JP2008218620A - Piezoelectric thin film element, method for manufacturing piezoelectric thin film element, ink jet head, and ink jet recording apparatus - Google Patents

Abstract

The present invention provides a piezoelectric thin film element that improves the piezoelectric performance of a piezoelectric thin film, has a crystal structure with excellent dependency of a piezoelectric constant on voltage, provides a high-performance and highly reliable piezoelectric thin film element, and provides a method for manufacturing the piezoelectric thin film element. An object of the present invention is to provide an ink jet head that sufficiently exhibits the piezoelectric performance of the thin film element and has excellent withstand voltage performance and driving reliability, and to provide a high-quality ink jet recording apparatus equipped with the ink jet.
A piezoelectric thin film element includes a crystal grain 50 of a piezoelectric thin film and a crystal grain boundary 51 formed between the crystal grains. The crystal grain boundary 51 and the crystal grain 50 have the same crystal orientation. Constitute.
[Selection] Figure 5

Description

  The present invention relates to a piezoelectric thin film element exhibiting an electromechanical conversion function, a method for manufacturing a piezoelectric thin film element, an ink jet head, and an ink jet recording apparatus.

In general, a piezoelectric thin film element includes a laminated body in which a piezoelectric body is sandwiched between two electrodes in the thickness direction. Here, the piezoelectric material is a material that converts mechanical energy into electrical energy, or converts electrical energy into mechanical energy. Typical examples of the piezoelectric material include lead zirconate titanate (Pb (Zr, Ti) O ₃ ) (hereinafter referred to as PZT) which is an oxide having a perovskite crystal structure, and magnesium, manganese, and PZT. , Nickel, niobium and the like.

  In particular, a large piezoelectric displacement is obtained in the <001> axis direction (C-axis direction) in the case of tetragonal PZT having a perovskite crystal structure and in the <111> axis direction in the case of rhombohedral PZT. However, many piezoelectric materials are polycrystalline bodies composed of aggregates of crystal grains, and each crystal axis is oriented in every direction. For this reason, the spontaneous polarization Ps is also arranged in all directions, but in the case of a piezoelectric thin film element using piezoelectricity, the sum of those vectors is made to be parallel to the electric field. And, in a piezoelectric actuator which is one form of this piezoelectric thin film element (a diaphragm is provided on the laminate), when a voltage is applied between both electrodes, mechanical displacement proportional to the magnitude of the voltage is effective. Can get to.

  A piezoelectric thin film used for a piezoelectric thin film element is formed by a physical vapor deposition method (PVD) such as a sputtering method, a chemical vapor deposition method (CVD), or a spin coating method such as a sol-gel method. Compared to the sintered body, the film thickness of the piezoelectric thin film can be formed with high accuracy and less variation. In addition, microfabrication by photolithography, dry etching, or the like can be applied, which is advantageous for downsizing and high density of elements. Recently, a technique called a hydrothermal synthesis method has been proposed in which seed crystals are grown in alkali-heated water.

  The piezoelectric thin film of this piezoelectric thin film element is generally composed of a polycrystalline body, and its crystal structure is composed of a plurality of crystal grains forming the piezoelectric thin film and crystal grain boundaries existing between the crystal grains. Various attempts have been proposed to improve and enhance the piezoelectric properties. In particular, to determine the degree of superiority or inferiority of the withstand voltage characteristic of the piezoelectric thin film, the influence of defects such as oxygen vacancies in the crystal grains and the influence of the crystal grain size and the state of the crystal grain boundaries are considered, for example (patent Document 1), Patent Document 2 and Patent Document 3 disclose several findings and improvements.

  Various studies have also been made on improving the piezoelectric performance. For example, in (Non-patent Document 1), a Pt electrode and a PZT thin film are formed on a single crystal substrate such as MgO by epitaxial growth. It has been proposed to form crystalline PZT thin films.

  Since the PZT thin film formed by epitaxial growth has no crystal grain boundaries, even if an electric field is applied to the piezoelectric thin film for polarization, the polarization axis direction is aligned from the beginning, so a very good polarization history is obtained. As a result, high followability and reproducibility are exhibited with respect to applied voltage history as well as high piezoelectric characteristics.

  On the other hand, in a piezoelectric thin film composed of a polycrystalline material, the domain (crystal grains) of the composed piezoelectric material moves so that the polarization direction matches the electric field direction when a voltage is applied. For example, in (Patent Document 4), a crystal grain boundary formed between crystal grains at that time greatly affects the residual strain, strain characteristics (displacement characteristics), and withstand voltage characteristics of the piezoelectric thin film. It is disclosed.

Further, (Patent Document 4) shows that when there are few or almost no foreign substances in the crystal grain boundary, the domain movement of the piezoelectric thin film is small and the generation of voids in the crystal grain boundary is suppressed by domain movement. Yes. However, the orientation at the crystal grain boundary is discontinuous with the crystal grain, and a peak that is not originally intended such as (110) is also observed in the result of XRD analysis. Furthermore, it is described that the precipitation of a compound having a composition that does not have piezoelectric properties such as PbO exists at the grain boundaries.
JP 2000-307163 A JP 2001-237468 A JP-A-10-217458 Japanese Patent Laid-Open No. 11-214763 JAE-HYUN JOO, YOU-JIN LEE, SEUNG-KI JOO, Feloelectrics, 1997, vol. 196; 1-4

  As described above, the voltage distortion characteristic (displacement characteristic) of the piezoelectric thin film has a problem that the linearity with respect to the voltage application history is inferior to the single crystal thin film when the piezoelectric thin film is a polycrystal. The displacement amount with respect to the applied voltage is small in the region where the electric field strength is low, and the displacement amount is relatively large in the region where the electric field is high. Since the piezoelectric constant d31 is proportional to the amount of displacement, there is a problem that the piezoelectric constant is not constant with respect to the applied voltage.

  On the other hand, in the case of a single crystal thin film, the amount of displacement has a first-order correlation with voltage, and the piezoelectric constant is constant with respect to the applied voltage. In the case of a polycrystal, the growth of crystal grains and the structure of crystal grain boundaries vary depending on the composition of the piezoelectric thin film, the manufacturing conditions, etc., so that the piezoelectric characteristics also have various pattern dependencies on the voltage. If the piezoelectric constant d31 is highly dependent on the voltage, for example, when a piezoelectric thin film element is used as an actuator of an inkjet head, accurate control cannot be performed when the amount of ink droplets to be ejected is controlled by the amount of displacement. Problems arise.

  In addition, as another problem of the polycrystalline body, there is a problem in that the domain movement caused by voltage application causes cracks in the crystal grain boundaries, and excessive Pb or the like precipitated in the crystal grain boundaries becomes a current leakage path. I have a problem.

  In order to solve these problems, it is conceivable to single-crystal the piezoelectric thin film. For example, it is difficult to increase the size of the MgO substrate, which is a single-crystal substrate. Is difficult.

