[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN100500610C - Dielectric ceramic, process for producing the same, and laminated ceramic capacitor - Google Patents

Dielectric ceramic, process for producing the same, and laminated ceramic capacitor Download PDF

Info

Publication number
CN100500610C
CN100500610C CNB2005800326931A CN200580032693A CN100500610C CN 100500610 C CN100500610 C CN 100500610C CN B2005800326931 A CNB2005800326931 A CN B2005800326931A CN 200580032693 A CN200580032693 A CN 200580032693A CN 100500610 C CN100500610 C CN 100500610C
Authority
CN
China
Prior art keywords
mentioned
added ingredients
principal constituent
dielectric
compound
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CNB2005800326931A
Other languages
Chinese (zh)
Other versions
CN101027264A (en
Inventor
加藤成
中村友幸
武藤和夫
笹林武久
佐野晴信
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Murata Manufacturing Co Ltd
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
Publication of CN101027264A publication Critical patent/CN101027264A/en
Application granted granted Critical
Publication of CN100500610C publication Critical patent/CN100500610C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C04B35/01—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
    • C04B35/6303—Inorganic additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/12—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/22—Nickel or cobalt
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • 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
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
    • C04B2235/365—Borosilicate glass
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6582—Hydrogen containing atmosphere
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C04B2235/6584—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage below that of air
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6588—Water vapor containing atmospheres
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/345—Refractory metal oxides
    • C04B2237/346—Titania or 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/405—Iron metal group, e.g. Co or Ni
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/407—Copper

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)
  • Ceramic Capacitors (AREA)

Abstract

The invention provides a dielectric ceramic and its manufacturing method as well as multilayer ceramic capacitor. Wherein, the dielectric ceramic of the invention comprises (Ba, Ca) (Ti, X) O<SUB>3</SUB> as the main component (wherein X is an element of valence greater than that of Ti) and per 100 mol of the main component, 0.1 to 4.0 mol of each of 1st to 3rd addition components. The 1st addition component is a given rare earth element, the 2nd addition component has a given element whose valence is smaller than that of Ti, and the 3rd addition component has a sintering auxiliary containing Si. In >=90% of the main component particles (1), the sum of the solid-solution ratios exhibiting the states of solid solution of individual addition components (2) in the main component particles (1) is <= 10% in terms of sectional area ratio. The molar ratio of Ca loaded is in the range of 0 to 0.20 (preferably 0.02 to 0.20), and the molar ratio (y) of element X loaded in B-site is in the range of 0.0001 to 0.005. As a result, even when the thickness of the dielectric layer is reduced to about 1 to 3 micrometers, a high specific inductive capacity can be exhibited, and excellent insulation and high-temperature load life can be attained without detriment to the temperature characteristic of electrostatic capacity.

