JP2013089848A - Method for manufacturing piezoelectric ceramic, method for manufacturing piezoelectric element, method for manufacturing liquid injection head, and method for manufacturing liquid injection apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method which improves the performance of a piezoelectric element, a liquid injection head, and a liquid injection apparatus, each having a piezoelectric layer containing at least Bi, Ba, Fe and Ti.SOLUTION: A precursor solution 31 containing at least Bi, Ba, Fe and Ti, whose pH, when made into an aqueous solution, is 7 or more, is coated on a lower electrode 20, and then the coated precursor solution 31 is crystallized to form a piezoelectric ceramic containing a perovskite-type oxide. A method for manufacturing a piezoelectric element includes a step of forming an electrode on a piezoelectric ceramic 30. A method for manufacturing a liquid injection head includes a step of forming a piezoelectric element according to the method for manufacturing a piezoelectric element.

Description

  The present invention relates to a piezoelectric ceramic manufacturing method, a piezoelectric element manufacturing method, a liquid ejecting head manufacturing method, and a liquid ejecting apparatus manufacturing method.

Piezoelectric materials that have the characteristics of being charged when the crystals are distorted or distorted when placed in an electric field are widely used in liquid ejecting apparatuses such as inkjet printers, actuators, sensors, and the like. As a typical piezoelectric material, PZT (lead zirconate titanate, Pb (Zr _x , Ti _1-x ) O ₃ ) is used. However, since PZT contains lead (Pb), research and development of lead-free piezoelectric materials not containing lead are widely performed from the viewpoint of environmental load.

In recent years, research and development of piezoelectric thin films made of lead-free piezoelectric materials and thin film piezoelectric elements using the piezoelectric thin films have been conducted. The thin film piezoelectric element is manufactured by, for example, a process of forming a piezoelectric thin film having a thickness of several μm or less on an electrode formed on a substrate and forming an upper electrode on the piezoelectric thin film. Since this process is performed by a fine process similar to the semiconductor process, the thin film piezoelectric element has an advantage that a high-density piezoelectric element can be formed as compared with a piezoelectric element using a bulk piezoelectric body. For example, the BiFeO ₃ —BaTiO ₃ material disclosed in Patent Document 1 has good characteristics as a lead-free thin film piezoelectric material.

  When forming a piezoelectric thin film by a liquid phase method such as a spin coating method, the piezoelectric thin film is formed by applying a precursor solution on an electrode and crystallizing the applied film. As the metal salt used in the precursor solution, an organic acid salt such as 2-ethylhexanoate is usually used, and when the precursor solution is an aqueous solution, the acidity becomes pH <7.

JP 2009-252790 A

However, when a piezoelectric element was fabricated using a BiFeO ₃ —BaTiO ₃ based piezoelectric material, it was found that the leakage current of the piezoelectric material was large compared with PZT, making it difficult to put it into practical use. Such a problem exists not only in the liquid ejecting head but also in a piezoelectric element such as a piezoelectric actuator or a sensor.

  In view of the above, one of the objects of the present invention is to improve the performance of a piezoelectric element, a liquid ejecting head, and a liquid ejecting apparatus each having a piezoelectric layer containing at least Bi, Ba, Fe, and Ti.

In order to achieve one of the above objects, the present invention includes a step of applying a precursor solution containing at least Bi, Ba, Fe, and Ti, and having a pH of 7 or more when an aqueous solution is formed. ,
And a step of crystallizing the applied precursor solution to form a piezoelectric ceramic containing a perovskite oxide, and a method for producing a piezoelectric ceramic.
The present invention also includes a step of forming piezoelectric ceramics by the method for manufacturing piezoelectric ceramics,
Forming an electrode on the piezoelectric ceramic. A method for manufacturing a piezoelectric element is provided.

Furthermore, the invention includes an aspect of a method for manufacturing a liquid jet head including the method for manufacturing a piezoelectric element.
Furthermore, the invention includes an aspect of a method of manufacturing a liquid ejecting apparatus including the method of manufacturing the liquid ejecting head.

