WO2005075378A1 - 強誘電体磁器組成物およびそれを用いた強誘電体応用素子 - Google Patents

強誘電体磁器組成物およびそれを用いた強誘電体応用素子 Download PDF

Info

Publication number
WO2005075378A1
WO2005075378A1 PCT/JP2004/017097 JP2004017097W WO2005075378A1 WO 2005075378 A1 WO2005075378 A1 WO 2005075378A1 JP 2004017097 W JP2004017097 W JP 2004017097W WO 2005075378 A1 WO2005075378 A1 WO 2005075378A1
Authority
WO
WIPO (PCT)
Prior art keywords
ferroelectric
sample
present
ceramic composition
general formula
Prior art date
Application number
PCT/JP2004/017097
Other languages
English (en)
French (fr)
Inventor
Yoshifumi Ogiso
Original Assignee
Murata Manufacturing Co.,Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Murata Manufacturing Co.,Ltd. filed Critical Murata Manufacturing Co.,Ltd.
Priority to JP2005517623A priority Critical patent/JP4407637B2/ja
Priority to US10/588,147 priority patent/US7381671B2/en
Publication of WO2005075378A1 publication Critical patent/WO2005075378A1/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—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
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
    • 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
    • C04B35/64—Burning or sintering processes
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/0009—Materials therefor
    • G02F1/0018—Electro-optical materials
    • G02F1/0027—Ferro-electric materials
    • 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
    • H01G4/002—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
    • H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • 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
    • C04B2235/3231—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
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
    • 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
    • C04B2235/3289—Noble metal oxides
    • C04B2235/3291—Silver oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/604—Pressing at temperatures other than sintering temperatures
    • 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
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • 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
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661—Multi-step sintering
    • 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
    • C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
    • 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
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry

Definitions

  • the present invention relates to a ferroelectric ceramic composition and a ferroelectric device using the same.
  • the present invention relates to a ferroelectric ceramic composition and a ferroelectric device using the same, particularly to a material for a piezoelectric electrostrictive ceramic device represented by, for example, a ceramic filter, a ceramic oscillator, and an actuator, or an electric device.
  • Ferroelectric ceramic compositions useful as materials for nonlinear optical elements typified by optical effect elements (Pockels cell), optical harmonic generation elements, and four-wave mixing elements (photorefractive elements) and ferroelectric compositions using the same. It relates to a dielectric application element.
  • Ferroelectric ceramic compositions containing lead oxide (PbTiO 3) as a main component are widely used. Also, non
  • Patent Document 1 and others include (Ba, Sr) NaNb O force or Non-Patent Document 2 describes Ba AgNb
  • Non-Patent Document 1 Am. Ceram. Soc., 52 (1976) 276
  • Non-Patent Document 2 J.J.Appl.Phys., 13 (1974) 1291
  • lead zirconate titanate or a piezoelectric ceramic composition containing lead titanate as a main component contains harmful Pb, it is necessary to take measures during production or disposal. Costs.
  • (Ba, Sr) NaNbO is a raw material in water because the Na compound is water-soluble.
  • An object of the present invention is to provide a piezoelectric ceramic element, an electrostrictive ceramic element, and a non-linear optical element such as an electro-optic effect element and an optical harmonic generation element using the same.
  • the ferroelectric porcelain composition according to the present invention is represented by the general formula (Ba Sr Ca) Ag Nb O and has a tungsten bronze structure in order to solve the above-mentioned technical problem. 5 15- d / 2
  • the x, y and d forces S are each 0.1.l ⁇ x + y ⁇ 0.8, 0 ⁇ d ⁇ 0.6.
  • the ferroelectric porcelain composition according to the present invention may further comprise, in addition to the main component, a general formula aMnO + bSiO (where a and b are the respective weights based on 100 parts by weight of the main component).
  • ferroelectric porcelain composition according to the present invention can be applied to a piezoelectric ceramic element or an electrostrictive ceramic element, and further to a non-linear optical element such as an electro-optic effect element and an optical harmonic generation element. It is.
  • ferroelectric ceramic composition and the ceramic electronic component of the present invention since they have the above-mentioned configurations, they do not contain Pb, which is a harmful substance, do not contain water-soluble alkali ions, and have sinterability. If it is good, the effect can be obtained.
  • FIG. 1 shows an embodiment of a ferroelectric applied device.
  • FIG. 2 is an electron micrograph of the surface of sample 1.
  • FIG. 3 is an electron micrograph of the surface of sample 13.
  • FIG. 4 is an X-ray diffraction diagram of Samples 10, 25, and 31.
  • the range of X and y is set to 0.1.l ⁇ x + y ⁇ 0.8, and the range of d is set to 0 ⁇ d ⁇ 0.6.
  • the firing temperature can be reduced by adding a Mn oxide or a Si oxide to the main component.
  • the Mn oxide and the Si oxide are each 5 parts by weight or less in terms of MnO and SiO in terms of 100 parts by weight of the main component.
  • the content is contained in the range, since the characteristics when not added are not deteriorated.
  • the ferroelectric porcelain composition according to the present invention may be a uniform solid solution or a mixture of solid solutions as long as the above requirements are satisfied. Further, the ferroelectric composition according to the present invention may be a polycrystal or a single crystal.
  • the ferroelectric porcelain composition of the present invention can be produced in the same manner as a normal ferroelectric or a dielectric material.
  • a normal ferroelectric or a dielectric material for example, first, BaCO
  • a porcelain comprising the ferroelectric porcelain composition of the present invention can be obtained. Furthermore, a single crystal can also be obtained by a zone melting method using a porcelain produced in the same manner as a raw material.
  • the ferroelectric ceramic composition according to the present invention can be used for a piezoelectric electrostrictive ceramic element or a nonlinear optical element. These devices have various known shapes. One of the simplest structures is a device having electrodes 12a and 12b on both sides of a flat ferroelectric material 11 as shown in FIG.
  • BaCO, SrCO, CaCO, Ag 0, Nb O, MnO, and SiO are used as starting materials.
  • the obtained composition was mixed in pure water and then dried. Then, it was calcined by an electric furnace in an oxidizing atmosphere at 1100 ° C to 1150 ° C for 10 hours.
  • the calcined material is pulverized, mixed with polyvinyl alcohol at 5 parts by weight with respect to 100 parts by weight of the powder, and dried to form a powder having a diameter of 12 mm and a thickness of lmm by a uniaxial press (pressure lGPa).
  • a disk-shaped sample was obtained. These samples were fired at the temperatures shown in Tables 1 and 2 in an oxidizing atmosphere. In the baking step, a part of Ag compounded may volatilize, and d in the general formula may become larger than 0.
  • a single crystal was prepared by a band melting method using a rod-shaped fired body prepared from the calcined powder of Sample 5 as a raw material, and cut into a lmm-thick. Thereafter, an Ag paste was applied to the upper and lower surfaces of the sample and baked at 800 ° C. With respect to the sample thus obtained, the relative polarization, the transition temperature, and the remanent polarization after applying 2 VZm at room temperature were measured. The composition was analyzed, and the value of d in the general formula was determined from the analysis value. The results are also shown in Tables 1, 2 and 3, respectively.
  • the samples without the asterisk (*) are the samples that satisfy the requirements of Claim 1 and also meet the requirements of Claim 2, and have the sample numbers with the asterisk (*).
  • the present invention is a sample having the requirements of claim 1 of the present invention, but having the requirements of claim 2.
  • Table 3 shows an example of the above-mentioned single crystal.
  • sample Nos. 43 to 47 examples satisfying the requirements of claims 1 and 2 of the present invention
  • Mn oxide and Z or Si oxide are not added (for example, Compared to sample No. 2-5)
  • the firing temperature can be lowered without significantly changing the transition temperature. It can be seen that the relative permittivity was stabilized and increased somewhat with the improvement in sinterability.
  • the remanent polarization after application of 2 VZ wm at room temperature was 0.90 to 1.01. It was found that the properties as a ferroelectric material were sufficiently secured. You.
  • Ba, Sr, Ca, Ag, Nb, Mn, and Si were each used as a raw material for BaCO, SrCO, CaCO, Ag0, NbO, MnO, and SiO. So
  • those prepared in the form of another compound such as an oxide, a hydroxide, a carbonate, or an organic salt may be used as a raw material.
  • the mixing and the like are performed in pure water, but this does not preclude the use of a common solvent such as ethyl alcohol.
  • the band melting method was used as a method for producing a single crystal, a usual Chiocular key method or LPE method can also be used.
  • FIG. 4 shows X-ray diffraction diagrams of Samples 10, 25, and 31 in the experimental example of the present invention. Each shows a tungsten bronze structure.
  • a ferroelectric porcelain composition which does not contain harmful substance Pb and does not contain water-soluble alkali ions and has excellent sinterability.
  • a ferroelectric ceramic composition it is possible to obtain highly reliable non-linear optical elements such as a piezoelectric ceramic element, an electrostrictive ceramic element, an electro-optical effect element, and an optical harmonic generation element having desired characteristics. Will be possible.
  • the present invention can be widely used in fields such as non-linear optical elements such as piezoelectric ceramic elements, electrostrictive ceramic elements, electro-optical effect elements, and optical harmonic generation elements.
  • non-linear optical elements such as piezoelectric ceramic elements, electrostrictive ceramic elements, electro-optical effect elements, and optical harmonic generation elements.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Nonlinear Science (AREA)
  • Thermal Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Piezo-Electric Or Mechanical Vibrators, Or Delay Or Filter Circuits (AREA)

