JP2015044321A - Liquid jetting head, liquid jetting device and piezoelectric element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid jetting head, a liquid jetting device and a piezoelectric element which preferentially orient a crystal of a BaTiOtype piezoelectric material in a predetermined direction and are excellent in piezoelectric characteristics.SOLUTION: A liquid jetting head is provided with a piezoelectric element 300 which includes a first electrode 60, at least one layer orientation control layer 72 which is disposed on the first electrode, a piezoelectric layer 70 disposed on the orientation control layer and a second electrode 80 disposed on the piezoelectric layer. Therein, the orientation control layer 72 comprises a complex oxide of a perovskite structure which contains bismuth, barium, iron and titanate, and the piezoelectric layer 70 comprises a complex oxide of a perovskite structure which contains at least barium and titanium and is preferentially oriented on a prescribed crystal surface.

Description

  The present invention relates to a liquid ejecting head, a liquid ejecting apparatus, and a piezoelectric element that include a piezoelectric element having a piezoelectric layer made of a piezoelectric material and an electrode and eject liquid droplets from nozzle openings.

  As a typical example of a liquid ejecting head, for example, a part of a pressure generation chamber communicating with a nozzle for ejecting ink droplets is configured by a vibration plate, and the vibration plate is deformed by a piezoelectric element to add ink in the pressure generation chamber. There is an ink jet recording head that presses and ejects ink droplets from a nozzle. As a piezoelectric element used for an ink jet recording head, there is one constituted by sandwiching a piezoelectric material exhibiting an electromechanical conversion function between two electrodes.

  As the piezoelectric material, lead zirconate titanate (PZT) having excellent piezoelectric characteristics is mainly used (see, for example, Patent Document 1).

On the other hand, from the viewpoint of environmental problems, development of piezoelectric materials that do not contain lead, that is, lead-free piezoelectric materials, is in progress. Examples of the lead-free piezoelectric material include barium titanate (BaTiO ₃ ) and bismuth ferrate (BiFeO ₃ ) having a perovskite structure represented by ABO ₃ (see, for example, Patent Documents 2 and 3).

In order to improve the piezoelectric characteristics of the piezoelectric material, it is desirable that the crystallinity is good and the crystal is preferentially oriented in a predetermined direction. For example, a technique for improving the piezoelectric characteristics by orienting crystals of a lead-free piezoelectric material in the (110) plane is known (see, for example, Patent Document 4). However, in order to make the piezoelectric characteristics of the lead-free piezoelectric material comparable to that of lead zirconate titanate (PZT), it is important to further improve the crystal orientation. In particular, among the lead-free piezoelectric materials, BaTiO ₃ has extremely small crystal lattice anisotropy, and it is extremely difficult to preferentially orient the crystal plane in a predetermined direction.

  Such a problem is not limited to a liquid jet head typified by an ink jet recording head, and similarly exists in a piezoelectric element such as an actuator device mounted in another device.

JP 2001-223404 A JP 2012-156493 A JP 2012-175092 A JP 2011-205067 A

In view of such circumstances, the present invention provides a liquid ejecting head, a liquid ejecting apparatus, and a piezoelectric element in which crystals of a BaTiO ₃ based piezoelectric material are preferentially oriented in a predetermined direction and have excellent piezoelectric characteristics. With the goal.

An aspect of the present invention for solving the above problems includes a first electrode, at least one orientation control layer provided on the first electrode, a piezoelectric layer provided on the orientation control layer, and the piezoelectric body. A liquid ejecting head including a piezoelectric element including a second electrode provided on the layer, wherein the orientation control layer is made of a complex oxide having a perovskite structure including bismuth, barium, iron, and titanium, The piezoelectric layer is made of a complex oxide having a perovskite structure containing at least barium and titanium, and is preferentially oriented in a predetermined crystal plane.
In this aspect, a liquid jet head in which the piezoelectric layer is preferentially oriented in a predetermined crystal plane and has excellent piezoelectric characteristics is realized.

Here, it is preferable that the orientation control layer further contains manganese, and the piezoelectric layer is preferentially oriented in the (110) plane.
According to this, the piezoelectric layer is strongly oriented in the (110) plane, and the piezoelectric characteristics are improved.

Here, the alignment control layer further includes a second alignment control layer on the first electrode side, and the second alignment control layer is made of a complex oxide having a perovskite structure containing bismuth and manganese, The piezoelectric layer is preferably preferentially oriented in the (100) plane.
According to this, the piezoelectric layer is strongly oriented in the (100) plane, and the piezoelectric characteristics are improved.

Here, the alignment control layer further includes a second alignment control layer on the first electrode side, and the second alignment control layer is a composite oxide having a perovskite structure containing bismuth, lanthanum, iron, and manganese. The piezoelectric layer is preferably preferentially oriented in the (111) plane.
According to this, the piezoelectric layer is strongly oriented in the (111) plane, and the piezoelectric characteristics are improved.

Here, it is preferable that the piezoelectric layer further contains lithium, boron, and copper.
According to this, the piezoelectric layer is strongly oriented in any one of the (110) plane, the (100) plane, and the (111) plane, and the piezoelectric characteristics are further improved.

  Here, it is preferable that the piezoelectric layer further contains manganese. According to this, leakage current is suppressed.

Another aspect of the invention is a liquid ejecting apparatus including the liquid ejecting head according to any one of the above aspects.
In this aspect, a liquid ejecting apparatus including a liquid ejecting head in which the piezoelectric layer is preferentially oriented in a predetermined crystal plane and has excellent piezoelectric characteristics is realized.

In another aspect of the present invention, a first electrode, at least one orientation control layer provided on the first electrode, a piezoelectric layer provided on the orientation control layer, and the piezoelectric layer The orientation control layer is made of a complex oxide having a perovskite structure containing bismuth, barium, iron, and titanium, and the piezoelectric layer has at least barium. And a perovskite structure composite oxide containing titanium and preferentially oriented in a predetermined crystal plane.
In such an embodiment, the piezoelectric layer is preferentially oriented in a predetermined crystal plane, and a piezoelectric element having excellent piezoelectric characteristics is realized.

FIG. 3 is an exploded perspective view illustrating a schematic configuration of the recording head according to the first embodiment. FIG. 3 is a plan view of the recording head according to the first embodiment. FIG. 3 is a cross-sectional view of the recording head according to the first embodiment. FIG. 3 is a cross-sectional view illustrating a manufacturing process of the recording head according to the first embodiment. FIG. 3 is a cross-sectional view illustrating a manufacturing process of the recording head according to the first embodiment. FIG. 3 is a cross-sectional view illustrating a manufacturing process of the recording head according to the first embodiment. FIG. 3 is a cross-sectional view illustrating a manufacturing process of the recording head according to the first embodiment. FIG. 3 is a cross-sectional view illustrating a manufacturing process of the recording head according to the first embodiment. FIG. 3 is a diagram showing an X-ray diffraction pattern of the piezoelectric layer of Example 1. FIG. 6 is a diagram showing an X-ray diffraction pattern of a piezoelectric layer according to Example 2. FIG. 6 is a diagram showing an X-ray diffraction pattern of a piezoelectric layer of Example 3. The figure which shows the X-ray-diffraction pattern of the piezoelectric material layer of the comparative example 1. FIG. 3 is an SEM photograph of the cross section of the piezoelectric layer of Example 1, the cross section of the piezoelectric layer of Examples 2 and 3, and the surface. The figure which shows the relationship between the current density and applied voltage of Example 3 and Comparative Example 1. 1 is a diagram illustrating a schematic configuration of a recording apparatus according to an embodiment of the present invention.

(Embodiment 1)
FIG. 1 is an exploded perspective view showing a schematic configuration of an ink jet recording head which is an example of a liquid ejecting head manufactured by a manufacturing method according to Embodiment 1 of the present invention, and FIG. 2 is a plan view of FIG. 3 is a cross-sectional view taken along the line AA 'of FIG. As shown in FIGS. 1 to 3, the flow path forming substrate 10 of the present embodiment is made of a silicon single crystal substrate, and an elastic film 50 made of silicon dioxide is formed on one surface thereof.

  A plurality of pressure generating chambers 12 are arranged in parallel in the width direction of the flow path forming substrate 10. In addition, a communication portion 13 is formed in a region outside the longitudinal direction of the pressure generation chamber 12 of the flow path forming substrate 10, and the communication portion 13 and each pressure generation chamber 12 are provided for each pressure generation chamber 12. Communication is made via a supply path 14 and a communication path 15. The communication part 13 communicates with a manifold part 31 of a protective substrate, which will be described later, and constitutes a part of a manifold that becomes a common ink chamber for each pressure generating chamber 12. The ink supply path 14 is formed with a narrower width than the pressure generation chamber 12, and maintains a constant flow path resistance of ink flowing into the pressure generation chamber 12 from the communication portion 13. In this embodiment, the ink supply path 14 is formed by narrowing the width of the flow path from one side. However, the ink supply path may be formed by narrowing the width of the flow path from both sides. Further, the ink supply path may be formed by narrowing from the thickness direction instead of narrowing the width of the flow path. In the present embodiment, the flow path forming substrate 10 is provided with a liquid flow path including the pressure generation chamber 12, the communication portion 13, the ink supply path 14, and the communication path 15.

  Further, on the opening surface side of the flow path forming substrate 10, a nozzle plate 20 having a nozzle opening 21 communicating with the vicinity of the end portion of each pressure generating chamber 12 on the side opposite to the ink supply path 14 is provided with an adhesive or It is fixed by a heat welding film or the like. The nozzle plate 20 is made of, for example, glass ceramics, a silicon single crystal substrate, stainless steel, or the like.

  On the other hand, the elastic film 50 is formed on the side opposite to the opening surface of the flow path forming substrate 10 as described above. On the elastic film 50, for example, titanium oxide having a thickness of about 30 to 50 nm or the like. An adhesion layer 56 for improving adhesion between the elastic film 50 and the first electrode 60 is provided. Note that an insulator film made of zirconium oxide or the like may be provided on the elastic film 50 as necessary.

  Further, on the adhesion layer 56, the first electrode 60, at least one orientation control layer 72 made of a composite oxide having a perovskite structure containing bismuth, barium, iron and titanium, which will be described in detail later, and at least barium and A piezoelectric layer 300 made of a composite oxide having a perovskite structure including titanium and a second electrode 80 are laminated to form a piezoelectric element 300 as pressure generating means for causing a pressure change in the pressure generating chamber 12. Yes. Here, the piezoelectric element 300 refers to a portion including the first electrode 60, the piezoelectric layer 70, and the second electrode 80. In general, one electrode of the piezoelectric element 300 is used as a common electrode, and the other electrode and the piezoelectric layer 70 are patterned for each pressure generating chamber 12.

  In the present embodiment, the first electrode 60 is a common electrode of the piezoelectric element 300, and the second electrode 80 is an individual electrode of the piezoelectric element 300. However, there is no problem even if this is reversed for the convenience of the drive circuit and wiring. Also, here, the piezoelectric element 300 and the diaphragm that is displaced by driving the piezoelectric element 300 are collectively referred to as an actuator device. In the above-described example, the elastic film 50, the adhesion layer 56, the first electrode 60, and the insulator film provided as necessary function as a vibration plate. However, the present invention is not limited to this. For example, the elastic film 50 and the adhesion layer 56 may not be provided. Further, the piezoelectric element 300 itself may substantially serve as a diaphragm. However, when the first electrode 60 is provided directly on the flow path forming substrate 10, it is preferable to protect the first electrode 60 with an insulating protective film or the like so that the first electrode 60 and the ink are not electrically connected.

  The orientation control layer 72 of the present embodiment has a crystal of the piezoelectric layer 70 containing Ba and Ti formed on the orientation control layer 72 in a predetermined direction (predetermined crystal plane), specifically, a (110) plane. , (100) plane and (111) plane are preferentially oriented.

  Here, “preferentially oriented in a predetermined direction” means that all the crystals of the piezoelectric layer 70 are oriented in a predetermined direction and that most crystals (for example, 50% or more) are in a predetermined direction. And the case where it is oriented.

Such an orientation control layer 72 is composed of at least one layer, and is composed of a complex oxide having a perovskite structure containing bismuth, barium, iron and titanium. In the perovskite structure, that is, the A site of the ABO ₃ type structure, oxygen is 12-coordinated, and oxygen is 6-coordinated at the B site to form an octahedron. Bi and Ba are located at the A site, and Fe and Ti are located at the B site.

  Here, in the case where the orientation control layer 72 is made of one composite oxide containing bismuth, barium, iron, and titanium and further manganese, the piezoelectric layer 70 is preferentially oriented in the (110) plane.

  In addition, the orientation control layer 72 is made of a composite oxide of two layers, and the second orientation control layer containing bismuth and manganese on the first electrode 60, and bismuth on the second orientation control layer, In the case of having the first orientation control layer containing barium, iron, and titanium, the piezoelectric layer 70 is preferentially oriented in the (100) plane.

  In addition, the orientation control layer 72 is made of a composite oxide of two layers, and the second orientation control layer containing bismuth, lanthanum, iron and manganese on the first electrode 60, and the second orientation control layer. When the first orientation control layer containing bismuth, barium, iron, and titanium is provided on the top, the piezoelectric layer 70 is preferentially oriented in the (111) plane.

  In this manner, by providing at least one orientation control layer 72 containing bismuth, barium, iron and titanium, depending on the composition of the orientation control layer 72, barium and titanium formed on the orientation control layer 72 are included. The piezoelectric layer 70 can be preferentially oriented in any one of the (110) plane, the (100) plane, and the (111) plane.