  The present invention has been made in view of the above-mentioned problems, and has improved the piezoelectric performance of a piezoelectric thin film, has a crystal structure excellent in dependency of piezoelectric constant on voltage, and has a high performance and high reliability. And to provide a method for producing the same. It is another object of the present invention to provide an ink jet head that sufficiently exhibits the piezoelectric performance of the piezoelectric thin film element and has excellent withstand voltage performance and driving reliability, and a high-quality ink jet recording apparatus equipped with the ink jet. And

  In order to achieve the above object, the piezoelectric thin film element of the present invention is a piezoelectric thin film element in which a piezoelectric thin film is provided between electrodes, and the piezoelectric thin film is formed between crystal grains and the crystal grains. The crystal grain boundary and the crystal orientation of the crystal grain are configured to be the same.

  According to the configuration of the piezoelectric thin film element according to the present invention, it is possible to provide a piezoelectric thin film element with improved piezoelectric performance, small dependency of the piezoelectric constant on the voltage, and excellent in withstand voltage performance.

  The piezoelectric thin film element of the present invention is a piezoelectric thin film element in which a piezoelectric thin film is provided between electrodes, and the piezoelectric thin film includes crystal grains and a crystal grain boundary formed between the crystal grains, The crystal grain boundaries and crystal orientations of the crystal grains are configured to be the same.

  As a result, the domain can be moved smoothly when a voltage is applied, and good piezoelectric characteristics can be obtained.

  In the present invention, the piezoelectric thin film is composed of a polycrystal having a (001) single orientation of crystal grains.

  As a result, the amount of domain movement at the time of voltage application is small, and no other peak is present, so that excellent piezoelectric characteristics can be obtained.

  In the present invention, the crystal grains are columnar crystals that grow in a substantially vertical direction from one end of the electrode.

  As a result, it is possible to obtain a crystal structure that is favorable for exhibiting piezoelectric characteristics.

  In the present invention, the crystal grain size is 0.02 to 0.5 μm, and the crystal grain boundary width is 1 to 5 nm.

  As a result, the crystal structure with excellent piezoelectricity can be obtained by controlling the crystal grain arrangement so that the crystal grain arrangement is fine and the width of the crystal grain boundary is narrow.

  The present invention also provides a crystal orientation peak intensity of the piezoelectric thin film that is 0 in terms of intensity ratio compared to the crystal orientation peak intensity of the (001) single crystal thin film having the same film thickness as the piezoelectric thin film. .15 or more.

  Thus, the piezoelectric thin film which is a polycrystalline body has a crystal structure with excellent orientation, and characteristics close to those of a single crystal piezoelectric thin film can be obtained.

  In the present invention, the crystal grain boundary formed between the crystal grains constituting the piezoelectric thin film includes at least a constituent element of the crystal grains and has a piezoelectric composition ratio.

  As a result, there is no foreign substance inhibiting the piezoelectricity at the crystal grain boundary, and a crystal structure with excellent piezoelectric characteristics and excellent withstand voltage characteristics can be obtained.

  In the present invention, the piezoelectric thin film is composed of an oxide having a perovskite structure containing Pb, Zr, and Ti.

  As a result, a composition and crystal structure exhibiting excellent piezoelectric characteristics can be obtained.

  In the present invention, the composition ratio of Zr is 0.3 <Zr / (Zr + Ti) <0.7.

  Thereby, it can be set as a composition with high piezoelectricity.

  In the present invention, the composition ratio of Pb is 1 <Pb / (Zr + Ti) <1.4.

  As a result, it is possible to prevent deterioration of the crystal structure due to Pb loss during film formation and to exhibit high piezoelectric characteristics.

  In the present invention, the piezoelectric thin film is formed by vapor phase growth methods such as sputtering, vacuum deposition, laser ablation, ion plating, MBE, MOCVD, and plasma CVD.

  By adopting such a construction method, the crystal growth and film thickness of the piezoelectric thin film can be controlled with high accuracy, and a piezoelectric thin film having excellent piezoelectric characteristics and withstand voltage characteristics can be formed.

  Further, according to the present invention, the piezoelectric constant d31 of the piezoelectric thin film has a variation range with respect to the applied voltage history, 0 ≦ 100 × {(d31 (maximum value) −d31 (minimum value)) / (d31 (maximum value) + d31 (minimum). Value))} The range of the piezoelectric constant d31 is set to be <10.

  As a result, a piezoelectric thin film element with little dependency on the voltage of piezoelectric characteristics, good controllability of displacement, and high reproducibility can be obtained.

  The ink jet head of the present invention is bonded to a diaphragm film provided on one of the above-described piezoelectric thin film elements on the electrode side surface, and a surface of the diaphragm film opposite to the piezoelectric thin film element. And a pressure chamber member having a pressure chamber for accommodating the pressure chamber, and the diaphragm film is displaced in the film thickness direction by the piezoelectric effect of the piezoelectric thin film element so that ink in the pressure chamber is ejected.

  As a result, it is possible to provide an ink jet head having high controllability and high ejection performance.

  The present invention also includes a diaphragm laminated on one of the electrodes, and the internal stress of the diaphragm is a compressive stress.

  As a result, the characteristics of the piezoelectric thin film element can be sufficiently exhibited, and a highly reliable ink jet head can be obtained.

  In the present invention, the internal stress of the diaphragm is set so that the sum of the internal stress of the diaphragm and the internal stress of the laminated piezoelectric thin film element is a compressive stress.

  As a result, it is possible to provide an ink jet head having excellent withstand voltage characteristics and excellent long-term driving reliability.

  An ink jet recording apparatus of the present invention includes a relative moving unit that relatively moves the above-described ink jet head and a recording medium, and the ink jet head is moved relative to the recording medium by the relative moving unit. Recording is performed by ejecting the ink contained in the pressure chamber to a recording medium from a nozzle hole provided in the head so as to communicate with the pressure chamber.

  Accordingly, an ink jet recording apparatus having high performance and high reliability can be provided.

  The method for manufacturing a piezoelectric thin film element of the present invention includes a step of forming a first electrode layer on a substrate, a step of forming a piezoelectric thin film layer on the first electrode layer using a sputtering method, and a piezoelectric Forming a second electrode layer on the body thin film layer, and forming the piezoelectric thin film layer while heating the substrate so that a predetermined crystal orientation is obtained. It is a thing.

  As a result, a piezoelectric thin film having a predetermined crystal orientation can be obtained simultaneously with film formation, and the composition of crystal grains and crystal grain boundaries can be made the same.

  In the present invention, the piezoelectric thin film layer is formed using a sputtering target composed of Pb, Zr, and Ti, and the sputtering target is the same as the composition of the target piezoelectric thin film element or Zr, Ti. The ratio is the same, and the excess amount of Pb is in the range of 0 to 0.4 mol.

  As a result, a piezoelectric thin film having a predetermined crystal orientation can be obtained simultaneously with film formation, and high piezoelectric characteristics can be exhibited.

(Embodiment 1)
Hereinafter, Embodiment 1 of the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically showing a piezoelectric thin film element according to Embodiment 1 of the present invention.

  In FIG. 1, reference numeral 11 denotes a substrate made of a φ4 inch silicon (Si) wafer having a thickness of 0.3 mm, and an adhesion layer 12 made of titanium (Ti) having a thickness of, for example, 0.02 μm is formed on the substrate 11. Has been. The substrate 11 is not limited to Si, and may be a glass substrate, a metal substrate, a ceramic substrate, or the like.

  A first electrode layer 13 made of platinum (Pt) having a thickness of 0.22 μm, for example, is formed on the adhesion layer 12.

