WO2017006984A1 - Composant électronique céramique piézoélectrique et procédé de fabrication d'un composant électronique céramique piézoélectrique - Google Patents

Composant électronique céramique piézoélectrique et procédé de fabrication d'un composant électronique céramique piézoélectrique Download PDF

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WO2017006984A1
WO2017006984A1 PCT/JP2016/070107 JP2016070107W WO2017006984A1 WO 2017006984 A1 WO2017006984 A1 WO 2017006984A1 JP 2016070107 W JP2016070107 W JP 2016070107W WO 2017006984 A1 WO2017006984 A1 WO 2017006984A1
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piezoelectric ceramic
mol part
electronic component
metal element
piezoelectric
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PCT/JP2016/070107
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Japanese (ja)
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石井　秀樹
裕之 林
慎一郎 川田
小川　弘純
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株式会社村田製作所
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Priority to JP2017527489A priority Critical patent/JP6489333B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B06—GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS IN GENERAL
    • B06B—METHODS OR APPARATUS FOR GENERATING OR TRANSMITTING MECHANICAL VIBRATIONS OF INFRASONIC, SONIC, OR ULTRASONIC FREQUENCY, e.g. FOR PERFORMING MECHANICAL WORK IN GENERAL
    • B06B1/00—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency
    • B06B1/02—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy
    • B06B1/06—Methods or apparatus for generating mechanical vibrations of infrasonic, sonic, or ultrasonic frequency making use of electrical energy operating with piezoelectric effect or with electrostriction
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • H10N30/01—Manufacture or treatment
    • H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
    • H10N30/053—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes by integrally sintering piezoelectric or electrostrictive bodies and electrodes
    • 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
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/093—Forming inorganic materials
    • 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
    • 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
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions

Definitions

  • the present invention relates to a piezoelectric ceramic electronic component and a method for manufacturing the piezoelectric ceramic electronic component, and more particularly to a piezoelectric ceramic electronic component such as a laminated piezoelectric actuator using a lead-free piezoelectric ceramic composition and a method for manufacturing the same.
  • This type of piezoelectric ceramic electronic component is generally manufactured by alternately laminating ceramic green sheets serving as piezoelectric ceramic layers and conductive films serving as internal electrodes and co-firing.
  • Ag-based materials such as Ag and Ag—Pd alloy have been widely used conventionally.
  • Ag-based materials are prone to migration, so that the occurrence of migration can be effectively suppressed.
  • Ni is also desirable to use Ni that is readily available at a relatively low price.
  • the main component is represented by the general formula ⁇ (1-x) (K 1-ab Na a Li b ) (Nb 1-c Ta c ) O 3 -xM2M4O 3 ⁇ (where M2 is Ca , Ba, and Sr, M4 is at least one of Zr, Sn, and Hf, and x, a, b, and c are 0.005 ⁇ x ⁇ 0.1, respectively. 0 ⁇ a ⁇ 0.9, 0 ⁇ b ⁇ 0.1, 0 ⁇ a + b ⁇ 0.9, and 0 ⁇ c ⁇ 0.3), and Mn is 100 mol of the main component.
  • Piezoelectric ceramic compositions containing 2 to 15 mol and M4 in the range of 0.1 to 5.0 mol with respect to 100 mol of the main component have been proposed.
  • Patent Document 1 a predetermined amount of Mn is contained in the piezoelectric ceramic composition, and Zr is contained in excess of the stoichiometric composition, thereby enabling firing in a reducing atmosphere in which Ni is not oxidized. .
  • Example 1 when Yb as a rare earth element was further contained, the content of Li and Ca relative to 1 mol part of Nb was set to 0.02 mol part and 0.04 mol part, respectively. Piezoelectric characteristics with a point Tc of 150 to 290 ° C., a piezoelectric constant d 33 of 85 to 143 pC / N, and an electromechanical coupling coefficient kp of 16.8 to 30.5% are obtained.
  • Example 1 of Patent Document 1 described above the piezoelectric constant d 33 is not 143pC / N obtained only at most, further improvement in piezoelectric characteristics has been demanded.
  • the present invention has been made in view of such circumstances, and by adjusting the blending ratio of the piezoelectric ceramic composition, lead-free lead can be further improved in piezoelectric characteristics compared to the conventional case even when co-fired with Ni. It is an object of the present invention to provide a piezoelectric ceramic electronic component and a method for manufacturing the piezoelectric ceramic electronic component.
  • a piezoelectric ceramic electronic component is a piezoelectric ceramic electronic component comprising a piezoelectric ceramic body and an internal electrode embedded in the piezoelectric ceramic body,
  • the ceramic body contains a lead-free perovskite compound containing at least Li and Nb, a composite oxide containing Zr, and a divalent metal element, and the molar content of Li is based on 1 mol part of Nb.
  • the content molar amount of the divalent metal element is 0.045 mol part or more and 0.086 mol part or less with respect to the Nb1 mol part
  • the total content of the Li and the divalent metal element is 0.076 mol part or more and 0.166 mol part or less relative to the Nb1 mol part
  • the internal electrode contains Ni. It is characterized in that.
  • the piezoelectric ceramic electronic component according to the present invention is a piezoelectric ceramic electronic component comprising a piezoelectric ceramic body and an external electrode formed on the surface of the piezoelectric ceramic body, wherein the piezoelectric ceramic body is The lead-containing perovskite compound containing at least Li and Nb, Zr, and a complex oxide containing a divalent metal element are contained, and the molar content of Li is 0.025 mole part relative to 1 mole part of Nb.
  • the content molar amount of the divalent metal element is 0.045 mol part or more and 0.086 mol part or less with respect to the Nb1 mol part, and the Li and the 2
  • the total content of valent metal elements is 0.076 mol part or more and 0.166 mol part or less with respect to 1 mol part of Nb, and the external electrode contains Ni. It is.
  • the molar content of Zr is equal to or greater than the molar content of the divalent metal element.
  • Zr contributes to the improvement of piezoelectric characteristics, even better piezoelectric characteristics can be obtained by setting the molar content of Zr to be equal to or greater than the molar content of the divalent metal element.
  • the perovskite compound contains at least one element of K and Na.
  • the divalent metal element is preferably Ba, and in this case, the piezoelectric ceramic body preferably contains Mn.
  • the method for manufacturing a piezoelectric ceramic electronic component according to the present invention is a method for manufacturing a piezoelectric ceramic electronic component that forms a piezoelectric ceramic body containing at least Nb, Li, Zr, and a divalent metal element, At least the Nb compound and the Li compound are mixed and calcined so that the Li content is 0.025 mol part or more and 0.080 mol part or less with respect to 1 mol part of the Nb, and the first calcined powder is obtained.
  • the method for manufacturing a piezoelectric ceramic electronic component according to the present invention includes a step of integrally forming the second calcined powder and an electrode material containing Ni to produce a formed body, and the forming body in a reducing atmosphere. And a step of baking below.
  • a piezoelectric ceramic electronic component having good piezoelectric characteristics can be obtained with high efficiency even if it is co-sintered with Ni.
  • a piezoelectric ceramic electronic component of the present invention after preliminarily synthesizing a perovskite compound having a predetermined composition, a predetermined amount of a metal element compound and a Zr compound are added and calcined again.
  • a piezoelectric ceramic electronic component having high piezoelectric characteristics can be efficiently produced.
  • FIG. 1 is a cross-sectional view showing an embodiment of a piezoelectric ceramic electronic component according to the present invention. It is a perspective view of the ceramic green sheet obtained in the manufacture process of the said multilayer piezoelectric actuator. It is a perspective view of the laminated piezoelectric actuator. It is sectional drawing which shows other embodiment of the piezoelectric ceramic electronic component which concerns on this invention. It is a figure which shows the mapping analysis of Ba element in the sample number 41. FIG. It is a figure which shows the mapping analysis of Ba element in sample number 41 '.
  • FIG. 1 is a cross-sectional view showing an embodiment of a laminated piezoelectric actuator as a piezoelectric ceramic electronic component according to the present invention.
  • the laminated piezoelectric actuator has a conductive material such as Ag at both ends of a piezoelectric ceramic body 1.
  • the external electrode 2 (2a, 2b) is formed, and the piezoelectric ceramic body 1 is embedded with internal electrodes 3 (3a to 3g).
  • one end of the internal electrodes 3a, 3c, 3e, and 3g is electrically connected to one external electrode 2a, and one end of the internal electrodes 3b, 3d, and 3f is electrically connected to the other external electrode 2b.
