CN101001818A - Piezoelectric ceramic composition and piezoelectric element - Google Patents
Piezoelectric ceramic composition and piezoelectric element Download PDFInfo
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- CN101001818A CN101001818A CN200580027005.2A CN200580027005A CN101001818A CN 101001818 A CN101001818 A CN 101001818A CN 200580027005 A CN200580027005 A CN 200580027005A CN 101001818 A CN101001818 A CN 101001818A
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Abstract
A piezoelectric ceramic composition comprising a main component of the general formula: {(1-n)(Ag<SUB>1-x</SUB>Li<SUB>x</SUB>)<SUB> m</SUB> (Nb<SUB>1-y</SUB>Ta<SUB>y</SUB>)O<SUB>3</SUB>-n(M1,M2)M3O<SUB>3</SUB>}<SUB/>or {(1-n)(Ag<SUB>1-x</SUB>Li<SUB>x</SUB>)<SUB> m</SUB> (Nb<SUB>1-y</SUB>Ta<SUB>y</SUB>)O<SUB>3</SUB>-nM4M5O<SUB>3</SUB>}, wherein x, y, z, m and n satisfy the relationships: 0.075<=x<0.40, 0<=y<0.2, 0.98<=m<=1.0 and 0.01<=n<=0.1. M1 is a trivalent metal element such as Bi; M2 is a monovalent metal element such as K, Na, Li or Ag; each of M3 and M5 is a tetravalent metal element such as Ti, Zr, Sn or Hf; and M4 is a bivalent metal element such as Ba, Sr, Ca or Mg. By virtue of this composition, there can be realized a non-lead piezoelectric ceramic composition of high reliability having a high specific inductive capacity and excelling in piezoelectric properties, such as electromechanical coupling factor K<SUB>33</SUB>and piezoelectric constant d<SUB>33</SUB>, and realized a piezoelectric element produced from the above piezoelectric ceramic composition.
Description
Technical field
The present invention relates to a kind of Piezoelecric ceramic compositions and piezoelectric element, the Piezoelecric ceramic compositions of the employed non-plumbous system of particularly various piezoelectric elements, and use this Piezoelecric ceramic compositions and the piezoelectric element of the piezoelectric vibrator made, piezoelectric actuator, piezoelectric filter, piezoelectric buzzer, piezoelectric sensor etc.
Background technology
As the former material of the piezoelectric element of piezoelectric vibrator etc., well-known have an O with Pb (Ti, Zr)
3(Pb-based lanthanumdoped zirconate titanates) and PbTiO
3(lead titanate) is the Piezoelecric ceramic compositions of principal constituent.
Yet,,, look forward to not containing the appearance of piezoelectric of the non-plumbous system of Pb composition in recent years so be not preferred on the environment because this Piezoelecric ceramic compositions contains the Pb composition.
Therefore up to now, proposed to contain the Piezoelecric ceramic compositions of following composition: by general expression (Ag
1-xLi
x) (Nb
1-yTa
y) O
3Expression consist of principal constituent, 0.075≤x＜0.40,0≤y＜0.20 is minor component (patent documentation 1) with at least a among Mn oxide compound and the Si oxide compound (5 weight fraction are following).
That is, piezoelectric element generally needs electricapparatus attachment coefficient K
33Very high, K
33Expression is by the exchange efficiency of the electric energy that applies between the electrode of piezoelectrics to mechanical energy, still, in above-mentioned patent documentation 1, has the Piezoelecric ceramic compositions of above-mentioned composition by use, can obtain can stand in the practicality electricapparatus attachment coefficient K
33It is the piezoelectric element more than 20%.
In addition, in patent documentation 2, disclose and contain, contain having of Nb and Ta stupalith uhligite (perovskite) structure, that use mainly as electrical condenser in the B position with two kinds of different, forms of the phases of difference and the composition that exists is respectively in the A position and contains Ag mutually separately.Specifically, be exactly open in described, use and form (Ag
1-yM
III y) ((Nb
1-xTa
x)
1-yM
IV y) O
3(wherein, M
IIIBe Bi or rare earth metal, M
IVBe In, Sc or Ga, 0.35≤x≤05 and 0≤y≤0.1), use and form (Ag
1-yM
III y) ((Nb
1-xTa
x)
1-yM
IV y) O
3(wherein, M
IIIBe Ba, Ca, Pb or Sr, M
IVBe Sn or Zr, 0.35≤x≤0.5 and 0≤y≤0.1).In addition, in patent documentation 1 this composition, demonstrate the such high-dielectric constant in ε＞300, demonstrate low dissipation loss, can access the little microwave device of TK ε.
Patent documentation 1: the spy opens the 2002-68836 communique
Patent documentation 2: special table 2004-507432 communique
, as piezoelectric element such as the above-mentioned electricapparatus attachment coefficient K that needs
33With piezoelectric constant d
33Greatly, but this piezoelectric element is assembled into as piezoelectric filter and piezoelectric vibrator when using in the electronic circuit, needs relative permittivity ε r (=ε/ε
0, ε: specific inductivity, ε
0: the specific inductivity of vacuum) moderately big.
That is, the piezoelectric element of piezoelectricity ripple device and piezoelectric vibrator etc. is assembled into when using in the electronic circuit, the impedance of piezoelectric element need be adjusted to prescribed value, but be used to determine that the principal element of impedance is the electrostatic capacitance of piezoelectric element.
So, because the electrostatic capacitance of piezoelectric element is directly proportional with relative permittivity,, reduce area even then make the piezoelectric element miniaturization if the relative permittivity ε r of piezoelectric uprises as well-known, also can be easy to the impedance that obtains to wish.
So when making the voltage component miniaturization,, then can obtain desired impedance easily, therefore need relative permittivity ε r moderately big if the relative permittivity ε r of piezoelectric is big.
Yet, in the Piezoelecric ceramic compositions of above-mentioned patent documentation 1, can only obtain relative permittivity ε r and be the low relative permittivity below 350, be difficult to obtain the such problem points of ideal impedance thereby exist.
And, in patent documentation 1, also have piezoelectric constant d
33Be lower than 50 situation generation, also have electricapparatus attachment coefficient K in addition
33Can not stably obtain the such problem points of high numerical value.
