WO1999055789A1 - Liquide de revetement utilise pour former un film a base de silice presentant une faible constante dielectrique et substrat sur lequel est couche un film a faible constante dielectrique - Google Patents
Liquide de revetement utilise pour former un film a base de silice presentant une faible constante dielectrique et substrat sur lequel est couche un film a faible constante dielectrique Download PDFInfo
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- WO1999055789A1 WO1999055789A1 PCT/JP1999/002017 JP9902017W WO9955789A1 WO 1999055789 A1 WO1999055789 A1 WO 1999055789A1 JP 9902017 W JP9902017 W JP 9902017W WO 9955789 A1 WO9955789 A1 WO 9955789A1
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- 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
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- 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
- G03F7/093—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antistatic means, e.g. for charge depletion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
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- 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
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249967—Inorganic matrix in void-containing component
- Y10T428/249969—Of silicon-containing material [e.g., glass, etc.]
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- 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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/24999—Inorganic
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2962—Silane, silicone or siloxane in coating
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- 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]
- Y10T428/31507—Of polycarbonate
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- 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 provides a coating liquid for forming a low dielectric constant silicon-based coating film having a relative dielectric constant as small as 3 or less and capable of easily forming an insulating film excellent in microphotolithographic processing. Further, the present invention relates to a substrate on which a low dielectric constant silicic coating having such characteristics is formed.
- the interlayer insulating film used for the above purpose is generally formed on a substrate by a vapor deposition method such as a CVD method or a coating method of forming an insulating film using a coating liquid for forming a film. I have.
- the relative dielectric constant of a silicon-based film obtained by a vapor deposition method such as CVD is limited to 3.5 for a fluorine-doped silicon film. It is difficult to form a system coating.
- polyaryl resin, fluorine-added polyimide resin ⁇ CVD films such as resins and films formed using these coating solutions have a relative dielectric constant of around 2, but have poor adhesion to the surface to be coated, and are difficult to use with resist materials used for microfabrication. Has poor adhesion, poor chemical resistance, poor oxygen plasma resistance and other disadvantages.
- a coating formed using a low dielectric constant silica-based coating liquid containing a reaction product of silica fine particles and a halogenated silane or a hydrolyzate thereof has a relative dielectric constant of 3%. It was found to be as small as the following, and also excellent in chemical resistance such as adhesion to the coated surface, mechanical strength, and alkali resistance, and at the same time, excellent in crack resistance. (See Japanese Patent Application Laid-open No. Hei 8-2996984).
- a silica-based coating is formed from a conventional coating solution containing a hydrolyzate of alkoxysilane or halogenated silane or a silica-based fine particle as a coating-forming component, hydrogen atoms bonded to Si atoms are obtained.
- a low dielectric constant film can be obtained by reducing the cross-link density of Si-O-Si bonds in the film due to fluorine atoms, organic groups, or interparticle vacancies of fine particles of silicon. These functional groups have poor plasma resistance, and It was found that the film quality deteriorated during the trilithographic processing, and that a stable low dielectric constant film could not always be obtained.
- the present invention is intended to solve the above-mentioned problems in the prior art, and has a dielectric constant as small as 3 or less, and an insulating material excellent in microphotolithographic processing.
- An object of the present invention is to provide a coating liquid for forming a low dielectric constant silicon-based film capable of forming a film, and a substrate on which a low dielectric constant silicon-based film having such properties is formed. It is.
- the coating liquid for forming a low dielectric constant silicon-based film according to the present invention comprises:
- the coating liquid for forming a low dielectric constant silica-based film according to the present invention is:
- the weight ratio of the silica-based fine particles having a phenyl group to the oxidatively decomposable resin was set to 0.
- Such an oxidatively decomposable resin can be dissolved in an organic solvent and fired in an oxygen-containing gas from room temperature to 500 ° C., or by using an ultraviolet ray, an infrared ray, an electron beam, or an X-ray. Or, a resin that is oxidatively decomposed by irradiation with oxygen plasma or the like is preferable.
- the silicic acid-based fine particles (i) having a phenyl group are obtained by hydrolyzing one or more of alkoxysilanes represented by the following general formula (I), or aging after hydrolysis. At least some of the surface
- X represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R 1 represents a hydrogen atom or 1 to 8 carbon atoms. Represents an alkyl group, an aryl group or a vinyl group, and n is an integer of 0 to 3.
- the phenyl group-containing alkoxysilane is represented by the following general formula (IV)
- the phenyl group-containing chlorosilane is represented by the following general formula (V).
- R 1 represents a hydrogen atom or a carbon atom.
- R 2 represents a phenyl group
- X ′ represents a chlorine atom
- p represents an integer of 0 to 3
- q represents 1 to 8
- p + q is an integer of 4 or less.
- the hydrolysis temperature or ripening temperature of alkoxysilane at the time of preparing fine particles of silicic acid from one or more of the alkoxysilanes represented by the general formula (I) may be 180 or more. I like it.