Description

The preparation method of dielectric ceramics, dielectric ceramics and multi-layer ceramic capacitor
Technical field
The present invention relates to the preparation method and the multi-layer ceramic capacitor of dielectric ceramics, dielectric ceramics, particularly relate to dielectric ceramics, the preparation method of dielectric ceramics and the multi-layer ceramic capacitor that uses this dielectric ceramics to be prepared from of the dielectric substance that is suitable for small-sized, jumbo multi-layer ceramic capacitor.
Background technology
Development along with in recent years electronics technology, miniaturization, the high capacity of multi-layer ceramic capacitor have been advanced, and this multi-layer ceramic capacitor, bury internal electrode underground by inside at ceramic sintered bodies, make dielectric layer thin layerization, multiple stratification, realize miniaturization, the high capacity of multi-layer ceramic capacitor.
And, dielectric ceramic composition has as follows been proposed at present, promptly this constituent is to by (Ba 1-xCa x) aTiO 2+a100 moles of interpolations of the main constituent of forming (Ba 1-ySr y) SiO 2+b0.3～1.5 mole of the oxide glass and the MgO-MnO-Ln of expression 2O 3(Ln is at least a for what select in the middle of Ho, Y, Yb, Er) obtains (patent documentation 1).
In this patent documentation 1, dielectric ceramic composition has above-mentioned composition, thus, dielectric layer thickness shows that more than 20 μ m specific inductivity is more than 3000, even use under the high strength of electric field of 5V/ μ m, the product that also can obtain electrostatic capacitance C and insulation resistance R is that CR amasss and has more than the 3000 Ω F under 20 ℃ and the good multi-layer ceramic capacitor of other each characteristics such as temperature profile.
In addition, as another kind of prior art, proposed following dielectric ceramic composition, it is to use Formula B aCa xTiO 3The calcium modified barium carbonate of expression is a principal constituent, has added MgO, MnO, BaO, CaO, the SiO of specified amount 2And the rare-earth oxide of regulation and obtain (patent documentation 2).
In this patent documentation 2,, improve its reducing resistance by replace the part of Ba composition with Ca, simultaneously, by MgO, MnO, BaO, CaO, SiO with specified amount 2And the rare-earth oxide of regulation adds in the above-mentioned principal constituent, obtains not only can not making specific inductivity to reduce and make the temperature profile variation of electrostatic capacitance, and insulating property are good and the also good multi-layer ceramic capacitor of weather resistance during high temperature load.
In addition, as another kind of prior art, proposed following dielectric ceramics, it is with general formula ABO 3(A be Ba, Ba+Ca, Ba+Sr or Ba+Ca+Sr, B be Ti, Ti+Zr, Ti+R or Ti+Zr+R (wherein, R represents rare earth element)) make principal constituent, have strong dielectric mutually part (core) with around this strong dielectric normal dielectric medium partly (shell position) mutually of part mutually, roughly be evenly distributed in whole zone (Patent Document 3) from more than one the added ingredients of selecting in the middle of Mn, V, Cr, Co, Ni, Fe, Nb, Mo, Ta and the W from crystal boundary to the center.
In this patent documentation 3, be selected from more than one added ingredients among Mn, V, Cr, Co, Ni, Fe, Nb, Mo, Ta and the W that helps to improve reducing resistance and roughly be evenly distributed in whole zone from crystal boundary to the center, therefore, strong dielectric part mutually also can improve reducing resistance, avoid its semiconductor transformation, and strong dielectric part mutually becomes high resistance, improves its insulating property thus.
Patent documentation 1: the spy opens the 2003-160378 communique
Patent documentation 2: the spy opens the 2002-29836 communique
Patent documentation 3: the spy opens flat 10-330160 communique
But, the problem that above-mentioned patent documentation 1,2 exists is, when dielectric layer thickness when 20 μ m are above, weather resistance in the time of can guaranteeing good insulation performance and high temperature load, if but dielectric layer is thinned to about 1～3 μ m, then the weather resistance variation when these insulating property and high temperature load causes reliability to reduce.
In addition, the problem that patent documentation 2 exists is, dielectric ceramic composition has the low normal dielectric medium of the specific inductivity core shell structure that exists of part mutually, and therefore, in a single day dielectric layer is thinned to about 1～3 μ m, will cause specific inductivity to reduce.
In addition, because patent documentation 3 has the low normal dielectric medium of the specific inductivity core shell structure of part existence mutually equally with patent documentation 2, therefore, in a single day dielectric layer is thinned to about 1～3 μ m, will cause specific inductivity to reduce.
Summary of the invention
The present invention constitutes in view of such problem, its purpose is, even provide dielectric layer to be thinned to about 1～3 μ m, also can access have high-k, do not damage the temperature profile of electrostatic capacitance and have the good insulation performance performance and the preparation method of the dielectric ceramics in high temperature load life-span, dielectric ceramics and use this dielectric ceramics preparation have high-k and a good multi-layer ceramic capacitor of reliability.
As dielectric ceramic material, (general formula is ABO to have the perovskite typed crystal structure with the replacement of Ca composition 3) BaTiO 3Or (Ba, Ca) TiO of the part of Ba composition 3Deng barium titanate class material is well-known.
In addition, be principal constituent with barium titanate class material usually, contain various added ingredientss by making this principal constituent, the raising of reducing resistance can be realized, and the insulativity and the reliability in high temperature load life-span can be improved.
For example, if add the W of V, Nb, Ta, Cr, Mo or 6 valencys of valence mumber 5 valencys higher than Ti in barium titanate class material, then these added ingredientss help the improvement in insulativity and high temperature load life-span in the solid solution of Ti position, can improve reliability.
In addition, if in barium titanate class material, add valence mumber divalent Mn, Ni, Mg, Fe, the Cr of 3 valencys, the Al lower, then just can improve reducing resistance than Ti.
In addition,, then just can improve insulativity and high temperature load life-span, can help the raising of reliability if in barium titanate class material, add rare earth elements such as Y and La.
Have again,, then can improve coking property if in barium titanate class material, add the glass ingredient that contains Si at least as sintering aid, can low-temperature sintering.
Therefore, select for use in the middle of the titanium acid titanate series and compare BaTiO 3(Ba, Ca) TiO that reliability is better 3, make (Ba, Ca) TiO 3In contain various added ingredientss, even in order to obtain with the further thin layerization of dielectric layer, the dielectric ceramic material that DIELECTRIC CONSTANT r height and reliability are good, present inventors painstakingly study the method that is used to obtain above-mentioned materials, obtain following opinion, make V, Nb, Ta, Cr, Mo or W solid solution in (Ba, Ca) TiO 3Formation is by (Ba, Ca) (Ti, X) O 3The principal constituent that (X is at least a kind that is selected from the middle of V, Nb, Ta, Cr, Mo and the W) formed, on the other hand, the added ingredients (Mn, Ni etc. and rare earth element, sintering aid) that makes other substantially not solid solution in (Ba, Ca) (Ti, X) O 3And being controlled to be more than 90% the principal constituent particle, the expression added ingredients is below 10% to the total of the solid solution rate of the solid solution condition of above-mentioned principal constituent particle by sectional area ratio, thus, even dielectric layer is thinned to 1～3 μ m, also can obtain having DIELECTRIC CONSTANT r and be the high dielectric-constant dielectric pottery more than 2500.
The present invention constitutes according to such discovery, and dielectric ceramics provided by the invention is characterized in that, with (Ba, Ca) (Ti, X) O 3(wherein X is for being selected from V, Nb, Ta, Cr, at least a kind of element in the middle of Mo and the W) be principal constituent, and contain the multiple added ingredients that is classified as first～the 3rd added ingredients at least, above-mentioned first added ingredients comprises and is selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, in the middle of Lu and the Y at least a kind, simultaneously, above-mentioned second added ingredients comprises and is selected from Mn, Ni, Fe, Co, in the middle of Mg and the Al at least a kind, and the 3rd added ingredients is made of the sintering aid that contains Si at least, wherein, for in the principal constituent particle more than 90% for, represent above-mentioned first～the 3rd added ingredients to the adding up to of the solid solution rate of the solid solution condition of above-mentioned principal constituent particle, by sectional area ratio below 10%.
In addition, for the temperature profile that makes electrostatic capacitance and insulativity, high temperature load life-span keep good, guarantee good reliability, preferably the content of above-mentioned first～the 3rd added ingredients, Ca content in the A position and the content of the element X in the B position are controlled in the setting range.
That is to say, the invention provides dielectric ceramics, it is characterized in that, the content of above-mentioned first～the 3rd added ingredients is with respect to 100 moles of above-mentioned principal constituents, be respectively 0.1～4.0 mole, and the mixing mol ratio x of the above-mentioned Ca in above-mentioned (Ba, Ca) is 0≤x≤0.20, and the mixing mol ratio y of the above-mentioned element X in above-mentioned (Ti, X) is 0.0001≤y≤0.005.
In addition, the reliability when making high temperature load further improves, and preferably above-mentioned mixing mol ratio x is adjusted into 0.02≤x≤0.20.
