WO2004026762A1 - Suspension de particules d'oxyde metallique ultra-fines et film mince de particules d'oxyde metallique ultra-fines - Google Patents

Suspension de particules d'oxyde metallique ultra-fines et film mince de particules d'oxyde metallique ultra-fines Download PDF

Info

Publication number
WO2004026762A1
WO2004026762A1 PCT/JP2003/011821 JP0311821W WO2004026762A1 WO 2004026762 A1 WO2004026762 A1 WO 2004026762A1 JP 0311821 W JP0311821 W JP 0311821W WO 2004026762 A1 WO2004026762 A1 WO 2004026762A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal oxide
thin film
solution
ultrafine
water
Prior art date
Application number
PCT/JP2003/011821
Other languages
English (en)
Japanese (ja)
Inventor
Yasuhisa Yamashita
Original Assignee
Murata Manufacturing Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co., Ltd. filed Critical Murata Manufacturing Co., Ltd.
Priority to AU2003264459A priority Critical patent/AU2003264459A1/en
Publication of WO2004026762A1 publication Critical patent/WO2004026762A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C01B13/328—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process by processes making use of emulsions, e.g. the kerosine process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/10—Metal-oxide dielectrics
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/441—Alkoxides, e.g. methoxide, tert-butoxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5463—Particle size distributions
    • C04B2235/5481—Monomodal

