WO2005068540A1 - 絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 - Google Patents
絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 Download PDFInfo
- Publication number
- WO2005068540A1 WO2005068540A1 PCT/JP2005/000374 JP2005000374W WO2005068540A1 WO 2005068540 A1 WO2005068540 A1 WO 2005068540A1 JP 2005000374 W JP2005000374 W JP 2005000374W WO 2005068540 A1 WO2005068540 A1 WO 2005068540A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- insulating film
- forming
- composition
- component
- Prior art date
Links
Classifications
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- 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
- C09D183/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/46—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes silicones
-
- 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
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
- H01L21/0234—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
- H01L21/02348—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to UV light
-
- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
- H01L21/02351—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to corpuscular radiation, e.g. exposure to electrons, alpha-particles, protons or ions
-
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to a composition for forming an insulating film and a method for producing the same, and a silica-based insulating film and a method for forming the same, and more particularly, to an insulating film that can be suitably used for an interlayer insulating film in a semiconductor device.
- the present invention relates to a film-forming composition and a method for producing the same, and a silica-based insulating film and a method for forming the same.
- silica (SiO 2) film formed by a vacuum process such as a CVD method has been frequently used as an interlayer insulating film in a semiconductor element or the like.
- a more uniform film thickness has been introduced.
- an interlayer insulating film For the purpose of forming an interlayer insulating film, a coating-type insulating film called a SOG (Spin on Glass) film, which is mainly composed of a hydrolysis product of tetraalkoxylan, has been used. Also, with the high integration of semiconductor devices and the like, an interlayer insulating film having a low relative dielectric constant, which is mainly composed of polyorganosiloxane called organic SOG, has been developed.
- SOG Spin on Glass
- a CMP (Chemical Mechanical Planarization) step for flattening an insulating layer and various cleaning steps are performed. Therefore, in order to be applied to an interlayer insulating film, a protective film, and the like of a semiconductor device, it is required to have a mechanical strength and a chemical solution resistance enough to withstand erosion by a chemical solution in addition to the dielectric constant characteristics.
- a composition comprising a mixture of fine particles obtained by condensing alkoxysilane in the presence of ammonia and a basic partial hydrolyzate of alkoxysilane (Japanese Unexamined Patent Application Publication No. No. 263045, Japanese Unexamined Patent Publication No. 5-315319) and a coating solution obtained by condensing a basic hydrolyzate of polyalkoxysilane in the presence of ammonia ( Japanese Patent Application Laid-Open Nos. 11-340219 and 11-340220 have been proposed.
- the materials obtained by these methods are not suitable for industrial use because the properties of the reaction products are not stable and the coatings have large variations in relative dielectric constant, crack resistance, mechanical strength, adhesion, etc. It was not suitable for production.
- the organometallic silane bonding property is determined by a method using an organic silicate polymer obtained by producing a carbon bridge-containing silane oligomer and then subjecting it to hydrolysis and condensation (
- An object of the present invention is to suitably use it in a semiconductor device or the like where high integration and multi-layering are desired, have a low relative dielectric constant, mechanical strength, storage stability, and a chemical solution.
- An object of the present invention is to provide an insulating film forming composition capable of forming an insulating film having excellent resistance and the like, and a method for producing the same.
- Another object of the present invention is to provide a silica-based insulating film having a low relative dielectric constant and excellent in mechanical strength, storage stability, chemical solution resistance, and the like, and a method for forming the same.
- composition for forming an insulating film of the present invention comprises:
- (B) Polycarbosilane (also referred to as “(B) component” in the present application) and (C) a silane monomer having a hydrolyzable group (A) in the presence of a basic catalyst.
- ⁇ ( ⁇ ) component a silane monomer having a hydrolyzable group
- the component (B) may have a hydrolyzable group.
- the component (A) is selected from the group consisting of compounds represented by the following general formulas (1) and (3). Is a kind of silani
- the component (B) can be a polycarbosilane conjugate represented by the following general formula (4).
- R represents a hydrogen atom, a fluorine atom or a monovalent organic group
- R 1 represents a monovalent organic group
- a represents an integer of 112.
- R 2 represents a monovalent organic group.
- R 3 — R 6 are the same or different, each represents a monovalent organic group, b and c are the same or different, and represent a number of 0-2, and R 7 represents an oxygen atom or a phenylene group.
- R 7 represents an oxygen atom or a phenylene group.
- 2 m represents a group represented by the formula (where m is an integer of 1 to 6), and d represents 0 or 1. )
- R 8 is a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an aryl group and a glycidyl group.
- R 9 is a halogen atom, hydroxy group, alkoxy group, Ashirokishi group, a sulfonic group, methanesulfonic group, Torifuruo b methanesulfonate group, an alkyl group, Ariru group, Ariru group and a glycidyl group mosquito ⁇ et group consisting R 10 and R 11 are the same or different and are a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methane sulfone group, a trifluoromethane sulfone group.
- R 12 to R 14 are the same or different and are substituted or unsubstituted methylene group, alkylene group, X, y, and z represent the numbers 0 to 10,000, respectively, and represent the conditions of 5 x + y + z and 10,000, respectively. Fulfill. )
- the component (A) is completely replaced with the component (A).
- the component (B) can be used in an amount of 1 to 1,000 parts by weight based on 100 parts by weight as converted into a hydrolyzed condensate.
- the basic catalyst (C) may be a nitrogen-containing compound represented by the following general formula (5).
- X 1 , X 2 , X 3 , and X 4 are the same or different and are each selected from the group consisting of a hydrogen atom, an alkyl group having 120 carbon atoms, a hydroxyalkyl group, an aryl group, and an arylalkyl group.
- Y represents a halogen atom or a monovalent tetravalent group, and a represents an integer of 114.
- the method for producing an insulating film-forming composition of the present invention comprises:
- the method may include a step of hydrolyzing and condensing (A) a silane monomer having a hydrolyzable group in the presence of (B) a polycarbosilane and (C) a basic catalyst.
- the method for producing the insulating film forming composition of the present invention may further include a step of dissolving the hydrolyzed condensate obtained by the hydrolytic condensation in an organic solvent.
- the component (B) is
- the component (A) is
- R represents a hydrogen atom, a fluorine atom or a monovalent organic group
- R 1 represents a monovalent organic group.
- R 2 represents a monovalent organic group.
- R 3 — R 6 are the same or different, each represents a monovalent organic group, b and c are the same or different, and represent a number of 0-2, and R 7 represents an oxygen atom or a phenylene group.
- R 7 represents an oxygen atom or a phenylene group.
- 2 m represents a group represented by the formula (where m is an integer of 1 to 6), and d represents 0 or 1. )
- R 8 is a group that also has a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an aryl group and a glycidyl group.
- R 9 represents a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfone group, an alkyl group, an aryl group, an aryl group or a glycidyl group.
- R 10 and R 11 are the same or different and each represents a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methanesulfone group, a trifluoromethanesulfon group, a C 2-6 Alkyl group, aryl group, aryl group and glycidyl group
- R 12 -R 14 are the same or different and represent a substituted or unsubstituted methylene group, an alkylene group, an alkenyl group, an alkyl group, an arylene group, and X, y and z represent 0-10, respectively. 000, which satisfies the condition of 5 x + y + z x 10,000.)
- the component (A) in the method for producing the composition for forming an insulating film of the present invention, the component (A)
- the component (B) can be used in an amount of 11 to 1000 parts by weight based on 100 parts by weight of the component (A) in terms of the complete hydrolytic condensation product.
- the basic catalyst (C) may be a nitrogen-containing compound represented by the following general formula (5). it can. [0025] (X'X ⁇ N) Y (5)
- X 1 , X 2 , X 3 , and X 4 are the same or different and are each selected from the group consisting of a hydrogen atom, an alkyl group having 120 carbon atoms, a hydroxyalkyl group, an aryl group, and an arylalkyl group.
- Y represents a halogen atom or a monovalent tetravalent group, and a represents an integer of 114.
- the method for forming a silica-based insulating film of the present invention comprises:
- composition for forming an insulating film of the present invention to a substrate to form a coating film, and subjecting the coating film to at least one kind of curing treatment selected from heating, electron beam irradiation, ultraviolet irradiation, and oxygen plasma. Performing the following.
- the silica-based insulating film according to the present invention is obtained by the above-described method for forming a silica-based insulating film of the present invention.
- the film-forming composition of the present invention it is obtained by hydrolytic condensation of (A) a hydrolyzable group-containing silane monomer in the presence of (B) polycarbosilane and (C) a basic catalyst. Including hydrolyzed condensates.
- (A) the hydrolyzable group-containing silane monomer is hydrolyzed to form a silanol group (-Si-OH), and (B) the silanol group ( The formation of (i-Si-OH) proceeds.
- This reaction proceeds in the presence of (C) a basic catalyst, and further causes a condensation reaction to form a Si—O—Si bond, so that the tertiary structure is highly branched and the molecular weight of the hydrolyzable condensate is large. Is obtained. Therefore, by using the composition for forming an insulating film of the present invention, it is possible to form a small dielectric film with a low relative dielectric constant.
- this hydrolyzed condensate forms a chemical bond with (B) a polysiloxane derived from (A) a hydrolyzable group-containing silane monomer, and is incorporated into the tertiary structure.
- a hydrolyzable group-containing silane monomer is hydrolyzed and condensed in the presence of (B) polycarbosilane and (C) a basic catalyst.
- the method for forming a silica-based insulating film of the present invention a step of applying the above-described composition for forming an insulating film of the present invention to a substrate to form a coating film; Irradiation, ultraviolet irradiation, and oxygen plasma force.
- the obtained silica-based insulating film is excellent in relative dielectric constant, mechanical strength, adhesion, and chemical resistance, and has no phase separation in the film.
- the film-forming composition according to the present invention (insulating film-forming composition) is obtained by hydrolyzing the component (A) in the presence of the component (B) and the basic catalyst (C), and condensing a hydrolyzed condensate. (Hereinafter, referred to as “specific hydrolysis condensate”) and an organic solvent.
- specific hydrolysis condensate a hydrolyzed condensate
- organic solvent an organic solvent
- the component (A) includes a compound represented by the following general formula (1) (hereinafter, referred to as “compound 1”), a compound represented by the following general formula (2) (hereinafter, referred to as “compound 2”) and Group strength of a compound represented by the following general formula (3) (hereinafter, referred to as "compound 3”): at least one selected silani conjugate.
- compound 1 a compound represented by the following general formula (1)
- compound 2 a compound represented by the following general formula (2)
- compound 3 Group strength of a compound represented by the following general formula (3)
- R represents a hydrogen atom, a fluorine atom or a monovalent organic group
- R 1 represents a monovalent organic group
- a represents an integer of 112.
- R 2 represents a monovalent organic group.
- R 3 — R 6 are the same or different, each represents a monovalent organic group, b and c are the same or different, and represent a number of 0-2, and R 7 represents an oxygen atom or a phenylene group.
- R 7 represents an oxygen atom or a phenylene group.
- 2 m represents a group represented by the formula (where m is an integer of 1 to 6), and d represents 0 or 1. )
- the term "hydrolysable group” refers to the amount of carohydrate at the time of producing the film forming composition of the present invention.
- a group that can be hydrolyzed are not particularly limited. Examples thereof include a hydrogen atom bonded to a silicon atom, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a sulfone group, a methane sulfone group, and a trifluoromethane sulfone group. Groups.
- examples of the monovalent organic group represented by R and R 1 include an alkyl group, an aryl group, an aryl group, a glycidyl group, and a butyl group.
- the monovalent organic group for R is particularly preferably an alkyl group or a phenyl group.
- examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group and the like, preferably having 15 to 15 carbon atoms, and these alkyl groups may be chain-like or branched.
- a hydrogen atom may be substituted with a fluorine atom, an amino group, or the like.
- examples of the aryl group include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a chlorophenol group, a bromophenyl group, a fluorophenyl group and the like. Can be mentioned.
- compound 1 examples include methyltrimethoxysilane, methyltriethoxysilane, methyltri-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltrimethylsilane.
- Particularly preferred compounds as compound 1 include methyltrimethoxysilane, methyltriethoxysilane, methyltri- ⁇ -propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and butyltrimethoxysilane.
- examples of the monovalent organic group for R 2 include the same groups as the monovalent organic groups exemplified as R, in the general formula (1).
- compound 2 examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-isopropoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraphenoxysilane And the like.
- Particularly preferred compounds include tetramethoxysilane and tetraethoxysilane. These may be used alone or in combination of two or more.
- examples of the monovalent organic group of R 3 to R 6 include the same groups as the monovalent organic groups exemplified as R and R 1 in the general formula (1).
- Silane 1, 1, 1, 2, 2-pentaethoxy-2-methyldisilane, 1,1,1,2,2-pentaphenoxy 2-methyldisilane, 1,1,1,2,2-pentamethoxy 2-Ethyldisilane, 1, 1, 1, 2, 2-pentaethoxy 2-Ethyldisilane, 1,1,1,2,2-pentaphenoxy 2-ethyldisilane, 1,1,1,2,2-penta Methoxy-2-phenyldisilane, 1,1,1,2,2-pentaethoxy-2-phenyldisilane, 1,1,1,2,2-pentaphenoxy-2-phenyldisilane, 1,1,2,2-pentaphenoxy-2-phenyldisilane, 1, 1,2,2-tetramethoxy-1,2-dimethyldisilane, 1,1,2,2-tetraethoxy 1,2-dimethyldisilane, 1,1,2,2-tetraf Enoxy 1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-
- R 7 is a compound of a group represented by — (CH 2) 1
- bis (trimethoxysilyl) methane bis (triethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1 (dimethoxymethylsilyl) ) -1 (Trimethoxysilyl) methane, 1- (Diethoxymethylsilyl) -1- (Triethoxysilyl) methane, 1 (Dimethoxymethylsilyl) -2- (Trimethoxysilyl) ethane, 1- (Jet (Toximethylsilyl) -2- (triethoxysilyl) ethane
- One or more of the compounds 13 may be used at the same time.