  The piezoelectric ceramic formed by this manufacturing method contains a perovskite oxide in which a precursor solution having a pH of 7 or higher is crystallized when an aqueous solution containing at least Bi, Ba, Fe, and Ti is used. A piezoelectric element having such a piezoelectric ceramic as a piezoelectric layer is compared with a piezoelectric element including a perovskite oxide obtained by crystallizing an acidic precursor solution when an aqueous solution containing at least Bi, Ba, Fe and Ti is used. It was found that leakage current was suppressed.

  Here, the precursor solution includes a state such as a sol. The precursor solution may contain a metal other than Bi, Ba, Fe, and Ti, such as Mn (manganese), or may contain impurities. The metal contained in the precursor solution naturally includes an ionic state. The piezoelectric layer may also contain a metal other than Bi, Ba, Fe, and Ti, such as Mn, or may contain impurities.

By the way, when amine is contained in the precursor solution, the pH when the precursor solution is an aqueous solution can be easily set to 7 or more. From the viewpoint of suppressing cracks in the piezoelectric layer, the amine in the precursor solution is preferably 3 to 30 vol%, and more preferably 3 to 10 vol%. These aspects can provide a preferable manufacturing method for suppressing the leakage current of the piezoelectric layer.
When Mn is contained in the precursor solution, an effect of increasing the insulation of the piezoelectric layer (improving leakage characteristics) is expected.

(A) is a flowchart which illustrates the manufacturing process of a piezoelectric element, (b), (c) is a figure which shows the measurement result of leakage current. FIG. 2 is an exploded perspective view for convenience illustrating the outline of the configuration of the recording head 1. FIGS. 3A to 3C are cross-sectional views for illustrating a manufacturing process of the recording head 1. FIGS. 3A to 3C are cross-sectional views for illustrating a manufacturing process of the recording head 1. 2 is a diagram illustrating an outline of a configuration of a recording apparatus 200. FIG. (A), (b) is a graph which shows the hysteresis characteristic of an Example. (A), (b) is a graph which shows the hysteresis characteristic of a comparative example. The graph which illustrates the pixel area ratio of the crack with respect to organic amine addition amount. (A)-(g) is a graph which shows a hysteresis characteristic.

  Embodiments of the present invention will be described below. Of course, the embodiments described below are merely illustrative of the present invention.

(1) Outline of manufacturing method of piezoelectric element, piezoelectric ceramic, liquid ejecting head and liquid ejecting apparatus:
First, an example of this manufacturing method will be described with reference to FIGS. The recording head (liquid ejecting head) 1 illustrated in FIGS. 2 and 4C includes a piezoelectric element 3 having a piezoelectric layer (piezoelectric ceramics) 30 and electrodes (20, 40), and a nozzle opening 71. A pressure generation chamber 12 in which a pressure change is generated by the element 3 is provided. Accordingly, the method for manufacturing the liquid ejecting head includes a step of forming a piezoelectric element and a step of forming a pressure generation chamber. The pressure generating chamber 12 is formed on the silicon substrate 15 of the flow path forming substrate 10. The nozzle opening 71 is formed in the nozzle plate 70. A lower electrode (first electrode) 20, a piezoelectric layer 30, and an upper electrode (second electrode) 40 are sequentially laminated on the elastic film (vibrating plate) 16 of the flow path forming substrate 10 to form the pressure generating chamber 12. A nozzle plate 70 is fixed to the silicon substrate 15.
In addition, the positional relationship demonstrated in this specification is only the illustration for demonstrating invention, and does not limit invention. Accordingly, the present invention also includes the second electrode disposed at a position other than the top of the first electrode, for example, below, left, right, and the like.