  Since the piezoelectric layer 70 has various physical properties such as a displacement amount, a dielectric constant, and a Young's modulus depending on the crystal orientation, the orientation of the piezoelectric layer 70 is a random orientation or a plurality of orientations in the case of a single orientation. It is possible to exhibit piezoelectric characteristics as compared with the case of having the following orientation. Since the piezoelectric layer 70 of the present embodiment is preferentially oriented in a predetermined direction by the orientation control layer 72, the crystallinity is good and current-voltage characteristics (IV characteristics) as shown in examples described later. Will be excellent.

  Furthermore, in this embodiment, a composite oxide having a perovskite structure containing bismuth, barium, iron, and titanium, which are piezoelectric materials, is used as at least one orientation control layer 72. Therefore, the orientation control layer 72 is an orientation control layer that preferentially orients the piezoelectric layer 70 in a predetermined direction, and also functions as a piezoelectric layer that exhibits piezoelectric characteristics. That is, in this embodiment, the piezoelectric characteristics are not deteriorated by providing the orientation control layer 72, but rather, excellent piezoelectric characteristics can be exhibited together with the piezoelectric layer 70. For this reason, the orientation control layer 72 and the piezoelectric material layer 74 described later can be collectively referred to as a piezoelectric layer 70.

Here, there is a case where one orientation control layer 72 is provided, in which the orientation control layer 72 is made of a composite oxide containing Bi, Ba, Fe and Ti, or a case where two orientation control layers 72 are provided. When the first orientation control layer provided on the second orientation control layer is made of a composite oxide containing Bi, Ba, Fe, and Ti, the composite oxide is composed of bismuth ferrate (BiFeO ₃ ) and barium titanate. It is expressed as a mixed solution with (BaTiO ₃ ) or as a solid solution in which bismuth ferrate and barium titanate are uniformly dissolved.

The composition of the orientation control layer in this case is represented by, for example, ((Bi, Ba) (Fe, Ti) O ₃ ), and typically represented as a mixed crystal represented by the following general formula (1). The Moreover, Formula (1) can also be represented by the following general formula (1 ′).

(1-x) [BiFeO ₃ ] -x [BaTiO ₃ ] (1)
(0 <x <0.40)
(Bi _1-x Ba _x ) (Fe _1-x Ti _x ) O ₃ (1 ′)
(0 <x <0.40)

In addition, when the orientation control layer 72 is provided in a single layer, the orientation control layer 72 is made of a composite oxide containing Bi, Ba, Fe, Ti, and Mn, or when the orientation control layer 72 is provided in two layers. When the first alignment control layer provided on the second alignment control layer is composed of a complex oxide containing Bi, Ba, Fe, Ti, and Mn, the complex oxide is bismuth iron manganate (Bi ( Fe, Mn) O ₃ ) and barium titanate (BaTiO ₃ ) or a solid solution in which bismuth ferrate manganate and barium titanate are uniformly dissolved.

The composition of the orientation control layer 72 in this case is represented by, for example, ((Bi, Ba) (Fe, Ti, Mn) O ₃ ), and is typically a mixed crystal represented by the following general formula (2). Represented as: Moreover, Formula (2) can also be represented by the following general formula (2 ′).

_{(1-x) [Bi (} Fe 1-y Mn y) O 3] -x [BaTiO 3] (2)
(0 <x <0.40, 0.01 <y <0.10)
_{(Bi 1-x Ba x)} ((Fe 1-y Mn y) 1-x Ti x) O 3 (2 ')
(0 <x <0.40, 0.01 <y <0.10)

  Here, the descriptions of the general formulas (1) and (2) and the general formulas (1 ′) and (2 ′) are compositional notations based on stoichiometry, and as described above, as long as a perovskite structure can be taken. However, inevitable compositional shift due to lattice mismatch, oxygen deficiency, etc., as well as partial substitution of elements are allowed. For example, if the stoichiometric ratio is 1, the range of 0.85 to 1.20 is allowed. Further, even if they are different from those represented by the above general formula, those having the same ratio of the A site element to the B site element may be regarded as the same composite oxide.

In addition, in the case where two orientation control layers 72 are provided, the second orientation control layer provided on the first electrode 60 includes a composite oxide containing Bi and Mn, or Bi, La, Fe, and Mn. When composed of complex oxides, the composition of these complex oxides is represented by bismuth manganate (BiMnO ₃ ) or bismuth lanthanum ferrate manganate ((Bi, La) (Fe, Mn) O ₃ ).

In the X-ray diffraction pattern, the above-mentioned composite oxides, that is, bismuth ferrate, barium titanate, bismuth ferrate manganate, bismuth manganate and bismuth lanthanum manganate are not detected alone. Further, these complex oxides are known piezoelectric materials each having a perovskite structure, and those having various compositions are known. For example, BiFeO ₃ , BaTiO ₃ , Bi (Fe, Mn) O ₃ , BiMnO ₃ and (Bi, La) (Fe, Mn) O _{3 are used} as elements (Bi, Fe, Ba, Ti, Mn, La and O). Is known to be partially missing or excessive, or a part of the element is replaced with another element. In this embodiment, bismuth ferrate, barium titanate, bismuth ferrate manganate, manganese When expressed as bismuth oxalate and bismuth lanthanum iron manganate, as long as the basic characteristics remain the same, those that deviate from the stoichiometric composition due to deficiency or excess, or some of the elements are replaced with other elements Is also included in the range of these complex oxides. Further, the ratio of BiFeO ₃ and BaTiO ₃ and the ratio of Bi (Fe, Mn) O ₃ and BaTiO ₃ can be variously changed.

  The thickness of the orientation control layer 72 is not limited, but is preferably thinner. For example, the thickness of the orientation control layer 72 is 80 nm or less, preferably 40 nm or less.

The piezoelectric layer 70 of the present embodiment is a piezoelectric material made of a complex oxide having a perovskite structure containing at least barium and titanium. A typical example is barium titanate (BaTiO ₃ ) in which Ba is located at the A site and Ti is located at the B site. The piezoelectric layer 70 includes not only those obtained by replacing barium of barium titanate or a part of titanium with other elements, but also those obtained by dissolving other perovskite structure piezoelectric materials not containing lead. Examples of the perovskite-type piezoelectric material that is solid-solved in barium titanate or a partially substituted one include bismuth sodium titanate, alkali niobium, and bismuth ferrate piezoelectric materials.

  Such barium titanate is considered to have difficulty in preferentially orienting crystal planes in a predetermined direction because crystal lattice anisotropy is extremely small among lead-free piezoelectric materials. However, by providing at least one orientation control layer 72 as described above, the piezoelectric layer 70, that is, the barium titanate crystal, has a predetermined direction, specifically, (110) plane, (100) plane, and (111). It becomes possible to preferentially orient to any one of the surfaces.