- the substrate with a low dielectric constant film according to the present invention is characterized by having a low dielectric constant silicic coating formed using the above-mentioned coating solution.
- first and second coating liquids for forming a low dielectric constant silicon-based film and the substrate with a low dielectric constant film according to the present invention will be specifically described.
- the first low dielectric constant silicon-based film-forming coating solution comprises (i) silicic acid-based fine particles having a phenyl group. And (ii) a hydrolyzate of alkoxysilane and / or halogenated silane, and polyxazane which is a reaction product of polysilazane.
- Silica-based fine particles having a phenyl group are represented by the following general formula (I) One or two or more alkoxysilanes are hydrolyzed in the presence of water, an organic solvent and ammonia, or hydrolyzed, and then aged to obtain silica particles. And chloro group-containing chlorosilane.
- X represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R 1 represents a hydrogen atom or a 1 to 8 carbon atom.
- N is an integer of 0-3.
- alkoxysilanes represented by the above formula (I) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and the like.
- Tetraoctylsilane methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltrisilane Toxicilane, ethyltriisopropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane Phenyl trimethoxy silane, phenol triethoxy silane, trimethoxy silane, triethoxy silane, triisopropoxy silane Fluorotrimethoxysilane, fluorotriethoxysilane, dimethyldimethoxysilane, dimethyljetoxysilane, getyldimethoxysilane, getyljetoxirane, dimethoxysilane, diethoxysilane, Diflu
- alcohols As the organic solvent, alcohols, ketones, ethers, esters, and the like are used. More specifically, for example, methanol, ethanol, prono, and the like. Alcohols such as ethanol, butanol, ketones such as methylethyl ketone, methyl isobutyl ketone, etc. And glycol ethers such as ethylene glycol, propylene glycol and hexyl glycol, and esters such as methyl acetate, ethyl acetate, methyl lactate and ethyl lactate.
- Alcohols such as ethanol, butanol, ketones such as methylethyl ketone, methyl isobutyl ketone, etc.
- glycol ethers such as ethylene glycol, propylene glycol and hexyl glycol
- esters such as methyl acetate, ethyl acetate, methyl lactate and ethyl lactate.
- a basic compound such as an amine, an alkali metal hydride, a quaternary ammonium compound, or an amine-based coupling agent may be used. it can.
- silica fine particles As a method for preparing the silica fine particles, a conventionally known method can be employed. The method of preparing such silica fine particles is described in further detail.For example, while stirring a water-alcohol mixed solvent, an alkoxysilane and ammonia water are added to the mixed solvent, and the reaction is performed. Let it.
- water is S i configuring the alkoxysilane down -.
- OR 1 group 1 mol per Ri 0 5-5 0 mol use an amount Do Let 's were rather becomes 1-2 5 mol favored, is This is desirable.
- ammonia an alkoxysilane in to come to have S i 0 2 terms, with respect to alkoxysilane down 1 mole, 0.0 1-1 mol, and rather the preferred 0.0 5 to 0.8 molar and Distribution It is desirable that they be combined.
- the hydrolysis and polycondensation reaction of the alkoxysilane is carried out at a temperature of 180 ° C or higher, preferably 200 ° C or higher, using a heat and pressure resistant container such as an autoclave.
- aging may be performed at the same temperature or a higher temperature.
- the higher the above reaction temperature and / or aging temperature the more the polycondensation of the alkoxysilane is promoted, and the inside of the silica fine particles becomes dense.
- the hydrolysis reaction and aging are performed at such a temperature, the silica fine particles are further densified, the hygroscopicity of the particles themselves is reduced, and the residual functional groups on the particle surface are reduced.
- a high-boiling solvent such as ethylene glycol may be added to a mixed solvent of water and alcohol under stirring to hydrolyze the alkoxysilane to generate and grow silica fine particles.
- a high-boiling solvent such as ethylene glycol may be added during the hydrolysis of the alkoxysilane, a transesterification reaction of the alkoxy group occurs, and the high-boiling solvent is taken into the inside of the silica particles, resulting in a low-density porous material. High quality silicon fine particles can be obtained.
- silica fine particles silica sol obtained by ion exchange or hydrolysis of an alkali metal silicate or the like may be used.
- silica sol obtained by ion exchange or hydrolysis of an alkali metal silicate or the like may be used.
- fine particles made of porous zeolite such as those obtained by removing aluminum from zeolite made of aluminosilicate, can also be used.
- the above-mentioned fine particles of silicon have an average particle diameter in the range of 30 to 100 A, preferably in the range of 50 to 50 OA. As long as the fine particles have an average particle diameter in this range, they may have a uniform particle diameter or a mixture of two or more kinds of fine particles having different particle diameters. This particle size If it is less than 300 A, it becomes difficult to lower the dielectric constant of a silica-based film obtained by applying a coating solution to be produced by this method. Defects are more likely to occur during microfabrication as small as photolithography.
- silica fine particles may be spherical or irregular.
- the silicic acid-based fine particles having a phenyl group used in the present invention can be obtained by reacting the above silicic acid fine particles with phenyl group-containing alkoxysilane and Z or phenyl group-containing chlorosilane.
- the alkoxysilane represented by the following general formula (IV) is used as the alkoxysilane having a phenyl group
- the chlorosilane represented by the following general formula (V) is used as the chlorosilane having a phenyl group. Is used.
- X represents a hydrogen atom, a fluorine atom or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R 1 represents a hydrogen atom or a 1 to 8 carbon atom
- R 2 represents a phenyl group
- X ′ represents a chlorine atom.
- the phenyl group may be substituted with an alkyl group having 1 to 8 carbon atoms.
- n is an integer of 0 to 3
- p is an integer of 0 to 3
- q is an integer of 1 to 3.
- p + q is an integer of 4 or less.
- alkoxysilanes or chlorosilanes include phenyltrimethoxysilane, phenyltriethoxysilane, Phenyl triacetoxy silane, phenyl methyl dimethyl silane, phenyl methyl ethoxy silane, phenyl dimethyl ethoxy silane, phenyl dimethyl acetate ethoxy silane, phenyl trichloro silane, phenyl Examples include methyldichlorosilane, phenylethylchlorosilane, phenyldimethylchlorosilane, phenylmethylchlorosilane, and phenyldichlorosilane.
- these phenyl group-containing alkoxysilanes and Z or phenyl group-containing chlorosilanes may be hydrolysates.
- the silicon fine particles and the phenyl group-containing alkoxysilane and Z or phenyl group-containing alkoxysilane no growth of the silicon fine particles or generation of new silica fine particles occurs, and the surface of the silicon fine particles does not occur.
- a surface reaction “if” occurs between the silica fine particles and the alkoxysilane containing phenyl group and / or the chlorosilane containing phenyl group, whereby silica fine particles having a phenyl group on the surface are obtained.
- the silica-based fine particles having a phenyl group used in the present invention are selected from the silica fine particles obtained as described above, and phenyl group-containing alkoxysilane and phenyl group-containing chlorosilane. It is obtained by mixing and reacting with one or more species. At this time, the mixing ratio of the two is calculated as Si02, and is 0.01 to 0.3 parts by weight, preferably 0.05 part by weight, per part by weight of the fine particles of silicon force. Parts to 0.2 parts by weight.
- the amount of alkoxysilane containing phenyl group and / or the amount of chlorosilane containing phenyl group is less than 0.01 part by weight, the amount of phenyl group on the surface of the silica-based fine particles becomes small, and the obtained silica is reduced.
- Mosquito coating is acid resistant It is inferior in chemical properties and tends to absorb moisture easily.
- the amount is more than 0.3 parts by weight, excess phenyl group-containing alkoxy silane or phenyl group-containing chlorosilane which does not participate in the surface reaction with the silica fine particles remains, and the coating solution produced therefrom is used.
- the silicon-based coating obtained by coating may have poor adhesion to the surface to be coated, mechanical strength, coatability, and the like.
- the reaction of the silica fine particles with a phenyl group-containing alkoxysilane or a phenyl group-containing chlorosilane generally requires water, an organic solvent, and a catalyst. Used. Used water, S i configuring the Fuweniru group-containing alkoxysilane emissions - OR 1 or Fuweniru group containing click Roroshira down S i configuring the -. Ri per X 'group 1 mol, 0 1 there in an amount more than the molar I just need.
- organic solvent examples include the same organic solvents as those used in the preparation of the silica fine particles.
- an acid catalyst can be used in addition to the same ones used in the above-mentioned preparation of the silica fine particles.
- inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid
- organic acids such as acetic acid, oxalic acid, and toluenesulfonic acid
- compounds that show acidity in an aqueous solution such as metal soap
- basic catalysts are preferred.
- the temperature is preferably about 100 ° C. or less. Is the temperature below 80 ° C and the force fluctuates due to this temperature condition? , Usually 0.5 to 50 hours, Heat treatment is preferably performed for 0.5 to 15 hours.
- a hydrolyzate of a phenyl group-containing alkoxysilane or a phenyl group-containing cuprosilane is bonded to at least a part of the surface of the silicon fine particles, and the phenyl group is formed. This gives a series of silicon-based fine particles.
- the unpurified silicic acid-based fine particles having a phenyl group obtained by the above method may be used as they are. However, prior to the reaction with the polyxanzan described below, ultrafiltration is performed in advance. Alternatively, it is desirable that the water-organic solvent system of the dispersion medium be solvent-replaced with an organic solvent by means such as distillation.
- the (ii) polysiloxazane used in the present invention is a reaction product of (ii-1) a hydrolyzate of alkoxysilane and Z or a halogenated silane, and (ii-2) polysilazane.
- an alkoxysilane represented by the following general formula (I) or a hydrolyzate of a halogenated silane represented by the following general formula (II) is used as a component for forming polysiloxazan.
- X represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group or a vinyl group
- X ′ represents a halogen atom.
- N is an integer from 0 to 3.
- alkoxysilane represented by the general formula (I) the same as those exemplified for the above-mentioned silicic fine particles can be mentioned.
- halogenated silane represented by the general formula (II) examples include trichlorosilan, tribromosilane, dichlorosilane, fluorotrichlorosilane, and fluorotribromosilane. And so on.
- the hydrolyzate used in the present invention is prepared by converting the alkoxysilane and Z represented by the above general formula (I) or the silane having a lip of the formula (II) into water, an organic solvent and water. It can be obtained by hydrolysis and polycondensation in the presence of a catalyst. As such a hydrolysis / polycondensation method, a conventionally known method can be used.
- Examples of the organic solvent include alcohols, ketones, ethers, and esters. Specific examples include methanol, ethanol, prono, and the like. Alcohols such as ethanol, butanol, ketones such as methylethyl ketone, methyl isobutyl ketone, methyl ethyl solvent, ethyl cellulose solvent, propylene glycol mono propylene Glycols such as ter, glycols such as ethylene glycol, propylene glycol, hexylene glycol, methyl acetate, methyl acetate, methyl lactate, methyl lactate Which esters are used.
- Alcohols such as ethanol, butanol, ketones such as methylethyl ketone, methyl isobutyl ketone, methyl ethyl solvent, ethyl cellulose solvent, propylene glycol mono propylene Glycols such as ter, glycols such as ethylene glycol, propylene glycol,
- the catalyst examples include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid; organic acids such as acetic acid, oxalic acid, and toluenesulfonate; Hydrogenation of alkaline metals Compounds, quaternary ammonium compounds, and basic compounds such as amine-based coupling agents.
- inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid
- organic acids such as acetic acid, oxalic acid, and toluenesulfonate
- Hydrogenation of alkaline metals Compounds, quaternary ammonium compounds, and basic compounds such as amine-based coupling agents.
- Water necessary for the hydrolysis reaction S i-0 constituting the alkoxysilane down - S constituting R 1 group, or a halogenated silane i - X 'Ri group 1 mol per usually 0.1 to 5 It is preferred that it be used in an amount of 0.1 mol to 2 mol, preferably 0.1 to 2 mol.
- the catalyst is desirably added in an amount of 0.01 to 1 mol per 1 mol of alkoxysilane or halogenated silane.
- the reaction conditions for the hydrolysis are not particularly limited. However, when the alkoxysilane is hydrolyzed, the reaction temperature is 0 to 80 ° (:, preferably 5 to 60 ° C). The reaction time is 0.1 to 10 hours, preferably 1 to 5 hours. When the halogenated silane is hydrolyzed, the reaction temperature is 0 to 50 ° C. Preferably, the temperature is 5 to 20 ° C, and the reaction time is 0.1 to 20 hours, preferably 1 to 10 hours.
- the number average molecular weight of the hydrolyzate thus obtained is 100 to 500,000, preferably 500 to 100,000 (molecular weight in terms of polystyrene). Is desirable.
- the alkoxysilane may be the same as or different from the one used for preparing the silica-based fine particles.
- R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an aryl group or a vinyl group.
- M is an integer.
- R 2 , R 3 and R 4 are all hydrogen atoms, and 55 to 65% by weight of a silicon atom and 20 to 30% by weight of a nitrogen atom in one molecule; Particular preference is given to inorganic polysilazanes in which the hydrogen atoms are present in an amount such that they are between 10 and 15% by weight.
- the ratio between Si atoms and N atoms in the polysilazane is preferably from 1.0 to 1.3.
- Such an inorganic polysilazane is produced, for example, by reacting dihalosilane with a base to form an adduct of dihalosilane, and then reacting with ammonia (Japanese Patent Publication No. Sho 63-16325). ), And a method of reacting ammonia with, for example, methyl phenyldichlorosilane or dimethyldichlorosilane (see Japanese Patent Application Laid-Open No. 62-88327). Can be manufactured.
- the polysilazane having a repeating unit represented by the above formula (III) may be linear or cyclic, and is a mixture of a linear polysilazane and a cyclic polysilazane. You may.
- the number average molecular weight (in terms of polystyrene) of these polysilazanes be in the range of 100 to 100; preferably in the range of 500 to 2000.
- the (ii) polysiloxazane used in the present invention is obtained by mixing (ii-1) the alkoxysilan and the hydrolyzate of Z or halogenated silane with the (ii-2) polysilazane in an organic solvent. Then, it is obtained by reacting.
- Any organic solvent may be used as long as it can dissolve the hydrolyzate of alkoxysilane or halogenated silane and polysilazane.
- ketones such as methylethylketone and methylisobutylketone can be used.
- aromatic hydrocarbons such as toluene, xylene and mesitylene.
- the mixing amount of the hydrolyzate of alkoxysilane or halogenated silane and polysilazane is in the range of 91 to 99% by weight of hydrolyzate of alkoxysilane or halogenated silane and 9-1 to 1% by weight of polysilazane. It is desirable. When the polysilazane content exceeds 9% by weight, Si—N bonds remain in the silica-based coating film obtained by applying the coating solution to be produced, and the dielectric constant increases. There is. If the polysilazane content is less than 1% by weight, adhesion to the surface to be coated, mechanical strength, and chemical resistance such as alkaline resistance may be poor.
- reaction conditions for the above (ii-1) alkoxysilane and the hydrolyzate of Z or halogenated silane with (ii-2) polysilazane are not particularly limited.
- (ii-1) alkoxysilane A mixture of the hydrolyzate of silane or halogenated silane and (ii-2) polysilazane is reacted at a reaction temperature of about 100 ° C or lower, preferably 80 ° C or lower, usually at 0.5 ° C. Heating for up to 5 hours, preferably 0.5 to 3 hours is desirable.
- alkoxysilane or halogenated silane (Ii) Polysiloxane is obtained by binding polysilazane to some ends of the hydrolyzate. (Ii) Number average molecular weight of polysiloxazan obtained
- (polystyrene conversion) be in the range of 100 to 500, preferably 500 to 100,000.
- the first coating liquid for forming low dielectric constant silicon-based film comprises the above-mentioned (i) silica-based fine particles having a phenyl group.
- the solvent-containing dispersion is mixed with ( ⁇ ⁇ ) polysiloxane and, if necessary, a solvent is added thereto, and the mixture is subjected to heat treatment to (i) silica-based fine particles having a phenyl group and (ii) polysiloxane. It is prepared by reacting and.
- the mixing ratio of (i) silica-based fine particles having a phenyl group and (ii) polysiloxazan is such that at least a part of the surface of (i) silica-based fine particles having a phenyl group has A sufficient amount of polysiloxazane to bind to polyxazane is sufficient, preferably a weight ratio of silica-based fine particles having a phenyl group to polysiloxazane (filament). (Weight of silicic acid-based fine particles having a group / weight of polyxazane)), and are mixed and reacted at a weight ratio of 0.1 to 20 and preferably 0.5 to 10 Is desirable.
- the obtained silica-based coating becomes porous containing a large number of inter-particle voids of the silica-based fine particles having a phenyl group, and a lower dielectric constant can be expected.
- the adhesion to the surface to be coated, the mechanical strength, and the flattening performance of the surface to be coated tend to deteriorate.
- the weight ratio becomes smaller than 0.1 the silicic coating obtained in the same manner has a polysiloxane having silicic fine particles having a phenyl group.
- the dielectric constant may not be reduced due to the filling by zircon.
- the heat treatment is usually carried out at a reaction temperature of about 100 ° C or less, preferably 80 ° C or less, for 0.5 to 5 hours, preferably about 0.5 to 3 hours. Desirable.
- the first coating liquid for forming a low dielectric constant silicon-based film according to the present invention manufactured as described above has a solid content (total of silica-based fine particles and a polyxanoxane) of 5 to 5%. 4 0 weight 0/0, preferred and rather is 1 0-3 0 weight 0/0 arbitrariness desired and this to contain an amount.
- the coating liquid for forming a low dielectric constant silicic film formed by the above method is replaced with a solvent such as methyl isobutyl ketone using a rotary evaporator or the like, and the alcohol or water generated by the reaction is removed. After complete removal of the concentration, the concentration may be adjusted to the above-mentioned solid concentration.
- the first coating liquid for forming a low dielectric constant silicon-based film according to the present invention as described above contains silica-based fine particles as a film-forming component, the space between the silicon-based particles is low. The pores can make the coating porous. Further, the phenyl group on the surface of the silicic acid-based fine particles has the effect of preventing water from re-adsorbing to the pores in the coating and has the property of high oxygen plasma resistance.
- silica-based fine particles having a phenyl group and poly- When a low dielectric constant silica-based coating is formed using a coating liquid for forming a low dielectric constant silicon-based coating containing a reaction product with siloxazan, plasma etching and resist during micro photolithography processing can be performed. Deterioration of film quality due to oxygen plasma at the time of peeling can be suppressed. Further, as described above, moisture re-adsorption to the coating film is also suppressed, so that the dielectric constant is low, and adhesion to the surface to be coated, chemical resistance such as alkali resistance, and cladding resistance are also achieved.
- the second low dielectric constant silica-based coating film forming coating solution comprises: (i) a silica-based silica-based coating solution Fine particles and (ii ') oxidatively decomposable resin
- the weight ratio of (i) silica-based fine particles having a phenyl group to (ii,) oxidatively decomposable resin is 0.5. It is contained so as to be in the range of ⁇ 5.
- the (i) silicic acid-based fine particles having a phenyl group may be the same as those described above.
- the oxidatively decomposable resin it can be dissolved in an organic solvent and fired in an oxygen-containing gas from room temperature to 500 ° C, or ultraviolet, infrared, electron beam, X-ray or oxygen plasma. Any resin may be used as long as it has a characteristic of being oxidatively decomposed by irradiation such as irradiation.
- cellulosic resins, polyamide resins, polyester resins, acrylic resins, polyethers examples include tellurium-based resins, polyolefin-based resins, polyol-based resins, and epoxy-based resins.
- cellulosic resins and acryl-based resins having particularly low residual carbon ratios are preferred.
- the number-average molecular weight of the oxidatively decomposable resin is desirably 100 to 500,000, preferably 500 to 100,000 (polystyrene equivalent molecular weight).
- the second coating solution for forming a low dielectric constant silicic acid-based film comprises silica-based fine particles having a phenyl group obtained as described above. Is prepared by mixing with an oxidatively decomposable resin. At this time, the silica-based fine particles having an unpurified fluorine group obtained by the above-described method may be used as they are, but prior to mixing both, ultrafiltration or distillation or the like is performed in advance. It is preferable that the water-organic solvent system of the dispersion medium is replaced with an organic solvent system by a means.
- the coating liquid for forming a low dielectric constant silicon-based film used in the present invention is obtained by mixing the silica-based fine particles having a phenyl group obtained as described above with an oxidatively decomposable resin.
- the oxidatively decomposable resin is bonded to at least a part of the surface of the fine particles.
- the mixing ratio of the two is determined by the weight of silica-based fine particles having a fluorine group (A) It is preferable to mix and combine them in a weight ratio such that B) is from 0.5 to 5, especially from 1 to 4.
- the coating obtained in the same manner contains a large amount of the oxidatively decomposable resin component, and thus the film obtained after the oxidative decomposition
- the formed porous low-k dielectric film shrinks, resulting in poor adhesion to the surface to be coated, mechanical strength, etc.o
- the heat treatment is usually carried out for 0.5 to 5 hours, preferably for 0.5 to 3 hours.
- the second low dielectric constant silicic film-forming coating according to the present invention in which the surface of the silica-based particles having a phenyl group is bonded with an oxidatively decomposable resin. A liquid is obtained.
- the second coating solution for forming a silica-based film according to the present invention includes, in addition to the phenyl group-containing fine particles and the oxidatively decomposable resin, the alkoxysilane represented by the above general formula (I) and / or A halogenated silane represented by the above general formula (II) or a hydrolyzate thereof, or a reaction product of the hydrolyzate with the polysilazane represented by the above general formula (II I) Polysiloxazan may be included.
- Such a coating liquid for forming a low dielectric constant silica-based film is usually formed through a two-step process.
- the coating liquid for forming a low dielectric constant silicic film is applied to the surface of a substrate, and then heated to form a film. Then, it is subjected to a microphotolithography process to form patterns such as wiring and via holes, to form a laminated film, etc., and then in an oxygen-containing gas from room temperature to 500 ° C. It oxidizes and decomposes the oxidatively decomposable resin contained in the binder by baking or irradiating ultraviolet rays, infrared rays, electron beams, X-rays or oxygen plasma.
- the oxidatively decomposable resin portion that has bound the particles of the silicic acid-based fine particles becomes voids and changes to a low dielectric constant silicic acid-based film.
- the phenyl group bonded to the surface of the silica-based fine particles has high heat resistance, and is present on the surface without being oxidized when oxidizing the oxidatively decomposable resin. Since the group has water repellency as described above, it has an effect of preventing water from being re-adsorbed to the pores between the silica-based fine particles, and has characteristics of high oxygen plasma resistance. are doing.
- the low dielectric constant silica-based film is formed using the second coating solution for forming a low dielectric constant silicon-based film according to the present invention
- the first low dielectric constant silica-based film is formed.
- it has a low dielectric constant, and is excellent in adhesion to the surface to be coated, chemical resistance such as alkali resistance, crack resistance, etc., and has good flattening characteristics and stability.
- a low dielectric constant silica-based film can be formed.
- a coating liquid for forming a low dielectric constant silicon-based film according to the present invention a semiconductor device is manufactured. In this case, the conductive yield can be improved.
- the substrate with a film according to the present invention is obtained by applying the first and second coating liquids for forming a low dielectric constant silicon film onto the surface of various substrates. It can be obtained by coating and heating.
- the heating temperature after application is usually in the range from 80 to 450 t :, preferably from 150 to 400 ° C. More specifically, when the first coating solution for forming a low dielectric constant silicon-based film is used, the temperature is usually from 300 to 450 ° C, preferably from 350 to 400 ° C. It is desirable to heat at a temperature of ° C, and when the second coating solution for forming a low dielectric constant silicon-based film is used, the oxidatively decomposable resin is decomposed at a later stage. Therefore, it is usually desirable to heat at a temperature of 80 to 400 ° C., preferably 150 to 300 ° C. This heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen.
- the polymerization of the resin component in the coating liquid progresses and cures, and at the same time, the melt viscosity of the polymer decreases in the heating process, and the coating film becomes uniform. And the flatness of the obtained film is improved.
- the refrigerating property due to low viscosity is maintained up to about 250 ° C. For this reason, a coating with further improved flatness can be obtained.
- the film thickness of the low dielectric constant silicon-based film formed in this manner is different depending on the base material on which the film is formed and the purpose of the film 5 ′. For example, it is usually 100 ⁇ m on a silicon substrate in a semiconductor device. Approximately 250 OA, and usually 300 000 A to 500 OA in the case of a multilayer wiring.
- the oxidatively decomposable resin contained as the binder may be oxidatively decomposed by irradiation with infrared rays, electron beams, X-rays, or oxygen plasma.
- the oxidatively decomposable resin, which is a binder component is oxidized and decomposed by baking in an oxygen-containing gas or by irradiation with ultraviolet rays, infrared rays, electron beams, X-rays, or oxygen plasma, etc.
- Examples of such a substrate with a low dielectric constant silicic film according to the present invention include a semiconductor device, a liquid crystal display device, and a photomask with a phase shifter.
- the low dielectric constant film is formed on a silicon substrate, between wiring layers of a multilayer wiring structure, on an element surface, or at a PN junction.
- the relative dielectric constant is as small as 3 or less, and furthermore, the microcloth is obtained.
- An insulating film with excellent photolithographic processing, chemical resistance such as alkali resistance, and crack resistance can be formed.
- a mixed solution of 139.lg of pure water and 169.9 g of methanol was held in a 601C, and water of tetraethoxysilane (ethylsilique-28, manufactured by Tama Chemical Industry) was added to the mixed solution.
- -Methanol solution (23.5 g of water / methanol mixture at a weight ratio of 2/8, plus 532.5 g of tetraethoxysilane) 2982.5 g and 0.25% 596.4 g of ammonia water was simultaneously added over 52 hours. After the addition was completed, the mixture was further aged at this temperature for 3 hours.
- MIBK methyl isobutyl ketone
- MIBK methyl isobutyl ketone
- trichlorosilane is subjected to water splitting in toluene using toluene sulphonic acid hydrate as a catalyst to obtain a high-molecular-weight compound having a number average molecular weight of 3500.
- Drozin Silsesquioki Sanpolymer was obtained.
- Hydrogensilsesquioxane polymer obtained as described above was dissolved in MIBK to prepare a 5% by weight solution, and the polysilazane solution was added over 3 hours. After reacting at 50 for 5 hours, the solvent was replaced with MIBK using a single evaporator to obtain a solution containing 5% by weight of a polyoxaxan having a number average molecular weight of 40000. .
- the silica-based fine particles (C) and (D) having a phenyl group obtained as described above and polysiloxane are mixed at a predetermined ratio shown in Table 1, and 50 is used for 1 Heated for hours. After that, the solvent is replaced again with methylisobutyl ketone in the mouth evaporator to completely remove the alcohol and water generated by the heat treatment, and the film having a silica concentration of 20% by weight is removed. Forming coating solutions 1 to 4 were prepared.
- silica microparticles (A) and (B) having no phenyl group were reacted in the same manner as the polyoxaxan to prepare coating solutions 5 and ⁇ for film formation.
- the silica-based fine particles (C) having a phenyl group obtained as described above and an ethanol solution of ethylcellulose were mixed at a predetermined ratio shown in Table 1, and mixed.
- Heat treatment was performed at ° C for 1 hour. Then, the solvent is replaced again with methyl isobutyl ketone on a rotary evaporator to completely remove the alcohol and water generated by the heat treatment, and to form a film having a concentration of 20% by weight.
- Coating solutions I to II were prepared.
- Table 1 shows the composition of the prepared coating solution for forming a film.
- Each of the coating liquids (1) to (4) was applied by spin coating to a semiconductor substrate provided with a metal wiring of a minimum of 0.25 rule, and dried at 250 ° C for 3 minutes. Thereafter, baking was performed at 400 T for 30 minutes in a nitrogen gas to form a silica-based film. The thickness of each of these silica coatings was 5000 A. Forming a S I_ ⁇ 2 film having a thickness of 4000 A by plasma CVD on these films, and flattening the wiring step in CMP (Chemi ca l Mechan i ca l Po 1 i sh i ng) method.
- the relative permittivity was calculated from the CV measurement between adjacent wirings, and the continuity yield of 100 continuous vias was evaluated by measuring the wiring resistance.
- the silicon-based coating film using the coating liquid according to the present invention has a small relative dielectric constant, excellent oxygen plasma resistance during microphotolithography processing, Strength, alkali resistance, etc. It is recognized that it has excellent chemical properties and crack resistance. Therefore, an excellent semiconductor device can be provided by using the coating liquid for forming a low dielectric constant silicic film according to the present invention.
