processed using a fluorine-based gas that provides a sufficiently high etching rate for the organic underlayer film as an etching gas.
- the photoresist formed on the resist underlayer film of the present invention is not particularly limited as long as it is sensitive to light used for exposure. Either a negative photoresist or a positive photoresist can be used.
- a positive photoresist comprising a novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist comprising a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, an acid
- a chemically amplified photoresist comprising a low-molecular compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate
- a chemically amplified photoresist composed of a low molecular weight compound that de
- Examples include trade name APEX-E manufactured by Shipley, trade name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and trade name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), Proc. SPIE, Vol. 3999, 365-374 (2000), and fluorine-containing polymer-based photoresists.
- a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), or the like can be used.
- post-exposure bake can be performed as necessary.
- the post-exposure heating is performed under conditions appropriately selected from a heating temperature of 70 ° C. to 150 ° C. and a heating time of 0.3 to 10 minutes.
- a resist for electron beam lithography or a resist for EUV lithography can be used instead of a photoresist as a resist.
- the electron beam resist either a negative type or a positive type can be used.
- Chemically amplified resist comprising a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate, a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist
- a chemically amplified resist comprising: a binder having a group that decomposes with an acid generator and an acid to change the alkali dissolution rate; and a chemically amplified resist comprising a low-molecular compound that decomposes with an acid to change the alkali dissolution rate of the resist,
- non-chemically amplified resists composed of a binder having a group that changes the alkali dissolution rate by being
- developer for example, an alkali developer
- a developer for example, an alkali developer
- Developers include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine, propylamine,
- An alkaline aqueous solution such as an aqueous amine solution such as ethylenediamine can be mentioned as an example.
- 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 to 600 seconds.
- an organic solvent can be used as a developer.
- development is performed with a developer (solvent).
- a developer solvent
- Developers include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxy acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl Ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl Cetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-me
- the resist underlayer film (intermediate layer) of the present invention is removed using the photoresist (upper layer) pattern thus formed as a protective film, and then the patterned photoresist and the resist underlayer film of the present invention are removed.
- the organic underlayer film (lower layer) is removed using the film made of (intermediate layer) as a protective film.
- the semiconductor substrate is processed using the patterned resist underlayer film (intermediate layer) and organic underlayer film (lower layer) of the present invention as a protective film.
- the resist underlayer film (intermediate layer) of the present invention in a portion where the photoresist has been removed is removed by dry etching to expose the semiconductor substrate.
- dry etching of the resist underlayer film of the present invention tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, carbon monoxide, argon, oxygen, Gases such as nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used.
- a halogen-based gas for dry etching of the resist underlayer film.
- a photoresist made of an organic substance is basically difficult to remove.
- the resist underlayer film of the present invention containing a large amount of silicon atoms is quickly removed by the halogen-based gas. Therefore, it is possible to suppress a decrease in the thickness of the photoresist accompanying dry etching of the resist underlayer film. As a result, the photoresist can be used as a thin film.
- the dry etching of the resist underlayer film is preferably performed using a fluorine-based gas.
- fluorine-based gas examples include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), and perfluoropropane (C 3 F 8 ). , Trifluoromethane, and difluoromethane (CH 2 F 2 ).
- the organic underlayer film is removed using the patterned photoresist and the film made of the resist underlayer film of the present invention as a protective film.
- the organic underlayer film (underlayer) is preferably formed by dry etching with an oxygen-based gas. This is because the resist underlayer film of the present invention containing a large amount of silicon atoms is difficult to remove by dry etching with an oxygen-based gas.
- the processing of the semiconductor substrate is preferably performed by dry etching with a fluorine-based gas.
- 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 ). Can be mentioned.
- an organic antireflection film can be formed on the resist underlayer film of the present invention before the formation of the photoresist.
- the antireflective coating composition used there is not particularly limited, and can be arbitrarily selected from those conventionally used in the lithography process, and can be used by a conventional method such as a spinner.
- the antireflection film can be formed by coating and baking with a coater.
- the substrate to which the resist underlayer film forming composition comprising the film forming composition 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.
- the resist underlayer film of the present invention can be formed thereon.
- the resist underlayer film formed from the resist underlayer film forming composition of the present invention may also absorb light depending on the wavelength of light used in the lithography process. In such a case, it can function as an antireflection film having an effect of preventing reflected light from the substrate. Furthermore, the resist underlayer film of the present invention is a layer for preventing the interaction between the substrate and the photoresist, the material used for the photoresist, or the function for preventing the adverse effect on the substrate of the material generated upon exposure to the photoresist.
- a layer having a function of preventing diffusion of the material generated from the substrate upon heating and baking into the upper layer photoresist It is also possible to do.
- the resist underlayer film formed from the resist underlayer film forming composition of the present invention is applied to a substrate on which via holes used in the dual damascene process are formed, and a hole filling material (embedding material) that can fill the holes without gaps. ) Can be used. Moreover, it can also be used as a planarizing material for planarizing the surface of an uneven semiconductor substrate.
- the lower layer film of the EUV resist can be used for the following purposes. Without intermixing with the EUV resist, it is possible to prevent reflection of unwanted exposure light such as UV and DUV (ArF light, KrF light) from the substrate or interface during EUV exposure (wavelength 13.5 nm).
- the resist underlayer film forming composition can be used as a resist underlayer antireflection film. Reflection can be efficiently prevented in the lower layer of the EUV resist.
- the process can be performed in the same manner as the photoresist underlayer film.
- R 1 represents formula (2 ′) And is bonded to a silicon atom by a Si—C bond or a Si—O bond.
- R 2 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkoxyaryl group, an alkenyl group, or an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or an organic group having a cyano group, Or a combination of these and bonded to a silicon atom by a Si—C bond.
- R 3 represents an alkoxy group, an acyloxy group, or a halogen group.
- a represents an integer of 1
- b represents an integer of 0 to 2
- a + b represents an integer of 1 to 3.
- R 4 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group
- R 5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom.
- R 6 represents an alkyl group having 1 to 10 carbon atoms
- n1 represents an integer of 0 to 10
- n2 represents 0 or 1 N3, n4 and n5 are integers
- n3 is 1 ⁇ n3 ⁇ 5, n4 is 0 ⁇ n4 ⁇ 4, and n5 is 0 ⁇ n5 ⁇ 4.
- K1 represents a bond end with a silicon atom when n1 represents 1 to 10
- k2 represents a bond end with a silicon atom when n1 represents 0 and n2 represents 1, and k3 represents n1. And when n2 shows 0, the bond end with a silicon atom is shown. What bind
- couples with a silicon atom in k1 part can be selected.
- hydrolyzable silane compound represented by the formula (1 ′) examples include the above formula (1-1), formula (1-2), formula (1-3), formula (1-5), formula (1- Examples thereof include compounds represented by 6), formula (1-7), formula (1-8) and formula (1-10). Further, 4- (trimethoxysilyl) benzyl acetate, 4- (triethoxysilyl) benzyl acetate and the like can be mentioned. A compound in which n2 is an integer of 1 in formula (1 ′) can be shown.
- the reaction solution A (containing 4- (1-ethoxyethoxy) -2,6-dimethylbromobenzene (containing 4-EOEO-2,6-DMePhBr)) was prepared by neutralizing with triethylamine (TEA) 0.63 g. After adding 6.09 g of dried magnesium powder, 0.53 g of iodine, and 189.2 g of tetrahydrofuran (dehydrated) to a 500 ml three-necked flask equipped with a stirrer chip and heating in an oil bath at 60 ° C. until the color of iodine disappears The reaction solution A was dropped at room temperature and reacted for 2 hours to obtain a reaction solution B.
- TAA triethylamine
- TMOS tetramethoxysilane
- 189.2 g of tetrahydrofuran dehydrated
- Reaction solution B was added dropwise at room temperature and reacted for 2 hours.
- the resulting solution was concentrated by evaporation, 500 ml of heptane solution was added, stirred and filtered.
- the obtained filtrate was concentrated and purified by distillation under reduced pressure to obtain the desired product (4- (1-ethoxyethoxy) -2,6-dimethylphenyl) trimethoxysilane (4-EOEO-2,6-DMePhTMOS). 35 g was obtained.
- the temperature was returned to room temperature, 56.157 g of ethyl acetate and 28.08 g of water were added, and the mixture was neutralized with 0.1N aqueous acetic acid solution. After transferring to a separatory funnel and washing three times with water, 25 g of propylene glycol monomethyl ether acetate was added, and the organic layer was concentrated to perform solvent replacement.
- the obtained polymer corresponds to the formula (3-2) as the polymer 2, and the molecular weight was Mw12800.
- the obtained polymer corresponds to the formula (3-5) as the polymer 5, and the molecular weight was Mw 5200.
- the obtained polymer corresponds to the formula (3-7) as the polymer 7, and the molecular weight was Mw 5600.
- the obtained polymer corresponds to the formula (3-8) as the polymer 8, and the molecular weight was Mw4300.