  Moreover, it is preferable that the composite oxide constituting the piezoelectric layer 70 further contains lithium, boron, and copper. Thereby, the crystal orientation of the piezoelectric layer 70 is further improved, and the current-voltage characteristics are improved.

  Here, the Li content is preferably 2 mol% or more and 5 mol% or less with respect to Ti, and the B content is preferably 2 mol% or more and 5 mol% or less with respect to Ti. Moreover, 3 mol% or less is preferable with respect to Ti, and, as for content of Cu, 0.5 mol% or more and 3 mol% or less are more preferable. Even if Li, B, and Cu are contained, the piezoelectric layer 70 has a perovskite structure, and Li, B, and Cu replace a part of Ba at the A site and Ti at the B site. Or presumably present at the grain interface.

  The piezoelectric layer 70 may further contain an element other than Ba, Ti, Li, B, and Cu. Examples of other elements include Mn, Co, and Cr, and preferably contains Mn. Thereby, the leak characteristic of the piezoelectric layer 70 is improved. In the case of containing Co or Cr, the leakage characteristics are improved as in the case of containing Mn.

  Even when the piezoelectric layer 70 is a composite oxide containing these other elements, it is necessary to have a perovskite structure. When the piezoelectric layer 70 contains Mn, Co, and Cr, Mn, Co, and Cr are located at the B site of the perovskite structure.

  Note that the thickness of the piezoelectric layer 70 is not limited. For example, the thickness of the piezoelectric layer 70 is 3 μm or less, preferably 0.3 μm or more and 1.5 μm or less.

  Each second electrode 80, which is an individual electrode of the piezoelectric element 300, is drawn from the vicinity of the end on the ink supply path 14 side and extends to the elastic film 50 or an insulator film provided as necessary. The lead electrode 90 to be connected is connected. The lead electrode 90 is made of, for example, gold (Au).

  At least a part of the manifold 100 is formed on the flow path forming substrate 10 on which such a piezoelectric element 300 is formed, that is, on the first electrode 60, the elastic film 50, the insulator film provided as necessary, and the lead electrode 90. A protective substrate 30 having a manifold portion 31 constituting the above is joined via an adhesive 35. In this embodiment, the manifold portion 31 penetrates the protective substrate 30 in the thickness direction and is formed across the width direction of the pressure generating chamber 12. As described above, the communication portion 13 of the flow path forming substrate 10. The manifold 100 is configured as a common ink chamber for the pressure generation chambers 12. Alternatively, the communication portion 13 of the flow path forming substrate 10 may be divided into a plurality of pressure generation chambers 12 and only the manifold portion 31 may be used as a manifold. Further, for example, only the pressure generation chamber 12 is provided in the flow path forming substrate 10 and a member (for example, an elastic film 50, an insulator film provided as necessary, etc.) interposed between the flow path forming substrate 10 and the protective substrate 30 ) May be provided with an ink supply path 14 for communicating the manifold 100 and each pressure generating chamber 12.

  A piezoelectric element holding portion 32 having a space that does not hinder the movement of the piezoelectric element 300 is provided in a region of the protective substrate 30 that faces the piezoelectric element 300. The piezoelectric element holding part 32 only needs to have a space that does not hinder the movement of the piezoelectric element 300, and the space may be sealed or unsealed.

  As such a protective substrate 30, it is preferable to use substantially the same material as the coefficient of thermal expansion of the flow path forming substrate 10, for example, glass, ceramic material, etc. In this embodiment, the same material as the flow path forming substrate 10 is used. The silicon single crystal substrate was used.

  The protective substrate 30 is provided with a through hole 33 that penetrates the protective substrate 30 in the thickness direction. The vicinity of the end portion of the lead electrode 90 drawn from each piezoelectric element 300 is provided so as to be exposed in the through hole 33.

  A drive circuit 120 for driving the piezoelectric elements 300 arranged in parallel is fixed on the protective substrate 30. For example, a circuit board or a semiconductor integrated circuit (IC) can be used as the drive circuit 120. The drive circuit 120 and the lead electrode 90 are electrically connected via a connection wiring 121 made of a conductive wire such as a bonding wire.

  In addition, a compliance substrate 40 including a sealing film 41 and a fixing plate 42 is bonded onto the protective substrate 30. Here, the sealing film 41 is made of a material having low rigidity and flexibility, and one surface of the manifold portion 31 is sealed by the sealing film 41. The fixing plate 42 is formed of a relatively hard material. Since the area of the fixing plate 42 facing the manifold 100 is an opening 43 that is completely removed in the thickness direction, one surface of the manifold 100 is sealed only with a flexible sealing film 41. Has been.

  In such an ink jet recording head I of this embodiment, ink is taken in from an ink introduction port connected to an external ink supply means (not shown), and the interior from the manifold 100 to the nozzle opening 21 is filled with ink, and then driven. In accordance with the recording signal from the circuit 120, a voltage is applied between each of the first electrode 60 and the second electrode 80 corresponding to the pressure generation chamber 12, and the elastic film 50, the adhesion layer 56, the first electrode 60, and the orientation control. By bending and deforming the layer 72 and the piezoelectric layer 70, the pressure in each pressure generating chamber 12 is increased, and ink droplets are ejected from the nozzle openings 21.

  Next, an example of a method for manufacturing the ink jet recording head of the present embodiment will be described with reference to FIGS. 4 to 8 are cross-sectional views in the longitudinal direction of the pressure generating chamber. In the present embodiment, a layer made of a composite oxide containing Bi, Ba, Fe, Ti and Mn is formed as the orientation control layer 72, and a piezoelectric material made of a composite oxide containing Ba and Ti is formed as the piezoelectric layer 70. An example in which nine material layers 74 are stacked will be described.

First, as shown in FIG. 4A, a silicon dioxide film made of silicon dioxide (SiO ₂ ) or the like constituting the elastic film 50 is formed by thermal oxidation or the like on the surface of a flow path forming substrate wafer 110 that is a silicon wafer. To do. Next, as shown in FIG. 4B, an adhesion layer 56 made of titanium oxide or the like is formed on the elastic film 50 (silicon dioxide film) by sputtering or thermal oxidation.

  Next, as shown in FIG. 5A, a first electrode 60 made of platinum is formed on the entire surface of the adhesion layer 56 by sputtering or vapor deposition. Next, as shown in FIG. 5B, patterning is performed simultaneously on the first electrode 60 so that the side surfaces of the adhesion layer 56 and the first electrode 60 are inclined using a resist (not shown) having a predetermined shape as a mask.

  Next, after removing the resist, an orientation control layer precursor film 71 is formed on the first electrode 60. This alignment control layer precursor film 71 is formed by, for example, applying a MOD (Metal-Organic Decomposition) method or a sol to obtain an alignment control layer 72 made of a metal oxide by applying and drying a solution containing a metal complex and baking at a high temperature. -It can be produced using a chemical solution method such as a gel method. In addition, the orientation control layer 72 can be manufactured by a laser ablation method, a sputtering method, a pulse laser deposition method (PLD method), a CVD method, an aerosol deposition method, or the like.