  A piezoelectric thin film layer 14 made of PZT having a rhombohedral or tetragonal perovskite crystal structure with a thickness of, for example, 3.5 μm is formed on the first electrode layer 13. The piezoelectric thin film layer 14 is preferentially oriented in the (001) plane. The composition of the piezoelectric thin film layer 14 is a composition (Zr / Ti = 53/47) near the boundary (morphotropic phase boundary) between the tetragonal crystal and the rhombohedral crystal. The Zr / Ti composition in the piezoelectric thin film layer 14 is not limited to Zr / Ti = 53/47, and may be Zr / Ti = 30/70 to 70/30. In addition, the constituent material of the piezoelectric thin film layer 14 may be a piezoelectric material mainly composed of PZT, such as PZT containing additives such as La, Sr, Nb, and Al, and may be PMN or PZN. It may be.

Moreover, even if it is a preferential orientation to (111) plane, it is sufficient if a single orientation is obtained. Piezoelectricity can be expressed even in other orientations, and the same effect can be obtained if the orientation is a single orientation. In the first embodiment, the piezoelectric thin film layer 14 does not have a peak of a Pb compound such as PbO that does not exhibit piezoelectricity or another compound composed of a constituent element such as TiO or ZrO ₂ .

  Furthermore, the film thickness of the piezoelectric thin film layer 14 may be in the range of 0.5 to 10.0 μm. The thickness is preferably 1.0 to 5.0 μm, and by setting this range, a sufficient amount of displacement as a piezoelectric actuator can be obtained.

  The piezoelectric thin film can be formed by using a film in a vacuum such as sputtering, laser ablation, and CVD, and by using a vacuum such as sol-gel, hydrothermal synthesis, and aerosol deposition. There is no known way. In any method, foreign matter such as a compound that does not express piezoelectricity from the outside is not mixed, and crystal grains 50 (see FIG. 4) constituting the piezoelectric thin film layer 14 made of a PZT film are uniformly and densely arranged. It suffices if the film forming conditions and the film forming environment capable of forming a single orientation with the same crystal orientation of 50 and the grain boundary 51 (see FIG. 4) can be realized.

  In the first embodiment, the film formation is performed using the sputtering method. However, by using the sputtering method, it is possible to more preferably “exclude the generation of a compound that does not exhibit piezoelectricity” as described above. . At this time, it is particularly effective to form a film using a PZT composition target having the same composition as that of the piezoelectric thin film to be prepared, or the ratio of Zr and Ti being the same and the Pb excess being in the range of 0 to 0.4 mol. .

  This is because in the sputtering method, since the substrate 11 is at a high temperature during film formation, the vapor pressure of Pb is low, so that Pb re-evaporates and Pb is easily removed from the film. Although the amount of Pb re-evaporation varies depending on the film forming conditions such as the sputtering pressure and the substrate 11 temperature, if the Pb amount of the PZT film to be produced is less than the theoretical value, the orientation and deterioration of the piezoelectric characteristics are caused. Therefore, it is necessary to add excess Pb to the target in advance.

  Further, in the first embodiment, the film is formed while heating the substrate 11 at a temperature at which a predetermined crystal orientation (for example, (001) orientation) is obtained when performing sputtering, and a predetermined crystal orientation is obtained simultaneously with the film formation. As a way to be.

  That is, in the sputtering method of the first embodiment, by using the sintered body target (PZT composition target) having the above-described composition, the ions in the plasma are struck against the target, so that the PZT particles (Pb, Ti, Zr, O ions and atoms) are ejected and reacted on the substrate 11 heated to a predetermined temperature to grow a crystalline PZT film.

  This is different from a method that is generally performed by a hydrothermal synthesis method or a sol-gel method, in which a film having a different crystallinity such as a precursor is first formed, and then preliminary firing and main firing are repeated. In the first embodiment, the sputtered particles fly on the heated substrate 11 and agglomerate on the surface of the substrate 11 to form nuclei, and the nuclei grow to form crystals. It becomes a grain. Furthermore, the crystal grains are grown and oriented. Since the flying particles correspond to atoms and ions constituting PZT, they all react to become PZT crystals and are taken into the crystal grains 50. For this reason, no foreign matter or crystals having a different orientation from the crystal grains 50 exist in the crystal grain boundaries 51. By such a process, the crystal orientation of the crystal grain boundary 51 and the crystal orientation of the crystal grain 50 become the same.

  In general, vapor phase growth methods such as PVD and CVD have high mechanical similarity and are suitable for forming a film having the same characteristics by setting film forming conditions. On the other hand, film formation methods such as the sol-gel method and hydrothermal synthesis method, unlike film formation in vacuum, require the prevention of foreign contamination from the outside during the process, and management of the purity of the starting material is also an issue. . In addition, since crystallization is performed in stages, a part of the crystal may not be completely crystallized, or a composition that inhibits piezoelectricity such as PbO may be deposited on the crystal grain boundary 51. These are difficult to control by controlling the film forming environment and film forming conditions, and there is a problem of reproducibility of film forming, and it is more preferable to use a vapor phase growth method.

  On the piezoelectric thin film layer 14, a second electrode layer 16 made of Pt having a thickness of, for example, 0.2 μm is formed. The material constituting the second electrode layer 16 is not limited to Pt, but may be any conductive material, and the film thickness may be in the range of 0.1 to 0.5 μm.

  The piezoelectric thin film element 15 is composed of a piezoelectric thin film layer 14 sandwiched between a first electrode layer 13 and a second electrode layer 16, and a displacement characteristic which is a piezoelectric distortion characteristic can be obtained by applying a voltage to both electrodes. it can.

  The film forming method of the piezoelectric thin film element 15 is preferably a vapor phase growth method such as sputtering, vacuum deposition, laser ablation, ion plating, MBE, MOCVD, plasma CVD, etc. Or a hydrothermal synthesis method that has recently been attracting attention.

  The adhesion layer 12 is for improving the adhesion between the substrate 11 and the first electrode layer 13, and is not limited to Ti, and may be composed of tantalum, iron, cobalt, nickel, chromium, or a compound thereof. Good. Moreover, the film thickness of the contact | adherence layer 12 should just be the range of 0.005-1.0 micrometer. The adhesion layer 12 is not necessarily required as long as the adhesion between the substrate 11 and the first electrode layer 13 can be secured.

(Example 1)
Hereinafter, Example 1 of the present invention will be described in more detail with reference to FIG.

  Example 1 details an example in which an adhesion layer 12, a first electrode layer 13, a piezoelectric thin film layer 14, and a second electrode layer 16 are sequentially formed on a substrate 11 made of Si by a sputtering method. Explained.

  The adhesion layer 12 is obtained by applying a high frequency power of 100 W while heating the substrate 11 to 400 ° C. using a Ti target and forming it in 1 Pa of argon gas for 1 minute.

  The first electrode layer 13 is obtained by using a Pt target and forming the substrate 11 with 200 W of high frequency power for 7 minutes in 1 Pa of argon gas while heating the substrate 11 to 600 ° C. Under such conditions, the film thickness of the first electrode layer 13 is 0.1 μm, and Pt constituting the first electrode layer 13 is oriented in the (111) plane. The first electrode layer 13 may be at least one kind of noble metal selected from the group of Pt, iridium, palladium and ruthenium or a compound thereof, and the film thickness may be in the range of 0.05 to 2.0 μm. That's fine.