- the component (B) is a polycarbosilane that can form a Si—O—Si bond by condensing with the component (A).
- the component (B) can be, for example, a polycarbosilane conjugate represented by the following general formula (4) (hereinafter, sometimes referred to as “compound 4” t).
- compound 4 a polycarbosilane conjugate represented by the following general formula (4) (hereinafter, sometimes referred to as “compound 4” t).
- the component (B) includes a case where the polycarbosilane conjugate is dissolved in an organic solvent.
- R 8 represents a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group, a sulfone group, a methane sulfone group, a trifluoromethane sulfone group, an alkyl group, an aryl group, an aryl group, A glycidyl group
- R 9 represents a halogen atom, a hydroxy group, an alkoxy group, a sulfone group, a methane sulfone group, a trifluoromethane sulfone group, an alkyl group, an aryl group, an aryl group, or a glycidyl group
- R 10 and R 11 Are the same or different, and Dorokishi group, an alkoxy group, a sulfonic group, methanesulfonic group, triflate Ruo b methanesulfonate group, an alkyl group having a carbon
- a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and the like
- an alkoxy group includes a methoxy group, an ethoxy group, a propyloxy group and a butoxy group
- an acyloxy group includes an acetyloxy group.
- alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and cyclohexyl groups, and aryl groups such as phenyl, naphthyl, and methylphenyl.
- aryl groups such as phenyl, naphthyl, and methylphenyl.
- Examples of the alkylene group include an ethylene group, a propylene group, a butylene group, a hexylene group, and a decylene group, and preferably have 2 to 6 carbon atoms, and these alkylene groups may be branched in a chain. Or a hydrogen atom which may further form a ring may be substituted with a fluorine atom or the like.
- examples of the alkoxyl group include an eturene group, a probenylene group, a 1-butylene group, a 2-butylene group, and the like.
- a hydrogen atom may be substituted with a fluorine atom or the like.
- the alkyl group include an acetylene group and a propylene group.
- the arylene group include a phenylene group and a naphthylene group.
- a hydrogen atom may be substituted with a fluorine atom or the like, and may be substituted!
- X, y, ⁇ a number between 0 and 10,000, and 5 ⁇ x + y + z ⁇ 10,000.
- x + y + z + 5 the storage stability of the film-forming composition may be poor, and in the case of 10,000 + x + y + z, the component (A) and Wakes up and forms a uniform film.
- X, y, and z are 0 ⁇ x ⁇ 800, 0 ⁇ y ⁇ 500, and 0 ⁇ 1,000, respectively, and more preferably, 0 ⁇ x ⁇ 500, 0 ⁇ y ⁇ 300, 0 ⁇ z ⁇ 500, and more preferably 0 ⁇ x ⁇ 100, 0 ⁇ y ⁇ 50, and 0 ⁇ z ⁇ 100.
- the mixing ratio of the component (A) to the component (B) is preferably such that the component (B) is used in an amount of 1 to 1,000 parts by weight based on 100 parts by weight of the completely hydrolyzed condensate of the component (A). In particular, it is more preferably 5 to 200 parts by weight, and still more preferably 5 to 100 parts by weight. If the component (B) is less than 1 part by weight, sufficient chemical resistance may not be exhibited after film formation, and if it exceeds 1000 parts by weight, a low dielectric constant of the film is achieved. It may not be possible.
- the weight average molecular weight in terms of polystyrene of the component (B) is preferably from 400 to 50,000, more preferably from 500 to 10,000, and more preferably from 500 to 3,000. Even more preferred. If the weight average molecular weight in terms of polystyrene of the component (B) exceeds 50,000, layer separation may occur with the component (A) and a uniform film may not be formed.
- the presence of (C) a basic catalyst and (B) component using compound 4 as (B) component By hydrolyzing and condensing the component (A), the hydrolysis and condensation of the component (B) and the polysiloxane derived from the component (A) can be advanced together with the hydrolysis and condensation of the components (A). it can.
- the resulting hydrolysis-condensation product is obtained by incorporating the polymer having the component (B) (polycarbosilane) as a core into the tertiary structure of the polysiloxane derived from the component (A) (hydrolyzable group-containing silane monomer).
- composition for forming an insulating film of the present invention contains the above-mentioned hydrolyzed condensate, the insulating material having a smaller relative dielectric constant, excellent mechanical strength, adhesion and chemical resistance, and having no phase separation in the film. A membrane can be obtained.
- the (C) basic catalyst according to the present invention includes, for example, methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanol.
- N-butylethanolamine N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, N-methylpropanolamine, N-ethylpropanolamine Min, N— Propylpropanolamine, N-butylpropanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-propylbutanolamine, N-butylbutanolamine, N, N-dimethylmethanolamine, N N, N-Diethylmethanolamine, N, N-Dibutylmethanolamine, N, N-Dimethylethanolamine, N, N-Diethylethanolamine, N, N— Dipropylethanolamine, N, N-dibutylethanolamine, N, N-dimethylpropanolamine, N, N-getylpropanolamine, N, N-dipropylpropanolamine, N, N-dibut
- the (C) basic catalyst is particularly preferably a nitrogen-containing compound represented by the following general formula (5) (hereinafter, also referred to as compound 5).
- X 1 , X 2 , X 3 , and X 4 are the same or different and are each a hydrogen atom, an alkyl group having 120 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, a butyl group).
- compound 5 examples include hydroxylated tetramethylammonium, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-iso-propylammonium hydroxide, and hydroxylated hydroxide.
- hydroxyl-tetramethylammonium hydroxyl-tetraethylammonium, hydroxyl-n-tetrapropylammonium, and hydroxyl-n-butylammonium-tetraammonium.
- One or more of the compounds 5 may be used simultaneously.
- the amount of the basic catalyst (C) to be used is generally 0.0001-1 mol, preferably 0.001- 1 mol, per 1 mol of the component (A) (total amount of the disulfide compound 113). 0.1 mole.
- the specific hydrolysis-condensation product is obtained by hydrolyzing and condensing component (A) in the presence of component (B) and basic catalyst (C).
- component (A) can be hydrolyzed in a state where component (A) and component (B) are dissolved in an organic solvent.
- organic solvent that can be used in this case include methanol , Ethanol, n -propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol and other alcoholic solvents; ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2 , 4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4 heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, Polyhydric alcohol solvents such as tripropylene glycol; polyhydric alcohols such as ethylene glycol monomethyl ether ether, ethylene
- System solvent etinoleatenole, i-propynoleatene, n-butynoleatel, n-hexylether, 2-ethylhexylether, ethyleneoxide, 1,2-propylenoxide, dioxolan, 4-methyldiene Ether-based solvents such as oxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycolone monoethylenate ethereone, etc .; acetone, methylethyl ketone, methyl n - propyl ketone, methyl n- butyl ketone, Jechiruketon, methyl-i Buchiruketon, methyl-n Penchiruketo down, Echiru n - butyl ketone, Kishiruketon to methyl-n-, di-i Buchiruketon, trimethylene
- the concentration of the total amount of the component (B) and the component (A) in the organic solvent is preferably 1 to 30% by weight.
