JP5382196B2 - Method for manufacturing liquid discharge head - Google Patents

Description

  The present invention relates to a method for manufacturing a liquid discharge head.

  Inkjet printers are known as printers that enable high image quality and high-speed printing. Control of the crystal orientation of the piezoelectric layer is important for improving the characteristics of the piezoelectric element in the liquid discharge head for an ink jet printer.

  As a method for controlling the crystal orientation of the piezoelectric layer, a method using a MgO (100) single crystal substrate is known (see Japanese Patent Application Laid-Open No. 2000-158648). However, this method may complicate the manufacturing process of the liquid discharge head.

JP 2000-158648 A

  One of the objects of the present invention is to provide a method of manufacturing a liquid discharge head having excellent aging characteristics.

A method for manufacturing a liquid discharge head according to the present invention includes:
Preparing a pressure chamber substrate on which the pressure chamber is formed;
Forming a diaphragm on one side of the pressure chamber substrate;
Forming a piezoelectric element at a position above the diaphragm and corresponding to a region where the pressure chamber is formed;
Forming the pressure chamber on the pressure chamber substrate;
Forming a nozzle plate having a nozzle hole communicating with the pressure chamber on the other side of the pressure chamber substrate,
The step of forming the piezoelectric element includes:
Forming a lower electrode above the diaphragm;
Forming an alignment layer above the lower electrode;
Forming a piezoelectric layer above the alignment layer;
Forming an upper electrode above the piezoelectric layer,
The alignment layer is formed by sputtering using a target containing lanthanum oxide, nickel oxide, and a silicon compound.

  According to the present invention, an alignment layer containing a mixed crystal of lanthanum nickelate can be obtained. A liquid discharge head having such an alignment layer has very good aging characteristics as well as piezoelectric characteristics.

  In the description according to the present invention, the word “upper” is used, for example, “specifically” (hereinafter referred to as “A”) is formed above another specific thing (hereinafter referred to as “B”). The word “above” is used to include the case where B is formed directly on A and the case where B is formed on A via another object. Used.

  In the method for manufacturing a liquid discharge head according to the present invention, the ratio of the silicon compound contained in the target may be 2 mol% to 10 mol%.

  In the method for manufacturing a liquid discharge head according to the present invention, the sputtering method may be a rotary magnetron sputtering method.

In the method for manufacturing a liquid discharge head of the present invention, the alignment layer includes a mixed crystal of lanthanum nickelate, and the mixed crystal is selected from LaNiO ₂ , LaNiO ₃ , La ₂ NiO _4, and La ₃ Ni ₂ O _7. Two or more lanthanum nickelates.

In the method for manufacturing a liquid discharge head according to the present invention, the mixed crystal may have a peak top position between 21 ° and 25 ° at a diffraction angle 2θ of X-ray diffraction by a θ-2θ method using CuKα rays. it can. Here, the “peak top position” indicates the peak apex resulting from the mixed crystal. Then, when I _{A is} a value obtained by integrating the peak intensity up to 21 ° from the peak top position, and I _B is a value obtained by integrating the peak intensity from the peak top position to 25 °, I _A > I _B , or , I _A <I _B. At this time, the mixed crystal may include LaNiO ₂ , LaNiO _3, and La ₂ NiO ₄ . At this time, the mixed crystal may have a molar ratio of lanthanum to nickel (La / Ni) of 1.5 or less.

In the method for manufacturing a liquid ejection head according to the present invention, the mixed crystal may have a peak top position between 30 ° and 33 ° at a diffraction angle 2θ of X-ray diffraction by a θ-2θ method using CuKα rays. it can. Then, when I _{C is} a value obtained by integrating the peak intensity from the peak top position to 30 °, and I _D is a value obtained by integrating the peak intensity from the peak top position to 33 °, I _C > I _D , or , I _C <I _D. At this time, the mixed crystal may include LaNiO ₂ , LaNiO ₃ , La ₂ NiO _4, and La ₃ Ni ₂ O ₇ . In this case, the mixed crystal may have a molar ratio of lanthanum to nickel (La / Ni) of 1.5 or more.

FIG. 3 is a cross-sectional view schematically showing a main part of the liquid discharge head. FIG. 3 is a cross-sectional view schematically showing a liquid discharge head. FIG. 3 is an exploded perspective view schematically showing a liquid discharge head. FIG. 6 is a diagram for explaining the operation of the liquid discharge head. The figure which shows typically the manufacturing method of the liquid discharge head which concerns on embodiment. The figure which shows typically the manufacturing method of the liquid discharge head which concerns on embodiment. The figure which shows typically the manufacturing method of the liquid discharge head which concerns on embodiment. The figure which shows the manufacturing method of the target used for a sputtering method. 1 is a schematic configuration diagram of an inkjet printer. The X-ray-diffraction figure of the (theta) -2 (theta) scan of the sample 1 which has a lanthanum nickelate film | membrane which concerns on an experiment example. The X-ray-diffraction figure of the (theta) -2theta scan of the sample 2 which has a lanthanum nickelate film | membrane which concerns on an experiment example. The X-ray-diffraction figure of the (theta) -2 (theta) scan of the sample 3 which has a lanthanum nickelate film | membrane which concerns on an experiment example. The X-ray-diffraction figure of the (theta) -2 (theta) scan of the sample 4 which has a lanthanum nickelate film | membrane which concerns on an experiment example. The figure which shows the orientation rate dependence of the lanthanum nickelate by the sputtering method of the sample which concerns on an experiment example. The X-ray-diffraction figure of the (theta) -2 (theta) scan of the sample which concerns on an experiment example and a comparative experiment example. The figure which shows the withstand voltage characteristic of the sample of an experiment example and a comparative experiment example. The figure which shows the aging characteristic of the sample of an experiment example and a comparative experiment example.

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

1. Liquid Discharge Head First, a liquid discharge head obtained by the manufacturing method according to this embodiment will be described. FIG. 1 is a cross-sectional view schematically illustrating an example of a main part of the liquid discharge head. FIG. 2 is a cross-sectional view schematically showing an example of the liquid discharge head. FIG. 3 is an exploded perspective view showing a schematic configuration of the liquid discharge head. Note that FIG. 3 is shown upside down from the state of normal use.

  As shown in FIG. 3, the liquid discharge head 50 is housed and fixed in a base 56. The base 56 is made of, for example, various resin materials, various metal materials, or the like. The liquid discharge head 50 constitutes an on-demand piezo jet head.