The manufacturing method illustrated in FIG. 1 includes steps S1 and S2.
In the application step S1, a precursor solution 31 having a pH of 7 or more when applied as an aqueous solution is a piezoelectric precursor solution containing at least Bi, Ba, Fe and Ti. In the example of FIG. 1A, the precursor solution 31 containing at least Bi, Ba, Fe, and Ti is applied in a film shape on the surface of the electrode (20). The precursor solution may contain another metal (for example, Mn) with Bi, Ba, Fe, and Ti as main components and in a small molar ratio. Here, the main component is one or more target components whose total molar ratio is larger than the molar ratio of the other contained components. The precursor solution can be applied by a liquid phase method such as a spin coating method, a dip coating method, or an ink jet method.

  In the piezoelectric layer forming step S2, the applied precursor solution 31 is crystallized to form a piezoelectric ceramic (piezoelectric layer) 30 containing a perovskite oxide. The obtained perovskite oxide contains at least Bi, Ba, Fe and Ti, and may contain another metal (for example, Mn) having a small molar ratio with Bi, Ba, Fe and Ti as main components. The piezoelectric ceramic (30) may contain a substance (for example, a metal oxide) other than the perovskite oxide.

  As illustrated in FIG. 1B and FIG. 1C, the leakage current is relatively large in the piezoelectric element using the acidic precursor solution with pH <7 when the aqueous solution is used. It was found that the piezoelectric element using the precursor solution having a pH ≧ 7 when the aqueous solution was used had a relatively small leakage current. The following reasons can be considered for this.

Unlike PZT, a piezoelectric layer having a perovskite oxide containing at least Bi, Ba, Fe and Ti tends to have a rough surface morphology. When the precursor solution is diluted with water to a predetermined magnification to obtain an aqueous solution, if the pH is 7 or more, preferably alkaline (for example, pH 7.1 or more), a metal salt such as an organic acid salt and a solvent such as an organic solvent in the precursor solution Is likely to be mixed, and the uniformity of the precursor solution is considered to be improved. When the precursor solution is acidic, it is presumed that the insufficiently mixed metal salt becomes a nucleus during crystallization and the surface of the piezoelectric layer becomes rough, and a portion where a leakage current is generated in the piezoelectric layer is generated. On the other hand, when the precursor solution has a pH of 7 or higher, the amount of insufficiently mixed metal salts is reduced, and such metal salts do not become nuclei during crystallization and the surface smoothness of the piezoelectric layer is improved. It is presumed that a portion where leakage current is generated is difficult to occur.
From the above, in order to suppress the leakage current, the pH should be 7 or more, preferably alkaline when the precursor solution containing at least Bi, Ba, Fe and Ti is used as an aqueous solution.

  In addition, if the surface morphology of the piezoelectric layer is rough, when a piezoelectric element is formed, a portion having a relatively small leakage current and a portion having a relatively large leakage current are generated, or a portion having a sufficient withstand voltage and a withstand voltage. In some cases, the reliability may be reduced, for example, a part where the temperature is reduced. When the precursor solution containing at least Bi, Ba, Fe, and Ti is made into an aqueous solution, by making the pH ≧ 7, the smoothness of the surface of the piezoelectric layer is improved and the performance variation of the piezoelectric element is reduced. Reliability, especially durability, is improved.

  For at least the metal salts of Bi, Ba, Fe and Ti contained in the precursor solution 31, organic acid salts such as 2-ethylhexanoate and acetate can be used. The precursor solution includes a solution in which the metal salt is dissolved in a solvent, a sol in which the metal salt is dispersed in a dispersion medium, and the like. For the solvent (including the dispersion medium) of the precursor solution, for example, an organic solvent such as octane, xylene, or a combination thereof can be used. Substances that bring the precursor solution to pH 7 or higher in the case of aqueous solution include amines such as 2-dimethylaminoethanol (DMAE), 2-diethylaminoethanol (DEAE), diethanolamine (DEA), and ammonia, etc. Can be used. In addition, the dilution rate at the time of making a precursor solution into aqueous solution is although it does not specifically limit, For example, it can be about 2-100 times.