  As a specific example of the formation procedure when the orientation control layer 72 is formed by the chemical solution method, first, as shown in FIG. 5C, a MOD solution containing a metal complex on the first electrode 60 made of Pt. An alignment control layer forming composition (orientation control layer precursor solution) made of sol or sol is applied using a spin coating method or the like to form an alignment control layer precursor film 71 (orientation control layer precursor solution application) Process).

  The precursor solution of the orientation control layer to be applied is obtained by mixing a metal complex capable of forming a composite oxide containing Bi, Ba, Fe, Ti and Mn by firing, and dissolving or dispersing the mixture in an organic solvent. is there. As a metal complex containing Bi, Ba, Fe, Ti, and Mn, for example, alkoxide, organic acid salt, β-diketone complex, and the like can be used. Examples of the metal complex containing Bi include bismuth 2-ethylhexanoate and bismuth acetate. Examples of the metal complex containing Ba include barium isopropoxide, barium 2-ethylhexanoate, barium acetylacetonate, and the like. Examples of the metal complex containing Fe include iron 2-ethylhexanoate, iron acetate, and tris (acetylacetonato) iron. Examples of the metal complex containing Ti include titanium isopropoxide, titanium 2-ethylhexanoate, titanium (di-i-propoxide) bis (acetylacetonate), and the like. Examples of the metal complex containing Mn include manganese 2-ethylhexanoate and manganese acetate. Of course, a metal complex containing two or more of Bi, Ba, Fe, Ti, Mn and the like may be used. Examples of the solvent for the orientation control layer precursor solution include propanol, butanol, pentanol, hexanol, octanol, ethylene glycol, propylene glycol, octane, decane, cyclohexane, xylene, toluene, tetrahydrofuran, acetic acid, octylic acid, and the like. It is done.

  Thus, in order to produce the orientation control layer 72, for example, a precursor solution containing a metal complex of Bi, Ba, Fe, Ti, and Mn is used, and this is applied onto the first electrode 60 made of Pt. What is necessary is just to bake. The composition of the raw material such as the precursor solution is not particularly limited, and may be mixed so that each metal has a desired molar ratio.

Next, the orientation control layer precursor film 71 is heated to a predetermined temperature (for example, 150 to 200 ° C.) and dried for a predetermined time (alignment control layer drying step). Next, the dried alignment control layer precursor film 71 is degreased by heating to a predetermined temperature (for example, 350 to 450 ° C.) and holding for a certain time (alignment control layer degreasing step). Degreasing as used herein refers to removing organic components contained in the alignment control layer precursor film 71 as, for example, NO ₂ , CO ₂ , H ₂ O, or the like. The atmosphere of the orientation control layer drying step and the orientation control layer degreasing step is not limited, and may be in the air, in an oxygen atmosphere, or in an inert gas.

  Next, as shown in FIG. 5D, the orientation control layer precursor film 71 is heated to a predetermined temperature, for example, about 600 to 850 ° C., and held for a certain time, for example, 1 to 10 minutes for crystallization. Then, the orientation control layer 72 made of a composite oxide containing elements of Bi, Ba, Fe, Ti and Mn is formed (orientation control layer firing step).

  Also in this orientation control layer firing step, the atmosphere is not limited, and it may be in the air, in an oxygen atmosphere, or in an inert gas. Examples of the heating device used in the orientation control layer drying step, the orientation control layer degreasing step, and the orientation control layer firing step include an RTA (Rapid Thermal Annealing) device that heats by irradiation with an infrared lamp and a hot plate.

  In the present embodiment, the orientation control layer 72 consisting of a single layer is formed as a single coating step, but the above-described orientation control layer coating step, orientation control layer drying step and orientation control layer degreasing step, orientation control layer coating step, The orientation control layer drying step, the orientation control layer degreasing step, and the orientation control layer firing step may be repeated a plurality of times depending on the desired film thickness and the like to form the orientation control layer 72 composed of a plurality of layers.

  Next, nine piezoelectric material layers 74 made of a composite oxide containing Ba and Ti are stacked on the orientation control layer 72 to form the piezoelectric layer 70. The piezoelectric material layer 74 can be manufactured using, for example, a chemical solution method such as a MOD method or a sol-gel method in which a solution containing a metal complex is applied and dried, and further baked at a high temperature. In addition, the piezoelectric material layer 74 can be manufactured by a laser ablation method, a sputtering method, a pulse laser deposition method (PLD method), a CVD method, an aerosol deposition method, or the like.

  As a specific example of the formation procedure when the piezoelectric material layer 74 is formed by the chemical solution method, first, as shown in FIG. 6A, a metal complex, specifically, Ba is formed on the orientation control layer 72. And a piezoelectric material layer forming composition (precursor solution) composed of a MOD solution containing a metal complex containing Ti and Ti or a sol by using a spin coating method or the like. A layer precursor film) 73 is formed (application process).

  The precursor solution to be applied is obtained by mixing a metal complex capable of forming a composite oxide containing Ba and Ti by firing, and dissolving or dispersing the mixture in an organic solvent. What is necessary is just to mix the mixing ratio of the metal complex each containing Ba and Ti so that each metal may become a desired molar ratio. The metal complex containing Ba and Ti is as described above. Of course, you may use the metal complex containing 2 or more types of Ba and Ti.

  In addition, when forming the piezoelectric material layer 74 which consists of complex oxide containing Li, B, and Cu, the precursor solution containing the metal complex which has Li, B, and Cu further is used. Examples of the metal complex containing Li include lithium 2-ethylhexanoate and alkyl lithium. Examples of the metal complex containing B include boron 2-ethylhexanoate, alkylboron and the like. Examples of the metal complex containing Cu include copper 2-ethylhexanoate and copper acetate. Of course, you may use the metal complex containing 2 or more types of Li, B, and Cu.

  Examples of the solvent for the precursor solution include propanol, butanol, pentanol, hexanol, octanol, ethylene glycol, propylene glycol, octane, decane, cyclohexane, xylene, toluene, tetrahydrofuran, acetic acid, octylic acid, and the like.

Next, the piezoelectric material layer precursor film 73 is heated to a predetermined temperature (for example, 150 to 200 ° C.) and dried for a predetermined time (drying step). Next, the dried piezoelectric material layer precursor film 73 is degreased by heating it to a predetermined temperature (for example, 350 to 450 ° C.) and holding it for a predetermined time (degreasing step). The degreasing referred to here is to release the organic component contained in the piezoelectric material layer precursor film 73 as, for example, NO ₂ , CO ₂ , H ₂ O or the like. The atmosphere of the drying step or the degreasing step is not limited, and may be in the air, in an oxygen atmosphere, or in an inert gas. In addition, you may perform an application | coating process, a drying process, and a degreasing process in multiple times.