  As shown in FIGS. 1 and 2, the liquid ejection head 50 includes a pressure chamber substrate 52 having a pressure chamber (cavity) 521, a vibration plate 55 provided on one side of the pressure chamber substrate 52, and a vibration plate 55. A piezoelectric element 54 provided at a position corresponding to the pressure chamber 521, a nozzle plate 51 provided on the other side of the pressure chamber substrate 52 and having a nozzle hole 511 communicating with the pressure chamber 521, Have

  As shown in FIG. 2, the pressure chamber 521 is disposed corresponding to each nozzle hole 511. The pressure chambers 521 each have a variable volume due to the vibration of the diaphragm 55. The pressure chamber 521 is configured to eject a liquid such as ink or a dispersion by this volume change. In order to obtain the pressure chamber substrate 52, a (110) -oriented silicon single crystal substrate can be used. Since this (110) -oriented silicon single crystal substrate is suitable for anisotropic etching, the pressure chamber substrate 52 can be easily and reliably formed by etching.

  The diaphragm 55 is fixed to one side of the pressure chamber substrate 52 as shown in FIGS. The diaphragm 55 can include the insulating layer 2 and the elastic layer 3 formed on the insulating layer 2. As the insulating layer 2, for example, silicon oxide can be used. For example, the insulating layer 2 can function as an etching stopper in a step of etching the pressure chamber substrate 52 from the back surface side in order to form the pressure chamber 521 of the liquid ejection head 50. As the elastic layer 3, for example, yttria stabilized zirconia, cerium oxide, zirconium oxide or the like can be used.

  The nozzle plate 51 is made of, for example, a stainless steel rolling plate or the like, and has a large number of nozzle holes 511 for discharging droplets formed in a row. The pitch between these nozzle holes 511 is appropriately set according to the printing accuracy.

  The nozzle plate 51 is fixed (fixed) to the other side of the pressure chamber substrate 52. As shown in FIGS. 2 and 3, the pressure chamber substrate 52 divides a plurality of pressure chambers 521, a reservoir 523, and a supply port 524 by a nozzle plate 51, a side wall (partition wall) 522, and a vibration plate 55. Formed. The reservoir 523 temporarily stores ink supplied from the ink cartridge 631 (see FIG. 9). Ink is supplied from the reservoir 523 to each pressure chamber 521 through the supply port 524.

  Next, the piezoelectric element 54 will be described.

  Each piezoelectric element 54 is electrically connected to a piezoelectric element driving circuit, which will be described later, and is configured to operate (vibrate, deform) based on a signal from the piezoelectric element driving circuit. That is, each piezoelectric element 54 functions as a vibration source (piezoelectric element). The vibration plate 55 vibrates (deflection) by the vibration (deflection) of the piezoelectric element 54 and functions to instantaneously increase the internal pressure of the pressure chamber 521.

  As shown in FIG. 1, the piezoelectric element 54 includes a lower electrode 4, an alignment layer 7, a piezoelectric layer 5, and an upper electrode 6.

  The lower electrode 4 is one electrode for applying a voltage to the piezoelectric layer 5. The material of the lower electrode 4 is not particularly limited as long as conductivity is ensured.

The lower electrode 4 is preferably made of a conductive material having a specific resistance lower than that of the alignment layer 7. The material of the lower electrode 4 can include, for example, at least one of a metal, an oxide of the metal, and an alloy made of the metal. The lower electrode 4 may have a structure in which a plurality of conductive layers are stacked. Here, as the metal, for example, at least one of Pt, Ir, Ru, Ag, Au, Cu, Al, Ti, and Ni can be used. Examples of the metal oxide include IrO ₂ and RuO ₂ . Examples of the metal alloy include Pt—Ir, Ir—Al, Ir—Ti, Pt—Ir—Al, Pt—Ir—Ti, Pt—Ir—Al—Ti, and the like. The crystal orientation of the conductive material is not particularly limited, and can be, for example, (111) oriented. The film thickness of the lower electrode 4 can be about 50 nm to 200 nm, for example.

  The alignment layer 7 includes a mixed crystal of lanthanum nickelate. That is, the alignment layer 7 includes a plurality of lanthanum nickelates. The orientation layer 7 can control the crystal orientation of the piezoelectric layer 5 to a predetermined orientation, and can improve characteristics such as the piezoelectric constant of the piezoelectric layer. Furthermore, as will be described later, by providing the alignment layer 7 containing a specific mixed crystal, the aging characteristics of the liquid discharge head 50 can be significantly improved. The alignment layer 7 has conductivity and can also serve as an electrode.

When the lanthanum nickelate contained in the mixed crystal is represented by the formula La _x Ni _y O _z , x is an integer from 1 to 3, y is 1 or 2, and z is an integer from 2 to 7. Can consist of Specifically, the mixed crystal contains two or more kinds of lanthanum nickelate selected from LaNiO ₂ , LaNiO ₃ , La ₂ NiO ₄ and La ₃ Ni ₂ O ₇ . The alignment layer 7 can further contain, for example, a silicon compound and other trace amounts of lanthanum nickelate.

  According to the present inventors, as will be described later, it has been confirmed that lanthanum nickelate contained in the mixed crystal depends on the method of forming the alignment layer 7.

For example, when the alignment layer 7 is formed by a rotary magnetron sputtering method, the composition of the mixed crystal varies depending on the film formation temperature. For example, when a film is formed at 150 ° C. to 250 ° C., the obtained mixed crystal contains LaNiO ₂ , LaNiO ₃ and La ₂ NiO ₄ as main components.

When the film is formed at such a relatively low temperature, the mixed crystal has a peak top position between 21 ° and 25 ° at the diffraction angle 2θ of X-ray diffraction by the θ-2θ method using CuKα rays. . Then, when I _{A is} a value obtained by integrating the peak intensity up to 21 ° from the peak top position, and I _B is a value obtained by integrating the peak intensity from the peak top position to 25 °, I _A > I _B , or , I _A <I _B. The relationship between I _A and I _B indicates that the peak in the θ-2θ method is asymmetric with respect to the peak top position, and that the peak is derived from a mixed crystal. When the peak in the θ-θ2 method is symmetric with respect to the peak top position, the peak is derived from the uniaxial orientation of LaNiO ₃ . Such relationship between I _A and I _B have the meaning similar in other peaks below. Furthermore, in this film formation, the mixed crystal has a molar ratio of lanthanum to nickel (La / Ni) of 1.5 or less, preferably 1 or more and 1.5 or less.