The metal contained in the precursor solution is arranged at a site corresponding to the atomic radius in the perovskite structure. The resulting perovskite oxide contains at least Bi and Ba at the A site and at least Fe and Ti at the B site. Such a perovskite oxide includes a lead-free perovskite oxide having a composition represented by the following general formula.
(Bi, Ba) (Fe, Ti) O _z (1)
(Bi, Ba, MA) (Fe, Ti) O _z (2)
(Bi, Ba) (Fe, Ti, MB) O _z (3)
(Bi, Ba, MA) (Fe, Ti, MB) O _z (4)
Here, MA is one or more metal elements excluding Bi, Ba and Pb, and MB is one or more metal elements excluding Fe, Ti and Pb. As for z, 3 is a standard, but may deviate from 3 within a range in which a perovskite structure can be taken. The ratio of the A site element to the B site element is 1: 1 as a standard, but may be deviated from 1: 1 within a range where a perovskite structure can be taken.

The molar ratio of Bi to the total molar number of Bi, Ba, MA can be, for example, about 50 to 99.9%. The mole number ratio of Ba to the total mole number of Bi, Ba, MA can be, for example, about 0.1 to 50%. The molar ratio of MA to the total molar number of Bi, Ba, MA can be, for example, about 0.1 to 33%.
The ratio of the number of moles of Fe to the total number of moles of Fe, Ti, MB can be, for example, about 50 to 99.9%. The mole number ratio of Ti with respect to the total mole number of Fe, Ti, and MB can be, for example, about 0.1 to 50%. The ratio of the number of moles of MB to the total number of moles of Fe, Ti, MB can be, for example, about 0.1 to 33%.

  MB elements that can be added to the precursor solution include Mn and the like. The molar concentration ratio of Mn in the B site constituent metal can be, for example, about 0.1 to 10%, with the total molar concentration ratio of the B site constituent metal being 100%. When Mn is added, an effect of increasing the insulating property of the piezoelectric layer (improving leakage characteristics) is expected, but a piezoelectric element having piezoelectric performance can be formed without Mn. Although the thickness of a coating film is not specifically limited, For example, it can be set as about 0.1 micrometer.

  The crystallization temperature of the piezoelectric layer 30 having a perovskite oxide containing at least Bi, Ba, Fe, and Ti is, for example, about 400 to 450 ° C.

Before the crystallization of the precursor solution 31, a first heating step of heating the coating film (31) on the surface of the electrode (20) at a temperature lower than the crystallization temperature of the perovskite oxide may be performed. Since the coating film (31) is dried before crystallization and the coating film (31) is degreased at a temperature higher than the degreasing temperature, the piezoelectric layer 30 can be formed satisfactorily. Moreover, the 2nd heating process of heating the coating film (31) on the surface of an electrode (20) above the crystallization temperature after a 1st heating process may be performed. By this firing, the piezoelectric layer 30 can be satisfactorily formed. Various devices can be used for heating. However, when an infrared lamp annealing device capable of using a rapid thermal annealing (RTA) method is used for heating at a temperature higher than the crystallization temperature, the piezoelectric layer 30 is satisfactorily formed. be able to.
In the first heating step, the coating film (31) on the surface of the electrode (20) is heated at the drying temperature such that the drying temperature <the degreasing temperature <the crystallization temperature, and then the coating film on the surface of the electrode (20) after the drying treatment. (31) may be heated at a degreasing temperature.

(2) Example of manufacturing method of piezoelectric element and liquid jet head:
FIG. 2 is an exploded perspective view in which an ink jet recording head 1 which is an example of a liquid ejecting head is disassembled for convenience. 3 and 4 are cross-sectional views for illustrating a method for manufacturing a recording head, and are vertical cross-sectional views along the longitudinal direction D2 of the pressure generating chamber 12. FIG. The layers constituting the recording head 1 may be bonded and laminated, or may be integrally formed by modifying the surface of a material that is not separated.