  The piezoelectric thin film layer 14 was produced using a multi-source sputtering apparatus.

As the target, a sintered body target of PZT (Zr / Ti = 53/47, Pb excess by 20 mol%) having a Pb amount larger than the stoichiometric composition was used. First, the substrate 11 is heated to a substrate temperature of 600 ° C. by heating with a heater, and then in a mixed atmosphere of argon and oxygen (gas volume ratio Ar: O ₂ = 19.5: 0.5), the degree of vacuum is 0.3 Pa, A film is deposited in a film formation time of 170 minutes under a film formation condition with a high frequency power of 250 W.

  Further, the second electrode layer 16 is obtained by forming for 14 minutes with high frequency power of 200 W in 1 Pa argon gas at room temperature using a Pt target.

  FIG. 2 is a view showing an SEM cross-sectional photograph of the piezoelectric thin film according to Example 1 of the present invention.

  FIG. 2 shows an SEM cross section of the piezoelectric thin film formed on Pt, which is the first electrode layer 13 before forming the second electrode layer 16, obtained in Example 1.

  FIG. 3 is a view showing an SEM surface photograph of the piezoelectric thin film according to Example 1 of the present invention.

  According to these drawings, PZT constituting the piezoelectric thin film layer 14 is made of a polycrystal, and columnar crystals grown in a columnar shape in the film thickness direction from the first electrode layer 13 are continuously formed in a substantially vertical direction. I understand that.

  Next, in order to observe the piezoelectric thin film layer 14 created in Example 1 in detail, observation was performed with a transmission electron microscope (TEM).

  FIG. 4 is a diagram showing a TEM observation image obtained by observing the piezoelectric thin film according to Example 1 of the present invention with a transmission electron microscope (TEM).

  According to FIG. 4, crystal grains 50 having a crystal grain size of 0.02 μm to 0.5 μm are formed adjacent to each other, and crystal grain boundaries 51 are formed between the crystal grains 50. The crystal grains 50 are densely arranged, and the width of the crystal grain boundary 51 existing between the two crystal grains 50 is substantially uniform. The width of the crystal grain boundary 51 is in the range of 1 nm to 5 nm, and no voids are observed.

  5 to 7 show the results of analyzing the composition of the crystal grains 50 and the crystal grain boundaries 51. FIG.

  FIG. 5 is a diagram showing a TEM observation image showing measurement points at which the composition analysis of the crystal grains 50 and the crystal grain boundaries 51 of the piezoelectric thin film according to Example 1 of the present invention was performed.

  In Example 1, composition analysis was performed at three points, points 1 to 3.

  Point 1 is a point 50 nm away from the crystal grain boundary 51, Point 2 is a crystal grain boundary 51 of about 2 nm, a point in the crystal grain boundary 51 that is substantially equidistant from the crystal grain 50 in contact with this, and Point 3 is a crystal grain This is a point in the crystal grain 50 that is about 5 nm away from the boundary 51. The measurement beam diameter for elemental analysis is about 0.5 nm, the composition of the crystal grain boundary 51 has sufficient resolution, and the composition ratio can be analyzed.

  FIG. 6 is a graph showing the results of elemental analysis of the piezoelectric thin film according to Example 1 of the present invention.

  As shown in FIG. 6, each of the above points showed almost the same peak profile, and the profiles of other elements as foreign matters were not observed.

  (Table 1) shows the results of calculating the atomic percentages of Pb, Zr, and Ti, which are PZT compositions, for each point.

  In the polycrystalline piezoelectric thin film element 15, the crystal grains 50 exhibit piezoelectric performance, and the composition thereof is also created so as to maximize the piezoelectric characteristics. On the other hand, since the crystal grain boundary 51 has conventionally had many compositions other than the constituent elements and many specific elements, it has been a factor that hinders the piezoelectric characteristics of the piezoelectric thin film element 15 as a whole.

  For example, in PZT, it has been reported that PbO, which is a Pb compound having a low melting point, precipitates, and this causes discontinuity in the crystallinity of the crystal grain boundary 51, which may increase the residual strain and affect the reliability. know.

  In the piezoelectric thin film element 15 created this time, the composition of the crystal grain boundary 51 in the piezoelectric thin film layer 14 is almost the same as the composition of the crystal grain 50 for the elements related to the piezoelectric characteristics, and even if measurement errors are taken into account. It has a composition ratio having piezoelectricity and does not hinder the piezoelectric characteristics of the entire piezoelectric thin film element 15.

  Furthermore, the result of having analyzed in detail the composition ratio of the piezoelectric thin film layer 14 made of PZT obtained in Example 1 is shown in Table 2.

  According to Table 2, it can be seen that the piezoelectric thin film of Example 1 contains excessive Pb. When the results shown in Table 1 and FIG. 6 are combined, it can be determined that both the crystal grains 50 and the crystal grain boundaries 51 constituting the piezoelectric thin film layer 14 contain excessive Pb.

  The excess amount of Pb is preferably in the range of 1.0 <Pb (Zr + Ti) <1.4, as compared with the molar ratio of the B site containing Zr or Ti.

  When Pb becomes smaller than 1.0 and Pb becomes deficient, the crystallinity deteriorates. Further, when the excess amount of Pb exceeds 1.4, it precipitates in the form of PbO or the like in the crystal grain boundary 51 and acts as a current leakage path when a voltage is applied, and the withstand voltage characteristic is remarkably deteriorated.

  The ratio of Zr to Ti is good in piezoelectricity within the range of 0.3 <Zr / (Zr + Ti) <0.7.

  In the piezoelectric thin film according to Example 1, the composition of the crystal grain boundary 51 is almost the same as that of the crystal grain 50, and the composition analysis has a uniform composition distribution with no variation at each measurement point.

  In order to measure the orientation of the piezoelectric thin film obtained in Example 1, XRD analysis was performed. XRD analysis was performed by the R2-UltimaIII manufactured by Rigaku Corporation using the θ-2θ method.

  FIG. 7 is a graph showing an XRD analysis result of the piezoelectric thin film according to Example 1 of the present invention.

  As shown in FIG. 7, other than the (001) peak, other peaks such as (111) and (101) are not observed on the orientation plane of PZT, which is a piezoelectric thin film, and the PZT (001) peak intensity ratio is not observed. Other minor peaks that are significant are also not observed.

  There is no pyrochlore phase or other orientation peak of the constituent elements in a part of the observed piezoelectric thin film region, and the crystal grain 50 and the crystal grain boundary 51 have the same (001) single crystal orientation. It is a body thin film. Further, in order to evaluate the orientation of the piezoelectric thin film prepared this time, in order to examine the peak intensity in the XRD analysis, measurement was performed at five points. For comparison, the peak intensity was measured with a single crystal thin film in which a Pt or PZT thin film formed by epitaxial growth on an MgO substrate was formed. The film thickness of the epitaxial PZT was the same as that of the polycrystalline thin film, the orientation was also (001) single orientation, and no other peak was observed.

  Table 3 shows the result of measuring the peak intensity of the (001) orientation of the epitaxially grown piezoelectric thin film and the piezoelectric thin film of Example 1 under the same XRD analysis measurement conditions.