Definitions

  • the present invention relates to a metal oxide ultrafine particle dispersion solution in which metal oxide ultrafine particles are dispersed, in particular, a metal oxide ultrafine particle dispersion solution suitable for producing a composite metal oxide ultrafine particle thin film, and a nano-sized metal oxide ultrafine particle.
  • the present invention relates to a metal oxide ultrafine particle thin film comprising fine particles and having excellent dielectric properties. Disclosure of invention
  • composite metal oxides such as barium titanate and lead zirconate titanate are widely used in multilayer capacitor actuators and the like because of their excellent dielectric properties and piezoelectric properties.
  • thinning of the element is indispensable.
  • ferroelectric materials are said to lose ferroelectricity at a certain critical grain size due to the size effect.
  • the ferroelectricity disappears at about 50 nm. It cannot be applied to electronic devices as a dielectric.
  • barium titanate of about 50 nm synthesized by a hydrolysis method for example, is grown to 100 nm or more by heat treatment to improve the crystallinity. It is manufactured by mixing and pulverizing with an agent and the like, forming a slurry, forming a sheet, stacking these, and further removing the binder and firing.
  • the thickness of the multilayer capacitor has been reduced to about 1 m, and in this case, in order to obtain sufficient reliability, for example, 10 Therefore, miniaturization to about 100 nm per particle is required.
  • the critical particle size of the thin film sample may be changed as compared with the powder sample due to the influence of stress from the substrate surface and the like.
  • MBE molecular beam epitaxy
  • CVD chemical vapor synthesis
  • PVD physical vapor deposition
  • thin film formation using a liquid phase method represented by a sol-gel method is more advantageous than a gas phase method from the viewpoints of composition controllability and cost, and has been extensively studied.
  • a precursor solution obtained by partially hydrolyzing a metal alkoxide solution as a raw material without adding K or adding a small amount of water is used. After the adjustment, the film is formed by spin coating or dip coating.
  • the film formed in this manner is generally amorphous containing an organic compound. To obtain a crystalline film, it is necessary to further bake the film after forming the film.
  • the amorphous phase of the film may form an intermediate phase during firing, causing problems such as an increase in surface roughness that hindered densification, and the formation of a different phase at the interface with the substrate. And deteriorated the characteristics.
  • the firing since it is necessary to perform the firing at a relatively high temperature, the firing causes grain growth, and it has been difficult to obtain a dense thin film while maintaining a sufficiently small particle size.
  • a film is formed by using the prepared dispersion solution, for example, by spin coating, dried, and then subjected to a heat treatment at a relatively low temperature, thereby forming a dense thin film while maintaining a sufficiently fine particle size. Can be obtained.
  • the key is to synthesize the ultrafine composite metal oxide particles with high crystallinity first, and then to keep the ultrafine particles once synthesized in a dispersed state without agglomeration.
  • Japanese Patent Application Laid-Open No. 2001-163617 discloses recently reported metals such as a metal colloid method, a microemulsion method (reverse micelle method), a polymer complex method, a metal alcohol hydrolysis method, and a Grignard method.
  • metals such as a metal colloid method, a microemulsion method (reverse micelle method), a polymer complex method, a metal alcohol hydrolysis method, and a Grignard method.
  • the production methods of the oxide ultrafine particles are listed.
  • the WZO (Water in Oil) microemulsion method involves adding water together with a surfactant to a hydrophobic liquid to disperse it as micro water droplets, and introducing the water by a reaction such as hydrolysis in these water droplets. This is a method of reacting raw materials to obtain ultrafine metal oxide particles. .
  • the target fine particles are separated and obtained by washing the mixture of the fine particles, which are the sediment, and the surfactant with an organic solvent or the like (see JP-A-9-1255331).
  • ultrafine particles synthesized by the microemulsion method can be dispersed in a solution without coagulation, they can be used as a solution for forming a thin film of metal oxide ultrafine particles. Can be.
  • the water droplets of the emulsion are thermodynamically stable and dispersed. However, as shown in Fig. 2, the individual droplets 1 and 1 repeat binding and dissociation.
  • the composite metal oxide ultrafine particles are synthesized by the microemulsion method, while the above-described bonding and dissociation are repeated, the synthesized fine particles gradually aggregate and precipitate.
  • the present invention has been made in view of the above points, and has a metal oxide superfine particle having a uniform composition, a uniform particle size and shape, and highly dispersed crystallized ultrafine metal oxide particles.
  • the main purpose is to provide a fine particle dispersion solution, and to provide a fine metal oxide ultrafine particle thin film having a small particle size by using the obtained composite metal oxide ultrafine particle dispersion solution. It is an object of the present invention to provide a thin film of nano-sized metal oxide ultrafine particles having excellent characteristics. Disclosure of the invention
  • the present inventors have conducted intensive studies to achieve the above object, and as a result, when synthesizing ultrafine metal oxide particles by the microemulsion method, as a raw material that consumes water in the emulsion during the reaction process, for example, A metal alkoxide is used.
  • a metal alkoxide is used as a raw material that consumes water in the emulsion during the reaction process.
  • the metal oxide ultrafine particle dispersion solution of the present invention is a metal oxide ultrafine particle produced by a hydrolysis reaction of a raw material in a microemulsion containing a dispersion medium that is a hydrophobic liquid, water, and a surfactant.
  • the amount of water used is 0.95 times or more and 3 times or less the amount of water required for hydrolysis of the raw material.
  • the ultrafine particles refer to, for example, particles having an average particle diameter of 100 nm or less.
  • the amount of water contained in the microemulsion is set to 0.95 times or more the guess required for the hydrolysis of the raw material, so that the undecomposed raw material without hydrolysis and the crystallinity are sufficient. It is possible to reduce the ratio of amorphous ultrafine particles that are not minute. Furthermore, since the amount of water contained in the microemulsion is less than three times the amount of water required for hydrolysis of the raw materials, aggregation of the metal oxide ultrafine particles generated after the reaction is suppressed, and highly dispersed transparent metal oxide It becomes an ultrafine particle dispersion solution.
  • the metal alkoxide solution serving as the raw material solution is a composite metal alkoxide solution in which a plurality of metal alkoxides are compounded, so that the ultrafine particles generated are very fine, have a uniform composition, and It becomes fine particles of a single phase composite metal oxide crystallized and uniform in diameter and shape.
  • At least one of the plurality of metal alkoxides is a barium alkoxide