Abstract

　有毒なＰｂを使用せず焼結性に優れた強誘電体磁器組成物およびそれを用いた非線形光学素子を提供する。 　一般式（Ｂａ1-x-yＳｒxＣａy）2Ａｇ1-dＮｂ5Ｏ15-d/2で表され、タングステンブロンズ構造を有する主成分と、一般式ａＭｎＯ2＋ｂＳｉＯ2（ただしａ、ｂは前記主成分１００重量部に対する各重量部を示す。）で表される副成分を含有し、前記ｘ、ｙ、ａ、ｂおよびｄが各々０．１≦ｘ＋ｙ≦０．８、ａ＋ｂ≦５、０≦ｄ≦０．６である。

Description

強誘電体磁器組成物およびそれを用いた強誘電体応用素子 技術分野
[0001] 本発明は、強誘電体磁器組成物およびそれを用いた強誘電体応用素子に関し、 特にたとえば、セラミックフィルタ、セラミック発振子およびァクチユエータに代表され る圧電電歪セラミック素子の材料、または電気光学効果素子 (ポッケルスセル）、光高 調波発生素子および四光波混合素子 (フォトリフラクティブ素子）に代表される非線 形光学素子の材料として有用な強誘電体磁器組成物およびそれを用いた強誘電体 応用素子に関する。
背景技術
[0002] 従来より、圧電素子には、チタン酸ジルコン酸鉛 (Pb (Ti Zr ) 0 )、または、チタン
1 3
酸鉛 (PbTiO )を主成分とする強誘電体磁器組成物が広く用いられている。また、非
3
特許文献 1などには、（Ba， Sr) NaNb O 力 あるいは非特許文献 2には Ba AgNb
2 5 15 2
O が報告されている。
5 15
非特許文献 1 : Am. Ceram. Soc. , 52 (1976) 276
非特許文献 2 :J. J. Appl. Phys. , 13 (1974) 1291
発明の開示
発明が解決しょうとする課題
[0003] しカゝしながら、チタン酸ジルコン酸鉛、または、チタン酸鉛を主成分とする圧電磁器 組成物は、有害な Pbが含まれているため、製造時あるいは廃棄時にその対策のため のコストがかかる。
[0004] また、（Ba, Sr) NaNb O は、原料の Na化合物が水溶性であるため水中で原料
2 5 15
を混合し、その後混合されたスラリーを乾燥するという簡便な工程を採用することがで きないという問題点力ある。さらに長期間の使用のうちに結晶中の Naイオンが拡散 · マイグレーションによって粒界や電極との界面に偏祈し、磁器が吸湿崩壊することが 懸念される。
[0005] また、 Ba AgNb O は、焼結が困難なため広く実用に供されるに至っていない。 [0006] 本発明はこのような事情に鑑みなされたものであって、有害物である Pbを含まず、 水溶性のアルカリイオンを含まず、焼結性の良好な強誘電体磁器組成物およびそれ を用いた圧電セラミック素子、電歪セラミック素子、さらには、電気光学効果素子、光 高調波発生素子等の非線形光学素子を提供することを目的とする。
課題を解決するための手段
[0007] この発明に係わる強誘電体磁器組成物は、上述した技術的課題を解決するため、 一般式（Ba Sr Ca ) Ag Nb O で表され、タングステンブロンズ構造を有す l 2 1- d 5 15- d/2
る主成分を含有し、前記 x、yおよび d力 S各々0. l≤x+y≤0. 8, 0≤d≤0. 6である ことを特徴とする。また、この発明に係わる強誘電体磁器組成物は、前記主成分に加 えて一般式 aMnO +bSiO (ただし a、 bは前記主成分 100重量部に対する各重量
2 2
部を示す。）で表される副成分を含有し、前記 aおよび b力 +b≤ 5であることを特徴 とする。さらに、この発明に係わる強誘電体磁器組成物は、圧電セラミック素子あるい は電歪セラミック素子、さらには、電気光学効果素子、光高調波発生素子等の非線 形光学素子への適用が可能である。
発明の効果
[0008] 本発明の強誘電体磁器組成物およびセラミック電子部品によれば、前記構成を備 えているため、有害物である Pbを含まず、水溶性のアルカリイオンを含まず、焼結性 が良好であると 、うと 、う効果が得られる。
図面の簡単な説明
[0009] [図 1]強誘電体応用素子の一形態である。
[図 2]試料 1表面の電子顕微鏡写真である。
[図 3]試料 13表面の電子顕微鏡写真である。
[図 4]試料 10、 25、 31の X線回折図である。
符号の説明
[0010] 11 強誘電体
12aゝ 12b 電極
発明を実施するための最良の形態 [0011] この発明に係わる強誘電体磁器組成物の一般式において、 x+yく 0. 1では、焼 結体の結晶粒径が異常に成長し、結晶粒界あるいは結晶粒内に発生する応力が異 常に大きくなることから、焼結体としての形状を保持できなくなるので好ましくない。 X +y>0. 8では、強誘電性にかかわる転移温度が 60°C以下と低くなるので好ましくな い。さらに x+y>0. 8では、 Agイオンが所定のサイトに入りにくぐ Agが揮発しやす くなり、結果として d>0. 6となる。
[0012] そこで、この発明では、 Xおよび yの範囲を 0. l≤x+y≤0. 8とし、 dの範囲を 0≤d ≤0. 6とした。
[0013] また、この発明にお ヽては、 Mn酸化物や Si酸化物を主成分に対して添加すること により焼成温度を低下させることができる。なお、 Mn酸化物および Si酸化物は前記 主成分 100重量部に対し、それぞれ MnO換算、 SiO換算して合計 5重量部以下の
2 2
範囲で含有することが添加しない時の特性を劣化させない点で好ましい。また、この 発明に係わる強誘電体磁器組成物は、前記要件を満たす限り均一な固溶体であつ てもよいし、固溶体の混合物であってもよい。さらに、この発明に係わる強誘電体組 成物は、多結晶体であってもよいし、単結晶体であってもよい。
[0014] 以下にこの発明に係わる強誘電体磁器組成物の特性を評価するために実施した 実験例について説明する。
[0015] この発明における強誘電体磁器組成物は、通常の強誘電体や、誘電体材料と同 様に作製できる。たとえば、まず、 BaCO
3、 SrCO
3、 CaCO
3、 Ag 0 b Oを所定量 2 、 N
2 5 調合し、純水中で、ジルコユアボールなどのメディアとともに 4一 24h混合する。その 際、より均一混合とするためにソルビタンエステルなどの分散剤を添加してもよい。そ の後、混合されたスラリーを乾燥させ、通常の電気炉により、酸化性雰囲気中、 800 °C一 1150°C、 1一 24h仮焼成する。この仮焼物を純水中にポリビュルアルコールな どのバインダーとともにメディアにより粉砕、混合し、これを乾燥させる。この乾燥粉末 を一軸プレスにより円板試料を作製する。さらに試料を酸化性雰囲気中、 950°C— 1 350°C、 3— 10h焼成する。これらの作業によりこの発明の強誘電体磁器組成物から なる磁器を得ることができる。さら〖こ、同様にして作製された磁器を原料として帯溶融 法により、単結晶を得ることもできる。 [0016] 本発明にかかる強誘電体磁器組成物は圧電電歪セラミック素子または非線形光学 素子に用いることができる。これら素子には公知の様々な形状のものがある力 最も 単純な構造のひとつとして図 1に示すように平板状の強誘電体 11の両面に電極 12a 、 12bを備えたものがある。
[0017] 以下に、この発明を実施例に基づいて説明する。
実施例 1
[0018] まず、出発原料として BaCO、 SrCO、 CaCO、 Ag 0、 Nb O、 MnO、 SiOを準
3 3 3 2 2 5 2 2 備した。次に、これらの原料粉末を、一般式 (Ba Sr Ca ) Ag Nb O で表さ
1-x-y x y 2 1-d 5 15-d/2 れる主成分と、一般式 aMnO +bSiO (ただし a、 bは前記主成分 100重量部に対す
2 2
る各重量部を示す。）で表される副成分とを含有し、前記 x、 y、 aおよび bが各々以下 の表 1一表 2に示す組成になるように配合した。ただし Ag Oの配合量のみ前記一般
2
式で d=0となるようにした。
[0019] 得られた配合物を純水中で混合した後、乾燥した。それから電気炉により、酸化性 雰囲気中、 1100°C— 1150°C、 10h仮焼成した。仮焼物を粉砕し、粉末 100重量部 に対しポリビニルアルコールが 5重量部となるように混合し、これを乾燥して得た粉末 を一軸プレス（圧力 lGPa)で直径 12mm、厚み lmmに成形し、円盤状試料を得た。 これらの試料を表 1および表 2に示す温度で、酸化性雰囲気中焼成した。この焼成ェ 程において配合された Agの一部が揮発し、一般式中の dが 0より大きくなることがある 。さらに、試料 5の仮焼粉から作製した棒状焼成体を原料とし帯溶融法により単結晶 を作製し、厚み lmmに切断した。その後、 Agペーストを試料上下面に塗付し、 800 °Cにて焼き付けた。このようにして得た試料について比誘電率、転移温度および室 温で 2VZ m印加後の残留分極を測定した。また組成を分析し、分析値から一般 式中の dの値を求めた。それらの結果もそれぞれ表 1、表 2および表 3に示す。
なお、表 1に示した各試料は、上記一般式 aMnO +bSiOにおける aおよび bの値
2 2
力 SOの試料 (すなわち、 Mn酸化物および Si酸化物を副成分として含有させて 、な ヽ 試料)である。
表 1にお!/、て、試料番号に「 *」を付して!/、な!/、ものは本発明の範囲内にある実施 例の試料であり、試料番号に「 *」を付したものは本発明の範囲外の比較例の試料 である。
また、表 2において、試料番号に「*」を付していないものは請求項 1の要件にカロえ 、請求項 2の要件をも満たす試料であり、試料番号に「*」を付したものは本発明の 請求項 1の要件は備えて 、るが、請求項 2の要件を備えて 、な 、試料である。 また、表 3には上述の単結晶の例を示している。
[表 1]
X y 仮焼温度 焼成温度 比^量傘転移温度 d 番号 / ¾ / °C / ¾
*1 0.0 0.0 1150 1350 430 420 0.97 0.19
2 0.1 0.0 1150 1300 642 360 1.05 0.09
3 0.0 0.1 1150 1250 387 350 1.01 0.t5
4 0.2 0.0 1150 1300 531 320 1.10 0.00
5 0.1 0.1 1150 1250 544 312 0.94 0.00
6 0.0 0.2 1150 1250 521 322 1.07 0.01
7 0.3 0.0 1150 1300 639 237 1.16 0.04
8 0.2 0.1 1150 1200 652 242 0.98 0.03
9 0.1 0.2 1150 1150 494 266 0.88 0.14
10 0.0 0.3 1150 1200 457 281 1.14 0.15
11 0.4 0.0 1150 1300 629 187 1.22 0.00
12 0.3 0.1 1150 1250 653 193 1.15 0.02
13 0.1 0.3 1150 1200 652 225 0.93 0.06
14 0.0 0.4 1150 1200 647 237 « 1.18 0.28
15 0.5 0.0 1150 1300 602 155 SE 1.29 0.07
16 0.4 0.1 1150 1250 626 157 1.18 0.10
17 0.3 0.2 1150 1200 625 171 0 E.95 0.03
18 0.1 0.4 1150 1150 671 203 1.08 0.12
19 0.0 0.5 1150 1150 659 196 1.24 0.22
20 0.6 0.0 1150 1250 933 125 1.28 0.14
21 0.5 0.1 1150 1200 875 131 1.08 0.10
22 0.3 0.3 1150 1200 765 142 0.96 0.43
23 0.1 0.5 1150 1150 632 146 1.16 0.42
24 0.0 0.6 1150 1200 565 146 1.29 0.48
25 0.7 0.0 1150 1250 1284 90 1.16 0.06
26 0.6 0.1 1150 1200 1221 91 0.94 0.24
27 0.4 0.3 1150 1200 1018 92 0.86 0.30
28 0.3 0.4 1150 1200 892 93 0.98 0.33
29 0.1 0.6 1150 1150 422 98 1.22 0.43
30 0.0 0.7 1150 1200 343 105 1.30 0.53
31 0.8 0.0 1150 1300 1 195 65 1.07 0.14
32 0.7 0.1 1150 1300 1190 63 0.73 0.18
33 0.5 0.3 1150 1300 1182 62 0.72 0.28
34 0.3 0.5 1150 1150 372 67 0.94 0.44
35 0.1 0.7 1150 1150 183 74 1.09 0.57
36 0.0 0.8 1150 1150 190 95 1.10 0.59
♦37 0.9 0.0 1150 1250 867 48 1.02 0.71
*38 0.7 0.2 1150 1300 245 23 0.37 0.80
♦39 0.5 0.4 1150 1100 47 2 0.47 0.80
*40 0.3 0.6 1150 1100 63 22 0.71 0.92
*41 0.1 0.8 1150 1100 92 55 0.78 0.88
*42 0.0 0.9 1150 1100 115 55 0.80 0.77 [0021] [表 2]
Figure imgf000008_0001
[0022] [表 3]
Figure imgf000008_0002
[0023] 表 1力らゎ力るように、 x+y力 ^0. 8より大さく d力 ^0. 6より大さ!/、試料番号 37力ら 42 では、転移温度が室温近くまで低下している。 x+yが 0. 1より小さい試料番号 1につ いては、辛うじて測定は可能であった力 試料は脆ぐ実際の使用には耐えられない 。図 2および図 3に本発明の実験例における試料 1、 13の表面の電子顕微鏡写真を それぞれ示す。試料 13は緻密な焼結体の様相を示しているのに対して、試料 1は結 晶が大きく成長し、クラックの生成がみられる。
[0024] また、表 2より、 Mn酸化物および Si酸化物の含有量の和（一般式中の aと bの和）が 5より大きい試料番号 48から 52の試料 (すなわち、本発明の請求項 1の要件は備え ているが、請求項 2の要件を備えていない試料）の場合、比誘電率が 277— 582、転 移温度が 304— 345°Cと、試料番号 43— 47と同じ程度の値は確保されているもの の、室温で 2VZ w m印加後の残留分極が 0. 45-0. 64 C' cm— 2と低くなつている ことがわかる。これに対し、 Mn酸化物および Zまたは Si酸化物を、それぞれ MnO
2 換算、 SiO換算して、主成分 100重量部に対し、合計 5重量部以下の範囲で含有さ
2
せた試料番号 43— 47の試料 (本発明の請求項 1及び 2の要件を備えた試料）の場 合、 Mn酸ィ匕物および Zまたは Si酸ィ匕物を添加しない場合 (例えば、表 1の試料番号 2-5)に比べて、転移温度を大きく変えることなしに焼成温度を低下させることが可 能になること、および焼結性の向上に伴い比誘電率が安定し、かつ、いくらか上昇し ていることがわかる。また、試料番号 43— 47の試料の場合、室温で 2VZ w m印加 後の残留分極が 0. 90-1. 01と高ぐ強誘電体としての特性が十分に確保されてい ることがゎカゝる。
なお、表 2の試料番号 43— 47の dの値が、表 1の試料番号 2— 5の dの値と異なつ ているが、これは副成分である Mn酸ィ匕物， Si酸ィ匕物の添カ卩の影響によるものであり 、表 2の試料番号 43— 47と、表 1の試料番号 2— 5における dの値の差程度であれば 、特性に与える影響はほとんどな 、ものと考えられる。
[0025] なお、上述した例では、 Ba、 Sr、 Ca、 Ag、 Nb、 Mnおよび Siの各々について、 Ba CO、 SrCO、 CaCO、 Ag 0、 Nb O、 MnOおよび SiOを原料として用いたが、そ
3 3 3 2 2 5 2 2
れぞれ別の、たとえば、酸化物、水酸化物、炭酸塩あるいは有機塩のような他の化合 物の状態で用意されたものを原料に用いてもよい。また、それらの混合などは純水中 で行って 、るが、エチルアルコールなど一般の溶剤を用いて行うことを妨げるもので はない。さらに、単結晶の作製方法として帯溶融法を用いたが、通常のチヨクラルス キー法や LPE法などを用いることも可能である。
[0026] 図 4に本発明の実験例における試料 10、 25、 31の X線回折図を示す。いずれもタ ングステンブロンズ構造を示す。
産業上の利用可能性
[0027] 本発明によれば、有害物である Pbを含まず、かつ、水溶性のアルカリイオンを含ま ない、焼結性に優れた強誘電体磁器組成物を得ることが可能になり、該強誘電体磁 器組成物を用いることにより、所望の特性を備えた信頼性の高い圧電セラミック素子 、電歪セラミック素子、電気光学効果素子、光高調波発生素子等の非線形光学素子 を得ることが可能になる。
したがって、本発明は、圧電セラミック素子、電歪セラミック素子、電気光学効果素 子、光高調波発生素子等の非線形光学素子などの分野に広く利用することが可能 である。

Claims

請求の範囲
[1] 一般式 (Ba Sr Ca ) Ag Nb O で表され、タングステンブロンズ構造を有す
1 2 1-d 5 15-d/2
る主成分を含有し、
前記 x、 yおよび dが各々
0. l≤x+y≤0. 8、
0≤d≤0. 6
であることを特徴とする強誘電体磁器組成物。
[2] Mn酸ィ匕物および Si酸ィ匕物を副成分として含有し、
前記酸化物を一般式 aMnO +bSiO (ただし a、 bは前記主成分 100重量部に対す
2 2
る各重量部を示す。）で表したとき、
前記 aおよび bが
a+b≤5、
であることを特徴とする、請求項 1に記載の強誘電体磁器組成物。
[3] 請求項 1または 2の 、ずれかの強誘電体磁器組成物を用いた圧電電歪セラミック素 子または非線形光学素子。
PCT/JP2004/017097 2004-02-06 2004-11-17 強誘電体磁器組成物およびそれを用いた強誘電体応用素子 WO2005075378A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2005517623A JP4407637B2 (ja) 2004-02-06 2004-11-17 強誘電体磁器組成物およびそれを用いた強誘電体応用素子
US10/588,147 US7381671B2 (en) 2004-02-06 2004-11-17 Ferroelectric ceramic composition and applied ferroelectric element including same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2004-031087 2004-02-06
JP2004031087 2004-02-06

Publications (1)

Publication Number Publication Date
WO2005075378A1 true WO2005075378A1 (ja) 2005-08-18

Family

ID=34836031

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/017097 WO2005075378A1 (ja) 2004-02-06 2004-11-17 強誘電体磁器組成物およびそれを用いた強誘電体応用素子

Country Status (3)

Country Link
US (1) US7381671B2 (ja)
JP (1) JP4407637B2 (ja)
WO (1) WO2005075378A1 (ja)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010053028A (ja) * 2008-07-30 2010-03-11 Canon Inc 金属酸化物および圧電材料
WO2010098227A1 (ja) * 2009-02-27 2010-09-02 国立大学法人長岡技術科学大学 光変調材料およびその製造方法
KR101368080B1 (ko) 2010-06-10 2014-02-26 캐논 가부시끼가이샤 압전 재료, 압전 소자, 액체 토출 헤드, 초음파 모터, 및 먼지 클리닝 장치
KR101368085B1 (ko) 2010-06-10 2014-02-26 캐논 가부시끼가이샤 압전 재료, 압전 소자, 액체 토출 헤드, 초음파 모터, 및 먼지 클리닝 장치
KR101368069B1 (ko) 2010-06-10 2014-02-26 캐논 가부시끼가이샤 압전 재료, 압전 소자, 액체 토출 헤드, 초음파 모터, 및 먼지 클리닝 장치
US20190103222A1 (en) * 2016-03-24 2019-04-04 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component
US20190115154A1 (en) * 2016-03-24 2019-04-18 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component
US20190256425A1 (en) * 2016-03-24 2019-08-22 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080005226A (ko) * 2005-04-18 2008-01-10 가부시키가이샤 무라타 세이사쿠쇼 유전체 세라믹 조성물 및 적층 세라믹 커패시터
KR101119804B1 (ko) * 2007-02-22 2012-03-22 가부시키가이샤 무라타 세이사쿠쇼 유전체 세라믹 조성물 및 적층 세라믹 콘덴서
JP2010021512A (ja) * 2008-01-30 2010-01-28 Ngk Insulators Ltd 圧電／電歪膜型素子及びその製造方法
JP5475272B2 (ja) * 2008-03-21 2014-04-16 日本碍子株式会社 圧電／電歪膜型素子
KR101333346B1 (ko) 2009-04-27 2013-11-28 고쿠리츠다이가쿠호징 야마나시다이가쿠 텅스텐 브론즈형 압전 재료 및 그의 제조 방법
KR101113441B1 (ko) * 2009-12-31 2012-02-29 삼성전기주식회사 유전체 자기 조성물 및 이를 포함하는 적층 세라믹 커패시터
CN101798219B (zh) * 2010-02-26 2012-10-31 上海海事大学 用于水声换能器的压电陶瓷及其制备方法
CN101798218B (zh) * 2010-03-18 2012-05-23 西安交通大学 一种锆钛酸钡和铌酸钾钠复合的无铅压电厚膜的制备方法
JP6249004B2 (ja) * 2015-10-06 2017-12-20 Tdk株式会社 誘電体組成物および電子部品

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001048646A (ja) * 1999-07-30 2001-02-20 Kyocera Corp 磁器及びその製法
JP2001196184A (ja) * 2000-01-14 2001-07-19 Tdk Corp 無機ｅｌ用誘電体厚膜、無機ｅｌ素子および誘電体厚膜
JP2003261379A (ja) * 2002-03-06 2003-09-16 National Institute Of Advanced Industrial & Technology 多結晶圧電材料及びその製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1173047A4 (en) * 2000-02-07 2009-05-27 Ifire Ip Corp COMPOSITE SUBSTRATE, THIN-FILM ELECTROLUMINESCENT DEVICE COMPRISING THE SAME, AND PROCESS FOR PRODUCING THE SAME
TW560094B (en) * 2001-06-15 2003-11-01 Tdk Corp Piezoelectric ceramic and method of manufacturing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001048646A (ja) * 1999-07-30 2001-02-20 Kyocera Corp 磁器及びその製法
JP2001196184A (ja) * 2000-01-14 2001-07-19 Tdk Corp 無機ｅｌ用誘電体厚膜、無機ｅｌ素子および誘電体厚膜
JP2003261379A (ja) * 2002-03-06 2003-09-16 National Institute Of Advanced Industrial & Technology 多結晶圧電材料及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAVEZ J. ET AL: "Cationic ordering in some ferroelectric "TKWB" phases.", FERROELECTRICS., vol. 81, 1988, pages 301 - 304, XP002983684 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010053028A (ja) * 2008-07-30 2010-03-11 Canon Inc 金属酸化物および圧電材料
US8518290B2 (en) 2008-07-30 2013-08-27 Canon Kabushiki Kaisha Piezoelectric material
WO2010098227A1 (ja) * 2009-02-27 2010-09-02 国立大学法人長岡技術科学大学 光変調材料およびその製造方法
KR101368080B1 (ko) 2010-06-10 2014-02-26 캐논 가부시끼가이샤 압전 재료, 압전 소자, 액체 토출 헤드, 초음파 모터, 및 먼지 클리닝 장치
KR101368085B1 (ko) 2010-06-10 2014-02-26 캐논 가부시끼가이샤 압전 재료, 압전 소자, 액체 토출 헤드, 초음파 모터, 및 먼지 클리닝 장치
KR101368069B1 (ko) 2010-06-10 2014-02-26 캐논 가부시끼가이샤 압전 재료, 압전 소자, 액체 토출 헤드, 초음파 모터, 및 먼지 클리닝 장치
US20190103222A1 (en) * 2016-03-24 2019-04-04 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component
US20190115154A1 (en) * 2016-03-24 2019-04-18 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component
US20190256425A1 (en) * 2016-03-24 2019-08-22 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component
US10759709B2 (en) * 2016-03-24 2020-09-01 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component
US10777355B2 (en) * 2016-03-24 2020-09-15 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component
US10777354B2 (en) * 2016-03-24 2020-09-15 Tdk Corporation Dielectric composition, dielectric element, electronic component, and multilayer electronic component

Also Published As

Publication number Publication date
US7381671B2 (en) 2008-06-03
US20070161497A1 (en) 2007-07-12
JPWO2005075378A1 (ja) 2008-01-10
JP4407637B2 (ja) 2010-02-03

Similar Documents

Publication Publication Date Title
Lidjici et al. XRD, Raman and electrical studies on the (1− x)(Na0. 5Bi0. 5) TiO3− xBaTiO3 lead free ceramics
Nagata et al. Additive effects on electrical properties of (Bi1/2Na1/2) TiO3 ferroelectric ceramics
WO2005075378A1 (ja) 強誘電体磁器組成物およびそれを用いた強誘電体応用素子
JP3259677B2 (ja) 圧電磁器組成物
Liu et al. Effect of sintering temperature on the structure and properties of cerium-doped 0.94 (Bi0. 5Na0. 5) TiO3–0.06 BaTiO3 piezoelectric ceramics
Chang et al. Effects of AETiO3 additions on phase structure, microstructure and electrical properties of (K0. 5Na0. 5) NbO3 ceramics
Laoratanakul et al. Phase formation and dielectric properties of bismuth sodium titanate–potassium sodium niobate ceramics
WO2017135298A1 (ja) 誘電体磁器組成物および電子部品
Chen et al. Electromechanical properties and morphotropic phase boundary of Na 0.5 Bi 0.5 TiO 3-K 0.5 Bi 0.5 TiO 3-BaTiO 3 lead-free piezoelectric ceramics
Shin et al. Piezoelectric and dielectric properties of B2O3-added (Ba0. 85Ca0. 15)(Ti0. 915Zr0. 085) O3 ceramics sintered at low temperature
Gong et al. Large electric field-induced strain in ternary Bi0. 5Na0. 5TiO3-BaTiO3-Sr2MnSbO6 lead-free ceramics
JP2009221096A (ja) 圧電／電歪磁器組成物
Wang et al. Structure and piezoelectric properties of (Ba1− xCax)(Ti0. 95Hf0. 05) O3 lead-free ceramics
Keswani et al. Correlation between structural, ferroelectric, piezoelectric and dielectric properties of Ba0. 7Ca0. 3TiO3-xBaTi0. 8Zr0. 2O3 (x= 0.45, 0.55) ceramics
Zhou et al. Dielectric and piezoelectric properties of Bi0. 5Na0. 5TiO3–Bi0. 5K0. 5TiO3–BiCrO3 lead-free piezoelectric ceramics
JP2007084408A (ja) 圧電セラミックス
Lee et al. Optimized piezoelectric and structural properties of (Bi, Na) TiO3–(Bi, K) TiO3 ceramics for energy harvester applications
Pengpat et al. Phase formation and electrical properties of lead-free bismuth sodium titanate–potassium niobate ceramics
Wongsaenmai et al. Improving ferroelectric properties of Pb (Zr0. 44Ti0. 56) O3 ceramics by Pb (Mg1/3Nb2/3) O3 addition
JP2007055867A (ja) 圧電磁器組成物
JP2003201172A (ja) 無鉛圧電磁器組成物及びその製造方法
Feng et al. Enhanced temperature stability of electric-field-induced strain in KNN-based ceramics
Bhaskar Reddy et al. Structural and dielectric characterization of Sr substituted Ba (Zr, Ti) O 3 based functional materials
Lee et al. Preparation and piezoelectric properties of CeO2-added (Na0. 475K0. 475Li0. 05)(Nb0. 92Ta0. 05Sb0. 03) O3 lead-free ceramics
Ariizumi et al. Effects of Mn additive on dielectric and piezoelectric properties of (Na0. 5K0. 5) NbO3–BaZrO3–(Bi0. 5K0. 5) TiO3 ternary system

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005517623

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2007161497

Country of ref document: US

Ref document number: 10588147

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase
WWP Wipo information: published in national office

Ref document number: 10588147

Country of ref document: US