  • the laminated piezoelectric actuator when a voltage is applied between the external electrode 2a and the external electrode 2b, the laminated piezoelectric actuator is displaced in the laminating direction indicated by the arrow X by the piezoelectric longitudinal effect.
  • the internal electrode 2 is formed of a conductive material containing Ni as a main component (for example, 30 wt% or more).
  • the piezoelectric ceramic body 1 is formed of a piezoelectric ceramic composition, and the piezoelectric ceramic composition includes an alkali niobate-based complex oxide whose main component is a lead-free perovskite compound, Zr, and divalent It is formed of a complex oxide containing the metal element.
  • M is a divalent metal element such as Ca, Ba, or Sr.
  • this piezoelectric ceramic composition contains x mol part of Li, y mol part of divalent metal element M, and z mol part of Zr with respect to 1 mol part of Nb.
  • the main component is an alkali niobate-based composite oxide represented by the general formula (A), a solid solution of a composite oxide containing Zr, and a divalent metal element has an abundance ratio of 80% or more. It means having.
  • the abundance ratio of the main component can be examined by a powder X-ray diffraction method (hereinafter referred to as “powder XRD method”).
  • powder X-ray diffraction method hereinafter referred to as “powder XRD method”.
  • a known amount of a compound different from the solid solution is mixed with the solid solution in advance, and the peak intensity of this mixture is measured. If the relationship between the amount of the compound different from the solid solution and the peak intensity is obtained as a calibration curve, the abundance ratio can be detected from the peak intensity of X-ray diffraction.
  • the solid solution means a state in which at least divalent metal elements M and Zr exist in the crystal or crystal grains of the alkali niobate complex oxide.
  • the component composition of this solid solution was determined by analyzing the crystals or crystal grains of the fired alkali niobate complex oxide with a transmission electron microscope (TEM), and using an energy dispersive X-ray analyzer (EDS). It can be identified by analyzing the ratio.
  • TEM transmission electron microscope
  • EDS energy dispersive X-ray analyzer
  • x and y satisfy the formulas (1) to (3).
  • (yMO + zZrO 2 ) is usually a complex oxide form of MZrO 3 , which is a composite of MO and ZrO 2, and is an alkali niobate complex oxide ⁇ (K a Na b ) It is dissolved in 1-x Li x ⁇ NbO 3 .
  • the piezoelectric ceramic composition represented by the general formula (A) satisfies only the formulas (1) to (3), and only the mixing ratio of the main component is adjusted without adding other additives.
  • the piezoelectric ceramic composition represented by the general formula (A) satisfies only the formulas (1) to (3), and only the mixing ratio of the main component is adjusted without adding other additives.
  • the inventors of the present invention have increased the Li content molar amount relative to Nb1 mol part from 0.016 mol part, while the Curie point Tc is increased while the second phase transition point T 2nd is decreased. It was found that the piezoelectric constant d 33 tends to be high.
  • the molar part x of Li with respect to Nb1 mol part is set to 0.025 mol part or more and 0.080 mol part or less.
  • the molar content of the divalent metal element M with respect Nb1 molar parts can be improved piezoelectric constant d 33 by 0.04 mol or more parts.
  • the main component composition for example, in order to obtain good piezoelectric characteristics with a piezoelectric constant d 33 of 170 pC / N or more and an Smax / Emax value of 120 pm / V or more, the divalent metal element M Even if the content molar amount of Li satisfies Formula (1), the content molar amount needs to be 0.045 mol part or more with respect to 1 mol part of Nb.
  • the content of the divalent metal element M exceeds 0.086 mol part with respect to 1 mol part of Nb, the content of the divalent metal element M becomes excessive, and the Curie point Tc is significantly lowered. It is not preferable.
  • the molar part y of the divalent metal element M relative to 1 part by mole of Nb is set to 0.045 mole part or more and 0.086 mole part or less.
  • the total (x + y) of the molar part of Li and the divalent metal element M with respect to 1 mol part of Nb is set to 0.076 mol part or more and 0.166 mol part or less.
  • the blending ratio of the piezoelectric ceramic composition is adjusted so that the general formula (A) satisfies the mathematical formulas (1) to (3), the reducing property is such that Ni is not oxidized. Even when fired in an atmosphere, a piezoelectric ceramic electronic component having even better piezoelectric characteristics than before can be obtained. In other words, even if Ni is used as the internal electrode material, it is possible to perform co-firing, thereby obtaining a lead-free multilayer piezoelectric actuator having even better piezoelectric characteristics than conventional ones at a stable and low cost. be able to.