  • the composite metal alkoxide solution contains a polymerization inhibitor that suppresses polymerization of the barium alkoxide.
  • polymerization inhibitor for example, benzene is preferable.
  • a polymerization inhibitor such as benzene that suppresses the polymerization of barium alkoxide is contained, polymerization of barium alkoxide is suppressed, and a homogeneous composite metal alkoxide of barium alkoxide and another metal alkoxide can be obtained. Can be.
  • the metal oxide ultrafine particle thin film according to the present invention is manufactured using the metal oxide ultrafine particle dispersion prepared by the method of the present invention.
  • a dense metal oxide ultrafine particle thin film having a small particle diameter can be obtained.
  • the metal oxide ultrafine particle film according to the present invention is ⁇ average particle diameter 1 5 nm or more 50 nm or less of the metal oxide ultrafine particles in the residual polarization (P r), 2P "mosquito 2 0 0 2 It has the above ferroelectric characteristics, and has a relative dielectric constant of 300 or more at a measurement frequency of 1 kHz.
  • the average particle diameter is 50 nm or less, it is possible to further reduce the thickness.
  • 2Pr is 2 ⁇ CZcm2.
  • An excellent thin film having the above ferroelectric properties and a relative dielectric constant of 300 or more at a measurement frequency of 1 kHz can be obtained.
  • the metal oxide ultrafine particles constituting the metal oxide ultrafine particle thin film of the present invention are a perovskite-type oxide containing titanium and barium.
  • a composite oxide such as a bevelskite-type oxide containing titanium and barium has an average particle diameter of 50 nm or less.
  • ferroelectric properties of 2 Pr of 2 Ccm2 or more and a relative dielectric constant of 300 or more at a measurement frequency of 1 kHz even if it is composed of ultrafine particles of 1550 nm. Can be.
  • the present invention since the amount of water contained in the microemulsion is limited, It is possible to easily obtain a metal oxide ultrafine particle dispersion in which the composition is uniform, the particle diameter and the shape are uniform, and the crystallized ultrafine metal oxide particles are highly dispersed.
  • the composite metal alkoxide is used as a raw material, it is possible to obtain a composite metal oxide ultrafine particle dispersion solution in which the composite metal oxide ultrafine particles are highly dispersed and a thin composite metal oxide ultrafine particle thin film having a small particle diameter. it can.
  • the average particle size is 50 nm or less, so that when used for a device, it is possible to reduce the size and thickness of the device and to reduce the size effect. It is possible to obtain excellent dielectric properties by suppressing the above.
  • Figure 1 is a schematic diagram of the mode of aggregation of ceramic fine particles via water.
  • FIG. 2 is a schematic diagram of a dispersion association mode of emulsion water droplets in a dispersion medium.
  • FIG. 3 is a schematic diagram of the ultrafine particle dispersion mode after microemulsion and hydrolysis.
  • FIG. 4 is a cross-sectional view showing a manufacturing process of a laminated condenser using the metal oxide ultrafine particle thin film of the present invention.
  • FIG. 5 is a sectional view of a thin film element using the present invention.
  • FIG. 6 is a particle size distribution diagram showing the particle size distribution of Example B of the present invention.
  • FIG. 7 is a SEM photograph of the example of the present invention.
  • FIG. 8 is a cross-sectional view of the measurement sample.
  • FIG. 9 is a diagram showing the hysteresis characteristics of the example of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
  • the microemulsion according to the present invention is a W / O microemulsion comprising a dispersion medium, which is a hydrophobic liquid, water, and a surfactant.
  • dispersion medium that is a hydrophobic liquid
  • examples of the dispersion medium that is a hydrophobic liquid include petroleum hydrocarbons such as kerosene, nonpolar hydrocarbons such as cyclohexane, hexane, cyclopentane, benzene, and octane, and ethers such as getyl ether and isopropyl ether.
  • petroleum hydrocarbons such as kerosene
  • nonpolar hydrocarbons such as cyclohexane, hexane, cyclopentane, benzene, and octane
  • ethers such as getyl ether and isopropyl ether.
  • AOT sodium bis (2-ethylhexyl) sulfosucciate
  • the raw material of the present invention is a composite metal alkoxide.
  • This composite metal alkoxide is usually obtained by mixing a plurality of single metal alkoxides in an alcohol to form a composite. It can also be obtained by mixing and mixing a plurality of composite metal alkoxides—single metal alkoxide and composite metal alkoxide in alcohol. '
  • Examples of the single metal alkoxide include, but are not limited to, barium methoxide, barium methoxide, barium propoxide, barium butoxide, titanium methoxide, titanoxide, and titanium propoxide.
  • This alcohol includes ethanol, propanol, butanol, isopropyl alcohol and the like.
  • the composite metal alkoxide is not particularly limited. Magnesium methoxide, magnesium titanium ethoxide and the like. Composite metal alkoxides
  • the amount of water in the microemulsion of the present invention is preferably 0.95 times or more and 3 times or less the amount of water required for hydrolyzing the metal alkoxide as a raw material.
  • the amount of water required for hydrolysis is defined by a chemical reaction formula, for example, a hydrolysis reaction of barium isopropoxide Ba (isop) 2 and titanium isopropoxide T i (isop) 4 Then, it becomes as follows.
  • the amount of water contained in the microemulsion must be 0.95 times or more and 3 times or less of the amount of water required for hydrolysis, that is, 2.85moI or more and 9moI or less. .
  • the amount of water When the amount of water is less than 1 time, water is completely consumed after the reaction, so that a very clear dispersion solution can be obtained.In addition, the solution remains without hydrolysis after the reaction or is amorphous and crystalline. Some of the fine particles that are not sufficient are included. However, since these phases may enter between the super-dispersed particles that form a film during film formation and increase the film density or act as a sintering aid, the amount of water is adjusted to 1 times or less and undecomposed. Or it may be better to adjust to include the amorphous part.
  • a composite metal oxide ultrafine particle dispersion solution which is clear, has high dispersion and high crystallinity.
  • the B a Z Ti ratio in a substance is an important factor in the properties, but it is known that in water, a part of lime is eluted.
  • the synthesis is carried out by the hydrolysis method, the synthesis is carried out using raw materials that have been adjusted in excess of vacuum.
  • barium ions do not dissolve into water, so that it is possible to obtain uniform ultrafine particles of interest with the adjusted raw material composition. it can.
  • the amount of water contained in the microemulsion is reduced to 0.95 times or more and 3 times or less, preferably 1.05 times or more and 1.2 times or less of the amount of water required for hydrolysis.
  • Also has the advantage that compositional deviations due to the remaining easily soluble components in the water can be almost eliminated.
  • microemulsion it is preferable to add one or more alcohols as another surfactant, so-called cosurfactant.
  • FIG. 3 is a schematic diagram showing the microemulsion solution and the vicinity of a part of the droplets in an enlarged manner, and also showing the state after the hydrolysis reaction with the addition of the composite metal alkoxide.