- the obtained polymer corresponds to the formula (3-9) as the polymer 9, and the molecular weight was Mw 4800.
- the temperature was returned to room temperature, 129.81 g of ethyl acetate was added, and the mixture was neutralized with 0.2N hydrochloric acid aqueous solution. After transferring to a separatory funnel and washing three times with water, 25 g of propylene glycol monomethyl ether acetate was added, and the organic layer was concentrated to perform solvent replacement.
- the obtained polymer corresponds to the formula (3-10) as the polymer 10, and the molecular weight was Mw 1500.
- the temperature was returned to room temperature, 33.77 g of ethyl acetate was added, and the mixture was neutralized with 0.2N hydrochloric acid aqueous solution. After transferring to a separatory funnel and washing three times with water, 25 g of propylene glycol monomethyl ether acetate was added, and the organic layer was concentrated to perform solvent replacement.
- the obtained polymer was a polymer 11 corresponding to the formula (3-11), and the molecular weight was Mw3500.
- the temperature was returned to room temperature, 62.00 g of ethyl acetate was added, and the mixture was neutralized with an aqueous 0.1N acetic acid solution. After transferring to a separatory funnel and washing three times with water, 30 g of propylene glycol monomethyl ether acetate was added, and the organic layer was concentrated to perform solvent replacement.
- the obtained polymer corresponds to the formula (3-12) as the polymer 12, and the molecular weight was Mw 4000.
- the obtained polymer corresponds to the formula (3-13) as the polymer 13, and the molecular weight was Mw2800.
- the temperature was returned to room temperature, 62.00 g of ethyl acetate was added, and the mixture was neutralized with an aqueous 0.1N acetic acid solution. After transferring to a separatory funnel and washing three times with water, 30 g of propylene glycol monomethyl ether acetate was added, and the organic layer was concentrated to perform solvent replacement.
- the obtained polymer corresponds to the formula (3-14) as the polymer 14, and the molecular weight was Mw3800.
- the temperature was returned to room temperature, 73.33 g of ethyl acetate was added, and the mixture was neutralized with a 0.1N acetic acid aqueous solution. After transferring to a separatory funnel and washing three times with water, 25 g of propylene glycol monomethyl ether acetate was added, and the organic layer was concentrated to perform solvent replacement.
- the obtained polymer corresponds to the formula (4-1) as the polymer 12, and the molecular weight was Mw5200.
- triphenylsulfonium trifluoromethanesulfonate is TPS105
- p-toluenesulfonic acid pyridinium salt is pPTS
- propylene glycol monomethyl ether acetate is PGMEA
- propylene glycol monomethyl ether is PGME
- DIC nonionic surfactant is R30N ( Product name).
- water ultrapure water was used. Each addition amount was shown in parts by mass.
- the mixture is filtered using a polyethylene microfilter having a pore size of 0.10 ⁇ m, and further filtered using a polyethylene microfilter having a pore size of 0.05 ⁇ m, so that the organic resist underlayer film forming composition used in the lithography process using a multilayer film is formed.
- a solution was prepared.
- the organic resist underlayer film forming composition was applied onto a silicon wafer and baked on a hot plate at 240 ° C. for 60 seconds to obtain an organic resist underlayer film having a thickness of 200 nm. Furthermore, the curable resin compositions prepared in Examples 1 to 10, Examples 13 to 15 and Comparative Example 1 were applied by a spinner. Then, it baked on a 215 degreeC hotplate for 1 minute, and formed the cured resin film (film thickness 0.08 micrometer). A commercially available photoresist solution (trade name: TDUR-P3435LP, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto the film with a spinner, and heated on a hot plate at 90 ° C.
- the curable resin compositions of Examples 1 to 15 and Comparative Examples 1 and 2 are applied onto the stepped substrate 2 using a spin coater, and then heated on a hot plate at 215 ° C. for 1 minute. As a result, a curable resin film 1 having a thickness of 180 nm was formed.
- a hole pattern made of CVD-TEOS having a height of 300 nm and a minimum width of 20 nm was used for the stepped substrate.
- the hole filling shape (embedding property) of the obtained substrate was observed with a cross-sectional SEM, and the hole filling characteristics were evaluated. A case where good embedding property was exhibited without generation of voids was regarded as good.
- the film forming composition of the present invention has good curability and good embedding in a stepped substrate.
- a good shape can be exhibited after exposure, development and etching. It can be used as a film forming composition having good effects such as curability and embedding property, and a resist underlayer film used in a lithography process of a semiconductor device.
Abstract
Description
即ち、少なくとも2つのオルガノポリシロキサン単位とメチロール基を有する含窒素化合物とを含む組成物を用いてオルガノポリシロキサンを架橋することが提案されている。
また、メチロール架橋を使った架橋材を有する組成物を半導体装置のリソグラフィー工程に用いるレジスト下層膜として用いることが提案されている(特許文献3参照)。
これら架橋システムでは低分子架橋剤が架橋反応に関与していて架橋不良がしばしば発生していた。
〔式(1)中、R1は式(2):