That is, the invention provides dielectric ceramics, it is characterized in that, above-mentioned mixing mol ratio x is 0.02≤x≤0.20.
And above-mentioned dielectric ceramics can prepare as follows, that is, make element X at (Ba, Ca) TiO 3The solid solution of B position and produce after the principal constituent, can not be solidly soluted into mode in the principal constituent particle according to first～the 3rd added ingredients, make this principal constituent particle contain above-mentioned first～the 3rd added ingredients.
Promptly, the invention provides the preparation method of dielectric ceramics, it is characterized in that, comprise: the principal constituent preparation section, the X compound that will contain Ba compound, Ca compound, Ti compound and be selected from least a kind of element X among V, Nb, Ta, Cr, Mo, the W is reacted, and preparation is with general formula (Ba, Ca) (Ti, X) O 3The principal constituent of expression; The title complex preparation section, the compound that contains the compound that is selected from least a kind of first added ingredients in the middle of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the Y and contain the compound that is selected from least a kind second added ingredients in the middle of Mn, Ni, Fe, Ag and the A1 and contain the 3rd added ingredients that contains Si at least added be mixed in the above-mentioned principal constituent preparation title complex; Ceramic sintered bodies prepares operation, and above-mentioned title complex is implemented sintering processes, the preparation ceramic sintered bodies.
In addition, the invention provides multi-layer ceramic capacitor, it comprises: the ceramic sintered bodies of forming by the ceramic laminated body of stacked a plurality of dielectric layers, side by side shape be embedded in this ceramic sintered bodies inside a plurality of internal electrodes, be arranged on the outer electrode of above-mentioned ceramic post sintering external surface, it is characterized in that above-mentioned ceramic sintered bodies forms with above-mentioned dielectric ceramics.
In addition, the invention provides multi-layer ceramic capacitor, it is characterized in that, above-mentioned internal electrode contains the easy oxidation metal material, and preferred said external electrode contains the easy oxidation metal material.
According to dielectric ceramics of the present invention, with (Ba, Ca) (Ti, X) O 3(wherein, X represents to be selected from V, Nb, Ta, Cr, at least a kind of element in the middle of Mo and the W) makes principal constituent, in principal constituent, add La, Ce, first added ingredients such as Pr, Mn, Ni, second added ingredients such as Fe, and as the 3rd added ingredients of sintering aid, for in the principal constituent particle more than 90% for, represent that the total of the solid solution rate of the solid solution condition of above-mentioned first～the 3rd added ingredients in above-mentioned principal constituent particle counts below 10% by sectional area ratio, therefore, even it is high dielectric-constant dielectric pottery more than 2500 that the dielectric layer thin layerization to 1～3 μ m, also can obtain having DIELECTRIC CONSTANT r.
In addition, the content of above-mentioned first～the 3rd added ingredients is respectively 0.1～4.0 mole with respect to 100 moles of principal constituents, and above-mentioned Ba is 0≤x≤0.20 (preferred 0.02≤x≤0.20) with respect to the cooperation mol ratio x of above-mentioned Ca, above-mentioned element X is 0.0001≤y≤0.005 with respect to the cooperation mol ratio y of above-mentioned Ti, therefore, can access and have high-k, and the good dielectric ceramics of reliability such as temperature profile and insulativity, high temperature load life-span.
In addition, according to the preparation method of dielectric ceramics of the present invention, because it comprises: make Ba compound, Ca compound, Ti compound and the reaction of X compound, preparation (Ba, Ca) (Ti, X) O 3The principal constituent preparation section of the principal constituent of expression; The compound that contains the compound of first added ingredients and contain the compound of second added ingredients and contain the 3rd added ingredients added be mixed into the title complex preparation section for preparing title complex in the above-mentioned principal constituent; The ceramic sintered bodies that above-mentioned title complex enforcement sintering processes is prepared ceramic sintered bodies prepares operation, therefore, can easily prepare the temperature profile that can obtain having high-k, electrostatic capacitance does not have impaired yet and has the dielectric ceramics of the good multi-layer ceramic capacitor of good insulation performance and the reliability in high temperature load life-span.
In addition, above-mentioned principal constituent production process carries out the optimization of maturing temperature etc. in order to improve degree of crystallinity.Thus, even in principal constituent, add first～the 3rd added ingredients, also can easily prepare the dielectric ceramics of solid solution hardly in this principal constituent.
In addition, multi-layer ceramic capacitor of the present invention possesses: the ceramic sintered bodies of forming by the ceramic laminated body of stacked a plurality of dielectric layers, side by side shape be embedded in this ceramic sintered bodies inside a plurality of internal electrodes, be formed at the outer electrode of above-mentioned ceramic post sintering external surface, wherein, above-mentioned ceramic sintered bodies forms with above-mentioned dielectric ceramics, therefore, the temperature profile that can easily obtain specific inductivity height, electrostatic capacitance does not have impaired and insulativity and the high temperature load life-span is good and reliability is good small-sized, jumbo multi-layer ceramic capacitor.
In addition, in the multi-layer ceramic capacitor of the present invention, above-mentioned internal electrode contains the easy oxidation metal material, and the said external electrode contains the easy oxidation metal material, therefore, can obtain the multi-layer ceramic capacitor that above-mentioned all characteristics are good and reliability is good at an easy rate.
Description of drawings
Fig. 1 is the sectional drawing that schematically illustrates the ceramic structure of dielectric ceramics of the present invention.
Fig. 2 is the figure that is used to illustrate X ray spectrographic half range value Δ H.
Fig. 3 is the sectional drawing of an embodiment of the expression multi-layer ceramic capacitor that uses dielectric ceramics preparation of the present invention.
Nomenclature
1 principal constituent particle
2 added ingredientss
3 ceramic sintered bodies
4 internal electrodes
5 outer electrodes
Embodiment
Below, describe embodiments of the present invention in detail.
In the dielectric ceramics of the present invention, using (Ba, Ca) (Ti, X) O 3Contain first～the 3rd added ingredients as shown in table 1 in the principal constituent of (wherein, X represents to be selected from least a kind of central element of V, Nb, Ta, Cr, Mo and W) expression.
Table 1
First added ingredients Be selected from least a kind in the middle of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the Y
Second added ingredients Be selected from least a kind in the middle of Mn, Ni, Fe, Mg and the Al
The 3rd added ingredients At least the sintering aid that contains Si
And, in this dielectric ceramics, for the principal constituent particle more than 90% in the principal constituent particle, represent that the total (below abbreviate " solid solution rate total " as) of the solid solution rate of the solid solution condition of above-mentioned first～the 3rd added ingredients in above-mentioned principal constituent particle is counted below 10% by sectional area ratio.
Fig. 1 is the sectional drawing that schematically illustrates the ceramic structure of dielectric ceramics of the present invention, among the figure, each crystalline particle (below be called " principal constituent particle ") of 1 expression principal constituent, 2 expression solid solutions each added ingredients (first～the 3rd added ingredients) in this principal constituent particle 1.
That is, principal constituent particle 1, be selected from least a kind of element in the middle of the valence mumber V higher, Nb, Ta, Cr, Mo and the W than Ti be element X solid solution in the Ti position, form O with (Ba, Ca) (Ti, X) 3The constituent of expression.
And, in principal constituent particle 1, though contain above-mentioned various added ingredientss, but in its addition manner, the solid solution rate total of representing the solid solution condition of each added ingredients in principal constituent particle 1 is expressed as below 10% with sectional area ratio, each added ingredients 2 can not solid solution more than 90% in principal constituent particle 1, and separate out in the grain boundary, form and 2 second phases and have (not shown).
And, form dielectric ceramics like this in the following manner, promptly for the principal constituent more than 90% 1 in the principal constituent particle 1, the solid solution rate total of representing the solid solution condition of each added ingredients 2 in principal constituent particle 1 is below 10% by sectional area ratio, thus, even the dielectric layer thin layerization to 1～3 μ m, also can be realized having DIELECTRIC CONSTANT r and is the high dielectric-constant dielectric pottery more than 2500.
That is, by making the complete solid solution of the valence mumber element X higher (V, Nb, Ta, Cr, Mo, W) in (Ba, Ca) TiO than Ti 3The Ti position, can improve insulativity and high temperature load life-span, thereby can realize the raising of reliability.
In addition, by adding rare earth elements such as Y or lanthanon to (Ba, Ca) (Ti, X) O as first added ingredients 3In, can improve insulativity and high temperature load life-span, can help the raising of reliability.Add (Ba, Ca) (Ti, X) O by the Mn that valence mumber is lower than Ti, Ni, Mg, Fe, Cr, Al to as second added ingredients 3In, can improve reducing resistance, in addition, contain the sintering aid (SiO for example of Si by interpolation 2, SiO 2-Li 2O 3, SiO 2-B 2O 3Deng) as the 3rd added ingredients, thus coking property is improved, can low-temperature sintering.
