CN112689908A - Piezoelectric laminated element - Google Patents
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- 239000000919 ceramic Substances 0.000 claims abstract description 80
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000010287 polarization Effects 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 230000014509 gene expression Effects 0.000 claims abstract description 8
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 5
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims abstract description 5
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims abstract description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 5
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 description 14
- 230000007547 defect Effects 0.000 description 9
- 238000010304 firing Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000010953 base metal Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- JXDXDSKXFRTAPA-UHFFFAOYSA-N calcium;barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[Ca+2].[Ti+4].[Ba+2] JXDXDSKXFRTAPA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- 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
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- 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
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- 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
- H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
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- 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
- H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure
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Abstract
A piezoelectric laminated element comprising a plurality of piezoelectric ceramic layers, internal electrodes formed between the piezoelectric ceramic layers, and external electrodes electrically connected to the internal electrodes, wherein the piezoelectric ceramic layers are composed ofThe composition formula is shown in the specification, { Ba1‑xCaxO}mTiO2+αRe2O3+ beta MgO + gamma MnO [ where, Re2O3Is from Y2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Yb2O3And La2O3Alpha, beta and gamma represent molar ratios and satisfy the relational expressions (1) to (5)]And { Ba ] with respect to the piezoelectric ceramic layer1‑xCaxO}TiO2The main component of 100 weight parts in the raw material contains SiO as accessory component of 0.2-0.8 weight parts2The piezoelectric ceramic layer has a residual polarization in a certain direction, and the internal electrode includes nickel, a nickel alloy, copper, or a copper alloy.
Description
Technical Field
The present invention relates to a piezoelectric laminated element.
Background
In recent years, there has been an increasing demand for piezoelectric laminated elements such as piezoelectric actuators that can obtain a large amount of displacement even with a small voltage.
Conventionally, PZT-based piezoelectric ceramics containing Pb have been used as piezoelectric ceramics because of their high piezoelectric characteristics, but in recent years, piezoelectric ceramics containing no Pb have been demanded because of the growing awareness of environmental protection. As a piezoelectric ceramic containing no Pb, BaTiO used for a multilayer capacitor is known3Piezoelectric ceramics of the kind.
BaTiO3Since piezoelectric characteristics of piezoelectric ceramics are significantly lower than those of PZT piezoelectric ceramics, a laminated structure is required for use in a piezoelectric actuator.
PILE-PISTON INTERNAL ELECTRODE AND BATiO3A multilayer capacitor is co-fired (patent document 1). However, because of its low piezoelectric characteristicsThe possibility of being a piezoelectric actuator has not been studied so far.
Prior art documents
Patent document
Patent document 1: japanese patent laid-open publication No. 2000-58378
Disclosure of Invention
Problems to be solved by the invention
In order to use the element as a piezoelectric actuator, it is necessary to perform polarization treatment in which a high electric field is applied for a certain period of time to evaluate the piezoelectric characteristics, but in practice, it has been found that the piezoelectric element is manufactured in a trial manner and polarized in the same composition as in the best mode sample 117 of patent document 1, and the piezoelectric characteristics are evaluated. Further, since the relative dielectric constant is very high as compared with the piezoelectric characteristics, the load on the actuator is high, and it is clear that the piezoelectric actuator cannot be used.
In addition, as the internal electrode, noble metals such as Ag and Pd are sometimes used, but if base metals such as Ni can be used, the raw material cost can be greatly reduced, which is preferable. In order to use a base metal such as Ni, it is necessary to perform co-firing with a base metal such as Ni by firing in a reducing atmosphere in which the base metal such as Ni is not oxidized in the firing step.
Therefore, a composition capable of being fired in a reducing atmosphere is required as a composition of a piezoelectric ceramic in the case of using a base metal such as Ni as an internal electrode.
The present invention has been made to solve these problems, and an object of the present invention is to provide a piezoelectric laminated element which has high piezoelectric characteristics, can be co-fired with a base metal such as Ni, has high reliability, and is suitable for a piezoelectric actuator.
Means for solving the problems
The piezoelectric laminated element of the present invention is a piezoelectric laminated element including a plurality of piezoelectric ceramic layers, internal electrodes formed between the piezoelectric ceramic layers, and external electrodes electrically connected to the internal electrodes,
the piezoelectric ceramic layer is represented by the following composition formula,
{Ba1-xCaxO}mTiO2+αRe2O3+βMgO+γMnO
[ wherein, Re2O3Is from Y2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Yb2O3And La2O3Alpha, beta and gamma represent molar ratios and satisfy the following relational expressions (1) to (5).
0.0010≤α≤(-65.32m+67.70)/100 (1)
0.0004≤β≤(-28.74m+29.79)/100 (2)
Gamma is not less than 0.0002 and not more than (-13.06m +13.54)/100[ m is not more than 1.006 ]
Gamma is more than or equal to 0.0002 and less than or equal to 0.004 when m is more than 1.006 ] (3)
0.995≤m≤1.011 (4)
0.01≤x≤0.25 (5)]
And { Ba ] corresponding to the ceramic layer for the piezoelectric body1-xCaxO}TiO2The main component of 100 weight parts in the raw material contains SiO as accessory component of 0.2-0.8 weight parts2，
The piezoelectric ceramic layer has residual polarization in a certain direction,
the internal electrode includes nickel, a nickel alloy, copper, or a copper alloy.
Another aspect of the piezoelectric multilayer element of the present invention is a piezoelectric multilayer element including a plurality of piezoelectric ceramic layers, internal electrodes formed between the piezoelectric ceramic layers, and external electrodes electrically connected to the internal electrodes,
the piezoelectric ceramic layer contains 0.2 to 0.8 parts by weight of SiO as a subcomponent per 100 parts by weight of a main component containing an oxide containing Ba, Ca, Ti, Mg, Mn, and Re (Re is at least one selected from Y, Gd, Tb, Dy, Ho, Er, Yb, and La)2，
Wherein the oxide as the main component satisfies the following relational expressions (1) to (5) when the total content of Ba and Ca is m moles, the content of Re is α moles, the content of Mg is β moles, and the content of Mn is γ moles with respect to 1 mole of Ti contained in the oxide,
0.0010≤α≤(-65.32m+67.70)/100 (1)
0.0004≤β≤(-28.74m+29.79)/100 (2)
gamma is not less than 0.0002 and not more than (-13.06m +13.54)/100[ m is not more than 1.006 ]
Gamma is more than or equal to 0.0002 and less than or equal to 0.004 when m is more than 1.006 ] (3)
0.995≤m≤1.011 (4)
0.01≤x≤0.25 (5)
And the piezoelectric ceramic layer has residual polarization in a certain direction,
the internal electrode includes nickel, a nickel alloy, copper, or a copper alloy.
Effects of the invention
According to the present invention, a piezoelectric multilayer element having high piezoelectric characteristics, capable of being co-fired with a base metal such as Ni, and having high reliability, and suitable for a piezoelectric actuator can be provided.
Drawings
Fig. 1 is a cross-sectional view schematically showing an example of the structure of a piezoelectric laminated element of the present invention.
Fig. 2 is a cross-sectional view schematically showing another example of the structure of the piezoelectric laminated element of the present invention.
Detailed Description
The piezoelectric multilayer element of the present invention will be described below.
However, the present invention is not limited to the following configuration, and can be applied with appropriate modifications within a scope not changing the gist of the present invention. In addition, the present invention is also directed to a combination of two or more of the preferred structures described below.
In the piezoelectric laminated element of the present invention, the ceramic that is the main component constituting the piezoelectric ceramic layer is (Ba, Ca) TiO3As a mother composition, and the A site (Ba, Ca content)/B site (T)The ratio of i) is specified to be within a certain range. The blending amount of the additive to be added to the base composition is set to a certain range. In addition, SiO as a subcomponent for securing reliability in firing in a reducing atmosphere2The amount of the additive (c) is specified to be within a certain range.
By satisfying these requirements, it is possible to satisfy high piezoelectric characteristics and a low relative dielectric constant required for a piezoelectric multilayer element such as a piezoelectric actuator.
Fig. 1 is a cross-sectional view schematically showing an example of the structure of a piezoelectric laminated element of the present invention.
The structure of the piezoelectric multilayer element of the present invention will be described below with reference to fig. 1.
The piezoelectric laminated element 1 shown in fig. 1 includes a laminated body 10. The laminate 10 has a structure in which piezoelectric ceramic layers 20a, 20b, 20c, 20d, 20e, and 20f and internal electrodes 22a, 21a, 22b, 21b, and 22c are alternately laminated.
The laminate 10 has a rectangular parallelepiped shape or a substantially rectangular parallelepiped shape, and has a 1 st main surface 11 and a 2 nd main surface 12 that face each other in a lamination direction (vertical direction in fig. 1), a 1 st end surface 13 and a 2 nd end surface 14 that face each other in a longitudinal direction (horizontal direction in fig. 1) orthogonal to the lamination direction, and a 1 st side surface and a 2 nd side surface (not shown in fig. 1) that face each other in a width direction (front-rear direction of the paper surface in fig. 1) orthogonal to the lamination direction and the longitudinal direction.
The internal electrodes 22a, 21a, 22b, 21b, 22c contain nickel, nickel alloy, copper, or copper alloy, and are co-fired with the piezoelectric ceramic layers 20a, 20b, 20c, 20d, 20e, and 20 f.
The internal electrode is preferably nickel or a nickel alloy.
The piezoelectric multilayer element 1 shown in fig. 1 further includes an external electrode 31 provided on the 1 st end face 13 of the multilayer body 10 and an external electrode 32 provided on the 2 nd end face 14 of the multilayer body 10. The external electrodes 31 and 32 preferably include a conductive material such as Ni — Cr alloy (Nichrome) or Ag.
In addition, electrodes may be provided on the front and back surfaces of the laminate in order to increase the number of driving layers. In fig. 2, a piezoelectric laminated element 2 is shown in which electrodes (external electrodes 31) are provided on both the front and back surfaces of the laminated body.
Piezoelectric ceramic layers 20a, 20b, 20c, 20d, 20e and 20f to convert (Ba, Ca) TiO into (Ba, Ca) TiO3The ceramic as the main component.
The ceramic as the main component is
{Ba1-xCaxO}mTiO2+αRe2O3+βMgO+γMnO
[ wherein, Re2O3Is from Y2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Yb2O3And La2O3Alpha, beta and gamma represent molar ratios and satisfy the following relational expressions (1) to (5).
0.0010≤α≤(-65.32m+67.70)/100 (1)
0.0004≤β≤(-28.74m+29.79)/100 (2)
Gamma is not less than 0.0002 and not more than (-13.06m +13.54)/100[ m is not more than 1.006 ]
Gamma is more than or equal to 0.0002 and less than or equal to 0.004 when m is more than 1.006 ] (3)
0.995≤m≤1.011 (4)
0.01≤x≤0.25 (5)]。
In the present specification, the term "main component" means a component having the largest existing proportion (mol%), and preferably means a component having an existing proportion exceeding 50 mol%.
(Ba, Ca) TiO contained in the ceramics as the main component defined by the formulas (1), (2) and (3)3The contents of Re, Mg and Mn of other additives.
The polarization defect rate is reduced by satisfying alpha, beta, and gamma of 0.0010. ltoreq. alpha, beta of 0.0004. ltoreq. beta, and gamma of 0.0002. ltoreq. respectively.
When α, β and γ satisfy α ≦ (-65.32m +67.70)/100, β ≦ (-28.74m +29.79)/100, γ ≦ 13.06m +13.54)/100[ m ≦ 1.006 ] or γ ≦ 0.004[ m > 1.006 ], respectively, it becomes easy to promote particle growth and exhibit piezoelectric characteristics.
In the region of 0.0010. ltoreq. alpha. ≦ (-65.32m +67.70)/100, 0.0004. ltoreq. beta. ≦ 28.74m +29.79)/100, 0.0002. ltoreq. gamma. ≦ 13.06m +13.54)/100[ m.ltoreq.1.006 ] or 0.0002. ltoreq. gamma. ≦ 0.004[ m > 1.006 ] satisfying the above-mentioned formulae (1) to (3), it is preferable that the value of m in the ceramic as the main component is 1.011, since the value of d (piezoelectric constant) becomes high.
In addition, in the region satisfying 0.0010. ltoreq. α.ltoreq (-65.32m +67.70)/100, 0.0004. ltoreq. β.ltoreq (-28.74m +29.79)/100, 0.0002. ltoreq. γ. ltoreq (-13.06m +13.54)/100[ m.ltoreq.1.006 ], or 0.0002. ltoreq. γ. ltoreq.0.004 [ m > 1.006 ], the value of m in the ceramic as the main component is preferably 0.995. ltoreq. m, since the polarization defect rate is lowered.
As described above, satisfying expressions (1), (2), (3), and (4) simultaneously lowers the polarization defect rate and increases the d value, and thus can satisfy the performance required for the piezoelectric multilayer element.
In addition, with respect to the formula (5), if x is 0.01. ltoreq. x.ltoreq.0.25, the same effect can be exerted.
The piezoelectric ceramic layer contains 0.2 to 0.8 parts by weight of SiO as a subcomponent with respect to 100 parts by weight of the main component2。
If SiO is used as a subcomponent2When the amount of (b) is 0.2 parts by weight or more, firing in a reducing atmosphere firing can be suitably performed.
If SiO is used as a subcomponent2When the amount of (B) is 0.8 parts by weight or less, piezoelectric properties can be exhibited.
In addition, Li may be contained as another subcomponent2O-(Si、Ti)O2MO (wherein MO is selected from Al)2O3And ZrO2At least one kind selected from) oxide of SiO2-TiO2Oxides of the XO type (XO is at least one selected from among BaO, CaO, SrO, MgO, ZnO and MnO).
In the piezoelectric multilayer element of the present invention, the average particle diameter of the ceramic contained in the piezoelectric ceramic layer is preferably 0.6 μm or more and 3.7 μm or less.
In order to be used as a piezoelectric multilayer element, it is preferable that the ceramics are grain-grown so as to have an average grain diameter within the above range.
The particle diameter of the ceramic can be determined by observing the ceramic contained in the piezoelectric ceramic layer with a scanning electron microscope and using an intercept method.
In the piezoelectric multilayer element of the present invention, the piezoelectric ceramic layers preferably have an average thickness of 5 μm or more and 60 μm or less per layer.
Unlike the ceramic layers used for the multilayer capacitor, the thickness of the ceramic layers is preferably set to a certain extent as described above in order to be used for the piezoelectric multilayer element.
In the piezoelectric multilayer element of the present invention, the residual polarization value of the piezoelectric ceramic layer is preferably 3.0 μ C/cm2The above. If the residual polarization value is 3.0 μ C/cm2The above can be preferably used as a piezoelectric multilayer element.
The residual polarization value can be determined by a ferroelectric tester.
In another embodiment of the piezoelectric multilayer element according to the present invention, the ceramic constituting the main component of the piezoelectric ceramic layer may be defined as follows.
In this case, the piezoelectric multilayer element of the present invention is a piezoelectric multilayer element including a plurality of piezoelectric ceramic layers, internal electrodes formed between the piezoelectric ceramic layers, and external electrodes electrically connected to the internal electrodes,
the piezoelectric ceramic layer contains 0.2 to 0.8 parts by weight of SiO as a subcomponent per 100 parts by weight of a main component containing an oxide containing Ba, Ca, Ti, Mg, Mn, and Re (Re is at least one selected from Y, Gd, Tb, Dy, Ho, Er, Yb, and La)2，
Wherein the oxide as the main component satisfies the following relational expressions (1) to (5) when the total content of Ba and Ca is m moles, the content of Re is α moles, the content of Mg is β moles, and the content of Mn is γ moles with respect to 1 mole of Ti contained in the oxide,
0.0010≤α≤(-65.32m+67.70)/100 (1)
0.0004≤β≤(-28.74m+29.79)/100 (2)
gamma is not less than 0.0002 and not more than (-13.06m +13.54)/100[ m is not more than 1.006 ]
Gamma is more than or equal to 0.0002 and less than or equal to 0.004 when m is more than 1.006 ] (3)
0.995≤m≤1.011 (4)
0.01≤x≤0.25 (5)
And the piezoelectric ceramic layer has residual polarization in a certain direction,
the internal electrode includes nickel, a nickel alloy, copper, or a copper alloy.
The piezoelectric multilayer element of the present invention can be configured in the same manner as the piezoelectric multilayer element of the present invention described above, except that the ceramic constituting the main component of the piezoelectric ceramic layer is defined differently.
The piezoelectric multilayer element of the present invention is preferably manufactured by the following method.
First, as a ceramic raw material, a raw material powder produced by a solid phase method in which an oxide, a carbonate, or the like is reacted at a high temperature, or a raw material powder produced by a wet synthesis method such as an alkoxide method or a hydrothermal synthesis method is prepared. In addition to powders of oxides, carbonates, and the like, solutions of alkoxides, organic metals, and the like can be used as additives and the like.
Then, the prepared raw materials were weighed to a predetermined composition ratio and mixed, and then an organic binder was added to form a slurry, which was molded into a sheet shape to obtain a green sheet. Next, an internal electrode containing nickel, a nickel alloy, copper, or a copper alloy is formed on one surface of the green sheet. The internal electrodes may be formed by screen printing or the like, or may be formed by vapor deposition or plating.
Then, green sheets having internal electrodes were stacked by a required number of sheets, and sandwiched between green sheets having no internal electrodes and pressure bonded to obtain a laminate. Then, the laminate is fired at a predetermined temperature (for example, 1200 ℃ to 1300 ℃) in a reducing atmosphere to obtain a ceramic laminate.
Then, a pair of external electrodes are formed on both end surfaces of the ceramic laminate so as to be electrically connected to the internal electrodes. In general, the external electrodes are formed by applying a metal powder paste as a material to the ceramic laminate obtained by firing and firing the paste, but may be formed simultaneously with the ceramic laminate by applying the paste before firing. Further, the external electrode can also be formed by sputtering.
Then, a given polarization treatment is performed. Thus, a piezoelectric multilayer element can be obtained.
Examples
Hereinafter, embodiments of the piezoelectric laminated element of the present invention are shown to be more specifically disclosed. The present invention is not limited to these examples.
First, TiO was prepared as a starting material2、BaCO3And CaCO3. After the mixing and pulverization, barium calcium titanate was synthesized by heating at a temperature of 1000 ℃ or higher. The particle diameter of the raw material was observed by a scanning electron microscope, and the average particle diameter was 0.5. mu.m. Further, SiO was prepared as an accessory component2And (3) powder.
Next, BaCO for adjusting the (Ba, Ca)/Ti molar ratio m of barium calcium titanate was prepared3Or TiO2And Dy with a purity of 99% or more2O3MgO, and MnO. For these raw material powders and the above SiO as a subcomponent2The powder was weighed. In addition, SiO2As the amount of (A) to be added, based on 100 parts by weight of the main component [ { Ba ]0.87Ca0.13O}mTiO2+αDy2O3+βMgO+γMnO]To 0.4 parts by weight. This time though as Re2O3And Dy is used2O3But even if Y is used2O3、Gd2O3、Tb2O3、Ho2O3、Er2O3、Yb2O3And La2O3The same effect can be obtained by selecting one of them.
In the samples of each sample number, raw material powders were weighed for each composition. The compositions of the samples of the respective sample numbers are shown in table 1.
In addition, SiO as a subcomponent was used in some of the samples2The amount of powder added varies.
Then, a polyvinyl butyral based binder and an organic solvent such as ethanol were added to the weighed materials, and wet mixing was performed by a ball mill to prepare a ceramic slurry. This ceramic slurry was subjected to sheet molding by a doctor blade method to obtain a rectangular green sheet having a thickness of 30.0 μm. Next, a conductive paste mainly containing Ni was printed on the ceramic green sheet to form a conductive paste layer for forming the internal electrodes.
Then, the ceramic green sheets on which the conductive paste layers were formed were stacked in a plurality of layers so that the drawn sides of the conductive paste layers were staggered, thereby obtaining a laminate. The laminate was heated to a temperature of 300 ℃ in an atmospheric atmosphere to burn the binder, and then oxygen partial pressure was set to 10-9Is more than or equal to 10 MPa-12Containing H under MPa2-N2-H2Firing the ceramic sintered body in a reducing atmosphere of O gas at a temperature of 1200 ℃ to 1300 ℃ for two hours to obtain a ceramic sintered body.
After sintering, in order to form electrodes on the front, back, and side surfaces of the sintered body, only the connection surface is cut to expose the electrodes, and then a conductive film mainly made of Ag is formed by sputtering, and the top and bottom surfaces are electrically connected to the side surfaces on one side, respectively.
The external dimensions of the piezoelectric laminated element thus obtained are width: 3.0mm, length: 13.0mm, thickness: 0.3mm, and the thickness of the piezoelectric ceramic layer interposed between the internal electrodes was 25 μm. The total number of effective piezoelectric ceramic layers was 11, and the area of the counter electrode per layer was 39 × 10-6m2。
The obtained piezoelectric multilayer element was polarized with a DC voltage of 2 kV/mm. In the polarization step, the samples having polarization current values of 40 μ a or more were regarded as polarization defects, and the occurrence rate of the polarization defects (polarization defect rate (%)) was determined for a plurality of samples with n being 10.
Next, the particle diameter of the ceramic included in the piezoelectric ceramic layer was observed with a scanning electron microscope on the surface of the obtained piezoelectric laminated element, and was determined by the intercept method. In the samples within the range of the present invention, the growth of particles was promoted and the particle diameter was 0.6 μm or more and 3.7 μm or less.
Further, the electrical characteristics of these piezoelectric laminated elements were measured. The residual polarization Pr was determined by a hysteresis loop using a ferroelectric tester at a frequency of 1kHz and. + -. 2 kV/mm. The capacitance C was measured at a frequency of 1kHz and a voltage of 0.5V, and the relative dielectric constant ε was calculated from the capacitance CT 33. Electromechanical coupling coefficient k in the longitudinal direction31The measurement was performed by a resonance-antiresonance method using an impedance analyzer. The density ρ is obtained by the archimedes method. In addition, the piezoelectric d31Relative dielectric constant ε obtained from the aboveT 33Electromechanical coupling coefficient k31And the density ρ are obtained by calculation.
These results are summarized and shown in table 1.
[ Table 1]
In samples 10 to 29 within the range of the present invention, the polarization defect rate was 0%. In addition, residual polarization Pr and relative dielectric constant εT 33Electromechanical coupling coefficient k31、d31The value of the constant becomes a preferable value.
In the samples outside the range of the present invention, the samples having a high polarization defect rate are increased. In samples 4 and 5, the residual polarization Pr and the electromechanical coupling coefficient k could not be measured although the polarization defect rate was 0%31、d31A constant.
Description of the reference numerals
1. 2: a piezoelectric laminated element;
10: a laminate;
11: a 1 st main surface;
12: a 2 nd main surface;
13: 1 st end face;
14: a 2 nd end surface;
20a, 20b, 20c, 20d, 20e, 20 f: a piezoelectric ceramic layer;
21a, 21b, 22a, 22b, 22 c: an internal electrode;
31. 32: an external electrode.
Claims (6)
1. A piezoelectric laminated element including a plurality of piezoelectric ceramic layers, internal electrodes formed between the piezoelectric ceramic layers, and external electrodes electrically connected to the internal electrodes,
the piezoelectric ceramic layer is represented by the following composition formula,
{Ba1-xCaxO}mTiO2+αRe2O3+βMgO+γMnO
wherein, Re2O3Is from Y2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Yb2O3And La2O3Alpha, beta and gamma represent molar ratios and satisfy the following relational expressions (1) to (5),
0.0010≤α≤(-65.32m+67.70)/100 (1)
0.0004≤β≤(-28.74m+29.79)/100 (2)
when m is less than or equal to 1.006, gamma is less than or equal to 0.0002 and less than or equal to (-13.06m +13.54)/100
When m is greater than 1.006, gamma is not less than 0.0002 and not more than 0.004 (3)
0.995≤m≤1.011(4)
0.01≤x≤0.25(5)
And { Ba ] with respect to the piezoelectric ceramic layer1-xCaxO}TiO2The main component of 100 weight parts in the raw material contains SiO as accessory component of 0.2-0.8 weight parts2，
The piezoelectric ceramic layer has a residual polarization in a certain direction,
the internal electrode includes nickel, a nickel alloy, copper, or a copper alloy.
2. The piezoelectric laminated element according to claim 1,
the average particle diameter of the ceramic contained in the piezoelectric ceramic layer is 0.6 [ mu ] m or more and 3.7 [ mu ] m or less.
3. The piezoelectric laminated element according to claim 1 or 2,
the piezoelectric ceramic layers each have an average thickness of 5 to 60 [ mu ] m.
4. The piezoelectric laminated element according to any one of claims 1 to 3,
the internal electrode includes nickel or a nickel alloy.
5. The piezoelectric laminated element according to any one of claims 1 to 4,
the residual polarization value of the piezoelectric ceramic layer is 3.0 mu C/cm2The above.
6. A piezoelectric laminated element including a plurality of piezoelectric ceramic layers, internal electrodes formed between the piezoelectric ceramic layers, and external electrodes electrically connected to the internal electrodes,
the piezoelectric ceramic layer contains 0.2 to 0.8 parts by weight of SiO as a subcomponent with respect to 100 parts by weight of a main component containing an oxide containing Ba, Ca, Ti, Mg, Mn, and Re2Wherein Re is at least one selected from Y, Gd, Tb, Dy, Ho, Er, Yb and La,
wherein the oxide as the main component satisfies the following relational expressions (1) to (5) when the total content of Ba and Ca is m moles, the content of Re is α moles, the content of Mg is β moles, and the content of Mn is γ moles with respect to 1 mole of Ti contained in the oxide,
0.0010≤α≤(-65.32m+67.70)/100 (1)
0.0004≤β≤(-28.74m+29.79)/100 (2)
when m is less than or equal to 1.006, gamma is less than or equal to 0.0002 and less than or equal to (-13.06m +13.54)/100
When m is greater than 1.006, gamma is not less than 0.0002 and not more than 0.004 (3)
0.995≤m≤1.011 (4)
0.01≤x≤0.25 (5)
And the piezoelectric ceramic layer has residual polarization in a certain direction,
the internal electrode includes nickel, a nickel alloy, copper, or a copper alloy.
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| JP2018184574 | 2018-09-28 | ||
| JP2018-184574 | 2018-09-28 | ||
| PCT/JP2019/036324 WO2020066739A1 (en) | 2018-09-28 | 2019-09-17 | Laminated piezoelectric element |
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Citations (8)
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|---|---|---|---|---|
| JP2000058377A (en) * | 1998-08-11 | 2000-02-25 | Murata Mfg Co Ltd | Laminated ceramic capacitor |
| CN1810713A (en) * | 2004-08-30 | 2006-08-02 | Tdk株式会社 | Dielectric ceramic composition and electronic device |
| JP2006282483A (en) * | 2005-04-04 | 2006-10-19 | Tdk Corp | Electronic component, dielectric ceramic composition, and method for producing the same |
| CN101193836A (en) * | 2005-06-10 | 2008-06-04 | 株式会社村田制作所 | Dielectric ceramic and multilayer ceramic capacitor |
| JP2011238766A (en) * | 2010-05-10 | 2011-11-24 | Japan Science & Technology Agency | Dielectric structure and manufacturing method thereof |
| US20140002955A1 (en) * | 2010-10-20 | 2014-01-02 | Taiyo Yuden Co., Ltd. | Laminated ceramic capacitor |
| JP2016147798A (en) * | 2015-01-09 | 2016-08-18 | キヤノン株式会社 | Piezoelectric material, piezoelectric element and an apparatus using the same |
| US20170186537A1 (en) * | 2015-12-28 | 2017-06-29 | Samsung Electro-Mechanics Co., Ltd. | Dielectric composition and multilayer ceramic capacitor containing the same |
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2019
- 2019-09-17 CN CN201980059781.2A patent/CN112689908A/en not_active Withdrawn
- 2019-09-17 WO PCT/JP2019/036324 patent/WO2020066739A1/en active Application Filing
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000058377A (en) * | 1998-08-11 | 2000-02-25 | Murata Mfg Co Ltd | Laminated ceramic capacitor |
| CN1810713A (en) * | 2004-08-30 | 2006-08-02 | Tdk株式会社 | Dielectric ceramic composition and electronic device |
| JP2006282483A (en) * | 2005-04-04 | 2006-10-19 | Tdk Corp | Electronic component, dielectric ceramic composition, and method for producing the same |
| CN101193836A (en) * | 2005-06-10 | 2008-06-04 | 株式会社村田制作所 | Dielectric ceramic and multilayer ceramic capacitor |
| JP2011238766A (en) * | 2010-05-10 | 2011-11-24 | Japan Science & Technology Agency | Dielectric structure and manufacturing method thereof |
| US20140002955A1 (en) * | 2010-10-20 | 2014-01-02 | Taiyo Yuden Co., Ltd. | Laminated ceramic capacitor |
| JP2016147798A (en) * | 2015-01-09 | 2016-08-18 | キヤノン株式会社 | Piezoelectric material, piezoelectric element and an apparatus using the same |
| US20170186537A1 (en) * | 2015-12-28 | 2017-06-29 | Samsung Electro-Mechanics Co., Ltd. | Dielectric composition and multilayer ceramic capacitor containing the same |
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