(式(2)中、R4は水素原子、炭素原子数1乃至10のアルキル基、又はアシル基を示し、R5は水素原子、炭素原子数1乃至10のアルキル基、又は炭素原子数1乃至10のアルコキシ基を有する炭素原子数1乃至10のアルキル基を示し、R6は炭素原子数1乃至10のアルキル基を示し、n1は0乃至10の整数を示し、n2は0又は1の整数を示し、n3、n4及びn5は整数であって、n3は1≦n3≦5、n4は0≦n4≦4、n5は0≦n5≦4を示す。そしてk1はn1が1乃至10を示すときの、ケイ素原子との結合端を示し、k2はn1が0を示し及びn2が1を示すときの、ケイ素原子との結合端を示し、k3はn1及びn2が0を示すときの、ケイ素原子との結合端を示す。)で示される有機基であり且つSi-C結合又はSi-O結合によりケイ素原子と結合しているものである。R2はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、アミノ基、もしくはシアノ基を有する有機基、又はこれらの組み合わせであり且つSi-C結合によりケイ素原子と結合しているものである。R3はアルコキシ基、アシルオキシ基、又はハロゲン基を示す。aは1の整数を示し、bは0乃至2の整数を示し、a+bは1乃至3の整数を示す。〕で示される加水分解性シランを含む膜形成組成物、
第2観点として、該加水分解性シランが、式(1)で示される加水分解性シランとその他の加水分解性シランの組み合わせであり、その他の加水分解性シランが式(3):
(式(3)中、R7はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアルキル基、アルコキシアリール基、アルコキシアルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、スルホンアミド基、もしくはシアノ基を有する有機基、又はこれらの組み合わせで且つSi-C結合によりケイ素原子と結合しているものであり、R8はアルコキシ基、アシルオキシ基、又はハロゲン基を示し、cは0乃至3の整数を示す。)で示される加水分解性シラン、及び式(4):
(式(4)中、R9はアルキル基で且つSi-C結合によりケイ素原子と結合しているものであり、R10はアルコキシ基、アシルオキシ基、又はハロゲン基を示し、Yはアルキレン基又はアリーレン基を示し、dは0又は1の整数を示し、eは0又は1の整数である。)で示される加水分解性シランからなる群より選ばれた少なくとも1種の加水分解性シランである第1観点に記載の膜形成組成物、
第3観点として、第1観点の式(1)で示される加水分解性シランと第2観点の式(3)で示される加水分解性シランの組み合わせからなる加水分解性シランの加水分解縮合物をポリマーとして含む膜形成組成物、
第4観点として、更に塩を含む第1観点乃至第3観点のいずれか一つに記載の膜形成組成物、
第5観点として、膜形成組成物が、リソグラフィー工程に使用されるレジスト下層膜形成組成物である第1観点乃至第4観点のいずれか一つに記載の膜形成組成物、
第6観点として、第5観点に記載のレジスト下層膜形成組成物の硬化物からなる、半導体基板上に形成されたレジスト下層膜、
第7観点として、第5観点に記載のレジスト下層膜形成組成物を半導体基板上に塗布し、焼成しレジスト下層膜を形成する工程、前記レジスト下層膜の上にレジスト組成物を塗布しレジスト膜を形成する工程、前記レジスト膜を露光する工程、露光後に該レジスト膜を現像しレジストパターンを得る工程、前記レジストパターンによりレジスト下層膜をエッチングする工程、及びパターン化されたレジストとレジスト下層膜により半導体基板を加工する工程を含む半導体装置の製造方法、
第8観点として、半導体基板上に有機下層膜を形成する工程、その上に第5観点に記載のレジスト下層膜形成組成物を塗布し焼成しレジスト下層膜を形成する工程、前記レジスト下層膜の上にレジスト組成物を塗布しレジスト膜を形成する工程、前記レジスト膜を露光する工程、露光後に該レジスト膜を現像しレジストパターンを得る工程、前記レジストパターンによりレジスト下層膜をエッチングする工程、パターン化されたレジスト下層膜により有機下層膜をエッチングする工程、及びパターン化された有機下層膜により半導体基板を加工する工程を含む半導体装置の製造方法、及び
第9観点として、式(1’):
〔式(1’)中、R1は式(2’):
(式(2’)中、R4は水素原子、炭素原子数1乃至10のアルキル基、又はアシル基を示し、R5は水素原子、炭素原子数1乃至10のアルキル基、又は炭素原子数1乃至10のアルコキシ基を有する炭素原子数1乃至10のアルキル基を示し、R6は炭素原子数1乃至10のアルキル基を示し、n1は0乃至10の整数を示し、n2は0又は1の整数を示し、n3、n4及びn5は整数であって、n3は1≦n3≦5、n4は0≦n4≦4、n5は0≦n5≦4を示す。そしてk1はn1が1乃至10を示すときの、ケイ素原子との結合端を示し、k2はn1が0を示し及びn2が1を示すときの、ケイ素原子との結合端を示し、k3はn1及びn2が0を示すときの、ケイ素原子との結合端を示す。)で示される有機基であり且つSi-C結合又はSi-O結合によりケイ素原子と結合しているものである。R2はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、アミノ基、もしくはシアノ基を有する有機基、又はこれらの組み合わせであり且つSi-C結合によりケイ素原子と結合しているものである。R3はアルコキシ基、アシルオキシ基、又はハロゲン基を示す。aは1の整数を示し、bは0乃至2の整数を示し、a+bは1乃至3の整数を示す。〕で示される加水分解性シランである。
本発明の膜形成組成物は、式(1)で示される加水分解性シラン、その加水分解物、又はその加水分解縮合物と、溶剤とを含む。そして任意成分として酸、水、アルコール、硬化触媒、酸発生剤、他の有機ポリマー、吸光性化合物、及び界面活性剤等を含むことができる。
固形分中に占める加水分解性シラン、その加水分解物、及びその加水分解縮合物の割合は、20質量%以上であり、例えば50乃至100質量%、60乃至99質量%、70乃至99質量%である。
式(2)中、R4は水素原子、炭素原子数1乃至10のアルキル基、又はアシル基を示し、R5は水素原子、炭素原子数1乃至10のアルキル基、又は炭素原子数1乃至10のアルコキシ基を有する炭素原子数1乃至10のアルキル基を示し、R6は炭素原子数1乃至10のアルキル基を示し、n1は0乃至10の整数を示し、n2は0又は1の整数を示し、n3、n4及びn5は整数であって、n3は1≦n3≦5、n4は0≦n4≦4、n5は0≦n5≦4を示す。k1部分、k2部分、又はk3部分はケイ素原子との結合端を示し、k1はn1が1乃至10を示すときの、ケイ素原子との結合端を示し、k2はn1が0を示し及びn2が1を示すときの、ケイ素原子との結合端を示し、k3はn1及びn2が0を示すときの、ケイ素原子との結合端を示す。
k1部分でケイ素原子と結合するものを選択することができる。
アクリロイル基を有する有機基としては、アクリロイルメチル、アクリロイルエチル、アクリロイルプロピル等が挙げられる。
メタクリロイル基を有する有機基としては、メタクリロイルメチル、メタクリロイルエチル、メタクリロイルプロピル等が挙げられる。
アミノ基を有する有機基としては、アミノ基、アミノメチル基、アミノエチル基とが挙げられる。
シアノ基を有する有機基としては、シアノエチル、シアノプロピル等が挙げられる。
式(3)中、R7はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアルキル基、アルコキシアリール基、アルコキシアルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、スルホンアミド基、もしくはシアノ基を有する有機基、又はこれらの組み合わせで且つSi-C結合によりケイ素原子と結合しているものであり、R8はアルコキシ基、アシルオキシ基、又はハロゲン基を示し、cは0乃至3の整数を示す。
アルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアルキル基、アルコキシアリール基、アルコキシアルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、スルホンアミド基、もしくはシアノ基を有する有機基、アルコキシ基、アシルオキシ基、ハロゲン基は上述の例示を用いることができる。
アルコキシアリール基はアルコキシ基が置換したアリール基であり、例えばメトキシフェニル基、エトキシフェニル基等が挙げられる。
アルコキシアルコキシアリール基はアルコキシ基がアルコキシ基に置換した有機基が置換したアリール基であり、メトキシメトキシフェニル基、メトキシエトキシフェニル基、エトキシメトキシフェニル基、エトキシエトキシフェニル基等が挙げられる。
GPCの測定条件は、例えばGPC装置(商品名HLC-8220GPC、東ソー株式会社製)、GPCカラム(商品名ShodexKF803L、KF802、KF801、昭和電工製)、カラム温度は40℃、溶離液(溶出溶媒)はテトラヒドロフラン、流量(流速)は1.0ml/分、標準試料はポリスチレン(昭和電工株式会社製)を用いて行うことができる。
また、加水分解性基の1モル当たり0.001乃至10モル、好ましくは0.001乃至1モルの加水分解触媒を用いることができる。
加水分解と縮合を行う際の反応温度は、通常20乃至80℃である。
加水分解し縮合させる際に触媒を用いることができる。
加水分解触媒としては、金属キレート化合物、有機酸、無機酸、有機塩基、無機塩基を挙げることができる。
無機塩基としては、例えばアンモニア、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、水酸化カルシウム等を挙げることができる。これら触媒の内、金属キレート化合物、有機酸、無機酸が好ましく、これらは1種あるいは2種以上を同時に使用しても良い。
硬化触媒としては、アンモニウム塩、ホスフィン類、ホスホニウム塩、スルホニウム塩を用いることができる。
(但し、mは2乃至11、nは2乃至3の整数を、R21 はアルキル基又はアリール基を、YA -は陰イオンを示す。)で示される構造を有する第4級アンモニウム塩、
式(D-2):
(但し、R22、R23、R24及びR25はアルキル基又はアリール基を、Nは窒素原子を、YA -は陰イオンを示し、且つR22、R23、R24、及びR25はそれぞれC-N結合により窒素原子と結合されているものである)で示される構造を有する第4級アンモニウム塩、
式(D-3):
(但し、R26及びR27はアルキル基又はアリール基を、YA -は陰イオンを示す)で示される構造を有する第4級アンモニウム塩、
式(D-4):
(但し、R28はアルキル基又はアリール基を、YA -は陰イオンを示す)で示される構造を有する第4級アンモニウム塩、
式(D-5):
(但し、R29及びR30はアルキル基又はアリール基を、YA -は陰イオンを示す)で示される構造を有する第4級アンモニウム塩、
式(D-6):
(但し、mは2乃至11、nは2乃至3の整数を、Hは水素原子を、YA -は陰イオンを示す)で示される構造を有する第3級アンモニウム塩が挙げられる。
(但し、R31、R32、R33、及びR34はアルキル基又はアリール基を、Pはリン原子を、YA -は陰イオンを示し、且つR31、R32、R33、及びR34はそれぞれC-P結合によりリン原子と結合されているものである)で示される第4級ホスホニウム塩が挙げられる。
(但し、R35、R36、及びR37はアルキル基又はアリール基を、Sは硫黄原子を、YA -は陰イオンを示し、且つR35、R36、及びR37はそれぞれC-S結合により硫黄原子と結合されているものである)で示される第3級スルホニウム塩が挙げられる。
また加えるアルコールとしては塗布後の加熱により飛散しやすいものが好ましく、例えばメタノール、エタノール、プロパノール、イソプロパノール、ブタノール等が挙げられる。加えるアルコールは膜形成組成物100質量部に対して1乃至20質量部とすることができる。
有機ポリマー化合物は一種のみを使用することができ、または二種以上を組み合わせて使用することができる。
有機ポリマー化合物が使用される場合、その割合としては、縮合物(ポリオルガノシロキサン)100質量部に対して、1乃至200質量部、または5乃至100質量部、または10乃至50質量部、または20乃至30質量部である。
酸発生剤としては、熱酸発生剤や光酸発生剤が挙げられる。