The flow path forming substrate 10 can be formed from a silicon single crystal substrate or the like. The elastic film 16 can be integrally formed with the silicon substrate 15 by, for example, thermally oxidizing one surface of the relatively thick and rigid silicon substrate 15 having a thickness of about 625 μm in a diffusion furnace at about 1100 ° C. , Silicon dioxide (SiO ₂ ) or the like. The thickness of the elastic film 16 is not particularly limited as long as it exhibits elasticity, but can be, for example, about 0.5 to 2 μm.

Next, as shown in FIG. 3A, the lower electrode 20 is formed on the elastic film 16 by sputtering or the like. In the example shown in FIG. 3B, patterning is performed after the lower electrode 20 is formed. As a constituent metal of the lower electrode 20, one or more metals such as Pt, Au, Ir, and Ti can be used. Although the thickness of the lower electrode 20 is not specifically limited, For example, it can be set as about 50-500 nm. In addition, after forming a layer such as a TiAlN (titanium nitride aluminum) film, an Ir film, an IrO (iridium oxide) film, a ZrO ₂ (zirconium oxide) film on the elastic film 16 as an adhesion layer or a diffusion prevention layer, The lower electrode 20 may be formed on the layer.

  Next, as shown in FIG. 1A, the precursor solution 31 containing at least Bi, Ba, Fe and Ti described above is applied to the surface of the lower electrode 20 (application step S1). The molar concentration ratio of the metal in the precursor solution can be determined according to the composition of the perovskite oxide to be formed. The molar ratio of the A-site constituent metal and the B-site constituent metal in the above formulas (1) to (4) is 1: 1 as a standard, but from 1: 1 within the range in which the perovskite oxide is formed. It may be shifted.

Next, the applied precursor solution 31 is crystallized to form the piezoelectric layer 30 containing a perovskite oxide (piezoelectric layer forming step S2). When the film of the precursor solution 31 is heated at a temperature higher than the crystallization temperature of the perovskite oxide, a thin film piezoelectric layer 30 containing the perovskite oxide is formed. Preferably, for example, heating to about 140 to 190 ° C. and drying (drying step), then heating to about 300 to 400 ° C. and degreasing (degreasing step), and then heating to, for example, about 550 to 850 ° C. To crystallize (firing step). In order to increase the thickness of the piezoelectric layer 30, the combination of the coating process, the drying process, the degreasing process, and the baking process may be performed a plurality of times. In order to reduce the firing process, the firing process may be performed after the combination of the coating process, the drying process, and the degreasing process is performed a plurality of times. Further, a combination of these steps may be performed a plurality of times.
The thickness of the formed piezoelectric layer 30 is not particularly limited as long as it exhibits an electromechanical conversion effect, but can be, for example, about 0.2 to 5 μm. Preferably, the thickness of the piezoelectric layer 30 is suppressed to such an extent that cracks do not occur in the manufacturing process, and the piezoelectric layer 30 is made thick enough to exhibit sufficient displacement characteristics.

  As a heating apparatus for performing the above-described drying process and degreasing process, a hot plate, an infrared lamp annealing apparatus for heating by irradiation with an infrared lamp, or the like can be used. An infrared lamp annealing device or the like can be used as a heating device for performing the firing step. Preferably, the temperature rising rate may be made relatively fast by using an RTA (Rapid Thermal Annealing) method or the like.