  • 2 is a surfactant
  • 3 is a cosurfactant
  • 4 is water
  • 5 is a reaction product
  • 6 is a dispersion medium such as cyclohexane.
  • E indicates the complex alkoxide
  • F indicates the hydrolysis
  • G indicates after the hydrolysis reaction.
  • the composite metal oxide enters between the interface of the composite oxide and the surfactant, and the surfactant remains around the composite oxide ultrafine particles.
  • the synthesized composite ultrafine particles can be stably dispersed in the same manner as in the case of water because they can exist in the form of surrounding water.
  • the cosurfactant has an effect of entering the hydrophilic portion of the surfactant, lowering the interfacial energy with water, and reducing the steric hindrance of the long carbon chain of the hydrophilic portion of the surfactant.
  • the carbon number of an appropriate alcohol depends on the length of the carbon chain of the hydrophilic part of the surfactant, but is preferably about 4 to 10.
  • the hydrophilicity is too high, so it is considered that it is dissolved in water and does not exist only at the water-surfactant interface.
  • a metal alkoxide is used as a raw material, and that each metal alkoxide is mixed and complexed before hydrolysis.
  • Paragraphs 5939-5942 state that crystals of BaTi (OCH (CH3) 2) -C6H6 can be obtained by aging an iso-propanol solution of barium and titanium in benzene. ing.
  • benzene hardly dissolves the metal alkoxide, helps stabilize and precipitate Ba T i (OCH (CH3) 2) -C6H6 crystals, and has the effect of suppressing the polymerization of barium alkoxide. Is suggested.
  • the metal oxide ultrafine particle thin film of the present invention is manufactured using the metal oxide ultrafine particle dispersion prepared by the method of the present invention.
  • ultra-fine particles of the metal oxide ultra-fine particle dispersion solution have high crystallinity, relatively low temperature, for example,
  • Heat treatment can be performed at 600 ° C. or less.
  • the metal oxide ultrafine particle thin film of the present invention is composed of metal oxide ultrafine particles having an average particle size of 15 nm or more and 50 nm or less and has ferroelectric properties.
  • 2 Pr has a ferroelectric property of 2 jU C / cm 2 or more in remanent polarization (P r), and the relative dielectric constant at a measurement frequency of 1 kHz (room temperature). Is 3 It is preferably at least oo.
  • a metal oxide ultrafine particle thin film composed of ultrafine particles of 15 to 50; Um as in the present invention, wherein 2 Pr is 2 jW CZ cm 2 or more in remanent polarization (P r). If it has ferroelectric characteristics and has a relative permittivity of 300 or more, it functions sufficiently as a ferroelectric device such as a thin film capacitor or a multilayer capacitor.
  • the metal oxide ultrafine particle thin film of the present invention when used as a thin film capacitor, it is composed of fine particles of 15 to 50 nm, so that the number of particles per layer can be increased and reliability is improved. In addition to being able to greatly improve, it is possible to further reduce the thickness and size.
  • the metal oxide ultrafine particle thin film of the present invention is obtained by synthesizing ultrafine and crystallized metal oxide ultrafine particles, for example, ceramic nanoparticles composed of a perovskite-type oxide containing titanate. Keeping it in a highly dispersed state as it is, forming a film on the substrate, then growing the grains to 15 nm or more and 50 nm or less by adding energy such as heat treatment, and further promoting densification and crystallization Manufactured.
  • ultrafine and crystallized metal oxide ultrafine particles for example, ceramic nanoparticles composed of a perovskite-type oxide containing titanate. Keeping it in a highly dispersed state as it is, forming a film on the substrate, then growing the grains to 15 nm or more and 50 nm or less by adding energy such as heat treatment, and further promoting densification and crystallization Manufactured.
  • Examples of such a film forming method include a solution in which ultrafine metal oxide particles having a uniform particle size distribution are kept in a highly dispersed state as they are, for example, from the microemulsion (ME) method.
  • a metal oxide ultrafine particle dispersion solution as a raw material solution, a thin film is prepared by a method of forming a film directly by spin coating, etc., and this is further heat-treated using an RTA (Rapid Thermal Annealing) furnace or the like. Can be manufactured.
  • RTA Rapid Thermal Annealing
  • the metal oxide ultrafine particle thin film of the present invention has an average particle diameter of, for example, 30 nm or less, for example, a ceramic oxide nanoparticle made of a perovskite-type oxide containing titanate.
  • a ceramic nanoparticle produced by a series of processes of synthesizing, maintaining the synthesized ceramic nanoparticles in a medium in a highly dispersed state, and forming a film of the highly dispersed ceramic nanoparticles on a substrate.
  • the thin film is manufactured by further grain growth of 15 nm to 50 nm by adding energy such as heat treatment.
  • ceramic fine particles that is, ceramic nanoparticles
  • ceramic nanoparticles are highly agglomerated, and once agglomerated, it is extremely difficult to redisperse them separately.-After synthesizing ceramic nanoparticles, It must be kept in a highly dispersed state in the medium.
  • wo Microemulsion is composed of a hydrophobic liquid dispersion medium, water, and a surfactant, and a water droplet having a diameter of several nm to several 10 nm is thermally dispersed in a hydrophobic solvent. Can be dispersed stably.
  • a Ba, Ti composite alkoxide raw material solution is dropped into the crystallized titanate, which is very fine and has a uniform particle size corresponding to the water droplet diameter.
  • Barium nanoparticles can be synthesized.
  • the synthesized barium titanate nanoparticles can be prevented from aggregating. A stable dispersed state can be obtained as it is.
  • the synthesized nanoparticles need to be subsequently grown to a particle size of 50 nm or less by heat treatment, so the synthesized nanoparticles are preferably as small as possible and the average particle size is small. It is preferably at least 30 nm or less, more preferably 10 nm or less.
  • the nanoparticle dispersion solution prepared in this manner is applied to a substrate by using, for example, a spin coating method, a dip coating method, a screen printing method, and the like.
  • a heat treatment step and a heat treatment step are performed to produce a dense barium titanate nanoparticle thin film.
  • Adjustment of the average particle size after film formation can be performed using an electric furnace, an infrared furnace, an RTA furnace, or the like.
  • infrared furnace RTA furnace high-speed temperature rise is possible, and high-speed temperature rise and short-time heat treatment are preferable because grain growth can be suppressed even at the same temperature.
  • Ultrafine metal oxide particles synthesized by the microemulsion method are deposited in a highly dispersed state, so even if they are nanoparticles, they are formed into dense thin films.
  • the formation of an intermediate layer does not hinder densification and does not greatly increase the surface roughness.
  • the finest and crystallized nanoparticles are grown as small as possible by heat treatment or the like, densification and crystallization are progressing even if the average particle size is as small as 50 nm or less. Excellent dielectric properties and reliability can be expected.