But, if make each above-mentioned added ingredients 2 in accordance with regulations the above ratio of ratio be solidly soluted in the principal constituent particle 1, then will make DIELECTRIC CONSTANT r be reduced to less than 2500, thereby shortcoming is as the practicality of dielectric ceramics.
Therefore, present inventors are carrying out deep research, the result makes each added ingredients 2 solid solution in principal constituent particle 1 by regulating preparation condition etc. hardly, particularly, as mentioned above, amounting to by the above-mentioned solid solution rate with 90% above particle in the principal constituent particle 1 and to be made as, is below 10% by sectional area ratio, obtains having DIELECTRIC CONSTANT r as can be known and be the high dielectric-constant dielectric pottery more than 2500.
The content of first～the 3rd added ingredients is preferably with respect to principal constituent (Ba, Ca) (Ti, X) O 3100 moles are respectively 0.1～4.0 mole.This be because, be made as below 10% by sectional area ratio by total the above-mentioned solid solution rate of 90% above principal constituent particle 1 in the principal constituent particle 1, can make DIELECTRIC CONSTANT r is more than 2500, but if the content of first～the 3rd added ingredients is outside above-mentioned scope, then insulativity reduces or the reduction of high temperature load life-span, may make to cause reliability to reduce.
In addition, the cooperation mol ratio x preferred 0～0.20 of the Ca in the A position.This be because, if cooperate mol ratio x to surpass 0.20,, insulativity or high temperature load life-span are worn out though can access the DIELECTRIC CONSTANT r 2500 or more, cause the reliability reduction.And the reliability when making high temperature load further improves, and more preferably will cooperate mol ratio x to be made as more than 0.02.
In addition, the cooperation mol ratio y of the element X in the B position is preferably 0.0001～0.005.This be because, when cooperating mol ratio y less than 0.0001, though DIELECTRIC CONSTANT r is good, the temperature profile deterioration of electrostatic capacitance and make temperature stability not good enough, the high temperature load life-span reduces and is weak aspect reliability simultaneously.On the other hand, though cooperating mol ratio y also good above 0.005 o'clock DIELECTRIC CONSTANT r, insulativity or high temperature load life-span reduce, and may cause reliability and reduce.
Below, be described in detail the preparation method of above-mentioned dielectric ceramics.
At first, difference weighing BaCO 3Deng Ba compound, CaCO 3Deng Ca compound and TiO 2Deng the Ti compound and be selected from V 2O 5, Nb 2O 5, Ta 2O 5, Cr 2O 3, MoO 3And WO 3The central X compound more than at least a kind, make above-mentioned cooperation mol ratio x, y be respectively 0.02～0.20,0.0001～0.005, it is knocked down in the ball mill, wet type is mixed pulverizing, afterwards, implement thermal treatment in 1 hour 1100～1200 ℃ temperature, thus, prepare (Ba, Ca) (Ti, X) O that high crystallization has been handled 3
Why improve (Ba, Ca) (Ti, X) O like this 3Degree of crystallinity, be because by improving degree of crystallinity, when having added first～the 3rd added ingredients described later, these each added ingredientss become and are difficult to solid solution in the principal constituent particle, thus, can control the solid solution of each added ingredients in the principal constituent particle.
In addition, principal constituent (Ba, Ca) (Ti, X) O 3Degree of crystallinity for example can be by measuring crystalline particle the half range value Δ H on specific crystal plane (hk1) of X ray intensity confirm.
Fig. 2 schematically illustrates X-ray diffraction spectrographic figure, and transverse axis is represented diffraction angle 2 θ, and the longitudinal axis is represented X ray intensity (cps).
That is, when the peak value of X ray intensity is the pinnacle, because the crystallinity height of crystalline particle, so 1/2 half range value Δ H by trying to achieve the height H that is equivalent to principal constituent (°), can estimate the degree of crystallinity of principal constituent particle.
Secondly, prepare to contain the rare-earth oxide of first added ingredients, that is, be selected from La 2O 3, CeO 2, Pr 5O 11, Nd 2O 3, Sm 2O 3, Eu 2O 3, Gd 2O 3, Tb 2O 3, Dy 2O 3, Ho 2O 3, Er 2O 3, Tm 2O 3, Yb 2O 3, Lu 2O 3And Y 2O 3The central rare-earth oxide more than at least a kind.
In addition, prepare to contain the metallic compound of second added ingredients, promptly be selected from MnO, NiO, Fe 2O 3, MgO and Al 2O 3In the middle of more than at least a kind.
And then preparation contains the SiO of Si at least 2As the 3rd added ingredients, prepare Li as required 2O 3, B 2O 3Deng.
Secondly, first～the 3rd added ingredients is come weighing according to being 0.1～4.0 mole with respect to 100 moles of principal constituents, it is knocked down ball mill, it is mixed and case of wet attrition with principal constituent, obtain title complex like this.
In the present embodiment, regulate degree of crystallinity by controlling above-mentioned heat-treat condition, according to for the principal constituent particle more than 90% in the principal constituent particle, it is that mode below 10% forms title complex that the solid solution rate of each added ingredients in the principal constituent particle amounts to by sectional area ratio.
And this title complex is made dielectric ceramics of the present invention being sintered processing in the preparation process at multi-layer ceramic capacitor like that as described later.
Fig. 3 is the sectional drawing of an embodiment of schematically representing to use the multi-layer ceramic capacitor of dielectric ceramics preparation of the present invention.
In this multi-layer ceramic capacitor, in the ceramic sintered bodies 3 that constitutes by dielectric ceramics of the present invention, bury internal electrode 4 (4a～4f) underground, simultaneously, both ends at this ceramic sintered bodies 3 form outer electrode 5a, 5b, and then form the first filming 6a, 6b and the second plated film 7a, 7b on the surface of this outer electrode 5a, 5b.
Particularly, each internal electrode 4a～4f is arranged side by side at stacked direction, and simultaneously, internal electrode 4a, 4c, 4e are electrically connected with outer electrode 5a, and internal electrode 4b, 4d, 4f are electrically connected with outer electrode 5b.And, between the opposed faces of internal electrode 4a, 4c, 4e and internal electrode 4b, 4d, 4f, form electrostatic capacitance.
Above-mentioned multi-layer ceramic capacitor is to use above-mentioned title complex to prepare with method as described below.
That is, above-mentioned title complex is knocked down ball mill with tackiness agent and organic solvent carry out wet mixing, the preparation ceramic slurry uses and to scrape the skill in using a kitchen knife in cookery etc. ceramic slurry is implemented forming process, and the thickness of making behind the sintering is the ceramic green sheet of 1～3 μ m.
Then, use internal electrode on ceramic green sheet, to implement screen painting, on above-mentioned ceramic green sheet, form the conducting film of predetermined pattern with conductive paste.
And as internal electrode with the conductive material that contains in the conductive paste, from the viewpoint of cost degradation, preferably use Ni, Cu or with the easy oxidation metal material of these alloys as principal constituent.
Then, the ceramic green sheet that will be formed with conducting film is seized on both sides by the arms with the ceramic green sheet that does not form conducting film in the stacked multi-disc of prescribed direction, carries out crimping, is cut to specified dimension, makes ceramic laminated body.And, under 300～500 ℃ of temperature, carry out the unsticking mixture to handle, and then oxygen partial pressure is being controlled at 10 thereafter -9～10 -12MPa by H 2-N 2-H 2Under the reducing atmosphere that O gas constitutes, carry out about 2 hours sintering processes 1000～1300 ℃ of temperature.Thus, conducting film by sintering, has obtained burying underground the ceramic sintered bodies 3 of internal electrode 4 with stupalith.
Secondly, the both ends of the surface coating outer electrode conductive paste at ceramic sintered bodies 3 carries out sintering processes, forms outer electrode 5a, 5b.
In addition, for the conductive material that contains in the conductive paste,, preferably use Cu or for outer electrode with the easy oxidation metal material of these alloys as principal constituent from the viewpoint of cost degradation.
In addition, as the formation method of outer electrode 5a, 5b, on the both ends of the surface of ceramic laminated body, applied outer electrode with conductive paste after, also can implement sintering processes simultaneously with ceramic laminated body.
At last, carry out the electrolysis plating, externally the surface of electrode 5a, 5b forms the first filming 6a, the 6b that is made of Ni, Cu, Ni-Cu alloy etc., and then forms the second plated film 7a, the 7b that is made of scolding tin and tin on the surface of this first filming 6a, 6b, thus, preparation multi-layer ceramic capacitor.
Like this, because this multi-layer ceramic capacitor is to use above-mentioned dielectric ceramics preparation, therefore, the multi-layer ceramic capacitor that even dielectric layer by further thin layerization, also can be easy to obtain having high-k, temperature profile does not have impaired and insulativity and the high temperature load life-span is good, reliability is good.
In addition, the invention is not restricted to above-mentioned embodiment.For example, with regard to above-mentioned embodiment, by with Ba compound, Ca compound, Ti compound and X compound being solid phase method making (Ba, Ca) (Ti, X) O of ceramic raw material (starting material) 3, implement thermal treatment and improve crystallinity, still, can also obtain desired crystallinity by moisture solution or hydrothermal synthesis method etc., in addition, also can use the ultra micro powdered ceramic raw material of 10～30nm to make (Ba, Ca) (Ti, X) O 3, improve crystallinity.
In addition, for Ba compound, Ca compound, Ti compound, except carbonate or oxide compound,, can suitably select nitrate, oxyhydroxide, organic acid salt, alkoxide, huge legendary turtle compound etc. according to the form of building-up reactions.