Though in patent documentation 2, disclose the big stupalith of relative permittivity ε r in addition,, thereby can't obtain sufficient relative permittivity ε r even greatly but still be lower than 600.And the stupalith of patent documentation 2 is the stupaliths that are used for microwave device, has electricapparatus attachment coefficient K
33With piezoelectric constant d
33Deng piezoelectric property can't obtain such problem points.
Summary of the invention
The present invention carries out in view of such problem points, and its purpose is to provide a kind of relative permittivity appropriateness big, and electricapparatus attachment coefficient K
33With piezoelectric constant d
33Deng good, reliability the is excellent Piezoelecric ceramic compositions of non-plumbous system of piezoelectric property and the piezoelectric element that uses this Piezoelecric ceramic compositions to make.
The present inventor is in order to reach above-mentioned purpose, with regard to perovskite composite oxide (the general expression ABO of non-plumbous system
3) obtain following discovery when studying with keen determination: will make Bi and K, Na, Li or Ag be solid-solubilized in the A position, and make the second composite oxides solid solution that Ti, Zr, Sn or Hf be solid-solubilized in the B position in by (Ag, Li) (Nb, Ta) O
3In the first represented composite oxides, and the mol ratio of modulating each composition, even be non-plumbous system thus, it is big also to access the relative permittivity appropriateness, electricapparatus attachment coefficient K
33With piezoelectric constant d
33Stablize the good Piezoelecric ceramic compositions of high piezoelectric property.
In addition, because the Bi in the A position solid solution of second composite oxides is the metallic element of 3 valencys, K, Na, Li or Ag are the metallic elements of 1 valency, in addition, at Ti, Zr, Sn, the Hf of the solid solution of B position is the metallic element of 4 valencys, therefore think these each valencys of use metallic element and when obtaining constituent, can both obtain same action effect.
The present invention is based on such discovery and carry out, Piezoelecric ceramic compositions of the present invention is characterized in that, contains by general expression { (1-n) (Ag
1-xLi
x)
m(Nb
1-yTa
y) O
3-n (M
1, M
2) M3O
3The principal constituent of (wherein, M1 represents the metallic element of 3 valencys, and M2 represents the metallic element of 1 valency, and M3 represents the metallic element of 4 valencys) expression, described x, y, m and n are respectively 0.075≤x＜0.40,0≤y＜0.2,0.98≤m≤1.0, and 0.01≤n≤0.1.
In addition, its feature of Piezoelecric ceramic compositions of the present invention in, described M1 is Bi, described M2 be among K, Na, Li and Ag, select more than at least a kind, described M3 be among Ti, Zr, Sn and Hf, select more than at least a kind.
In addition, the present inventor continues further with keen determination, and the result of research distinguishes as follows: as second composite oxides, even use the metallic element that makes divalent in the A position (for example among Ba, Sr, Ca and the Mg more than at least a kind) solid solution, when making the oxide compound of perovskite typed of metallic element (for example among Ti, Zr, Sn and the Hf more than at least a kind) solid solution of 4 valencys in the B position, also, can access big, the electricapparatus attachment coefficient K of relative permittivity appropriateness with above-mentioned same
33With piezoelectric constant d
33Stablize the good Piezoelecric ceramic compositions of high piezoelectric property.
That is, Piezoelecric ceramic compositions of the present invention is characterized in that, contains by general expression { (1-n) (Ag
1-xLi
x)
m(Nb
1-yTa
y) O
3-nM4M5O
3The principal constituent of (wherein, M4 represents the metallic element of divalent, and M5 represents the metallic element of 4 valencys) expression, described x, y, z, m and n are respectively 0.075≤x＜0.40,0≤y＜0.2,0.98≤m≤1.0, and 0.01≤n≤0.1.
In addition, piezoelectric ceramics of the present invention becomes thing, it is characterized in that, described M4 be among Ba, Sr, Ca and Mg, select more than at least a kind, M5 be among Ti, Zr, Sn and Hf, select more than at least a kind.
In addition, piezoelectric element of the present invention is characterized in that, is formed with outer electrode on the surface of the ceramic sintered bodies that is formed by above-mentioned Piezoelecric ceramic compositions.
In addition, piezoelectric element of the present invention is characterized in that, internal electrode is embedded in the described ceramic sintered bodies.
According to above-mentioned piezoelectrics ceramic composition, contain by general expression { (1-n) (Ag
1-xLi
x)
m(Nb
1-yTa
y) O
3-n (M
1, M
2) M3O
3(wherein, M1 represents the metallic element of 3 valencys, M2 represents the metallic element of 1 valency, M3 represents the metallic element of 4 valencys) expression principal constituent, described x, y, m and n are respectively 0.075≤x＜0.40,0≤y＜0.2,0.98≤m≤1.0, and 0.01≤n≤0.1, therefore can access that relative permittivity ε r is moderately big, electricapparatus attachment coefficient K
33With piezoelectric constant d
33Well, the Piezoelecric ceramic compositions of piezoelectric property excellence.
In addition, Piezoelecric ceramic compositions of the present invention, because described M1 is Bi, described M2 be among K, Na, Li and Ag, select more than at least a kind, described M3 be among Ti, Zr, Sn and Hf, select more than at least a kind, so can obtain the good Piezoelecric ceramic compositions of piezoelectric property, the high relative permittivity that it has more than 600 has the electricapparatus attachment coefficient K more than 25%
33With the piezoelectric constant d more than the 50pC/N
33, and can guarantee Curie temperature Tc more than 200 ℃.
In addition, even above-mentioned Piezoelecric ceramic compositions contains by general expression { (1-n) (Ag
1-xLi
x)
m(Nb
1-yTa
y) O
3-nM4M5O
3(wherein, M4 represents the metallic element of divalent, M5 represents the metallic element of 4 valencys) expression principal constituent, described x, y, z, m and n are respectively 0.075≤x＜0.40,0≤y＜0.2,0.98≤m≤1.0, and 0.01≤n≤0.1 o'clock, also, can access big, the electricapparatus attachment coefficient K of relative permittivity ε r appropriateness with above-mentioned the same
33With piezoelectric constant d
33Well, the Piezoelecric ceramic compositions of piezoelectric property excellence.