When the mixed crystal is formed at a relatively high temperature of, for example, 400 ° C. to 600 ° C., the mixed crystal contains LaNiO ₂ , LaNiO ₃ , La ₂ NiO _4, and La ₃ Ni ₂ O ₇ as main components. . In this case, the mixed crystal has a peak between 30 ° and 33 ° at a diffraction angle 2θ of X-ray diffraction by the θ-2θ method using CuKα rays. When I _{C is} a value obtained by integrating the peak intensities from the peak top position to 30 ° and I _D is a value obtained by integrating the peak intensities from the peak top position to 33 °, I _C > I _D or I _C < _ID . Further, in this case, the mixed crystal has a molar ratio of lanthanum to nickel (La / Ni) of 1.5 or more, preferably 1.5 or more and 2 or less.

  The piezoelectric layer 5 can be made of, for example, a piezoelectric body having a perovskite structure. The piezoelectric layer 5 is in contact with the alignment layer 7. The piezoelectric body constituting the piezoelectric layer 5 may be rhombohedral or a mixed crystal of tetragonal and rhombohedral and may be oriented in (100). The piezoelectric layer 5 made of such a piezoelectric body generally has a high piezoelectric constant.

This piezoelectric body can be represented by, for example, a general formula of ABO ₃ . Here, A can include Pb, and B can include at least one of Zr and Ti. Furthermore, B can also contain at least one of V, Nb, and Ta. In this case, the piezoelectric body can include at least one of Si and Ge. More specifically, the piezoelectric body includes, for example, lead zirconate titanate (Pb (Zr, Ti) O ₃ ), lead niobate zirconate titanate (Pb (Zr, Ti, Nb) O ₃ ), titanate. Lead lanthanum ((Pb, La) TiO ₃ ), lead lanthanum zirconate titanate ((Pb, La) ZrTiO ₃ ), lead magnesium niobate titanate (Pb (Mg, Nb) TiO ₃ ), zirconate magnesium niobate Lead titanate (Pb (Mg, Nb) (Zr, Ti) O ₃ ), lead zinc niobate titanate (Pb (Zn, Nb) TiO ₃ ), scandium lead niobate titanate (Pb (Sc, Nb) TiO 3 _3), nickel niobate titanate (Pb (Ni, Nb) TiO 3), and indium magnesium niobate titanate of (Pb (in, Mg, Nb ) TiO 3) Chino may include at least one.

The piezoelectric body may be, for example, (Ba _1-x Sr _x ) TiO ₃ (0 ≦ x ≦ 0.3), Bi ₄ Ti ₃ O ₁₂ , SrBi ₂ Ta ₂ O ₉ , LiNbO ₃ , LiTaO ₃ , and It can consist of at least one of KNbO ₃ .

  The film thickness of the piezoelectric layer 5 can be, for example, not less than 0.1 μm and not more than 5 μm.

  The upper electrode 6 is the other electrode for applying a voltage to the piezoelectric layer 5. As the material of the upper electrode 6, the same material as that of the lower electrode 4 can be used. The upper electrode 6 may be a stacked body of a plurality of conductive layers. For example, the upper electrode 6 may be a laminate of a conductive oxide layer and a metal layer.

  Next, the operation of the liquid discharge head 50 will be described. The liquid ejection head 50 is in a state where a predetermined ejection signal is not input via the piezoelectric element driving circuit, that is, in a state where no voltage is applied between the lower electrode 4 and the upper electrode 6 of the piezoelectric element 54. As shown in FIG. 1, the piezoelectric layer 5 is not deformed. For this reason, the vibration plate 55 is not deformed, and the volume of the pressure chamber 521 is not changed. Accordingly, no droplet is ejected from the nozzle hole 511.

  On the other hand, in a state where a predetermined ejection signal is input via the piezoelectric element driving circuit, that is, in a state where a voltage is applied between the lower electrode 4 and the upper electrode 6 of the piezoelectric element 54, as shown in FIG. In the piezoelectric layer 5, bending deformation occurs in the minor axis direction (the direction of the arrow s shown in FIG. 4). As a result, the diaphragm 55 bends and a volume change of the pressure chamber 521 occurs. At this time, the pressure in the pressure chamber 521 increases instantaneously, and the droplet 58 is discharged from the nozzle hole 511.

  That is, when a voltage is applied, the crystal lattice of the piezoelectric layer 5 is stretched in the direction perpendicular to the plane direction (the direction of the arrow d shown in FIG. 4), but is simultaneously compressed in the plane direction. In this state, the tensile stress f acts on the piezoelectric layer 5 in the plane. Therefore, the diaphragm 55 is deflected and bent by the tensile stress f. The greater the displacement amount (absolute value) of the piezoelectric layer 5 in the minor axis direction of the pressure chamber 521, the greater the deflection amount of the diaphragm 55, and more efficiently a liquid material such as ink (hereinafter referred to as “liquid”). It is possible to discharge a droplet of “also”.

  When the ejection of one droplet is completed, the piezoelectric element driving circuit stops applying the voltage between the lower electrode 4 and the upper electrode 6. Thereby, the piezoelectric element 54 returns to the original shape shown in FIG. 1, and the volume of the pressure chamber 521 increases. At this time, a pressure (a pressure in the positive direction) acting from the container (for example, the ink cartridge 631 (see FIG. 9)) to the nozzle hole 511 is applied to the liquid. For this reason, air is prevented from entering the pressure chamber 521 from the nozzle hole 511, and an amount of ink commensurate with the liquid discharge amount is supplied from the ink cartridge 631 to the pressure chamber 521 via the reservoir 523.

  In this way, by sequentially inputting ejection signals to the piezoelectric element 54 at a position where the droplet is to be ejected via the piezoelectric element driving circuit, the droplet is ejected to a desired position on the ejection medium such as paper. Can be supplied.

  Next, main features of the liquid discharge head 50 obtained by the manufacturing method according to this embodiment to be described later will be described.

  According to the liquid discharge head 50, by using a mixed crystal of lanthanum nickelate as the orientation layer 7, the crystal orientation of the piezoelectric layer 5 can be controlled to a predetermined orientation, and characteristics such as the piezoelectric constant of the piezoelectric layer 5 are improved. Can be made. As a result, the amount of deflection of the diaphragm 55 is increased, and droplets can be discharged more efficiently. Here, “efficient” means that the same amount of droplets can be ejected with a smaller voltage. In other words, the drive circuit can be simplified and power consumption can be reduced at the same time, so that the pitch of the nozzle holes 511 can be formed at a higher density. Therefore, high-density printing and high-speed printing are possible. Furthermore, since the length of the major axis of the pressure chamber 521 can be shortened, the entire head can be reduced in size.