本発明の膜形成組成物に含まれる光酸発生剤としては、オニウム塩化合物、スルホンイミド化合物、及びジスルホニルジアゾメタン化合物等が挙げられる。
光酸発生剤が使用される場合、その割合としては、縮合物(ポリオルガノシロキサン)100質量部に対して、0.01乃至5質量部、または0.1乃至3質量部、または0.5乃至1質量部である。
本発明の膜形成組成物に含まれる界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフエノールエーテル、ポリオキシエチレンノニルフエノールエーテル等のポリオキシエチレンアルキルアリルエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロツクコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、商品名エフトップEF301、EF303、EF352((株)トーケムプロダクツ製)、商品名メガファックF171、F173、R-08、R-30、R-30N、R-40LM(DIC(株)製)、フロラードFC430、FC431(住友スリーエム(株)製)、商品名アサヒガードAG710,サーフロンS-382、SC101、SC102、SC103、SC104、SC105、SC106(旭硝子(株)製)等のフッ素系界面活性剤、及びオルガノシロキサンポリマ-KP341(信越化学工業(株)製)等を挙げることができる。これらの界面活性剤は単独で使用してもよいし、また二種以上の組み合わせで使用することもできる。界面活性剤が使用される場合、その割合としては、縮合物(ポリオルガノシロキサン)100質量部に対して0.0001乃至5質量部、または0.001乃至1質量部、または0.01乃至1質量部である。
また、EUVレジストとしてはメタクリレート樹脂系レジストを用いることができる。
現像液としては、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリンなどの水酸化四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミンなどのアミン水溶液等のアルカリ性水溶液を例として挙げることができる。さらに、これらの現像液に界面活性剤などを加えることもできる。現像の条件としては、温度5乃至50℃、時間10乃至600秒から適宜選択される。
また、本発明では現像液として有機溶剤を用いることができる。露光後に現像液(溶剤)によって現像が行なわれる。これにより、例えばポジ型フォトレジストが使用された場合は、露光されない部分のフォトレジストが除去され、フォトレジストのパターンが形成される。
また、EUVレジストの下層膜としてはハードマスクとしての機能以外に以下の目的にも使用できる。EUVレジストとインターミキシングすることなく、EUV露光(波長13.5nm)に際して好ましくない露光光、例えば上述のUVやDUV(ArF光、KrF光)の基板又は界面からの反射を防止することができるEUVレジストの下層反射防止膜として、上記レジスト下層膜形成組成物を用いることができる。EUVレジストの下層で効率的に反射を防止することができる。EUVレジスト下層膜として用いた場合は、プロセスはフォトレジスト用下層膜と同様に行うことができる。
で示される加水分解性シランに関する。
式(1’)中、R1は式(2’)
で示される有機基であり且つSi-C結合又はSi-O結合によりケイ素原子と結合しているものである。R2はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、アミノ基、もしくはシアノ基を有する有機基、又はこれらの組み合わせであり且つSi-C結合によりケイ素原子と結合しているものである。R3はアルコキシ基、アシルオキシ基、又はハロゲン基を示す。aは1の整数を示し、bは0乃至2の整数を示し、a+bは1乃至3の整数を示す。
式(2’)中、R4は水素原子、炭素原子数1乃至10のアルキル基、又はアシル基を示し、R5は水素原子、炭素原子数1乃至10のアルキル基、又は炭素原子数1乃至10のアルコキシ基を有する炭素原子数1乃至10のアルキル基を示し、R6は炭素原子数1乃至10のアルキル基を示し、n1は0乃至10の整数を示し、n2は0又は1の整数を示し、n3、n4及びn5は整数であって、n3は1≦n3≦5、n4は0≦n4≦4、n5は0≦n5≦4を示す。そしてk1はn1が1乃至10を示すときの、ケイ素原子との結合端を示し、k2はn1が0を示し及びn2が1を示すときの、ケイ素原子との結合端を示し、k3はn1及びn2が0を示すときの、ケイ素原子との結合端を示す。
k1部分でケイ素原子と結合するものを選択することができる。
式(1’)においてn2が1の整数である化合物を示すことができる。
マグネチックスターラーを備えた1000mlナスフラスコにヒドロキシベンジルアルコール20.0g、エタノール400.0gを加え、溶解させた。そこに濃硫酸を0.32g加え、加熱して20時間還流させた。室温に戻し、水酸化ナトリウムで中和した後、エバポレーションにてエタノールを除去した。300mlの三口フラスコに移し、そこに水酸化ナトリウム6.44g、トルエン40g、N-メチルピロリドン(以下、NMPと略することもある。)40gを加え、オイルバス中130℃にて水、トルエンを除去しながら、4時間反応させた。そこにクロロメチルトリエトキシシラン34.28gを滴下し、130℃にて4時間加熱撹拌した。得られた溶液を室温に戻し、分液ロートに移しかえてトルエン120g、水90gを加えて有機層を洗浄した。洗浄は3回繰り返し行った。次に、有機層に硫酸マグネシウムを加え乾燥させた後、ろ過し、溶媒をエバポレーションにて除去して粗物を得た。その後、減圧蒸留にて精製し目的物である化合物1を15g得た。
1H-NMR(500MHz、DMSO-d6):1.13ppm(t、3H)、1.19ppm(t、9H)、3.43ppm(q、2H)、3.68ppm(s、2H)、3.86ppm(q、6H)、4.36ppm(s、2H)、6.95ppm(d、2H)、7.22ppm(d、2H)
マグネチックスターラーを備えた1000mlナスフラスコに2,6-ビス(ヒドロキシメチル)-p-クレゾール 30.0g、メタノール600.0gを加え、溶解させた。そこに濃硫酸を0.35g加え、加熱して20時間還流させた。室温に戻し、水酸化ナトリウムで中和した後、エバポレーションにてメタノールを除去した。300mlの三口フラスコに移し、そこに水酸化ナトリウム7.13g、トルエン60g、NMP60gを加え、オイルバス中130℃にて水、トルエンを除去しながら、4時間反応させた。そこに3-クロロプロピルトリメトキシシラン35.54gを滴下し、130℃にて4時間加熱撹拌した。得られた溶液を室温に戻し、分液ロートに移しかえてトルエン120g、水90gを加えて有機層を洗浄した。洗浄は3回繰り返し行った。次に、有機層に硫酸マグネシウムを加え乾燥させた後、ろ過し、溶媒をエバポレーションにて除去して粗物を得た。その後、減圧蒸留にて精製し目的物である化合物2を5g得た。
1H-NMR(500MHz、DMSO-d6):0.70ppm(t、2H)、1.74ppm(quin、2H)、2.22ppm(s、3H)、3.27ppm(s、6H)、3.47ppm(s、9H)、3.67ppm(t、2H)、4.35ppm(s、4H)、7.07ppm(s、2H)
マグネチックスターラーを備えた1000mlナスフラスコにバニリルアルコール20.0g、メタノール400.0gを加え、溶解させた。そこに濃硫酸を0.25g加え、加熱して1時間還流させた。室温に戻し、水酸化ナトリウムで中和した後、エバポレーションにてメタノールを除去した。300mlの三口フラスコに移し、そこに水酸化ナトリウム5.19g、トルエン40g、NMP40gを加え、オイルバス中130℃にて水、トルエンを除去しながら、4時間反応させた。そこにクロロメチルトリエトキシシラン27.60gを滴下し、130℃にて4時間加熱撹拌した。得られた溶液を室温に戻し、分液ロートに移しかえてトルエン120g、水90gを加えて有機層を洗浄した。洗浄は3回繰り返し行った。次に、有機層に硫酸マグネシウムを加え乾燥させた後、ろ過し、溶媒をエバポレーションにて除去して粗物を得た。その後、減圧蒸留にて精製し目的物である化合物3を15g得た。
1H-NMR(500MHz、DMSO-d6):1.20ppm(t、9H)、3.26ppm(s、3H)、3.68ppm(s、2H)、3.75ppm(s、3H)、3.87ppm(q、6H)、4.32ppm(s、2H)、6.83ppm(d、1H)、6.89ppm(s、1H)、7.00ppm(d、2H)
マグネチックスターラーを備えた300mlの三口フラスコに4-クロロメチルフェニルトリメトキシシラン(Gelest社製)40g、NMP80gを加え、オイルバス中130℃に加熱撹拌させた。そこにナトリウムメトキシド8.76g加え、130℃にて4時間加熱撹拌した。得られた溶液を室温に戻し、分液ロートに移しかえてトルエン200g、水100gを加えて有機層を洗浄した。洗浄は3回繰り返し行った。次に、有機層に硫酸マグネシウムを加え乾燥させた後、ろ過し、溶媒をエバポレーションにて除去して粗物を得た。その後、減圧蒸留にて精製し目的物である化合物4を5g得た。
1H-NMR(500MHz、DMSO-d6):3.30ppm(s、3H)、3.53ppm(s、9H)、4.43ppm(s、2H)、7.37ppm(d、2H)、7.56ppm(d、2H)
1000mlナスフラスコに、2,6-ビス(ヒドロキシメチル)-p-クレゾール20.00g(0.119mol)、メタノール400g、濃硫酸0.23g(0.002mol)を入れ、還流状態で20時間加熱した。室温に戻し、水酸化ナトリウムで中和した後、エバポレーションにてメタノールを除去した。300mlの三口フラスコに移し、そこに、トルエン40g、N-メチルピロリドン40g、水酸化ナトリウム4.99g(0.125mol)を加え、オイルバス中130℃にて水、トルエンを除去しながら、4時間反応させた。そこにクロロメチルトリエトキシシラン25.30g(0.119mol)を滴下し、120℃にて4時間反応させた。反応液は、トルエンおよびアセトン、水にて分液を行った後、エバポレーターにて有機溶媒を除去することで、粗物を得た。粗物を、減圧蒸留することで、目的物である化合物を得た。
1H-NMR(500MHz、DMSO-d6):1.23ppm(t、9H)、2.26ppm(s、3H)、3.31ppm(s、6H)、3.59ppm(s、2H)、3.89ppm(q、6H)、4.40ppm(s、4H)、7.10ppm(s、2H)
マグネチックスターラーを備えた300ml三口フラスコに酢酸ナトリウム30.0g、NMP150.0gを加え、オイルバス中130℃に加熱した。そこに(p-クロロメチル)フェニルトリメトキシシラン90.25gを滴下し、4時間加熱撹拌した。得られた溶液を室温に戻し、分液ロートに移しかえてトルエン300g、水90gを加えて有機層を洗浄した。洗浄は3回繰り返し行った。次に、有機層に硫酸マグネシウムを加え乾燥させた後、ろ過し、溶媒をエバポレーションにて除去して粗物を得た。その後、減圧蒸留にて精製し目的物である4-(トリメトキシシリル)ベンジルアセテートを60g得た。
1H-NMR(500MHz、DMSO-d6):2.08ppm(s、3H)、3.54ppm(s、9H)、5.10ppm(s、2H)、7.42ppm(d、2H)、7.58ppm(d、2H)
マグネチックスターラーを備えた300mlナスフラスコに4-ブロモ-3,5-ジメチルフェノール(4-BP)42.0g、テトラヒドロフラン(THF)(脱水)94.6g、ピリジニウムp-トルエンスルホン酸(PPTS)1.57gを加え、溶解させた。そこにエチルビニルエーテル(EV)を22.59g加え、室温にて20時間反応させた。トリエチルアミン(TEA)0.63gで中和し、反応溶液A(4-(1-エトキシエトキシ)-2,6-ジメチルブロモベンゼン(4-EOEO-2,6-DMePhBr)を含む)を作製した。スターラーチップを備えた500mlの三口フラスコに乾燥させたマグネシウム粉末6.09g、ヨウ素0.53g、テトラヒドロフラン (脱水)189.2gを加え、オイルバス中60℃にてヨウ素の色がなくなるまで加熱した後、室温に戻し、反応溶液Aを室温にて滴下して2時間反応させ、反応溶液Bを得た。スターラーチップを備えた1000mlの三口フラスコにテトラメトキシシラン(TMOS)95.39g、テトラヒドロフラン(脱水)189.2gを加え、攪拌した。室温にて反応溶液Bを滴下し、2時間反応させた。得られた溶液をエバポレーションにて濃縮後、500mlのヘプタン溶液を加え攪拌し、ろ過した。得られたろ液を濃縮後、減圧蒸留にて精製し目的物である(4-(1-エトキシエトキシ)-2,6-ジメチルフェニル)トリメトキシシラン(4-EOEO-2,6-DMePhTMOS)を35g得た。