In addition, Piezoelecric ceramic compositions of the present invention, even described M4 be among Ba, Sr, Ca and Mg, select more than at least a kind, M5 be among Ti, Zr, Sn and Hf, select more than at least a kind the time, also equally can obtain the good Piezoelecric ceramic compositions of piezoelectric property with above-mentioned, the high relative permittivity that it has more than 600 has the electricapparatus attachment coefficient K more than 25%
33With the piezoelectric constant d more than the 50pC/N
33, and can guarantee Curie temperature Tc more than 200 ℃.
In addition, according to above-mentioned piezoelectric element, because be formed with outer electrode, so can access the various piezoelectric elements that piezoelectric property is good, reliability is excellent on the surface of the ceramic sintered bodies that forms by above-mentioned Piezoelecric ceramic compositions.
In addition, because internal electrode is embedded in the described ceramic sintered bodies, so can access the various piezoelectric elements that piezoelectric property is good, reliability is excellent equally with above-mentioned.
Description of drawings
Fig. 1 is the stereographic map of expression as an embodiment of the piezoelectric vibrator of piezoelectric element of the present invention.
Fig. 2 is the sectional view of the A-A of Fig. 1.
The explanation of symbol
1 piezoelectric ceramics (ceramic sintered bodies)
2 internal electrodes
3 outer electrodes
4 outer electrodes
Embodiment
Next describe embodiments of the present invention in detail.
The Piezoelecric ceramic compositions of first embodiment of the present invention is represented by general expression (A).
(1-n)(Ag
1-xLi
x)
m(Nb
1-yTa
y)O
3-n(M
1、M
2)M3O
3
…(A)
Here, mol ratio x, y, m and n satisfy following numerical expression (1) to (4).
0.075≤x＜0.40…(1)
0≤y＜0.2…(2)
0.98≤m≤1.0…(3)
0.01≤n≤0.1…(4)
That is, this Piezoelecric ceramic compositions is made up of the synthetics of 2 kinds of composite oxides with perovskite typed structure, makes second composite oxides (M1, M2) M3O
3Solid solution is in first composite oxides (Ag, Li) (Nb, the Ta) O as principal constituent
3In.M1 is made of the metallic element of 3 valencys in addition, and M2 is made of the metallic element of 1 valency, and M3 is made of the metallic element of 4 valencys, on chemical structure by charge compensation.But if reach degree no problem on the characteristic, the existence of M1 and M2 is than also departing from from 1: 1.
So this Piezoelecric ceramic compositions is modulated in the mode that general expression (A) satisfies numerical expression (1)～(4), therefore can access high, the electricapparatus attachment coefficient K of relative permittivity ε r appropriateness
33With piezoelectric constant d
33The Piezoelecric ceramic compositions that stably high piezoelectric property is good.
Specifically,, can use for example Bi, La, Nd, Sm, Gd, Y, Sc, especially preferably use Bi as the metallic element M1 of 3 valencys.In addition, metallic element M2 as 1 valency can use for example Li, Na, K, Ag etc., metallic element M3 as 4 valencys, can use Ti, Zr, Sn, Hf etc., by using these metallic elements M1～M3, can access the good Piezoelecric ceramic compositions of piezoelectric property, it has relative permittivity ε r is high relative permittivity more than 600, electricapparatus attachment coefficient K
33Be more than 25%, and piezoelectric constant d
33More than 50pC/N, and can guarantee Curie temperature Tc more than 200 ℃.
Next, set forth each mol ratio x, y, m that principal constituent is formed, and second composite oxides (M1, M2) M3O
3For first composite oxides (Ag, Li) (Nb, Ta) O
3Mol ratio n be limited to the reason of the scope of numerical expression (1)～(4).
(1) mol ratio x
In order can under hot environment, to use, requiring strong dielectric body to shift is that normal dielectric material or antiferroelectric Curie temperature Tc want height, but if the mol ratio x of Li is lower than 0.075, then Curie temperature Tc is reduced to below 200 ℃, and the temperature stability of piezoelectric element worsens.
On the other hand, if mol ratio x is more than 0.4, then coking property worsens, and insulation impedance reduces and the processing that is difficult to polarize.
Therefore, the dispensing mode of the mol ratio x of Li is 0.075≤x＜0.40 in the present embodiment.
(2) mol ratio y
Because Ta has the effect identical substantially with Nb, so can in this Piezoelecric ceramic compositions, contain as required, but be in more than 0.2 for the mol ratio y of Nb as if Ta, then the situation with above-mentioned mol ratio x is the same, Curie temperature Tc is reduced to below 200 ℃, and the temperature stability of piezoelectric element worsens.
Therefore, Ta allocates in the mode of 0≤y＜0.2 for the mol ratio y of Nb in the mode of this enforcement.
(3) mol ratio m
If the A position composition (Ag, Li) of first composite oxides is lower than 0.98 with the mol ratio m of B position composition (Nb, Ta), B position composition (Nb, Ta) surplus then, on the other hand, if mol ratio m surpasses 1.0, A position composition surplus then, any situation coking property all worsens, and insulation impedance reduces, and difficult treatment therefore polarizes.
Therefore, in the present embodiment, the dispensing mode of mol ratio m is 0.98≤m≤1.0.
(4) mol ratio n
By at first composite oxides (Ag, Li) (Nb, Ta) O
3An amount of second composite oxides (M1, the M2) M3O of middle interpolation
3, can realize the raising of relative permittivity ε r, still, if second composite oxides (M1, M2) M3O
3For first composite oxides (Ag, Li) (Nb, Ta) O
3Mol ratio n surpass 0.1, then can not be with electricapparatus attachment coefficient K
33Keep highly, be difficult to material use as piezoelectric filter and piezoelectric vibrator etc.On the other hand, if mol ratio n is lower than 0.01, then relative permittivity ε r is lower than 600, the relative permittivity ε r that can not obtain wishing, and the impedance matching when making the piezoelectric element miniaturization (impedance matching) worsens.
Therefore, in the present embodiment, with second composite oxides (M1, M2) M3O
3For first composite oxides (Ag, Li) (Nb, Ta) O
3Mol ratio n be made as 0.01≤n≤0.1.
Next, be illustrated with regard to the piezoelectric element that uses this Piezoelecric ceramic compositions manufacturing.
Fig. 1 is the stereographic map as the piezoelectric vibrator of an embodiment of above-mentioned piezoelectric element, and Fig. 2 is the A-A sectional view of Fig. 1.
That is, this piezoelectric vibrator be 2 former materials of piezoelectric ceramics (the former material 1a of piezoelectric ceramics, 1b) of on the arrow B direction, having polarized via internal electrode 2 by stacked and integrated mutually, and be formed with outer electrode 3,4 at the outside of the former material 1a of piezoelectric ceramics, 1b table.
In addition, outer electrode 3,4 is formed on the outside surface of former material 1a of first piezoelectric ceramics or the former material 1b of second piezoelectric ceramics in the mode of subtend shape via the former material 1a of first and second piezoelectric ceramics, 1b, be formed with discoid vibration section 3a, 4a at the cardinal principle central part, and be provided with lead division 3b, the 4b of T word shape from all ora terminalis of this vibration section 3a, 4a, this lead division 3b, 4b are from the another side exposing surface of piezoelectric vibration.
Then, lead division 2b is connected to a side outside terminal 6a via a Square wire 5a, and lead division 3b, 4b are connected to the opposing party's outside terminal 6b via the opposing party's lead 5b.
Next, the manufacture method of above-mentioned piezoelectric vibrator is described.
At first, prepare following compound as starting material: the Ag compound that contains Ag; The Li compound that contains Li; The Nb compound that contains Nb; The Ta compound that contains Ta; The M1 compound that contains metallic element M1; The M2 compound that contains metallic element M2; And contain the M3 compound of metallic element M3.
Then, forming these each compounds of weighing according to the regulation shown in the general expression (A), with the ball mill of the pulverizing media of zirconium white etc. is arranged in these weighing thing inputs, is the combination treatment that solvent carried out 4～24 hours with pure water and ethanol, makes thin pulp.Also have, under this situation,, preferably add the dispersion agent of sorbitan ester (sorbitan ester) etc. in order to reach the more admixture of homogeneous.
Then, make this thin pulp drying after, under oxidizing atmosphere, implement 1～24 hour calcination processing down 800 ℃～1100 ℃ of temperature, obtain calcined material.There are pure water and ethanol etc. in solvent, to contain the tackiness agent of polyvinyl alcohol (polyvinyl alcohol) etc. in this calcined material put into and pulverize in the ball mill of media and pulverize, mix, and make it dry.Then, by single shaft extruding etc. this dried powder is configured as for example prismaticly, then under oxidizing atmosphere, burnt till 3～10 hours, make the piezoelectric ceramics 1a, the 1b that form by above-mentioned Piezoelecric ceramic compositions thus with 950 ℃～1200 ℃ temperature.
Secondly, preparation contains the electroconductibility lotion of the conductive material of Ag etc., the described electroconductibility lotion of two sided coatings and make it dry and form conductive layer in the table of piezoelectric ceramics 1a, 1b, under specified temperature with specified time add the voltage of regulation, implement polarization at the thickness direction of piezoelectric ceramics 1a, 1b and handle thereafter.
Then, for the first piezoelectric ceramics 1a, mask process is carried out at the position that is equivalent to outer electrode 3, internal electrode 2, removes the conductive layer at the position of exposing surface with solvent, face side at the first piezoelectric ceramics 1a forms outer electrode 3, and side forms internal electrode 2 overleaf.In addition, be that mask process is carried out at the position that is equivalent to outer electrode 4 too for the second piezoelectric ceramics 1b, remove the conductive layer at the position of exposing surface with solvent, be formed on the second piezoelectric ceramics 1b that the back side is formed with outer electrode 4.
Next, the coating epoxy is a tackiness agent on the surface of the second piezoelectric ceramics 1b (not forming the face of outer electrode 4), overlaps the bonding first piezoelectric ceramics 1a and the second piezoelectric ceramics 1b so that direction of polarization becomes equidirectional mode, makes piezoelectric vibrator thus.
So, because its piezoelectric ceramics of this piezoelectric vibrator 1a, 1b are formed by above-mentioned Piezoelecric ceramic compositions, so it is moderately high to access relative permittivity ε r, electricapparatus attachment coefficient K
33With piezoelectric constant d
33Stablize the good piezoelectric vibrator of high piezoelectric property.
Specifically, can access exactly that to have relative permittivity ε r be the piezoelectric element of the high relative permittivity more than 600, therefore, impedance matching is also good, can access small-sized and can obtain the piezoelectric vibrator of wishing impedance.
In addition, can access electricapparatus attachment coefficient K
33Be more than 25%, and piezoelectric constant d
33More than 50pC/N, and can guarantee the piezoelectric vibrator that piezoelectric property is good, reliability is excellent of the Curie temperature Tc more than 200 ℃.
Next describe in detail with regard to second embodiment of the present invention.
The Piezoelecric ceramic compositions of second embodiment of the present invention is represented by general expression (B).
(1-n)(Ag
1-xLi
x)
m(Nb
1-yTa
y)O
3-nM4M5O
3…(B)
Here, M4 is the metallic element of divalent, and M5 is the metallic element of 4 valencys, in addition, for the same reason of above-mentioned first embodiment, mol ratio x, y, m and n modulate in the mode that satisfies above-mentioned numerical expression (1)～(4).
That is, this second mode of implementing, that use as second composite oxides is the metallic element M4 that makes A position solid solution divalent, makes the oxide compound of perovskite typed of the metallic element M5 of B position solid solution 4 valencys, even so by composition formula M4M5O
3When forming second composite oxides, also the same with first embodiment, can access that relative permittivity ε r is moderately high, electricapparatus attachment coefficient K
33With piezoelectric constant d
33Also have Curie temperature Tc to stablize the good Piezoelecric ceramic compositions of high piezoelectric property.
In addition, metallic element M4 as divalent, can use for example Ba, Sr, Ca, Mg, as the element M 5 of 4 valencys, can use for example Ti, Zr, Sn, Hf, by using these metallic elements, same with first embodiment, can access the good Piezoelecric ceramic compositions of piezoelectric property, it has relative permittivity ε r is high relative permittivity more than 600, electricapparatus attachment coefficient K
33Be more than 25%, and piezoelectric constant d
33More than 50pC/N, and can guarantee Curie temperature Tc more than 200 ℃.
Then, the same by using the Piezoelecric ceramic compositions (general expression B) of this second embodiment with above-mentioned first embodiment, can access piezoelectric vibrator as shown in Figures 1 and 2.
Also have, the present invention is not limited to the mode of above-mentioned enforcement.As the form of Piezoelecric ceramic compositions,, be preferably and make second composite oxides (M1, M2) M3O as the mode of above-mentioned enforcement
3Or M4M5O
3For first composite oxides (Ag, Li) (Nb, Ta) O
3The sosoloid of solid solution, but second combined oxidation (M1, M2) M3 O
3Or M4M5O
3Not fully solid solution in first composite oxides (Ag, Li) (Nb, Ta) O
3, also can be present in the form of crystal boundary as a part, also can be first composite oxides (Ag, Li) (Nb, Ta) O
3With second composite oxides (M1, M2) M3O
3Or M4M5O
3Mixture.
In addition, in the above-described embodiment, be, but also can make the former material of piezoelectric ceramics by so-called substrate constructional method by extrusion molding processing and fabricating piezoelectric ceramics 1a, 1b.Promptly, also can carry out the ceramic thin pulps of making such as case of wet attrition to ceramic raw material, by drawout finishing (doctor blademethod) wait ceramic thin pulp implemented be shaped process and make ceramic printed-circuit board thereafter, with the ceramic printed-circuit board of regulation sheet number stacked after, burn till processing, make the former material of piezoelectric ceramics thus.
In addition, in the mode of above-mentioned enforcement, be to be that example is illustrated with the piezoelectric vibrator as piezoelectric element, but for piezoelectric actuator, piezoelectric filter, piezoelectric buzzer, piezoelectric sensor too.
Next specify embodiments of the invention.
At first, press following each powder of moiety weighing of table 1: Ag
2O, Li
2CO
3, Nb
2O
5, Ta
2O
5, Bi
2O
3, Na
2CO
3, K
2CO
3, TiO
2, ZrO
2, SnO
2, HfO
2, use electric furnace under oxidizing atmosphere, with 850 ℃～1100 ℃ temperature each weighing thing is carried out precalcining in 10 hours and handles, obtain the precalcining thing.
Secondly, this precalcining thing is carried out after case of wet attrition handles, and is 5 weight fraction with respect to making the polyvinyl alcohol resin as tackiness agent with calcined material 100 weight fraction, so mixes described precalcining thing and described polyvinyl alcohol resin, after then implementing drying treatment, use the single shaft extrusion machine with 9.8 * 10
8The exert pressure of pa becomes the prismatic of vertical 12mm, horizontal 12mm, thick 2.5mm, then under oxidizing atmosphere, burns till 3～10 hours with 950 ℃～1200 ℃ temperature, makes piezoelectric ceramics thus.
Then, two sided coatings Ag lotion burns into capable decorated fire with 800 ℃ in the table of piezoelectric ceramics.Thereafter, add the volts DS 10～30 minutes of 20kV/cm～100kV/cm with 40～150 ℃ temperature in insulation oil groove (oil bath), processing polarizes.
Then, downcut the prism of indulging 2mm, horizontal 2mm, thick 3mm, obtain the piezoelectric element of test portion numbering 1～38 with cutting machine.
Then, carry out electricapparatus attachment coefficient K under relative permittivity ε r, the thickness vibration for each piezoelectric element of test portion numbering 1～38
33, the piezoelectric constant d under the thickness vibration
33, and the mensuration of Curie temperature Tc.
Here, relative permittivity ε r, electricapparatus attachment coefficient K
33And piezoelectric constant d
33Be to use RF electric impedance analyzer (impedance analyzer) (the system HP4194A of Hewlett-Packard), measure by resonance-anti-resonance method.
In addition, measure electricapparatus attachment coefficient K
33Temperature profile, according to the temperature described electricapparatus attachment coefficient K that rises
33Become 0 temperature, the temperature that is about to the piezoelectricity disappearance is as Curie temperature Tc.
Table 1 shows the moiety and the measurement result of test portion numbering 1～38.
[table 1]
| Test portion No | (1-n)(Ag 1-xLi x) m(Nb 1-yTa y)O 3-n(M 1M 2)M 3O 3 | Relative permittivity ε r | Electricapparatus attachment coefficient k33 (%) | Piezoelectric constant d33 (pC/N) | Curie temperature Tc (℃) | ||||||
| x | y | m | n | M 1 | M 2 | M 3 | |||||
| 1* | 0.100 | 0.00 | 1.0 | 0.00 | - | - | - | 304 | 41 | 55 | 290 |
| 2 | 0.075 | 0.00 | 1.0 | 0.10 | Bi | Na | Ti | 800 | 45 | 110 | 230 |
| 3 | 0.100 | 0.00 | 1.0 | 0.05 | Bi | Na | Ti | 1000 | 48 | 100 | 270 |
| 4 | 0.150 | 0.00 | 1.0 | 0.01 | Bi | Na | Ti | 750 | 35 | 70 | 300 |
| 5 | 0.200 | 0.00 | 1.0 | 0.05 | Bi | Na | Ti | 650 | 28 | 65 | 290 |
| 6 | 0.300 | 0.00 | 1.0 | 0.10 | Bi | Na | Ti | 1500 | 30 | 70 | 300 |
| 7 | 0.100 | 0.05 | 1.0 | 0.05 | Bi | Na | Ti | 650 | 44 | 85 | 260 |
| 8 | 0.100 | 0.10 | 1.0 | 0.01 | Bi | Na | Ti | 700 | 45 | 50 | 250 |
| 9* | 0.100 | 0.05 | 1.0 | 0.20 | Bi | Na | Ti | 450 | 15 | 45 | 140 |
| 10 | 0.075 | 0.05 | 1.0 | 0.05 | Bi | Na | Ti | 650 | 40 | 60 | 220 |
| 11 | 0.150 | 0.10 | 1.0 | 0.05 | Bi | Na | Ti | 680 | 45 | 55 | 200 |
| 12* | 0.400 | 0.10 | 1.0 | 0.05 | Bi | Na | Ti | Can not polarize | |||
| 13* | 0.100 | 0.00 | 1.0 | 0.15 | Bi | Na | Ti | 2000 | 18 | 30 | 100 |
| 14 | 0.100 | 0.00 | 1.0 | 0.05 | Bi | Li | Ti | 950 | 45 | 95 | 280 |
| 15 | 0.150 | 0.00 | 1.0 | 0.01 | Bi | K | Ti | 700 | 30 | 65 | 310 |
| 16 | 0.100 | 0.00 | 1.0 | 0.05 | Bi | Ag | Ti | 950 | 43 | 90 | 280 |
| 17 | 0.150 | 0.00 | 1.0 | 0.01 | Bi | Na | Zr | 800 | 38 | 75 | 310 |
| 18 | 0.075 | 0.05 | 1.0 | 0.05 | Bi | Na | Zr | 680 | 43 | 65 | 230 |
| 19 | 0.150 | 0.10 | 1.0 | 0.05 | Bi | Na | Zr | 700 | 46 | 60 | 210 |
| 20 | 0.100 | 0.00 | 0.98 | 0.05 | Bi | Na | Ti | 1000 | 48 | 100 | 270 |
| 21 | 0.150 | 0.00 | 0.98 | 0.01 | Bi | Na | Ti | 750 | 35 | 70 | 300 |
| 22 | 0.150 | 0.00 | 0.98 | 0.01 | Bi | K | Ti | 700 | 30 | 85 | 310 |
| 23 | 0.100 | 0.00 | 0.98 | 0.05 | Bi | Ag | Ti | 950 | 43 | 80 | 280 |
| 24 | 0.150 | 0.00 | 0.98 | 0.01 | Bi | Na | Zr | 800 | 38 | 75 | 310 |
| 25* | 0.100 | 0.05 | 0.97 | 0.05 | Bi | Na | Ti | Can not polarize | |||
| 26 | 0.100 | 0.00 | 0.98 | 0.05 | Bi | Na/Li(0.5/0.5) | Ti | 980 | 45 | 90 | 260 |
| 27 | 0.150 | 0.00 | 0.98 | 0.01 | Bi | Na/K(0.5/0.5) | Ti | 780 | 35 | 65 | 300 |
| 28 | 0.150 | 0.00 | 0.98 | 0.01 | Bi | Na/Ag(0.5/0.5) | Ti | 680 | 28 | 60 | 300 |
| 29 | 0.100 | 0.00 | 0.98 | 0.05 | Bi | Li/Ag(0.5/0.5) | Ti | 900 | 40 | 85 | 270 |
| 30 | 0.100 | 0.00 | 1.0 | 0.05 | Bi | Li | Zr | 900 | 42 | 90 | 270 |
| 31 | 0.150 | 0.00 | 1.0 | 0.01 | Bi | K | Zr | 650 | 26 | 60 | 310 |
| 32 | 0.100 | 0.00 | 1.0 | 0.05 | Bi | Ag | Zr | 900 | 40 | 85 | 280 |
| 33 | 0.075 | 0.00 | 1.0 | 0.10 | Bi | Na | Hf | 780 | 40 | 80 | 210 |
| 34 | 0.100 | 0.00 | 1.0 | 0.05 | Bi | Na | Hf | 950 | 42 | 85 | 230 |
| 35 | 0.100 | 0.00 | 1.0 | 0.05 | Bi | Na | Sn | 900 | 35 | 70 | 240 |
| 36 | 0.150 | 0.00 | 1.0 | 0.01 | Bi | Na | Sn | 650 | 27 | 55 | 270 |
| 37* | 0.050 | 0.00 | 1.0 | 0.01 | Bi | Na | Ti | 300 | 43 | 60 | 150 |
| 38* | 0.100 | 0.20 | 1.0 | 0.01 | Bi | Na | Ti | 250 | 45 | 55 | 160 |
* outside the scope of the invention
As indicated in this table 1, test portion numbering 1 is not because contain second composite oxides (M1, M2) M3O as can be known
3So relative permittivity ε r is low to moderate 304.
Test portion numbers 9 as can be known, because mol ratio n greatly to 0.20, reaches 140 ℃, relative permittivity ε r, electricapparatus attachment coefficient K so Curie temperature Tc is low
33And piezoelectric constant d
33Also low.
Greatly to 0.400, so coking property is poor, insulation impedance is low because of mol ratio x for test portion numbering 12, and processing therefore can not polarize.
Test portion numbering 13, mol ratio n is 0.15 as can be known, therefore second composite oxides (M1, M2) M3O
3Contain molar weight surplus, electricapparatus attachment coefficient K
33Be low to moderate 18%, and piezoelectric constant d
33Tc also reduces with Curie temperature.
Test portion numbering 25 is because mol ratio m is little of 0.97, so B position composition (Nb, the Ta) surplus of first composite oxides, coking property is poor, and insulation impedance is low, and processing therefore can not polarize.
Test portion numbering 37, as can be known because mol ratio x very few be 0.050, so Curie temperature Tc is reduced to 150 ℃, relative permittivity ε r, electricapparatus attachment coefficient K
33And piezoelectric constant d
33Also low.
Test portion numbering 38, because mol ratio y is greatly to 0.2, so Curie temperature Tc is reduced to 160 ℃ as can be known, relative permittivity ε r, electricapparatus attachment coefficient K
33And piezoelectric constant d
33Also low.
With respect to this, test portion numbering 2～8,10,11,14～24 and 26～36 is in the scope of the present invention because of mol ratio x, y, m, n as can be known, be 0.075≤x＜0.4,0≤y＜0.2,0.98≤m≤1.0,0.01≤n≤0.1, the second composite oxides (M1, M2) M3O
3Solid solution is in the first composite oxides (Ag
1-xLi
x)
m(Nb
1-yTa
y) O
3So, can access relative permittivity ε r and be the high relative permittivity ε r more than 600, electricapparatus attachment coefficient K
33Be more than 25%, and piezoelectric constant d
33More than 50pC/N, Curie temperature Tc is the piezoelectric element of the piezoelectric property excellence more than 200 ℃.
Press following each powder of moiety weighing of table 2: Ag
2O, Li
2CO
3, Nb
2O
5, Ta
2O
5, BaO
3, SrCO
3, CaCO
3, MgO, TiO
2, ZrO
2, SnO
2, HfO
2, use electric furnace under oxidizing atmosphere, with 800 ℃～1100 ℃ temperature each weighing thing is carried out precalcining in 10 hours and handles, obtain the precalcining thing.
According to similarly to Example 1 method, step obtain the piezoelectric element of test portion numbering 41～80 thereafter.
Then, according to method, step similarly to Example 1, carry out electricapparatus attachment coefficient K under relative permittivity ε r, the thickness vibration for the piezoelectric element of test portion numbering 41～80
33, the piezoelectric constant d under the thickness vibration
33, and the mensuration of Curie temperature Tc.
Table 2 shows the moiety and the measurement result of test portion numbering 41～80.
[table 2]
| Test portion No. | (1-n)(Ag 1-xLi x) m(Nb 1-yTa y)O 3-nM4M5O 3 | Relative permittivity ε r | Electricapparatus attachment coefficient k33 (%) | Piezoelectric constant d33 (pC/N) | Curie temperature Tc (℃) | |||||
| x | y | m | n | M4 | M5 | |||||
| 41* | 0.100 | 0.00 | 1.0 | 0.00 | - | - | 304 | 41 | 55 | 290 |
| 42 | 0.075 | 0.00 | 1.0 | 0.10 | Ba | Ti | 800 | 47 | 130 | 210 |
| 43 | 0.100 | 0.00 | 1.0 | 0.05 | Ba | Ti | 950 | 49 | 110 | 250 |
| 44 | 0.150 | 0.00 | 1.0 | 0.01 | Ba | Ti | 700 | 37 | 80 | 300 |
| 45 | 0.200 | 0.00 | 1.0 | 0.05 | Ba | Ti | 630 | 31 | 75 | 280 |
| 46 | 0.300 | 0.00 | 1.0 | 0.10 | Ba | Ti | 1500 | 34 | 90 | 290 |
| 47 | 0.100 | 0.05 | 1.0 | 0.05 | Ba | Ti | 640 | 47 | 100 | 250 |
| 48 | 0.100 | 0.10 | 1.0 | 0.01 | Ba | Ti | 670 | 47 | 55 | 250 |
| 49* | 0.100 | 0.20 | 1.0 | 0.01 | Ba | Ti | 400 | 21 | 50 | 130 |
| 50* | 0.100 | 0.45 | 1.0 | 0.01 | Ba | Ti | 550 | |||
| 51* | 0.000 | 0.15 | 1.0 | 0.1 | Ba | Ti | 400 | |||
| 52 | 0.075 | 0.05 | 1.0 | 0.05 | Ba | Ti | 620 | 43 | 70 | 210 |
| 53 | 0.150 | 0.10 | 1.0 | 0.05 | Ba | Ti | 660 | 48 | 65 | 200 |
| 54* | 0.400 | 0.10 | 1.0 | 0.05 | Ba | Ti | Can not polarize | |||
| 55* | 0.100 | 0.00 | 1.0 | 0.15 | Ba | Ti | 1800 | 20 | 40 | 100 |
| 56 | 0.100 | 0.00 | 1.0 | 0.05 | Ba/Sr(0.5/0.5) | Ti | 880 | 46 | 105 | 260 |
| 57 | 0.150 | 0.00 | 1.0 | 0.01 | Ca | Ti | 640 | 32 | 70 | 290 |
| 58 | 0.100 | 0.00 | 1.0 | 0.05 | Mg | Ti | 860 | 44 | 95 | 260 |
| 59 | 0.150 | 0.00 | 1.0 | 0.01 | Ba | Zr | 770 | 40 | 80 | 300 |
| 60 | 0.075 | 0.05 | 1.0 | 0.05 | Ba | Zr | 650 | 46 | 80 | 220 |
| 61 | 0.150 | 0.10 | 1.0 | 0.05 | Ba | Zr | 670 | 48 | 75 | 210 |
| 62 | 0.100 | 0.00 | 0.98 | 0.05 | Ba | Ti | 910 | 50 | 115 | 250 |
| 63 | 0.150 | 0.00 | 0.98 | 0.01 | Ba | Ti | 720 | 37 | 80 | 280 |
| 64 | 0.150 | 0.00 | 0.98 | 0.01 | Sr | Ti | 630 | 32 | 70 | 290 |
| 65 | 0.100 | 0.00 | 0.98 | 0.05 | Ba/Ca(0.5/0.5) | Ti | 890 | 45 | 100 | 270 |
| 66 | 0.150 | 0.00 | 0.98 | 0.01 | Ba | Zr | 740 | 40 | 85 | 290 |
| 67* | 0.100 | 0.05 | 0.97 | 0.05 | Ba | Ti | Can not polarize | |||
| 68 | 0.100 | 0.00 | 0.98 | 0.05 | Ba/Mg(0.5/0.5) | Ti | 910 | 46 | 95 | 240 |
| 69 | 0.150 | 0.00 | 0.98 | 0.01 | Ca/Sr(0.5/0.5) | Ti | 700 | 36 | 70 | 290 |
| 70 | 0.150 | 0.00 | 0.98 | 0.01 | Ca/Mg(0.5/0.5) | Ti | 600 | 29 | 65 | 290 |
| 71 | 0.100 | 0.00 | 0.98 | 0.05 | Sr/Mg(0.5/0.5) | Ti | 820 | 41 | 90 | 250 |
| 72 | 0.100 | 0.00 | 1.0 | 0.05 | Ba | Zr | 840 | 44 | 100 | 250 |
| 73 | 0.150 | 0.00 | 1.0 | 0.01 | Ba | Zr | 620 | 29 | 65 | 300 |
| 74 | 0.100 | 0.00 | 1.0 | 0.05 | Ba/Ca/Sr/Mg (0.25/0.25/0.25/0.25) | Zr | 870 | 42 | 95 | 260 |
| 75 | 0.075 | 0.00 | 1.0 | 0.10 | Ba | Hf | 780 | 43 | 95 | 200 |
| 76 | 0.100 | 0.00 | 1.0 | 0.05 | Ba | Hf | 900 | 44 | 95 | 210 |
| 77 | 0.100 | 0.00 | 1.0 | 0.05 | Ba | Sn | 670 | 38 | 80 | 220 |
| 78 | 0.150 | 0.00 | 1.0 | 0.01 | Ba | Sn | 620 | 30 | 60 | 250 |
| 79* | 0.050 | 0.00 | 1.0 | 0.01 | Ba | Ti | 280 | 45 | 70 | 140 |
| 80* | 0.100 | 0.00 | 1.1 | 0.05 | Ba | Ti | ||||
* outside the scope of the invention
Test portion numbering 41 is not because contain the second composite oxides M4M5O
3So the same with the test portion numbering 1 of embodiment 1, relative permittivity ε r is low to reach 304.
Test portion numbering 49, as can be known because mol ratio y greatly to 0.20, so Curie temperature Tc is reduced to 130 ℃, relative permittivity ε r, electricapparatus attachment coefficient K
33And piezoelectric constant d
33Also step-down.
Test portion numbering 50 because mol ratio y greatly to 0.45, so, can't confirm resonance-anti-resonance, electricapparatus attachment coefficient K though carried out polarization and handle
33, piezoelectric constant d
33And Curie temperature Tc all can not measure.
Test portion numbering 51, because mol ratio x is little of 0, so though carried out the polarization processing, the same with test portion numbering 50, can't confirm resonance-anti-resonance, electricapparatus attachment coefficient K
33, piezoelectric constant d
33And Curie temperature Tc all can not measure.
Test portion numbering 54, because mol ratio x is greatly to 0.400, so coking property is poor, insulation impedance is low, processing therefore can not polarize.
Test portion numbering 55 mol ratio n as can be known is 0.15, therefore the second composite oxides M
4M
5O
3Contain molar weight surplus, electricapparatus attachment coefficient K
33Be low to moderate 20%, in addition piezoelectric constant d
33Tc also reduces with Curie temperature.
Test portion numbering 67 is because mol ratio m is little of 0.97, so B position composition (Nb, the Ta) surplus of first composite oxides, coking property is poor, and insulation impedance is low, and processing therefore can not polarize.
Test portion numbering 79 reaches 0.050 because mol ratio x is very few as can be known, so Curie temperature is reduced to 140 ℃, and relative permittivity ε r, electricapparatus attachment coefficient K
33And other piezoelectric constant d
33Also step-down.
Greatly to 1.1, so the A position composition surplus of first composite oxides, coking property worsens test portion numbering 80 because of mol ratio, and insulation impedance reduces, and processing therefore can not polarize.
With respect to this, test portion numbering 42～48,52,53,56～66 and 68～78 is in the scope of the present invention because of mol ratio x, y, m, n as can be known, be 0.075≤x＜0.4,0≤y＜0.2,0.98≤m≤1.0,0.01≤n≤0.1, the second composite oxides M4M5O
3Solid solution is in the first composite oxides (Ag
1-xLi
x)
m(Nb
1-yTa
y) O
3So, can access relative permittivity ε r and be the high relative permittivity ε r more than 600, electricapparatus attachment coefficient K
33Be more than 25%, piezoelectric constant d
33More than 50pC/N, Curie temperature Tc is the piezoelectric element of the piezoelectric property excellence more than 200 ℃.In addition, even make two or more metallic element solid solutions in the second composite oxides M4M5O
3A position composition in the time, (test portion numbering 56,65,68～71 and 74) also can be confirmed to access above-mentioned ideal piezoelectric property.
Claims (6)
1. a Piezoelecric ceramic compositions is characterized in that, contains by general expression { (1-n) (Ag
1-xLi
x)
m(Nb
1-yTa
y) O
3-n (M
1, M
2) M3O
3The expression principal constituent, wherein, M1 represents the metallic element of 3 valencys, M2 represents the metallic element of 1 valency, M3 represents the metallic element of 4 valencys, described x, y, z, m and n are respectively
0.075≤x＜0.40、
0≤y＜0.2、
0.98≤m≤1.0, and
0.01≤n≤0.1。
2. Piezoelecric ceramic compositions according to claim 1 is characterized in that described M1 is Bi, described M2 be among K, Na, Li and Ag, select more than at least a kind, described M3 be among Ti, Zr, Sn and Hf, select more than at least a kind.
3. a Piezoelecric ceramic compositions is characterized in that, contains by general expression { (1-n) (Ag
1-xLi
x)
m(Nb
1-yTa
y) O
3-nM4M5O
3The expression principal constituent, wherein, M4 represents the metallic element of divalent, M5 represents the metallic element of 4 valencys, described x, y, z, m and n are respectively
0.075≤x＜0.40、
0≤y＜0.2、
0.98≤m≤1.0, and
0.01≤n≤0.1。
4. Piezoelecric ceramic compositions according to claim 3 is characterized in that, described M4 be among Ba, Sr, Ca and Mg, select more than at least a kind, M5 be among Ti, Zr, Sn and Hf, select more than at least a kind.
5. a piezoelectric element is characterized in that, is formed with outer electrode on the surface of the ceramic sintered bodies that is formed by each described Piezoelecric ceramic compositions in the claim 1～4.
6. piezoelectric element according to claim 5 is characterized in that internal electrode is embedded in the described ceramic sintered bodies.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102789858A (en) * | 2012-07-23 | 2012-11-21 | 深圳甲艾马达有限公司 | Strong-vibration-sense direct current micromotor |
| CN112592190A (en) * | 2020-12-10 | 2021-04-02 | 中国科学技术大学 | Piezoelectric ceramic and preparation method thereof |
| CN113698203A (en) * | 2021-08-26 | 2021-11-26 | 郑州轻工业大学 | Yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material and preparation method thereof |
| CN114455944A (en) * | 2022-01-28 | 2022-05-10 | 厦门乃尔电子有限公司 | Bismuth layer-structured piezoelectric ceramic material and preparation method thereof |
-
2005
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102789858A (en) * | 2012-07-23 | 2012-11-21 | 深圳甲艾马达有限公司 | Strong-vibration-sense direct current micromotor |
| CN102789858B (en) * | 2012-07-23 | 2015-07-08 | 深圳甲艾马达有限公司 | Strong-vibration-sense direct current micromotor |
| CN112592190A (en) * | 2020-12-10 | 2021-04-02 | 中国科学技术大学 | Piezoelectric ceramic and preparation method thereof |
| CN113698203A (en) * | 2021-08-26 | 2021-11-26 | 郑州轻工业大学 | Yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material and preparation method thereof |
| CN113698203B (en) * | 2021-08-26 | 2022-07-08 | 郑州轻工业大学 | Yttrium and hafnium co-doped silver niobate lead-free antiferroelectric ceramic material and preparation method thereof |
| CN114455944A (en) * | 2022-01-28 | 2022-05-10 | 厦门乃尔电子有限公司 | Bismuth layer-structured piezoelectric ceramic material and preparation method thereof |
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