  The epitaxially grown piezoelectric thin film is a single crystal thin film, and its orientation is remarkably excellent and exhibits a very high peak intensity.

  So far, the conventional polycrystalline thin film has a difference in peak intensity ratio of at least about two digits compared to the thin film (single crystal film) formed by epitaxial growth, but as shown in Table 3, Example 1 The piezoelectric thin film (polycrystal) prepared in (1) has very good crystal orientation, and a strength ratio of 0.15 or more of a single crystal film is obtained. Thereby, it is conceivable that characteristics close to a single crystal can be obtained in terms of piezoelectric characteristics and electrical characteristics. Specifically, the domain followability with respect to the applied voltage is excellent, and the linearity of the history of piezoelectric characteristics with respect to the applied voltage is improved.

  Next, in order to evaluate the piezoelectric characteristics of the piezoelectric thin film prepared in Example 1, a cantilever cut out to 15 mm × 2 mm by dicing using 10% of the state before forming the second electrode layer 16 was used. After that, the second electrode layer 16 having a thickness of 0.2 μm was formed by sputtering, and the piezoelectric constant d31 was measured (for the method of measuring the piezoelectric constant d31, for example, Japanese Patent Laid-Open No. 2001-021052). It is described in).

  In the conventional polycrystal, since the orientation of the crystal grain boundaries 51 and foreign substances obstruct domain movement, the piezoelectric constant at a low voltage is low and the piezoelectric constant at a high voltage is large. Depending on the material composition and preparation conditions of the piezoelectric thin film, there are some that have a fluctuation of the piezoelectric constant d31 of about 30% with respect to the voltage. The reproducibility of was also poor. In order to compare the voltage dependence of the piezoelectric constant with respect to the voltage of Example 1, the value of (Equation 1) was calculated.

100 × {(d31 (maximum value) −d31 (minimum value)) / (d31 (maximum value) + d31 (minimum value))} (Equation 1)
Table 4 shows the measured value of the piezoelectric constant d31 with respect to the voltage of the piezoelectric thin film manufactured in Example 1, and the calculation result of the voltage dependence.

  The piezoelectric thin film prepared according to Example 1 has a small dependency of the piezoelectric constant d31 on the voltage, and is excellent in reproducibility by the voltage history.

(Embodiment 2)
FIG. 8 is a configuration diagram showing the overall configuration of the inkjet head according to Embodiment 2 of the present invention.

  FIG. 9 is a main part configuration diagram showing the main part configuration of the ink jet head according to the second embodiment of the present invention.

  Hereinafter, the configuration of the inkjet head according to Embodiment 2 will be described with reference to FIGS. 8 and 9.

  8 and 9, A is a pressure chamber member, and a pressure chamber opening 101 penetrating in the thickness direction (vertical direction) is formed in the pressure chamber member A. B is an actuator portion arranged to cover the upper end opening of the pressure chamber opening 101, and C is an ink flow path member arranged to cover the lower end opening of the pressure chamber opening 101. The pressure chamber opening 101 of the pressure chamber member A constitutes a pressure chamber 102 by being closed by an actuator portion B and an ink flow path member C positioned above and below the pressure chamber opening 101, respectively.

  The actuator section B has a first electrode layer 103 (individual electrode) positioned almost directly above each pressure chamber 102. The pressure chamber 102 and the first electrode layer 103 are staggered as shown in FIG. Many are arranged in a shape.

  The ink flow path member C includes a common liquid chamber 105 shared by the pressure chambers 102 arranged in the ink supply direction, a supply port 106 for supplying ink in the common liquid chamber 105 to the pressure chamber 102, And an ink flow path 107 for discharging the ink.

  D is a nozzle plate, and a nozzle hole 108 communicating with the ink flow path 107 is formed in the nozzle plate D. Further, E is an IC chip, and a voltage is supplied from the IC chip to each individual electrode 103 via a bonding wire BW.

  FIG. 10 is a configuration diagram showing the configuration of the actuator part B in the second embodiment of the present invention.

  FIG. 10 shows a cross section in a direction orthogonal to the ink supply direction shown in FIG.

  Hereinafter, the configuration of the actuator part B will be described with reference to FIG.

  FIG. 10 schematically illustrates the pressure chamber member A having the four pressure chambers 102 arranged in the orthogonal direction.

  As described above, the actuator portion B includes the first electrode layer 103 positioned substantially directly above each pressure chamber 102 and the orientation provided on each first electrode layer 103 (lower side in FIG. 10). The control layer 104, the piezoelectric thin film layer 110 provided on the orientation control layer 104 (on the lower side), and the piezoelectric thin film layer 110 (on the lower side) provided on the entire piezoelectric thin film layer 110. A common second electrode layer 112 (common electrode) and a vibration that is provided on the second electrode layer 112 (on the lower side) and is displaced in the thickness direction by the piezoelectric effect of the piezoelectric thin film layer 110 and vibrates. A plate 111 and an intermediate layer 113 (vertical wall) provided on the diaphragm 111 (lower side) and positioned above the partition wall 102a that partitions each pressure chamber 102; 1 electrode layer 103, piezoelectric thin film layer 110, and second electrode layer 11 It will constitute a piezoelectric thin-film element which they are stacked in this order.

  The diaphragm 111 is provided on the surface of the piezoelectric thin film element on the second electrode layer 112 side, and is formed so that the internal stress becomes a compressive stress. The compressive stress of the diaphragm 111 is set to a predetermined value so as not to affect other constituent materials, particularly the piezoelectric thin film layer 110, such as cracks.

  The compressive stress of the diaphragm 111 is preferably the sum of the internal stress of the piezoelectric thin film element formed of the piezoelectric thin film layer 110 formed on the diaphragm 111 and the internal stress of the diaphragm 111 is the compressive stress. Is set to be When the internal stress of the piezoelectric thin film element is a tensile stress, the compressive stress of the diaphragm 111 is increased so that the sum of the stresses of the two layers is compressed. When the internal stress of the piezoelectric thin film element is a compressive stress, the internal stress of the diaphragm 111 is preferably 0 or a weak compressive stress.

  By making the internal stress of the vibration plate 111 a compressive stress, it becomes strong against a peeling force due to mechanical contraction when a voltage is applied, and it is possible to prevent peeling and cracking.

  Further, since the sum of the internal stresses of the piezoelectric thin film element and the diaphragm 111 becomes a compressive stress, the effect of improving the reliability can be expected, for example, the adhesion of each layer is improved.

  In FIG. 10, reference numeral 114 denotes an adhesive that bonds the pressure chamber member A and the actuator portion B. Each of the intermediate layers 113 is partitioned by a part of the adhesive 114 when bonded using the adhesive 114. Even when it protrudes outward from the wall 102a, the upper surface of the pressure chamber 102 and the lower surface of the diaphragm 111 are arranged so that the adhesive plate 114 does not adhere to the diaphragm 111 and causes the diaphragm 111 to undergo the desired displacement and vibration. It has a role to expand the distance. As described above, the pressure chamber member A is preferably joined to the side surface of the vibration plate 111 of the actuator portion B opposite to the second electrode layer 112 via the intermediate layer 113, but the second electrode layer 112 of the vibration plate 111. The pressure chamber member A may be directly joined to the opposite side surface.