1H-NMR(500MHz、DMSO-d6):1.06ppm(t、3H)、1.34ppm(d、3H)、2.36ppm(s、6H)、3.47ppm(s、9H)、3.53ppm(multi、2H)、5.46ppm(q、1H)、6.61(s、2H)
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.251g、水0.777g、イソプロパノール7.014g、テトラヒドロフラン3.846gを加え撹拌した。そこに化合物3を5g(全シラン中で50モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン4.157g(全シラン中で50モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル54.942g、水27.471gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー1として、式(3-1)に相当し、分子量はMw7200であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.263g、水0.815g、イソプロパノール7.169g、テトラヒドロフラン3.931gを加え撹拌した。そこに化合物1を5g(全シラン中で50モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン4.360g(全シラン中で50モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル56.157g、水28.08gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー2として、式(3-2)に相当し、分子量はMw12800であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.178g、水0.553g、イソプロパノール4.18g、テトラヒドロフラン2.290gを加え撹拌した。そこに化合物4を2.5g(全シラン中で50モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン2.955g(全シラン中で50モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル32.73g、水16.36gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー3として、式(3-3)に相当し、分子量はMw7300であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.232g、水0.719g、イソプロパノール6.775g、テトラヒドロフラン7.315gを加え撹拌した。そこに化合物5を5g(全シラン中で50モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン3.844g(全シラン中で50モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル53.06g、水26.53gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー4として、式(3-4)に相当し、分子量はMw2200であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.287g、水0.888g、イソプロパノール8.001g、テトラヒドロフラン4.387gを加え撹拌した。そこに化合物3を4g(全シラン中で35モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン4.751g(全シラン中で50モル%)、トリメトキシ(3-(フェナントレン-9-イル)プロピル)シラン1.695g(全シラン中で15モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル62.67g、水31.34gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー5として、式(3-5)に相当し、分子量はMw5200であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.287g、水0.888g、イソプロパノール7.959g、テトラヒドロフラン4.364gを加え撹拌した。そこに化合物3を4g(全シラン中で35モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン4.751g(全シラン中で50モル%)、カルバゾールプロピルトリメトキシシラン1.640g(全シラン中で15モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル62.34g、水31.17gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテル25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー6として、式(3-6)に相当し、分子量はMw5000であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.287g、水0.888g、イソプロパノール7.910g、テトラヒドロフラン7.951gを加え撹拌した。そこに化合物3を4g(全シラン中で35モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン4.751g(全シラン中で50モル%)、(4-(メチルチオ)フェノキシ)メチルトリエトキシシラン1.575g(全シラン中で15モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル61.96g、水30.98gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー7として、式(3-7)に相当し、分子量はMw5600であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.287g、水0.888g、イソプロパノール7.750g、テトラヒドロフラン4.318gを加え撹拌した。そこに化合物3を4g(全シラン中で35モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン4.751g(全シラン中で50モル%)、8-(3-(トリメトキシシリル)プロポキシ)キノリン1.530g(全シラン中で15モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル61.96g、水30.98gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテル25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー8として、式(3-8)に相当し、分子量はMw4300であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.287g、水0.888g、イソプロパノール8.196g、テトラヒドロフラン4.494gを加え撹拌した。そこに化合物3を4g(全シラン中で35モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン4.751g(全シラン中で50モル%)、4-メトキシ-N-(3-(トリエトキシシリル)プロピル)ベンゼンスルホンアミド1.949g(全シラン中で15モル%)を室温で加え、40℃に加熱して6時間反応させた。室温に戻し、酢酸エチル64.20g、水32.10gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテル25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー9として、式(3-9)に相当し、分子量はMw4800であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液8.88g、イソプロパノール30.72g、テトラヒドロフラン30.72gを加え撹拌した。そこに化合物3を3.62g(全シラン中で10モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン3.01g(全シラン中で10モル%)、メチルトリエトキシシラン15.00g(全シラン中で80モル%)を室温で加え、40℃に加熱して4時間反応させた。室温に戻し、酢酸エチル129.81gを加え、0.2N塩酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー10として、式(3-10)に相当し、分子量はMw1500であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液1.541g、イソプロパノール7.99g、テトラヒドロフラン7.99gを加え撹拌した。そこに化合物3を0.63g(全シラン中で10モル%)、(3-ビフェノキシ)メチルトリエトキシシラン5.00g(全シラン中で90モル%)を室温で加え、40℃に加熱して4時間反応させた。室温に戻し、酢酸エチル33.77gを加え、0.2N塩酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー11として、式(3-11)に相当し、分子量はMw3500であった。
100mlの反応フラスコに35重量%のテトラエチルアンモニウム水溶液0.34g、超純水1.94g、イソプロパノール4.13g、テトラヒドロフラン4.13gを加え撹拌した。そこに化合物3を6.89g、アセトキシメチルトリエトキシシラン2.36g、(4-(1-エトキシエトキシ)-2,6-ジメチルフェニル)トリメトキシシラン(化合物7)3.14gを室温で加え、40度に加熱して4時間反応させた。室温に戻し、酢酸エチル62.00gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート30gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー12として、式(3-12)に相当し、分子量はMw4000であった。
100mlの反応フラスコに35重量%のテトラエチルアンモニウム水溶液0.419g、超純水2.42g、イソプロパノール5.45g、テトラヒドロフラン5.45gを加え撹拌した。そこに化合物3を8.57g、トリエトキシ(3-((テトラヒドロ―2H-ピラン―2イル)オキシ)プロピル)シラン1.53g、(4-(1-エトキシエトキシ)-2,6-ジメチルフェニル)トリメトキシシラン(化合物7)6.26gを室温で加え、40度に加熱して4時間反応させた。室温に戻し、酢酸エチル82.00gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート30gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー13として式(3-13)に相当し、分子量はMw2800であった。
