WO2006129434A1 - 圧電素子 - Google Patents
圧電素子 Download PDFInfo
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- WO2006129434A1 WO2006129434A1 PCT/JP2006/308564 JP2006308564W WO2006129434A1 WO 2006129434 A1 WO2006129434 A1 WO 2006129434A1 JP 2006308564 W JP2006308564 W JP 2006308564W WO 2006129434 A1 WO2006129434 A1 WO 2006129434A1
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- 239000000919 ceramic Substances 0.000 claims abstract description 102
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- IXHBTMCLRNMKHZ-LBPRGKRZSA-N levobunolol Chemical compound O=C1CCCC2=C1C=CC=C2OC[C@@H](O)CNC(C)(C)C IXHBTMCLRNMKHZ-LBPRGKRZSA-N 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 abstract description 30
- 239000007772 electrode material Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 239000010953 base metal Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000000523 sample Substances 0.000 description 37
- 230000007423 decrease Effects 0.000 description 20
- 239000000843 powder Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 12
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000010344 co-firing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910003286 Ni-Mn Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 229910008651 TiZr Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C04B35/49—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
- C04B35/491—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
- C04B35/493—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 zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT containing also other lead compounds
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- H10N30/01—Manufacture or treatment
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Definitions
- the present invention relates to a piezoelectric element, and more particularly to a piezoelectric element such as a piezoelectric actuator having a piezoelectric ceramic whose main component is a mouth-bumite complex oxide and an electrode whose main component is Cu.
- Piezoelectric actuators utilizing the electrostrictive effect generated by applying voltage to piezoelectric ceramics are widely used for positioning of precision machine tools, printer heads of ink jet printers, and the like.
- a piezoelectric element used as such a piezoelectric actuator is generally a ceramic green sheet in which a conductive layer is formed by printing a conductive paste on a ceramic green sheet containing piezoelectric ceramic powder, and the conductive layer is formed. After a predetermined number of layers are laminated, the conductive layer and the ceramic green sheet are fired at the same time, thereby forming a piezoelectric ceramic body in which the piezoelectric ceramic and the internal electrode are co-sintered, and then both ends of the piezoelectric ceramic body. Fabricated by forming external electrodes on the surface.
- Patent Document 1 discloses a PZT (Pb (Ti, Zr) 2 O: lead zirconate titanate) type piezoelectric.
- a multilayer piezoelectric element in which ceramics and Cu, Ag, Ag—Pd isoelectric electrodes are alternately laminated.
- Patent Document 2 discloses that a PZT-based piezoelectric ceramic and an internal electrode are integrally fired, and the internal electrode has a base metal material such as Cu or Cu alloy having a rigidity of 160 GPa or less.
- An electromechanical transducer having a material as a main component is disclosed.
- Patent Document 3 discloses a piezoelectric structure element comprising a PZT piezoelectric ceramic and an electrode containing Cu, and the B site of the PZT piezoelectric ceramic has an action as an acceptor 2
- a piezoelectric structure element partially substituted with a valent metal cation or a pentavalent metal cation having an action as a donor is also disclosed.
- Patent Document 1 Japanese Patent Application Laid-Open No. 2002-255644
- Patent Document 2 Japanese Patent Laid-Open No. 2002-261343
- Patent Document 3 Special Table 2003-529917
- the piezoelectric element used as the piezoelectric actuator is used as a mechanical drive source, and therefore requires a large amount of displacement. Therefore, in order to obtain a large amount of displacement with a limited element size, the piezoelectric constant d needs to be large.
- the present invention has been made in view of such problems, and even when an inexpensive base metal material mainly composed of Cu is used as an electrode material, good piezoelectric characteristics can be obtained.
- An object of the present invention is to provide a piezoelectric element that can be used.
- the inventors of the present invention have intensively studied to achieve the above object.
- the third component is more donor than the stoichiometric composition.
- an electrode mainly composed of Cu which is a piezoelectric element in which the above-mentioned belovskite-type composite oxide contains Pb at the A site, Ti at the B site, Zr, 2 bivalent Akuseputa element comprising a metal element M ", and the donor element M V consisting of pentavalent metal element are contained, respectively, the Akuseputa element ⁇ occupied in ⁇ site" content of and the donor element M V the total molar ratio zeta, the molar amount of the Akuseputa element Micromax "and said donor element M V 1: (2 + b ), and ⁇ molar ratio in the site of Ti when the X, 0 05 ⁇ z ⁇ 0. 40, 0 ⁇ bz / 3 ⁇ 0. 035, 0. 345 ⁇ x ⁇ 0.