In addition, in the preparation process of above-mentioned multi-layer ceramic capacitor, Al, Sr, Zr, Fe, Hf, Na, Co etc. sneak into as impurity, may be present in crystal grain inside or crystal boundary, but can not impact the electrical characteristic of electrical condenser.
In addition, in the sintering processes of multi-layer ceramic capacitor, the internal electrode composition may be diffused into crystal grain inside and crystal boundary, but this situation can not impact the electrical characteristic of electrical condenser yet.
Below, specifically describe embodiments of the invention.
Embodiment 1
At first, as ceramic raw material, preparing median size is the BaCO of 50nm 3, CaCO 3, TiO 2And V 2O 5, measure these ceramic raw materials of weighing in accordance with regulations, after this weighed object is dropped into ball mill, carried out 24 hours mixed pulverizing with wet type.Then, under 1000～1150 ℃ temperature, heat-treat, make of chemical constitution formula (Ba 0.90Ca 0.10) (Ti 0.999V 0.001) O 3The embodiment 1～3 of expression and the principal constituent of comparative example 1～3.
Then, measure the X ray spectrum of these each principal constituents with XRD (X-Ray Diffraction:X ray diffraction device), measure half range value Δ H (°).
Then, preparation is as the Y that contains Y of first added ingredients 2O 3, as the MnCO that contains Mn of second added ingredients 3, as the SiO that contains Si of the 3rd added ingredients 2
And, with respect to 100 moles of principal constituents, difference weighing Y 2O 3, MnCO 3, SiO 2, make it be respectively Y:1.0 mole, Mn:0.5 mole, Si:2.5 mole, it is knocked down ball mill and principal constituent carry out 24 hours mixed pulverizing with damp process jointly, obtain the title complex of embodiment 1～3 and comparative example 1～3.
Principal constituent composition, the half range value of principal constituent particle, each added ingredients kind and molar content thereof of each title complex of table 2 expression embodiment 1～3 and comparative example 1～3.
Table 2
Figure C200580032693D00151
By this table 2 as can be known, be 0.37 °～0.45 ° with respect to the half range value Δ H of comparative example 1～3, the half range value Δ H of embodiment 1～3 is little of 0.26 °～0.33 °, and embodiment 1～3 compares with comparative example 1～3, the crystallinity height.
Then, with above-mentioned each title complex with polyvinyl butyral acetal class tackiness agent, knock down ball mill as the ethanol of organic solvent and carry out wet mixing, make ceramic slurry, and then ceramic slurry is implemented forming process, make rectangular-shaped ceramic green sheet by scraping the skill in using a kitchen knife in cookery etc.
Then, the conductive paste screen painting that will be principal constituent with Ni forms conducting film on the surface of this ceramic green sheet on above-mentioned ceramic green sheet.
Then, the ceramic green sheet that will be formed with conducting film is seized on both sides by the arms with the ceramic green sheet that does not form conducting film in the stacked multi-disc of pre-determined direction, carries out crimping, cuts into specified dimension, makes ceramic laminated body.And, in nitrogen atmosphere, under 300 ℃ of temperature, carry out the unsticking mixture to handle, and then be controlled in 10 at oxygen partial pressure thereafter -10MPa by H 2-N 2-H 2Under the reducing atmosphere that O gas constitutes, under 1250 ℃ of temperature, carry out 2 hours sintering processes, made the ceramic sintered bodies of having buried internal electrode underground.
Then, will contain B 2O 3-Li 2O-SiO 2The Cu cream of-BaO class glass ingredient is coated on the both ends of the surface of ceramic sintered bodies, implements sintering processes under nitrogen atmosphere, 800 ℃ of temperature, forms outer electrode, makes the multi-layer ceramic capacitor of embodiment 1～3 and comparative example 1～3.
In addition, each multi-layer ceramic capacitor, its physical dimension is: vertical 0.8mm, horizontal 1.6mm, thick 0.8mm, the thickness of being located at internal electrical interpolar dielectric ceramics layer is 2 μ m.In addition, effectively the lamination sheets number of dielectric layer is 150, and the counter electrode area of each layer is 0.9mm 2
Secondly, for the various embodiments described above and comparative example, to using TEM (Transmission ElectrorMicroscope: the observed crystalline particle Clairvoyant type electron microscope), the probe bore that uses 2nm is with EDX (Energy Dispersive X-ray Spectroscopy: energy distributing x-ray analysis) analyze, obtain the solid solution rate of added ingredients in each principal constituent particle and amount to (%), and then obtain the ratio (principal constituent ratio) of solid solution rate total at the principal constituent particle below 10%.In addition, the analysis number of crystalline particle is carried out analysis meter with 10 points and is calculated mean value as one group at embodiment and per 20 of comparative example, calculates that the solid solution rate amounts to and the solid solution rate adds up to principal constituent ratio below 10%.
In addition, using automatic bridge-type tester, is that 1kHz, virtual voltage are that 1Vrms, temperature are to measure electrostatic capacitance C under 25 ℃ the condition in frequency, calculates DIELECTRIC CONSTANT r by electrostatic capacitance C.
In addition, using insulating-resistance meter, is under 25 ℃ and 125 ℃ in temperature, measure apply 2 minutes 20V (10kV/mm) volts DS the time insulation resistance R, electrostatic capacitance C and insulation resistance R are multiplied each other, calculating CR product.
With regard to the temperature profile of electrostatic capacitance R, because must satisfy the X7R characteristic of formulating by EIA (EIA), so to the electrostatic capacitance under+25 ℃ being rate of change of capacitance (the Δ C/C-55 ℃～+ 125 ℃ scope of benchmark 25) carry out evaluation of measuring.Here, so-called X7R characteristic is meant that with+25 ℃ be rate of change of capacitance (the Δ C/C of the electrostatic capacitance of benchmark 25) satisfy ± 15% characteristic-55 ℃～+ 125 ℃ temperature ranges.
In addition, carry out the high temperature load test, estimated the high temperature load life-span.That is,, under 175 ℃ hot conditions, apply the voltage of 40V (20kV/mm) to each 100 of the test films of embodiment and comparative example, measured insulation resistance through the time change.Then, will be after on-test the test film that is reduced to below the 200k Ω of insulation resistance R during through 1000 hours and 2000 hours be judged to unacceptable product, count the number of this unacceptable product and estimated the high temperature load life-span.
Table 3 is illustrated in every measurement result of embodiment 1～3 and comparative example 1～3.
Table 3
Figure C200580032693D00171
In the comparative example 1, though the solid solution rate adds up to 9.5%, because the principal constituent ratio that the solid solution rate adds up to below 10% is low to 85%, so DIELECTRIC CONSTANT r is low to 2276, and the CR product is also low to being 1841 Ω F 25 ℃ the time, is 20 Ω F under 125 ℃, thereby poor insulativity as can be known.
In the comparative example 2 and 3, the solid solution rate amounts to respectively up to 12.8%, 18.2%, and the solid solution rate amounts at the principal constituent ratio below 10% low respectively to 75%, 20%, therefore, DIELECTRIC CONSTANT r is also low respectively to 2000,1655, and the CR product also low be 1049 Ω F, 58 Ω F during to 25 ℃, be 1 Ω F, 0 Ω F in the time of 125 ℃, thereby poor insulativity as can be known.
Relative therewith, among the embodiment 1～3, because the solid solution rate amounts to and is respectively below 0.8～7.5% and 10%, and solid solution rate total is more than 90～100% and 90% at the principal constituent ratio below 10%, so DIELECTRIC CONSTANT r also has the high-k more than 3145～3490 and 2500, the CR product is 2946～3937 Ω F during also up to 25 ℃, in the time of 125 ℃ 104 Ω F～762 Ω F, insulativity is good, even in the high temperature load test, passed through and also do not produced unacceptable product in 2000 hours, therefore thought to access good reliability.Think that in addition the temperature profile of electrostatic capacitance also satisfies the X7R characteristic, rate of change of capacitance (Δ C/C 25) be-10.6～-11.5%.
Embodiment 2
Prepare BaCO 3, CaCO 3, TiO 2, V 2O 5, Nb 2O 5, Ta 2O 5, Cr 2O 3, MoO 3And WO 3,, make (Ba, Ca) (Ti, X) O by embodiment 11～33 with cooperation mol ratio as shown in table 4 by method, the operation roughly the same with [embodiment 1] 3The principal constituent that (X=V, Nb, Ta, Cr, Mo and W in the middle of at least a kind) forms with XRD instrumentation X ray spectrum, is measured half range value Δ H to this principal constituent.
Then, preparation is as the La of rare-earth oxide 2O 3, CeO 2, Pr 5O 11, Nd 2O 3, Sm 2O 3, Eu 2O 3, Gd 2O 3, Tb 2O 3, Dy 2O 3, Ho 2O 3, Er 2O 3, Tm 2O 3, Yb 2O 3, Lu 2O 3And Y 2O 3, in addition, prepare MnO, NiO, Fe as metal oxide 2O 3, MgO, Al 2O 3, and then preparation is as the SlO of sintering aid 2, Li 2O 3, B 2O 3, Dy 2O 3, MgO, SiO 2, Li 2O 3Various added ingredientss, each added ingredients carries out weighing by having the composition of recording and narrating as table 2, uses method, the operation roughly the same with [embodiment 1] thereafter, adds these added ingredientss and carry out wet mixing in principal constituent, obtains the title complex of embodiment 11～33.
The principal constituent composition of each title complex of table 4 expression embodiment 11～33, the half range value of principal constituent particle, the kind and the molar content thereof of each added ingredients.
Table 4
Figure C200580032693D00191
Then, use above-mentioned each title complex, use the method same, the multi-layer ceramic capacitor of sequentially built embodiment 11～33 with [embodiment 1].
Then,, use the method same, in proper order, obtain that the solid solution rate amounts to, the solid solution rate amounts at the principal constituent ratio below 10%, DIELECTRIC CONSTANT r, rate of change of capacitance (Δ C/C with [embodiment 1] to each multi-layer ceramic capacitor of embodiment 11～33 25), the CR product when under 25 ℃ and 125 ℃ of conditions, having applied the volts DS of 20V (10V/mm), and then carry out the high temperature load test.