100mlの反応フラスコに35重量%のテトラエチルアンモニウム水溶液0.34g、超純水1.94g、イソプロパノール4.13g、テトラヒドロフラン4.13gを加え撹拌した。そこに化合物3を6.89g、3-グリシドキシプロピルトリメトキシシラン2.36g、(4-(1-エトキシエトキシ)-2,6-ジメチルフェニル)トリメトキシシラン(化合物7)3.14gを室温で加え、40度に加熱して4時間反応させた。室温に戻し、酢酸エチル62.00gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート30gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー14として式(3-14)に相当し、分子量はMw3800であった。
100mlの反応フラスコに35質量%のテトラエチルアンモニウム水溶液0.436g、水1.351g、イソプロパノール9.362g、テトラヒドロフラン5.133gを加え撹拌した。そこにフェニルトリメトキシシランを5.000g(全シラン中で50モル%)、(4-(1-エトキシエトキシ)フェニル)トリメトキシシラン7.222g(全シラン中で50モル%)を室温で加え、40℃に加熱して4時間反応させた。室温に戻し、酢酸エチル73.33gを加え、0.1N酢酸水溶液にて中和した。分液ロートに移し、水で3回洗浄した後、プロピレングリコールモノメチルエーテルアセテート25gを添加し、有機層を濃縮して溶媒置換を行った。得られたポリマーはポリマー12として、式(4-1)に相当し、分子量はMw5200であった。
上記合成例1乃至14及び比較合成例1で得られたケイ素含有ポリマー、酸、硬化触媒、添加剤、溶媒を表1に示す割合になるように混合し、0.02μmのフッ素樹脂製のフィルターで濾過することによって、膜形成組成物である硬化性樹脂組成物の溶液をそれぞれ調製した。表1中のポリマーの割合はポリマー溶液の質量ではなく、ポリマー自体の質量を示した。
表1中でトリフェニルスルホニウムトリフルオロメタンスルホネートはTPS105、p-トルエンスルホン酸ピリジニウム塩はpPTS、プロピレングリコールモノメチルエーテルアセテートはPGMEA、プロピレングリコールモノメチルエーテルはPGME、DIC社製非イオン性界面活性剤をR30N(製品名)とした。水は超純水を用いた。各添加量は質量部で示した。
実施例1乃至15、比較例1乃至2で調製した硬化性樹脂組成物をスピナーを用い、シリコンウェハ上にそれぞれ塗布した。ホットプレート上で215℃1分間加熱し、硬化性樹脂組成膜(膜厚0.05μm)を形成した。そして、硬化性樹脂組成膜を分光エリプソメーター(J.A.Woollam社製、VUV-VASEVU-302)を用い、屈折率(n値)及び光学吸光係数(k値、減衰係数とも呼ぶ)を測定した。
実施例1乃至15、比較例1乃至2で調製した硬化性樹脂組成物をスピナーを用い、シリコンウェハ上にそれぞれ塗布した。ホットプレート上で215℃1分間加熱し、硬化性樹脂組成膜(膜厚0.05μm)を形成した。その後、プロピレングリコールモノメチルエーテルアセテートに浸し、浸漬前後の膜厚測定を行い、5nm以上変化したものを×とした。
ダイセル化学工業(株)製、商品名:EHPE3150(40.0g)と9-アントラセンカルボン酸(20.3g)と安息香酸(13.7g)をプロピレングリコールモノメチルエーテル(302.0g)に溶解させた後、ベンジルトリエチルアンモニウム1.5gを加え、24時間還流し反応させた。反応後溶液をイオン交換法を用いて精製し、ポリマー溶液を得た。得られたポリマー(式(5-1)に相当)のGPC分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は4100であった。
得られたポリマー溶液5g(ポリマーの固形分は16質量%)に、テトラメトキシメチルグリコールウリル0.2g、ピリジニウム-p-トルエンスルホナート0.03g、メガファック[登録商標]R-30(DIC(株)(旧大日本インキ化学(株))製、商品名)0.0008g、プロピレングリコールモノメチルエーテル6.4g、プロピレングリコールモノメチルエーテルアセテート4.5gを混合して溶液とした。その後、孔径0.10μmのポリエチレン製ミクロフィルターを用いて濾過し、更に、孔径0.05μmのポリエチレン製ミクロフィルターを用いて濾過して、多層膜によるリソグラフィープロセスに用いる有機レジスト下層膜形成組成物の溶液を調製した。
図1に示すように段差基板2上に、スピンコーターを用いて、実施例1乃至15、比較例1乃至2の硬化性樹脂組成物を塗布し、その後215℃のホットプレート上で1分間加熱することにより、膜厚180nmの硬化性樹脂膜1を形成した。前記段差基板は、CVD-TEOSから成る高さ300nm、最少幅が20nmのホールパターンを用いた。次いで、得られた基板を断面SEMにより穴埋め形状(埋め込み性)を観察し、穴埋め特性を評価した。ボイドの発生無く良好な埋め込み性示した場合を良好とした。
硬化性や埋め込み性等の良好な効果を有する膜形成組成物、半導体装置のリソグラフィー工程に用いるレジスト下層膜として使用することができる。
2 段差基板
Claims (9)
- シランとして加水分解性シラン、その加水分解物、又はその加水分解縮合物を含み、該加水分解性シランが式(1):
〔式(1)中、R1は式(2):
(式(2)中、R4は水素原子、炭素原子数1乃至10のアルキル基、又はアシル基を示し、R5は水素原子、炭素原子数1乃至10のアルキル基、又は炭素原子数1乃至10のアルコキシ基を有する炭素原子数1乃至10のアルキル基を示し、R6は炭素原子数1乃至10のアルキル基を示し、n1は0乃至10の整数を示し、n2は0又は1の整数を示し、n3、n4及びn5は整数であって、n3は1≦n3≦5、n4は0≦n4≦4、n5は0≦n5≦4を示す。そしてk1はn1が1乃至10の整数を示すときの、ケイ素原子との結合端を示し、k2はn1が0を示し及びn2が1を示すときの、ケイ素原子との結合端を示し、k3はn1及びn2が0を示すときの、ケイ素原子との結合端を示す。)で示される有機基であり且つSi-C結合又はSi-O結合によりケイ素原子と結合しているものである。R2はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、アミノ基、もしくはシアノ基を有する有機基、又はこれらの組み合わせであり且つSi-C結合によりケイ素原子と結合しているものである。R3はアルコキシ基、アシルオキシ基、又はハロゲン基を示す。aは1の整数を示し、bは0乃至2の整数を示し、a+bは1乃至3の整数を示す。〕で示される加水分解性シランを含む膜形成組成物。 - 該加水分解性シランが、式(1)で示される加水分解性シランとその他の加水分解性シランの組み合わせであり、その他の加水分解性シランが式(3):
(式(3)中、R7はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアルキル基、アルコキシアリール基、アルコキシアルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、スルホンアミド基、もしくはシアノ基を有する有機基、又はこれらの組み合わせで且つSi-C結合によりケイ素原子と結合しているものであり、R8はアルコキシ基、アシルオキシ基、又はハロゲン基を示し、cは0乃至3の整数を示す。)で示される加水分解性シラン、及び式(4):
(式(4)中、R9はアルキル基で且つSi-C結合によりケイ素原子と結合しているものであり、R10はアルコキシ基、アシルオキシ基、又はハロゲン基を示し、Yはアルキレン基又はアリーレン基を示し、dは0又は1の整数を示し、eは0又は1の整数である。)で示される加水分解性シランからなる群より選ばれた少なくとも1種の加水分解性シランである請求項1に記載の膜形成組成物。 - 請求項1の式(1)で示される加水分解性シランと請求項2の式(3)で示される加水分解性シランの組み合わせからなる加水分解性シランの加水分解縮合物をポリマーとして含む膜形成組成物。
- 更に塩を含む請求項1乃至請求項3のいずれか1項に記載の膜形成組成物。
- 膜形成組成物が、リソグラフィー工程に使用されるレジスト下層膜形成組成物である請求項1乃至請求項4のいずれか1項に記載の膜形成組成物。
- 請求項5に記載のレジスト下層膜形成組成物の硬化物からなる、半導体基板上に形成されたレジスト下層膜。
- 請求項5に記載のレジスト下層膜形成組成物を半導体基板上に塗布し、焼成しレジスト下層膜を形成する工程、前記レジスト下層膜の上にレジスト組成物を塗布しレジスト膜を形成する工程、前記レジスト膜を露光する工程、露光後に該レジスト膜を現像しレジストパターンを得る工程、前記レジストパターンによりレジスト下層膜をエッチングする工程、及びパターン化されたレジストとレジスト下層膜により半導体基板を加工する工程を含む半導体装置の製造方法。
- 半導体基板上に有機下層膜を形成する工程、その上に請求項5に記載のレジスト下層膜形成組成物を塗布し焼成しレジスト下層膜を形成する工程、前記レジスト下層膜の上にレジスト組成物を塗布しレジスト膜を形成する工程、前記レジスト膜を露光する工程、露光後に該レジスト膜を現像しレジストパターンを得る工程、前記レジストパターンによりレジスト下層膜をエッチングする工程、パターン化されたレジスト下層膜により有機下層膜をエッチングする工程、及びパターン化された有機下層膜により半導体基板を加工する工程を含む半導体装置の製造方法。
- 式(1’):
〔式(1’)中、R1は式(2’):
(式(2’)中、R4は水素原子、炭素原子数1乃至10のアルキル基、又はアシル基を示し、R5は水素原子、炭素原子数1乃至10のアルキル基、又は炭素原子数1乃至10のアルコキシ基を有する炭素原子数1乃至10のアルキル基を示し、R6は炭素原子数1乃至10のアルキル基を示し、n1は0乃至10の整数を示し、n2は0又は1の整数を示し、n3、n4及びn5は整数であって、n3は1≦n3≦5、n4は0≦n4≦4、n5は0≦n5≦4を示す。そしてk1はn1が1乃至10を示すときの、ケイ素原子との結合端を示し、k2はn1が0を示し及びn2が1を示すときの、ケイ素原子との結合端を示し、k3はn1及びn2が0を示すときの、ケイ素原子との結合端を示す。)で示される有機基であり且つSi-C結合又はSi-O結合によりケイ素原子と結合しているものである。R2はアルキル基、アリール基、ハロゲン化アルキル基、ハロゲン化アリール基、アルコキシアリール基、アルケニル基、又はエポキシ基、アクリロイル基、メタクリロイル基、メルカプト基、アミノ基、もしくはシアノ基を有する有機基、又はこれらの組み合わせであり且つSi-C結合によりケイ素原子と結合しているものである。R3はアルコキシ基、アシルオキシ基、又はハロゲン基を示す。aは1の整数を示し、bは0乃至2の整数を示し、a+bは1乃至3の整数を示す。〕で示される加水分解性シラン。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/528,037 US10845703B2 (en) | 2014-11-19 | 2015-11-09 | Film-forming composition containing silicone having crosslinking reactivity |
SG11201704070SA SG11201704070SA (en) | 2014-11-19 | 2015-11-09 | Film-forming composition containing silicone having crosslinking reactivity |
JP2016560150A JP6788222B2 (ja) | 2014-11-19 | 2015-11-09 | 架橋反応性シリコン含有膜形成組成物 |
CN201580059708.7A CN107075302B (zh) | 2014-11-19 | 2015-11-09 | 含交联反应性硅的膜形成用组合物 |
KR1020177008835A KR102543831B1 (ko) | 2014-11-19 | 2015-11-09 | 가교반응성 실리콘함유 막 형성 조성물 |
EP15860187.2A EP3222688A4 (en) | 2014-11-19 | 2015-11-09 | Film-forming composition containing crosslinkable reactive silicone |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-234590 | 2014-11-19 | ||