- the stoichiometric composition is tetravalent. Therefore, in the PZT-based piezoelectric ceramics, a divalent metal element (acceptor element M ") having an action as an acceptor and a pentavalent metal element (donor element M v ) having an action as a donor are ⁇ site elements, that is, If you replace the part of Ti and Zr, the blending molar ratio of the Akuseputa element M "as a donor element M v is 1 in the stoichiometric composition: 2.
- the average valence titer of the B site is opposite to that of Cu, so Cu is fixed to the B site as an acceptor. It dissolves and acts to reduce the average valence. [0020] Therefore, in the present invention, by setting the B-site average valence in advance to a donor excess composition greater than 4 valences, even if Cu in the electrode diffuses to the piezoelectric ceramic side and is dissolved in the B-site, It is possible to compensate for the decrease in the average valence due to Cu diffusion, thereby suppressing the decrease in the piezoelectric constant d.
- the piezoelectric element of the present invention is characterized in that the acceptor element M "includes at least one selected from the group of Ni, Zn, Mn, Co, Fe, Cr, and Cu. .
- the piezoelectric element of the present invention is characterized in that the electrode constitutes an internal electrode and has a laminated structure in which the internal electrode and the piezoelectric ceramic are alternately laminated.
- the molar ratio of the combination of the A site and the B site may be shifted as necessary, or the main component of the A site may be shifted. It was found that a piezoelectric element having a desired high, piezoelectric constant d, high, and Curie point Tc can be obtained even if a part of the component Pb is replaced with a predetermined metal element.
- the piezoelectric element of the present invention includes the piezoelectric ceramic force yarn and the synthetic Pb Me [(M "
- the present inventors have been able to increase the piezoelectric constant d by including Ni in the electrode, and this effect is achieved in all metal components. It became a component that it became prominent when the Ni content exceeded 10%.
- the piezoelectric element of the present invention is characterized in that the electrode contains Ni.
- the electrode has a Cu content of 70 ⁇ % or more and 90wt% or less in a metal component, and a Ni content of 10wt% or more and 30wt% or less ( However, it is characterized in that the conductive paste prepared to have a total Cu and Ni content of 100 wt% or less) is sintered.
- the present inventors examined a cross section near the electrode of a piezoelectric element having an electrode containing 10 wt% or more of Ni in a metal component. As a result, a Cu phase was formed in the internal electrode.
- NiO was present in at least one of the interface between the Cu phase and the piezoelectric ceramic and the vacancies formed in the Cu phase, and this state improved the piezoelectric constant d. It is thought that it contributed.
- the electrode is formed with a Cu phase consisting essentially of Cu, and an interface between the Cu phase and the piezoelectric ceramic and a void formed in the Cu phase.
- NiO is present in at least one of the two, and is characterized by! /
- the acceptor element M preferably contains at least Ni.
- Piezoelectric element made by simultaneously firing a piezoelectric ceramic mainly composed of an object and an electrode mainly composed of Cu, which contains Pb at the A site and Ti, Zr, divalent at the B site.
- Akuseputa element comprising a metal element M "(Ni, Zn, Mn, etc.), and a pentavalent metallic element donor element M v (Nb, Sb, Ta, etc.) are contained, respectively, the Akuse Puta occupying in B site element M "and the donor element M v z the total content molar ratio of the Akuseputa one element M" and the molar amount of the donor element M v 1: (2 + b ), and in Ti B site When the content of ktt is X, 0.
- the electrode forms an internal electrode, and the internal electrode and the piezoelectric ceramic are crossed. Since they have a laminated structure in which they are laminated together, a piezoelectric element having a large amount of displacement can be obtained effectively even with limited element dimensions.
- the electrode contains Ni, a higher piezoelectric constant can be obtained. This is presumably because the presence of Ni, which is more easily oxidized than Cu, in the electrode prevents the Cu from oxidizing and diffusing into the piezoelectric ceramic during firing. .
- the electrode has a Cu content of 70 wt% or more and 90 wt% or less in a metal component, and a Ni content of 10 wt% or more and 30 wt% or less (however, the total content of Cu and Ni) Since the conductive paste prepared to 100 wt% or less) is sintered, the improvement of the piezoelectric constant d can be exhibited more remarkably.
- the electrode is formed with a Cu phase substantially composed of Cu, and at least one of the interface between the Cu phase and the piezoelectric ceramic and the voids formed in the Cu phase.