Its result of table 5 expression.
Figure C200580032693D00211
Among the embodiment 11～33, the solid solution rate adds up to below 3.2～5.4% and 10%, and it is 90～100% that the solid solution rate amounts at the principal constituent ratio below 10%, and therefore, DIELECTRIC CONSTANT r 2863～4343 has the high-k more than 2500.And for the temperature profile of electrostatic capacitance, rate of change of capacitance (Δ C/C 25) be-0.8～-14.5%, satisfy the X7R characteristic.
But, among the embodiment 24, because the addition of first～the 3rd added ingredients all surpasses 4.0 moles with respect to 100 moles of principal constituents, therefore, in high temperature load test, produce 30 unacceptable products in 100 1000 hours the time, produced 98 unacceptable products in the time of 2000 hours in 100.
In addition, among the embodiment 25, since as the Co addition of second added ingredients with respect to 100 moles of principal constituents above 4.5 moles and 4.0 moles, therefore, CR amasss in the time of 25 ℃ low to 1832 Ω F, low to 48 Ω F 125 ℃ the time, insulativity worsens, and has produced 11 unacceptable products in 100 1000 hours the time in the high temperature load test, has produced 76 unacceptable products in the time of 2000 hours in 100.
Among the embodiment 26, since as the interpolation total amount of the Dy of first added ingredients and Y with respect to 100 moles of principal constituents above 6 moles and 4.0 moles, therefore, CR amasss in the time of 25 ℃ low to 1255 Ω F, low to 3 Ω F 125 ℃ the time, insulativity worsens, having produced 41 unacceptable products in 100 1000 hours the time in high temperature load test, is unacceptable product all in the time of 2000 hours.
Among the embodiment 27, because the interpolation total amount as the sintering aid that contains Si of the 3rd added ingredients has surpassed 5 moles and 4.0 moles with respect to 100 moles of principal constituents, therefore, in high temperature load test, produce 8 unacceptable products in 100 1000 hours the time, produced 85 unacceptable products in the time of 2000 hours in 100.
Among the embodiment 28, owing to surpassed 4.0 moles with respect to 100 moles of principal constituents as the Ce of first added ingredients with as the addition of the sintering aid that contains Si of the 3rd added ingredients, therefore, having produced 61 unacceptable products in 100 1000 hours the time in high temperature load test, is unacceptable product all in the time of 2000 hours.
Among the embodiment 29, owing to surpassed 4.0 moles respectively with respect to 100 moles of principal constituents as the Ce of first added ingredients with as the addition of the Al of second added ingredients, therefore, having produced 48 unacceptable products in 100 1000 hours the time in high temperature load test, is unacceptable product all in the time of 2000 hours.
Among the embodiment 30, owing to surpassed 4.0 moles respectively with respect to 100 moles of principal constituents as the Ni of second added ingredients with as the addition of the sintering aid that contains Si of the 3rd added ingredients, therefore, in high temperature load test, produce 6 unacceptable products in 100 1000 hours the time, produced 64 unacceptable products in the time of 2000 hours in 100.
Among the embodiment 31, because the addition as the sintering aid that contains Si of the 3rd added ingredients has surpassed 5 moles and 4.0 moles with respect to 100 moles of principal constituents, therefore, in high temperature load test, produce 5 unacceptable products in 100 1000 hours the time, produced 49 unacceptable products in the time of 2000 hours in 100.
Among the embodiment 32, since as the addition of the Fe of second added ingredients with respect to 0.08 mole and 0.1 mole of 100 moles of less than of principal constituent, therefore in the high temperature load test, produce 15 unacceptable products in 100 1000 hours the time, produced 85 unacceptable products in the time of 2000 hours in 100.
Among the embodiment 33, since as the addition of the sintering aid that contains Si of the 3rd added ingredients with respect to 0.05 mole and 0.1 mole of 100 moles of less than of principal constituent, therefore, CR amasss in the time of 25 ℃ low to 1985 Ω F, low to 24 Ω F 125 ℃ the time, insulativity worsens, having produced 25 unacceptable products in 100 1000 hours the time in high temperature load test, is unacceptable product all in the time of 2000 hours.
In sum, though the poor reliability during embodiment 24～33 high temperature load can satisfy more than 2500 than DIELECTRIC CONSTANT r.
Relative therewith, among the embodiment 11～23, because the addition of first～the 3rd added ingredients all is 0.1～4.0 mole, therefore, CR amass in the time of 25 ℃ up to 2567～4500 Ω F, 125 ℃ the time also up to 165 Ω F～1135 Ω F, insulativity is good, does not also produce unacceptable product in 2000 hours even passed through in the high temperature load test, shows to access good reliability.
Find out thus, by the solid solution rate is amounted to below 10%, the solid solution rate is amounted to be reached more than 90% in the principal constituent ratio below 10%, and make the addition of first～the 3rd added ingredients also be 0.1～4.0 mole, thus, can access and have DIELECTRIC CONSTANT r to be that the temperature profile of high-k more than 2500 and electrostatic capacitance does not have impaired, have good insulation performance and the good multi-layer ceramic capacitor of the reliability in high temperature load life-span.
Embodiment 3
Prepare BaCO 3, CaCO 3, TiO 2, and Nb 2O 5, by with [embodiment 1] roughly the same method, in proper order, make embodiment 41～53 with cooperation mol ratio as shown in table 6 by (Ba, Ca) (Ti, Nb) O 3The principal constituent of forming with XRD instrumentation X ray spectrum, is measured half range value Δ H to this principal constituent.
Then, prepare Dy 2O 3, MgO, SiO 2, Li 2O 3These various added ingredientss, the various added ingredientss of composition weighing that have by table 6 thereafter, are used the method roughly same with [embodiment 1], in proper order, carry out wet mixing add these added ingredientss in principal constituent after, have obtained the title complex of embodiment 41～53.
Principal constituent composition, the half range value of principal constituent particle, each added ingredients kind and molar content thereof of each title complex of table 6 expression embodiment 41～53.
Table 6
Figure C200580032693D00251
Then, use above-mentioned each title complex, use the method same, in proper order, make the multi-layer ceramic capacitor of embodiment 41～53 with [embodiment 1].
Then,, use the method same, in proper order, obtain that the solid solution rate amounts to, the solid solution rate amounts at the principal constituent ratio below 10%, DIELECTRIC CONSTANT r, rate of change of capacitance (Δ C/C with [embodiment 1] to the multi-layer ceramic capacitor of embodiment 41～53 25), the CR product when under 25 ℃ and 125 ℃ of conditions, having applied the volts DS of 20V (10V/mm), also carried out the high temperature load test.
Its result of table 7 expression.
Table 7
Figure C200580032693D00271
Among the embodiment 41～53, because the solid solution rate adds up to below 3.5～5.1% and 10%, its principal constituent ratio also is 90～100%, so DIELECTRIC CONSTANT r is 2640～4015, has the high-k more than 2500.
But, among the embodiment 49 because the cooperation mol ratio of the Ca in the A position is few to 0.01, though so passed through in the high temperature load test and do not produce unacceptable product in 1000 hours, in 2000 hours, produced 9 unacceptable products in 100 samples.
Among the embodiment 50, because at not solid solutions of element such as B position V, Nb, maximum capacitor velocity of variation (Δ C/C 25) be-15.8%, to the minus side skew, therefore can not fully satisfy the X7R characteristic above-15%, in addition, in the high temperature load test, produced 73 unacceptable products in 100 samples in 2000 hours.
Among the embodiment 51, because therefore the cooperation mol ratio of the Nb in the B position is up to 0.01,, CR amasss in the time of 25 ℃ low to 2150 Ω F, low to 2 Ω F 125 ℃ the time, poor insulativity has produced 5 unacceptable products, the reliability variation in 100 samples in 2000 hours in addition in the high temperature load test.
Among the embodiment 52, because therefore the cooperation mol ratio of the Ca in the A position is up to 0.25,, CR amasss in the time of 25 ℃ low to 2342 Ω F, low to 10 Ω F 125 ℃ the time, poor insulativity has produced 40 unacceptable products, the reliability variation in 100 samples in 2000 hours in addition in the high temperature load test.
Among the embodiment 53,,, 32 unacceptable products have been produced in 100 samples when having passed through 2000 hours although therefore in the high temperature load test, do not produce unacceptable product within 1000 hours owing to do not contain Ca in the A position.
Relative therewith, among the embodiment 41～48, because the cooperation mol ratio of Ca is 0.02～0.20, the cooperation mol ratio of Nb (element X) is 0.0001～0.005, therefore CR amass in the time of 25 ℃ up to 2818～4127 Ω F, 125 ℃ the time up to 429 Ω F～743 Ω F, insulativity is good, does not also produce unacceptable product in 2000 hours even passed through in the high temperature load test, can access good reliability.Also as can be known, for the temperature profile of electrostatic capacitance, rate of change of capacitance (Δ C/C 25) be-6.3～-14.4%, satisfy the X7R characteristic.
Like this, the solid solution rate is amounted to below 10%, the solid solution rate is amounted to be reached more than 90% at the principal constituent ratio below 10%, and the cooperation mol ratio that makes the Ca in the A position is 0～0.20, the cooperation mol ratio that makes the element X in the B position is 0.0001～0.005, thus, can access that to have DIELECTRIC CONSTANT r be the multi-layer ceramic capacitor that high-k more than 2500 and the temperature profile of neither damaging electrostatic capacitance have the good insulation performance and the reliability brilliance in the high temperature load life-span more than 1000 hours again.Also showing, is 0.02～0.20 by the cooperation mol ratio that makes Ca, can access the high temperature load life-span more than 2000 hours.