After the piezoelectric layer 30 is formed, as shown in FIG. 3B, the upper electrode 40 is formed on the piezoelectric layer 30 by sputtering or the like. As the metal constituting the upper electrode 40, one or more metals such as Ir, Au, and Pt can be used. Although the thickness of the upper electrode 40 is not specifically limited, For example, it can be set as about 50-200 nm. In the example shown in FIG. 3C, after the upper electrode 40 is formed, the piezoelectric layer 30 and the upper electrode 40 are patterned in a region facing each pressure generating chamber 12 to form the piezoelectric element 3. .
In general, one of the electrodes of the piezoelectric element 3 is used as a common electrode, and the other electrode and the piezoelectric layer 30 are patterned for each pressure generating chamber 12 to configure the piezoelectric element 3. The piezoelectric element 3 shown in FIGS. 2 and 4 uses the lower electrode 20 as a common electrode and the upper electrode 40 as an individual electrode.

  Thus, the piezoelectric element 3 having the piezoelectric layer 30 and the electrodes (20, 40) is formed, and the piezoelectric actuator 2 including the piezoelectric element 3 and the elastic film 16 is formed.

  Next, as shown in FIG. 3C, the lead electrode 45 is formed. For example, after forming a gold layer over the entire surface of the flow path forming substrate 10, the lead electrode 45 is provided by patterning for each piezoelectric element 3 through a mask pattern made of a resist or the like. Connected to each upper electrode 40 shown in FIG. 2 is a lead electrode 45 extending on the elastic film 16 from the vicinity of the end on the ink supply path 14 side.

  The lower electrode 20, the upper electrode 40, and the lead electrode 45 can be formed by a sputtering method such as a DC (direct current) magnetron sputtering method. The thickness of each layer can be adjusted by changing the voltage applied to the sputtering apparatus and the sputtering processing time.

  Next, as shown in FIG. 4A, the protective substrate 50 on which the piezoelectric element holding portion 52 and the like are formed in advance is bonded onto the flow path forming substrate 10 with, for example, an adhesive. As the protective substrate 50, for example, a silicon single crystal substrate, glass, a ceramic material, or the like can be used. Although the thickness of the protective substrate 50 is not specifically limited, For example, it can be set as about 400 micrometers. The reservoir portion 51 penetrating in the thickness direction of the protective substrate 50 constitutes the reservoir 9 serving as a common ink chamber (liquid chamber) together with the communication portion 13. The piezoelectric element holding portion 52 provided in the region facing the piezoelectric element 3 has a space that does not hinder the movement of the piezoelectric element 3. In the through hole 53 of the protective substrate 50, the vicinity of the end portion of the lead electrode 45 drawn from each piezoelectric element 3 is exposed.

Next, after polishing the silicon substrate 15 to a certain thickness, the silicon substrate 15 is further etched to a predetermined thickness (for example, about 70 μm) by wet etching with hydrofluoric acid. Next, as shown in FIG. 4B, a mask film 17 is newly formed on the silicon substrate 15 and patterned into a predetermined shape. Silicon nitride (SiN) or the like can be used for the mask film 17. Next, the silicon substrate 15 is anisotropically etched (wet etching) using an alkaline solution such as KOH. As a result, a plurality of liquid flow paths including the pressure generating chambers 12 defined by the plurality of partition walls 11 and the narrow ink supply paths 14, and a communication portion 13 that is a common liquid flow path connected to each ink supply path 14. And are formed. The liquid flow paths (12, 14) are arranged in the width direction D1, which is the short direction of the pressure generating chamber 12.
The pressure generation chamber 12 may be formed before the piezoelectric element 3 is formed.

  Next, unnecessary portions at the peripheral portions of the flow path forming substrate 10 and the protective substrate 50 are removed by cutting, for example, by dicing. Next, as shown in FIG. 4C, the nozzle plate 70 is bonded to the surface of the silicon substrate 15 opposite to the protective substrate 50. The nozzle plate 70 can be made of glass ceramics, silicon single crystal substrate, stainless steel, or the like, and is fixed to the opening surface side of the flow path forming substrate 10. For this fixation, an adhesive, a heat welding film, or the like can be used. The nozzle plate 70 is formed with nozzle openings 71 communicating with the vicinity of the end of each pressure generating chamber 12 on the side opposite to the ink supply path 14. Therefore, the pressure generation chamber 12 communicates with the nozzle opening 71 that discharges the liquid.