  Next, as shown in FIG. 6B, the piezoelectric material layer precursor film 73 is heated to a predetermined temperature, for example, about 600 to 850 ° C., and is baked by holding for a certain time, for example, 1 to 10 minutes. (Baking process). As a result, the piezoelectric material layer 74 is crystallized and is made of a composite oxide having a perovskite structure containing Ba and Ti. Also in this firing step, the atmosphere is not limited, and may be in the air, in an oxygen atmosphere, or in an inert gas. Examples of the heating device used in the drying step, the degreasing step, and the firing step include an RTA (Rapid Thermal Annealing) device that heats by irradiation with an infrared lamp, a hot plate, and the like.

  Next, a plurality of piezoelectric material layers 74 are formed by repeating the above-described coating process, drying process, degreasing process, coating process, drying process, degreasing process, and firing process a plurality of times according to a desired film thickness and the like. As shown in FIG. 6C, in the present embodiment, the piezoelectric layer 70 composed of nine piezoelectric material layers 74 is formed. For example, when the film thickness of the coating solution per one time is about 0.1 μm, the entire film thickness is obtained by combining the single orientation control layer 72 and the piezoelectric layer 70 composed of nine piezoelectric material layers 74. Is about 1.0 μm. The piezoelectric material layer 74 may be only one layer.

  Thus, by providing one orientation control layer 72 made of a composite oxide containing Bi, Ba, Fe, Ti and Mn, the piezoelectric layer 70 containing Ba and Ti formed thereon has a (110) plane. Preferred orientation. Thereby, the crystallinity of the piezoelectric layer 70 is improved, and the piezoelectric characteristics of the piezoelectric layer 70 are improved. Specifically, the piezoelectric layer 70 formed on the orientation control layer 72 is compared with a piezoelectric layer without the orientation control layer 72, that is, a piezoelectric layer in which crystals are not preferentially oriented in the (110) plane. Thus, the leakage current is suppressed. This is because the crystal growth of the perovskite structure of the piezoelectric layer 70 formed thereon is promoted by the orientation control layer 72.

  After the piezoelectric layer 70 is formed, as shown in FIG. 7A, a second electrode 80 made of platinum or the like is formed on the piezoelectric layer 70 by sputtering or the like, and faces each pressure generating chamber 12. In the region, the orientation control layer 72, the piezoelectric layer 70, and the second electrode 80 are simultaneously patterned to form the piezoelectric element 300 having the first electrode 60, the orientation control layer 72, the piezoelectric layer 70, and the second electrode 80. To do. The patterning of the orientation control layer 72, the piezoelectric layer 70, and the second electrode 80 can be performed collectively by dry etching through a resist (not shown) formed in a predetermined shape. Then, you may anneal in the temperature range of 600-850 degreeC as needed, for example. As a result, a good interface between the orientation control layer 72 and the first electrode 60 or between the piezoelectric layer 70 and the second electrode 80 can be formed, and the crystallinity of the piezoelectric layer 70 can be further increased. it can.

  Next, as shown in FIG. 7B, a lead electrode 90 made of, for example, gold (Au) or the like is formed over the entire surface of the flow path forming substrate wafer 110, and then a mask pattern made of, for example, a resist or the like. Patterning is performed for each piezoelectric element 300 via (not shown).

  Next, as shown in FIG. 7C, a protective substrate wafer 130 that is a silicon wafer and serves as a plurality of protective substrates 30 is placed on the piezoelectric element 300 side of the flow path forming substrate wafer 110 via an adhesive 35. After the bonding, the flow path forming substrate wafer 110 is thinned to a predetermined thickness.

  Next, as shown in FIG. 8A, a mask film 52 is newly formed on the flow path forming substrate wafer 110 and patterned into a predetermined shape.

  Then, as shown in FIG. 8B, the flow path forming substrate wafer 110 is anisotropically etched (wet etching) using an alkaline solution such as KOH through the mask film 52 to form the piezoelectric element 300. Corresponding pressure generating chambers 12, communication portions 13, ink supply passages 14, communication passages 15 and the like are formed.

  Thereafter, unnecessary portions of the outer peripheral edge portions of the flow path forming substrate wafer 110 and the protective substrate wafer 130 are removed by cutting, for example, by dicing. Then, after removing the mask film 52 on the surface opposite to the protective substrate wafer 130 of the flow path forming substrate wafer 110, the nozzle plate 20 having the nozzle openings 21 formed therein is bonded, and the protective substrate wafer 130 is also formed. The compliance substrate 40 is bonded to the substrate, and the flow path forming substrate wafer 110 or the like is divided into a single chip size flow path forming substrate 10 or the like as shown in FIG. To do.

  In this embodiment, by providing one orientation control layer 72 containing Bi, Ba, Fe, Ti and Mn, the piezoelectric layer 70 containing Ba and Ti can be preferentially oriented in the (110) plane. . Thereby, a piezoelectric element, a liquid ejecting head, and a liquid ejecting apparatus having excellent piezoelectric characteristics are realized.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to a following example.

(Example 1)
A silicon dioxide film having a thickness of 1200 nm was formed on the surface of the single crystal silicon substrate oriented in the (100) plane by thermal oxidation. Next, a titanium film with a thickness of 40 nm was formed on the silicon dioxide film by RF magnetron sputtering, and a titanium oxide film was formed by thermal oxidation. Next, a platinum film having a thickness of 100 nm was formed on the titanium oxide film by RF magnetron sputtering, and the first electrode 60 oriented in the (111) plane was formed, whereby a substrate with an electrode was obtained.

  Subsequently, an n-octane solution of bismuth 2-ethylhexanoate, barium 2-ethylhexanoate, iron 2-ethylhexanoate, manganese 2-ethylhexanoate, and titanium 2-ethylhexanoate was added to Bi: Ba: Fe: Mn. : Ti was mixed at a ratio of 75: 25: 71.25: 3.75: 25 to prepare an orientation control layer precursor solution.

  This alignment control layer precursor solution was applied onto the first electrode 60 by spin coating at 2500 rpm (alignment control layer application step). Next, the substrate with the electrode was placed on a hot plate, dried at 180 ° C. for 2 minutes (alignment control layer drying step), and then degreased at 350 ° C. for 3 minutes (alignment control layer degreasing step). Then, in an oxygen atmosphere, firing was performed at 750 ° C. for 5 minutes using an RTA (Rapid Thermal Annealing) apparatus (alignment control layer firing step), thereby forming an orientation control layer 72 having a thickness of about 40 nm.

  Then, each n-octane solution of barium 2-ethylhexanoate, titanium 2-ethylhexanoate, copper 2-ethylhexanoate, lithium 2-ethylhexanoate and boron 2-ethylhexanoate was mixed, and Ba: Ti: A piezoelectric film precursor solution was prepared by mixing such that the molar ratio of Cu: Li: B was 100: 100: 1: 3: 3.