  • an alkali niobate composite oxide is calcined and then an oxide containing a divalent metal element M and Zr is added.
  • the divalent metal elements M and Li can be successfully solid-solved in the crystal grains, thereby efficiently obtaining the piezoelectric ceramic electronic component having a desired solid solution as a main component. be able to.
  • the molar content of Zr is not particularly limited, but Zr is present in the form of MZrO 3 in combination with the divalent metal element M in the piezoelectric ceramic composition, and Zr is piezoelectric. Since it contributes to the improvement of the characteristics, it is possible to further improve the piezoelectric characteristics such as the piezoelectric constant d 33 by containing the same or more than the stoichiometric composition represented by MZrO 3 . That is, it is preferable that the molar part z with respect to the Nb1 molar part of Zr is equal to or more than the molar part y of the divalent metal element M with respect to the Nb1 molar part, and specifically satisfies the formula (4). preferable.
  • the content molar amount of K and Na after firing in the general formula (A) is not particularly limited, and is arbitrary in the range of 0.02 ⁇ a ⁇ 1.00 and 0 ⁇ b ⁇ 0.98, for example. Value can be set.
  • the main component only needs to satisfy the general formula (A), and it is also preferable to add various additives as necessary.
  • various additives for example, it is also preferable to contain Mn as a subcomponent with respect to the main component, which can improve piezoelectric characteristics such as an electromechanical coupling coefficient and a piezoelectric constant.
  • the divalent metal element M is formed of Ba
  • Ba may be segregated in the piezoelectric ceramic composition if Mn is not contained in the piezoelectric ceramic composition. If Ba segregates in the piezoelectric ceramic composition in this way, such segregated portions may hinder the expression of characteristics, and the piezoelectric characteristics may not be sufficiently improved.
  • the piezoelectric ceramic composition can be represented by the general formula (B).
  • Mn is contained as a subcomponent
  • Mn is solid-solved as an acceptor at the Nb site, and it is possible to compensate to some extent the charge of oxygen vacancies formed during firing in a reducing atmosphere.
  • Zr is added in excess of the stoichiometric composition (y ⁇ z), as with Mn, it becomes a solid solution at the Nb site as an acceptor, and the charge of oxygen vacancies formed during firing in a reducing atmosphere is effective. Therefore, it is possible to stably obtain a laminated piezoelectric actuator capable of further improving the piezoelectric characteristics, and to improve the reliability.
  • this invention is also preferable to contain additives, such as Ni, like Example 3 of patent document 1, and this demonstrates the synergistic effect with optimization of the compounding ratio of a main component composition, and is better Realization of a laminated piezoelectric actuator having excellent piezoelectric characteristics is expected.
  • Li-containing Li compound and Nb-containing Nb compound are prepared as ceramic raw materials, and K-containing K compound and Na-containing Na compound are prepared as necessary.
  • the form of the ceramic raw material compound may be any of oxide, carbonate, hydroxide, fluoride, and chloride.
  • the ceramic raw material is adjusted so that the content of Li in the fired piezoelectric ceramic composition (piezoelectric ceramic body) is 0.032 mole part or more and 0.075 mole part or less with respect to 1 mole part of Nb. Then, these weighed materials are put into a ball mill containing a grinding medium such as partially stabilized zirconia (hereinafter referred to as “PSZ”) balls, and sufficiently wet-ground in a solvent such as ethanol to obtain a mixture. obtain.
  • a grinding medium such as partially stabilized zirconia (hereinafter referred to as “PSZ”) balls
  • the mixture is calcined at a predetermined temperature (for example, 850 to 1000 ° C.) for a predetermined time to synthesize, pulverize, and thereby the first calcined composed of the alkali niobate complex oxide.
  • a predetermined temperature for example, 850 to 1000 ° C.
  • a powder is obtained (first calcination treatment).
  • an M compound containing a divalent metal element M and a Zr compound containing Zr are prepared.
  • the form of the M compound and the Zr compound may be any of oxide, carbonate, hydroxide, and chloride.