- the reaction temperature in the hydrolytic condensation is 0 to 100 ° C, preferably 20 to 80 ° C, and the reaction time is
- each component is not particularly limited !, but, for example, a solution obtained by adding (C) a basic catalyst to an organic solvent, a component (A) and a component (B) to an organic solvent, respectively. Add the added one by one! / The preferred method is ⁇ .
- the weight average molecular weight in terms of polystyrene of the obtained specific hydrolysis condensate is usually 1,5.
- Examples of the organic solvent contained in the composition for forming an insulating film of the present invention include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic solvents, and solvents.
- Group strength of halogen solvent At least one selected from the group consisting of halogen solvents is used.
- alcohol solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, and sec-pentanol.
- T-pentanol 3-methoxybutanol, n-xanol, 2-methylpentanol, sec-xanol, 2-ethylbutanol, sec-ptanol, 3-ptanol, n-octanol, 2-ethylhexanol, sec-octanol N-Alcohol, 2,6-dimethyl-41-heptanol n-decanol, sec- decyl alcohol, trimethyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furfuryl alcohol, pheno , Cyclohexanol, methylcyclo Monoalcohol solvents such as xanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol; ethylene glycolone, 1,2 propylene glycol, 1,3-butylene glycol, 2,4-pentanediol Poly
- Ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, getyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-xyl ketone, and di-butyl ketone.
- Ketone solvents such as trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-xanone, methylcyclohexanone, 2,4 pentanedione, acetonylaceton, diacetone alcohol, acetphenenone, and fenchone. Can be mentioned. One or more of these ketone solvents may be used simultaneously.
- amide solvents include ⁇ , ⁇ dimethylimidazolidinone, ⁇ ⁇ ⁇ methylformamide, ⁇ ,
- nitrogen-containing solvents such as ⁇ -dimethylformamide, ⁇ , ⁇ -getylformamide, acetoamide, ⁇ ⁇ ⁇ methylacetamide, ⁇ , ⁇ -dimethylacetoamide, ⁇ ⁇ ⁇ methylpropionamide, and ⁇ ⁇ ⁇ methylpyrrolidone.
- nitrogen-containing solvents such as ⁇ -dimethylformamide, ⁇ , ⁇ -getylformamide, acetoamide, ⁇ ⁇ ⁇ methylacetamide, ⁇ , ⁇ -dimethylacetoamide, ⁇ ⁇ ⁇ methylpropionamide, and ⁇ ⁇ ⁇ methylpyrrolidone.
- amide solvents such as ⁇ -dimethylformamide, ⁇ , ⁇ -getylformamide, acetoamide, ⁇ ⁇ ⁇ methylacetamide, ⁇ , ⁇ -dimethylacetoamide, ⁇ ⁇ ⁇ methylpropionamide, and ⁇ ⁇ ⁇ methylpyrrol
- Examples of the ether solvent system include ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylenoxide, dioxolan, and 4-methyldioxide.
- ester-based solvent examples include getyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, ⁇ -butyrolataton, ⁇ -valerolatone, ⁇ -propyl acetate, propyl acetate, ⁇ -butyl acetate, i-butyl acetate, and sec-butyl acetate.
- Examples of the aliphatic hydrocarbon solvent include n-pentane, i-pentane, n-xane, and i- And aliphatic hydrocarbon solvents such as n-heptane, i-heptane, 2,2,4 trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane.
- aliphatic hydrocarbon solvents such as n-heptane, i-heptane, 2,2,4 trimethylpentane, n-octane, i-octane, cyclohexane and methylcyclohexane.
- aromatic hydrocarbon solvent examples include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, getylbenzene, ibutylbenzene, triethylbenzene, Examples thereof include aromatic hydrocarbon solvents such as diisopropylbenzene, n-amylnaphthalene, and trimethylbenzene. One or more of these aromatic hydrocarbon solvents may be used simultaneously.
- the halogen-containing solvent include halogen-containing solvents such as dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, and dichlorobenzene.
- alcohol solvents are particularly preferred as the solvent species for which it is desirable to use an organic solvent having a boiling point of less than 150 ° C. It is desirable to use two or more species simultaneously.
- organic solvents may be the same as those used for the synthesis of the specific hydrolysis condensate, or may be replaced with a desired organic solvent after the synthesis of the specific hydrolysis condensate is completed. Talk about this.
- Components such as an organic polymer and a surfactant may be further added to the composition for forming an insulating film of the present invention.
- these additives may be added to a solvent in which the components (A) and (B) are mixed or dissolved before the components are mixed.
- organic polymer examples include a polymer having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound polymer, a dendrimer, a polyimide, a polyamic acid, a polyarylene, a polyamide, and a polymer.
- examples include quinoxaline, polyoxadiazole, fluorine-based polymers, and polymers having a polyalkylene oxide structure.
- Examples of the polymer having a polyalkylene oxide structure include a polymethylene oxide structure , A polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, a polybutylene oxide structure, and the like.
- Ether type compounds such as ethylene oxide
- Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structures.
- n a number of 0-90.
- polyoxyethylene alkyl ether polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene anolequinolate ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester Ether-type compounds such as oxyethylene sorbitol fatty acid ester can be mentioned as more preferable examples.
- One or more of the aforementioned organic polymers may be used simultaneously.
- the surfactant examples include a nonionic surfactant, an anionic surfactant, Examples include cationic surfactants and amphoteric surfactants, and further include fluorine-based surfactants, silicone-based surfactants, polyalkylene oxide-based surfactants, and poly (meth) acrylate-based surfactants. And preferably a fluorine-based surfactant and a silicone-based surfactant.
- the amount of the surfactant to be used is generally 0.000001 to 11 parts by weight based on 100 parts by weight of the obtained polymer. These may be used alone or in combination of two or more.
- the method for forming a film (insulating film) of the present invention includes a step of applying a film-forming composition to a substrate to form a coating film, and a step of subjecting the coating film to a heat treatment.
- Substrates to which the film-forming composition is applied include Si, SiO
- Si-containing layers such as SiN, SiC and SiCN.
- a coating method such as spin coating, dipping, roll coating, or spraying is used. After applying the film-forming composition to the substrate, the solvent is removed to form a coating film. In this case, a dry film thickness of 0.05 to 2.5 / ⁇ can be formed with a single coating, and a coating film with a thickness of 0.1 to 5 can be formed with a double coating. . Thereafter, the obtained coating film is subjected to a curing treatment to form a silica-based film.
- Examples of the curing treatment include heating, electron beam irradiation, ultraviolet irradiation, and plasma treatment.
- this coating film is heated to 80 ° C. to 450 ° C. in an inert atmosphere or under reduced pressure.
- a heating method at this time a hot plate, an oven, a furnace, or the like can be used, and the heating can be performed under an inert atmosphere or under reduced pressure.
- heating may be performed stepwise, or an atmosphere such as nitrogen, air, oxygen, or reduced pressure may be selected. Through such steps, a silica-based film can be manufactured.
- the interlayer for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM is used. It is particularly excellent as an insulating film.It is also an etching stopper film, a protective film such as a surface coat film of a semiconductor element, an intermediate layer in a semiconductor manufacturing process using a multilayer resist, an interlayer insulating film of a multilayer wiring substrate, and a liquid crystal display. It can be suitably used as a protective film or an insulating film for an element.
- the composition for forming a film is coated on an 8-inch silicon wafer by a spin coating method, dried on a hot plate at 90 ° C for 3 minutes, and then dried at 200 ° C for 3 minutes in a nitrogen atmosphere. Under a reduced pressure (vacuum atmosphere) at 420 ° C. in a vertical furnace for 1 hour.
- An aluminum electrode pattern was formed on the obtained film by a vapor deposition method, and a sample for measuring relative permittivity was prepared. With respect to the sample, the relative dielectric constant of the film was measured by a CV method at a frequency of 100 kHz using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd.
- a barco-pitch type indenter was attached to a micro hardness tester (Nanoindentator XP) manufactured by MTS, and the universal hardness of the obtained insulating film was determined.
- the elastic modulus was measured by a continuous stiffness measuring method.
- the film-forming composition stored at 40 ° C for 30 days is applied to the substrate by spin coating, and the substrate is placed on a hot plate at 90 ° C for 3 minutes and then at 200 ° C in a nitrogen atmosphere for 3 minutes. Was dried, and further baked for 1 hour in a vertical furnace at 420 ° C. under a reduced pressure of 50 mTorr.
- the film thickness of the coating film thus obtained was measured at 50 points within the coating film surface using an optical film thickness meter (Spectra Laser200, manufactured by Rudolph Technologies). Measure the thickness of the obtained film Then, storage stability was evaluated based on the film thickness increase rate obtained by the following equation.
- Thickness increase rate (%) ((thickness after storage) (thickness before storage)) ⁇ (thickness before storage) X 10 0
- the film thickness increase rate is 4% or less.
- the 8-inch wafer on which the silica-based film was formed was immersed in a 0.2% dilute hydrofluoric acid aqueous solution for 1 minute at room temperature, and the change in the thickness of the silica-based film before and after immersion was observed. If the residual film ratio defined below is 99% or more, it is judged that the chemical resistance is good.
- Residual film ratio (%) (Film thickness after immersion) ⁇ (Film thickness before immersion) X 100
- the residual film ratio is 99% or more.
- the residual film ratio is less than 99%.
- the cross section of the insulating film was cut for observation by a focused ion beam method, and the appearance was examined at 18,000 times using a TEM. The judgment result is shown as follows.
- reaction solution containing a hydrolyzed condensate having a weight average molecular weight of 55,000 in terms of polystyrene was obtained.
- Olg of a 20% acetic acid aqueous solution were added.
- the reaction solution was concentrated under reduced pressure until the solid concentration became 10%, to obtain a composition 2 for film formation.
- reaction solution containing a hydrolyzed condensate having a weight average molecular weight in terms of polystyrene of 40,000.
- reaction solution was cooled to room temperature, 650.84 g of propylene glycol monopropyl ether and 12.83 g of a 20% aqueous acetic acid solution were obtained.
- the reaction solution was concentrated under reduced pressure until the solid content concentration became 10%, to obtain Composition 3 for film formation.
- reaction solution containing a hydrolysis condensate having a weight average molecular weight of 48,000 in terms of polystyrene was obtained.
- 624.16 g of propylene glycol monopropyl ether and 19.32 g of a 20% acetic acid aqueous solution were added.
- the reaction solution was concentrated under reduced pressure until the solid content concentration became 10%, to obtain Composition 4 for film formation.
- reaction solution was left to cool, diluted with 250 ml of ethyl ether, and washed 3-4 times with distilled water until the pH became neutral.
- 200 g of propylene glycol monopropyl ether is added to this solution, and then the solution is concentrated to 20% (in terms of complete 311 hydrolyzed condensate) using an evaporator at 50 ° C. 20% of a propylene glycol monopropyl ether solution was added to obtain a film-forming composition 6.
- reaction was carried out at 55 ° C for 1 hour to obtain a reaction solution containing a hydrolyzed condensate having a weight average molecular weight of 2,300 in terms of polystyrene, and 825.50 g of propylene glycol monoethyl ether was added. Cool. The reaction solution was concentrated under reduced pressure until the solid content concentration became 10%, to obtain a film-forming composition 8.
- reaction solution containing a hydrolyzed condensate having a weight average molecular weight of 2,500 in terms of polystyrene.
- 100.25 g of propylene glycol monoethyl ether was added, and the reaction solution was cooled to room temperature. .
- the reaction solution was concentrated under reduced pressure until the solid content concentration became 10%, to obtain composition 9 for film formation.
- Example 16 Using the film-forming composition 1-13 obtained in Example 16 and Comparative Example 1-17, the specific dielectric constant, elastic modulus, hardness, chemical resistance, storage stability and cross-sectional observation results were evaluated. went. Table 1 shows the evaluation results.
- Comparative Example 1 is an example in which the basic catalyst of Example 5 was replaced with an acidic catalyst. According to a comparison between Comparative Example 1 and Example 5, hydrolysis and condensation were performed using a basic catalyst. It is clear that a homogeneous coating film without phase separation can be obtained by performing the reaction.
- Comparative Example 6 was obtained when the hydrolysis condensation reaction was performed in the absence of polycarbosilane. However, degradation of chemical resistance has been observed, indicating that hydrolytic condensation in the presence of polycarbosilane is useful.
- the silica-based film obtained by the present invention is excellent in mechanical strength, low in relative dielectric constant, and also excellent in chemical resistance and storage stability, so that it is suitable as an interlayer insulating film for semiconductor elements and the like. Can be used.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20050703613 EP1705208B1 (en) | 2004-01-16 | 2005-01-14 | Composition for forming insulating film, method for producing same, silica insulating film, and method for forming same |
KR1020067016326A KR101185644B1 (ko) | 2004-01-16 | 2005-01-14 | 절연막 형성용 조성물 및 그의 제조 방법, 및 실리카절연막 및 그의 형성 방법 |
JP2005517077A JP5105041B2 (ja) | 2004-01-16 | 2005-01-14 | 絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 |
US11/486,085 US7875317B2 (en) | 2004-01-16 | 2006-07-14 | Composition for forming insulating film, method for producing same, silica-based insulating film, and method for forming same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004-009205 | 2004-01-16 | ||
JP2004009205 | 2004-01-16 | ||
JP2004-141200 | 2004-05-11 | ||
JP2004141200 | 2004-05-11 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/486,085 Continuation US7875317B2 (en) | 2004-01-16 | 2006-07-14 | Composition for forming insulating film, method for producing same, silica-based insulating film, and method for forming same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005068540A1 true WO2005068540A1 (ja) | 2005-07-28 |
Family
ID=34797750
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/000374 WO2005068540A1 (ja) | 2004-01-16 | 2005-01-14 | 絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 |
PCT/JP2005/000375 WO2005068541A1 (ja) | 2004-01-16 | 2005-01-14 | 有機シリカ系膜の形成方法、有機シリカ系膜、配線構造体、半導体装置、および膜形成用組成物 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/000375 WO2005068541A1 (ja) | 2004-01-16 | 2005-01-14 | 有機シリカ系膜の形成方法、有機シリカ系膜、配線構造体、半導体装置、および膜形成用組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US7875317B2 (ja) |
EP (1) | EP1705208B1 (ja) |
JP (1) | JP5105041B2 (ja) |
KR (1) | KR101185644B1 (ja) |
TW (1) | TW200538491A (ja) |
WO (2) | WO2005068540A1 (ja) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005350653A (ja) * | 2004-05-11 | 2005-12-22 | Jsr Corp | 有機シリカ系膜の形成方法、有機シリカ系膜、配線構造体、半導体装置、および膜形成用組成物 |
JP2005350651A (ja) * | 2004-05-11 | 2005-12-22 | Jsr Corp | 絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 |
JP2007070480A (ja) * | 2005-09-07 | 2007-03-22 | Fujifilm Corp | 膜形成用組成物、絶縁膜およびその製造方法 |
WO2008066060A1 (fr) * | 2006-11-30 | 2008-06-05 | Jsr Corporation | Procédé de fabrication d'un polymère, composition de formation d'un film isolant et film isolant de silice et son procédé de fabrication |
US7497965B2 (en) * | 2005-08-11 | 2009-03-03 | Fujifilm Corporation | Insulating film-forming composition, insulating film and production method thereof |
JP2010106099A (ja) * | 2008-10-29 | 2010-05-13 | Jsr Corp | 絶縁膜形成用組成物、ならびに絶縁膜およびその形成方法 |
US20100140807A1 (en) * | 2007-07-06 | 2010-06-10 | Fujitsu Limited | Insulating film material, multilayer wiring board and production method thereof, and semiconductor device and production method thereof |
JP5013045B2 (ja) * | 2004-01-16 | 2012-08-29 | Jsr株式会社 | ポリマーの製造方法 |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3951124B2 (ja) * | 2002-12-06 | 2007-08-01 | Jsr株式会社 | 絶縁膜 |
US8656039B2 (en) * | 2003-12-10 | 2014-02-18 | Mcafee, Inc. | Rule parser |
EP1719793A4 (en) * | 2004-02-26 | 2009-05-20 | Jsr Corp | POLYMER AND MANUFACTURING METHOD THEREFOR, COMPOSITION FOR FORMING AN INSULATING FILM AND PRODUCTION METHOD THEREFOR |
WO2005108469A1 (ja) * | 2004-05-11 | 2005-11-17 | Jsr Corporation | 有機シリカ系膜の形成方法、有機シリカ系膜、配線構造体、半導体装置、および膜形成用組成物 |
EP1981074B1 (en) * | 2006-02-02 | 2011-06-22 | JSR Corporation | Organic silica film and method for forming same, composition for forming insulating film of semiconductor device and method for producing same, wiring structure and semiconductor device |
WO2008020592A1 (fr) * | 2006-08-15 | 2008-02-21 | Jsr Corporation | Matériau filmogène, film isolant contenant du silicium et procédé de formation de celui-ci |
KR20090119903A (ko) * | 2007-02-14 | 2009-11-20 | 제이에스알 가부시끼가이샤 | 규소 함유 막 형성용 재료, 및 규소 함유 절연막 및 그의 형성 방법 |
US20100261925A1 (en) * | 2007-07-10 | 2010-10-14 | Jsr Corporation | Method for producing silicon compound |
US20090081598A1 (en) * | 2007-09-24 | 2009-03-26 | International Business Machines Corporation | Functionalized carbosilane polymers and photoresist compositions containing the same |
US20090081579A1 (en) * | 2007-09-24 | 2009-03-26 | International Business Machines Corporation | Functionalized carbosilane polymers and photoresist compositions containing the same |
KR20100126327A (ko) * | 2008-03-26 | 2010-12-01 | 제이에스알 가부시끼가이샤 | 화학 기상 성장법용 재료, 규소 함유 절연막 및 그의 제조 방법 |
JP5365785B2 (ja) * | 2008-05-30 | 2013-12-11 | Jsr株式会社 | 有機ケイ素化合物の製造方法 |
KR100968803B1 (ko) * | 2008-06-24 | 2010-07-08 | 주식회사 티씨케이 | 폴리카르보실란 및 그 제조방법 |
JP4379637B1 (ja) | 2009-03-30 | 2009-12-09 | Jsr株式会社 | 有機ケイ素化合物の製造方法 |
MY195756A (en) | 2012-09-17 | 2023-02-09 | Grace W R & Co | Functionalized Particulate Support Material and Methods of Making and Using the Same |
CA2885263C (en) | 2012-09-17 | 2021-11-16 | W. R. Grace & Co.-Conn. | Chromatography media and devices |
WO2014078665A1 (en) * | 2012-11-15 | 2014-05-22 | Elantas Pdg, Inc. | Composite insulating film |
WO2015049696A1 (en) * | 2013-10-01 | 2015-04-09 | Tata Steel Limited | A chromium-free water based coating for treating a galvannealed or galvanized steel surface |
JP6853670B2 (ja) | 2014-01-16 | 2021-04-07 | ダブリュー・アール・グレース・アンド・カンパニー−コーンW R Grace & Co−Conn | 親和性クロマトグラフィー媒体及びクロマトグラフィーデバイス |
WO2015168383A1 (en) | 2014-05-02 | 2015-11-05 | W. R. Grace & Co.-Conn. | Functionalized support material and methods of making and using functionalized support material |
SG10201911134QA (en) | 2015-06-05 | 2020-01-30 | Grace W R & Co | Adsorbent bioprocessing clarification agents and methods of making and using the same |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5461299A (en) * | 1977-10-26 | 1979-05-17 | Tokushiyu Muki Zairiyou Kenkiy | Polycarbosilane partially containing siloxane linkage and method of making same |
JPH05105759A (ja) * | 1991-10-17 | 1993-04-27 | Kanegafuchi Chem Ind Co Ltd | ケイ素系ハイブリツド材料 |
JP2000309752A (ja) * | 1999-04-27 | 2000-11-07 | Jsr Corp | 膜形成用組成物および絶縁膜形成用材料 |
JP2001127152A (ja) * | 1999-10-25 | 2001-05-11 | Fujitsu Ltd | 低誘電率絶縁膜の形成方法及び該方法で形成された低誘電率絶縁膜及び該低誘電率絶縁膜を用いた半導体装置 |
JP2001345317A (ja) * | 2000-03-29 | 2001-12-14 | Fujitsu Ltd | 低誘電率被膜形成材料、及びそれを用いた被膜と半導体装置 |
WO2002098955A1 (en) * | 2001-06-07 | 2002-12-12 | Lg Chem, Ltd. | Organosilicate polymer and insulating film therefrom |
JP2003115482A (ja) * | 2001-10-05 | 2003-04-18 | Asahi Kasei Corp | 絶縁膜形成用組成物 |
US20040007753A1 (en) * | 2002-04-25 | 2004-01-15 | Kyocera Corporation | Photoelectric conversion device and manufacturing process thereof |
JP2005076031A (ja) * | 2003-09-01 | 2005-03-24 | Samsung Electronics Co Ltd | 新規のシロキサン樹脂及びこれを用いた半導体層間絶縁膜 |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5248903B2 (ja) * | 1974-06-19 | 1977-12-13 | ||
GB2009196B (en) * | 1977-10-26 | 1982-04-15 | Res Inst For Special Inorganic | Polycarbosilane process for its prudiction and its use as material for producing silicon carbide |
JPS6169836A (ja) * | 1984-09-12 | 1986-04-10 | Chisso Corp | けい素含有ステツプラダ−ポリマ−及びその製造方法 |
JPH04100873A (ja) * | 1990-08-21 | 1992-04-02 | Ube Ind Ltd | 耐熱性塗料 |
JP3320440B2 (ja) | 1992-03-17 | 2002-09-03 | 触媒化成工業株式会社 | 被膜形成用塗布液およびその製造方法 |
JP3073313B2 (ja) | 1992-05-12 | 2000-08-07 | 触媒化成工業株式会社 | 半導体装置およびその製造方法 |
JPH08217879A (ja) * | 1995-02-15 | 1996-08-27 | Mitsubishi Rayon Co Ltd | 耐熱性樹脂およびその製造方法 |
US6652922B1 (en) * | 1995-06-15 | 2003-11-25 | Alliedsignal Inc. | Electron-beam processed films for microelectronics structures |
US6042994A (en) * | 1998-01-20 | 2000-03-28 | Alliedsignal Inc. | Nanoporous silica dielectric films modified by electron beam exposure and having low dielectric constant and low water content |
DE19810803A1 (de) * | 1998-03-12 | 1999-09-16 | Wacker Chemie Gmbh | Verfahren zur Herstellung mikroverkapselter Produkte mit Organopolysiloxanwänden |
JP4473352B2 (ja) | 1998-05-26 | 2010-06-02 | 東京応化工業株式会社 | 低比誘電率シリカ系被膜、それを形成するための塗布液、その塗布液の調製方法 |
JPH11340220A (ja) | 1998-05-26 | 1999-12-10 | Tokyo Ohka Kogyo Co Ltd | シリカ系被膜形成用塗布液及びその製造方法 |
JP2000336169A (ja) * | 1999-05-26 | 2000-12-05 | Dow Corning Asia Ltd | 架橋されたポリシリレンメチレンおよび架橋されたポリシリレンメチレン組成物の製造方法 |
US6225238B1 (en) * | 1999-06-07 | 2001-05-01 | Allied Signal Inc | Low dielectric constant polyorganosilicon coatings generated from polycarbosilanes |
JP3941327B2 (ja) * | 2000-02-01 | 2007-07-04 | Jsr株式会社 | シリカ系膜の製造方法、シリカ系膜、絶縁膜および半導体装置 |
US7128976B2 (en) * | 2000-04-10 | 2006-10-31 | Jsr Corporation | Composition for film formation, method of film formation, and silica-based film |
JP4117436B2 (ja) * | 2000-04-10 | 2008-07-16 | Jsr株式会社 | 膜形成用組成物、膜の形成方法およびシリカ系膜 |
DE10041417A1 (de) * | 2000-08-23 | 2002-03-21 | Beru Ag | Elektronische Ansteuerung für Heizelemente |
JP4545973B2 (ja) * | 2001-03-23 | 2010-09-15 | 富士通株式会社 | シリコン系組成物、低誘電率膜、半導体装置および低誘電率膜の製造方法 |
JP3797260B2 (ja) * | 2002-03-29 | 2006-07-12 | Jsr株式会社 | 半導体装置用カルボシラン系膜の製造方法、および半導体装置用カルボシラン系絶縁膜 |
EP1500685A4 (en) * | 2002-04-12 | 2007-02-21 | Az Electronic Materials Usa | COMPOSITION OF SILICONE-CONTAINING COPOLYMER, SOLUBLE-SOLUBLE SILICONE-CONTAINING COPOLYMER SOLVED IN SOLVENT AND HARDENED OBJECTS OBTAINED THEREFROM |
US6809041B2 (en) * | 2002-07-01 | 2004-10-26 | Rensselaer Polytechnic Institute | Low dielectric constant films derived by sol-gel processing of a hyperbranched polycarbosilane |
US7462678B2 (en) * | 2003-09-25 | 2008-12-09 | Jsr Corporation | Film forming composition, process for producing film forming composition, insulating film forming material, process for forming film, and silica-based film |
JP4737361B2 (ja) * | 2003-12-19 | 2011-07-27 | Jsr株式会社 | 絶縁膜およびその形成方法 |
WO2005068539A1 (ja) * | 2004-01-16 | 2005-07-28 | Jsr Corporation | ポリマーの製造方法、ポリマー、絶縁膜形成用組成物、絶縁膜の製造方法、および絶縁膜 |
JP5110238B2 (ja) * | 2004-05-11 | 2012-12-26 | Jsr株式会社 | 絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 |
EP1615260A3 (en) * | 2004-07-09 | 2009-09-16 | JSR Corporation | Organic silicon-oxide-based film, composition and method for forming the same, and semiconductor device |
JP4355939B2 (ja) * | 2004-07-23 | 2009-11-04 | Jsr株式会社 | 半導体装置の絶縁膜形成用組成物およびシリカ系膜の形成方法 |
-
2005
- 2005-01-14 JP JP2005517077A patent/JP5105041B2/ja not_active Expired - Fee Related
- 2005-01-14 KR KR1020067016326A patent/KR101185644B1/ko not_active IP Right Cessation
- 2005-01-14 WO PCT/JP2005/000374 patent/WO2005068540A1/ja active Application Filing
- 2005-01-14 WO PCT/JP2005/000375 patent/WO2005068541A1/ja active Application Filing
- 2005-01-14 EP EP20050703613 patent/EP1705208B1/en not_active Not-in-force
- 2005-01-14 TW TW94101154A patent/TW200538491A/zh not_active IP Right Cessation
-
2006
- 2006-07-14 US US11/486,085 patent/US7875317B2/en not_active Expired - Fee Related
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5461299A (en) * | 1977-10-26 | 1979-05-17 | Tokushiyu Muki Zairiyou Kenkiy | Polycarbosilane partially containing siloxane linkage and method of making same |
JPH05105759A (ja) * | 1991-10-17 | 1993-04-27 | Kanegafuchi Chem Ind Co Ltd | ケイ素系ハイブリツド材料 |
JP2000309752A (ja) * | 1999-04-27 | 2000-11-07 | Jsr Corp | 膜形成用組成物および絶縁膜形成用材料 |
JP2001127152A (ja) * | 1999-10-25 | 2001-05-11 | Fujitsu Ltd | 低誘電率絶縁膜の形成方法及び該方法で形成された低誘電率絶縁膜及び該低誘電率絶縁膜を用いた半導体装置 |
JP2001345317A (ja) * | 2000-03-29 | 2001-12-14 | Fujitsu Ltd | 低誘電率被膜形成材料、及びそれを用いた被膜と半導体装置 |
WO2002098955A1 (en) * | 2001-06-07 | 2002-12-12 | Lg Chem, Ltd. | Organosilicate polymer and insulating film therefrom |
JP2003115482A (ja) * | 2001-10-05 | 2003-04-18 | Asahi Kasei Corp | 絶縁膜形成用組成物 |
US20040007753A1 (en) * | 2002-04-25 | 2004-01-15 | Kyocera Corporation | Photoelectric conversion device and manufacturing process thereof |
JP2005076031A (ja) * | 2003-09-01 | 2005-03-24 | Samsung Electronics Co Ltd | 新規のシロキサン樹脂及びこれを用いた半導体層間絶縁膜 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5013045B2 (ja) * | 2004-01-16 | 2012-08-29 | Jsr株式会社 | ポリマーの製造方法 |
JP5110243B2 (ja) * | 2004-01-16 | 2012-12-26 | Jsr株式会社 | ポリマーの製造方法 |
JP2005350653A (ja) * | 2004-05-11 | 2005-12-22 | Jsr Corp | 有機シリカ系膜の形成方法、有機シリカ系膜、配線構造体、半導体装置、および膜形成用組成物 |
JP2005350651A (ja) * | 2004-05-11 | 2005-12-22 | Jsr Corp | 絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 |
US7497965B2 (en) * | 2005-08-11 | 2009-03-03 | Fujifilm Corporation | Insulating film-forming composition, insulating film and production method thereof |
JP2007070480A (ja) * | 2005-09-07 | 2007-03-22 | Fujifilm Corp | 膜形成用組成物、絶縁膜およびその製造方法 |
WO2008066060A1 (fr) * | 2006-11-30 | 2008-06-05 | Jsr Corporation | Procédé de fabrication d'un polymère, composition de formation d'un film isolant et film isolant de silice et son procédé de fabrication |
JPWO2008066060A1 (ja) * | 2006-11-30 | 2010-03-04 | Jsr株式会社 | ポリマーの製造方法、絶縁膜形成用組成物、ならびにシリカ系絶縁膜およびその製造方法 |
US20100140807A1 (en) * | 2007-07-06 | 2010-06-10 | Fujitsu Limited | Insulating film material, multilayer wiring board and production method thereof, and semiconductor device and production method thereof |
US8580907B2 (en) * | 2007-07-06 | 2013-11-12 | Fujitsu Limited | Insulating film material, multilayer wiring board and production method thereof, and semiconductor device and production method thereof |
JP2010106099A (ja) * | 2008-10-29 | 2010-05-13 | Jsr Corp | 絶縁膜形成用組成物、ならびに絶縁膜およびその形成方法 |
Also Published As
Publication number | Publication date |
---|---|
TWI316524B (ja) | 2009-11-01 |
JP5105041B2 (ja) | 2012-12-19 |
US20070020467A1 (en) | 2007-01-25 |
EP1705208A1 (en) | 2006-09-27 |
WO2005068541A1 (ja) | 2005-07-28 |
JPWO2005068540A1 (ja) | 2007-12-27 |
EP1705208A4 (en) | 2012-03-28 |
KR20060123547A (ko) | 2006-12-01 |
KR101185644B1 (ko) | 2012-09-24 |
EP1705208B1 (en) | 2013-03-20 |
US7875317B2 (en) | 2011-01-25 |
TW200538491A (en) | 2005-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2005068540A1 (ja) | 絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 | |
KR101168452B1 (ko) | 절연막 형성용 조성물, 그의 제조 방법, 실리카계 절연막및 그의 형성 방법 | |
JP5110243B2 (ja) | ポリマーの製造方法 | |
WO2005082976A1 (ja) | ポリマーおよびその製造方法、絶縁膜形成用組成物、ならびに絶縁膜およびその形成方法 | |
WO2007139004A1 (ja) | 絶縁膜形成用組成物およびその製造方法、ならびにシリカ系絶縁膜およびその形成方法 | |
JP4662000B2 (ja) | 膜形成用組成物、膜の形成方法および絶縁膜 | |
JP5099302B2 (ja) | 絶縁膜形成用組成物、ポリマーおよびその製造方法、絶縁膜の製造方法、ならびにシリカ系絶縁膜 | |
JP2010106100A (ja) | 絶縁膜形成用組成物、ならびに絶縁膜およびその形成方法 | |
JP5423937B2 (ja) | 絶縁膜形成用組成物の製造方法、ポリマーの製造方法 | |
JP2002167438A (ja) | ケイ素ポリマー、膜形成用組成物および絶縁膜形成用材料 | |
JP4022802B2 (ja) | 膜形成用組成物、膜の形成方法および絶縁膜 | |
JP5099301B2 (ja) | 絶縁膜形成用組成物、ポリマーおよびその製造方法、絶縁膜の製造方法、ならびにシリカ系絶縁膜 | |
JP4101989B2 (ja) | ポリオルガノシロキサン系組成物の製造方法、ポリオルガノシロキサン系組成物、および膜 | |
JP2007262255A (ja) | ポリマーおよびその製造方法、絶縁膜形成用組成物、絶縁膜の製造方法、ならびにシリカ系絶縁膜 | |
JPWO2008096656A1 (ja) | ケイ素含有ポリマーおよびその合成方法、膜形成用組成物、ならびにシリカ系膜およびその形成方法 | |
JP2001049184A (ja) | 膜形成用組成物、膜の形成方法および低密度化膜 | |
JP2009227910A (ja) | 絶縁膜形成用組成物、ならびにシリカ系膜およびその形成方法 | |
JPWO2008066060A1 (ja) | ポリマーの製造方法、絶縁膜形成用組成物、ならびにシリカ系絶縁膜およびその製造方法 | |
JP2001354901A (ja) | 膜形成用組成物の製造方法、膜形成用組成物、膜の形成方法およびシリカ系膜 | |
JP5376118B2 (ja) | 絶縁膜形成用組成物の製造方法、ならびに絶縁膜の形成方法 | |
JP2001335744A (ja) | 膜形成用組成物、膜の形成方法およびシリカ系膜 | |
JP2008198852A (ja) | 絶縁膜形成用組成物、ならびにシリカ系膜およびその形成方法 | |
JP2008260917A (ja) | 膜形成用組成物およびシリカ系膜とその形成方法 | |
JP2010043190A (ja) | 絶縁膜形成用組成物、ならびにシリカ系膜およびその形成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005517077 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11486085 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005703613 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020067016326 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2005703613 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020067016326 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 11486085 Country of ref document: US |