WO2013005701A1 - Piezoelectric element, multilayered piezoelectric element, liquid discharge head, liquid discharge apparatus, ultrasonic motor, optical apparatus, and electronic apparatus - Google Patents
Piezoelectric element, multilayered piezoelectric element, liquid discharge head, liquid discharge apparatus, ultrasonic motor, optical apparatus, and electronic apparatus Download PDFInfo
- Publication number
- WO2013005701A1 WO2013005701A1 PCT/JP2012/066837 JP2012066837W WO2013005701A1 WO 2013005701 A1 WO2013005701 A1 WO 2013005701A1 JP 2012066837 W JP2012066837 W JP 2012066837W WO 2013005701 A1 WO2013005701 A1 WO 2013005701A1
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- WIPO (PCT)
- Prior art keywords
- piezoelectric element
- piezoelectric
- weight
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14201—Structure of print heads with piezoelectric elements
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- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14201—Structure of print heads with piezoelectric elements
- B41J2/14233—Structure of print heads with piezoelectric elements of film type, deformed by bending and disposed on a diaphragm
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- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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Definitions
- PIEZOELECTRIC ELEMENT MUL ILAYERED PIEZOELECTRIC ELEMENT, LIQUID DISCHARGE HEAD, LIQUID DISCHARGE APPARATUS, ULTRASONIC MOTOR, OPTICAL APPARATUS, AND
- the present invention generally relates to
- the present invention relates to a piezoelectric element, a multilayered piezoelectric element, a liquid discharge head, a liquid discharge
- AB0 3 perovskite-type metal oxides such as lead zirconate titanate (referred to as "PZT” hereinafter) are typically used as piezoelectric materials. Since PZT contains lead as the A site element, a concern has been raised over PZT 1 s impact on the environment . Thus ,
- piezoelectric materials that use lead-free perovskite-type metal oxides are highly desirable.
- PTL 1 discloses a piezoelectric element that uses barium titanate with the addition of Mn, Fe, or Cu and with some of the A sites being substituted with Ca.
- PTL 2 discloses an actuator and a liquid discharge head that use a material prepared by adding Ba and B to barium titanate. This material has an advantage of low sintering temperature but has a piezoelectric constant d 33 as low as 65 [pC/N] . Thus, high voltage has been required to drive the piezoelectric element .
- Piezoelectric materials having a Curie temperature of 80° C or less may undergo depolarization in a severe environment such as car compartments under summer sun and may lose piezoelectricity as a result. Piezoelectricity may be lost by heat generated as a result of driving of
- the invention provides a lead-free piezoelectric element that stably operates in a wide operating temperature range .
- a first aspect of the invention provides a
- piezoelectric element that includes a first electrode, a second electrode, and a piezoelectric material.
- piezoelectric material includes a perovskite-type metal oxide represented by general formula (1) as a main component, and manganese incorporated in the perovskite-type metal oxide :
- a manganese content relative to 100 parts by weight of the perovskite-type metal oxide is 0.02 parts by weight or more and 0.40 parts by weight or less on a metal basis.
- a second aspect of the present invention provides a multilayered piezoelectric element that includes
- the piezoelectric material layers and electrodes including an internal electrode.
- the piezoelectric material layers and the electrodes are alternately stacked.
- the piezoelectric material layers each contain a perovskite-type metal oxide represented by general formula ( 1 ) as a main component , and manganese incorporated in the perovskite-type metal oxide: (Bai- x Ca x ix-yZryJOa (where 1.00 ⁇ a ⁇ 1.01, 0.02 ⁇ x ⁇ 0.30, 0.020 ⁇ y ⁇ 0.095, and y ⁇ x) (1)
- the manganese content relative to 100 parts by weight of the perovskite-type metal oxide is 0.02 parts by weight or more and 0.40 parts by weight or less on a metal basis.
- a third aspect of the present invention provides a liquid discharge head that includes a liquid reservoir including a vibrating unit that includes the piezoelectric element or the multilayered piezoelectric element described above, and a discharge port in communication with the liquid reservoir.
- a fourth aspect of the present invention provides a liquid discharge head that includes a liquid reservoir including a vibrating unit that includes the piezoelectric element or the multilayered piezoelectric element described above, and a discharge port in communication with the liquid reservoir.
- a liquid discharge apparatus that includes a transport unit configured to transport a recording medium and the liquid discharge head described above.
- a fifth aspect of the present invention provides an ultrasonic motor that includes a vibrating member including the piezoelectric element or the multilayered piezoelectric described above and a moving member in contact with the vibrating member.
- a sixth aspect of the present invention provides an optical apparatus that includes a driving unit including the ultrasonic motor described above.
- a seventh aspect of the present invention provides an electronic apparatus that includes a piezoelectric acoustic component including the piezoelectric element or the multilayered piezoelectric element described above.
- a lead-free piezoelectric element that stably operates in a wide operating temperature range can be provided.
- a liquid discharge head, a liquid discharge apparatus, an ultrasonic motor, an optical apparatus, and an electronic apparatus that use this lead-free piezoelectric element can also be provided.
- Fig. 1 is a schematic view showing a piezoelectric element according to an embodiment of the invention.
- FIGs. 2A and 2B show a liquid discharge head according to an embodiment of the invention.
- FIGs. 3A and 3B are each a schematic view showing an ultrasonic motor according to an embodiment of the invention .
- Fig. 4 is a graph showing the relationship between x and y of piezoelectric ceramics of Production Examples 1 to 73.
- Figs. 5A and 5B are each a cross -sectional view showing a multilayered piezoelectric element according to an embodiment of the invention.
- Fig. 6 is a schematic view showing a liquid
- FIG. 7 is another schematic view showing the liquid discharge apparatus .
- FIGS. 8A and 8B are schematic views showing an optical apparatus according to an embodiment of the
- Fig. 9 is a schematic view showing the optical apparatus .
- Fig. 10 is a schematic view showing an electronic apparatus according to an embodiment of the invention.
- Fig. 1 is a schematic view showing a piezoelectric element according to one embodiment of the present invention.
- the piezoelectric element includes a piezoelectric material 2, and a first electrode 1 and a second electrode 3
- the piezoelectric element includes at least a first electrode, a piezoelectric material, and a second electrode.
- the piezoelectric material contains a perovskite-type metal oxide represented by general formula ( 1 ) as a main component and manganese (Mn) incorporated in the perovskite-type metal oxide :
- the Mn content relative to 100 parts by weight of the metal oxide is 0.02 parts by weight or more and 0.40 parts by weight or less on a metal basis.
- Each of the first and second electrodes is
- the material used to form the electrodes may be any material commonly used in piezoelectric elements. Examples thereof include metals such as Ti, Pt , Ta, Ir, Sr, In, Sn, Au, Al, Fe, Cr, Ni, Pd, Ag, and Cu and compounds thereof.
- the first and second electrodes may each be
- the first and second electrodes may be composed of materials different from each other.
- the electrodes may be any.
- the electrodes may be formed by baking a metal paste, by sputtering, or by vapor deposition.
- the first and second electrode may be patterned as desired.
- a perovskite-type metal oxide refers to a metal oxide having a perovskite-type structure which is ideally a cubic crystal structure as described in Iwanami Rikagaku Jiten, 5th edition (published February 20, 1998 by Iwanami Shoten Publishers).
- a metal oxide having a perovskite-type structure is usually expressed by a chemical formula, ABO 3 .
