WO2014156302A1 - 誘電体磁器組成物、および誘電体素子 - Google Patents

誘電体磁器組成物、および誘電体素子 Download PDF

Info

Publication number
WO2014156302A1
WO2014156302A1 PCT/JP2014/052480 JP2014052480W WO2014156302A1 WO 2014156302 A1 WO2014156302 A1 WO 2014156302A1 JP 2014052480 W JP2014052480 W JP 2014052480W WO 2014156302 A1 WO2014156302 A1 WO 2014156302A1
Authority
WO
WIPO (PCT)
Prior art keywords
dielectric
ceramic composition
dielectric ceramic
oxide
composition
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.)
Ceased
Application number
PCT/JP2014/052480
Other languages
English (en)
French (fr)
Inventor
友哉 井村
剛士 田内
正仁 古川
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.)
TDK Corp
Original Assignee
TDK Corp
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 TDK Corp filed Critical TDK Corp
Priority to EP14775500.3A priority Critical patent/EP2980043B1/en
Priority to CN201480017478.3A priority patent/CN105073684B/zh
Priority to US14/780,017 priority patent/US9530563B2/en
Publication of WO2014156302A1 publication Critical patent/WO2014156302A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • C04B35/01—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
    • C04B35/475—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 bismuth titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • 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
    • 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
    • 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
    • C04B2235/3215—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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate

Definitions

  • the present invention relates to a dielectric porcelain composition and an electronic component using the same, and more particularly to a dielectric porcelain composition and a dielectric element that are suitably used for medium to high voltage applications having a relatively high rated voltage.
  • the rated voltage used in equipment such as ECM (engine electric computer module), fuel injection device, electronic control throttle, inverter, converter, HID headlamp unit, hybrid engine battery control unit, digital still camera, etc. will exceed 100V
  • ECM engine electric computer module
  • fuel injection device fuel injection device
  • electronic control throttle electronic control throttle
  • inverter electronic control throttle
  • inverter converter
  • HID headlamp unit hybrid engine battery control unit
  • digital still camera digital still camera
  • the conventional dielectric ceramic composition has been designed on the assumption that it is used under a DC voltage with a low electric field strength of, for example, about 1 V / ⁇ m, so that the multilayer ceramic capacitor used has been made thinner.
  • DC bias rate of change the rate of change of capacitance with respect to an applied DC electric field
  • high electric field refers to, for example, an electric field strength of 5 V / ⁇ m
  • a high dielectric constant refers to, for example, 1000.
  • barium titanate having an alkali metal oxide content of 0.02% by weight or less, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide , Erbium oxide, thulium oxide and ytterbium oxide, barium zirconate, magnesium oxide, and manganese oxide, and the following composition formula: ⁇ BaO ⁇ m TiO2 + ⁇ R2O3 + ⁇ BaZrO3 + ⁇ MgO + gMnO (However, R2O3 is at least one selected from Eu2O3, Gd2O3, Tb2O3, Dy2O3, Ho2O3, Er2O3, Tm2O3 and Yb2O3, and ⁇ , ⁇ , ⁇ and g are mo.
  • the perovskite-type barium titanate crystal particles (BCT-type crystal particles) containing Ca, Sr, Mg, Mn, and rare earth elements and part of the A site substituted with the Ca are described above.
  • the main crystal particles have a core-shell structure in which the Ca concentration is larger on the particle surface side than the particle center, and Sr, Mg, Mn, and rare earth elements are unevenly distributed on the particle surface side, and the average particle size is 0.1 to
  • a dielectric ceramic composition characterized by a thickness of 0.5 ⁇ m is disclosed.
  • the relative dielectric constant is as large as 2500 or more, but the DC bias change rate of 5 V / ⁇ m is as large as ⁇ 70%, so that the DC bias characteristic is large. Is not good.
  • the present invention has been made in view of such a situation, and the object thereof is suitable for use in medium- and high-voltage applications having a relatively high rated voltage, and the DC bias change rate of 5 V / ⁇ m is as very small as ⁇ 15%.
  • a dielectric ceramic composition having a relatively high relative dielectric constant of 1000 or more, and a dielectric element using the dielectric ceramic composition.
  • the present invention provides a dielectric ceramic composition which is a composite oxide represented by the following formula (1).
  • A represents at least one element selected from Li, Na, and K.
  • a, b, c, d, s, t, u, v, and x are numbers satisfying the following expressions, respectively.
  • the dielectric ceramic composition of the present invention has the above-described configuration, the DC bias change rate of 5 V / ⁇ m is very small within ⁇ 15% and a relatively high relative dielectric constant of 1000 or more can be obtained.
  • the present invention also provides a dielectric element comprising the above dielectric ceramic composition.
  • Such a dielectric element has the above dielectric ceramic composition, it is useful for a capacitor for protecting a circuit used in, for example, a high electric field application circuit that requires a large dielectric constant when a high electric field is applied. is there.
  • the DC bias change rate of 5 V / ⁇ m is very small within ⁇ 15% and a relatively high relative dielectric constant of 1000 or more.
  • a dielectric element using the dielectric ceramic composition is very small.
  • FIG. 1 is a preferred embodiment of a dielectric element according to the present invention. It is sectional drawing which shows another embodiment of the dielectric material which concerns on this invention.
  • FIG. 1 shows a preferred embodiment of a dielectric element according to the present invention.
  • a dielectric element 100 shown in FIG. 1 forms a capacitor including a disk-shaped dielectric 1 and a pair of electrodes 2 and 3 formed on both surfaces of the dielectric 1.
  • Dielectric 1 is formed of a dielectric ceramic composition represented by the following formula (1).
  • A represents at least one element selected from Li, Na, and K.
  • a, b, c, d, s, t, u, v, and x are numbers satisfying the following expressions, respectively.
  • Such a dielectric porcelain composition has the above-described configuration, so that the DC bias change rate of 5 V / ⁇ m can be made extremely small within ⁇ 15% while the relative dielectric constant is 1000 or more.
  • the dielectric ceramic of the present invention is a combination of a ferroelectric and an antiferroelectric composition. By having this specific combination, a dielectric ceramic composition having a relatively high relative dielectric constant and good DC bias characteristics is obtained. can get.
  • the dielectric constant will be 1000 or less, the DC bias change rate of 5 V / ⁇ m will be -15% or more, and the withstand voltage will be low. Therefore, it is not preferable.
  • the content of the composite oxide represented by the formula (1) is 90% by mass or more based on the entire dielectric ceramic composition.
  • the balance may contain impurities such as P and Zr that may be mixed in the manufacturing process in addition to the subcomponents such as the paraelectric ceramic composition.
  • the composition of the dielectric ceramic composition can be measured by, for example, fluorescent X-ray analysis or ICP emission spectroscopic analysis.
  • the relative density of the dielectric ceramic composition is preferably 95% or more.
  • the relative density refers to a measured value of density with respect to the theoretical density.
  • the theoretical density is calculated from the lattice constant obtained by X-ray diffraction and the stoichiometric ratio obtained by assuming a perfect crystal.
  • the relative density of the dielectric ceramic composition can be measured, for example, by the Archimedes method.
  • the relative density of the dielectric ceramic composition can be adjusted by changing the firing temperature and firing time.
  • the powder raw material is weighed so that the dielectric ceramic composition (sintered body) after the main firing satisfies the composition of the dielectric ceramic composition according to the present embodiment.
  • each raw material powder weighed is wet mixed by a ball mill or the like.
  • a calcined product is obtained by calcining the mixture obtained by wet mixing.
  • the calcination is usually performed in air.
  • the calcination temperature is preferably 700 to 900 ° C., and the calcination time is preferably 1 to 10 hours.
  • the obtained calcined product is wet pulverized with a ball mill or the like and then dried to obtain a calcined powder.
  • a small amount of a binder is added to the obtained calcined powder and press-molded to obtain a molded body.
  • the molding pressure is preferably about 5 t / cm 2 .
  • the shape of a molded object For example, it can be set as the disk shaped molded object of planar dimension (PHI) 17mm and thickness about 1mm.
  • a dielectric ceramic composition sample is obtained by firing the obtained molded body.
  • the firing is usually performed in air.
  • the firing temperature is preferably 950 to 1300 ° C., and the firing time is preferably 2 to 10 hours.
  • metal electrodes such as silver are formed on both surfaces of the obtained dielectric ceramic composition sample.
  • the electrodes are formed by methods such as vapor deposition, sputtering, baking, and electroless plating.
  • FIG. 2 is a cross-sectional view showing another embodiment of the dielectric element according to the present invention.
  • a laminated dielectric element 200 shown in FIG. 2 includes a rectangular parallelepiped laminated body 5 and a pair of terminal electrodes 11 ⁇ / b> A and 11 ⁇ / b> B respectively formed on opposite end surfaces of the laminated body 5.
  • the laminated body 5 includes an element body 8 formed by alternately laminating internal electrode layers (electrode layers) 6A and 6B via a dielectric layer 7, and the element body 8 is arranged on both end surfaces in the laminating direction (upper and lower sides in the figure). It is comprised from a pair of protective layers 9 and 10 provided so that it may be inserted
  • the dielectric layer 7 is a layer made of the dielectric ceramic composition according to the present invention.
  • the thickness per layer of the dielectric layer 7 can be arbitrarily set, and can be set to 1 to 100 ⁇ m, for example.
  • the internal electrode layers 6A and 6B are provided in parallel to each other.
  • the internal electrode layer 6 ⁇ / b> A is formed so that one end is exposed on the end surface of the multilayer body 5 where the terminal electrode 11 ⁇ / b> A is formed.
  • the internal electrode layer 6B is formed so that one end portion is exposed on the end surface of the multilayer body 5 where the terminal electrode 11B is formed.
  • the internal electrode layer 6A and the internal electrode layer 6B are arranged so that most of them overlap in the stacking direction.
  • a metal such as Au, Pt, or Ag is used as the material of the internal electrode layers 6A and 6B.
  • the terminal electrodes 11A and 11B are in contact with the end portions of the internal electrode layers 6A and 6B exposed at the end surfaces at the end surfaces of the multilayer body 5 on which the terminal electrodes 11A and 11B are provided. Thereby, terminal electrode 11A, 11B is electrically connected with internal electrode layer 6A, 6B, respectively.
  • the terminal electrodes 11A and 11B can be made of a conductive material whose main component is Ag, Au, Cu or the like.
  • the thicknesses of the terminal electrodes 11A and 11B are appropriately set depending on the application, the size of the multilayer dielectric element, and the like, but can be set to 10 to 50 ⁇ m, for example.
  • the dielectric ceramic composition and the dielectric element of the present embodiment have been described above. However, since the dielectric ceramic composition has good DC bias characteristics when a high electric field is applied, for example, it is relatively rated. It can be suitably used for medium and high voltage capacitors having a high voltage.
  • the present invention is not limited to the above embodiment.
  • a known element can be used as a configuration other than the dielectric ceramic composition.
  • the calcined powder can be produced by a hydrothermal synthesis method or the like.
  • (BiNa) TiO 3 , (BiK) TiO 3 , BaTiO 3 , and NaNbO 3 can be prepared, mixed, and sintered as precursors.
  • Example 1 to 26 In order to produce a dielectric ceramic composition, as starting materials, bismuth oxide (Bi 2 O 3 ), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), barium carbonate (BaCO 3 ), titanium oxide (TiO 2 ) and niobium oxide (Nb 2 O 5 ) powder were prepared. In Example 15, in addition to the above, a powder of lithium carbonate (Li 2 CO 3 ) was also prepared. For Examples 16 and 17, in addition to the above, a powder of potassium carbonate (K 2 CO 3 ) was also prepared.
  • a, b, c, d, s + u, t, v, and x in Table 1 are numerical values of a, b, c, d, s + u, t, v, and x in the following formula (1), respectively. Indicates. For Examples and Comparative Examples other than Examples 15 to 17, the A component is Na, Example 15 is the A component Li, Example 16 is K, and Example 17 is Na and K.
  • each raw material powder weighed was wet mixed by a ball mill, and the obtained mixture was calcined in air at 850 ° C. for 2 hours to obtain a calcined product.
  • the obtained calcined product was wet pulverized by a ball mill to obtain a calcined powder.
  • a small amount of binder was added to the calcined powder, and it was molded at a pressure of about 5 t / cm 2 to obtain a disk-shaped molded body having a planar dimension of ⁇ 17 mm and a thickness of about 1 mm.
  • the obtained molded body is fired in the air at a firing temperature of 950 to 1300 ° C. and a firing time of 2 to 10 hours under a relative density of 95% to obtain a dielectric ceramic composition sample. It was.
  • the density measurement was performed on the obtained dielectric ceramic sample, the density of all the samples was 95% or more of the theoretical density.
  • composition of the obtained dielectric ceramic composition sample was analyzed, it was equal to the weighed composition ratio.
  • An Ag electrode was vapor-deposited on both surfaces of the obtained dielectric ceramic composition sample to produce a dielectric element.
  • a withstand voltage test was performed by applying a DC electric field of 10 V / ⁇ m to each dielectric element.
  • Table 1 shows the dielectric constant and DC bias characteristics at room temperature of 25 ° C.
  • the bar portion in the table indicates that charge leaked during measurement and the value was not obtained.
  • those that did not break down were indicated by ⁇ , and those that did break down were indicated by ⁇ .
  • Those having a relative dielectric constant of 1000 or more, a DC bias change rate of 5 V / ⁇ m within ⁇ 15%, and having no dielectric breakdown in a DC electric field of 10 V / ⁇ m were judged good.
  • the dielectric ceramic compositions of Examples 01 to 26 had a small DC bias change rate and a practically sufficiently large dielectric constant when a high electric field was applied.

Landscapes

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

Abstract

【課題】５Ｖ／μｍのＤＣバイアス変化率が－１５％以内と非常に小さく、かつ１０００以上の比較的高い比誘電率を有する誘電体磁器組成物と、その誘電体磁器組成物を用いた誘電体素子を提供すること。 【解決手段】下記式（１）で表される複合酸化物である誘電体磁器組成物。　｛［（ＢｉｓＮａｔ）ａ　（ＢｉｕＫｖ）ｂＢａｃ］１－ｄＡｄ｝ｘＴｉ１－ｄＮｂｄＯ３…（１）　［式（１）中、ＡはＬｉ、Ｎａ、Ｋから選ばれる少なくとも一種の元素を示す。ａ、ｂ、ｃ、ｄ、ｓ、ｔ、ｕ、ｖ及びｘは、それぞれ、下記式を満たす数である。］　０．１０≦ａ＜０．９５　０．００＜ｂ≦０．８５　０．０５≦ｃ≦０．７０　ａ＋ｂ＋ｃ＝１　０．１０≦ｄ≦０．５０　０．９０≦ｓ＋ｕ≦１．００　０．４５≦ｔ≦０．５０　０．４５≦ｖ≦０．５０　０．９５≦ｘ≦１．０５

Description

誘電体磁器組成物、および誘電体素子
　本発明は、誘電体磁器組成物およびこれを用いた電子部品に係り、さらに詳しくは、比較的に定格電圧が高い中高圧用途に好適に用いられる誘電体磁器組成物および誘電体素子に関する。
　近年、電子回路の高密度化に伴う電子部品の小型化に対する要求は高く、積層セラミックコンデンサの小型・大容量化が急速に進むとともに、用途も拡大し、要求される特性は様々である。
　例えば、ＥＣＭ（エンジンエレクトリックコンピュータモジュール）、燃料噴射装置、電子制御スロットル、インバータ、コンバータ、ＨＩＤヘッドランプユニット、ハイブリッドエンジンのバッテリコントロールユニット、デジタルスチールカメラ等の機器に用いられる定格電圧が１００Ｖを超えるような中高圧用コンデンサには、高い電界強度下において高い静電容量が要求される。
　しかしながら、従来の誘電体磁器組成物は、例えば１Ｖ／μｍ程度の低電界強度の直流電圧下で使用されることを前提に設計されていたので、用いられる積層セラミックコンデンサの薄層化が進んで、高い電界強度下で使用されると、印加直流電界に対する静電容量の変化率（以下ＤＣバイアス変化率）が大きくなるという問題があった。
　ＤＣバイアス変化率が大きいと、積層セラミックコンデンサの実効容量が低下してしまい、設計の段階で必要としていた静電容量を満たさなくなるため、それが用いられている電子機器の動作が不安定になり、延いては動作しなくなるという不具合が発生することが懸念される。
　したがって、高電界下での利用を目的としたコンデンサにはＤＣバイアス変化率が小さく、また、高電界印加時に高い誘電率を有する誘電体磁器組成物を用いることが望ましい。なお、ここで言う「高電界」とはたとえば５Ｖ／μｍの電界強度、高い誘電率とは例えば１０００を指す。
　このような課題を解決するべく、下記の特許文献１では、アルカリ金属酸化物の含有量が０．０２重量％以下のチタン酸バリウムと、酸化ユーロピウム、酸化ガドリニウム、酸化テルビウム、酸化ジスプロシウム、酸化ホルミウム、酸化エルビウム、酸化ツリウムおよび酸化イッテルビウムの中から選ばれる少なくとも１種と、ジルコン酸バリウムと、酸化マグネシウムと、酸化マンガンとからなり、かつ、次の組成式、｛ＢａＯ｝ｍ　ＴｉＯ２　＋αＲ２　Ｏ３　＋βＢａＺｒＯ３　＋γＭｇＯ＋ｇＭｎＯ（ただし、Ｒ２　Ｏ３　はＥｕ２　Ｏ３　、Ｇｄ２　Ｏ３　、Ｔｂ２Ｏ３　、Ｄｙ２　Ｏ３　、Ｈｏ２　Ｏ３　、Ｅｒ２　Ｏ３　、Ｔｍ２　Ｏ３　およびＹｂ２　Ｏ３　の中から選ばれる少なくとも１種であり、α、β、γおよびｇはモル比を表し、０．００１≦α≦０．０６、０．００５≦β≦０．０６、０．００１＜γ≦０．１２、０．００１＜ｇ≦０．１２、γ＋ｇ≦０．１３、１．０００＜ｍ≦１．０３５の範囲内にある。）で表される主成分を含有するとともに、副成分として酸化珪素を、前記主成分１００モルに対して、ＳｉＯ２　に換算して０．２～５．０モル含有していることを特徴とする誘電体磁器組成物が開示されている。
　しかしながら、特許文献１に示すような誘電体磁器組成物を誘電体としたセラミックコンデンサは、比誘電率が１５００程度と比較的大きいものの、５Ｖ／μｍのＤＣバイアス変化率が－４５％以内と大きいため、更なるＤＣバイアス特性の改善が望まれていた。
　また、特許文献２では、ＣａとＳｒとＭｇとＭｎと希土類元素を含有するとともに、Ａサイトの一部が該Ｃａで置換されたペロブスカイト型チタン酸バリウム結晶粒子（ＢＣＴ型結晶粒子）に、前記ＣａとＳｒとＭｇとＭｎと希土類元素の少なくとも一部が固溶してなる主結晶粒子を含有し、Ａｌ元素の含有量が酸化物換算で０．０１質量％以下である誘電体磁器であって、前記主結晶粒子は、Ｃａ濃度が粒子中心よりも粒子表面側において大きく、ＳｒとＭｇとＭｎ及び希土類元素が粒子表面側に偏在したコアシェル型構造であり、平均粒径が０．１～０．５μｍであることを特徴とする誘電体磁器組成物が開示されている。
　しかしながら、特許文献２に示されるようなＢＣＴ型の誘電体磁器組成物では、比誘電率は２５００以上と大きいが、５Ｖ／μｍのＤＣバイアス変化率が－７０％以内と大きいため、ＤＣバイアス特性が良好であるとは言えない。
特開平１１－３２２４１４号公報 特開２００６－２０６３６２号公報
　本発明は、このような実状に鑑みてなされ、その目的は、比較的に定格電圧が高い中高圧用途に好適に用いられ、５Ｖ／μｍのＤＣバイアス変化率が－１５％以内と非常に小さく、かつ１０００以上の比較的高い比誘電率を有する誘電体磁器組成物と、その誘電体磁器組成物を用いた誘電体素子を提供することである。
　上記目的を達成するため、本発明は、下記式（１）で表される複合酸化物である誘電体磁器組成物を提供する。
　｛［（ＢｉｓＮａｔ）ａ　（ＢｉｕＫｖ）ｂＢａｃ］１－ｄＡｄ｝ｘＴｉ１－ｄＮｂｄＯ３…（１）
　式（１）中、ＡはＬｉ、Ｎａ、Ｋから選ばれる少なくとも一種の元素を示す。ａ、ｂ、ｃ、ｄ、ｓ、ｔ、ｕ、ｖ及びｘは、それぞれ、下記式を満たす数である。
　　０．１０≦ａ＜０．９５
　　０．００＜ｂ≦０．８５
　　０．０５≦ｃ≦０．７０
　　ａ＋ｂ＋ｃ＝１
　　０．１０≦ｄ≦０．５０
　　０．９０≦ｓ＋ｕ≦１．００
　　０．４５≦ｔ≦０．５０
　　０．４５≦ｖ≦０．５０
　　０．９５≦ｘ≦１．０５
　本発明の誘電体磁器組成物は、上記構成を有することにより、５Ｖ／μｍのＤＣバイアス変化率が－１５％以内と非常に小さく、かつ１０００以上の比較的高い比誘電率が得られる。　
　また、本発明は、上記誘電体磁器組成物を備える誘電体素子を提供する。
　このような誘電体素子は上記誘電体磁器組成物を備えるため、高電界を印加した場合に大きな誘電率を必要とする、例えば高電界印加回路に使用される回路保護用などのコンデンサに有用である。
　本発明によれば、比較的に定格電圧が高い中高圧用途に好適に用いられ、５Ｖ／μｍのＤＣバイアス変化率が－１５％以内と非常に小さく、かつ１０００以上の比較的高い比誘電率を有する誘電体磁器組成物と、その誘電体磁器組成物を用いた誘電体素子を提供することができる。
本発明に係る誘電体素子の好適な一実施形態である。 本発明に係る誘電体素子の別の実施形態を示す断面図である。
　以下、場合により図面を参照して、本発明の好適な実施形態について説明する。なお、各図面において、同一または同等の要素には同一の符号を付与し、重複する説明を省略する。
　図１は本発明に係る誘電体素子の好適な一実施形態である。図１に示す誘電体素子１００は、円盤状の誘電体１と、この誘電体１の両面に形成された一対の電極２および３を備えたコンデンサを形成している。
　誘電体１は、下記式（１）で示される誘電体磁器組成物で形成される。
　｛［（ＢｉｓＮａｔ）ａ　（ＢｉｕＫｖ）ｂＢａｃ］１－ｄＡｄ｝ｘＴｉ１－ｄＮｂｄＯ３…（１）
　式（１）中、ＡはＬｉ、Ｎａ、Ｋから選ばれる少なくとも一種の元素を示す。ａ、ｂ、ｃ、ｄ、ｓ、ｔ、ｕ、ｖ及びｘは、それぞれ、下記式を満たす数である。
　　０．１０≦ａ＜０．９５
　　０．００＜ｂ≦０．８５
　　０．０５≦ｃ≦０．７０
　　ａ＋ｂ＋ｃ＝１
　　０．１０≦ｄ≦０．５０
　　０．９０≦ｓ＋ｕ≦１．００
　　０．４５≦ｔ≦０．５０
　　０．４５≦ｖ≦０．５０
　　０．９５≦ｘ≦１．０５
　このような誘電体磁器組成物は、上記構成を有することにより、比誘電率を１０００以上としつつ、５Ｖ／μｍのＤＣバイアス変化率を－１５％以内と非常に小さくすることができる。
　本発明の誘電体磁器は強誘電体および反強誘電体組成物の組み合わせであり、この特定の組み合わせを有することにより比誘電率が比較的高く、ＤＣバイアス特性が良好な誘電体磁器組成物が得られる。
　ａ、ｂ、ｃが上記範囲をはずれると、比誘電率が１０００以下となってしまったり、５Ｖ／μｍのＤＣバイアス変化率が－１５％以上となってしまったり、耐電圧が低くなってしまうため好ましくない。
　ｄが０．１０未満ではＤＣバイアス特性が悪くなってしまい、０．５０より大きくなると誘電率が１０００未満となってしまうため好ましくない。
　ｓ＋ｕ、ｔ、ｖが上記範囲を外れると欠陥が生成されたり、十分な焼結密度が得られず、電荷のリークが生じたり、耐電圧が低くなってしまうため好ましくない。
　ｘが０．９５未満又は１．０５を超えると十分な焼結密度を得られず、絶縁抵抗が低くなるため、高電界を印加して使用することは困難になる。
　誘電体磁器組成物として実用に十分な誘電率が得られる等の観点から、式（１）で表される複合酸化物の含有量は、誘電体磁器組成物全体を基準として、９０質量％以上であることが好ましく、残部には常誘電体磁器組成物などの副成分のほか、作製プロセス上混入する可能性がある、ＰやＺｒなどの不純物を含んでいても良い。
　ここで、誘電体磁器組成物の組成は、例えば、蛍光Ｘ線分析やＩＣＰ発光分光分析で測定することができる。
　上記誘電体磁器組成物の相対密度は、９５％以上の相対密度を有することが好ましい。ここで、本明細書において、相対密度とは、理論密度に対する、密度の実測値をいう。なお、理論密度は、Ｘ線回折によって求めた格子定数と、完全結晶を仮定して求めた量論比により計算される。誘電体磁器組成物の相対密度は、例えば、アルキメデス法によって測定することができる。ここで、誘電体磁器組成物の相対密度は、焼成温度や焼成時間を変えることによって調整することができる。
　次に、図１に示す誘電体素子の製造方法の一例について以下に説明する。
　まず、誘電体１の出発原料として、酸化ビスマス（Ｂｉ２Ｏ３）、炭酸ナトリウム（Ｎａ２ＣＯ３）、炭酸カリウム（Ｋ２ＣＯ３）、炭酸バリウム（ＢａＣＯ３）、酸化チタン（ＴｉＯ２）及び酸化二オブ（Ｎｂ２Ｏ５）等の粉末を準備する。
　そして、本焼成後の誘電体磁器組成物（焼結体）が、本実施形態に係る誘電体磁器組成物の組成を満たすものとなるように、上記粉末原料を秤量する。
　次に、秤量した各原料粉末を、ボールミル等により湿式混合する。そして、湿式混合により得られた混合物を仮焼することにより仮焼物を得る。ここで、仮焼は、通常空気中で施される。また、仮焼温度は７００～９００℃であることが好ましく、仮焼時間は１～１０時間が好ましい。
　得られた仮焼物を、ボールミル等で湿式粉砕した後、これを乾燥させることにより、仮焼物粉体を得る。次いで、得られた仮焼物粉体に少量の結合剤を添加し、プレス成形することにより、成形体を得る。ここで、成形圧力は５ｔ／ｃｍ２程度であることが好ましい。成形体の形状に特に制限はなく、例えば、平面寸法Φ１７ｍｍ、厚さ１ｍｍ程度の円板状成形体とすることができる。
　そして、得られた成形体を焼成することにより誘電体磁器組成物試料を得る。ここで、焼成は、通常空気中で施される。また、焼成温度は９５０～１３００℃であることが好ましく、焼成時間は２～１０時間であることが好ましい。
　次いで、得られた誘電体磁器組成物試料の両面に、銀等の金属電極を形成する。電極の形成は蒸着、スパッタリング、焼付け、無電解めっき等の方法による。
　図２は本発明に係る誘電体素子の別の実施形態を示す断面図である。図２に示す積層型誘電体素子２００は、直方体状の積層体５と、この積層体５の対向する端面にそれぞれ形成された一対の端子電極１１Ａ、１１Ｂとを備えている。
　積層体５は、誘電体層７を介して内部電極層（電極層）６Ａ、６Ｂを交互に積層してなる素体８と、この素体８をその積層方向の両端面側（図中上下方向）から挟み込むように設けられた一対の保護層９及び１０とから構成される。素体８においては、誘電体層７と内部電極層６Ａ、６Ｂとが交互に積層されている。
　誘電体層７は、本発明に係る誘電体磁器組成物からなる層である。
　誘電体層７の１層当たりの厚さは、任意に設定することができるが、例えば１～１００μｍにすることができる。
　内部電極層６Ａ、６Ｂはそれぞれ平行となるように設けられている。内部電極層６Ａは、一方の端部が積層体５における端子電極１１Ａが形成された端面に露出するように形成されている。また、内部電極層６Ｂは、一方の端部が積層体５における端子電極１１Ｂが形成された端面に露出するように形成されている。さらに、内部電極層６Ａと内部電極層６Ｂとは、これらの大部分が積層方向に重なり合うように配置されている。
　内部電極層６Ａ、６Ｂの材質としては、例えば、Ａｕ，Ｐｔ若しくはＡｇ等の金属が用いられる。
　端子電極１１Ａ，１１Ｂは、これらが設けられている積層体５の端面において、当該端面に露出している内部電極層６Ａ、６Ｂの端部とそれぞれ接している。これにより、端子電極１１Ａ，１１Ｂは、内部電極層６Ａ、６Ｂとそれぞれ電気的に接続される。この端子電極１１Ａ，１１Ｂは、Ａｇ，Ａｕ，Ｃｕ等を主成分とする導電材料から構成することができる。端子電極１１Ａ，１１Ｂの厚さは、用途や積層型誘電素子のサイズ等によって適宜設定されるが、例えば１０～５０μｍにすることができる。
　以上、本実施形態の誘電体磁器組成物および誘電体素子について説明したが、当該誘電体磁器組成物は、高電界を印加した時のＤＣバイアス特性が良好であるため、例えば、比較的に定格電圧が高い中高圧コンデンサに好適に用いることができる。
　また、本発明は上記実施形態に限定されるものではない。例えば、上記誘電体素子において、誘電体磁器組成物以外の構成として、公知のものを用いることもできる。また、例えば、上記誘電体素子の製造において、当該仮焼物粉体を水熱合成法等により製造することもできる。また、前駆体として（ＢｉＮａ）ＴｉＯ３、（ＢｉＫ）ＴｉＯ３、ＢａＴｉＯ３、およびＮａＮｂＯ３を作製し、混合、焼結することもできる。
　以下、実施例及び比較例を用いて、本発明を更に詳細に説明する。ただし、本発明は以下の実施例に限定されるものではない。
（実施例１～２６、比較例１～１６）
　誘電体磁器組成物を作製するため、出発原料として、酸化ビスマス（Ｂｉ２Ｏ３）、炭酸ナトリウム（Ｎａ２ＣＯ３）、炭酸カリウム（Ｋ２ＣＯ３）、炭酸バリウム（ＢａＣＯ３）、酸化チタン（ＴｉＯ２）及び酸化二オブ（Ｎｂ２Ｏ５）の粉末を準備した。実施例１５については上記に加えさらに炭酸リチウム（Ｌｉ２ＣＯ３）の粉末も準備した。実施例１６、１７については上記に加えさらに炭酸カリウム（Ｋ２ＣＯ３）の粉末も準備した。
　本焼成後の誘電体磁器組成物（焼結体）が、表１の組成を満たすものとなるように、上記粉末原料を秤量した。なお、ここで、表１中のａ、ｂ、ｃ、ｄ、ｓ＋ｕ、ｔ、ｖ及びｘは、それぞれ下記式（１）におけるａ、ｂ、ｃ、ｄ、ｓ＋ｕ、ｔ、ｖ及びｘの数値を示す。実施例１５～１７以外の実施例および比較例については、Ａ成分がＮａであり、実施例１５はＡ成分がＬｉ、実施例１６はＫ、実施例１７はＮａおよびＫとなる。
　｛［（ＢｉｓＮａｔ）ａ　（ＢｉｕＫｖ）ｂＢａｃ］１－ｄＡｄ｝ｘＴｉ１－ｄＮｂｄＯ３…（１）
　次に、秤量した各原料粉末を、ボールミルにより湿式混合した後、得られた混合物を、空気中において８５０℃で２時間仮焼して仮焼物を得た。そして、得られた仮焼物をボールミルで湿式粉砕して、仮焼物粉体を得た。次いで、仮焼物粉体に少量の結合剤を添加し、約５ｔ／ｃｍ２の圧力で成形し、平面寸法Φ１７ｍｍ、厚さ１ｍｍ程度の円板状成形体を得た。
　次に、得られた成形体を空気中において、焼成温度９５０～１３００℃、焼成時間２～１０時間の範囲で、相対密度９５％となる条件で焼成して、誘電体磁器組成物試料を得た。得られた誘電磁器試料について密度測定を行ったところ、すべての試料の密度が、理論密度に対し９５％以上であった。
　得られた誘電体磁器組成物試料の組成を分析したところ、秤量した組成比と等しかった。
　得られた誘電体磁器組成物試料の両面にＡｇ電極を蒸着し、誘電体素子を作製した。
　得られた各誘電体素子のＤＣバイアス特性を最大印加電界Ｅｍａｘ＝５Ｖ／μｍの条件で測定を実施した。
　また、各誘電体素子に１０Ｖ／μｍの直流電界を印加し、耐電圧試験を実施した。
　室温２５℃での比誘電率およびＤＣバイアス特性を表１に示す。また、表中の棒線部は測定時に電荷がリークしてしまい、値が得られなかったことを示す。また、表中の耐電圧試験の項で、絶縁破壊しなかったものは○、絶縁破壊したものは×で示した。比誘電率が１０００以上、かつ５Ｖ／μｍのＤＣバイアス変化率が－１５％以内であり、かつ１０Ｖ／μｍの直流電界で絶縁破壊しなかったものを良好と判断した。
Figure JPOXMLDOC01-appb-T000001
　以上より、実施例０１～２６の誘電体磁器組成物はＤＣバイアス変化率が小さく、また、高電界印加時の誘電率が実用上十分大きいことを確認した。
　１…誘電体、２，３…電極、５…積層体、６Ａ、６Ｂ…内部電極層、７…誘電体層、８…素体、９、１０…保護層、１１Ａ，１１Ｂ…端子電極、１００…誘電体素子、２００…積層誘電体素子

Claims (2)

  1. 　下記一般式（１）の組成を有することを特徴とする誘電体磁器組成物。
    　｛［（ＢｉｓＮａｔ）ａ　（ＢｉｕＫｖ）ｂＢａｃ］１－ｄＡｄ｝ｘＴｉ１－ｄＮｂｄＯ３…（１）
    式（１）中、ＡはＬｉ、Ｎａ、Ｋから選ばれる少なくとも一種の元素を示す。ａ、ｂ、ｃ、ｄ、ｓ、ｔ、ｕ、ｖ及びｘは、それぞれ、下記式を満たす数である。
    　　０．１０≦ａ＜０．９５
    　　０．００＜ｂ≦０．８５
    　　０．０５≦ｃ≦０．７０
    　　ａ＋ｂ＋ｃ＝１
    　　０．１０≦ｄ≦０．５０
    　　０．９０≦ｓ＋ｕ≦１．００
    　　０．４５≦ｔ≦０．５０
    　　０．４５≦ｖ≦０．５０
    　　０．９５≦ｘ≦１．０５
  2. 　請求項１に記載の誘電体磁器組成物を備える誘電体素子。
PCT/JP2014/052480 2013-03-28 2014-02-04 誘電体磁器組成物、および誘電体素子 Ceased WO2014156302A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP14775500.3A EP2980043B1 (en) 2013-03-28 2014-02-04 Dielectric ceramic composition and dielectric element
CN201480017478.3A CN105073684B (zh) 2013-03-28 2014-02-04 介电陶瓷组合物以及介电元件
US14/780,017 US9530563B2 (en) 2013-03-28 2014-02-04 Dielectric ceramic composition and dielectric element

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-067857 2013-03-28
JP2013067857A JP6102410B2 (ja) 2013-03-28 2013-03-28 誘電体磁器組成物、および誘電体素子

Publications (1)

Publication Number Publication Date
WO2014156302A1 true WO2014156302A1 (ja) 2014-10-02

Family

ID=51623303

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/052480 Ceased WO2014156302A1 (ja) 2013-03-28 2014-02-04 誘電体磁器組成物、および誘電体素子

Country Status (5)

Country Link
US (1) US9530563B2 (ja)
EP (1) EP2980043B1 (ja)
JP (1) JP6102410B2 (ja)
CN (1) CN105073684B (ja)
WO (1) WO2014156302A1 (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016189003A1 (en) * 2015-05-27 2016-12-01 Epcos Ag Bismuth sodium strontium titanate-based dielectric composition, dielectric element, electronic component and laminated electronic component thereof
WO2016189005A1 (en) * 2015-05-27 2016-12-01 Epcos Ag Bismuth sodium strontium titanate-based dielectric composition, dielectric element, electronic component and laminated electronic component thereof
CN107851512A (zh) * 2015-07-17 2018-03-27 埃普科斯股份有限公司 介电组成、介电元件、电子部件和层压电子部件

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6102405B2 (ja) * 2013-03-27 2017-03-29 Tdk株式会社 誘電体磁器組成物、および誘電体素子
JP2016060647A (ja) * 2014-09-12 2016-04-25 エプコス アクチエンゲゼルシャフトＥｐｃｏｓ Ａｇ 誘電体組成物、誘電体素子、電子部品および積層電子部品
KR102115523B1 (ko) * 2014-12-08 2020-05-26 삼성전기주식회사 유전체 자기 조성물 및 이를 포함하는 적층 세라믹 커패시터
KR102098869B1 (ko) * 2015-07-17 2020-04-08 티디케이 일렉트로닉스 아게 유전체 조성물, 유전체 소자, 전자 부품 및 적층 전자 부품
WO2017012797A1 (en) * 2015-07-17 2017-01-26 Epcos Ag Dielectric composition, dielectric element, electronic component and multi-layer electronic component
CN107836030B (zh) * 2015-07-17 2020-03-03 埃普科斯股份有限公司 介电组成、介电元件、电子部件和多层电子部件
JP6564930B2 (ja) * 2015-07-17 2019-08-21 ティーディーケイ・エレクトロニクス・アクチェンゲゼルシャフトＴｄｋ Ｅｌｅｃｔｒｏｎｉｃｓ Ａｇ 誘電体組成物、誘電体素子、電子部品および積層電子部品
EP3326183B1 (en) 2015-07-17 2019-12-18 TDK Electronics AG Dielectric composition, dielectric element, electronic component and laminated electronic component
KR102100572B1 (ko) * 2015-07-17 2020-04-13 티디케이 일렉트로닉스 아게 다층 세라믹 커패시터
CN107836029B (zh) * 2015-07-17 2019-08-16 埃普科斯股份有限公司 介电组成、介电元件、电子部件和层压电子部件
JP6457415B2 (ja) * 2016-03-10 2019-01-23 太陽誘電株式会社 圧電素子及びその製造方法
KR101853191B1 (ko) 2016-07-28 2018-04-27 삼성전기주식회사 유전체 자기 조성물, 이를 포함하는 적층 세라믹 커패시터 및 적층 세라믹 커패시터의 제조 방법
KR102847109B1 (ko) * 2021-01-29 2025-08-14 삼성전자주식회사 유전체, 그 제조방법, 및 이를 포함하는 디바이스
KR20230055288A (ko) * 2021-10-18 2023-04-25 삼성전자주식회사 커패시터 소자 및 이를 포함하는 반도체 소자
KR20240093098A (ko) 2022-12-15 2024-06-24 삼성전기주식회사 적층형 전자 부품

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11322414A (ja) 1998-05-12 1999-11-24 Murata Mfg Co Ltd 誘電体磁器組成物および積層セラミックコンデンサ
JP2002321976A (ja) * 2001-02-22 2002-11-08 Tdk Corp 圧電磁器
JP2006206362A (ja) 2005-01-27 2006-08-10 Kyocera Corp 誘電体磁器及びこれを用いた積層セラミックコンデンサ

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1340731B1 (en) * 2000-11-21 2009-01-07 TDK Corporation Piezoelectric ceramic
JP4674405B2 (ja) * 2000-11-21 2011-04-20 Ｔｄｋ株式会社 圧電磁器
JP5435732B2 (ja) * 2010-04-28 2014-03-05 Ｎｅｃトーキン株式会社 圧電磁器組成物
JP6016333B2 (ja) * 2011-05-27 2016-10-26 キヤノン株式会社 ニオブ酸ナトリウム粉末、ニオブ酸ナトリウム粉末の製造方法、板状粒子、板状粒子の製造方法、配向セラミックスの製造方法
JP6102405B2 (ja) * 2013-03-27 2017-03-29 Tdk株式会社 誘電体磁器組成物、および誘電体素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11322414A (ja) 1998-05-12 1999-11-24 Murata Mfg Co Ltd 誘電体磁器組成物および積層セラミックコンデンサ
JP2002321976A (ja) * 2001-02-22 2002-11-08 Tdk Corp 圧電磁器
JP2006206362A (ja) 2005-01-27 2006-08-10 Kyocera Corp 誘電体磁器及びこれを用いた積層セラミックコンデンサ

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DITTMER,ROBERT ET AL.: "A High-Temperature- Capacitor Dielectric Based on K0.5Na0.5NbO3- Modified Bi1/2Na1/2TiO3-Bi1/2K1/2TiO3", JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol. 95, no. 11, November 2012 (2012-11-01), pages 3519 - 3524, XP055291254 *
DITTMER,ROBERT ET AL.: "Lead-free high- temperature dielectrics with wide operational range", JOURNAL OF APPLIED PHYSICS, vol. 109, 2011, pages 034107-1 - 034107-5, XP012147488 *
LIU, YANG ET AL.: "TEMPERATURE-INDEPENDENT DIELECTRIC PROPERTIES OF 0.82[0.94Bi0.5Na0.5 Ti03-0.06BaTiO3]-0.18K0.5Na0.5NbO3 CERAMICS", JOURNAL OF ADVANCED DIELECTRICS, vol. 2, no. 1, 2012, pages 1250006-1 - 1250006-6, XP035390338 *
RODEL, JURGEN ET AL.: "Electric-Field Effects in Bi-based Perovskites", 3RD INTERNATIONAL CONGRESS ON CERAMICS (ICC3) MEETING GUIDE, 14 November 2010 (2010-11-14), XP055298997 *
ZHU,MANKANG ET AL.: "Dependence of depolarization temperature on cation vacancies and lattice distortion for lead-free 74(Bil/ 2Na1/2)TiO3-20.8(Bi1/2K1/2)TiO3-5.2BaTiO3 ferroelectric ceramics", APPLIED PHYSICS LETTERS, vol. 94, 2009, pages 182901-1 - 182901-3, XP012121168 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107710361B (zh) * 2015-05-27 2020-06-05 爱普科斯公司 介电组合物、介电元件、电子部件和层叠电子部件
WO2016189005A1 (en) * 2015-05-27 2016-12-01 Epcos Ag Bismuth sodium strontium titanate-based dielectric composition, dielectric element, electronic component and laminated electronic component thereof
CN107710361A (zh) * 2015-05-27 2018-02-16 爱普科斯公司 钛酸铋钠锶基介电组合物及其介电元件、电子部件和层叠电子部件
WO2016189003A1 (en) * 2015-05-27 2016-12-01 Epcos Ag Bismuth sodium strontium titanate-based dielectric composition, dielectric element, electronic component and laminated electronic component thereof
CN107851514A (zh) * 2015-05-27 2018-03-27 爱普科斯公司 基于铋钠锶钛酸盐的介电组合物、其介电元件、电子组件和层叠电子组件
EP3304572A1 (en) * 2015-05-27 2018-04-11 Epcos AG Bismuth sodium strontium titanate-based dielectric composition, dielectric element, electronic component and laminated electronic component thereof
US10388456B2 (en) 2015-05-27 2019-08-20 Tdk Electronics Ag Dielectric composition, dielectric element, electronic component and laminated electronic component
CN111875373A (zh) * 2015-05-27 2020-11-03 爱普科斯公司 基于铋钠锶钛酸盐的介电组合物、其介电元件、电子组件和层叠电子组件
US10501374B2 (en) 2015-05-27 2019-12-10 Tdk Electronics Ag Dielectric composition, dielectric element, electronic component and laminated electronic component
CN107851514B (zh) * 2015-05-27 2020-08-21 爱普科斯公司 基于铋钠锶钛酸盐的介电组合物、其介电元件、电子组件和层叠电子组件
CN107851512A (zh) * 2015-07-17 2018-03-27 埃普科斯股份有限公司 介电组成、介电元件、电子部件和层压电子部件
CN107851512B (zh) * 2015-07-17 2020-04-17 埃普科斯股份有限公司 介电组成、介电元件、电子部件和层压电子部件
US10497514B2 (en) 2015-07-17 2019-12-03 Tdk Electronics Ag Dielectric composition, dielectric element, electronic component and laminated electric component

Also Published As

Publication number Publication date
CN105073684A (zh) 2015-11-18
EP2980043B1 (en) 2018-01-17
US20160049248A1 (en) 2016-02-18
CN105073684B (zh) 2018-03-02
JP6102410B2 (ja) 2017-03-29
US9530563B2 (en) 2016-12-27
JP2014189465A (ja) 2014-10-06
EP2980043A1 (en) 2016-02-03
EP2980043A4 (en) 2016-12-28

Similar Documents

Publication Publication Date Title
JP6102410B2 (ja) 誘電体磁器組成物、および誘電体素子
JP5067401B2 (ja) 誘電体セラミックおよびその製造方法ならびに積層セラミックコンデンサ
JP5211262B1 (ja) 積層セラミックコンデンサ
JP6316985B2 (ja) 誘電体組成物、誘電体素子、電子部品および積層電子部品
JP5234035B2 (ja) 誘電体セラミックおよび積層セラミックコンデンサ
JP6257802B2 (ja) 誘電体組成物、誘電体素子、電子部品および積層電子部品
JP4525680B2 (ja) 誘電体セラミック組成物および積層セラミックコンデンサ
JP2016060647A (ja) 誘電体組成物、誘電体素子、電子部品および積層電子部品
KR102222606B1 (ko) 유전체 조성물 및 이를 포함하는 적층 세라믹 커패시터
JPWO2009041160A1 (ja) 誘電体セラミック及び積層セラミックコンデンサ
JP6102405B2 (ja) 誘電体磁器組成物、および誘電体素子
JP4797693B2 (ja) 誘電体セラミック組成物、およびそれを用いた積層セラミックコンデンサ
CN106605282B (zh) 介电组合物、介电元件、电子组件和层压电子组件
JP4697582B2 (ja) 誘電体セラミック及び誘電体セラミックの製造方法、並びに積層セラミックコンデンサ
JP2008297133A (ja) 誘電体磁器およびコンデンサ
JP2004210613A (ja) 誘電体磁器、その製造方法、及び積層セラミックコンデンサ
JP7574931B2 (ja) 誘電体磁器組成物および積層セラミックコンデンサ

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201480017478.3

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14775500

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2014775500

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 14780017

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE