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Patent Analysis of

Composite piezoelectric ceramic and piezoelectric device

Updated Time 12 June 2019

Patent Registration Data

Publication Number

US10003009

Application Number

US14/633649

Application Date

27 February 2015

Publication Date

19 June 2018

Current Assignee

TDK CORPORATION

Original Assignee (Applicant)

TDK CORPORATION

International Classification

H01L41/187,H01L41/083

Cooperative Classification

H01L41/1873,H01L41/1871,H01L41/083

Inventor

FURUKAWA, MASAHITO,SHIMURA, YOSHIKAZU,MASAI, TAKU,WADA, SATOSHI

Patent Images

This patent contains figures and images illustrating the invention and its embodiment.

US10003009 Composite piezoelectric ceramic piezoelectric 1 US10003009 Composite piezoelectric ceramic piezoelectric 2 US10003009 Composite piezoelectric ceramic piezoelectric 3
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Abstract

A composite piezoelectric ceramic includes a compact of crystal particles including at least one of potassium niobate (KNbO3) and sodium niobate (NaNbO3) and optionally further including lithium niobate (LiNbO3), and a layer containing barium titanate (BaTiO3) that is disposed on the surface of the compact while forming a heterojunction with the compact. A piezoelectric device includes the composite piezoelectric ceramic.

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Claims

1. A composite piezoelectric ceramic comprising: a solid solution including at least one of potassium niobate (KNbO3) and sodium niobate (NaNbO3), and a compound layer disposed on the surface of the solid solution while forming a heterojunction at the interface therebetween, the compound layer including barium titanate (BaTiO3), wherein the molar ratio of BaTiO3 relative to the total of components forming the solid solution is 0.2 to 1.0.

2. The composite piezoelectric ceramic according to claim 1, wherein the solid solution further includes lithium niobate (LiNbO3).

3. A piezoelectric device comprising: a pair of electrodes, and a piezoelectric material disposed between the pair of electrodes, the piezoelectric material including the composite piezoelectric ceramic described in claim 1.

4. A piezoelectric device comprising: an element including an alternate stack of the composite piezoelectric ceramics described in claim 1 and internal electrodes, and a pair of terminal electrodes electrically connected to the internal electrodes.

5. A piezoelectric device comprising: a pair of electrodes, and a piezoelectric material disposed between the pair of electrodes, the piezoelectric material including the composite piezoelectric ceramic described in claim 2.

6. A piezoelectric device comprising: an element including an alternate stack of the composite piezoelectric ceramics described in claim 2 and internal electrodes, and a pair of terminal electrodes electrically connected to the internal electrodes.

7. The composite piezoelectric ceramic according to claim 1, wherein the molar ratio of BaTiO3 relative to the total of components forming the solid solution is 0.2 to 0.8.

8. The composite piezoelectric ceramic according to claim 1, wherein the molar ratio of BaTiO3 relative to the total of components forming the solid solution is 0.2 to 0.5.

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Claim Tree

  • 1
    1. A composite piezoelectric ceramic comprising:
    • a solid solution including at least one of potassium niobate (KNbO3) and sodium niobate (NaNbO3), and a compound layer disposed on the surface of the solid solution while forming a heterojunction at the interface therebetween, the compound layer including barium titanate (BaTiO3), wherein the molar ratio of BaTiO3 relative to the total of components forming the solid solution is 0.2 to 1.0.
    • 2. The composite piezoelectric ceramic according to claim 1, wherein
      • the solid solution further includes lithium niobate (LiNbO3).
    • 7. The composite piezoelectric ceramic according to claim 1, wherein
      • the molar ratio of BaTiO3 relative to the total of components forming the solid solution is 0.2 to 0.8.
    • 8. The composite piezoelectric ceramic according to claim 1, wherein
      • the molar ratio of BaTiO3 relative to the total of components forming the solid solution is 0.2 to 0.5.
  • 3
    3. A piezoelectric device comprising:
    • a pair of electrodes, and a piezoelectric material disposed between the pair of electrodes, the piezoelectric material including the composite piezoelectric ceramic described in claim 1.
  • 4
    4. A piezoelectric device comprising:
    • an element including an alternate stack of the composite piezoelectric ceramics described in claim 1 and internal electrodes, and a pair of terminal electrodes electrically connected to the internal electrodes.
  • 5
    5. A piezoelectric device comprising:
    • a pair of electrodes, and a piezoelectric material disposed between the pair of electrodes, the piezoelectric material including the composite piezoelectric ceramic described in claim 2.
  • 6
    6. A piezoelectric device comprising:
    • an element including an alternate stack of the composite piezoelectric ceramics described in claim 2 and internal electrodes, and a pair of terminal electrodes electrically connected to the internal electrodes.
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Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to composite piezoelectric ceramics and piezoelectric devices.

2. Description of the Related Art

Piezoelectric ceramics produce a mechanical strain and a stress in response to the application of an electric field. Piezoelectric ceramics showing such a piezoelectric phenomenon are used in various piezoelectric devices such as actuators, piezoelectric oscillations, speakers and sensors. Further, the materials have recently found use in vibration power generation.

Piezoelectric ceramic actuators have characteristics such as the ability to produce slight displacements with high precision and the ability to generate a high stress. For example, the piezoelectric ceramic actuators are used for positioning in precision machine tools and optical apparatuses. The most frequent piezoelectric ceramic used in such actuators is lead zirconate titanate (PZT) having excellent piezoelectricity. However, the fact that PZT contains a large amount of lead (Pb) has recently given rise to a concern about its adverse effects on global environment such as the elution of Pb by acid rain. Thus, there has been a demand that PZT be replaced by a piezoelectric ceramic material having a sufficiently decreased amount of Pb. In response to such needs, various Pb-free piezoelectric ceramic materials have been proposed.

Barium titanate (BaTiO3) and potassium niobate (KNbO3) are known Pb-free piezoelectric ceramic materials. To obtain improved piezoelectric characteristics, piezoelectric ceramic materials that are solid solutions including BaTiO3 and KNbO3 have been proposed.

For example, a piezoelectric ceramic composition represented by the chemical formula x(Ba1-aCaa)TiO3-yKNbO3-zNaNbO3 has been proposed (see Japanese Unexamined Patent Application Publication No. 2003-252681).

A piezoelectric ceramic that is a solid solution of plural components is generally known to exhibit high piezoelectric characteristics due to the presence of a morphotropic phase boundary (MPB), for example, a tetragonal/orthorhombic phase boundary. Thus, crystal phase boundaries in binary or ternary solid solutions have been actively studied.

Japanese Unexamined Patent Application Publication No. 2009-227482 discloses a piezoelectric ceramic that is based on a binary solid solution containing KNbO3 and BaTiO3, the molar ratio of KNbO3 relative to the total of the two components being 0.5 to 0.9.

In a binary system such as that in Japanese Unexamined Patent Application Publication No. 2009-227482, it has been recognized that a crystal phase boundary exists in a composition containing the two components in extremely different proportions. Thus, it has been considered that piezoelectricity is exhibited only when the material has an unbalanced composition containing the components in extremely different proportions.

Further, the KNbO3/BaTiO3 binary system has a very narrow range of temperatures at which it can be sintered. Consequently, the material cannot be sintered at an excessively low sintering temperature to fail to achieve sufficient piezoelectric characteristics, whereas excessively high sintering temperatures cause problems such as variations in the composition due to the evaporation of elements such as potassium (K).

Japanese Unexamined Patent Application Publication No. 2012-254913 discloses a composite piezoelectric ceramic which has a layer including at least one of KNbO3 and NaNbO3 on the surface of a compact of BaTiO3 crystal particles.

Because the structure described in Japanese Unexamined Patent Application Publication No. 2012-254913 is based on a compact of BaTiO3 crystal particles, a tetragonal to cubic structural change occurs at near the Curie temperature (Tc) of BaTiO3, resulting in significant changes in dielectric constant and piezoelectric characteristics. Once a cubic structure has been formed at or above the Tc, it is impossible to obtain sufficient piezoelectric characteristics even after the temperature is decreased.

The Tc of BaTiO3 is as low as about 120° C. This fact disadvantageously limits the service temperature of piezoelectric ceramics composed solely of or based on BaTiO3 to 100° C. or below.

Solid solutions of BaTiO3 and other components proposed in the art compare unfavorably to Pb-containing materials in terms of piezoelectric characteristics and are incapable of producing a sufficiently large displacement. Thus, there have been demands for piezoelectric ceramics that are composed of Pb-free materials, are free from the limitation of use temperatures (in contrast to the use temperatures being limited to 100° C. or below as described above) and exhibit sufficient and excellent piezoelectric characteristics, as well as demands for processes for the production of such piezoelectric ceramics.

SUMMARY OF THE INVENTION

The present invention has been made in light of the circumstances discussed above. It is therefore an object of the invention to provide composite piezoelectric ceramics and piezoelectric devices which are configured such that the displacement of actuators may be increased without the use of Pb, that the ceramics contain a reduced amount of BaTiO3 and consequently the Tc of the composite piezoelectric ceramics may be increased as compared to BaTiO3 alone or as the base and the dependency of the displacement on temperatures may be enhanced, and further that the materials may be easily produced into compacts at a low temperature of 300° C. or below.

To achieve the above object, the present inventors have invented a composite piezoelectric ceramic including a solid solution and a compound layer disposed on the surface of the solid solution while forming a heterojunction at the interface therebetween, the solid solution including at least one of KNbO3 and NaNbO3, the compound layer including BaTiO3.

An increase in Tc may be obtained by disposing a thin layer including BaTiO3 so as to form a heterojunction with the surface of a compact of a solid solution which includes high-Tc components such as KNbO3. The thickness of the BaTiO3 layer is preferably 10 nm to 500 nm. This thickness ensures that the influence of the Tc of BaTiO3 is limited and the composite piezoelectric ceramic may exhibit piezoelectric characteristics (produce a displacement) even at temperatures exceeding 100° C.

With the above configuration, a composite piezoelectric ceramic may be obtained which exhibits piezoelectric characteristics (produces a displacement) even at temperatures exceeding 100° C. Further, the above configuration makes it possible to decrease the sintering temperature to low temperatures of 300° C. or below.

In the composite piezoelectric ceramic provided according to the invention, the solid solution may further include LiNbO3.

The addition of LiNbO3 to the crystal particle compact further enhances the piezoelectric characteristics (the displacement).

In the composite piezoelectric ceramic provided according to the invention, the BaTiO3 constituting the layer having a heterojunction with the solid solution may have a molar ratio of 0.05 to 1.0 relative to the total of KNbO3, NaNbO3 and LiNbO3.

If the molar ratio of BaTiO3 relative to the total of KNbO3, NaNbO3 and LiNbO3 is less than 0.05, the BaTiO3 phase is not grown sufficiently and high piezoelectric characteristics (a large displacement) cannot be obtained.

If the molar ratio of BaTiO3 exceeds 1.0, the high proportion of BaTiO3 leads to a decrease in the influence of the core having a high Tc, namely, the solid solution including at least one of KNbO3 and NaNbO3. Consequently, a phase change is caused at high temperatures exceeding 100° C., resulting in a marked decrease in piezoelectric characteristics (displacement).

Another aspect of the invention resides in a piezoelectric device including a pair of electrodes and the composite piezoelectric ceramic disposed between the pair of electrodes.

Another aspect of the invention resides in a piezoelectric device including an element and a pair of terminal electrodes disposed on both end faces of the element so as to sandwich the element, the element including an alternate stack of the composite piezoelectric ceramics and internal electrodes, the terminal electrodes being electrically connected to the internal electrodes.

In the invention, a compact includes a solid solution containing at least one oxide having a chemical composition different from BaTiO3, namely, at least one of KNbO3 and NaNbO3, and a layer including BaTiO3 is formed on the surface of the compact while forming a heterojunction. With this configuration, it becomes possible to provide piezoelectric devices having a piezoelectric ceramic that exhibits excellent piezoelectric characteristics and temperature characteristics without the use of Pb.

An increase in Tc may be obtained by disposing a BaTiO3-containing layer in a small thickness on the surface of a compact of a solid solution which includes high-Tc components such as KNbO3 while forming a heterojunction. Such composite piezoelectric ceramics exhibit piezoelectric characteristics (produce a displacement) even at temperatures exceeding 100° C. Further, the materials may be produced at a low sintering temperature of 300° C. or below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view illustrating an embodiment of piezoelectric devices of the invention;

FIG. 2 is a LaMer diagram illustrating the progress of a reaction in the invention;

FIG. 3 is an X-ray diffraction pattern showing the presence of a heterojunction in the invention, specifically, the evaluation result ⊙ in Table 1 (Example 3);

FIG. 4 is an X-ray diffraction pattern showing the presence of a heterojunction in the invention, specifically, the evaluation result ∘ in Table 1 (Example 1);

FIG. 5 is an X-ray diffraction pattern showing a failure of appropriate formation of a heterojunction in the invention, specifically, the evaluation result x in Table 1 (Comparative Example 2); and

FIGS. 6A to 6E are STEM-EDS images illustrating a composite ceramic having a heterojunction in the invention, specifically, the evaluation result ⊙ in Table 1 (Example 3).

FIG. 7 is a schematic cross section showing a piezoelectric device according to another embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Some aspects and embodiments of the present invention will be described in detail with reference to the drawings. The embodiments described below are only illustrative and do not limit the scope of the invention. The constituent elements described below comprehend other elements easily anticipated by the skilled person or substantially identical elements. The constituent elements described below may be combined appropriately. The same reference signs will be used for similar or equivalent features throughout the description with reference to the drawings, and any overlaps will not be explained at each occurrence.

FIG. 1 is a perspective view illustrating an embodiment of piezoelectric devices of the invention. A piezoelectric device 4 includes a composite piezoelectric ceramic 1 and a pair of electrodes 2 and 3 disposed on a pair of opposite faces of the composite piezoelectric ceramic 1.

For example, the composite piezoelectric ceramic 1 is polarized in the thickness direction, namely, in the direction in which the pair of electrodes 2 and 3 are opposed to each other. The application of a voltage through the electrodes 2 and 3 causes the composite piezoelectric ceramic to be oscillated vertically in the thickness direction and planarly in the radius direction. For example, the electrodes 2 and 3 are made of a metal such as Au. The electrodes 2 and 3 may be electrically connected to an external power supply via wires or the like (not shown).

The composite piezoelectric ceramic 1 includes a compact of composite oxide crystal particles including at least one of KNbO3 and NaNbO3 and optionally further including LiNbO3, and the surface of the compact is coated with a layer which contains BaTiO3 in a molar ratio (z) of 0.05 to 1.0 relative to the total of KNbO3, NaNbO3 and LiNbO3.

The molar ratio is preferably 0.2 to 1.0, and particularly preferably 0.2 to 0.8.

The compositional formula of the composite piezoelectric ceramic may be represented by General Formula (1):

(1-x-y)KNbO3-xNaNbO3-yLiNbO3-zBaTiO3  (1)

Effects may be obtained when the NaNbO3 molar ratio (x) is in the range of 0 to 1.0. On the other hand, the LiNbO3 molar ratio (y) is preferably 0 to 0.1, and particularly preferably 0 to 0.05.

In General Formula (1), niobium (Nb) may be partially replaced by tantalum (Ta); titanium (Ti) may be partially replaced by zirconium (Zr) and/or hafnium (Hf); and barium (Ba) may be partially replaced by magnesium (Mg), calcium (Ca) or strontium (Sr).

For example, the composite piezoelectric ceramic 1 may be produced by solvothermal synthesis. Solvothermal synthesis is a method that produces compounds by reaction at high pressure using an organic solvent. With this technique, the synthesis is possible at low temperatures of 300° C. or below. In the process of growing a compound layer on the surface of cores such as ceramic particles, calcined products or compacts, the ability to allow the layer to grow (react) at low temperatures suppresses the reaction (dissolution) between the ceramics. The synthesis method is not limited to solvothermal synthesis and may be a general hydrothermal synthesis method.

FIG. 2 is a LaMer diagram illustrating the progress of a solvothermal reaction, the horizontal axis representing the temperature and the vertical axis the concentration of an element participating in the reaction (in the invention, Ba(OH)2).

Crystal nucleation occurs above the critical supersaturation curve. In the metastable zone, the crystal nucleus grows but no crystal nucleation occurs. First, the conditions that cause the generation of BaTiO3 crystal nucleus (nucleation) to occur, and the metastable zone conditions are examined. By allowing the reaction to take place in the metastable zone (temperatures and concentrations), a BaTiO3 layer may be grown on the surface of KNbO3 particles as the core while forming a heterojunction. In this manner, a composite piezoelectric ceramic 1 having an artificial heterojunction (an MPB structure) may be prepared.

The relative density of the composite piezoelectric ceramic 1 is preferably not less than 30%. When the composite piezoelectric ceramic 1 is used in a piezoelectric power generation device, a large amount of power generation may be obtained by reducing the relative density to below the level used in usual piezoelectric ceramics.

For use in other devices such as actuators, the relative density of the composite piezoelectric ceramic 1 is preferably not less than 90%. The relative density of the composite piezoelectric ceramic 1 may be determined by an Archimedes method. The relative density of the composite piezoelectric ceramic 1 may be controlled by adjusting the density of the crystal particle compact (by adjusting conditions such as the type and the amount of a binder, and the compacting pressure), and the conditions of the solvothermal reaction (such as the concentration, the reaction temperature and the reaction time).

As auxiliary components, the composite piezoelectric ceramic 1 may contain manganese (Mn) compounds such as Mn oxide and copper (Cu) compounds such as Cu oxide.

The addition of Mn compounds and Cu compounds may enhance the mechanical quality factor (Qm) of the composite piezoelectric ceramic 1.

The composite piezoelectric ceramic 1 has a stoichiometric composition including KNbO3 and BaTiO3. The composition is not necessarily exactly stoichiometric because the production with the exact stoichiometric composition is difficult and also because higher reliability may be obtained by intentional manipulation of the composition such as by reducing the amount of potassium (K).

The composite piezoelectric ceramic 1 may contain Pb, but the Pb content is preferably not more than 1 mass %. It is more preferable that Pb be completely absent.

The reduction of Pb content to a sufficiently low level makes it possible to decrease to the minimum the volatilization of Pb during calcination and also to minimize the discharge of Pb to the environment when the piezoelectric ceramics marketed as piezoelectric components such as piezoelectric devices are disposed of.

For example, the composite piezoelectric ceramics 1 may be suitably used as materials in various piezoelectric devices, for example, piezoelectric power generation devices, oscillation devices such as actuators, and buzzers, speakers and sensors.

FIG. 7 is a schematic cross section showing another embodiment of a piezoelectric device of the invention. A piezoelectric device 7 includes a plurality of composite piezoelectric ceramic layers 1 and a plurality of internal electrodes 5 stacked alternately. The internal electrodes 5 are extended alternately in the opposite directions and electrically connected at the extended opposite ends thereof to a pair of terminal electrodes (external electrodes) 6.

Next, there will be described a process for producing the piezoelectric device 4 illustrated in FIG. 1.

First, a raw material of a main component of the composite piezoelectric ceramic 1, for example, a KNbO3 powder, is provided and is sufficiently dried. Separately, a titanium oxide (TiO2) powder as a raw material for forming BaTiO3 on the surface of KNbO3 is dried similarly. The KNbO3 powder and the TiO2 powder are weighed and are mixed with each other in a ball mill. The mixture is dried and is admixed with an organic solvent containing a binder. The resultant mixture is dried and is compacted into a disc. The disc of the mixture of KNbO3 and TiO2 is heated at 500° C. to 800° C. for 2 to 12 hours to remove the binder, thus affording a mixture powder compact.

Components such as a solvent and a prescribed amount of Ba(OH)2 are added to a container and are sufficiently mixed together by stirring. The mixture powder compact is placed into the solvent, and a reaction is performed in an autoclave at 170° C. to 250° C. for 2 to 24 hours (solvothermal synthesis). After the reaction, the mixture powder compact is washed with ethanol and pure water and is dried at 150° C. to 300° C. A KNbO3—BaTiO3 composite piezoelectric ceramic 1 is thus obtained.

Next, the composite piezoelectric ceramic 1 obtained is processed as required, and electrodes 2 and 3 are formed on a pair of surfaces of the composite piezoelectric ceramic 1. In a hot silicone oil, an electric field is applied to perform a polarization treatment. In this manner, there may be obtained the composite piezoelectric ceramic 1 illustrated in FIG. 1, and the piezoelectric device 4 which includes the composite piezoelectric ceramic 1 and the electrodes 2 and 3 disposed to interpose the composite piezoelectric ceramic 1 therebetween. The electrodes 2 and 3 may be formed by sputtering a metal such as Au.

EXAMPLES

Examples 1 to 6

<Preparation of KnbO2—Batio2 Composite Piezoelectric Ceramic>

A KNbO3 powder and a TiO2 powder were provided and were dried sufficiently. The powders were weighed so as to obtain a BaTiO3/MbO3 ratio (after the reaction) described in Table 1, and were added to a fluorine-coated resin container together with zirconia balls (3 mm in diameter). Ethyl alcohol was added, and mixing was performed for 16 hours.

The slurry of the mixture was separated from the zirconia balls, dried at 80° C., and crushed with a mortar and a pestle. As a binder, polyvinyl butyral (PVB) was added in an amount of 2 wt % relative to the dry powder and was mixed therewith sufficiently. The mixture was classified with a sieve having an opening of 250 μm.

After the classification, approximately 0.5 g of the powder was weighed and was placed into a mold 10 mm in diameter. With an oil hydraulic press machine, the powder was compacted into a disc under a pressure of 2 ton. The KNbO3—TiO2 disc obtained by the compaction was heated at 600° C. for 10 hours to remove the binder, thus affording a mixture powder compact.

Into a 25 ml volume container, 10 ml of water as the solvent and an amount of Ba(OH)2 prescribed to obtain the molar ratio described in Table 1 were added and were sufficiently mixed together by stirring. The KNbO5—TiO2 mixture powder compact that had been cleaned of the binder was placed into the liquid, and a reaction was performed in an autoclave at 180° C. for 20 hours. After the reaction, the mixture powder compact was washed with ethanol and pure water and was dried at 200° C. A KNbO3—BaTiO3 composite piezoelectric ceramic 1 was thus obtained.

<Electrical Evaluation of KNbO3—BaTiO3 Composite Piezoelectric Ceramic>

Au electrodes 2 and 3 illustrated in FIG. 1 were formed by a sputtering method on the samples prepared in Examples 1 to 6, thereby producing piezoelectric devices 4 illustrated in FIG. 1. The piezoelectric devices 4 were subjected to an electric field at 0.1 Hz frequency and 1 to 30 kV/cm, and the piezoelectric strain (the displacement) was measured with use of an electric field induced strain meter (JP005-SE manufactured by Kitamoto Denshi Kabushiki Kaisha). The piezoelectric constant d33 was calculated from the strain, the results being shown in Table 1. As a result, it was confirmed that high piezoelectric characteristics were obtained when the BaTiO3 ratio was in the range of 0.05 to 1.5.


TABLE 1
Change in specific
Solid solution composition
Molar ratio of
Reaction
BaTiO3
dielectric constant
KNbO3
NaNbO3
LiNbO3
BaTiO3 to
temperature
phase
d33
by temperature
molar ratio
molar ratio
molar ratio
solid solution
(° C.)
(by XRD)
(pm/V)
(−40 to 150° C.) (%)
Ex. 1
1.00
0.00
0.00
0.05
180
152
2.5
Ex, 2
1.00
0.00
0.00
0.20
180
268
6.7
Ex. 3
1.00
0.00
0.00
0.50
180
283
−2.4
Ex. 4
1.00
0.00
0.00
0.80
180
311
−7.0
Ex. 5
1.00
0.00
0.00
1.00
180
294
−9.2
Ex. 6
1.00
0.00
0.00
1.50
180
296
−24.6
Ex. 7
0.00
1.00
0.00
0.50
180
277
−7.9
Ex. 8
0.50
0.50
0.00
0.50
180
283
−7.3
Ex. 9
0.495
0.495
0.01
0.50
180
298
−7.0
Ex. 10
0.49
0.49
0.02
0.50
180
291
−8.1
Ex. 11
0.45
0.45
0.10
0.50
180
288
−8.3
Comp. Ex. 1
1.00
0.00
0.00
0.00
X
1.4
Comp. Ex. 2
1.00
0.00
0.00
0.02
180
X
82
1.9
Comp. Ex. 3
0.44
0.44
0.12
0.50
180
236
−8.9
Comp. Ex. 4
1.00
0.00
0.00
0.20
1150
128
6.5
Comp. Ex. 5
1.00
0.00
0.00
0.50
1150
260
−9.3

Further, the samples were tested in a thermostatic chamber with an impedance analyzer (4294A manufactured by Agilent Technologies, Inc.) to determine the temperature dependency of specific dielectric constant at −40° C. to 150° C. With the specific dielectric constant at 25° C. as the reference, the greatest change in specific dielectric constant caused in the above temperature range was measured, the results being shown in Table 1. As a result, the samples having a BaTiO3 ratio of 0.05 to 1.0 exhibited a good temperature dependency with the greatest change in specific dielectric constant being within 100, whereas a BaTiO3 ratio of 1.5 resulted in equal to or more than 20% change in specific dielectric constant.

<Identification of BaTiO3 Phase>

The KNbO3—BaTiO3 composite piezoelectric ceramics 1 were analyzed on an X-ray diffractometer manufactured by Rigaku Corporation using a CuKα ray at a tube voltage of 50 kV, a tube current of 40 mA and a scanning rate of 20°/min.

Regarding the crystal structure of the composite piezoelectric ceramic 1, in particular, the peaks assigned to a (220) plane and a (002) plane of the solid solution including orthorhombic KNbO3 change their shapes between before and after the reaction. Because KNbO3 and BaTiO3 are both perovskite structures having similar lattice constants, the growth of BaTiO3 may be confirmed based on changes in the shapes of the peaks assigned to the above planes of the KNbO3 crystal particles.

As an example, XRD peaks in Example 3 illustrated in FIG. 3 will be discussed. The peaks are assigned to a (220) plane and a (002) plane of orthorhombic KNbO3. In the XRD pattern after the solvothermal reaction, the (220) and (002) peaks of KNbO3 are smaller than the KNbO3 peaks before the reaction, and a peak assigned to (200) of tetragonal BaTiO3 appears near 45.2° to cause the profile of the peaks to be distorted. This change indicates the formation of BaTiO3. The results of the identification of BaTiO3 are described in Table 1. In Table 1, ⊙ shows that the intensity of the BaTiO3 (200) peak was approximately 0.7 to 2 times greater than the intensity of the KNbO3 (220) peak as was the case in FIG. 3.

FIG. 4 shows peaks assigned to a (220) plane and a (002) plane of orthorhombic KNbO3 in Example 1. As compared to FIG. 3, the decrease in the intensity of the (220) plane peak and the (002) plane peak of orthorhombic KNbO3 is small and the peak assigned to (200) of BaTiO3 is also small. This indicates that the amount of BaTiO3 formed is small. In Table 1, ◯ shows that the intensity of the BaTiO3 (200) peak was less than 0.7 times the intensity of the KNbO3 (220) peak as was the case in Example 1.

The formation of tetragonal BaTiO3 on the surface of orthorhombic KNbO3 results in a strain at the interface due to a slight lattice constant mismatch. This is probably the reason why dielectric characteristics and piezoelectric characteristics are enhanced.

The KNbO3—BaTiO3 composite piezoelectric ceramic 1 of Example 3 was processed into thin films with use of focused ion beam (FIB), thereby preparing samples for microstructure analysis and composition analysis. With a STEM manufactured by Hitachi High-Technologies Corporation, scanning transmission images of the samples were taken at an accelerating voltage of 200 kV and a field-of-view size of about 1×1 μm. With the attached energy-dispersive spectrometer (EDS), elements were mapped using characteristic X-rays, specifically, an Lβ2 X-ray for Ba, a Kα X-ray for Ti, a Kα X-ray for K, and an Lα X-ray for Nb. The results are illustrated in FIGS. 6A to 6E. FIG. 6A is a STEM image, FIG. 6B Ba distribution, FIG. 6C Ti distribution, FIG. 6D K distribution, and FIG. 6E Nb distribution. In the images, the elements are distributed in higher concentrations in whiter regions. FIGS. 6B to 6E show that BaTiO3 covers the KNbO3 core.

Further, the lattices were observed using the STEM and a heterojunction between KNbO3 and BaTiO3 was confirmed.

Examples 7 to 11

Samples were prepared and evaluated in the same manner as in Examples 1 to 6, except that the KNbO3 powder was replaced by a NaNbO3 powder, that the KNbO3 powder was combined with a NaNbO3 powder, or that the KNbO3 powder was combined with a NaNbO3 powder and a LiNbO3 powder. The results are described in Table 1. All the samples exhibited high piezoelectric characteristics, and the temperature dependency of specific dielectric constant was within 10% in all cases. The presence of BaTiO3 was confirmed by XRD.

Comparative Examples 1 to 3

KNbO3, NaNbO3, LiNbO3—BaTiO3 composite piezoelectric ceramics 1 were produced in the same manner as in Examples 1 to 11, except that the molar ratio of BaTiO3 to KNbO3, NaNbO3 and LiNbO3 was changed as described in Table 1. Electrodes were formed in the similar manner, and the piezoelectric strain (the displacement) and the piezoelectric constant d33 were measured, the results being described in Table 1. The measurement of d33 was infeasible when BaTiO3 had failed to form a layer with a heterojunction with the core. When the BaTiO3 ratio was 0.02, a low piezoelectric constant d33 was observed. The addition of LiNbO3 in a molar ratio of 0.12 resulted in a marked decrease in d33.

Further, the identification of a BaTiO3 phase was performed in the same manner as in Examples 1 to 11, the results being described in Table 1. In Comparative Example 2, as illustrated in FIG. 5, the XRD pattern after the solvothermal reaction had only the peaks assigned to the (220) and (002) planes of orthorhombic KNbO3, and no peak assigned to BaTiO3 was observed (x in Table 1).

Comparative Examples 4 and 5

KNbO3—BaTiO3 piezoelectric ceramics were produced through conventional ceramic production steps (a solid phase process) at a sintering temperature of 1150° C. They were evaluated by the same methods as in Examples 1 to 11 to determine the piezoelectric constant d33. The results are described in Table 1. The piezoelectric constant d33 was as low as 128 pm/V when the BaTiO3 ratio was 0.2, but was increased to 260 pm/v when the BaTiO3 ratio was raised to 0.5. However, the high synthesis (sintering) temperature is a factor that increases the cost due to the large amount of energy consumed during the sintering.

Piezoelectric ceramics produce a mechanical strain and a stress in response to the application of an electric field. Piezoelectric ceramics showing such a piezoelectric phenomenon are used in various piezoelectric devices such as actuators, piezoelectric buzzers, speakers and sensors. Further, the materials have recently found use in vibration power generation. The composite piezoelectric ceramics of the invention are highly useful in such piezoelectric applications.

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31.0/100 Score

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75.0/100 Score

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79.0/100 Score

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Citation

Patents Cited in This Cited by
Title Current Assignee Application Date Publication Date
複合圧電セラミックスおよび圧電素子 TDK株式会社 28 February 2012 27 December 2012
Piezoelectric ceramic composition KONICA MINOLTA HOLDINGS, INC. 07 November 2008 21 October 2010
Multilayer electronic component and method for manufacturing the same MURATA MANUFACTURING CO., LTD. 28 April 2008 04 September 2008
Piezoelectric ceramic and piezoelectric device containing the same TDK CORPORATION 14 May 2013 20 November 2014
圧電磁器組成物 NEC TOKIN CORP 05 March 2002 10 September 2003
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US10003009 Composite piezoelectric ceramic piezoelectric 1 US10003009 Composite piezoelectric ceramic piezoelectric 2 US10003009 Composite piezoelectric ceramic piezoelectric 3