- Element A and element B in a perovskite-type metal oxide take form of ions and occupy particular
- element A occupies vertexes of the cube and element B occupies the body-centered position of the cube.
- Element O is oxygen in the form of an anion and occupies face-centered positions of the cube.
- barium (Ba) and calcium (Ca) are metal elements that occupy A sites and titanium (Ti) and zirconium (Zr) are metal elements that occupy B sites. Note that some of the Ba and Ca atoms may occupy B sites and/or some of the Ti and Zr atoms may occupy A sites .
- the molar ratio of the B- site element to O is 1:3.
- a metal oxide having a B-site element/O ratio slightly deviated therefrom, e.g., 1.00:2.94 to 1.00:3.06, is still included in the scope of the present invention as long as the metal oxide has a perovskite-type structure as a main phase.
- Structural analysis through X-ray diffraction or electron beam diffraction can be used to determine whether a metal oxide has a perovskite-type structure, for example.
- the piezoelectric material may take any form, for example, a ceramic, powder, single crystal, film, slurry, or the like but is preferably a ceramic.
- a “ceramic” refers to an aggregate (also referred to as bulk) of crystal grains basically composed of a metal oxide and consolidated by heat treatment, and is a polycrystal.
- a “ceramic” may also refer to a ceramic that has been
- a represents the ratio of the total molar amount of Ba and Ca in A sites to the total molar amount of Ti and Zr in B sites and is in a range of 1.00 ⁇ a ⁇ 1.01.
- a is smaller than 1.00, abnormal grain growth readily occurs and the mechanical strength of the material is decreased.
- a is greater than 1.01, the temperature needed for grain growth becomes excessively high and sintering cannot be achieved in a common firing furnace.
- "sintering cannot be achieved” refers to a state in which the density is not sufficiently increased or a large number of pores and defects are present in the piezoelectric material.
- x represents the molar ratio of Ca in A sites and is in a range of 0.02 ⁇ x ⁇ 0.30.
- x is less than 0.02, the dielectric loss (tan6)
- the piezoelectric property may not be sufficient.
- y represents the molar ratio of Zr in B sites and is in a range of 0.020 ⁇ y ⁇ 0.095.
- y is less than 0.020, the piezoelectric
- T c Curie temperature
- a Curie temperature refers to a temperature at which ferroelectricity is lost .
- Examples of the method for detecting the temperature include a method of directly measuring the temperature at which
- ferroelectricity is lost by varying the measurement
- the crystal structure phase transition temperature (phase transition point) can be shifted from near room temperature to a temperature below the operating temperature range and thus the device can be stably driven in a wide temperature range .
- the method for determining the composition of the piezoelectric material used in the piezoelectric element is not particularly limited. Examples of the method include X- ray fluorescence analysis, inductively coupled plasma (ICP) atomic emission spectroscopy, and atomic absorption
- the weight ratios and compositional ratios of the elements contained in the piezoelectric material can be determined by any of these methods .
- the piezoelectric element has a Mn content of 0.02 parts by weight or more and 0.40 parts by weight or less on a metal basis relative to 100 parts by weight of the metal oxide.
- the piezoelectric material having a Mn content within this range exhibits an improved insulation property and an improved mechanical quality factor.
- the mechanical quality factor refers to a factor that indicates an elastic loss caused by oscillation when the piezoelectric material is used in an oscillator.
- the magnitude of the mechanical quality factor is observed as a sharpness of a resonance curve in impedance measurement . In other words , the
- mechanical quality factor is a factor that indicates the sharpness of the resonance of an oscillator.
- the insulating property and the mechanical quality factor are improved by introduction of defect dipoles due to Mn having a valence different from that of Ti and Zr and
- a piezoelectric element formed by using the piezoelectric material and operated by applying voltage exhibits long-term reliability.
- the term "on a metal basis" with reference to the Mn content refers to a value determined by first determining the oxide-based amounts of elements constituting the metal oxide represented by general formula (1) based on the Ba, Ca, Ti, Zr, and Mn contents measured by XRF, ICP atomic emission spectroscopy, atomic absorption spectroscopy, or the like and then calculating the ratio of the weight of Mn relative to 100 parts by weight of the total amount of the elements constituting the metal oxide on a weight basis.
- the effect of the polarization treatment is not sufficient to drive the device.
- the Mn content is greater than 0.40 parts by weight, the piezoelectric
- Manganese is not limited to metallic Mn and may take any form as long as manganese is contained as a
- manganese may be dissolved in B sites or may be included in grain boundaries.
- Manganese may take the form of a metal, ion, oxide, metal salt, or complex in the piezoelectric material.
- manganese is dissolved in B sites from the viewpoints of insulating property and sinterability.
- a preferable range of the molar ratio A/B for resonator devices such as piezoelectric sensors, piezoelectric transformers, and ultrasonic motors, that operate at resonance frequencies is 0.993 ⁇ A/B ⁇ 0.998, where A is the molar amount of Ba and Ca in A sites and B is the molar amount of Ti, Zr, and Mn in B sites.
- a piezoelectric element having an A/B within this range exhibits a high piezoelectric constant and a high mechanical quality factor and thus forms a device having superior durability.
- Piezoelectric elements having an A/B within these ranges can exhibit a high piezoelectric constant, a low dielectric loss, and high durability.
- auxiliary components other than the compound represented by general formula (1) and Mn as long as the properties are not changed.
- the total content of the auxiliary components may be 1.2 parts by weight or less relative to 100 parts by weight of the metal oxide
- the content of the metal elements other than Ba, Ca, Ti, Zr, and Mn among the auxiliary components is preferably 1.0 parts by weight or less on an oxide basis or 0.9 parts by weight or less on a metal basis relative to the piezoelectric material.
- metal elements include semimetal elements such as Si, Ge, and Sb.
- the piezoelectric property and the insulating property of the piezoelectric material may be significantly degraded.
- the total content of Li, Na, Mg, and Al among the auxiliary components may be 0.5 parts by weight or less on a metal basis relative to the piezoelectric material.
- auxiliary components may be 0.2 parts by weight or less on a metal basis relative to the piezoelectric material.
- the polarization treatment may become difficult.
- auxiliary components include sintering aids such as Si and Cu.
- sintering aids such as Si and Cu.
- Commercially available Ba and Ca raw materials contain Sr as an unavoidable impurity and thus the piezoelectric material may contain an impurity amount of Sr.
- a commercially available Ti raw material contains Nb as an unavoidable impurity and a commercially available Zr raw material contains Hf as an unavoidable impurity.
- the piezoelectric material may contain impurity amounts of Nb and Hf .
- the method for measuring the weights of the auxiliary components is not particularly limited. Examples of the method include X-ray fluorescence analysis, ICP atomic emission spectroscopy, and atomic absorption
- piezoelectric element may be constituted by crystal grains having an average circular equivalent diameter of 1 ⁇ or more and 10 ⁇ or less .
- the average circular equivalent diameter 1 ⁇ or more and 10 ⁇ or less .
- the piezoelectric material can exhibit good piezoelectric property and
- the piezoelectric property may be insufficient.
- a more preferable range is 3 ⁇ or more and 8 ⁇ or less.
- the method for measuring the circular equivalent diameter is not particularly limited. For example, an image of a surface of a piezoelectric
- the material may be obtained with a polarizing microscope or a scanning electron microscope and the image may be processed to determine the circular equivalent diameter. Since the optimum magnification differs depending on the grain
- the circular equivalent diameter may be determined from an image of a polished surface or a cross section instead of a surface of the material.