  Furthermore, as will be described later, by providing the alignment layer 7 whose main component is a mixed crystal of lanthanum nickelate, the liquid discharge head 50 with excellent aging characteristics can be obtained. That is, as is clear from the experimental examples described later, by using the specific alignment layer 7, the displacement reduction rate in the aging process described later can be suppressed to an extremely small range of about 5% or less. Therefore, even after the aging process, members constituting the liquid discharge head 50, such as the piezoelectric element 54 and the diaphragm 55, can be approximated to the initial design values. Therefore, according to the liquid ejection head 50, it has excellent aging characteristics, and furthermore, the change over time of the displacement amount of the piezoelectric element 54 and the diaphragm 55 can be made extremely small, and it has excellent durability. Can do.

2. Manufacturing method of liquid discharge head 2.1. Manufacturing Method Next, a manufacturing method of the liquid ejection head 50 according to the present embodiment will be described with reference to FIGS. 1 and 5 to 7.

  First, a (110) -oriented silicon substrate 1 serving as a base material of the pressure chamber substrate 52 is prepared.

  Next, as shown in FIG. 5, the insulating layer 2 is formed on the silicon substrate 1. The insulating layer 2 is made of, for example, silicon oxide. The insulating layer 2 made of silicon oxide can be formed on the surface of the silicon substrate 1 by a thermal oxidation method, for example. The insulating layer 2 can be formed by a CVD method or the like.

  Next, the elastic layer 3 is formed on the insulating layer 2. The elastic layer 3 can be formed by, for example, a CVD method, a sputtering method, a vapor deposition method, or the like. As the material of the elastic layer 3, those described above can be used.

  Next, the lower electrode 4 is formed on the elastic layer 3. In the present embodiment, since the alignment layer 7 is provided, the crystal orientation of the conductive material constituting the lower electrode 4 is not particularly limited, and therefore the manufacturing conditions and manufacturing method of the lower electrode 4 can be appropriately selected. For example, the lower electrode 4 can be formed by sputtering, vacuum deposition, or the like. The temperature at which the lower electrode 4 is formed can be, for example, room temperature to 600 ° C. As the material of the lower electrode 4, those described above can be used.

  Next, the alignment layer 7 is formed on the lower electrode 4. The alignment layer 7 can be formed by sputtering, for example. When the alignment layer 7 is formed by sputtering, rotary magnetron sputtering or fixed sputtering can be used. The target used for the sputtering method will be described later.

When the rotary magnetron sputtering method is used, the power can be set to 0.5 to 1.5 kW, and the film formation temperature can be set to 150 to 600 ° C. In the rotary magnetron sputtering method, sputtering is performed while rotating a magnet provided immediately below a target. When this rotary magnetron sputtering method is used, there is an advantage that erosion (erosion) due to partial concentration of discharge on the target is suppressed and the target can be used uniformly and without waste. Further, when the fixed sputtering method is used, the power can be set to 0.5 to 1.5 kW and the film forming temperature can be set to 300 to 600 ° C. The rotary magnetron sputtering method is more preferable than the fixed sputtering method in that the film forming temperature can be lowered. In the sputtering method, the ratio of oxygen in argon and oxygen (O ₂ / (Ar + O ₂ )) can be set to, for example, 0% to 50%.

  As already described, the alignment layer 7 contains a mixed crystal of lanthanum nickelate. That is, the alignment layer 7 includes a plurality of lanthanum nickelates. The orientation layer 7 can control the crystal orientation of the piezoelectric layer 5 to a predetermined orientation, and can improve characteristics such as the piezoelectric constant of the piezoelectric layer. Furthermore, as will be described later, by providing the alignment layer 7 containing a specific mixed crystal, the aging characteristics of the liquid discharge head 50 can be significantly improved. The alignment layer 7 has conductivity and can also serve as an electrode.

  Since lanthanum nickelate contained in the mixed crystal has already been described, description thereof is omitted here.

  Next, the piezoelectric layer 5 is formed on the alignment layer 7. The piezoelectric layer 5 can be formed by, for example, a sputtering method or a sol-gel method. As the material of the piezoelectric layer 5, those described above can be used.

  Next, the upper electrode 6 is formed on the piezoelectric layer 5. The upper electrode 6 can be formed by, for example, a sputtering method, a vacuum deposition method, or the like. As the material of the upper electrode 6, those described above can be used.

  Next, as shown in FIG. 6, the upper electrode 6, the piezoelectric layer 5, the alignment layer 7, and the lower electrode 4 are patterned to correspond to the individual pressure chambers 521, and the number corresponding to the number of the pressure chambers 521. A piezoelectric element 54 is formed. When the lower electrode 6 is used as a common electrode, the lower electrode 6 can be separately patterned.

  Next, as shown in FIG. 7, the silicon substrate 1 is patterned using a known lithography technique, and concave portions that respectively become pressure chambers 521 are provided at positions corresponding to the piezoelectric elements 54, and a reservoir 523 and a supply are provided at predetermined positions. The pressure chamber substrate 52 is formed by forming a recess that becomes the port 524.

  In this embodiment, since the (110) -oriented silicon substrate is used as the pressure chamber substrate 52, wet etching (anisotropic etching) using a high-concentration alkaline aqueous solution is preferably employed. In wet etching with a high concentration aqueous alkali solution, the insulating layer 2 can function as an etching stopper as described above. Accordingly, the pressure chamber substrate 52 can be formed more easily.

  Thus, the pressure chamber substrate 52 is formed by etching and removing the silicon substrate 1 in the thickness direction until the diaphragm 55 is exposed. At this time, a portion left without being etched becomes the side wall 522.

  Next, the nozzle plate 51 in which the plurality of nozzle holes 511 are formed is aligned so that each nozzle hole 511 corresponds to a recess that becomes each pressure chamber 521, and bonded in that state. Thereby, a plurality of pressure chambers 521, a reservoir 523, and a plurality of supply ports 524 are formed. For the joining of the nozzle plate 51, for example, an adhesive method using an adhesive or a fusion method may be used. Next, the pressure chamber substrate 52 is attached to the base 56.

  The liquid discharge head 50 can be manufactured through the above steps.

  Next, the aging process will be described. An aging process can be performed as follows, for example.

  After the pressure chamber 521 is formed, an aging process can be added. In the aging process, a predetermined number of pulses are applied to the piezoelectric element 54 with a drive signal having a higher voltage and higher frequency than in actual use, and the piezoelectric element 54 is driven by generating a higher electric field strength than in actual use. The process of carrying out. By the aging process, fluctuations in the displacement amount of the piezoelectric element 54 and the diaphragm 55 during actual use are suppressed to be extremely small, and stable liquid ejection characteristics can always be obtained. That is, by executing the aging process, the piezoelectric layer 5 constituting the piezoelectric element 54 is polarized and the internal stress of the diaphragm is alleviated, so that the piezoelectric element 54 and the diaphragm 55 in actual use are relaxed. The variation in the amount of displacement of the is significantly reduced.

  The electric field strength generated in the piezoelectric layer 5 in the aging process is not particularly limited as long as the electric field strength is higher than that in actual use, but can be 300 kV / cm or more. This is because, when this electric field strength is used, the piezoelectric layer 5 can be polarized in a relatively short time. For example, in this embodiment, the electric field strength of 455 kV / cm can be generated in the piezoelectric layer 5 by setting the maximum voltage of the drive signal applied to the piezoelectric element 54 to 50V. Further, the frequency of the drive signal is not particularly limited as long as it is higher than that during actual use, but can be about 50 kHz to 200 kHz. If the frequency is too low, the aging process takes too much time, and if the frequency is too high, the piezoelectric element 54 may be destroyed.

  The waveform of the drive signal can be a waveform having a single frequency, such as a sin wave or a rectangular wave. This is because with such a simple waveform, the piezoelectric element 54 can be driven a predetermined number of times in a relatively short time, and the aging time can be shortened. Further, the burden on the piezoelectric element 54 and the burden on the drive circuit that drives the piezoelectric element 54 can be suppressed. Further, the number of pulses of the drive signal needs to be appropriately determined according to the intensity of the electric field generated in the piezoelectric element 54, the frequency of the drive signal, etc., but is preferably at least 10 million pulses or more. Thereby, the internal stress of the diaphragm 55 is reliably relieved, and the piezoelectric layer 5 is also reliably polarized. As a result, variations in the displacement amount of the piezoelectric element 54 and the diaphragm 55 during actual use can be suppressed to a small level.

  In addition, about the aging process, the method described in the patent application (Japanese Patent Application No. 2002-374607) by the applicant of this application is employable, for example.

2.2. Target used for film formation of alignment layer 7 Next, an insulating target used for film formation of the alignment layer 7 will be described. This insulating target has the same characteristics as the insulating target material described in the patent application (Japanese Patent Application No. 2005-235809) filed by the applicant of the present application.

  This insulating target includes an oxide of lanthanum, an oxide of nickel, and a silicon compound. By including the Si compound in the insulating target, it becomes an excellent insulating target having high homogeneity and high insulating properties, as will be apparent from Examples described later. The silicon compound is preferably an oxide.

  The insulating target can be formed by the following method. This method is the same as the method described in Japanese Patent Application No. 2005-235809 described above.

  First, lanthanum oxide and nickel oxide are mixed, and the mixed powder is heat treated and pulverized to obtain a first powder; a solution containing the first powder and a silicon raw material And then collecting the powder to obtain a second powder; heat treating the second powder to pulverize it to obtain a third powder; and the third powder. Heat-treating.

  Specifically, the manufacturing method can include the steps shown in FIG.

(1) Production of First Powder A lanthanum oxide powder and a nickel oxide powder are mixed, for example, at a composition ratio of 1: 1 (step S1). Next, the obtained mixed material is temporarily fired at 900 ° C. to 1000 ° C. and then pulverized to obtain a first powder (step S2). The first powder thus obtained contains lanthanum oxide and nickel oxide.

(2) Production of second powder The first powder and a solution containing a silicon raw material are mixed (step S3). As a silicon raw material, an alkoxide, an organic acid salt, an inorganic acid salt, or the like that can be used as a precursor material by a sol-gel method or a MOD method can be used. As the solution, a silicon raw material dissolved in an organic solvent such as alcohol can be used. The silicon raw material may be included in a ratio of 2 mol% to 10 mol% with respect to the obtained conductive complex oxide.

  The silicon raw material is preferably a liquid at room temperature or soluble in a solvent. Examples of silicon raw materials include organic salts, alkoxides, and inorganic salts. Specific examples of the organic salt include silicon formate, acetate, propionate, butyrate, octylate, and stearate. Specific examples of the alkoxide include silicon ethoxide, propoxide and butoxide, and mixed alkoxides may be used. Specific examples of the inorganic salt include silicon hydroxide, chloride, and fluoride. These may be used as they are at room temperature, or may be used by dissolving in other solvents. The silicon raw material is not limited to these, and many silicon salts can be used.

  Thereafter, the powder and the solution are separated by filtration or the like, and the powder is collected to obtain a second powder (step S4). The second powder thus obtained is a mixture of the first powder and the solution.

(3) Production of third powder Next, the second powder is calcined at 900 ° C. to 1000 ° C. and then pulverized to obtain a third powder (step S5). The third powder thus obtained contains lanthanum oxide, nickel oxide and silicon oxide.

  (4) Sintering Next, the third powder is sintered by a known method (step S6). For example, the third powder can be put in a mold and sintered by a vacuum hot press method. Sintering can be performed at 1000 to 1500 ° C. In this way, an insulating target can be obtained.

  (5) Polishing If necessary, the surface of the obtained insulating target can be polished by wet polishing.

  According to the manufacturing method described above, it is possible to obtain an insulating target that is homogeneous and has high insulating properties by including the step of mixing the first powder and the silicon raw material solution. Moreover, according to this manufacturing method, an insulating target having high crystal orientation controllability and surface morphology of the conductive composite oxide film obtained can be obtained.

  As the target obtained by this manufacturing method, a target having a ratio of lanthanum oxide to nickel oxide of 1 or a ratio close thereto can be used. Further, the target may contain silicon in a proportion of 2 mol% to 10 mol%.

  According to the method for manufacturing the liquid discharge head 50 according to the present embodiment, the alignment layer 7 made of a mixed crystal of lanthanum nickelate can be formed by a sputtering method. The characteristics of the liquid discharge head 50 including the piezoelectric element 54 having the alignment layer 7 are as described above.

  That is, according to the manufacturing method of the present embodiment, the alignment layer 7 including a mixed crystal of lanthanum nickelate can be formed. By using this orientation layer 7, the crystal orientation of the piezoelectric layer 5 can be controlled to a predetermined orientation, and characteristics such as the piezoelectric constant of the piezoelectric layer 5 can be improved. As a result, the amount of deflection of the diaphragm 55 is increased, and droplets can be discharged more efficiently. Accordingly, high-density printing and high-speed printing are possible, and further, the length of the major axis of the pressure chamber 521 can be shortened, so that the entire head can be reduced in size.

  Furthermore, according to the manufacturing method according to the present embodiment, by forming the alignment layer 7 containing a mixed crystal of lanthanum nickelate as a main component, it is possible to obtain the liquid discharge head 50 with extremely excellent aging characteristics. That is, as is clear from the experimental examples described later, by using the specific alignment layer 7, the displacement reduction rate in the aging process described later can be suppressed to an extremely small range of about 5% or less. Therefore, even after the aging process, members constituting the liquid discharge head 50, such as the piezoelectric element 54 and the diaphragm 55, can be approximated to the initial design values.

3. Experimental Example (1) Production of Target Used for Sputtering Method The insulating target used in the experimental example and the comparative experimental example was formed by the following method.

  First, a first powder was produced. Specifically, La oxide powder and Ni oxide powder were mixed at a composition ratio of 1: 1. Next, the obtained mixed material was temporarily fired at 900 ° C. to 1000 ° C. and then pulverized to obtain a first powder.

  Next, a second powder was produced. Specifically, the first powder and a silicon alkoxide solution were mixed. The silicon alkoxide solution is obtained by dissolving silicon alkoxide in alcohol at a ratio of 5 mol%.

  Thereafter, the powder and the solution were separated by filtration, and the powder was collected to obtain a second powder. The second powder thus obtained is a mixture of the first powder and the solution.

  Thereafter, the second powder was calcined at 900 ° C. to 1000 ° C. and then pulverized to obtain a third powder.

  Next, the third powder was sintered by a known method. Specifically, the third powder was placed in a mold and sintered by a vacuum hot press method. Sintering was performed at 1400 ° C. In this way, a target sample was obtained. It was confirmed that the target sample had a uniform surface and no defects such as cracks.

(2) Dependence of mixed crystal of lanthanum nickelate on film formation temperature (2) -1. Sample Formed at Low Temperature First, a sample 1 on which a lanthanum nickelate film 1 formed using the target sample by a rotary magnetron sputtering method will be described.

Sample 1 is a mixed crystal of lanthanum nickelate having a film thickness of 40 nm on a (110) -oriented silicon substrate under conditions of RF power of 1 kW, substrate temperature of 200 ° C., and Ar / O ₂ = 30/20 sccm. A lanthanum nickelate film (hereinafter referred to as “lanthanum nickelate film 1”) is formed.

FIG. 10 is a diagram showing an X-ray diffraction result by the θ-2θ method using the CuKα ray of Sample 1. FIG. From FIG. 10, the peak top position of the mixed crystal of lanthanum nickelate (mixed crystal LNO) was confirmed between 21 ° and 25 ° at the diffraction angle 2θ. The peak between 21 ° and 25 ° was asymmetric with respect to the peak top position. It was confirmed that this mixed crystal mainly contains LaNiO ₂ (LNO2), LaNiO ₃ (LNO3) and La ₂ NiO ₄ (L2NO4). Further, when the molar ratio of lanthanum to nickel (La / Ni) in the mixed crystal of the lanthanum nickelate film 1 was examined by an ICP (Inductively Coupled Plasma) method, it was confirmed to be 1.24.

  A sample 2 was formed by forming a lanthanum nickelate film 2 in the same manner as in the case of the silicon substrate except that the substrate for forming the lanthanum nickelate film was changed to a laminate. The laminate used in this experimental example is a silicon oxide layer (film thickness: about 1 μm), a zirconium oxide layer (film thickness: about 0.4 μm), and a platinum layer (film thickness: about 0.1 μm) on a (110) oriented silicon substrate. 1 μm) is formed.

FIG. 11 is a diagram showing an X-ray analysis result of Sample 2. From FIG. 11, the peak top position of the mixed crystal of lanthanum nickelate (mixed crystal LNO) was confirmed between 21 ° and 25 ° at the diffraction angle 2θ as in FIG. The peak between 21 ° and 25 ° was asymmetric with respect to the peak top position. It was confirmed that this mixed crystal mainly contains LaNiO ₂ (LNO2), LaNiO ₃ (LNO3) and La ₂ NiO ₄ (L2NO4).

(2) -2. First, a sample 3 on which a lanthanum nickelate film 3 formed using the target sample by the rotary magnetron sputtering method is formed will be described.

Sample 3 is a mixed crystal of lanthanum nickelate having a film thickness of 40 nm on a (110) -oriented silicon substrate under conditions of RF power of 1 kW, substrate temperature of 550 ° C., and Ar / O ₂ = 30/20 sccm. A lanthanum nickelate film 3 is formed.

FIG. 12 is a diagram showing an X-ray analysis result of Sample 3. From FIG. 12, the peak top position of the mixed crystal of lanthanum nickelate (mixed crystal LNO) was confirmed between 30 ° and 33 ° at the diffraction angle 2θ. The peak between 30 ° and 33 ° was asymmetric with respect to the peak top position. This mixed crystal LNO was confirmed to contain mainly LaNiO ₂ (LNO ₂ ), LaNiO ₃ (LNO ₃ ), La ₂ NiO ₄ (L ₂ NO ₄ ), and La ₃ Ni ₂ O ₇ (L ₃ N ₂ O ₇ ). Further, when the molar ratio of lanthanum to nickel (La / Ni) in the lanthanum nickelate film 3 was examined by the ICP method, it was confirmed to be 1.54.

  A sample 4 was obtained by forming the lanthanum nickelate film 4 in the same manner as in the case of the silicon substrate except that the substrate for forming the lanthanum nickelate film was changed to a laminate. The laminate used in this experimental example is the above (2) -1. It is the same as the laminate described in. That is, the laminated body is obtained by forming a silicon oxide layer, a zirconium oxide layer, and a platinum layer on a (110) oriented silicon substrate.

FIG. 13 is a diagram showing an X-ray analysis result of Sample 4. In FIG. From FIG. 13, similarly to FIG. 12, a lanthanum nickelate mixed crystal (mixed crystal LNO) peak was observed between 30 ° and 33 ° at the diffraction angle 2θ. The peak between 30 ° and 33 ° was asymmetric with respect to the peak top position. It was confirmed that this mixed crystal mainly contains LaNiO ₂ (LNO2), LaNiO ₃ (LNO3) and La ₂ NiO ₄ (L2NO4).

From the above, it was confirmed that the mixed crystal component of the lanthanum nickelate film depends on the deposition temperature. Specifically, when the film formation temperature is 150 ° C. to 250 ° C., a mixed crystal mainly containing LaNiO ₂ (LNO ₂ ), LaNiO ₃ (LNO ₃ ) and La ₂ NiO ₄ (L ₂ NO ₄ ) is obtained, and the film formation temperature is 400 ° C. From 600 to 600 ° C., it was confirmed that LaNiO ₂ (LNO2), LaNiO ₃ (LNO3), La ₂ NiO ₄ (L2NO4) and La ₃ Ni ₂ O ₇ (L3N2O7) were contained. Furthermore, it was confirmed that the composition ratio of lanthanum and nickel in the mixed crystal varies depending on the film formation temperature.

(3) Dependence of Lanthanum Nickelate Orientation by Sputtering Method FIG. 14 is a diagram showing the relationship between the film formation temperature and the crystal orientation when using the rotary magnetron sputtering method and the fixed sputtering method. The orientation ratio shown in FIG. 14 is obtained by setting the intensity at the peak top position between 21 ° and 25 ° at the diffraction angle 2θ of X-ray diffraction by the θ-2θ method using CuKα rays as “mixed crystal LNO intensity A”. When the intensity of the peak top position between ° and 33 ° is “mixed crystal LNO intensity B”,
Orientation ratio = mixed crystal LNO strength A / (mixed crystal LNO strength A + mixed crystal LNO strength B)
It is expressed.

  In FIG. 14, the symbol a is a graph when the rotary magnetron sputtering method is used, and the symbol b is a graph when the fixed sputtering method is used.

  FIG. 14 shows that when the rotary magnetron sputtering method is used, an orientation ratio of about 60% or more can be obtained when the film forming temperature is about 150 ° C. to 350 ° C.

  On the other hand, it was found that when the fixed sputtering method is used, an orientation ratio of about 60% or more can be obtained when the film forming temperature is higher than about 250 ° C.

(4) Crystal Orientation of Piezoelectric Layer In the following, the crystal orientation of a piezoelectric layer when a mixed crystal film of lanthanum nickelate was used as the orientation layer and when such a mixed crystal film was not used was investigated. Describe the results.

(4) -1. Experimental example using alignment layer Above (2) -1. A lanthanum nickelate film having a film thickness of 40 nm was formed by a rotary magnetron sputtering method under the same conditions as described above. Further, a 1.3 μm PZT layer was formed on the lanthanum nickelate film by a sol-gel method. This PZT layer was formed as follows. First, after applying the sol-gel raw material on the platinum layer, it was calcined at 100 to 150 ° C., degreased at 400 ° C., and further calcined at 700 ° C. in an oxygen atmosphere. A PZT layer was formed by repeating this process until a desired film thickness was obtained. The laminated body thus obtained is referred to as Sample 5.

15 is a result of X-ray diffraction performed on Sample 5 by the θ-2θ method using CuKα rays. From FIG. 15, in sample 5, a strong peak top position derived from PZT which is a piezoelectric layer was confirmed. Moreover, when the orientation rate of PZT (100) was calculated | required from the diffraction result of FIG. 15, it was 96-99. Here, the PZT orientation ratio is defined as the intensity of the peak top position between 21 ° and 25 ° at the diffraction angle 2θ of X-ray diffraction by the θ-2θ method using CuKα rays is “PZT (100) intensity”. When the intensity at the peak top position between ° and 33 ° is “PZT (110) intensity” and the intensity at the peak top position between 37 ° and 39 ° is “PZT (111) intensity”,
Orientation ratio of PZT (100) = PZT (100) strength / (PZT (100) strength + PZT (110) strength + PZT (111) strength)
It is expressed. Furthermore, when the half width of PZT (200) was determined by the rocking curve method using CuKα rays, it was 10.4 °.

(4) -2. Experimental example using no alignment layer The above (4) -1, except that a 4 nm titanium layer was used as a seed layer instead of using an alignment layer made of a mixed crystal of lanthanum nickelate on the platinum layer. A sample was obtained in the same manner as above. The laminate thus obtained is referred to as a comparative sample 6.

  In FIG. 15, the diagram indicated by symbol b is the result of X-ray diffraction performed on Sample 6 by the θ-2θ method using CuKα rays. From FIG. 15, a peak derived from PZT which is a piezoelectric layer was confirmed in the sample 6 for comparison, but this peak was smaller than that in the sample 5. From the diffraction result of FIG. 15, the orientation ratio of PZT (100) was determined to be 90 to 95. Moreover, it was 22.4 degrees when the half width of the peak of PZT (200) was calculated | required.

  From the above, it is confirmed that Sample 5 of this experimental example has higher crystal orientation of the PZT layer, smaller peak half-value width, and more aligned crystal axes than Comparative Sample 6. It was.

(5) Dielectric strength test by difference in alignment layer The sample 7 using the mixed crystal of lanthanum nickelate according to the present embodiment as the alignment layer and the sample 8 for comparison using LaNiO ₃ as the alignment layer were performed. The withstand voltage test is described. The result is shown in FIG. In FIG. 16, the graph indicated by the symbol a indicates the result of the sample 7, and the graph indicated by the symbol b indicates the result of the sample 8 for comparison.

(2) -1. The occurrence of cracks was examined by changing the applied voltage for Sample 7 produced in the same manner as Sample 2 described in (1). As a result, in sample 7 , it was confirmed that even when a voltage of about 80 V was applied, cracks were hardly generated in the piezoelectric layer (PZT layer) and the piezoelectric element was not destroyed.

On the other hand, in the comparative sample 8 using LaNiO ₃ as the alignment layer, cracks started to occur in the piezoelectric layer at about 35V, and the element was destroyed at about 40V. In the sample 8 for comparison, a YBCO / CeO ₂ / YSZ buffer layer is formed on a Si substrate by a PLD (pulse laser deposition) method, and a (100) -oriented lanthanum nickelate film (LaNiO ₃ ) is formed thereon. Is epitaxially grown.

(6) Aging characteristics Sample 9 produced in the same manner as Sample 2 and Comparative Sample 10 produced in the same manner as Sample 2 except that a titanium layer was used as a seed layer instead of an alignment layer made of lanthanum nickelate Aging characteristics were investigated. The result is shown in FIG. In FIG. 17, the horizontal axis represents the number of times of driving (shot), and the vertical axis represents the displacement reduction rate from the initial state. In FIG. 17, the graph indicated by the symbol a indicates the result of the sample 9, and the graph indicated by the symbol b indicates the result of the sample 10 for comparison.

  The experimental conditions for investigating the aging characteristics were stricter than those during actual use. That is, an aging test was performed at an electric field strength of 300 kV / cm and a drive signal frequency of 50 kHz.

  From FIG. 17, in Sample 9, the displacement reduction rate was within 5%. On the other hand, in the comparative sample 10, the displacement reduction rate was 15% or more. From this, it was confirmed that the sample of this experimental example has a remarkably small displacement reduction rate in the aging process compared to the comparative sample.

4). Next, an ink jet printer will be described as an example of a liquid ejecting apparatus to which the liquid ejection head 50 obtained by the manufacturing method of the present embodiment is applied. That is, an example of an ink jet printer having the liquid discharge head 50 will be described. FIG. 9 is a schematic configuration diagram showing the ink jet printer 600. The inkjet printer 600 can function as a printer that can print on paper or the like. In the following description, the upper side in FIG. 9 is referred to as “upper part” and the lower side is referred to as “lower part”.

  The ink jet printer 600 has an apparatus main body 620, a tray 621 for setting the recording paper P in the upper rear, a discharge port 622 for discharging the recording paper P in the lower front, and an operation panel 670 on the upper surface. Have.

  Inside the apparatus main body 620, there are mainly a printing apparatus 640 having a reciprocating head unit 630, a paper feeding apparatus 650 for feeding the recording paper P one by one to the printing apparatus 640, the printing apparatus 640 and the paper feeding apparatus 650. And a control unit 660 for controlling.

  The printing apparatus 640 includes a head unit 630, a carriage motor 641 serving as a driving source for the head unit 630, and a reciprocating mechanism 642 that receives the rotation of the carriage motor 641 to reciprocate the head unit 630.

  The head unit 630 has a liquid discharge head 50 having the above-described many nozzle holes 511, an ink cartridge 631 for supplying ink to the liquid discharge head 50, and the liquid discharge head 50 and the ink cartridge 631 mounted below the head unit 630. A carriage 632.

  The reciprocating mechanism 642 includes a carriage guide shaft 644 whose both ends are supported by a frame (not shown), and a timing belt 643 extending in parallel with the carriage guide shaft 644. The carriage 632 is supported by the carriage guide shaft 644 so as to be reciprocally movable, and is fixed to a part of the timing belt 643. When the timing belt 643 travels forward and backward through a pulley by the operation of the carriage motor 641, the head unit 630 reciprocates while being guided by the carriage guide shaft 644. During this reciprocation, ink is appropriately discharged from the liquid discharge head 50 and printing on the recording paper P is performed.

  The sheet feeding device 650 includes a sheet feeding motor 651 serving as a driving source thereof, and a sheet feeding roller 652 that is rotated by the operation of the sheet feeding motor 651. The paper feed roller 652 includes a driven roller 652 a and a drive roller 652 b that are opposed to each other across the feeding path (recording paper P) of the recording paper P, and the driving roller 652 b is connected to the paper feeding motor 651. Has been.

  According to the ink jet printer 600, since the liquid ejection head 50 having high performance and high nozzle density is provided, high density printing and high speed printing are possible. Furthermore, since the ink jet printer 600 has the liquid ejection head 50 with excellent aging characteristics, highly accurate printing can be performed over a long period of time.

  The inkjet printer 600 can also be used as an industrially used liquid ejecting apparatus. In that case, as the ink to be ejected (liquid material), various functional materials can be used by adjusting them to an appropriate viscosity with a solvent or a dispersion medium.

  Although the embodiments of the present invention have been described in detail as described above, it will be readily understood by those skilled in the art that many modifications can be made without substantially departing from the novel matters and effects of the present invention. . Accordingly, all such modifications are intended to be included in the scope of the present invention.

  1 substrate, 2 insulating layer, 3 elastic layer, 4 lower electrode, 5 piezoelectric layer, 6 upper electrode, 7 orientation layer, 50 liquid ejection head, 51 nozzle plate, 52 ink chamber substrate, 54 piezoelectric element, 55 vibration plate, 511 Nozzle hole, 521 Pressure chamber, 522 Side wall, 523 Reservoir, 524 Supply port, 531 Communication hole, 600 Inkjet printer, 620 Main body, 621 Tray, 622 Discharge port, 630 Head unit, 631 Ink cartridge, 632 Carriage, 640 Printing Device, 641 Carriage motor, 642 Reciprocating mechanism, 643 Timing belt, 644 Carriage guide shaft, 650 Paper feed device, 651 Paper feed motor, 652 Paper feed roller, 660 Control unit, 670 Operation panel.

Claims (4)

Forming a lower electrode above the substrate ;
Forming an alignment layer above the lower electrode;
Forming a piezoelectric layer above the alignment layer;
Forming an upper electrode above the piezoelectric layer,
The alignment layer is a method of manufacturing a piezoelectric element formed by a rotary magnetron sputtering method at a temperature of 150 to 250 ° C. using a target including lanthanum oxide, nickel oxide, and a silicon compound. In claim 1,
The method of manufacturing a piezoelectric element , wherein a ratio of the silicon compound contained in the target is 2 mol% to 10 mol%. In either claim 1 or 2,
The alignment layer includes a mixed crystal of lanthanum nickelate,
The mixed crystal is composed of two or more lanthanum nickelates selected from LaNiO2, LaNiO3, and La2NiO4, and the mixed crystal is at a diffraction angle 2θ of X-ray diffraction by a θ-2θ method using CuKα rays. A method of manufacturing a piezoelectric element having a peak top position between 21 ° and 25 °. In claim 3,
When the value obtained by integrating the peak intensity up to 21 ° from the peak top position is IA, and the value obtained by integrating the peak intensity up to 25 ° from the peak top position is IB,
Piezoelectric element manufacturing method satisfying IA> IB or IA <IB

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