  • the metal oxide ultrafine particle thin film obtained in this way may be a nanoparticle having an average particle size smaller than the generally known critical size due to the influence of stress from the substrate. May exhibit ferroelectricity.
  • the metal oxide ultrafine particle thin film obtained by the production method of the present invention exhibited ferroelectricity even when the average particle diameter was 50 nm or less, and also had excellent dielectric properties.
  • the metal oxide ultrafine particle thin film formed in this manner is formed in a series of steps from synthesis to dispersion and film formation, it does not involve multiple steps, and the apparatus and the manufacturing process are not complicated. It also has points.
  • FIG. 4 shows an example of a configuration when applied to a multilayer capacitor.
  • a ceramic layer 8 is formed on a substrate 7 such as the alumina substrate shown in FIG. 1A, as shown in FIG. 2B, and a first-layer conductor electrode 9a is formed thereon. Then, a ceramic layer 8 is formed thereon, a second-layer conductor electrode 9b is further formed, a ceramic layer 8 is further formed, and a third-layer conductor electrode 9a is formed thereon. You.
  • a plurality of conductor electrodes 9a and 9b and a plurality of ceramic layers 8 are alternately laminated on the surface of the substrate 7, and a plurality of conductor electrodes 9a and 9b are formed.
  • a ceramic-metal laminate 10 including a plurality of ceramic layers 8 is formed.
  • each ceramic layer 8 is formed by the method for producing a metal oxide ultrafine particle thin film of the present invention, and each of the conductor electrodes 9 a and 9 b is formed by any one of a CVD method, a vapor deposition method, and a sputtering method.
  • the thickness of each ceramic layer 8 and each conductor electrode 9a, 9b is, for example, 1; Um or less.
  • the conductor electrodes 9a and 9b serving as internal electrodes are patterned by using a mask, and the odd-numbered conductor electrodes 9a and the even-numbered conductor electrodes 9b are alternately opposite. Side end.
  • the odd-numbered conductor electrodes 9a conduct with one external electrode 11a, and the even-numbered conductive electrodes 9a.
  • the body electrode 9b is electrically connected to the other external electrode 11b, and an ultra-small multilayer ceramic capacitor 12 as shown in FIG.
  • FIG. 5 shows an example of a configuration in which the metal oxide ultrafine particle thin film of the present invention is applied to a dielectric thin film element.
  • a substrate 13 constituting a lower layer of a dielectric thin film element and a platinum film 14 as a lower electrode formed thereon were prepared as follows.
  • the surface of the silicon plate 15 is forcibly oxidized to prevent silicon from diffusing into the platinum film 14 serving as the lower electrode.
  • an aluminum oxide film 17 was formed by 1000 ⁇ sputtering to improve the adhesion between the silicon plate 15 and the platinum film 14.
  • a platinum film 14 as a lower electrode was formed by sputtering 300 ⁇ on a substrate 13 composed of the silicon plate 15, the silicon oxide film 16, and the aluminum oxide film 17 thus formed. .
  • a dielectric thin film 18 composed of ultrafine metal oxide particles having an average particle size of 15 to 50 nm of the present invention was formed.
  • the WZO microemulsion solution contains cyclohexane as a dispersion medium and NP-10 as a surfactant: (p-C9H19) -C6H4-O- (CH2CH2O) 10CH2CH20H
  • the mixture was mixed at a ratio of 1 to obtain a W / O microemulsion solution.
  • the barium-titanium composite alkoxide is added to the prepared microemulsion solution so that the amount of water in the microemulsion becomes 0.95 times, 1.2 times, and 3 times the amount of water required for hydrolysis of the barium-titanium composite alkoxide.
  • the solutions were each fractionated using a micropip, and introduced into each microemulsion solution using a tube pump.
  • the resulting dispersion of ultrafine particles of barium titanate is light-brown and transparent, and is hydrolyzed. It was confirmed that the generated barium titanate ultrafine particles were highly dispersed.
  • the ultrafine particle dispersion solution is highly dispersed in crystallized ultrafine particles of about 8 nm. It was found to have applicability.
  • the ultrafine particle dispersion solution can freely adjust the concentration of the ultrafine particles in the liquid by adding an organic dispersion medium occupying a volume ratio of about 90% by partially evaporating with an evaporator or the like, or conversely. Can be adjusted.
  • the SEM photograph of the surface of the barium titanate ultrafine particle thin film confirmed that ultrafine particles of parium titanate of about 1 Onm were formed at a high density.
  • Example 2 a palladium-titanium composite alkoxide solution prepared in the same manner as in Example 1 was added to these two microemulsion solutions so that the water amount of the microemulsion was three times the water amount required for hydrolysis of the alkoxide raw material.
  • the microemulsion solution and introduced into each microemulsion solution using a tube pump.
  • the mixture was stirred and mixed for 1 day in a glove box under an Ar atmosphere to obtain a dispersion solution of barium titanate ultrafine particles.
  • microemulsion solution uses a micropipet with a barium-titanium composite alkoxide solution such that the amount of water in the microemulsion is five times the amount of water required for hydrolysis of the barium-titanium composite alkoxide.
  • the fractions were collected and introduced into each of the mic mouth emulsion solutions using a tube pump.
  • the mixture was stirred and mixed for 1 day in a glove box in an Ar atmosphere to obtain a dispersion of ultrafine particles of barium titanate.
  • a barium-titanium composite alkoxide solution was added to each of the prepared microemulsion solutions using a micropipet so that the amount of water in the microemulsion was 50 times the amount of water required for the hydrolysis of the barium-titanium composite alkoxide. It was separated and introduced into each microemulsion solution using a tube pump.
  • the mixture was stirred and mixed for 1 day in a glove box in an Ar atmosphere to obtain a dispersion of ultrafine particles of barium titanate.
  • a barium-titanium composite alkoxide solution is added to the prepared microemulsion solution using a micropipet so that the amount of water in the microemulsion becomes 0.75 times the amount of water required for hydrolysis of the barium-titanium composite alkoxide. , And introduced into each microemulsion solution using a tube pump.
  • the mixture was stirred and mixed for 1 day in a glove box in an Ar atmosphere to obtain a dispersion of ultrafine particles of barium titanate.
  • the barium acetate powder was dissolved in water to prepare a 0.1 mo I / I barium acetate aqueous solution.
  • the adjusted barium acetate aqueous solution: 1-octanol: NP-10: cyclohexane 5: 9: 7.5: 150 was mixed to obtain a W / O microemulsion solution.
  • the mixture was stirred and mixed in a glove box in an Ar atmosphere to obtain a titanic acid / lithium ultrafine particle dispersion solution.
  • a barium-titanium composite alkoxide solution prepared in the same manner as in Example 1 was added to the microemulsion solution so that the amount of water in the microemulsion was 50 times the amount of water required for hydrolysis of the alkoxide raw material.
  • the solution was collected by a pipette and introduced into each microemulsion solution using a tube pump.
  • Table 1 shows the dispersion state and crystal phase of the obtained barium titanate ultrafine particle dispersion solution.