Claims (7)

1, a kind of dielectric ceramics is characterized in that:
With (Ba, Ca) (Ti, X) O 3As principal constituent, contain the multiple added ingredients that is classified into first～the 3rd added ingredients at least, wherein X represents to be selected from least a kind of central element of V, Nb, Ta, Cr, Mo and W,
Above-mentioned first added ingredients comprises at least a kind that is selected from the middle of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dv, Ho, Er, Tm, Yb, Lu and the Y, simultaneously, above-mentioned second added ingredients comprises at least a kind that is selected from the middle of Mn, Ni, Fe, Co, Mg and the Al, and then the 3rd added ingredients form by the sintering aid that contains Si at least
For the principal constituent particle more than 90% in the principal constituent particle, represent that the total of the solid solution rate of the solid solution condition of above-mentioned first～the 3rd added ingredients in above-mentioned principal constituent particle is illustrated in below 10% by sectional area ratio.
2, dielectric ceramics as claimed in claim 1 is characterized in that:
The content of above-mentioned first～the 3rd added ingredients is respectively 0.1～4.0 mole with respect to 100 moles of above-mentioned principal constituents,
And, the cooperation mol ratio x of the above-mentioned Ca in above-mentioned (Ba, Ca) be 0≤x≤0.20,
The cooperation mol ratio y of above-mentioned element X in above-mentioned (Ti, X) is 0.0001≤y≤0.005.
3, dielectric ceramics as claimed in claim 1 or 2 is characterized in that: above-mentioned cooperation mol ratio x is 0.02≤x≤0.20.
4, a kind of preparation method of dielectric ceramics is characterized in that, comprises:
The principal constituent production process, with Ba compound, Ca compound, Ti compound and the X compound that contains at least a kind of element X that is selected among V, Nb, Ta, Cr, Mo, the W, under 1100～1200 ℃ temperature, implement thermal treatment and react, make of general formula (Ba, Ca) (Ti, X) O 3The principal constituent of expression;
The title complex production process, with contain the compound of first added ingredients, the compound that contains the compound of second added ingredients and contain the 3rd added ingredients that comprises Si at least adds in the above-mentioned principal constituent and mix, make title complex, wherein, first added ingredients comprises at least a kind that is selected among La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the Y; Second added ingredients comprises at least a kind that is selected among Mn, Ni, Fe, Cr, Mg and the Al;
Ceramic sintered body is made operation, above-mentioned title complex is implemented sintering processes make ceramic sintered bodies.
5, a kind of multi-layer ceramic capacitor, it comprises:
The ceramic sintered bodies of forming by the ceramic laminated body of stacked a plurality of dielectric layers, side by side shape be embedded in this ceramic sintered bodies inside a plurality of internal electrodes, be formed at the outer electrode of the outside surface of above-mentioned ceramic sintered bodies, it is characterized in that:
Above-mentioned ceramic sintered bodies forms with each described dielectric ceramics in the claim 1～3.
6, multi-layer ceramic capacitor as claimed in claim 5 is characterized in that: above-mentioned internal electrode contains the easy oxidation metal material.
7, as claim 5 or 6 described multi-layer ceramic capacitors, it is characterized in that: the said external electrode contains the easy oxidation metal material.
CNB2005800326931A 2004-09-28 2005-06-28 Dielectric ceramic, process for producing the same, and laminated ceramic capacitor Active CN100500610C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004281408 2004-09-28
JP281408/2004 2004-09-28