- the piezoelectric constant is high, and a piezoelectric element can be obtained. This is presumably because the presence of the NiO phase suppressed CuO formed by oxidation during firing from diffusing into the piezoelectric ceramic.
- FIG. 2 is a cross-sectional view showing another embodiment of a piezoelectric element according to the present invention.
- FIG. 1 is a cross-sectional view showing an embodiment of a piezoelectric element according to the present invention.
- internal electrodes 12a and 12b mainly composed of Cu are built in the laminated sintered body 10, and external electrodes 20a and 20b are formed on end faces of the laminated sintered body 10. Yes.
- the laminated sintered body 10 has a laminated structure in which the internal electrodes 12a and 12b and the piezoelectric ceramics 11 are alternately laminated, and the internal electrode 12a can be electrically connected to the external electrode 20b.
- the internal electrode 12b is drawn to the other end face so that it can be electrically connected to the external electrode 20a.
- the internal electrodes 12a and 12b and the piezoelectric ceramic 11 are fired at the same time in the firing process of the manufacturing process, and thereby the laminated sintered body 10 is formed.
- M ′′ is an acceptor element made of a divalent metal element
- M v is a donor element made of a pentavalent metal element
- composition formula [I] is derived from a perovskite type complex acid compound represented by the general formula
- the acceptor element ⁇ is not particularly limited as long as it is a divalent metal element that acts as an acceptor for tetravalent Ti or Zr, but Ni, Zn, Co, Mn, Fe
- the donor element M IV is not particularly limited as long as it is a pentavalent metallic element having an action as a donor to tetravalent Ti or Zr, Nb, Sb, Ta, and V It can be used with preference.
- z is the force ⁇ that defines the molar ratio of the third component (M “, M v ) in the B site exceeds 0.40, causing a decrease in the Curie point Tc and a decrease in the critical temperature at which the piezoelectricity disappears. That is, the complex oxide of the third component (M “, M v ) and Pb has a characteristic that the Curie point Tc is lower than that of ordinary PZT, and in particular, z is 0.40. If the third component (M “, M v ) is excessively contained in excess of, the Curie point Tc is lowered, which is preferable.
- the content molar ratio z of the third component (M ", M V ) in the B site is set to 0.05 ⁇ z ⁇ 0.40! [0059] (2) bz / 3
- bzZ3 is the force that determines the content of the donor element M v in the B site.
- the molar ratio of the third component (M ", M v ) becomes the stoichiometric composition or excess acceptor.
- Piezoelectric constant d may be reduced, that is, if an electrode composed mainly of Cu and a piezoelectric ceramic are fired at the same time, a part of Cu that constitutes the electrode is oxidized during the firing process to become CuO.
- the firing temperature needs to be about 1000 ° C or less, but bzZ3 is 0.3. If it exceeds 1, the firing temperature exceeds 1000 ° C., and it becomes difficult to obtain the internal electrodes 12a and 12b by simultaneous firing.
- the bzZ3 defining the content of the donor element M v in B site as 0 ⁇ bz / 3 ⁇ 0. 35! /, Ru.
- PZT-based piezoelectric ceramics have a high solid solution composition near the MPB (phase transition boundary). I Piezoelectric constant d can be obtained.
- the content molar ratio z of the third component (M ", M v ) in the B site is set to 0.05 ⁇ ⁇ ⁇ 0.40.
- the Ti molar ratio X in the site is less than 0.345 or more than 0.480, the solid solution composition is greatly separated from the MPB, leading to a decrease in the piezoelectric constant d.
- the Ti molar ratio X in the B site is set to 0.345 ⁇ x ⁇ 0.480.
- the piezoelectric ceramic 11 represented by the composition formula [I] is blended so as to satisfy the formulas (1) to (3), Even if the internal electrodes 12a and 12b are mainly composed of Cu, the piezoelectric ceramic 11 and the internal electrodes 12a and 12b can be fired simultaneously. A piezoelectric element can be obtained that can suppress the deterioration of the piezoelectric characteristics due to the diffusion of Cu.
- the piezoelectric ceramic 11 is represented by the composition formula [II].
- alkaline earth metals such as Ca, Ba and Sr, rare earth metals such as Sc, Y, La and Nd, or Bi can be preferably used.
- ⁇ is a force that defines the molar ratio of the A site and the B site, a. When it is less than 0.965, it is too far from the stoichiometric composition and the sinterability decreases, and the firing temperature is about 1000 ° C. It cannot be bonded, and it is difficult to obtain the internal electrodes 12a and 12b mainly composed of Cu by simultaneous firing.
- the self-monolithic ktt ⁇ is set to 0.965 ⁇ ⁇ 1. Necessary power of 020 S.
- a is the force that determines the substitution molar ratio in the A site.
- a exceeds 0.05, the sinterability decreases and the piezoelectric ceramic cannot be sintered at a firing temperature of about 1 000 ° C.
- the partial electrodes 12a and 12b cannot be obtained by simultaneous firing.
- substitution molar ratio a in the A site needs to be 0 ⁇ a ⁇ 0.05.
- substitution molar ratio a increases, the piezoelectric constant d increases, while the one-point Tc decreases, so that the desired piezoelectric constant and the Curie point Tc depend on the substitution element Me described above. It is preferable to appropriately set the substitution molar ratio a within the range of 0 ⁇ a ⁇ 0.05 so that it can be obtained.
- the internal electrode is premised on that Cu is a main component, but it is preferable that Ni be contained as the remaining component. By including Ni, a piezoelectric element having a large piezoelectric constant d can be obtained.
- the constituent elements of the piezoelectric ceramic 11 such as Pb, Zr and Ti are acid.
- the electrode material Cu is fired under an oxygen partial pressure that does not oxidize, but the difference in equilibrium oxygen partial pressure of the acid-reduction reaction between Pb and Cu is so small that Cu is inevitable. It will be oxidized.
- Ni in the conductive paste to be the internal electrode in advance, it is easier to oxidize than Cu! /, Ni is oxidized and Cu oxidation is suppressed, and CuO is moved to the piezoelectric ceramic side. It is presumed that the deterioration of the characteristics of the piezoelectric element due to the diffusion of is suppressed.
- the internal electrodes 12a and 12b are formed with a Cu phase substantially consisting of Cu and at the interface between the Cu phase and the piezoelectric ceramic 11 and in the Cu phase.
- NiO is present in at least one of the vacancies, and it is possible to more effectively suppress the diffusion of CuO formed by acidification during firing to the piezoelectric ceramic 11 side.
- the Cu content in the metal component is 70 wt% or more and 90 wt% or less, and the Ni content is 10 wt% or more 3 ( ⁇ % or less).
- the Cu content is 70wt% or more and 85wt% or less, and the Ni content force is Sl5wt% or more and 30wt% or less (however, the total content of Cu and Ni is 100wt% or less) Desirable.
- a multilayer piezoelectric element having a multilayer structure is illustrated as a piezoelectric element.
- a single plate in which electrodes 32a and 32b are formed on both main surfaces of the piezoelectric ceramic 31 of the present invention is also applicable to the type of piezoelectric element.
- Pb O, TiO, ZrO, NiO, and Nb O powders were prepared as ceramic raw materials.
- the calcined powder and a binder are mixed with pure water to produce a ceramic slurry.
- a ceramic green sheet having a thickness of 60 m was prepared by a doctor blade method.
- the laminate was subjected to a binder removal treatment at a temperature of 500 ° C, and then subjected to a firing treatment at a temperature of 1000 ° C for 5 hours in a nitrogen atmosphere having an oxygen concentration of 1 to 2ppm. Get It was.
- this ceramic sintered body is cut into dimensions of 7 mm in length, 7 mm in width, and 6 mm in thickness to produce a laminated sintered body, and conductive paste containing Ag powder is applied to both ends of the ceramic body.
- a baking treatment was performed at a temperature of 780 ° C to form an external electrode, and then a polarization treatment was performed by applying an electric field strength of 3 kVZmm in oil at a temperature of 80 ° C. ⁇ 35 piezoelectric elements were obtained.
- a triangular wave with a frequency of 0.1 Hz is applied to the piezoelectric elements of sample numbers 1 to 35 so that the electric field strength varies in the range of 0 to 2 kVZmm, and the thickness distortion amount is measured with the inductive probe and the differential transformer. And measured by. Then, the measured thickness strain is divided by the electric field strength to obtain a piezoelectric constant d
- Table 1 shows the component composition, piezoelectric constant d, and Curie point Tc for sample numbers 1-35.
- Sample Nos. 13, 19, and 25 have a bz / 3 force of 0 and a piezoelectric constant d force of S460 to 535 pm / V.