- the relative density of the piezoelectric material used in the piezoelectric element may be 93% or more and 100% or less.
- the piezoelectric property and/or mechanical quality factor may not be satisfactory and the mechanical strength may be degraded.
- the main component of the piezoelectric material used in the piezoelectric element has x and y satisfying 0.125 ⁇ x ⁇ 0.175 and 0.055 ⁇ y ⁇ 0.090, respectively and the Mn content is 0.02 parts by weight or more and 0.10 parts by weight or less relative to 100 parts by weight of the metal oxide.
- a piezoelectric element that uses a piezoelectric material within this compositional range is particularly suited for a displacement actuator (a.k.a., soft device) such as an optical pickup actuator or a liquid discharge head.
- a displacement actuator a.k.a., soft device
- the durability may be degraded.
- x is larger than 0.175, the piezoelectric strain constant may be
- the piezoelectric strain constant may be decreased.
- y indicates the molar ratio of Zr is less than 0.055
- the piezoelectric strain constant may be decreased.
- the Mn content is less than 0.02 parts by weight, the polarization treatment may not be conducted satisfactorily.
- the piezoelectric strain constant may be decreased.
- a preferable range for a is 1.000 ⁇ a ⁇ 1.005.
- the main component of the piezoelectric material used in the piezoelectric element preferably has x and y respectively satisfying 0.155 ⁇ x ⁇ 0.300 and 0.041 ⁇ y ⁇ 0.069.
- the Mn content is preferably 0.12 parts by weight or more and 0.40 parts by weight or less on a metal basis relative to 100 parts by weight of the main component metal oxide .
- a piezoelectric element using the piezoelectric material within this compositional range is particularly suited for resonance devices (hard devices) such as
- piezoelectric sensors When x indicating the molar ratio of Ca is less than 0.155, the mechanical quality factor may be decreased. When x is greater than 0.300, the piezoelectric strain constant may be degraded. Preferably, 0.160 ⁇ x ⁇ 0.300. When y indicating the molar ratio of Zr is less than 0.041, the piezoelectric strain constant may be decreased. When y is greater than 0.069, the operating temperature range of the device may be narrowed. Preferably, 0.045 ⁇ y ⁇ 0.069.
- the mechanical quality factor may be decreased and the power consumption during operation of the device at a resonant frequency may increase.
- the Mn content is greater than 0.40 parts by weight, the piezoelectric strain constant may be decreased and a higher voltage may be needed to drive the device.
- the Mn content is 0.20 parts by weight or more and 0.40 parts by weight or less.
- a preferable range for a is 1.004 ⁇ a ⁇ 1.009.
- a method for making the piezoelectric material used in the piezoelectric element is not particularly limited.
- solid powders such as oxides, carbonate salts, nitrate salts, oxalate salts, and the like containing elements constituting the ceramic may be sintered at a normal pressure, which is a typical process.
- the raw materials are metal compounds such as a Ba compound, a Ca compound, a Ti compound, a Zr compound, and a Mn compound.
- Ba compound examples include barium oxide, barium carbonate, barium oxalate, barium acetate, barium nitrate, barium titanate, barium zirconate, and barium zirconate titanate.
- Ca compound examples include barium oxide, barium carbonate, barium oxalate, barium acetate, barium nitrate, barium titanate, barium zirconate, and barium zirconate titanate.
- titanium oxide examples include titanium oxide, barium titanate, barium zirconate titanate, and calcium titanate.
- zirconium oxide examples include zirconium oxide, barium zirconate, barium zirconate titanate, and calcium zirconate.
- manganese carbonate include manganese carbonate, manganese oxide, manganese dioxide, manganese acetate, and trimanganese tetraoxide.
- the raw materials for adjusting the molar ratio a i.e., the molar amount of Ba and Ca in A sites to the molar amount of Ti and Zr in B sites of the piezoelectric ceramic used in the piezoelectric element are not particularly limited. The same effect can be achieved from a Ba compound, a Ca compound, a Ti compound, and a Zr compound.
- the method for granulating raw material powders of the piezoelectric ceramic used in the piezoelectric element is not particularly limited. From the viewpoint of
- a spray dry method may be employed.
- binder used in granulation examples include polyvinyl alcohol (PVA), polyvinyl butyral (PVB) , and acrylic resins.
- the amount of binder added is preferably 1 to 10 parts by weight and more preferably 2 to 5 parts by weight from the viewpoint of increasing the density of a compact .
- the method for sintering the piezoelectric ceramic used in the piezoelectric element is not particularly
- Sintering may be conducted with an electric
- Sintering using an electric furnace or gas may be conducted in a continuous furnace or a batch furnace.
- the sintering temperature of the ceramic in the sintering method described above is not particularly limited.
- the sintering temperature may be a temperature that allows the compounds to react and undergo sufficient crystal growth.
- the sintering temperature is preferably 1200° C or more and 1550° C or less and more preferably 1300" or more and 1480° C or less from the viewpoint of making the grain diameter of the ceramic to be within the range of 1 ⁇ to 10 ⁇ .
- a piezoelectric ceramic sintered within this temperature range exhibits a good piezoelectric property.
- the sintering temperature may be kept constant within the above described range and sintering may be conducted for 2 to 24 hours.
- a two-step sintering method may be employed but rapid temperature changes are not desirable from the viewpoint of productivity.
- the piezoelectric ceramic may be heat-treated at a temperature of 1000° C or higher after being polished.
- a piezoelectric ceramic is mechanically polished, a residual stress occurs inside the piezoelectric ceramic.
- This residual stress can be relaxed by heat-treating at 1000° C or higher and the piezoelectric property of the piezoelectric ceramic can be further improved.
- the heat treatment also has an effect of eliminating raw material powders, such as barium carbonate, precipitated in grain boundary portions. The amount of time for the heat treatment is not
- the piezoelectric element may have polarization axes oriented in a particular direction.
- polarization axes are oriented in a particular direction, the
- the piezoelectric constant of the piezoelectric element is increased.
- the polarization method for the piezoelectric element is not particularly limited.
- the polarization treatment may be conducted in air or in silicone oil.
- the temperature during polarization may be 60° C to 100° C but optimum conditions slightly vary depending on the
- composition of the piezoelectric ceramic constituting the device The electric field applied to conduct the polarization treatment may be 800 V/mm to 2.0 kV/mm.
- the piezoelectric constant and mechanical quality factor of the piezoelectric element can be calculated from a resonant frequency and an antiresonant frequency measured with a commercially available impedance analyzer on the basis of Electronic Materials Manufacturers Association of Japan Standard (EMAS-6100). This method is hereinafter referred to as a resonance-antiresonance method.
- EANS-6100 Electronic Materials Manufacturers Association of Japan Standard
- Multilayered piezoelectric elements according to embodiments of the invention will now be described.
- a multilayered piezoelectric element according to an embodiment is constituted by alternately stacking
- the piezoelectric material layers are each composed of a piezoelectric material that contains a perovskite-type metal oxide represented by general formula (1) below as a main component and manganese (Mn) incorporated in the perovskite-type metal oxide:
- Figs. 5A and 5B are each a cross-sectional view showing a structure of a multilayered piezoelectric element according to one embodiment.
- the multilayered piezoelectric element includes piezoelectric material layers and
- the piezoelectric material layers are composed of the aforementioned piezoelectric material.
- the electrodes may include internal electrodes and external electrodes .
- Fig. 5A shows a multilayered piezoelectric element according to an embodiment.
- the multilayered piezoelectric element includes two piezoelectric material layers 54 and one layer of an inner electrode 55 alternately stacked, and the resulting stack is sandwiched between a first electrode 51 and a second electrode 53.
- the number of layers of the piezoelectric material layers and the number of layers of inner electrodes may be increased as shown in Fig. 5B and are not particularly limited.
- Fig. 5B shows a multilayered piezoelectric element according to another embodiment.
- piezoelectric element includes nine layers of piezoelectric material layers 504 and eight layers of inner electrodes 505 that are alternately stacked, and the resulting stack is sandwiched between a first electrode 501 and a second electrode 503.
- An external electrode 506a and an external electrode 506b for short-circuiting the inner electrodes alternately stacked are disposed on side surfaces of the stack.
- electrodes 506a and 506b may have a size and a shape
- piezoelectric material layers 54 and 504 different from those of the piezoelectric material layers 54 and 504 and may be divided into a plurality of segments.
- Each of the inner electrodes 55 and 505 and the external electrodes 506a and 506b is constituted by a
- the material therefor is not particularly limited and any material that is usually used in piezoelectric elements can be used. Examples of such a material include metals such as Ti, Pt, Ta, Ir, Sr, In, Sn, Au, Al, Fe, Cr, Ni, Pd, Ag, and Cu and compounds thereof.
- Each of the inner electrodes 55 and 505 and the external electrodes 506a and 506b may be composed of one of these materials or a mixture or an alloy of two or more of these materials , or may be constituted by a multilayered structure prepared by stacking two or more of these materials .
- the electrodes may be composed of
- the inner electrodes 55 and 505 may be mainly composed of Ni since Ni is a low- cost electrode material.
- the electrodes including the inner electrodes 505 may be short-circuited from each other to make driving voltage phases match.
- the inner electrodes 505, the first electrode 501, and the second electrode 503 may be short-circuited in an
- Electrodes and/or wires may be formed on side surfaces of a
- multilayered piezoelectric element to conduct short- circuiting, or through holes penetrating the piezoelectric material layers 504 may be formed and filled with a
- the method for making a multilayered piezoelectric element is not particularly limited.
- One example is a method that includes a step (A) of preparing slurry by dispersing a metal compound powder containing at least Ba, Ca, Ti, Zr, and Mn, a step (B) of obtaining a compact by placing the slurry on a substrate, a step (C) of forming an electrode on the compact, and a step (D) of obtaining a multilayered piezoelectric element by sintering the compact on which the electrode has been formed.
- a “powder” refers to a group of solid particles.
- a powder may be a group of particles that each contain Ba, Ca, Ti, Zr, and Mn or a group of a plurality of types of particles containing different
- Examples of the metal compound powder used in the step (A) include a Ba compound, a Ca compound, a Ti compound, a Zr compound, and a Mn compound.
- titanium oxide examples include titanium oxide, barium titanate, barium zirconate titanate, and calcium titanate.
- zirconium oxide examples include zirconium oxide, barium zirconate, barium zirconate titanate, and calcium zirconate.
- manganese carbonate include manganese carbonate, manganese oxide, manganese dioxide, manganese acetate, and trimanganese tetraoxide.
- An example of a method for preparing a slurry in the step (A) is as follows. To a metal compound powder, a solvent having a weight 1.6 to 1.7 greater than that of the metal compound powder is added, followed by mixing.
- Examples of the solvent that can be used include toluene, ethanol, a toluene-ethanol mixed solvent, n-butyl acetate. and water. The resulting mixture is mixed in a ball mill for 24 hours and a binder and a plasticizer are added thereto.
- Examples of the binder include polyvinyl alcohol (PVA), polyvinyl butyral (PVB), and acrylic resins. When PVB is used as the binder, the binder is weighed so that the solvent-to-PVB weight ratio is, for example, 88:12.
- plasticizer examples include dioctyl sebacate, dioctyl phthalate, and dibutyl phthalate.
- dibutyl phthalate is used as the plasticizer, dibutyl phthalate is weighed so that the weight thereof is the same as that of the binder. Then the resulting mixture is again mixed in a ball mill overnight. The amounts of the solvent and the binder are adjusted so that the viscosity of the slurry is 300 to 500 mPa's.
- the compact prepared in the step (B) is a sheet- shaped mixture of the metal compound powder, the binder, and the plasticizer.
- An example of a method for preparing the compact in the step (B) is a sheet-forming method.
- a doctor blade method may be employed in the sheet-forming method.
- a doctor blade method is a method that includes applying slurry to the substrate by using a doctor blade and drying the applied slurry to form a sheet-shaped compact.
- a polyethylene terephthalate (PET) film may be used as the substrate, for example.
- a surface of a PET film on which the slurry is to be placed may be coated with a fluorine coating in advance to facilitate separation of the compact.
- the slurry may be dried by air or hot air.
- the thickness of the compact is not particularly limited and can be adjusted according to the thickness of the multilayered piezoelectric element. The thickness of the compact can be increased by increasing the viscosity of the slurry, for example.
- the method for making the electrodes e.g., inner electrodes 505 and external electrodes 506a and 506b, in the step (C) is not particularly limited.
- the electrodes may be formed by firing a metal paste, or by a method such as sputtering, vapor deposition, or printing.
- the thickness and pitch of the piezoelectric material layers 504 may be decreased to decrease the driving voltage.
- a process of forming a stack including precursors of the piezoelectric material layers 504 and inner electrodes 505 and then firing the resulting stack is selected.
- the material of the inner electrodes 505 is desirably a material that does not undergo changes in shapes or deterioration of conductivity at a temperature needed to sinter the piezoelectric material layers 504.
- Electrodes such as Ag, Pd, Au, Cu, and Ni, which have lower melting points and are less expensive than Pt, and alloys of such metals can be used to form electrodes such as inner electrodes 505 and the external electrodes 506a and 506b.
- the external electrodes 506a and 506b may be formed after the stack has been fired and, in such a case, may be composed of Al or a carbon-based electrode material in addition to Ag, Pd, Cu, or Ni.
- the electrodes may be formed by a screen-printing method.
- a screen-printing method involves applying a metal paste onto a compact on a substrate through a screen plate by using a spatula.
- a screen mesh is formed in at least part of the screen plate.
- the screen mesh in the screen plate may have a pattern formed therein. The pattern is transferred to the compact by using the metal paste so as to form a patterned electrode on the compact .
- the substrate one or a plurality of layers of the compacts are press-bonded.
- the press-bonding method include uniaxial pressing, cold isostatic pressing, and hot
- the press -bonding may be conducted by hot isostatic pressing since pressure can be evenly and isostatically applied to the compacts. Press bonding may be conducted under heating at a temperature near the glass transition temperature of the binder for satisfactory bonding.
- Two or more of the compacts may be stacked and press-bonded until a desired thickness is achieved. For example, 10 to 100 layers of compacts may be stacked and thermally press -bonded for 10 seconds to 10 minutes by applying a pressure of 10 to 60 MPa in the stacking
- Alignment marks may be attached to the electrodes so that a plurality of layers of compacts can be accurately aligned and stacked. Alternatively, accurate stacking may be conducted by forming through holes for alignment in the compacts .
- the sintering temperature of the compact in the step (D) is not particularly limited, the sintering temperature may be a temperature at which compounds can react and sufficient crystal growth occurs .
- the sintering temperature is preferably 1200° C or more and 1550° C or less and more preferably 1300° C or more and 1480° C or less to adjust the grain diameter of the ceramic to be within a range of 1 ⁇ to 10 ⁇ .
- a multilayered piezoelectric element sintered within this temperature range exhibits a good piezoelectric property.
- the step (D) may be
- a reducing atmosphere refers to an atmosphere mainly composed of a mixed gas of hydrogen (H 2 ) and nitrogen (N 2 ) .
- the mixed gas may contain oxygen.
- the oxygen concentration is 10 "12 Pa or more and 10 "4 Pa or less and preferably 10 "8 Pa or more and 10 "5 Pa or less.
- the oxygen concentration can be measured with a zirconia-type oxygen sensor. Since Ni electrodes are used, the
- the multilayered piezoelectric element can be manufactured at a low cost.
- the compact After firing in the reducing atmosphere, the compact may be cooled to 600° C and the atmosphere may be changed to ambient atmosphere (oxidative atmosphere) to conduct an oxidation treatment.
- ambient atmosphere oxidative atmosphere
- a conductive paste is applied to a side surface of the compact in which ends of the inner electrodes are exposed, and dried to form an external electrode.
- a liquid discharge head includes at least a discharge port in communication with a liquid reservoir equipped with a vibrating unit that includes a piezoelectric element or multilayered piezoelectric element.
- Figs. 2A and 2B show a structure of a liquid discharge head according to one embodiment of the present invention.
- the liquid discharge head includes a piezoelectric element 101.
- the piezoelectric element 101 includes a first electrode 1011, a piezoelectric material 1012, and a second electrode 1013.
- the piezoelectric material 1012 is patterned as needed as shown in Fig. 2B.
- Fig. 2B is a schematic view of the liquid discharge head.
- the liquid discharge head includes discharge ports 105, individual liquid reservoirs 102, connecting holes 106 connecting the individual liquid reservoirs 102 to the discharge ports 105, partitions 104, a common liquid
- the shape may be any other shape, such as an elliptical shape, a circular shape, or a rectangular parallelepiped shape.
- the piezoelectric material 1012 follows the shape of the individual liquid reservoir 102.
- Fig. 2A is a cross- sectional view of the piezoelectric element shown in Fig. 2B taken in the width direction.
- the cross-sectional shape of the piezoelectric element 101 in the drawing is rectangular, the cross-sectional shape may be any other shape, such as a trapezoidal shape or an inverted trapezoidal shape.
- the first electrode 1011 is used as a lower electrode and the second electrode 1013 is used as an upper electrode.
- the arrangement of the first electrode 1011 and the second electrode 1013 is not limited to this.
- the first electrode 1011 may be used as the lower electrode or the upper electrode.
- the second electrode 1013 may be used as the upper electrode or the lower electrode.
- a buffer layer 108 may be present between the vibrating plate 103 and the lower electrode.
- the vibrating plate 103 of the liquid discharge head moves in vertical directions as the piezoelectric material 1012 expands and contracts, and applies pressure to liquid in the individual liquid reservoir 102. As a result, liquid is ejected from the discharge port 105.
- the liquid discharge head can be used in printers and for production of electronic devices.
- the thickness of the vibrating plate 103 is 1.0 ⁇ or more and 15 ⁇ or less and preferably 1.5 ⁇ or more and 8
- the material for forming the vibrating plate 103 is not particularly limited but may be silicon. Silicon constituting the vibrating plate 103 may be doped with boron or phosphorus.
- the buffer layer 108 on the vibrating plate 103 and the electrode on the buffer layer 108 may constitute part of the vibrating plate 103. The thickness of the
- buffer layer 108 is 5 nm or more and 300 nm or less and preferably 10 nm or more and 200 nm or less.
- the size of the discharge port 105 is 5 ⁇ or more and 40 ⁇ or less in terms of circular equivalent diameter.
- the shape of the discharge port 105 may be circular, star-shaped, rectangular, or triangular, for example.
- the liquid discharge apparatus includes the liquid discharge head described above.
- FIG. 7 shows the state in which outer casings 882 to 885 and 887 are removed from a liquid discharge apparatus (ink jet
- the recording apparatus 881 includes an automatic feeding unit 897 configured to automatically feed a recording paper sheet, i.e., a recording medium, into a main body 896.
- the ink jet recording apparatus 881 also includes a transport unit 899 that guides the recording sheet fed from the automatic feeding unit 897 to a particular recording position and to a discharge slot 898 from the recording position, a recording unit 891 configured to conduct recording on the recording sheet transferred to the recording position, and a recovery unit 890 configured to conduct a recovery process on the recording unit 891.
- the recording unit 891 has a carriage 892 that houses the liquid discharge head and moves on a rail in a reciprocating manner.
- This liquid discharge apparatus can eject liquid uniformly at a high speed and is small-sized.
- the liquid discharge apparatus may be used in industrial liquid discharge apparatuses and drawing apparatuses configured to draw images, characters, etc., on media in addition to printing apparatus such as facsimile machines, multifunction apparatuses, and ink jet recording apparatuses.
- Ultrasonic motor configured to draw images, characters, etc., on media in addition to printing apparatus such as facsimile machines, multifunction apparatuses, and ink jet recording apparatuses.
- An ultrasonic motor includes at least a moving member that contacts a vibrating member equipped with a piezoelectric material or multilayered piezoelectric element .
- Figs. 3A and 3B are each a schematic view showing a structure of an ultrasonic motor according to an embodiment of the present invention.
- Fig. 3A shows an ultrasonic motor that includes a piezoelectric element having a single-layer structure.
- the ultrasonic motor includes a vibrator 201, a rotor 202 pressure-contacting a sliding surface of the vibrator 201 due to the pressing force from a pressing spring (not shown in the drawing), and an output shaft 203 integral with the rotor 202.
- the vibrator 201 is
- the piezoelectric element 2012 is composed of a piezoelectric material sandwiched between a first electrode and a second electrode which are not shown in the drawing.
- the piezoelectric material When voltage is applied to the piezoelectric material, the piezoelectric material expands and contracts due to the piezoelectric transversal effect.
- an elastic member such as a metal member is in contact with the piezoelectric element, the elastic member is bent as the piezoelectric material expands and contracts .
- FIG. 3B shows an example of an ultrasonic motor including a piezoelectric element having a multilayered structure.
- a vibrator 204 includes a cylindrical metal elastic member 2041 and a multilayered piezoelectric element 2042 provided in the metal elastic member 2041.
- multilayered piezoelectric element 2042 is constituted by a plurality layers of piezoelectric materials although this is not shown in the drawing.
- a first electrode and a second electrode are disposed on outer surfaces of the stack and inner electrodes are provided inside the stack.
- the metal elastic member 2041 is bolted to sandwich the multilayered piezoelectric element 2042 to thereby constitute the
- the optical apparatus includes an ultrasonic motor in a drive unit .
- FIGs. 8A and 8B are each a cross-sectional view of a related part of a replaceable lens barrel of a single-lens reflex camera, which is an example of an imaging apparatus according to an embodiment of the present invention.
- Fig. 9 is an exploded perspective view of the replaceable lens barrel .
- a fixed barrel 712, linear guide barrel 713, and a front lens group barrel 714 are fixed to a mount 711 detachable from and attachable to a camera. These are fixed members of the replaceable lens barrel.
- a linear guide groove 713a extending in an optical axis direction is formed in the linear guide barrel 713 to guide a focus lens 702.
- a cam roller 717a and a cam roller 717b protruding in an outer radial direction are fixed with a shaft screw 718 to a rear lens group barrel 716 holding the focus lens 702.
- the cam roller 717a is fitted in the linear guide groove 713a.
- a cam ring 715 is rotatably fitted to the inner periphery of the linear guide barrel 713. Relative
- a rotation transmitting ring 720 is provided on the outer peripheral side of the fixed barrel 712.
- the rotation transmitting ring 720 is held by a ball race 727 so that it can rotate at a particular position relative to the fixed barrel 712.
- a roller 722 is rotatably held by a shaft 720f extending in a radial manner from the rotation transmitting ring 720, and a large-diameter portion 722a of the roller 722 is in contact with a mount-side end surface 724b of a manual focus ring 724.
- a small-diameter portion 722b of the roller 722 is in contact with a joint member 729.
- Six equally spaced rollers 722 are arranged on the outer
- a low-friction sheet (washer member) 733 is arranged on the inner radial portion of the manual focus ring 724.
- the low-friction sheet 733 is interposed between a mount-side end surface 712a of the fixed barrel 712 and a front-side end surface 724a of the manual focus ring 724.
- the outer radial surface of the low-friction sheet 733 has a ring shape and is fitted in an inner radial portion 724c of the manual focus ring 724.
- the inner radial portion 724c of the manual focus ring 724 is fitted in an outer radial portion 712b of the fixed barrel 712.
- the low-friction sheet 733 reduces the friction in a rotary ring mechanism in which the manual focus ring 724 is rotated relative to the fixed barrel 712 about the optical axis.
- the large-diameter portion 722a of the roller 722 and a mount-side end surface 724b of the manual focus ring 724 contact each other under pressure by being pressed by a wave washer 726 that presses an ultrasonic motor 725 toward the front side of the lens.
- the force from the wave washer 726 pressing the ultrasonic motor 725 toward the front side of the lens also causes the small-diameter portion 722b of the roller 722 and the joint member 729 to contact each other under an adequate degree of pressure.
- the wave washer 726 is confined from moving in the mount direction by a washer 732 bayonet -mounted to the fixed barrel 712.
- the spring force (urging force) generated by the wave washer 726 is transmitted to the ultrasonic motor 725 and to the roller 722 and serves as thrusting force of the manual focus ring 724 against the mount-side end surface 712a of the fixed barrel 712.
- the manual focus ring 724 is assembled while being urged against the mount -side end surface 712a of the fixed barrel 712 via the low-friction sheet 733.
- the roller 722 rotates about the center of the shaft 720f because the joint member 729 makes frictional contact with the small-diameter portion 722b of the roller 722.
- the rotation transmitting ring 720 is rotated about the optical axis (automatic focusing
- Two focus keys 728 are installed in the rotation transmitting ring 720 at positions opposite to each other and fitted in notches 715b at the front tip of the cam ring 715.
- the rotation transmitting ring 720 is rotated about the optical axis, the rotation force is transmitted to the cam ring 715 via the focus keys 728.
- apparatus may be any type of camera such as a compact camera, an electronic still camera, or the like, or may be a
- An optical apparatus having an ultrasonic motor in a driver unit is also within the range of the present invention.
- the piezoelectric acoustic component may be a speaker, a microphone, a surface acoustic wave (SAW) device, or the like .
- SAW surface acoustic wave
- Fig. 10 is a perspective view of a digital camera, which is an example of the electronic apparatus according to the present invention, as viewed from the front of a main body 931.
- An optical device 901, a microphone 914, a strobe light unit 909, and an auxiliary light unit 916 are
- a power button 933, a speaker 912, a zoom lever 932, and a release button 908 for executing focusing operation are installed in the upper surface of the main body 931.
- the speaker 912 is built inside the main body 931 and is indicated by a broken line . Holes for outputting sound are formed at the front of the speaker 912.
- the piezoelectric acoustic component is used in at least one of the microphone 914, speaker 912, and a SAW device .
- the electronic apparatus is not limited to this and may be any electronic apparatus equipped with a piezoelectric
- acoustic component such as a sound-reproducing apparatus, a sound-recording apparatus, a cellular phone, and an
- the embodiments of the piezoelectric element and the multilayered piezoelectric element described above are suitable for use in a liquid discharge head, a liquid discharge apparatus, an ultrasonic motor, an optical apparatus, and an electronic apparatus.
- a liquid discharge head that has a nozzle density
- a liquid discharge apparatus equipped with a liquid discharge head according to an embodiment of the present invention can exhibit discharge force and discharge accuracy comparable or superior to a liquid discharge apparatus that uses a liquid discharge head including a lead-containing piezoelectric element.
- An ultrasonic motor that uses the piezoelectric element or the multilayered piezoelectric element according to an embodiment of the present invention exhibits driving force and durability comparable or superior to an ultrasonic motor that uses a lead-containing piezoelectric element.
- An optical apparatus that uses the ultrasonic motor can exhibit durability and operation accuracy comparable or superior to an optical apparatus that uses an ultrasonic motor that includes a lead-containing piezoelectric element.
- embodiment of the present invention exhibits a sound- generating property comparable or superior to an electronic apparatus that includes a lead-containing piezoelectric element .
- a piezoelectric ceramic for use in a piezoelectric element was prepared.
- Barium titanate having an average particle diameter of 100 nm (BT-01 produced by Sakai Chemical Industry Co., Ltd.), calcium titanate having an average particle diameter of 300 nm (CT-03 produced by Sakai Chemical Industry Co., Ltd. ) , and calcium zirconate having an average particle diameter of 300 nm (CZ-03 produced by Sakai Chemical
- the granulated powder was charged in a mold and pressed under 200 MPa of forming pressure with a press- molding machine to prepare a disk- shaped compact.
- the compact may be further pressed by using a cold isostatic press -molding machine.
- the compact was placed in an electric furnace and sintered in an air atmosphere for a total of 24 hours during which a maximum temperature of 1400° C was retained for 5 hours .
- the average circular equivalent diameter was 6.2 ⁇ and the relative density was 94.9%.
- a polarizing microscope was mainly used to observe crystal grains. The diameter of small crystal grains was determined by using a scanning electron microscope (SEM). The average circular equivalent diameter was calculated on the basis of the observation results. The relative density was evaluated by the Archimedean method.
- the ceramic was polished to a thickness of 0.5 mm and the crystal structure of the ceramic was analyzed by X- ray diffraction. As a result, only peaks attributable to a perovskite-type structure were observed.
- composition prepared by weighing matches the composition after sintering.
- the contents of the elements other than Ba, Ca, Ti, Zr, and Mn were below detection limits, i.e., less than 0.1 parts by weight.
- Barium titanate having an average particle diameter of 100 nm (BT-01 produced by Sakai Chemical Industry Co., Ltd.), calcium titanate having an average particle diameter of 300 nm (CT-03 produced by Sakai Chemical Industry Co., Ltd.), and calcium zirconate having an average particle diameter of 300 nm (CZ-03 produced by Sakai Chemical
- Tables 1-1 and 1-2 was weighed. These powders were dry- mixed in a ball mill for 24 hours. In Example 48, 0.8 parts by weight of Si on an oxide basis was added as an auxiliary component. In Example 52, a total of 1.0 parts by weight of Si and Cu on an oxide basis were added as auxiliary
- manganese ( II ) acetate in an amount on a manganese metal basis shown in Tables 1-1 and 1-2 and 3 parts by weight of a PVA binder relative to the mixed powder were caused to adhere to surfaces of the mixed powder by using a spray dryer in order to granulate the mixed powder.
- the granulated powder was charged in a mold and pressed under 200 MPa of forming pressure with a press - molding machine to prepare a disk-shaped compact.
- the compact may be further pressed by using a cold isostatic press-molding machine.
- the compact was placed in an electric furnace and sintered in an air atmosphere for a total of 24 hours, during which a maximum temperature of 1350° C to 1480° C was retained for 5 hours .
- the maximum temperature was increased as the amount of Ca was increased.
- the ceramic was polished to a thickness of 0.5 mm and the crystal structure of the ceramic was analyzed by X- ray diffraction. As a result, only peaks attributable to a perovskite-type structure were observed in all samples.
- a ceramic was prepared under the same conditions as in Examples 2 to 52, 72, and 73 by using each of the
- Each resulting ceramic was polished to a thickness of 0.5 mm and the crystal structure of the ceramic was analyzed by X-ray diffraction. As a result, only peaks attributable to a perovskite-type structure were observed in all samples .
- composition of the ceramic was analyzed by X- ray fluorescence analysis. The results are shown in Tables 3-1 and 3-2. As a result, it was found that the composition prepared by weighing matched the composition after sintering in all samples .
- piezoelectric materials of Production Examples 1 to 73 is shown in the graph of Figure 1.
- the range marked by a broken line indicates the range of x and y of general formula (1) representing the perovskite-type metal oxide described in the embodiment .
- Example 1 Production Example 1 0.095 0.030 1.002 0.08 0.0
- Example 2 Production Example 2 0.050 0.050 1.003 0.10 0.0
- Example 3 Production Example 3 0.020 0.020 1.002 0.10 0.0
- Example 4 Production Example 4 0.095 0.060 1.001 0.08 0.0
- Example 5 Production Example 5 0.095 0.095 1.002 0.06 0.0
- Example 6 Production Example 6 0.125 0.020 1.003 0.08 0.0
- Example 7 Production Example 7 0.125 0.050 1.001 0.06 0.0
- Example 8 Production Example 8 0.125 0.055 1.000 0.06 0.0
- Example 9 Production Example 9 0.125 0.090 1.000 0.06 0.0
- Example 10 Production Example 10 0.140 0.075 1.003 0.02 0.0
- Example 11 Production Example 1 1 0.140 0.075 1.000 0.02 0.0
- Example 12 Production Example 12 0.140 0.075 1.003 0.07 0.0
- Example 13 Production Example 13 0.140 0.075 1.000 0.07 0.0
- Example 14 Production Example 14 0.140 0.075 1.001 0.08 0.0
- Example 15 Production Example 15 0.155 0.020 1.005 0.15 0.0
- Example 16 Production Example 16 0.155 0.035 1.006 0.18 0.0
- Example 17 Production Example 17 0.155 0.041 1.004 0.18 0.0
- Example 18 Production Example 18 0.155 0.065 1.000 0.02 0.0
- Example 19 Production Example 19 0.155 0.065 1.001 0.06 0.0
- Example 20 Production Example 20 0.155 0.065 1.004 0.06 0.0
- Example 21 Production Example 21 0.155 0.065 1.001 0.10 0.0
- Example 22 Production Example 22 0.155 0.065 1.005 0.10 0.0
- Example 23 Production Example 23 0.155 0.069 1.004 0.18 0.0
- Example 24 Production Example 24 0.175 0.030 1.004 0.15 0.0
- Example 25 Production Example 25 0.175 0.055 1.004 0.06 0.0
- Example 26 Production Example 26 0.175 0.090 1.007 0.10 0.0
- Example 27 Production Example 27 0.187 0.060 1.001 0.12 0.0
- Example 28 Production Example 28 0.187 0.060 1.007 0.18 0.0
- Example 29 Production Example 29 0.187 0.060 1.003 0.18 0.0
- Example 30 Production Example 30 0.187 0.060 1.009 0.24 0.0
- Example 31 Production Example 31 0.187 0.060 1.003 0.24 0.0
- Example 32 Production Example 32 0.187 0.060 1.008 0.30 0.0
- Example 33 Production Example 33 0.200 0.035 1.006 0.20 0.0
- Example 34 Production Example 34 0.200 0.055 1.005 0.22 0.0
- Example 35 Production Example 35 0.200 0.070 1.007 0.24 0.0
- Example 36 Production Example 36 0.200 0.090 1.006 0.26 0.0
- Example 37 Production Example 37 0.220 0.030 1.005 0.22 0.0
- Example 38 Production Example 38 0.220 0.065 1.005 0.15 0.0
- Example 39 Production Example 39 0.220 0.065 1.002 0.15 0.0
- Example 40 Production Example 40 0.220 0.065 1.007 0.20 0.0 [ 0155 ]
- Example 41 Production Example 41 0.220 0.065 1.006 0.20 0.0
- Example 42 Production Example 42 0.220 0.065 1.005 0.25 0.0
- Example 43 Production Example 43 0.220 0.080 1.006 0.28 0.0
- Example 44 Production Example 44 0.260 0.020 1.006 0.22 0.0
- Example 45 Production Example 45 0.260 0.045 1.004 0.24 0.0
- Example 46 Production Example 46 0.260 0.065 1.004 0.26 0.0
- Example 47 Production Example 47 0.260 0.070 1.005 0.28 0.0
- Example 48 Production Example 48 0.300 0.020 1.004 0.26 0.0
- Example 49 Production Example 49 0.300 0.041 1.007 0.26 0.8
- Example 50 Production Example 50 0.300 0.050 1.006 0.28 0.0
- Example 51 Production Example 51 0.300 0.069 1.009 0.30 0.0
- Example 52 Production Example 52 0.300 0.095 1.008 0.30 1.0
- Example 53 Production Example 72 0.187 0.060 1.010 0.40 0.0
- Example 54 Production Example 73 0.160 0.059 1.009 0.40 0.0 Preparation of piezoelectric element and evaluation of static characteristics
- Piezoelectric elements of Example 1 to 54 were fabricated by using ceramics of Production Examples 1 to 52, 72, and 73.
- a gold electrode having a thickness of 400 nm was formed on both sides of the disk-shaped ceramic described above by DC sputtering.
- a titanium film functioning as an adhesive layer and having a thickness of 30 nm was formed between the electrode and the ceramic.
- the ceramic with the electrodes was cut into a strip- shaped piezoelectric element 10 mm x 2.5 mm x 0.5 mm in size.
- the piezoelectric element was placed on a hot plate having a surface adjusted to 60° C to 100° C and a 1 kV/mm electric field was applied to the piezoelectric element for 30 minutes to conduct a polarization treatment.
- the static characteristics of the piezoelectric element i.e., the Curie temperature, the dielectric loss, the piezoelectric constant d 3i , and the mechanical quality factor (Qm) , of the polarized piezoelectric element were evaluated. The results are shown in Tables 4-1 and 4-2. The mechanical quality factor is indicated in Table 6.
- the Curie temperature was determined from the temperature at which the dielectric constant measured under application of a 1 kHz micro AC field while varying measurement temperature was maximal. The dielectric loss was also measured
- Tables 4-1 and 4-2 also shows the amounts of Ba and Ca on a molar basis and the Ti/Zr/Mn molar ratio. In the table, "X" indicates that evaluation could not be conducted.
- Example 7 Production Example 7 114 100 0.3 0.999
- Example 10 Production Example 10 100 106 0.4 1.002
- Example 11 Production Example 1 1 100 111 0.3 0.999
- Example 14 Production Example 14 100 100 0.3 0.998
- Example 19 Production Example 19 106 100 0.3 0.999
- Example 21 Production Example 21 106 90 0.2 0.997
- Example 36 Production Example 36 90 84 0.1 0.996
- Example 39 Production Example 39 105 81 0.1 0.996
- Piezoelectric elements of Comparative Examples 1 to 19 were fabricated by using ceramics of Production Examples 53 to 71. Fabrication and evaluation of the devices were conducted as in Examples 1 to 54.
- the piezoelectric constant d 3i was as low as 36 [pC/N] .
- the value of a was as large as 1.030 and grain growth was insufficient due to insufficient sintering.
- the piezoelectric constant d 3i was as low as 20 [pC/N] and the dielectric loss was as high as 0.9%.
- the Mn content was as high as 0.45 parts by weight and thus the piezoelectric constant was low although the dielectric loss was low.
- the average circular equivalent diameter of grains was smaller than 1 ⁇ , the piezoelectric constant was low, and the dielectric loss was high.
- Comparative Example 18 abnormal growth of grains growing to larger than 100 ⁇ in terms of average circular equivalent diameter of the grains was observed and thus the static characteristics other than the Curie temperature could not be evaluated due to the same reason as the sample of
- Comparative Example 12 In Comparative Example 19 in which the relative density was lower than 93%, the piezoelectric constant was low and the dielectric loss was high. Note that the static characteristics of Comparative Example 2 were comparable to those of samples of Examples . In
- Barium titanate having an average particle diameter of 100 nm (BT-01 produced by Sakai Chemical Industry Co., Ltd.), calcium titanate having an average particle diameter of 300 nm (CT-03 produced by Sakai Chemical Industry Co., Ltd. ) , and calcium zirconate having an average particle diameter of 300 nm (CZ-03 produced by Sakai Chemical
- a conductive paste for forming internal electrodes was applied onto the green sheet by printing.
- conductive paste was a Ni paste.
- Nine green sheets onto which the conductive paste was applied were stacked and the resulting stack was thermally press -bonded.
- a sintered body obtained as such was cut into a 10 mm x 2.5 mm piece.
- the side surfaces of the piece were polished and a pair of external electrodes (first and second electrodes) that alternately short-circuit the internal electrodes were formed on the polished side surfaces by Au sputtering.
- a multilayered piezoelectric element as shown in Fig. 3B was fabricated.
- piezoelectric element was placed on a hot plate having a surface adjusted to 60° C to 100" C and an electric field of 1 kV/mm was applied to the multilayered piezoelectric element on the hot plate for 30 minutes to conduct a polarization treatment .
- Example 55 A multilayered piezoelectric element was fabricated as in Example 55. However, the composition was the same as that in Production Example 64. The piezoelectric material layers of the multilayered piezoelectric element was
- Liquid discharge head including a piezoelectric element of Example 9
- Example 9 fabricated by using a piezoelectric element of Example 9. Discharge of ink in response to input electrical signals was confirmed.
- Liquid discharge apparatus including a liquid
- a liquid discharge apparatus shown in Fig. 6 was fabricated by using a liquid discharge head shown in Fig. 2 including a piezoelectric element of Example 9. Discharge of ink onto a recording medium in response to input
- FIG. 8 An optical apparatus shown in Fig. 8 was fabricated by using an ultrasonic motor that uses a piezoelectric element of Example 31. Automatic focusing operation in response to applied AC voltage was confirmed.
- FIG. 10 An electronic apparatus shown in Fig. 10 was fabricated by using a piezoelectric acoustic component including a piezoelectric element of Example 31. Operation of the speaker in accordance with an AC voltage applied was confirmed.
- Liquid discharge head including a multilayered piezoelectric element of Example 55
- Example 55 fabricated by using a multilayered piezoelectric element of Example 55. Discharge of ink in response to input
- a liquid discharge apparatus shown in Fig. 6 was fabricated by using a liquid discharge head shown in Fig. 2 including a multilayered piezoelectric element of Example 55. Discharge of ink onto a recording medium in response to input electrical signals was confirmed.
- An ultrasonic motor shown in Fig. 3B was fabricated by using a multilayered piezoelectric element of Example 55. Rotation of a motor in response to applied AC voltage was confirmed.
- FIG. 8A and 8B An optical apparatus shown in Figs. 8A and 8B was fabricated by using a multilayered piezoelectric element of Example 55. Automatic focusing operation in response to applied AC voltage was confirmed.
- Example 55 fabricated by using a piezoelectric acoustic component including a multilayered piezoelectric element of Example 55. Operation of a speaker in response to applied AC voltage was confirmed.
- a piezoelectric element according to the invention operates stably in a wide operating temperature range, has low impact on the environment , and can be used in
- apparatuses such as liquid discharge heads and ultrasonic motors, that use a large quantity of piezoelectric materials in piezoelectric elements, etc.
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Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2014103798/04A RU2561601C1 (en) | 2011-07-05 | 2012-06-26 | Piezoelectric element, multilayer piezoelectric element, fluid discharge head, fluid discharge device, ultrasonic motor, optical device and electronic device |
EP17191864.2A EP3293874B1 (en) | 2011-07-05 | 2012-06-26 | Piezoelectric element, multilayered piezoelectric element, liquid discharge head, liquid discharge apparatus, ultrasonic motor, optical apparatus, and electronic apparatus |
KR1020187018325A KR102069989B1 (en) | 2011-07-05 | 2012-06-26 | Piezoelectric element, multilayered piezoelectric element, liquid discharge head, liquid discharge apparatus, ultrasonic motor, optical apparatus, and electronic apparatus |
CN201280033361.5A CN103650323B (en) | 2011-07-05 | 2012-06-26 | Piezoelectric element, multilayer piezoelectric element, liquid discharge head, pumping equipment, ultrasonic motor, Optical devices and electronic installation |
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BR112014000104-9A BR112014000104B1 (en) | 2011-07-05 | 2012-06-26 | PIEZOELECTRIC ELEMENT, MULTI-LAYER PIEZOELECTRIC ELEMENT, LIQUID DISCHARGE HEAD, LIQUID DISCHARGE APPLIANCE, ULTRASONIC MOTOR, OPTICAL APPLIANCE, AND ELECTRONIC APPLIANCE |
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US15/098,169 US10424721B2 (en) | 2011-07-05 | 2016-04-13 | Piezoelectric element, multilayered piezoelectric element, liquid discharge head, liquid discharge apparatus, ultrasonic motor, optical apparatus, and electronic apparatus |
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KR20140040257A (en) | 2014-04-02 |
RU2607947C2 (en) | 2017-01-11 |
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CN103650323A (en) | 2014-03-19 |
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EP3293874A1 (en) | 2018-03-14 |
RU2014103798A (en) | 2015-08-10 |
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CN107651956A (en) | 2018-02-02 |
CN107651956B (en) | 2021-08-20 |
EP3293874B1 (en) | 2019-10-23 |
BR112014000104B1 (en) | 2021-08-03 |
CN103650323B (en) | 2017-11-03 |
KR20180075715A (en) | 2018-07-04 |
RU2561601C1 (en) | 2015-08-27 |
US10424721B2 (en) | 2019-09-24 |
KR101874022B1 (en) | 2018-07-05 |
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