  This piezoelectric layer precursor solution was applied onto the orientation control layer by spin coating at 1500 rpm (application process). Next, the substrate with the electrode was placed on a hot plate, dried at 150 ° C. for 2 minutes (drying step), and then degreased at 350 ° C. for 2 minutes (degreasing step). Then, in an oxygen atmosphere, firing was performed at 800 ° C. for 5 minutes using an RTA (Rapid Thermal Annealing) apparatus (firing step), and the piezoelectric material layer 74 was formed. This coating step, drying step, degreasing step, and firing step were repeated eight times to obtain a piezoelectric layer 70 having a thickness of about 900 nm consisting of nine piezoelectric material layers 74.

  Thereafter, a second electrode 80 made of a platinum film having a diameter of 500 μm and a film thickness of 100 nm is formed on the piezoelectric layer 70 by DC sputtering, and baked at 650 ° C. for 5 minutes using RTA to form the piezoelectric element 300. did.

(Example 2)
As the orientation control layer 72, a second orientation control layer containing Bi and Mn is formed on the first electrode 60, and Bi, Ba, and Fe having the same configuration as in Example 1 are formed on the second orientation control layer. The piezoelectric element 300 was formed in the same procedure as in Example 1 except that the first orientation control layer containing Ti and Mn was formed.

  First, an n-octane solution of bismuth 2-ethylhexanoate and manganese 2-ethylhexanoate is mixed on the first electrode 60 in such a ratio that the molar ratio of Bi: Mn is 1: 1. A second alignment control layer precursor solution was prepared, and the second alignment control layer precursor solution was applied onto the first electrode 60 to form a second alignment control layer having a thickness of about 20 nm.

  Next, the same orientation control layer precursor solution as in Example 1 was applied on the second orientation control layer to form the first orientation control layer. Except this, the piezoelectric element 300 was formed in the same procedure as in Example 1.

Example 3
A piezoelectric element 300 was formed in the same procedure as in Example 2 except that a second alignment control layer containing Bi, La, Fe, and Mn was formed on the first electrode 60 as the alignment control layer 72.

  An n-octane solution of bismuth 2-ethylhexanoate, lanthanum 2-ethylhexanoate, iron 2-ethylhexanoate, manganese 2-ethylhexanoate on the first electrode 60 is added to a Bi: La: Fe: Mn mole. The second alignment control layer precursor solution is prepared by mixing at a ratio of 85: 15: 97: 3, and this second alignment control layer precursor solution is applied onto the first electrode 60. As a result, a second alignment control layer having a thickness of about 40 nm was formed. Except this, the piezoelectric element 300 was formed in the same procedure as in Example 2.

(Comparative Example 1)
A piezoelectric element was formed in the same procedure as in Example 1 except that the orientation control layer was not formed.

(Test Example 1)
The piezoelectric layers of Examples 1 to 3 and Comparative Example 1 were measured for X-ray diffraction using “D8 Discover” manufactured by Bruker AXS. The measurement results of Examples 1 to 3 are shown in FIGS. 9 to 11, respectively, and the measurement result of Comparative Example 1 is shown in FIG.

  As shown in FIGS. 9 and 12, when the peak of Example 1 is compared with the peak of Comparative Example 1, in Example 1, the peak indicating the (100) plane is weaker than Comparative Example 1, and (110) It turned out that the peak which shows a surface is sharp. Accordingly, it was found that the piezoelectric layer is preferentially oriented in the (110) plane by providing the orientation control layer containing Bi, Ba, Fe, Ti, and Mn.

  Further, from the comparison between FIG. 10 and FIG. 12, the piezoelectric layer of Comparative Example 1 has almost no peak indicating the (100) plane, whereas the piezoelectric layer of Example 2 has the (100) plane. It was found that the peak indicating was large and sharp. Thereby, the piezoelectric layer is formed by configuring the orientation control layer with two layers of the first orientation control layer containing Bi, Ba, Fe, Ti and Mn and the second orientation control layer containing Bi and Mn. , (100) plane was found to be preferentially oriented.

  Further, from the comparison between FIG. 11 and FIG. 12, the piezoelectric layer of Comparative Example 1 showed almost no peak showing the (111) plane, but the piezoelectric layer of Example 3 showed the (111) plane. A peak was recognized sharply, and peaks indicating (100) plane and (110) plane were hardly recognized. Thereby, by constituting the orientation control layer with two layers of the first orientation control layer containing Bi, Ba, Fe, Ti and Mn and the second orientation control layer containing Bi, La, Fe and Mn, It was found that the piezoelectric layer is preferentially oriented in the (111) plane.

(Test Example 2)
Regarding the piezoelectric layer 70 in which the second electrode 80 is not formed, the cross section of the piezoelectric layer 70 in Example 1 and the cross section and the surface of the piezoelectric layer 70 in Examples 2 and 3 are scanned with an electron microscope (SEM). Was observed at 50,000 times. The result is shown in FIG.

  From the cross-sectional photographs of the piezoelectric layers of Examples 1 to 3, it was found that all the crystals were columnar and dense. Also, it was found from the surface photographs of the piezoelectric layers of Examples 2 and 3 that the crystals were dense. Furthermore, it was found from these surface photographs that the crystal grain sizes were uniform. This is because by providing the orientation control layer, the crystal growth of the perovskite structure of the piezoelectric layers of Examples 1 to 3 is preferentially oriented in a predetermined direction, and the crystallinity is improved.

(Test Example 3)
For the piezoelectric elements of Example 3 and Comparative Example 1, a voltage of ± 50 V was applied to determine the relationship between the current density and the applied voltage. The result is shown in FIG.

  As shown in FIG. 14, it was found that the piezoelectric element of Example 3 had a smaller leakage current value than the piezoelectric element of Comparative Example 1, and improved current-voltage characteristics (IV characteristics).

From the results of Test Examples 1 to 3, by providing at least one orientation control layer containing Bi, Ba, Fe, Ti, and Mn, the BaTiO ₃ -based piezoelectric layer is preferentially oriented in a predetermined direction and the piezoelectric characteristics are improved. I found out that Therefore, according to the present invention, a highly reliable liquid ejecting head, liquid ejecting apparatus, and piezoelectric element are realized.

(Other embodiments)
As mentioned above, although one Embodiment of this invention was described, the basic composition of this invention is not limited to what was mentioned above.

The piezoelectric layer 70 according to the present invention, that is, the BaTiO ₃ film preferentially oriented in any one of the (110) plane, the (100) plane, and the (111) plane, is a seed of a sintered body (bulk) of BaTiO _3. It can also be used as a layer.

In the prior art, methods for producing a sintered body of BaTiO ₃ oriented in a predetermined direction include so-called template particle growth method and reactive template particle growth method. In these methods, plate-like BaTiO ₃ powder, needle-like TiO ₂ particles, and the like are used as template particles. However, selection and synthesis of the template particles are complicated. Specifically, in order to obtain a sintered body of BaTiO ₃ oriented in the (100) plane is used BaTiO ₃ particles plate surface of the plate-like BaTiO ₃ particles are arranged in parallel by tape casting as a template particles There is a need. In order to obtain a sintered body of BaTiO ₃ oriented in the (111) plane, plate-like BaTiO ₃ powder and TiO ₂ powder are reacted by a two-stage melting method, and then BaCO ₃ is further added. In addition, it is necessary to use synthesized BaTiO ₃ particles as template particles.

If the BaTiO ₃ film preferentially oriented in any one of the (110) plane, the (100) plane, and the (111) plane according to the present invention is used as a seed layer, template particles as in the prior art become unnecessary, and the seed layer A BaTiO ₃ sintered body oriented in a predetermined direction can be obtained by a simple method by providing and laminating BaTiO ₃ powder or the like thereon. The obtained sintered body of BaTiO ₃ can be used as a piezoelectric material, a dielectric material, a semiconductor, and other various electronic device materials.

  In the embodiment described above, a silicon single crystal substrate is exemplified as the flow path forming substrate 10, but the present invention is not particularly limited thereto, and for example, a material such as an SOI substrate or glass may be used.

  Furthermore, in the above-described embodiment, the piezoelectric element 300 in which the first electrode 60, the piezoelectric layer 70, and the second electrode 80 are sequentially stacked on the substrate (the flow path forming substrate 10) is illustrated, but the present invention is not particularly limited thereto. For example, the present invention can also be applied to a longitudinal vibration type piezoelectric element in which piezoelectric materials and electrode forming materials are alternately stacked to expand and contract in the axial direction.

  In addition, the ink jet recording head of these embodiments constitutes a part of a recording head unit including an ink flow path communicating with an ink cartridge or the like, and is mounted on the ink jet recording apparatus. FIG. 15 is a schematic view showing an example of the ink jet recording apparatus.

  In the ink jet recording apparatus II shown in FIG. 15, the recording head units 1A and 1B having the ink jet recording head I are detachably provided with cartridges 2A and 2B constituting the ink supply means, and the recording head units 1A and 1B. Is mounted on a carriage shaft 5 attached to the apparatus main body 4 so as to be movable in the axial direction. The recording head units 1A and 1B, for example, are configured to eject a black ink composition and a color ink composition, respectively.

  The driving force of the driving motor 6 is transmitted to the carriage 3 via a plurality of gears and timing belt 7 (not shown), so that the carriage 3 on which the recording head units 1A and 1B are mounted is moved along the carriage shaft 5. The On the other hand, the apparatus body 4 is provided with a platen 8 along the carriage shaft 5, and a recording sheet S that is a recording medium such as paper fed by a paper feed roller (not shown) is wound around the platen 8. It is designed to be transported.

  In the above-described embodiment, the ink jet recording head has been described as an example of the liquid ejecting head. However, the present invention is widely applied to all liquid ejecting heads, and the liquid ejecting ejects a liquid other than ink. Of course, it can also be applied to the head. Other liquid ejecting heads include, for example, various recording heads used in image recording apparatuses such as printers, color material ejecting heads used in the manufacture of color filters such as liquid crystal displays, organic EL displays, and FEDs (field emission displays). Examples thereof include an electrode material ejection head used for electrode formation, a bioorganic matter ejection head used for biochip production, and the like.

  Further, the piezoelectric element according to the present invention is not limited to the piezoelectric element used in the liquid ejecting head, and can be used in other devices. Other devices include, for example, an ultrasonic device such as an ultrasonic transmitter, an ultrasonic motor, a temperature-electric converter, a pressure-electric converter, a ferroelectric transistor, a piezoelectric transformer, and a filter for blocking harmful rays such as infrared rays. And filters such as an optical filter using a photonic crystal effect by quantum dot formation, an optical filter using optical interference of a thin film, and the like. The present invention can also be applied to a piezoelectric element used as a sensor and a piezoelectric element used as a ferroelectric memory. Examples of the sensor using the piezoelectric element include an infrared sensor, an ultrasonic sensor, a thermal sensor, a pressure sensor, a pyroelectric sensor, and a gyro sensor (angular velocity sensor).

I ink jet recording head (liquid ejecting head), 10 flow path forming substrate, 12 pressure generating chamber, 13 communicating portion, 14 ink supply path, 15 communicating path, 20 nozzle plate, 21 nozzle opening, 30 protective substrate, 40 compliance substrate , 50 elastic film, 56 adhesion layer, 60 first electrode, 70 piezoelectric layer, 72 orientation control layer, 74 piezoelectric material layer, 80 second electrode, 90 lead electrode, 100 manifold, 120 drive circuit, 300 piezoelectric element

Claims (8)

A first electrode; at least one orientation control layer provided on the first electrode; a piezoelectric layer provided on the orientation control layer; and a second electrode provided on the piezoelectric layer. A liquid ejecting head including a piezoelectric element comprising:
The orientation control layer is composed of a complex oxide having a perovskite structure including bismuth, barium, iron and titanium,
The liquid jet head according to claim 1, wherein the piezoelectric layer is made of a complex oxide having a perovskite structure including at least barium and titanium, and is preferentially oriented in a predetermined crystal plane. The orientation control layer further contains manganese,
The liquid jet head according to claim 1, wherein the piezoelectric layer is preferentially oriented in a (110) plane. The alignment control layer further includes a second alignment control layer on the first electrode side,
The second orientation control layer is made of a composite oxide having a perovskite structure containing bismuth and manganese,
The liquid jet head according to claim 1, wherein the piezoelectric layer is preferentially oriented in a (100) plane. The alignment control layer further includes a second alignment control layer on the first electrode side,
The second orientation control layer is made of a complex oxide having a perovskite structure containing bismuth, lanthanum, iron and manganese,
The liquid jet head according to claim 1, wherein the piezoelectric layer is preferentially oriented in a (111) plane.   The liquid ejecting head according to claim 1, wherein the piezoelectric layer further contains lithium, boron, and copper.   The liquid jet head according to claim 1, wherein the piezoelectric layer further contains manganese.   A liquid ejecting apparatus comprising the liquid ejecting head according to claim 1. A first electrode; at least one orientation control layer provided on the first electrode; a piezoelectric layer provided on the orientation control layer; and a second electrode provided on the piezoelectric layer. A piezoelectric element comprising:
The orientation control layer is composed of a complex oxide having a perovskite structure including bismuth, barium, iron and titanium,
The piezoelectric element is characterized in that the piezoelectric layer is made of a complex oxide having a perovskite structure containing at least barium and titanium, and is preferentially oriented in a predetermined crystal plane.