  The constituent materials of the first electrode layer 103, the piezoelectric thin film layer 110, and the second electrode layer 112 are the same as those of the first electrode layer 13, the piezoelectric thin film layer 14, and the second electrode layer described in the first embodiment. 16 (all refer to FIG. 1), respectively (some of the constituent elements have different contents). The diaphragm 111 is made of a metal thin film of Cu, Cr, Ti, an oxide ceramic such as zirconium oxide, or the like.

  Hereinafter, an ink jet head excluding the IC chip E of FIG. 8, that is, a method of manufacturing an ink jet head including the pressure chamber member A, the actuator portion B, the ink flow path member C and the nozzle plate D shown in FIG. This will be explained based on.

  FIG. 11 is an explanatory diagram showing a laminating process, a pressure chamber opening 101 forming process, and an adhesive 114 applying process in the inkjet head manufacturing method according to the second embodiment of the present invention.

  As shown in FIG. 11A, an adhesion layer 121, a first electrode layer 103, a piezoelectric thin film layer 110, a second electrode layer 112, a vibration plate 111, and an intermediate layer 113 are sequentially sputtered on a substrate 120. A film is formed by the method and laminated. Note that the adhesion layer 121 is equivalent to the adhesion layer 12 (see FIG. 1) described in Embodiment 1, and is used to increase the adhesion between the substrate 120 and the first electrode layer 103. It is formed between the first electrode layer 103 (the adhesive layer 121 is not necessarily formed when the adhesiveness between the two can be sufficiently ensured). As will be described later, the adhesive layer 121 is removed in the same manner as the substrate 120, as is unnecessary for the head configuration. Further, Cr is used for the material of the diaphragm 111 and Ti is used for the intermediate layer 113.

  As the substrate 120, a Si substrate cut into 18 mm square is used. The substrate 120 is not limited to Si, and may be a glass substrate, a metal substrate, or a ceramic substrate. Further, the substrate size is not limited to 18 mm square, and a wafer having a diameter of 2 to 10 inches may be used as long as it is a Si substrate.

  Piezoelectric elements sequentially formed from the adhesion layer 121 are formed in the same manner as the steps shown in the first embodiment.

  The diaphragm 111 is obtained by using a Cr target and forming it at room temperature for 150 minutes with a high frequency power of 200 W in an argon gas of 0.3 Pa. The film thickness of the diaphragm 111 is 3 μm. The internal stress of the diaphragm 111 is adjusted according to the film forming conditions of sputtering. Whether the internal stress is compression can be confirmed by forming a Si substrate together as a dummy substrate during film formation and measuring the amount of warpage of the substrate after taking it out after film formation. Before the film formation, the amount of warpage of the dummy Si substrate is measured in advance. After the film formation, the film formation surface faces up, and the convex warpage amount becomes the compression stress. Thus, if the amount of warp on the convex side is obtained, it becomes a compressive stress.

  Since the internal stress can be calculated from the amount of warpage, the internal stress is adjusted according to the film forming conditions. Generally, in the sputtering method, the greater the Ar implantation energy, the easier it is to obtain a compressive stress. Therefore, the compressive stress is adjusted by adjusting the parameters of gas pressure and input power. The total sum of internal stresses between the piezoelectric element and the diaphragm 111 is calculated by the same method.

  It is possible to estimate the total internal stress from the warpage amount after the initial warpage amount of the substrate 120 and the vibration plate 111 are laminated. In general, since the internal stress of the piezoelectric thin film undergoes a high temperature process, it is difficult to adjust the internal stress, and the internal stress is set as a compressive stress by the stress of the diaphragm 111. The material of the diaphragm 111 is not limited to Cr, but may be nickel, aluminum, tantalum, tungsten, silicon, or an oxide or nitride thereof (for example, silicon dioxide, aluminum oxide, zirconium oxide, silicon nitride) or the like. . Moreover, the film thickness of the diaphragm 111 should just be 0.5-10 micrometers.

  The intermediate layer 113 is obtained by forming it with a high frequency power of 200 W in argon gas of 1 Pa at room temperature for 5 hours using a Ti target. In the second embodiment, the thickness of the intermediate layer 113 is 5 μm. The material of the intermediate layer 113 is not limited to Ti but may be a conductive metal such as Cr. Moreover, the film thickness of the intermediate | middle layer 113 should just be 3-10 micrometers.

  FIG. 16 is a plan view showing a silicon substrate 130 used for manufacturing the inkjet head in the second embodiment of the present invention.

  Hereinafter, the description will be continued with FIG.

  After each layer is formed as described above, a pressure chamber member A is formed as shown in FIG. The pressure chamber member A is formed using a silicon substrate 130 (see FIG. 16) having a size larger than the substrate 120 made of Si, for example, a 4-inch wafer.

  Specifically, first, a plurality of pressure chamber openings 101 are patterned on the silicon substrate 130 (for pressure chamber members). In this patterning, as can be seen from FIG. 11B, the four pressure chamber openings 101 are set as one set, and the partition wall 102b that partitions each set defines the pressure chamber openings 101 in each set. It is set to twice the thickness of the partition wall 102a (thickness width). Thereafter, the patterned silicon substrate 130 is processed by chemical etching, dry etching, or the like to form four pressure chamber openings 101 in each set, and the pressure chamber member A is obtained.

  Thereafter, the substrate 120 (for film formation) after the above-described Si film formation and the pressure chamber member A are bonded using an adhesive 114 made of resin. The formation of the adhesive 114 is by electrodeposition.

  That is, first, as shown in FIG. 11C, the adhesive 114 is attached by electrodeposition to the upper surfaces of the partition walls 102a and 102b of the pressure chamber as an adhesive surface on the pressure chamber member A side. Specifically, although not shown, a Ni thin film with a thickness of several hundreds of centimeters thin enough to transmit light is formed as a base electrode film on the upper surfaces of the partition walls 102a and 102b by sputtering. Then, a patterned adhesive 114 is formed. At this time, as the electrodeposition liquid, a solution obtained by adding 0 to 50 parts by weight of pure water to the acrylic resin aqueous dispersion and stirring and mixing it well is used. The reason why the thickness of the Ni thin film is set to be thin enough to transmit light is to make it easy to visually recognize that the adhesive (adhesive resin) 114 is completely attached to the silicon substrate 130 (for the pressure chamber member). is there.

  According to experiments, the electrodeposition conditions are preferably a liquid temperature of about 25 ° C., a DC voltage of 30 V, and an energization time of 60 seconds. Under these conditions, an acrylic resin of about 3 to 10 μm is applied to the silicon substrate 130 (for pressure chamber members). An electrodeposition resin is formed on the Ni thin film.

  FIG. 12 is an explanatory diagram showing a bonding process between the substrate 120 and the pressure chamber member A after film formation and a vertical wall forming process in the method for manufacturing an inkjet head according to the second embodiment of the present invention.