JP2014234590 | 2014-11-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016080226A1 true WO2016080226A1 (ja) | 2016-05-26 |
Family
ID=56013771
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/081476 WO2016080226A1 (ja) | 2014-11-19 | 2015-11-09 | 架橋反応性シリコン含有膜形成組成物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US10845703B2 (ja) |
EP (1) | EP3222688A4 (ja) |
JP (1) | JP6788222B2 (ja) |
KR (1) | KR102543831B1 (ja) |
CN (1) | CN107075302B (ja) |
SG (1) | SG11201704070SA (ja) |
TW (1) | TWI712659B (ja) |
WO (1) | WO2016080226A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170154766A1 (en) * | 2015-11-27 | 2017-06-01 | Shin-Etsu Chemical Co., Ltd. | Silicon-containing condensate, composition for forming a silicon-containing resist under layer film, and patterning process |
WO2017154545A1 (ja) * | 2016-03-10 | 2017-09-14 | Jsr株式会社 | レジストプロセス用膜形成材料、パターン形成方法及び重合体 |
WO2019009413A1 (ja) * | 2017-07-06 | 2019-01-10 | 日産化学株式会社 | アルカリ性現像液可溶性シリコン含有レジスト下層膜形成組成物 |
JP2019077808A (ja) * | 2017-10-25 | 2019-05-23 | ユーエムジー・エービーエス株式会社 | 重合体、グラフト重合体および熱可塑性樹脂組成物 |
WO2019124514A1 (ja) * | 2017-12-20 | 2019-06-27 | 日産化学株式会社 | 光硬化性シリコン含有被覆膜形成組成物 |
JP2021522681A (ja) * | 2018-04-25 | 2021-08-30 | ヘルムホルツ−ツェントルム ベルリン フュア マテリアリエン ウント エナギー ゲゼルシャフト ミット ベシュレンクテル ハフツングHelmholtz−Zentrum Berlin fuer Materialien und Energie GmbH | ペロブスカイト太陽電池のための正孔導電性自己組織化単分子層 |
WO2022039246A1 (ja) * | 2020-08-21 | 2022-02-24 | 日産化学株式会社 | Euvレジスト下層膜形成組成物 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107077072B (zh) * | 2014-11-19 | 2021-05-25 | 日产化学工业株式会社 | 能够湿式除去的含有硅的抗蚀剂下层膜形成用组合物 |
US11561472B2 (en) | 2015-06-11 | 2023-01-24 | Nissan Chemical Industries, Ltd. | Radiation sensitive composition |
CN111433675B (zh) * | 2017-12-13 | 2023-08-29 | 株式会社尼康 | 图案形成方法、晶体管的制造方法和图案形成用部件 |
WO2019181873A1 (ja) * | 2018-03-19 | 2019-09-26 | 日産化学株式会社 | 保護されたフェノール基と硝酸を含むシリコン含有レジスト下層膜形成組成物 |
US11972948B2 (en) | 2018-06-13 | 2024-04-30 | Brewer Science, Inc. | Adhesion layers for EUV lithography |
US20210011383A1 (en) * | 2019-07-12 | 2021-01-14 | Inpria Corporation | Stabilized interfaces of inorganic radiation patterning compositions on substrates |
US20240010870A1 (en) * | 2020-08-20 | 2024-01-11 | Bar-Ilan University | Uv-blocking coatings and anti-fogging and superhydrophobic coatings |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3427340A (en) * | 1966-02-01 | 1969-02-11 | Dow Corning | Alkoxyalkarylsilanes and condensates thereof |
US5648201A (en) * | 1991-04-25 | 1997-07-15 | The United Sates Of America As Represented By The Secretary Of The Navy | Efficient chemistry for selective modification and metallization of substrates |
JPH1160735A (ja) * | 1996-12-09 | 1999-03-05 | Toshiba Corp | ポリシランおよびパターン形成方法 |
WO2006126406A1 (ja) * | 2005-05-24 | 2006-11-30 | Nissan Chemical Industries, Ltd. | ポリシラン化合物を含むリソグラフィー用下層膜形成組成物 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3461027A (en) | 1966-02-01 | 1969-08-12 | Dow Corning | Bonding of thermoplastic polymer resins to silane-primed siliceous or metallic materials |
JP2873855B2 (ja) | 1990-03-26 | 1999-03-24 | 三菱レイヨン株式会社 | 被覆材組成物及びそれを用いた耐摩耗性合成樹脂成形品の製造方法 |
DE102006022842A1 (de) | 2006-05-16 | 2007-11-22 | Wacker Chemie Ag | Über Methylolgruppen vernetzbare Siliconpolymere |
EP1908472A1 (en) | 2006-10-02 | 2008-04-09 | Bayer Schering Pharma Aktiengesellschaft | Silicon derivatives for PET imaging |
JP2010100591A (ja) * | 2008-10-27 | 2010-05-06 | Nissan Chem Ind Ltd | ハロゲン置換芳香環含有ポリシロキサン |
JP5538941B2 (ja) | 2010-02-18 | 2014-07-02 | Jsr株式会社 | レジスト下層膜形成方法、パターン形成方法、および組成物、レジスト下層膜形成材料用添加剤、架橋剤並びにレジスト下層膜 |
WO2012039337A1 (ja) | 2010-09-21 | 2012-03-29 | 日産化学工業株式会社 | 保護された脂肪族アルコールを含有する有機基を有するシリコン含有レジスト下層膜形成組成物 |
TWI618985B (zh) | 2011-08-10 | 2018-03-21 | 日產化學工業股份有限公司 | 具有碸構造之含矽阻劑底層膜形成組成物 |
EP2916170A4 (en) | 2012-10-31 | 2016-06-08 | Nissan Chemical Ind Ltd | ESTER GROUP-CONTAINING COMPOSITION FOR FORMING SILICON RESERVE UNDERLAYER FILM |
KR102182360B1 (ko) | 2012-12-19 | 2020-11-24 | 닛산 가가쿠 가부시키가이샤 | 환상 디에스테르기를 갖는 실리콘 함유 레지스트 하층막 형성 조성물 |
-
2015
- 2015-11-09 JP JP2016560150A patent/JP6788222B2/ja active Active
- 2015-11-09 CN CN201580059708.7A patent/CN107075302B/zh active Active
- 2015-11-09 US US15/528,037 patent/US10845703B2/en active Active
- 2015-11-09 EP EP15860187.2A patent/EP3222688A4/en not_active Withdrawn
- 2015-11-09 WO PCT/JP2015/081476 patent/WO2016080226A1/ja active Application Filing
- 2015-11-09 KR KR1020177008835A patent/KR102543831B1/ko active IP Right Grant
- 2015-11-09 SG SG11201704070SA patent/SG11201704070SA/en unknown
- 2015-11-17 TW TW104137922A patent/TWI712659B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3427340A (en) * | 1966-02-01 | 1969-02-11 | Dow Corning | Alkoxyalkarylsilanes and condensates thereof |
US3427339A (en) * | 1966-02-01 | 1969-02-11 | Dow Corning | Alkoxyalkarylalkylsilanes and condensates thereof |
US5648201A (en) * | 1991-04-25 | 1997-07-15 | The United Sates Of America As Represented By The Secretary Of The Navy | Efficient chemistry for selective modification and metallization of substrates |
JPH1160735A (ja) * | 1996-12-09 | 1999-03-05 | Toshiba Corp | ポリシランおよびパターン形成方法 |
WO2006126406A1 (ja) * | 2005-05-24 | 2006-11-30 | Nissan Chemical Industries, Ltd. | ポリシラン化合物を含むリソグラフィー用下層膜形成組成物 |
Non-Patent Citations (11)
Title |
---|