Publications (2)

Publication Number Publication Date
CN101027264A CN101027264A (en) 2007-08-29
CN100500610C true CN100500610C (en) 2009-06-17

Family

ID=36118687

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005800326931A Active CN100500610C (en) 2004-09-28 2005-06-28 Dielectric ceramic, process for producing the same, and laminated ceramic capacitor

Country Status (4)

Country Link
KR (1) KR20070050090A (en)
CN (1) CN100500610C (en)
TW (1) TW200621672A (en)
WO (1) WO2006035535A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101801882A (en) * 2007-09-19 2010-08-11 株式会社村田制作所 Dielectric ceramics and laminated ceramic capacitor
CN102510845B (en) * 2009-09-28 2014-07-30 株式会社村田制作所 Dielectric ceramic and laminated ceramic capacitor
JP5548924B2 (en) * 2009-11-06 2014-07-16 Ｔｄｋ株式会社 Dielectric porcelain composition and electronic component
JP5582150B2 (en) * 2010-02-10 2014-09-03 株式会社村田製作所 Ceramic sintered body and method for producing the same
JP5234035B2 (en) * 2010-03-24 2013-07-10 株式会社村田製作所 Dielectric ceramic and multilayer ceramic capacitors
KR20160095383A (en) * 2015-02-03 2016-08-11 삼성전기주식회사 Dielectric composition and multilayer ceramic capacitor comprising the same
CN105198418A (en) * 2015-09-26 2015-12-30 桂林理工大学 High curie-point positive temperature coefficient resistance material Li4BaWTiO8 and preparation method thereof
CN106810236B (en) * 2017-01-22 2020-03-27 苏州新锐合金工具股份有限公司 Preparation method of superfine (Ti, Mo, W) (C, N) composite solid solution powder
CN106810237B (en) * 2017-02-13 2019-10-01 哈尔滨工业大学 Single-phase more iron ceramic materials of one kind and preparation method thereof
KR20190116109A (en) 2019-06-13 2019-10-14 삼성전기주식회사 Dielectric ceramic composition and multilayer ceramic capacitor comprising the same
KR102225451B1 (en) 2019-06-28 2021-03-09 삼성전기주식회사 Dielectric composition and multilayered electronic component comprising the same
CN111559911B (en) * 2020-06-04 2022-04-12 中科传感(佛山)科技有限公司 High-sensitivity negative temperature coefficient thermistor material and preparation method thereof
JP7544593B2 (en) * 2020-12-21 2024-09-03 Tdk株式会社 Dielectric ceramic composition and electronic components
CN114956807A (en) * 2021-09-15 2022-08-30 深圳先进电子材料国际创新研究院 Capacitor ceramic chip and preparation method and application thereof
CN115141013A (en) * 2022-07-28 2022-10-04 电子科技大学 BaTiO 3 X8R-based ceramic substrate material and preparation method thereof

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS589877A (en) * 1981-07-08 1983-01-20 松下電器産業株式会社 High dielectric constant ceramic composition
JPS58142704A (en) * 1982-02-17 1983-08-24 松下電器産業株式会社 High dielectric constant porcelain composition
JP3418091B2 (en) * 1997-05-30 2003-06-16 太陽誘電株式会社 Dielectric porcelain and manufacturing method thereof
JP2004217520A (en) * 1999-02-26 2004-08-05 Tdk Corp Method for manufacturing dielectric porcelain composition and method for manufacturing electronic component containing dielectric layer
JP2002080276A (en) * 2000-06-30 2002-03-19 Taiyo Yuden Co Ltd Dielectric ceramic composition and ceramic capacitor
JP4392821B2 (en) * 2000-10-24 2010-01-06 株式会社村田製作所 Dielectric ceramic, manufacturing method thereof, and multilayer ceramic capacitor
JP2003176180A (en) * 2001-12-10 2003-06-24 Murata Mfg Co Ltd Method for manufacturing dielectric ceramic powder and dielectric ceramic powder
JP4863597B2 (en) * 2002-07-18 2012-01-25 株式会社村田製作所 Dielectric ceramic, manufacturing method thereof, and multilayer ceramic electronic component
JP4457630B2 (en) * 2002-10-17 2010-04-28 株式会社村田製作所 Dielectric ceramic and multilayer ceramic capacitors
JP4552419B2 (en) * 2002-11-29 2010-09-29 株式会社村田製作所 Dielectric ceramic and multilayer ceramic capacitors
JP4100173B2 (en) * 2003-01-08 2008-06-11 株式会社村田製作所 Dielectric ceramic and multilayer ceramic capacitors
JP4110978B2 (en) * 2003-01-24 2008-07-02 株式会社村田製作所 Dielectric ceramic, manufacturing method thereof, and multilayer ceramic capacitor
JP4111006B2 (en) * 2003-03-03 2008-07-02 株式会社村田製作所 Dielectric ceramic, manufacturing method thereof, and multilayer ceramic capacitor

Also Published As

Publication number Publication date
KR20070050090A (en) 2007-05-14
TW200621672A (en) 2006-07-01
WO2006035535A1 (en) 2006-04-06
TWI314922B (en) 2009-09-21
CN101027264A (en) 2007-08-29

Similar Documents

Publication Publication Date Title
CN101006027B (en) Dielectric ceramic and monolithic ceramic capacitor
EP0992469B1 (en) Dielectric ceramic composition and monolithic ceramic capacitor
US7796373B2 (en) Dielectric ceramic and monolithic ceramic capacitor
US7501371B2 (en) Dielectric ceramic, method for manufacturing dielectric ceramic, and monolithic ceramic capacitor
EP0858086B1 (en) Monolithic ceramic capacitor
CN102498081B (en) Dielectric ceramic constituent and monolithic ceramic capacitor
KR100271726B1 (en) Ceramic composirion and multilayer ceramic capacitor made therefrom
KR100278417B1 (en) Dielectric ceramic, method for producing the same, laminated ceramic electronic element, and method for producing the same
US7498285B2 (en) Nonreducing dielectric ceramic, and manufacturing method and monolithic ceramic capacitor of the same
JP3705141B2 (en) Dielectric ceramic, manufacturing method and evaluation method thereof, and multilayer ceramic electronic component
US8358494B2 (en) Dielectric ceramic and manufacturing method therefor and laminated ceramic capacitor
CN100500610C (en) Dielectric ceramic, process for producing the same, and laminated ceramic capacitor
CN102417351B (en) Dielectric ceramic and laminated ceramic capacitor
US7638451B2 (en) Dielectric ceramic, method of producing the same, and monolithic ceramic capacitor
CN101801882A (en) Dielectric ceramics and laminated ceramic capacitor
EP0820074B1 (en) Monolithic ceramic capacitor
US11066332B2 (en) Dielectric ceramic composition and ceramic electronic component
JP4480367B2 (en) Dielectric porcelain and its manufacturing method, and multilayer electronic component and its manufacturing method
CN100592442C (en) Electric assembly
US6002577A (en) Monolithic ceramic capacitor
CN107836030A (en) Dielectric composition, dielectric element, electronic unit and multi-layered electronic parts
US20220130608A1 (en) Dielectric ceramic and multilayer ceramic capacitor
JP4863597B2 (en) Dielectric ceramic, manufacturing method thereof, and multilayer ceramic electronic component
JPH11219844A (en) Dielectric ceramic and laminated ceramic capacitor
JPH1121166A (en) Dielectric porcelain and multilayer ceramic capacitor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant