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 PDFInfo
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- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 239000000919 ceramic Substances 0.000 title claims abstract description 28
- 230000005621 ferroelectricity Effects 0.000 title description 2
- 230000003287 optical effect Effects 0.000 claims abstract description 14
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 13
- 229910014307 bSiO Inorganic materials 0.000 claims description 4
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001125046 Sardina pilchardus Species 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000019512 sardine Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- -1 sorbitan ester Chemical class 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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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.
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US10/588,147 US7381671B2 (en) | 2004-02-06 | 2004-11-17 | Ferroelectric ceramic composition and applied ferroelectric element including same |
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 |
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US7381671B2 (en) | 2008-06-03 |
JPWO2005075378A1 (ja) | 2008-01-10 |
US20070161497A1 (en) | 2007-07-12 |
JP4407637B2 (ja) | 2010-02-03 |
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