- Each of the coating liquids (1) to (4) was applied on a semiconductor substrate provided with a metal wiring of at least 0.25 micron rule by a spin coat method, and dried at 80 for 3 minutes. Then, it was baked at 250 in nitrogen for 30 minutes to form a film. The thickness of each of these films was 5000 A. To form the S i0 2 film having a film thickness of 1000 A by plasma CVD on these films. A single micro-photolithography process is performed to form a vial, and the remaining resist is removed by RIE, and the vial is washed with organic amine and water. did.
- Vias were formed by forming TiN as a nodal metal by a sputtering method, and further forming a W plug by a CVD method and a CMP method. Then, oxygen plasma was irradiated to oxidatively decompose the ethyl cellulose. Next, a metal wiring was formed in the upper layer, and a semiconductor device was fabricated.
- Table 3 shows the results obtained by measuring the relative permittivity of the silicon-based coating of each semiconductor device and the continuity yield of 100 continuous vias.
- Comparative Example 5 (11) 3.3 23.4
- the relative dielectric constant was high and the yield of conduction of 100 continuous vias was low because the film quality was deteriorated by oxygen plasma irradiation and moisture absorption during cleaning occurred.
- the low dielectric constant silica-based coating according to the present invention has a small relative dielectric constant, excellent oxygen plasma resistance during microphotolithographic processing, and at the same time, mechanical strength. It was also found to be excellent in chemical resistance such as alkaline resistance and crack resistance.
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US09/446,686 US6562465B1 (en) | 1998-04-24 | 1999-04-15 | Coating liquid for forming a silica-containing film with a low-dielectric constant and substrate coated with such a film |
EP19990913676 EP0992556B1 (en) | 1998-04-24 | 1999-04-15 | Coating liquid for forming silica-based film having low dielectric constant and substrate having film of low dielectric constant coated thereon |
KR1019997012205A KR100600630B1 (ko) | 1998-04-24 | 1999-04-15 | 저유전율 실리카계 피막 형성용 도포액 및 저유전율피막으로 도포된 기재 |
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JP10/115082 | 1998-04-24 | ||
JP11508298A JP4162060B2 (ja) | 1998-04-24 | 1998-04-24 | 低誘電率シリカ系被膜形成用塗布液および低誘電率被膜付基材 |
JP13972398A JP4149031B2 (ja) | 1998-05-21 | 1998-05-21 | 低誘電率シリカ系被膜形成用塗布液および低誘電率被膜付基材 |
JP10/139723 | 1998-05-21 |
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PCT/JP1999/002017 WO1999055789A1 (fr) | 1998-04-24 | 1999-04-15 | Liquide de revetement utilise pour former un film a base de silice presentant une faible constante dielectrique et substrat sur lequel est couche un film a faible constante dielectrique |
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US (1) | US6562465B1 (ja) |
EP (2) | EP1790703B1 (ja) |
KR (2) | KR100600631B1 (ja) |
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US6562465B1 (en) * | 1998-04-24 | 2003-05-13 | Catalysts & Chemicals Industries Co., Ltd. | Coating liquid for forming a silica-containing film with a low-dielectric constant and substrate coated with such a film |
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- 1999-04-15 WO PCT/JP1999/002017 patent/WO1999055789A1/ja active IP Right Grant
- 1999-04-15 US US09/446,686 patent/US6562465B1/en not_active Expired - Lifetime
- 1999-04-15 EP EP19990913676 patent/EP0992556B1/en not_active Expired - Lifetime
- 1999-04-15 KR KR1019997012205A patent/KR100600630B1/ko not_active IP Right Cessation
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US6562465B1 (en) * | 1998-04-24 | 2003-05-13 | Catalysts & Chemicals Industries Co., Ltd. | Coating liquid for forming a silica-containing film with a low-dielectric constant and substrate coated with such a film |
US7754003B2 (en) * | 2003-08-12 | 2010-07-13 | Az Electronic Materials Usa Corp. | Coating composition and low dielectric siliceous material produced by using same |
Also Published As
Publication number | Publication date |
---|---|
EP0992556B1 (en) | 2012-05-09 |
EP1790703B1 (en) | 2014-07-30 |
EP1790703A8 (en) | 2010-06-30 |
EP0992556A4 (en) | 2005-04-27 |
EP0992556A1 (en) | 2000-04-12 |
EP1790703A3 (en) | 2009-08-12 |
KR20060066137A (ko) | 2006-06-15 |
TWI221159B (en) | 2004-09-21 |
KR100600630B1 (ko) | 2006-07-13 |
KR20010014143A (ko) | 2001-02-26 |
US6562465B1 (en) | 2003-05-13 |
KR100600631B1 (ko) | 2006-07-13 |
EP1790703A2 (en) | 2007-05-30 |
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