- Sample No. 35 has an X-force of 0.3400 and is less than 0.345, so the piezoelectric constant d-force is as low as 05pmZV. That is, with sample numbers 30 and 35
- sample numbers 2-6, 9-12, 15-18, 21-24, and 31-34 have z, bz / 3, and x force 0.05.z ⁇ 0.440. Since 0 ⁇ bz / 3 ⁇ 0.035 and 0.345 ⁇ x ⁇ 0.480 are both within the scope of the present invention, a piezoelectric constant d of 550 pmZV or more
- Sample No. 41 has an ⁇ force of 030, 1. Since it exceeds 020, piezoelectric constant d force 410p
- Sample No. 47 had a of 0.960 and less than 0.965, resulting in a decrease in sinterability. Under the above firing conditions (nitrogen atmosphere, firing temperature 1000 ° C), the internal electrode and piezoelectric The ceramics could not be fired at the same time, and the desired sintered body could not be obtained.
- ⁇ is set to 1. 000, z is set to 0.2, bz / 3 is set to 0.010, x is set to 0.4225, and a part of Pb in the powerful A side is replaced with the metal element Me. Calcination powders of sample numbers 51 to 58 were obtained.
- Table 3 shows the component composition, piezoelectric constant d, and Curie point Tc of sample numbers 51 to 58.
- Sample No. 53 had a of 0.075 and exceeded 0.05, which caused a decrease in sinterability. Under the above firing conditions (nitrogen atmosphere, firing temperature 1000 ° C), The piezoelectric ceramic could not be fired at the same time, and the desired sintered body could not be obtained.
- a is 0.05 or less, ⁇ is 1. 000, ⁇ is 0.2, bz / 3 force ⁇ ). 010, X force ⁇ 0.44225
- the piezoelectric constant d force is as high as 00 to 805 pmZV, and the Curie point Tc is also as high as 240 to 270 ° C.
- Table 4 shows the component composition, piezoelectric constant d, and Curie point Tc of sample numbers 61 to 65.
- acceptor element M divalent transition metals such as Co, Fe, Cr, and Cu having properties similar to Ni, Zn, or Mn are also considered to be useful, and as the donor element Mv Pentavalent transition metals such as V, which have similar properties to Nb, Sb, and Ta, are also considered useful.
- the acceptor element M ′′ it was also found that the piezoelectric elements d of the sample numbers 62 to 65 containing Ni were higher than the sample number 61 not containing Ni, and the piezoelectric constant d could be obtained.
- a conductive paste was prepared so that the mixing ratio of Cu powder and Ni powder was as shown in Table 5 by weight.
- Ni which is easier to oxidize than Cu, exceeds 50 wt% in the metal component of the conductive paste, exceeding 30 wt%. For this reason, most Ni is oxidized during firing. Therefore, it was found that the metal component in the internal electrodes 12a and 12b became too small, and the coverage of the internal electrodes 12a and 12b decreased.
- the piezoelectric constant d can be further improved by increasing the Ni content.
- FIG. 3 is a cross-sectional view schematically showing a cross section near the internal electrode of sample number 72
- FIG. 4 is a cross-sectional view schematically showing a cross section near the internal electrode of sample number 74.
- the internal electrode 44 has a CuO phase 43 formed around an alloy or mixture 42 of Cu and Ni. Observed.
- reference numeral 41 denotes a piezoelectric ceramic.
- NiO phase 47 is distributed in a large amount at the interface between the Cu phase 46 and the piezoelectric ceramic 41 as follows. That is, since Ni is included in the composition of the piezoelectric ceramic 41, NiO is prevented from excessively diffusing into the piezoelectric ceramic 41, and as a result, it cannot be fully diffused into the piezoelectric ceramic 41. It is thought that strong NiO was distributed at the interface between Cu phase 46 and piezoelectric ceramics 41.
- the vacancy 48 is a force that is thought to be generated due to a decrease in the coverage of the Cu phase 46. In this case, it was also confirmed that the vacancy 48 was filled with the NiO phase 47 as described above. .
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Abstract
Description
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JP2007518880A JP4873327B2 (ja) | 2005-06-03 | 2006-04-24 | 圧電素子 |
EP20060732274 EP1887638B1 (en) | 2005-06-03 | 2006-04-24 | Piezoelectric element |
CN2006800197070A CN101189743B (zh) | 2005-06-03 | 2006-04-24 | 压电元件 |
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JP4873327B2 (ja) | 2012-02-08 |
CN101189743A (zh) | 2008-05-28 |
CN101189743B (zh) | 2011-04-13 |
EP1887638A4 (en) | 2011-03-02 |
JPWO2006129434A1 (ja) | 2008-12-25 |
US7605522B2 (en) | 2009-10-20 |
US20080074004A1 (en) | 2008-03-27 |
EP1887638B1 (en) | 2013-06-26 |
EP1887638A1 (en) | 2008-02-13 |
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