JP2011238710A - Manufacturing method of liquid injection head and liquid injection device using the same, and manufacturing method of piezo-electric element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a liquid injection head capable of suppressing a leak current equal to or more than 1.0×10A per cm, and a liquid injection device using the same, and a manufacturing method of a piezo-electric element.SOLUTION: This is a manufacturing method for a liquid injection head which has a piezo-electric layer 70 held between a first electrode 60 and a second electrode 80 and a piezo-electric element 300 which causes pressure change in a pressure generation chamber 12. The method includes; a first electrode forming process where the first electrode 60 is formed including a process in which a diffusion suppressing layer 62 consisting of at least one of platinum and iridium is formed by an evaporation method; a piezo-electric layer forming process where the piezo-electric layer 70 made of complex oxide consisting of titanium, bismuth, barium, potassium and sodium is formed on the first electrode 60; and a second electrode forming process where the second electrode 80 is formed on the piezo-electric layer 70.

Description

  The present invention relates to a method for manufacturing a liquid jet head, a liquid jet apparatus using the same, and a method for manufacturing a piezoelectric element.

  As a typical example of a liquid ejecting head, for example, a part of a pressure generation chamber communicating with a nozzle opening for ejecting ink droplets is configured by a vibration plate, and the vibration plate is deformed by a piezoelectric element so that the ink in the pressure generation chamber is There is an ink jet recording head that pressurizes and ejects ink droplets from nozzle openings. As a piezoelectric element used in an ink jet recording head, there is a piezoelectric material having an electromechanical conversion function, for example, a piezoelectric material layer composed of piezoelectric ceramics sandwiched between two electrodes. Such a piezoelectric element is mounted on a liquid ejecting head as an actuator device in a flexural vibration mode.

  A liquid jet head using lead zirconate titanate (PZT) having high displacement characteristics is known as a piezoelectric ceramic (see Patent Document 1).

JP 2001-223404 A

In Patent Document 1, PZT is used as the piezoelectric ceramic. Currently, however, there is a demand for a liquid ejecting head using piezoelectric ceramic that does not contain lead or suppress the lead content from the viewpoint of environmental pollution. However, when a piezoelectric ceramic containing an alkali metal such as bismuth sodium titanate (BiNaTiO ₃ ) (hereinafter simply referred to as BNT) is used for the piezoelectric layer of a thin film as a piezoelectric ceramic not containing lead, There is a problem in that a large leak current of 1.0 × 10 ⁻¹ A / cm ² or more is generated due to the diffusion of the alkali metal into the electrode. On the other hand, since the piezoelectric characteristics of the piezoelectric ceramic are improved by containing an alkali metal in the bulk, a piezoelectric element having such a thin film structure of the piezoelectric ceramic containing the alkali metal is desirable. In addition, when a leakage current is generated in the piezoelectric element as described above, there is a problem that the displacement characteristics of the actuator using the piezoelectric element and the liquid ejecting characteristics of the liquid ejecting head and the liquid ejecting apparatus are deteriorated.

  Such a problem is not limited to the ink jet recording head, and is a problem common to liquid ejecting heads. Further, this is a problem common not only to piezoelectric elements used in liquid jet heads but also to piezoelectric elements used in other devices such as ultrasonic devices.

In view of such circumstances, the present invention includes a method for manufacturing a liquid jet head that does not contain lead and can suppress a leak current of 1.0 × 10 ⁻¹ A / cm ² or more, and a liquid jet device using the same. It is another object of the present invention to provide a method for manufacturing a piezoelectric element.

  A method of manufacturing a liquid jet head according to the present invention is a method of manufacturing a liquid jet head including a piezoelectric layer sandwiched between a first electrode and a second electrode, wherein at least one of platinum or iridium is deposited by vapor deposition. A first electrode forming step of forming the first electrode including a step of forming a diffusion suppressing layer, and the piezoelectric body comprising a composite oxide containing titanium, bismuth, barium, potassium and sodium on the first electrode. A piezoelectric layer forming step of forming a layer; and a second electrode forming step of forming the second electrode on the piezoelectric layer.