  • the evaluation of the dispersion state is a visual evaluation, where ⁇ indicates a completely transparent state, ⁇ indicates a transparent state, indicates a cloudy state, and X indicates a state where precipitation has occurred. and that c first, by using the raw material solution was combined alkoxide of the produced by adjusting the W / O micro Emar Ji below 3 times 0.9 5 times more water necessary for hydrolysis of the raw material solution Gyotsu Examples of the dispersion solution of ultrafine particles of barium titanate are shown in Examples 1 and 2.
  • the generated ultrafine particles are very fine, have a uniform composition, and have a uniform particle size and shape and are crystallized single-phase ultrafine particles of a composite metal oxide. On the other hand, when the amount of water is larger than that, as shown in Comparative Example 1, the generated ultrafine particles aggregate and precipitate.
  • the sample subjected to heat treatment after centrifugation and washing was confirmed to be composed of a BaTi03 phase and a BaTi204 phase, and was found to be in excess of titanium.
  • the barium-titanium composite alkoxide solution was introduced into the microemulsion solution so that the amount of water in the microemulsion was adjusted to 1.5 times the amount of water required for hydrolysis of the lium-titanium composite alkoxide.
  • the mixture was stirred and mixed in a glove box in an Ar atmosphere to obtain a dispersion solution of ultrafine particles of barium titanate. It was confirmed by TEM observation that the titanium titanate in the dispersion solution was crystallized fine nanoparticles of about 8 nm.
  • Example A is a barium titanate ultrafine particle thin film having an average particle size of 15.2 nm subjected to heat treatment at 600 ° C.
  • Example B is an average particle size
  • Example C is a barium titanate ultrafine particle thin film having an average particle size of 48.9 nm, which was heat-treated at 900 ° C.
  • the average particle size of the obtained ultrafine particle of barium titanate was determined from a digitizer measurement of 100 particles from a SEM photograph of the surface of the thin film, and obtained from the average.
  • FIG. 6 is a particle size distribution diagram showing the particle size distribution of Example B.
  • This particle size distribution is obtained by measuring the particle size of arbitrary 100 particles from an SEM photograph and calculating the standard deviation ( ⁇ ) from the distribution.
  • the standard deviation (b) at 800 ° C. and the average particle size of the heat treatment temperature at 19.6 nm is as narrow as 1.21.
  • FIG. 7 shows an S-photograph of Example II.
  • XRD measurement confirmed that the thin film was a crystalline titanic acid / cream single phase.
  • an upper electrode was fabricated by Pt sputtering on the surface of the obtained barium titanate nanoparticles, and the relative permittivity and dielectric loss at room temperature and a measurement frequency of 1 kHz were measured with an LCR meter. The ferroelectricity was evaluated by hysteresis measurement.
  • the withstand voltage was evaluated by using the sample used for dielectric loss measurement, applying a current from the electrode and applying 200 kV / cm to the sample. If not, it was marked as ⁇ .
  • Figure 8 shows the configuration of the sample used for the evaluation of the electrical characteristics.
  • Si 02 is laminated on Si as an insulating layer, and AI 203 is laminated as a buffer layer. Further, the above-mentioned SiZSi02 / AI203 / Pt substrate 20 on which Pt21 was laminated as a lower electrode was used.
  • a dispersion of ultrafine particles of barium titanate was obtained in the same manner as in Example A.
  • the obtained barium titanate ultrafine particle dispersion solution was spin-coated on a Si ZSi 02ZA I 203 / Pt substrate several times, and heat-treated at 300 ° C in air. Thereafter, heat treatment was performed in an RTA furnace at 500 ° C. to obtain an ultrafine particle of parium titanate ultrafine particles of Comparative Example A having an average particle size of 12.6 nm.
  • the obtained barium titanate ultrafine particle thin film was confirmed to be a dense nanoparticle thin film having a small surface roughness according to the observations of 3 31 ⁇ 1 and 31 ⁇ 1.
  • Comparative Example B was an ultrafine fine particle of barium titanate having an average particle diameter of 33.2 nm that had been subjected to heat treatment at 500 ° C, and Comparative Example C had an average particle diameter of 450 that had been heat treated at 700 ° C. . 6 nm ultra-fine particle of barium titanate.
  • the thin film that had been heat-treated at 500 ° C. had only a halo peak and was not crystallized.
  • the thin film subjected to the heat treatment at 00 ° C. was confirmed to have a peak due to titanium titanate, a halo peak was also observed, indicating that an amorphous phase was included.
  • the resulting solution was aged for 3 days while stirring in the presence of steam to produce a partially hydrolyzed raw material solution.
  • Table 2 shows the surface state, dielectric properties, and crystal phase of the obtained ultrafine particle of barium titanate.
  • Table 3 shows the relative permittivity, dielectric loss, and residual polarization P r X of each sample at room temperature. 2 is shown.
  • the film is formed from the metal oxide ultrafine particle dispersion maintained in a highly dispersed state. Therefore, even if it is a nanoparticle, it becomes a homogeneous and dense thin film, and since it has already been well crystallized, the surface roughness will increase greatly due to the reaction even after heat treatment, and cracks will be formed. Is not significantly reduced, but rather, heat treatment is performed to grow fine nanoparticles, so that densification and crystallization are further promoted.
  • a thin film device using such a thin film as a device has a good dielectric property with a dielectric loss of less than 4%.
  • the withstand voltage is preferably 200 kV cm or more, which is preferable.
  • Comparative Example A having an average particle diameter of 15 nm or less, ferroelectric properties were not obtained at 2 Pr ⁇ 2.0 ⁇ CZ cm2, and the relative dielectric constant was 300 or less. No ferroelectric characteristics were obtained.
  • Comparative Examples B and C when a film was formed by a general sol-gel method, there was a problem in crystallinity, and in Comparative Example C where heat treatment was performed at 500 ° C. It is an amorphous phase.
  • Comparative Example B which was heat-treated at 700 ° C., the crystallinity was poor, and although some still contained an amorphous phase, the crystallized barium titanate was formed. The cracks were observed in some places and the film quality was greatly reduced.
  • Comparative Example D in which a film was formed using a raw material solution that had been partially hydrolyzed in advance by the sol-gel method, the reaction volume after film formation was reduced, or slight improvement in surface roughness was observed. Both become barium titanate single phase after heat treatment at 700 ° C, but the dispersion and crystallinity of nanoparticles generated by partial hydrolysis are still not enough, as shown in Examples A to C. The dielectric loss is large and the relative dielectric constant is as small as 300 or less, probably because the surface roughness is larger than that of the thin film and the low dielectric constant phase is included as in Comparative Examples B and C. became. Industrial applicability
  • the metal oxide ultrafine particle dispersion according to the present invention and the metal oxide ultrafine particles
  • the element thin film is useful as a thin film part of an electronic device such as a multilayer capacitor actuator, and is particularly suitable for use in a thin film part of an electronic device that requires both miniaturization and ferroelectric characteristics.