  Next, as shown in FIG. 12A, the substrate 120 (for film formation) on which Si is formed and the pressure chamber member A are bonded using an electrodeposited adhesive 114. This bonding is performed using the intermediate layer 113 formed on the substrate 120 (for film formation) as the substrate-side bonding surface. Further, since the substrate 120 (for film formation) on which Si is formed has a size of 18 mm, and the silicon substrate 130 on which the pressure chamber member A is formed is as large as 4 inches, FIG. 12A and FIG. ), A plurality of (for example, 14 in the case of the silicon substrate shown in FIG. 16) substrates 120 (for film formation) are attached to one pressure chamber member A (silicon substrate 130). As shown in FIG. 12B, this pasting is performed in a state in which the center of each substrate 120 (for film formation) is positioned so as to be positioned at the center of the thick partition wall 102b of the pressure chamber member A. Is called.

  After this bonding, the pressure chamber member A is pressed and brought into close contact with the substrate 120 (for film formation) side to increase the adhesive pressure between them. Further, the bonded substrate 120 (for film formation) and the pressure chamber member A are gradually heated in a heating furnace to completely cure the adhesive 114. Subsequently, plasma treatment is performed to remove the protruding pieces of the adhesive 114.

  In FIG. 12A, the substrate 120 after film formation (for film formation) and the pressure chamber member A are bonded, but the silicon substrate 130 (for pressure chamber member) at a stage where the pressure chamber opening 101 is not formed. ) May be bonded to the substrate 120 (for film formation) after Si film formation.

  Thereafter, as shown in FIG. 12 (b), the intermediate layer 113 is etched into a predetermined shape by using the partition walls 102a and 102b of the pressure chamber member A as a mask (a shape continuous with the partition walls 102a and 102b). (Longitudinal wall)).

  FIG. 13 is an explanatory diagram showing a step of removing the substrate 120 (for film formation) and the adhesion layer 121 and a step of individualizing the first electrode layer 103 in the method for manufacturing an inkjet head according to the second embodiment of the present invention. It is.

  Next, as shown in FIG. 13A, the substrate 120 (for film formation) and the adhesion layer 121 are removed by etching.

  Subsequently, as shown in FIG. 13B, the first electrode layer 103 located on the pressure chamber member A is etched using the photolithography technique and individualized for each pressure chamber 102.

  FIG. 14 is an explanatory diagram showing an individualizing process of the piezoelectric thin film layer 110 and a cutting process of the silicon substrate 130 (for the pressure chamber member) in the method for manufacturing the ink jet head according to the second embodiment of the present invention.

  Next, as illustrated in FIG. 14A, the piezoelectric thin film layer 110 is etched using a photolithography technique to be individualized into the same shape as the first electrode layer 103. The first electrode layer 103 and the piezoelectric thin film layer 110 after the etching are positioned above each of the pressure chambers 102, and the centers in the width direction of the first electrode layer 103 and the piezoelectric thin film layer 110 correspond to each other. The pressure chamber 102 is formed to coincide with the center in the width direction with high accuracy. After the first electrode layer 103 and the piezoelectric thin film layer 110 are individually provided for each pressure chamber 102 in this way, as shown in FIG. 14B, the silicon substrate 130 (for the pressure chamber member) has a thickness of each thickness. By cutting at the partition wall 102b, four sets of the pressure chamber member A having four pressure chambers 102 and the actuator portion B fixed to the upper surface thereof are completed.

  FIG. 15 shows a production process of the ink flow path member C and the nozzle plate D, a bonding process between the ink flow path member C and the nozzle plate D, a pressure chamber in the method of manufacturing an ink jet head according to the second embodiment of the present invention. It is explanatory drawing which shows the adhesion process of the member A and the ink flow path member C, and the completed inkjet head.

  Subsequently, as shown in FIG. 15A, the common liquid chamber 105, the supply port 106, and the ink flow path 107 are formed in the ink flow path member C, and the nozzle hole 108 is formed in the nozzle plate D. Next, as illustrated in FIG. 15B, the ink flow path member C and the nozzle plate D are bonded using an adhesive 109.

  Thereafter, as shown in FIG. 15C, an adhesive (not shown) is transferred to the lower end surface of the pressure chamber member A or the upper end surface of the ink channel member C, and the pressure chamber member A and the ink channel member C are transferred. The two are bonded with an adhesive (not shown).

  As a result, an ink jet head having a pressure chamber member A, an actuator portion B, an ink flow path member C, and a nozzle plate D is completed as shown in FIG.

(Embodiment 3)
FIG. 17 is a configuration diagram showing the configuration of the ink jet recording apparatus 27 according to Embodiment 3 of the present invention.

  The ink jet recording apparatus 27 includes an ink jet head 28 similar to that described in detail in the second embodiment. In the ink jet head 28, the ink in the pressure chamber 102 is transferred from the nozzle hole (nozzle hole 108 described in the second embodiment) provided to communicate with the pressure chamber (the pressure chamber 102 described in the second embodiment). (Recording paper or the like) is configured to be discharged and recorded.

  The ink jet head 28 is mounted on a carriage 31 provided on a carriage shaft 30 extending in the main scanning direction X shown in FIG. 17, and the carriage 31 reciprocates along the carriage shaft 30 in the main scanning direction. It is configured to reciprocate in X. Thus, the carriage 31 constitutes a relative movement unit that relatively moves the inkjet head 28 and the recording medium 29 in the main scanning direction X.

  In addition, the ink jet recording apparatus 27 includes a plurality of rollers 32 that move the recording medium 29 in the sub scanning direction Y substantially perpendicular to the main scanning direction X (width direction) of the ink jet head 28. Thus, the plurality of rollers 32 constitute a relative moving unit that relatively moves the inkjet head 28 and the recording medium 29 in the sub-scanning direction Y. In FIG. 10, Z is a vertical direction (a direction orthogonal to both the main scanning direction X and the sub-scanning direction Y).

  When the inkjet head 28 is moved in the main scanning direction X by the carriage 31, ink is ejected from the nozzle holes of the inkjet head 28 onto the recording medium 29. When this one-scan recording is completed, the recording is performed by the roller 32. The medium 29 is moved by a predetermined amount to perform the next one-scan recording.

  As described above, the piezoelectric thin film element of the present invention is most suitable for an ink jet head and an ink jet recording apparatus.

  In addition, thin film capacitors, non-volatile memory element charge storage capacitors, various actuators, infrared sensors, ultrasonic sensors, pressure sensors, angular velocity sansei, acceleration sensors, flow sensors, shock sensors, piezoelectric transformers, piezoelectric ignitions The present invention can also be applied to elements, piezoelectric speakers, piezoelectric microphones, piezoelectric filters, piezoelectric pickups, tuning fork oscillators, delay lines, and the like.

  In particular, in a head support mechanism in which a head for recording or reproducing information with respect to a disk that is rotationally driven in a disk device (used as a storage device of a computer) is provided on a substrate, a piezoelectric provided on the substrate. The thin film element can be suitably used for a piezoelectric thin film actuator for a disk device (for example, see Japanese Patent Application Laid-Open No. 2001-332041) that deforms the substrate and displaces the head.

Sectional drawing which shows typically the piezoelectric material thin film element which concerns on Embodiment 1 of this invention. The figure which shows the SEM cross-section photograph of the piezoelectric material thin film based on Example 1 of this invention. The figure which shows the SEM surface photograph of the piezoelectric material thin film which concerns on Example 1 of this invention. The figure which shows the TEM observation image which observed the piezoelectric material thin film which concerns on Example 1 of this invention with the transmission electron microscope (TEM). The figure which shows the TEM observation image which shows the measurement point which performed the composition analysis of the crystal grain and crystal grain boundary of the piezoelectric material thin film which concerns on Example 1 of this invention The graph which shows the result of the elemental analysis of the piezoelectric material thin film based on Example 1 of this invention The graph which shows the XRD analysis result of the piezoelectric material thin film which concerns on Example 1 of this invention The block diagram which shows the whole structure of the inkjet head which concerns on Embodiment 2 of this invention. Main part block diagram which shows the structure of the principal part of the inkjet head which concerns on Embodiment 2 of this invention. The block diagram which shows the structure of the actuator part in Embodiment 2 of this invention. Explanatory drawing which shows the lamination process, the formation process of the opening part for pressure chambers, and the adhesion process of an adhesive agent in the manufacturing method of the inkjet head which concerns on Embodiment 2 of this invention. Explanatory drawing which shows the adhesion process of the board | substrate and pressure chamber member after film-forming, and the formation process of a vertical wall in the manufacturing method of the inkjet head which concerns on Embodiment 2 of this invention. Explanatory drawing which shows the removal process of a board | substrate (for film-forming) and an adhesion layer, and the individualization process of a 1st electrode layer in the manufacturing method of the inkjet head which concerns on Embodiment 2 of this invention. Explanatory drawing which shows the individualization process of a piezoelectric thin film layer, and the cutting process of a silicon substrate (for pressure chamber members) in the manufacturing method of the inkjet head which concerns on Embodiment 2 of this invention. In the ink jet head manufacturing method according to Embodiment 2 of the present invention, the ink flow path member and the nozzle plate generation step, the ink flow path member and the nozzle plate bonding step, the pressure chamber member and the ink flow path member Explanatory drawing showing the bonding process and the completed inkjet head In Embodiment 2 of this invention, the top view which shows the silicon substrate used for manufacture of an inkjet head The block diagram which shows the structure of the ink jet type recording apparatus which concerns on Embodiment 3 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Substrate 12 Adhesion layer 13 1st electrode layer 14 Piezoelectric thin film layer 15 Piezoelectric thin film element 16 2nd electrode layer 27 Inkjet recording device 28 Inkjet head 29 Recording medium 30 Carriage shaft 31 Carriage (relative movement means)
32 roller 101 pressure chamber opening 102 pressure chamber 102a partition wall 102b partition wall 103 first electrode layer (individual electrode)
104 orientation control layer 105 common liquid chamber 106 supply port 107 ink flow path 108 nozzle hole 109 adhesive 110 piezoelectric thin film layer 111 diaphragm 112 second electrode layer (common electrode)
113 Middle layer (vertical wall)
114 Adhesive 120 Substrate 121 Adhesion layer 130 Silicon substrate A Pressure chamber member B Actuator part C Ink flow path member D Nozzle plate E IC chip

Claims (17)

A piezoelectric thin film element in which a piezoelectric thin film is provided between electrodes,
The piezoelectric thin film is
Crystal grains,
Including the grain boundaries formed between the grains,
A piezoelectric thin film element in which the crystal grain boundaries and the crystal grains have the same crystal orientation. The piezoelectric thin film element according to claim 1,
A piezoelectric thin film element in which the piezoelectric thin film is formed of a polycrystal having a crystal orientation of the crystal grains of (001). The piezoelectric thin film element according to claim 1,
A piezoelectric thin film element in which the crystal grains are columnar crystals grown in a substantially vertical direction from one end of the electrode. The piezoelectric thin film element according to claim 1,
The crystal grain size is 0.02 to 0.5 μm,
A piezoelectric thin film element having a crystal grain boundary width of 1 to 5 nm. The piezoelectric thin film element according to claim 1,
The crystal orientation peak intensity of the piezoelectric thin film is 0.15 or more in terms of intensity ratio, compared with the crystal orientation peak intensity of the single crystal thin film having the same thickness as the (001) single crystal thin film. Piezoelectric thin film element. A piezoelectric thin film element in which a piezoelectric thin film is provided between electrodes,
A crystal grain boundary formed between crystal grains constituting the piezoelectric thin film,
A piezoelectric thin film element including at least a constituent element of the crystal grains and having a composition ratio having piezoelectricity. The piezoelectric thin film element according to claim 6,
A piezoelectric thin film element in which the piezoelectric thin film is made of an oxide having a perovskite structure containing Pb, Zr, and Ti. The piezoelectric thin film element according to claim 7,
A piezoelectric thin film element in which the composition ratio of Zr is 0.3 <Zr / (Zr + Ti) <0.7. The piezoelectric thin film element according to claim 7,
A piezoelectric thin film element in which the composition ratio of Pb is 1 <Pb / (Zr + Ti) <1.4. The piezoelectric thin film element according to claim 1 or 6,
A piezoelectric thin film element formed by vapor phase epitaxy such as sputtering, vacuum deposition, laser ablation, ion plating, MBE, MOCVD, plasma CVD or the like. The piezoelectric thin film element according to any one of claims 1 to 10,
The piezoelectric constant d31 of the piezoelectric thin film constituting the piezoelectric thin film element is a variation range with respect to the history of applied voltage.
0 ≦ 100 × {(d31 (maximum value) −d31 (minimum value)) / (d31 (maximum value) + d31 (minimum value))} <10
A piezoelectric thin film element in which the range of the piezoelectric constant d31 is set so that The piezoelectric thin film element according to any one of claims 1 to 11,
A diaphragm film provided on the surface of any one of the piezoelectric thin film elements;
A pressure chamber member having a pressure chamber which is bonded to a surface of the diaphragm film opposite to the piezoelectric thin film element and accommodates ink;
An inkjet head configured to discharge the ink in the pressure chamber by displacing the diaphragm film in the film thickness direction by the piezoelectric effect of the piezoelectric thin film element The inkjet head according to claim 12, wherein
An ink jet head comprising a diaphragm laminated on one of the electrodes, wherein the internal stress of the diaphragm is a compressive stress. The inkjet head according to claim 12, wherein
An ink jet head in which the internal stress of the diaphragm is set such that the sum of the internal stress of the diaphragm and the internal stress of the laminated piezoelectric thin film element is a compressive stress. An inkjet head according to any one of claims 11 to 14,
A relative movement means for relatively moving the inkjet head and the recording medium,
When the inkjet head is moved relative to the recording medium by the relative movement means,
An ink jet recording apparatus configured to perform recording by discharging ink contained in the pressure chamber to the recording medium from a nozzle hole provided to communicate with the pressure chamber in the ink jet head. Forming a first electrode layer on a substrate;
Forming a piezoelectric thin film layer on the first electrode layer by sputtering;
Forming a second electrode layer on the piezoelectric thin film layer;
Have
A method of manufacturing a piezoelectric thin film element, wherein in the step of forming the piezoelectric thin film layer, film formation is performed while heating the substrate so as to obtain a predetermined crystal orientation. A method of manufacturing a piezoelectric thin film element according to claim 16,
The piezoelectric thin film layer is formed using a sputtering target composed of Pb, Zr, Ti,
Production of a piezoelectric thin film element in which this sputtering target has the same composition as the target piezoelectric thin film element, or the ratio of Zr and Ti is the same, and the excess amount of Pb is in the range of 0 to 0.4 mol. Method.

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