  • the content molar amount of the divalent metal element M in the fired piezoelectric ceramic composition is 0.045 mol part or more and 0.086 mol part or less with respect to 1 mol part of Nb, and the divalent metal element M is And the total content of Li is 0.075 mol part or more and 0.166 mol part or less with respect to 1 mol part of Nb, and the Zr content mol amount is preferably equal to the divalent metal element M content mol amount.
  • the first calcined powder, the M compound, and the Zr compound are weighed, and these weighed products are put into a ball mill containing a grinding medium such as a PSZ ball, and sufficiently in a solvent such as ethanol. To obtain a mixture.
  • the mixture is dried and then calcined at a predetermined temperature (for example, 850 to 1000 ° C.) for a predetermined time to synthesize and pulverize to obtain a second calcined powder as a main component powder (second Calcination treatment).
  • a predetermined temperature for example, 850 to 1000 ° C.
  • the piezoelectric ceramic composition in which both Li and the divalent metal element M are solid-solved in the crystal grains can be obtained.
  • a solid solution capable of exhibiting the effects of the present invention is formed even when a divalent metal element compound and a Zr compound are added and fired. I can't. This is because once the alkali niobate complex oxide is synthesized, the divalent metal element compound or Zr compound cannot be dissolved in the alkali niobate complex oxide.
  • a desired piezoelectric ceramic composition mainly composed of a solid solution of 3 and MZrO 3 can be obtained. That is, a part of alkali metal such as Li is volatilized in the first calcining treatment, but the alkali metal that has not volatilized is coordinated to the crystal lattice of the perovskite structure and is solidly dissolved in the crystal grains. Thus, a first calcined powder made of an alkali niobate-based composite oxide having a desired composition can be produced.
  • the first calcined powder maintains its composition and the M compound and Zr. It is considered that a piezoelectric ceramic composition in which a desired solid solution is formed by solid solution with a complex oxide containing a compound can be obtained.
  • various additives such as MnCO 3 are added to the second calcined powder thus obtained, if necessary, and then an organic binder and a dispersant are added. Wet mix in to obtain a ceramic slurry. And after that, a ceramic green sheet is produced by carrying out a shaping
  • a conductive paste for internal electrodes containing Ni as a main component is used, and a conductive layer 5 (5a-5g) having a predetermined shape is formed on the ceramic green sheets 4 (4a-4g) by screen printing as shown in FIG. Form.
  • the ceramic green sheets 4a to 4g on which the conductive layers 5a to 5g are formed are stacked, and then sandwiched between the ceramic green sheets 6a and 6b on which the conductive layers 5a to 5g are not formed, followed by pressure bonding. Thereby, a ceramic laminate in which the conductive layers 5a to 5g and the ceramic green sheets 4a to 4g are alternately laminated is manufactured.
  • the ceramic laminate is cut into a predetermined size and accommodated in an alumina pod (sheath), subjected to a binder removal treatment at a predetermined temperature (for example, 250 to 500 ° C.), and then a predetermined temperature (
  • a predetermined temperature for example, 250 to 500 ° C.
  • a predetermined temperature for example, 250 to 500 ° C.
  • the piezoelectric ceramic body 1 in which the internal electrodes 3a to 3g are embedded is formed by firing at 1000 to 1160 ° C.).
  • an external electrode conductive paste made of Ag or the like is applied to both ends of the piezoelectric ceramic body 1 and subjected to a baking process at a predetermined temperature (for example, 750 ° C. to 850 ° C.), as shown in FIG. 2a and 2b are formed. Thereafter, a predetermined polarization process is performed, whereby a laminated piezoelectric actuator is manufactured.
  • the external electrodes 2a and 2b may be formed by a thin film forming method such as a sputtering method or a vacuum vapor deposition method as long as the adhesion is good.
  • a first calcined powder having a desired composition made of an alkali niobate-based composite oxide is produced, and then the metal element compound and the Zr compound are mixed with the first calcined powder and again. Since the second calcined powder is calcined, the volatilization of alkali metal such as Li is suppressed in the second calcining process and the divalent metal elements M and Zr are easily contained in the crystal grains. Thus, it is possible to obtain a laminated piezoelectric actuator having a good piezoelectric characteristic composed mainly of a solid solution having a desired composition.
  • the ceramic green sheet 4 is formed of the piezoelectric ceramic composition, and the internal electrode is mainly composed of Ni, not a noble metal material such as Ag. Therefore, the multilayer piezoelectric actuator has good piezoelectric characteristics at low cost. Thus, it is possible to obtain a piezoelectric ceramic electronic component with excellent practicality that is effective in suppressing the occurrence of migration.
  • FIG. 4 is a sectional view showing another embodiment of a single plate type piezoelectric actuator as another embodiment of the piezoelectric ceramic electronic component according to the present invention.
  • a conductive paste for external electrodes mainly composed of Ni is applied to both surfaces of the molded body.
  • the present invention is not limited to the above embodiment.
  • the multilayer piezoelectric actuator and the single plate type piezoelectric actuator are exemplified as the piezoelectric ceramic electronic component, but it goes without saying that the piezoelectric ceramic electronic component can be applied to various piezoelectric components.
  • divalent metal element M examples include Ca, Sr, and Ba, but other divalent metal elements such as Mg may be included.
  • Mg may be dissolved in Ca, Sr, or Ba and exist in the crystal grains, but does not affect the characteristics.
  • Table 1 shows the composition components at the time of preparation of the samples of sample numbers 1 to 24.
  • K 2 CO 3 , Na 2 CO 3 , Li 2 CO 3 , and Nb 2 O 5 were prepared as ceramic raw materials. Then, in the general formula: [ ⁇ (K a Na b ) 1-x Li x ⁇ NbO 3 ], the ceramic raw materials were weighed so that the charged amounts of a, b, and x were as shown in Table 1. Next, these weighed materials were put into a ball mill containing PSZ balls having a diameter of 2 mm, and thoroughly wet mixed using ethanol as a solvent. And after drying the obtained mixture, it calcined for 2 hours in air
  • Non-Patent Document 1 describes powder X-ray diffraction data of (Na 0.35 K 0.65 ) NbO 3 .
  • the XRD data of the second calcined powder and the XRD data described in Non-Patent Document 1 are compared, and the intensity ratio of each peak and the peak position with respect to the surface interval d are similar.
  • it can be determined as a perovskite type compound containing an alkali metal and niobium.
  • this second calcined powder and MnCO 3 were prepared.
  • the amount of w charged was as shown in Table 1. Weigh it so that it becomes, put it into a ball mill containing PSZ balls together with an organic binder, dispersant, and pure water, mix thoroughly by wet, and then perform molding using the doctor blade method, thickness A ceramic green sheet having a thickness of 120 ⁇ m was obtained.
  • this ceramic green sheet is punched out into a circular shape with a diameter of 10 mm after firing, and thereafter, 11 ceramic green sheets punched into this circular shape are stacked and applied at a pressure of about 2.45 ⁇ 10 7 Pa. To obtain a ceramic molded body.
  • the ceramic molded body is fired at a temperature of about 1100 ° C. for 2 hours in a reducing atmosphere adjusted so that the metal Ni and NiO are on the reduction side 0.5 digit from the equilibrium oxygen partial pressure at which the metal Ni and NiO are in an equilibrium state.
  • a piezoelectric ceramic body was obtained.
  • sputtering is performed on both main surfaces of this piezoelectric ceramic body to form an external electrode made of Ag, and then an electric field of 3 kV / mm is applied in silicone oil at 80 ° C. for 30 minutes. ⁇ 24 samples were obtained.
  • the piezoelectric constant d 33 the Smax / Emax value, the Curie point Tc, the second phase transition point T 2nd , and the electromechanical coupling coefficient kp of the radial resonance vibration were measured for each of the sample numbers 1 to 24.
  • the piezoelectric constant d 33 was obtained from the amount of generated charges at the measurement frequency of 110 Hz with a force of 0.25 N rms loaded using a d 33 meter.
  • the strain S was determined, and then the strain S was divided by the electric field E to calculate the displacement characteristic value S / E.
  • the maximum value of the displacement characteristic value S / E was defined as the Smax / Emax value.
  • Curie point Tc was measured by measuring the temperature characteristic of relative permittivity ⁇ r at a measurement frequency of 1 kHz with an impedance analyzer, and calculating the maximum temperature of relative permittivity ⁇ r, which was taken as Curie point Tc.
  • the second phase transition point T 2nd than the Curie point Tc to calculate the maximum temperature of the relative dielectric constant of the low temperature side, which was used as a second phase transition point T 2nd.
  • the powder XRD method was used, the temperature was changed, and the crystal system of the main component with respect to the temperature was analyzed.
  • the crystal system changes at the Curie point Tc and the second phase transition point T 2nd . Therefore, from the analysis of such a crystal system, it is found that the temperature at the boundary between the tetragonal crystal and the cubic crystal is the Curie point Tc, and the temperature at the boundary between the orthorhombic or rhombohedral crystal and the tetragonal crystal is the second phase transition point T 2nd. confirmed.
  • the electromechanical coupling coefficient kp was obtained by a resonance-antiresonance method using an impedance analyzer. That is, Formula (1) is established between the electromechanical coupling coefficient kp, the resonance frequency Fr, and the antiresonance frequency Fa.
  • Non-Patent Document 2 Published by Japan Electronics and Information Technology Industries Association, "JEITA EM-4501 Electrical Testing Method for Piezoelectric Ceramic Vibrators", September 2010
  • each of the samples Nos. 1 to 24 was subjected to composition analysis using inductively coupled plasma-emission spectroscopy (Inductively-Coupled-Plasma-Atomic-Emission-Spectroscopy; hereinafter referred to as "ICP-AES”), and Nb1 mol.
  • ICP-AES Inductively-Coupled-Plasma-Atomic-Emission-Spectroscopy
  • Nb1 mol Nb1 mol.
  • Table 2 shows the measurement results of the component compositions after firing of sample numbers 1 to 24, the piezoelectric constant d 33 , the Smax / Emax value, the Curie point Tc, the second phase transition point T 2nd , and the electromechanical coupling coefficient kp. .
  • the piezoelectric constant d 33 is 170 pC / N or more, the Smax / Emax value is 120 pm / V or more, the Curie point Tc is 160 ° C. or more, the second phase transition point T 2nd is 100 ° C. or less, and the electromechanical coupling coefficient kp is 31%. The above was judged as a good product.
  • Sample No. 1 does not contain Li in the piezoelectric ceramic composition, so that the piezoelectric constant d 33 is 133 pC / N and the Smax / Emax value is low at 86 pm / V, indicating that the piezoelectric characteristics are inferior. It was.
  • the total (x + y) of the mole parts of Li and Ba relative to 1 mole part of Nb is 0.051 to 0.074 mole part, and is less than 0.076 mole part. Therefore, the piezoelectric constant d 33 was 146 to 165 pC / N, and Smax / Emax values were low, 109 to 118 pm / V, indicating that the piezoelectric properties were inferior.
  • Sample No. 15 has a small molar portion y is 0.034 mole of Ba with respect Nb1 molar parts, although the piezoelectric constant d 33 of the order 190pC / N was obtained, Smax / Emax values as low as 115pm / V It was.
  • Sample Nos. 7, 9 to 13, 16 to 18, 21, and 22 have a molar part x of Li and a molar part y of Ba of 0.025 to 0.080 mole part, and Nb1 mole part, respectively. Since the total amount (x + y) of the molar parts of Li and Ba is 0.076 to 0.166 mole part within the range of the present invention, the piezoelectric constant d 33 is 170.
  • Smax / Emax values are as large as 122 to 187 pm / V
  • Curie point Tc is as high as 160 to 310 ° C.
  • second phase transition point T 2nd is as low as 30 to 100 ° C.
  • Curie point Tc is It was found that the difference from the phase transition point T 2nd was sufficient, and the electromechanical coupling coefficient kp was 31.2 to 38.3%, and good piezoelectric characteristics were obtained.
  • this calcined powder is put into a ball mill containing PSZ balls together with an organic binder, a dispersant, and pure water and mixed sufficiently wet, and then subjected to a molding process using a doctor blade method, A ceramic green sheet having a thickness of 120 ⁇ m was obtained.
  • K 2 CO 3 , Na 2 CO 3 , Li 2 CO 3 , Nb 2 O 5 , and ZrO 2 were prepared.
  • the preparation amounts of a, b, x, y, and z are the compositions shown in the production process (4) in Table 3. Weighed so that
  • this second calcined powder and MnCO 3 are prepared.
  • the amount of w charged is as shown in Table 3.
  • the composition was weighed so as to have the composition shown in the production process (4).
  • Table 3 shows the composition of the components of Sample No. 12 and Sample Nos. 31 to 35 when charged.
  • composition analysis was performed using ICP-AES in the same manner and procedure as in Example 1, and K, Na, Li, Ba, Each molar part of (Li + Ba), Zr, and Mn was determined, and the piezoelectric constant d 33 and Smax / Emax value were measured.
  • Table 4 shows the composition components after firing of the sample numbers 31 to 35, the piezoelectric constant d 33 and the Smax / Emax values. In Table 4, the measurement result of sample number 12 is shown again.
  • each ceramic raw material contributing to the formation of the main component is weighed and calcined at the same time. Therefore, the piezoelectric constant d 33 is 105 to 143 pC / N, and the Smax / Emax value is 75 to 111 pm / V, which is lower than that of Sample No. 12.
  • sample No. 12 was calcined and synthesized after the alkali niobate-based composite oxide was calcined, and BaCO 3 , ZrO 2 , and MnCO 3 were added and calcined again. Therefore, the piezoelectric constant d 33 was 230 pC / The N and Smax / Emax values were 179 pm / V, and good results were obtained.
  • samples Nos. 41 and 42 were prepared by the same method and procedure as in Example 1.
  • composition analysis was performed using ICP-AES in the same manner and procedure as in Example 1, and K, Na, Li, Ba, (Li + Ba), The molar parts of Zr and Mn were determined, and the piezoelectric constant d 33 and Smax / Emax values were measured.
  • Table 5 shows the component composition at the time of preparation of sample numbers 41 and 42
  • Table 6 shows the component composition after firing, the piezoelectric constant d 33 and the Smax / Emax value.
  • sample number 12 is shown again for comparison.
  • a sample No. 41 ′ having the same composition as Sample No. 41 was prepared except that Mn was not added.
  • FIG. 5 is a diagram showing a mapping analysis of sample number 41
  • FIG. 6 is a diagram showing a mapping analysis of sample number 41 ′.
  • Sample No. 41 ′ not containing Mn shows that Ba is segregated in the piezoelectric ceramic composition as shown in FIG. 6 (indicated by S in the figure).

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  • Engineering & Computer Science (AREA)
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  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • General Electrical Machinery Utilizing Piezoelectricity, Electrostriction Or Magnetostriction (AREA)

Abstract

Dans un composant électronique céramique piézoélectrique, des électrodes internes 3 sont incorporées dans un ensemble 1 d'éléments céramiques piézoélectriques. L'ensemble 1 d'éléments céramiques piézoélectriques contient Zr, un composé pérovskite sans plomb comprenant au moins Li et Nb, et un oxyde composite comprenant un élément métallique bivalent. La teneur en moles de Li et de l'élément métallique bivalent, et leur teneur en moles combinée, sont respectivement de 0,025 à 0,080 partie en moles, de 0,045 à 0,086 partie en moles, et de 0,076 à 0,166 partie en moles, pour 1 partie en moles de Nb. Les électrodes internes 3 contiennent Ni. L'ensemble 1 d'éléments céramiques piézoélectriques est obtenu par mise en œuvre d'une synthèse par calcination du composé pérovskite, puis addition d'un composé d'un élément métallique et d'un composé de Zr, et mise en œuvre de nouveau d'une synthèse par calcination, puis cuisson du produit. Par ajustement du rapport de mélange de la composition céramique piézoélectrique sans plomb, on obtient un composant électronique céramique piézoélectrique sans plomb et un procédé de fabrication de ce dernier, par lesquels il est possible de renforcer encore plus les caractéristiques piézoélectriques par rapport à la technique antérieure, même si la cuisson est mise en œuvre en même temps qu'avec Ni.
PCT/JP2016/070107 2015-07-09 2016-07-07 Composant électronique céramique piézoélectrique et procédé de fabrication d'un composant électronique céramique piézoélectrique WO2017006984A1 (fr)

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JP2023066639A (ja) 2021-10-29 2023-05-16 日本特殊陶業株式会社 圧電素子、および圧電素子の製造方法

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JP2007258280A (ja) * 2006-03-20 2007-10-04 Tdk Corp 積層型圧電素子
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JP7352140B2 (ja) 2019-06-26 2023-09-28 株式会社村田製作所 圧電磁器組成物の製造方法及び圧電セラミック電子部品

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