Abstract

Cette invention concerne une suspension de particules d'oxyde métallique ultra-fines obtenue par la réaction hydrolytique d'une matière brute dans une micro-émulsion contenant un milieu dispersé hydrophobe (6), de l'eau (4) et un tensioactif (2), la matière brute contenant un alkoxyde de métal composite et la quantité d'eau de la micro-émulsion étant de 0,95 à 3 fois supérieure à la quantité requise pour l'hydrolyse de l'alkoxyde de métal composite ; et une film de particules d'oxyde métallique ultra-fines obtenu à partir de la suspension susmentionnée. Les particules d'oxyde métallique ultra-fines de la suspension présentent une composition, un diamètre et une taille presque uniformes, sont cristallisées et très dispersées dans le milieu. Les particules du film de particules d'oxyde métallique sont de moindre taille et fortement tassées.
PCT/JP2003/011821 2002-09-20 2003-09-17 Suspension de particules d'oxyde metallique ultra-fines et film mince de particules d'oxyde metallique ultra-fines WO2004026762A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003264459A AU2003264459A1 (en) 2002-09-20 2003-09-17 Ultra-fine metal oxide particle suspension and ultra-fine metal oxide particle thin film

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2002/274598 2002-09-20
JP2002274598 2002-09-20
JP2003077651 2003-03-20
JP2003/77651 2003-03-20
JP2003/313463 2003-09-05
JP2003313463A JP4311134B2 (ja) 2002-09-20 2003-09-05 金属酸化物超微粒子分散溶液、及び金属酸化物超微粒子薄膜

Publications (1)

Publication Number Publication Date
WO2004026762A1 true WO2004026762A1 (fr) 2004-04-01

Family

ID=32034074

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/011821 WO2004026762A1 (fr) 2002-09-20 2003-09-17 Suspension de particules d'oxyde metallique ultra-fines et film mince de particules d'oxyde metallique ultra-fines

Country Status (3)

Country Link
JP (1) JP4311134B2 (fr)
AU (1) AU2003264459A1 (fr)
WO (1) WO2004026762A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100746067B1 (ko) * 2002-11-13 2007-08-03 닛뽕소다 가부시키가이샤 금속-산소 결합을 갖는 분산질, 금속산화물막 및 단분자막
JP4946163B2 (ja) * 2005-07-21 2012-06-06 ソニー株式会社 金属酸化物ナノ粒子の製造方法
DE102006025770A1 (de) * 2006-05-31 2007-12-13 Jürgen Dr. Dornseiffer Herstellung von Beschichtungslösungen nebst hergestellten Produkten
JP5446052B2 (ja) 2008-02-28 2014-03-19 株式会社村田製作所 酸化亜鉛超微粒子分散溶液、及び該酸化亜鉛超微粒子分散溶液の製造方法、並びに酸化亜鉛薄膜
JP2009280416A (ja) * 2008-05-19 2009-12-03 Taiyo Yuden Co Ltd 誘電体薄膜の製造方法及び薄膜電子部品
JP5338175B2 (ja) * 2008-07-28 2013-11-13 株式会社村田製作所 金属酸化物超微粒子の製造方法
JP5575609B2 (ja) * 2010-11-02 2014-08-20 日本碍子株式会社 鉛系圧電材料及びその製造方法
JP7145650B2 (ja) * 2018-05-31 2022-10-03 昭和電工株式会社 熱交換器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02233505A (ja) * 1989-03-06 1990-09-17 Ricoh Co Ltd 超微粒子状金属酸化物組成物の製法
JPH0369506A (ja) * 1989-08-07 1991-03-25 Ricoh Co Ltd 複合金属酸化物超微粒子
JPH0346401B2 (fr) * 1983-04-15 1991-07-16 Kanegafuchi Chemical Ind

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0346401B2 (fr) * 1983-04-15 1991-07-16 Kanegafuchi Chemical Ind
JPH02233505A (ja) * 1989-03-06 1990-09-17 Ricoh Co Ltd 超微粒子状金属酸化物組成物の製法
JPH0369506A (ja) * 1989-08-07 1991-03-25 Ricoh Co Ltd 複合金属酸化物超微粒子

Also Published As

Publication number Publication date
JP4311134B2 (ja) 2009-08-12
JP2004300013A (ja) 2004-10-28
AU2003264459A1 (en) 2004-04-08

Similar Documents

Publication Publication Date Title
Pithan et al. Progress in the synthesis of nanocrystalline BaTiO3 powders for MLCC
Caruntu et al. Solvothermal synthesis and controlled self-assembly of monodisperse titanium-based perovskite colloidal nanocrystals
Huang et al. Barium titanate nanocrystals and nanocrystal thin films: Synthesis, ferroelectricity, and dielectric properties
US9214279B2 (en) Ultrafine metal oxide particle dispersion liquid and ultrafine metal oxide particle thin film
TWI301477B (en) Barium titanate, and manufacturing method therefor, dielectric ceramic, and ceramic electronic component
JP5562673B2 (ja) 強誘電体材料、強誘電体薄膜、強誘電体材料の製造方法および強誘電体素子
US8937030B2 (en) Preparation of perovskite nanocrystals via reverse micelles
EP2417063A2 (fr) Procédé
Schneller et al. Nanocomposite thin films for miniaturized multi-layer ceramic capacitors prepared from barium titanate nanoparticle based hybrid solutions
US10943733B2 (en) Ceramic dielectric and method of manufacturing the same and ceramic electronic component and electronic device
Ahmad et al. Structural and dielectric characterization of nanocrystalline (Ba, Pb) ZrO3 developed by reverse micellar synthesis
WO2004026762A1 (fr) Suspension de particules d'oxyde metallique ultra-fines et film mince de particules d'oxyde metallique ultra-fines
JP2002234771A (ja) 正方晶ペロブスカイト構造を有する酸化物粉末およびその製造方法、誘電体セラミックならびに積層セラミックコンデンサ
WO2004097854A1 (fr) Composition liquide permettant de former un film mince ferroelectrique et procede associe
JP4384419B2 (ja) 酸化物セラミックスナノシートおよびその製造方法
Ng et al. Processing and Characterization of Microemulsion‐Derived Lead Magnesium Niobate
JP2005306691A (ja) チタン酸バリウム粉末及びその製造方法
Calzada Sol–gel electroceramic thin films
JP2009538948A (ja) コーティング溶液の作製並びに制作物
OHNO et al. Preparation of Barium Titanate Nanocoated Silica Nanoparticles by Chemical Solution Deposition
JPH06309925A (ja) 誘電体組成物、その製造法、その薄膜の製造法および薄膜コンデンサ
Du et al. Effect of polyvinylpyrrolidone on the formation of perovskite phase and rosette-like structure in sol-gel–derived PLZT films
JP3389370B2 (ja) セラミックコンデンサ
JPS5939724A (ja) 厚膜用誘電体粉末の製造法
JPH08290964A (ja) 誘電体組成物、その製造方法およびその用途

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 BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ 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): GH GM KE LS MW MZ 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 IT LU MC NL 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
122 Ep: pct application non-entry in european phase