A.BOCKHOLT ET AL.: "Neutral and cationic silicon species containing aryl-OCO- or aryl- SCS-type pincer ligands: synthesis, structure, bonding, and comparison with aryl-NCN systems", ZEITSCHRIFT FUER ANORGANISCHE UND ALLGEMEINE CHEMIE, vol. 635, no. 9-10, 2009, pages 1326 - 1334, XP055441759 * |
A.HOEHNE ET AL.: "Organofluorosilanes as model compounds for 18F-labeled silicon-based PET tracers and their hydrolytic stability: Experimental data and theoretical calculations (PET = positron emission tomography", CHEMISTRY - A EUROPEAN JOURNAL, vol. 15, no. 15, 2009, pages 3736 - 3743, XP055441747 * |
A.MIX ET AL.: "2-(Alkoxymethyl)phenylsilicon compounds: the search for pentacoordination", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 521, no. 1-2, 1996, pages 177 - 183, XP004036359, DOI: doi:10.1016/0022-328X(96)06326-7 * |
A.P.KOSTIKOV ET AL.: "Oxalic Acid Supported Si- 18F-Radiofluorination: One-Step Radiosynthesis of N-Succinimidyl 3-(Di-tert-butyl[18F] fluorosilyl)benzoate ([18F]SiFB) for Protein Labeling", BIOCONJUGATE CHEMISTRY, vol. 23, no. 1, 2012, pages 106 - 114, XP055441733 * |
DATABASE CAS Database accession no. 1443325-86-7 * |
DATABASE REGISTRY [o] 8 July 2013 (2013-07-08), retrieved from STN * |
L.IOVKOVA ET AL.: "para-functionalized aryl-di- tert-butylfluorosilanes as potential labeling synthons for 18F Radiopharmaceuticals", CHEMISTRY - A EUROPEAN JOURNAL, vol. 15, no. 9, 2009, pages 2140 - 2147, XP055071336 * |
L.IOVKOVA-BERENDS ET AL.: "t-Bu2SiF-derivatized D2-receptor ligands: the first SiFA-Containing small molecule radiotracers for target-specific PET-imaging", MOLECULES, vol. 16, 2011, pages 7458 - 7479, XP055441737 * |
See also references of EP3222688A4 * |
W.J.LEIGH ET AL.: "Intramolecular Nucleophile- Induced Photorearrangements and Silene Formation from an o-(Methoxymethyl) phenylsilacyclobutane", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 125, no. 27, 2003, pages 8096 - 8097, XP055442046 * |
W.W.SCHOELLER ET AL.: "Pentacoordination at fluoro-substituted silanes by weak Lewis donor addition", EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2000, pages 375 - 381, XP055442055 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20170154766A1 (en) * | 2015-11-27 | 2017-06-01 | Shin-Etsu Chemical Co., Ltd. | Silicon-containing condensate, composition for forming a silicon-containing resist under layer film, and patterning process |
WO2017154545A1 (ja) * | 2016-03-10 | 2017-09-14 | Jsr株式会社 | レジストプロセス用膜形成材料、パターン形成方法及び重合体 |
WO2019009413A1 (ja) * | 2017-07-06 | 2019-01-10 | 日産化学株式会社 | アルカリ性現像液可溶性シリコン含有レジスト下層膜形成組成物 |
JP7157392B2 (ja) | 2017-07-06 | 2022-10-20 | 日産化学株式会社 | アルカリ性現像液可溶性シリコン含有レジスト下層膜形成組成物 |
JPWO2019009413A1 (ja) * | 2017-07-06 | 2020-05-07 | 日産化学株式会社 | アルカリ性現像液可溶性シリコン含有レジスト下層膜形成組成物 |
US11281104B2 (en) | 2017-07-06 | 2022-03-22 | Nissan Chemical Corporation | Alkaline developer soluable silicon-containing resist underlayer film-forming composition |
JP7011444B2 (ja) | 2017-10-25 | 2022-01-26 | テクノUmg株式会社 | グラフト重合体および熱可塑性樹脂組成物 |
JP2019077808A (ja) * | 2017-10-25 | 2019-05-23 | ユーエムジー・エービーエス株式会社 | 重合体、グラフト重合体および熱可塑性樹脂組成物 |
JPWO2019124514A1 (ja) * | 2017-12-20 | 2021-01-14 | 日産化学株式会社 | 光硬化性シリコン含有被覆膜形成組成物 |
WO2019124514A1 (ja) * | 2017-12-20 | 2019-06-27 | 日産化学株式会社 | 光硬化性シリコン含有被覆膜形成組成物 |
JP7315900B2 (ja) | 2017-12-20 | 2023-07-27 | 日産化学株式会社 | 光硬化性シリコン含有被覆膜形成組成物 |
JP2021522681A (ja) * | 2018-04-25 | 2021-08-30 | ヘルムホルツ−ツェントルム ベルリン フュア マテリアリエン ウント エナギー ゲゼルシャフト ミット ベシュレンクテル ハフツングHelmholtz−Zentrum Berlin fuer Materialien und Energie GmbH | ペロブスカイト太陽電池のための正孔導電性自己組織化単分子層 |
WO2022039246A1 (ja) * | 2020-08-21 | 2022-02-24 | 日産化学株式会社 | Euvレジスト下層膜形成組成物 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2016080226A1 (ja) | 2017-09-28 |
KR20170088827A (ko) | 2017-08-02 |
EP3222688A1 (en) | 2017-09-27 |
US10845703B2 (en) | 2020-11-24 |
CN107075302A (zh) | 2017-08-18 |
CN107075302B (zh) | 2020-08-04 |
US20180335698A1 (en) | 2018-11-22 |
TW201634614A (zh) | 2016-10-01 |
JP6788222B2 (ja) | 2020-11-25 |
SG11201704070SA (en) | 2017-06-29 |
EP3222688A4 (en) | 2018-06-27 |
KR102543831B1 (ko) | 2023-06-15 |
TWI712659B (zh) | 2020-12-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5768991B2 (ja) | 新規なシリルイソシアヌレート化合物 | |
JP6150088B2 (ja) | スルホン構造を有する新規シラン化合物 | |
JP5534250B2 (ja) | スルホンアミド基を有するシリコン含有レジスト下層膜形成組成物 | |
JP5618095B2 (ja) | スルフィド結合を有するシリコン含有レジスト下層膜形成組成物 | |
JP6788222B2 (ja) | 架橋反応性シリコン含有膜形成組成物 | |
JP6436301B2 (ja) | エステル基を有するシリコン含有レジスト下層膜形成組成物 | |
JP5590354B2 (ja) | アミック酸を含むシリコン含有レジスト下層膜形成組成物 | |
JP6217940B2 (ja) | 環状ジエステル基を有するシリコン含有レジスト下層膜形成組成物 | |
JP6597980B2 (ja) | ハロゲン化スルホニルアルキル基を有するシリコン含有レジスト下層膜形成組成物 | |
WO2010071155A1 (ja) | アニオン基を有するシリコン含有レジスト下層膜形成組成物 | |
WO2012039337A1 (ja) | 保護された脂肪族アルコールを含有する有機基を有するシリコン含有レジスト下層膜形成組成物 | |
JP6882724B2 (ja) | フェニル基含有クロモファーを有するシラン化合物 | |
JP5818026B2 (ja) | ジケトン構造含有有機基を含むシリコン含有レジスト下層膜形成組成物 | |
WO2016009965A1 (ja) | 脂肪族多環構造含有有機基を有するシリコン含有レジスト下層膜形成組成物 | |
WO2016093172A1 (ja) | ハロゲン含有カルボン酸アミド基を有する加水分解性シランを含むリソグラフィー用レジスト下層膜形成組成物 | |
WO2016121686A1 (ja) | カーボネート骨格を有する加水分解性シランを含むリソグラフィー用レジスト下層膜形成組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15860187 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016560150 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20177008835 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11201704070S Country of ref document: SG Ref document number: 15528037 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015860187 Country of ref document: EP |