According to another aspect of the present invention, there is provided a method for manufacturing a liquid jet head comprising: a first electrode forming step of forming the first electrode including a step of forming a diffusion suppression layer including at least one of platinum and iridium by vapor deposition; Since the diffusion suppression layer that suppresses the diffusion of the alkali metal can be formed, a piezoelectric element in which the alkali metal is not diffused into the first electrode and does not contain lead can be formed, whereby 1.0 × 10 ^−1. A leakage current of A / cm ² or more can be suppressed. As a result, a liquid ejecting head having good liquid ejecting characteristics can be manufactured.

  In the first electrode forming step, it is preferable that the first electrode layer is formed by a sputtering method, and then the diffusion suppression layer is formed on the first electrode layer by an evaporation method. By comprising in this way, the 1st electrode which has favorable adhesiveness and can suppress a leakage current can be formed.

  The diffusion suppressing layer is preferably formed so as to have a thickness of 40 nm or more. With this thickness, the leakage current can be further suppressed.

  As a preferred embodiment of the present invention, in the piezoelectric layer forming step, a piezoelectric precursor film is formed on the first electrode, and the piezoelectric precursor film crystallized by firing the piezoelectric precursor film is formed. Forming a piezoelectric layer having the piezoelectric film.

  According to another aspect of the invention, a liquid ejecting apparatus includes the liquid ejecting head manufactured by the method of manufacturing a liquid ejecting head. By including the liquid ejecting head manufactured by the above-described liquid ejecting head manufacturing method, it is possible to prevent the liquid ejecting characteristics from being deteriorated.

The piezoelectric element manufacturing method of the present invention includes a first electrode forming step of forming a first electrode including a step of forming a diffusion suppression layer containing at least one kind of platinum or iridium by vapor deposition, and on the first electrode. A piezoelectric layer forming step of forming a piezoelectric layer made of a composite oxide containing titanium, bismuth, barium, potassium, and sodium; and a second electrode forming step of forming the second electrode on the piezoelectric layer; It is characterized by providing. In the piezoelectric element manufacturing method of the present invention, a lead-free piezoelectric body is formed by the first electrode forming step of forming the first electrode including the step of forming a diffusion suppression layer containing at least one kind of platinum or iridium by vapor deposition. Since the diffusion suppressing layer that suppresses the diffusion of alkali metal from the layer can be formed, the alkali metal is not diffused to the first electrode, thereby causing a leakage current of 1.0 × 10 ⁻¹ A / cm ² or more. Can be suppressed.

FIG. 2 is an exploded perspective view of a recording head according to an embodiment. 2A and 2B are a plan view and a cross-sectional view of the recording head according to the embodiment. FIG. 6 is a schematic cross-sectional view of the main part showing the manufacturing process of the recording head according to the embodiment. FIG. 6 is a schematic cross-sectional view of the main part showing the manufacturing process of the recording head according to the embodiment. FIG. 6 is a schematic cross-sectional view of the main part showing the manufacturing process of the recording head according to the embodiment. The graph which shows the measurement result of the current density with respect to the applied voltage of an Example and a comparative example. The graph which shows the measurement result of the current density with respect to the applied voltage of an Example and a comparative example. The graph which shows the measurement result of the current density with respect to the applied voltage of an Example and a comparative example. It is a perspective view of the liquid ejecting apparatus according to the embodiment.

(Liquid jet head)
FIG. 1 is an exploded perspective view showing a schematic configuration of an ink jet recording head which is an example of a liquid jet head according to Embodiment 1 of the present invention. FIG. 2 is a plan view of FIG. 1 and its AA ′ line. It is sectional drawing.

  As shown in FIGS. 1 and 2, an elastic film 50 is formed on one surface of the flow path forming substrate 10 of the present embodiment. The flow path forming substrate 10 is made of, for example, a silicon single crystal substrate. 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 reservoir part 31 of a protective substrate, which will be described later, and constitutes a part of the reservoir 100 that serves as a common ink chamber for the pressure generating chambers 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.

  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 of each pressure generating chamber 12 on the side opposite to the ink supply path 14 is provided with an adhesive. Or a heat-welded 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. Examples of the elastic film 50 include a silicon dioxide film. On the elastic film 50, a first electrode 60, a thin piezoelectric layer 70 having a thickness of 10 μm or less, preferably 0.3 to 1.5 μm, and a second electrode 80 are laminated and formed. A piezoelectric element 300 is configured. As will be described in detail later, the first electrode 60 is formed of a deposited film in which at least the interface with the piezoelectric layer 70 is formed by a deposition method. In addition, an adhesion layer 61 is formed between the first electrode 60 and the elastic film 50. The adhesion layer 61 is not particularly limited as long as it improves the adhesion between the first electrode 60 and the elastic film 50. For example, titanium (Ti), chromium (Cr) having a thickness of 10 to 50 nm, The main component is at least one element selected from the group consisting of tantalum (Ta), zirconium (Zr), and tungsten (W). In this embodiment, titania (TiO ₂ ). Thus, by providing the adhesion layer 61 between the first electrode 60 and the elastic film 50, the adhesion force between the elastic film 50 and the first electrode 60 can be increased.

  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. Here, the piezoelectric element 300 provided so as to be displaceable is referred to as an actuator device.

The piezoelectric layer 70 formed on the first electrode 60 is a composite oxide containing titanium (Ti), bismuth (Bi), barium (Ba), potassium (K), and sodium (Na). Examples of such a piezoelectric layer 70 include bismuth sodium titanate (for example, (Bi, Na) TiO ₃ , hereinafter referred to as BNT), bismuth potassium titanate (for example, (Bi, K) TiO ₃ , hereinafter referred to as BKT). )), A complex oxide having a perovskite structure containing barium titanate (for example, BaTiO ₃ , hereinafter referred to as BT), and a solid solution. In this embodiment, it has the piezoelectric ceramic which does not have lead in this way.

This composite oxide preferably has a composition ratio represented by, for example, the following general formula (1), and more preferably in the general formula (1), 0.6 ≦ x ≦ 0.8 0 <y ≦ 0.1. _{Incidentally, [(Bi a, Na 1} -a) TiO 3]: [(Bi b, K 1-b) TiO 3] = x: a 1-x (molar _{ratio), [(Bi a, Na} 1- _a ) Total amount of TiO ₃ ] and [( _{B i b} , K _1-b ) TiO ₃ ]: [BaTiO ₃ ] = 1: y (molar ratio).
_{{x [(Bi a, Na} 1-a) TiO 3] - (1-x) [(Bi b, K 1-b) TiO 3]} - y [BaTiO 3] (1)
(0.4 <a <0.6, 0.4 <b ≦ 0.6, 0.5 ≦ x ≦ 0.9, 0 <y ≦ 0.2)

  In the present embodiment, the piezoelectric layer 70 forms a complex oxide having a composition within the above range by using a precursor solution, for example, BNT: BKT: BT = 80: 20: 3, in a manufacturing process described in detail later. is doing.

  In this embodiment, the piezoelectric element 300 including the piezoelectric layer 70 made of such a complex oxide can be driven at a low voltage because the piezoelectric layer 70 includes BNT, BKT, and BT, and has piezoelectric characteristics. high.

  The piezoelectric layer 70 is a thin film having a thickness of 0.5 to 1.5 μm. In this embodiment, as will be described later, a plurality of piezoelectric precursor films are laminated and heated by a sol-gel method.

The first electrode 60 will be described in detail in the manufacturing method described later. However, the first electrode 60 is formed on the interface between the first electrode layer 63 and the first electrode layer 63, that is, at the interface between the piezoelectric layer 70 and functions as an electrode. And a diffusion suppression layer 62. Since the first electrode 60 has the diffusion suppression layer 62 at the interface with the piezoelectric layer 70 in this way, the alkali metals contained in the BNT and BKT included in the piezoelectric layer 70, that is, Na and K, are heated during heating. Diffusion in one electrode 60 is suppressed, and a leak current of 1.0 × 10 ⁻¹ A / cm ² or more is suppressed. That is, the diffusion suppressing layer 62 suppresses alkali metal diffusion in the piezoelectric layer 70 and also functions as an electrode by constituting a part of the first electrode 60.

  The thickness of the first electrode layer 63 is 30 to 80 nm, preferably 40 to 80 nm, and the thickness of the diffusion suppression layer 62 is 20 to 150 nm, preferably 40 to 150 nm. . Moreover, the 1st electrode 60 should just have the diffusion suppression layer 62 at least, and may consist only of the diffusion suppression layer 62. FIG.

  Each second electrode 80 that 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 extended to the elastic film 50, for example, gold (Au) or the like. The lead electrode 90 which consists of is connected.

  On the flow path forming substrate 10 on which the piezoelectric element 300 is formed, that is, on the first electrode 60, the elastic film 50, and the lead electrode 90, the protection having the reservoir portion 31 constituting at least a part of the reservoir 100. The substrate 30 is bonded via an adhesive 35. In the present embodiment, the reservoir portion 31 is formed across the protective substrate 30 in the thickness direction and across the width direction of the pressure generating chamber 12, and as described above, the communication portion 13 of the flow path forming substrate 10 is formed. The reservoir 100 is configured as a common ink chamber for the pressure generating 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 reservoir portion 31 may be used as the reservoir 100. Further, for example, only the pressure generating chamber 12 is provided in the flow path forming substrate 10, and the reservoir 100 and each pressure generating chamber 12 are disposed on a member (for example, the elastic film 50) interposed between the flow path forming substrate 10 and the protective substrate 30. An ink supply path 14 that communicates with each other may be provided.

  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 reservoir portion 31 is sealed by the sealing film 41. The fixing plate 42 is formed of a relatively hard material. Since the region of the fixing plate 42 facing the reservoir 100 is an opening 43 that is completely removed in the thickness direction, one surface of the reservoir 100 is sealed only with a flexible sealing film 41. Has been.

  In such an ink jet recording head 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 reservoir 100 to the nozzle opening 21 is filled with ink. In accordance with a recording signal from 120, a voltage is applied between each of the first electrode 60 and the second electrode 80 corresponding to the pressure generating chamber 12, and the elastic film 50, the first electrode 60, and the piezoelectric layer 70 are bent and deformed. By doing so, the pressure in each pressure generating chamber 12 increases, and ink droplets are ejected from the nozzle openings 21.

(Manufacturing method of liquid jet head)
A method of manufacturing the ink jet recording head of this embodiment will be described with reference to FIGS. 3 to 5 are cross-sectional views showing a method for manufacturing the ink jet recording head of this embodiment.

  First, as shown in FIG. 3A, an oxide film 51 constituting an elastic film 50 is formed on the surface of a flow path forming substrate wafer 110, which is a silicon wafer in which a plurality of flow path forming substrates 10 are integrally formed. To do. The formation method of the oxide film 51 is not particularly limited, but in this embodiment, the flow path forming substrate wafer 110 is thermally oxidized to form the oxide film 51 to be the elastic film 50 on the surface thereof.

  Then, as shown in FIG. 3B, an adhesion layer 61 is formed on the oxide film 51. Although the formation method of the contact | adherence layer 61 is not specifically limited, It can form in sputtering method, CVD method, etc.

  Next, as shown in FIG. 3C, a first electrode 60 made of platinum (Pt) and having a thickness of 50 to 500 nm is formed on the adhesion layer 61, and the first electrode 60 and the adhesion layer 61 are formed in a predetermined shape. To pattern. The first electrode 60 includes a first electrode layer 63 and a diffusion suppression layer 62. The formation method of the 1st electrode layer 63 is not specifically limited, It forms by sputtering methods, such as DC sputtering method, vapor deposition methods, such as laser beam vapor deposition.

The formation method of the diffusion suppression layer 62 is a vapor deposition method. That is, when heating is performed when forming a thin piezoelectric layer 70 having a thickness of 0.5 to 1.5 μm, alkali metals present in the composite oxide, that is, Na and K, are moved to the first electrode 60 side. As a result, a leakage current of 1.0 × 10 ⁻¹ A / cm ² or more is likely to occur in the driving voltage region (around 25 to 30 V) of the piezoelectric element, and holes are formed at the A site. As a result, the piezoelectric characteristics of the piezoelectric layer 70 deteriorate, and it is necessary to suppress this. For this reason, in this embodiment, in order to suppress this, the diffusion suppression layer 62 formed by the vapor deposition method is provided on the surface of the first electrode 60. Thereby, the diffusion of alkali metal to the first electrode 60 is suppressed.

  Here, in this embodiment, the vapor deposition method means a vacuum vapor deposition method in which an evaporation substance such as an ion beam vapor deposition method or a flash vapor deposition method is evaporated by high-temperature heating to form a film. The chemical vapor deposition method for forming a film by chemical vapor phase reaction such as physical vapor deposition method or thermal CVD method for forming a film by sputtering is excluded. In this embodiment, it formed using the ion beam vapor deposition method among vapor deposition methods. This is because according to this ion beam evaporation method, the diffusion of alkali metal into the first electrode 60 can be further suppressed.

In the present embodiment, the first electrode 60 is configured by forming the first electrode layer 63 by a sputtering method and forming the diffusion suppression layer 62 by a vapor deposition method. Thus, by forming the 1st electrode layer 63 by sputtering method, while improving the adhesiveness of the contact | adherence layer 61 and the 1st electrode layer 63, by forming the diffusion suppression layer 62 by vapor deposition method, it is 1st. Alkali metal hardly diffuses into the electrode 60, and a leak current of 1.0 × 10 ⁻¹ A / cm ² or more can be suppressed. The conditions of the sputtering method for forming the first electrode layer 63 are not particularly limited. For example, the film forming temperature is 300 ° C., the film forming pressure is 0.4 Pa, and the DC power density is 1.2 W / cm. ² is mentioned.

If the conditions of the vapor deposition method for forming the diffusion suppression layer 62 are based on, for example, the ion beam vapor deposition method, the temperature in the heater of the film forming apparatus: room temperature (about 25 ° C.) to 300 ° C., beam current: 350 mA to 450 mA, The pressure in the chamber (1.0 × 10 ^{−4 to} 1.10 × 10 ⁻⁵ Pa). The reason for this range is as follows. That is, when the temperature in the heater of the film forming apparatus exceeds 300 ° C., the film density of the lower electrode is lowered. Also, if the beam current is lower than 350 mA, a film cannot be formed, and if it exceeds 450 mA, foreign matter is likely to adhere. Furthermore, if the pressure in the chamber is not within this range, the film quality is likely to deteriorate.

  The first electrode 60 including the first electrode layer 63 and the diffusion suppressing layer 62 is made of at least one selected from platinum (Pt), iridium (Ir), or iridium oxide. For example, a diffusion suppression layer 62 made of platinum formed by vapor deposition may be formed on the first electrode layer 63 made of platinum formed by sputtering, or from platinum formed by sputtering. A diffusion suppression layer 62 made of iridium formed by a vapor deposition method may be formed on the first electrode layer 63.

Moreover, it is preferable that the film thickness of the diffusion suppression layer 62 is 40 nm or more. This is because if the film thickness is 40 nm or more, it is possible to sufficiently suppress the occurrence of a leak current of 1.0 × 10 ⁻¹ A / cm ² or more in the driving voltage region of the piezoelectric element. The formation method of the first electrode layer 63 is not limited, and is formed by, for example, a sputtering method in the present embodiment. Although the thickness of the 1st electrode layer 63 is not specifically limited, For example, it is 30-80 nm.

  Examples of the patterning described above include dry etching such as reactive ion etching and ion milling.

  Next, a piezoelectric layer 70 that is a complex oxide containing BNT, BKT, and BT is formed. Examples of the method for manufacturing the piezoelectric layer 70 include a sol-gel method, a MOD (Metal-Organic Decomposition) method, and a sputtering method. In the present embodiment, the piezoelectric layer 70 is formed using a sol-gel method. This is because the formation of the piezoelectric layer 70 by the sol-gel method using the sol of the present embodiment, which will be described later, can suppress the occurrence of cracks in the piezoelectric layer 70 and reduce the cost. Because it can.

  A specific method will be described below. A sol containing BNT, BKT, and BT is applied onto the flow path forming substrate 10 on which the first electrode 60 is formed to form a piezoelectric precursor film (application process). A sol containing BNT, BKT, and BT has a composition ratio of BNT: BKT: BT = x: y: z (molar ratio), for example, 50 ≦ x ≦ 90, 10 ≦ y ≦ 50, 0 <z ≦ 3. It is. In the present embodiment, the piezoelectric precursor film has a thickness of 1.0 to 2.0 μm, preferably 1.5 to 2.0 μm.

  Subsequently, it heats to predetermined temperature and is made to dry for a fixed time (drying process). For example, in this embodiment, it is made to dry by hold | maintaining at 150-180 degreeC for 2 to 10 minutes.

Next, the dried piezoelectric precursor film is degreased by heating to a predetermined temperature and holding for a certain time (degreasing step). For example, in this embodiment, the piezoelectric precursor film was degreased by heating to a temperature of about 300 to 450 ° C. and holding for about 2 to 10 minutes. Here, degreasing refers, the organic components contained in the piezoelectric precursor film, for example, is to be detached as _{NO 2, CO 2, H 2} O or the like. After repeating the coating step, the drying step and the degreasing step a plurality of times in this order, the piezoelectric precursor film is heated to a predetermined temperature (about 750 to 850 ° C.) by an infrared heating device and is crystallized by holding it for a certain period of time. To form a piezoelectric film (firing step).

  A piezoelectric film made of a complex oxide including BNT, BKT, and BT is formed by repeating a piezoelectric film forming process including a coating process, a drying process, a degreasing process, and a baking process a plurality of times. Layer 70 is formed. Moreover, you may perform post-annealing in the temperature range of 600 degreeC-800 degreeC before and after formation of the 2nd electrode 80 as needed. Thereby, a good interface between the piezoelectric layer 70 and the first electrode 60 or the second electrode 80 can be formed, and the crystallinity of the piezoelectric layer 70 can be improved.

  Next, as shown in FIG. 4A, the second electrode 80 is formed over the piezoelectric layer 70. Then, as shown in FIG. 4B, the piezoelectric element 300 is formed by patterning the piezoelectric layer 70 and the second electrode 80 in regions facing the pressure generating chambers 12. Examples of the patterning of the piezoelectric layer 70 and the second electrode 80 include dry etching such as reactive ion etching and ion milling.

  Next, the lead electrode 90 is formed. Specifically, as shown in FIG. 4C, the 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 made of, for example, a resist or the like. It is formed by patterning each piezoelectric element 300 via a mask pattern (not shown).

  Next, as shown in FIG. 5A, a protective substrate wafer 130 which 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. Join.

  Next, as shown in FIG. 5B, the flow path forming substrate wafer 110 is thinned to a predetermined thickness.

  Next, as shown in FIG. 5C, a mask film 52 is newly formed on the flow path forming substrate wafer 110 and patterned into a predetermined shape. Then, the flow path forming substrate wafer 110 is anisotropically etched (wet etching) using an alkaline solution such as KOH through the mask film 52, so that the pressure generating chamber 12 and the communication portion 13 corresponding to the piezoelectric element 300 are obtained. The ink supply path 14 and the communication path 15 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. The nozzle plate 20 having the nozzle openings 21 formed on the surface of the flow path forming substrate wafer 110 opposite to the protective substrate wafer 130 is bonded, and the compliance substrate 40 is bonded to the protective substrate wafer 130. By dividing the flow path forming substrate wafer 110 and the like into a single chip size flow path forming substrate 10 and the like as shown in FIG. 1, an ink jet recording head I of this embodiment is obtained as shown in FIG. .

Sample 1 according to Example 1 was produced as follows.
First, a single crystal silicon substrate was thermally oxidized to form an elastic film 50 made of silicon dioxide with a thickness of 1300 nm. An adhesion layer made of titania was formed on the obtained elastic film 50 so as to have a thickness of 40 nm by a sputtering method.

Next, the first electrode layer 63 made of platinum was formed by DC sputtering so as to have a thickness of 30 nm under the film forming conditions of film forming temperature: 330 ° C. and DC power density: 1.2 W / cm ² . Next, a diffusion suppression layer 62 made of platinum was formed to have a thickness of 100 nm by ion beam evaporation. The film forming conditions of the vapor deposition method were heater temperature: 25 ° C., beam current: 400 mA, and chamber pressure: 1.0 × 10 ⁻⁵ Pa.

  After that, a sol containing BNT, BKT, and BT is applied by spin coating at 500 rpm for 10 seconds and then at 2500 rpm for 30 seconds to form a piezoelectric precursor film having a desired film thickness (0.5 μm). did. The sol containing BNT, BKT, and BT had a composition ratio of BNT: BKT: BT = 80: 20: 3.

  Then, the drying process was performed at 400 degreeC for 3 minutes, and the degreasing process was then performed at 400 degreeC for 3 minutes. After repeating the coating step, the drying step and the degreasing step three times in this order, baking was carried out at 750 ° C. for 3 minutes while introducing oxygen gas at 5 L / min with an RTA (Rapid Thermal Annealing) apparatus. After these piezoelectric film forming steps were repeated twice, oxygen gas was baked again at 5 L / min at 750 ° C. for 3 minutes using the RTA apparatus to obtain the piezoelectric layer 70.

  Next, a second electrode 80 made of platinum was formed on the piezoelectric layer 70 so as to have a thickness of 100 nm by sputtering. As a result, a piezoelectric element 300 was formed as Sample 1.

(Comparative Example 1)
The piezoelectric element 300 was formed under the same conditions as Example 1 except that the diffusion suppression layer 62 was not provided, and Sample 2 according to Comparative Example 1 was obtained.

Comparative Example 1 was manufactured under the same conditions except that the diffusion suppressing layer 62 made of platinum was formed on the first electrode layer 63 so as to have a film thickness of 40 nm by vapor deposition. The film formation conditions of the diffusion suppression layer 62 in Example 2 are a heater temperature: 25 ° C., a beam current: 400 mA, and a chamber internal pressure: 1.0 × 10 ⁻⁵ Pa. Changed.

It was manufactured under the same conditions as in Example 2 except that the film thickness of the diffusion suppressing layer 62 was 60 nm. The film formation conditions of the diffusion suppressing layer 62 in Example 3 are a heater temperature: 25 ° C., a beam current: 400 mA, and a chamber pressure: 1.0 × 10 ⁻⁵ Pa. Changed.

Example 1 was produced under the same conditions as in Example 1 except that a diffusion suppression layer 62 made of iridium was formed to a thickness of 20 nm on the first electrode layer 63 by vapor deposition. The film formation conditions of the diffusion suppressing layer 62 in Example 4 are a heater temperature: 25 ° C., a beam current: 400 mA, and a chamber pressure: 1.0 × 10 ⁻⁵ Pa. Changed.

It was manufactured under the same conditions as Example 4 except that the film thickness of the diffusion suppressing layer 62 was 40 nm. The film formation conditions of the diffusion suppressing layer 62 in Example 5 are heater temperature: 25 ° C., beam current: 400 mA, chamber internal pressure: 1.0 × 10 ⁻⁵ Pa, and film formation time is different from that in Example 4. Changed.

It was manufactured under the same conditions as Example 4 except that the film thickness of the diffusion suppressing layer 62 was 60 nm. The film formation conditions of the diffusion suppression layer 62 in Example 6 are heater temperature: 25 ° C., beam current: 400 mA, and chamber pressure: 1.0 × 10 ⁻⁵ Pa. Changed.

  For these obtained samples according to Examples 1 to 6 and Comparative Example 1, the current density with respect to the applied voltage was measured.

The results of Example 1 and Comparative Example 1 are shown in FIG. As shown in FIG. 6, in the case of Sample 2 in which the diffusion suppression layer 62 was not provided, a leak current of 1.0 × 10 ⁻¹ A / cm ² or more occurred in the vicinity of −30V. In the case of Sample 1 in which the diffusion suppression layer 62 is provided, the leakage current is suppressed in any voltage region as compared with Comparative Example 1 in which the diffusion suppression layer 62 is not provided, and the drive voltage region (about 20 to 30 V). The leakage current was 1.0 × 10 ⁻⁵ A / cm ² or less.

The results of Comparative Example 1 and Examples 2 and 3 are shown in FIG. In the case of Comparative Example 1 in which the diffusion suppression layer 62 was not provided, a leak current of 1.0 × 10 ⁻¹ A / cm ² or more was generated near −30 V as described above. Compared with Comparative Example 1 in which the diffusion suppression layer 62 is not provided, a leakage current of 1.0 × 10 ⁻¹ A / cm ² or more is suppressed in any voltage region, and 1.0 × 10 ⁻² A / cm. The leakage current was ² or less.

The results of Comparative Example 1, Examples 4, 5, and 6 are shown in FIG. In the case of Comparative Example 1 in which the diffusion suppression layer 62 was not provided, a leak current of 1.0 × 10 ⁻¹ A / cm ² or more was generated in the vicinity of −30 V as described above. 6, a leakage current of 1.0 × 10 ⁻¹ A / cm ² or more is suppressed in any voltage region as compared with Comparative Example 1 in which the diffusion suppression layer 62 is not provided, and 1.0 × 10 ⁻² A The leakage current was less than / cm ² .

  Therefore, according to the present embodiment, the leakage current can be suppressed by forming the diffusion suppression layer 62 by the vapor deposition method. Further, from the results of FIGS. 7 and 8, it was found that the leakage current is more easily suppressed as the diffusion suppression layer 62 is thicker.

(Inkjet recording device)
In the ink jet recording apparatus II shown in FIG. 9, the recording head units 1A and 1B having the ink jet recording head I obtained by the manufacturing method of the present embodiment are detachable from the cartridges 2A and 2B constituting the ink supply means. The carriage 3 on which the recording head units 1A and 1B are mounted is provided 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.

  The configuration of the ink jet recording head I is not limited to the above-described embodiment. For example, an iridium oxide film or the like as an insulating film may be formed on the elastic film 50.

  In the present embodiment, the first electrode layer 63 and the diffusion suppressing layer 62 are separately formed. However, in order to suppress the diffusion of the alkali metal from the piezoelectric layer 70 to the first electrode 60, at least the piezoelectric layer is used. The diffusion suppression layer 62 may be formed at the interface with the body layer 70. For example, the first electrode 60 may be configured of the diffusion suppression layer 62.

  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) has been exemplified. 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 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.

  The piezoelectric material of the present invention can be applied to a piezoelectric element of a liquid jet head typified by an ink jet recording head as described above in order to exhibit good piezoelectric characteristics, but is not limited thereto. It is not a thing. For example, it can be applied to an ultrasonic device such as an ultrasonic transmitter, an ultrasonic motor, a piezoelectric transformer, and piezoelectric elements such as various sensors such as an infrared sensor, an ultrasonic sensor, a thermal sensor, a pressure sensor, and a pyroelectric sensor. . Further, the present invention can be similarly applied to a ferroelectric element such as a ferroelectric memory.

  I ink jet recording head (liquid ejecting head), II ink jet recording apparatus (liquid ejecting apparatus), 10 flow path forming substrate, 12 pressure generating chamber, 13 communicating portion, 14 ink supply path, 20 nozzle plate, 21 nozzle opening, 30 Protection substrate, 31 Reservoir part, 32 Piezoelectric element holding part, 40 Compliance substrate, 60 First electrode, 61 Adhesion layer, 62 Diffusion suppression layer, 63 First electrode layer, 70 Piezoelectric layer, 80 Second electrode, 90 Lead Electrode, 100 reservoir, 120 drive circuit, 121 connection wiring, 300 piezoelectric element

Claims (6)

A method of manufacturing a liquid jet head including a piezoelectric layer sandwiched between a first electrode and a second electrode,
A first electrode forming step of forming the first electrode including a step of forming a diffusion suppression layer containing at least one of platinum or iridium by a vapor deposition method;
Forming a piezoelectric layer made of a composite oxide containing titanium, bismuth, barium, potassium and sodium on the first electrode; and forming the second electrode on the piezoelectric layer. A second electrode forming step;
A method of manufacturing a liquid jet head, comprising:   2. The liquid jet head according to claim 1, wherein in the first electrode forming step, the first electrode layer is formed by a sputtering method, and then the diffusion suppression layer is formed on the first electrode layer by an evaporation method. Manufacturing method.   The method of manufacturing a liquid jet head according to claim 1, wherein the diffusion suppression layer is formed to have a thickness of 40 nm or more.   In the piezoelectric layer forming step, a piezoelectric precursor film is formed on the first electrode, and the piezoelectric precursor film is formed by baking the piezoelectric precursor film to form the piezoelectric film. The method for manufacturing a liquid jet head according to claim 1, wherein a piezoelectric layer is formed.   A liquid ejecting apparatus comprising the liquid ejecting head manufactured by the method of manufacturing a liquid ejecting head according to claim 1. A first electrode forming step of forming a first electrode including a step of forming a diffusion suppression layer containing at least one of platinum or iridium by a vapor deposition method;
Forming a piezoelectric layer comprising a composite oxide containing titanium, bismuth, barium, potassium, and sodium on the first electrode; and
A second electrode forming step of forming the second electrode on the piezoelectric layer;
A method for manufacturing a piezoelectric element, comprising:

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