  Next, the compliance substrate 60 having the sealing film 61 and the fixing plate 62 is bonded onto the protective substrate 50 and divided into a predetermined chip size. The sealing film 61 is made of, for example, a material having low rigidity and flexibility such as a polyphenylene sulfide (PPS) film having a thickness of about 6 μm, and seals one surface of the reservoir unit 51. The fixed plate 62 is made of a hard material such as a metal such as stainless steel (SUS) having a thickness of about 30 μm, for example, and an area facing the reservoir 9 is an opening 63.

A driving circuit 65 for driving the piezoelectric elements 3 arranged in parallel is fixed on the protective substrate 50. For the drive circuit 65, a circuit board, a semiconductor integrated circuit (IC), or the like can be used. The drive circuit 65 and the lead electrode 45 are electrically connected via the connection wiring 66. As the connection wiring 66, a conductive wire such as a bonding wire can be used.
Thus, the recording head 1 is manufactured.

The recording head 1 takes in ink from an ink introduction port connected to an external ink supply unit (not shown), and fills the interior from the reservoir 9 to the nozzle opening 71 with ink. When a voltage is applied between the lower electrode 20 and the upper electrode 40 for each pressure generation chamber 12 in accordance with a recording signal from the drive circuit 65, the deformation of the piezoelectric layer 30, the lower electrode 20, and the elastic film 16 causes deformation from the nozzle opening 71. Ink droplets are ejected.
The recording head may have a common lower electrode structure in which the lower electrode is a common electrode and the upper electrode is an individual electrode, or a common upper electrode structure in which the upper electrode is a common electrode and the lower electrode is an individual electrode. Alternatively, the lower electrode and the upper electrode may be a common electrode, and an individual electrode may be provided between the two electrodes.

(3) Liquid ejecting apparatus:
FIG. 5 shows the appearance of a recording apparatus (liquid ejecting apparatus) 200 having the recording head 1 described above. When the recording head 1 is incorporated in the recording head units 211 and 212, the recording apparatus 200 can be manufactured. In the recording apparatus 200 shown in FIG. 5, the recording head 1 is provided in each of the recording head units 211 and 212, and ink cartridges 221 and 222 as external ink supply units are detachably provided. A carriage 203 on which the recording head units 211 and 212 are mounted is provided so as to be able to reciprocate along a carriage shaft 205 attached to the apparatus main body 204. When the driving force of the driving motor 206 is transmitted to the carriage 203 via a plurality of gears and a timing belt 207 (not shown), the carriage 203 moves along the carriage shaft 205. A recording sheet 290 fed by a sheet feeding roller (not shown) is conveyed onto the platen 208 and printed by ink supplied from the ink cartridges 221 and 222 and ejected from the recording head 1.

(4) Example:
Hereinafter, although an example is shown, the present invention is not limited by the following examples.

[Fabrication of substrate with lower electrode laminated]
A substrate having each layer of Pt / TiO _x (titanium oxide) / SiO ₂ / Si was produced as follows.
First, the Si substrate was thermally oxidized at 1100 ° C. in a diffusion furnace to form a 1.3 μm thick SiO ₂ film on the Si substrate surface. Next, a Ti film having a thickness of 20 nm was formed on the surface of the SiO ₂ film by DC sputtering, and heat treatment was performed in oxygen at 700 ° C. for 5 minutes with a lamp heat treatment apparatus (RTA method) to form a TiO _x thin film. Further, a 130 nm thick Pt thin film was formed on the surface of the TiO _x film by DC sputtering at 330 ° C. and 300 W.

[Examples 1 and 2 and Comparative Examples 1 and 2]
(Preparation of BFM-BT precursor solution)
2-ethylhexanoate was used as a precursor material for each metal element of Bi, Fe, Mn, Ba, and Ti. The molar ratio of the dissolved metal was Bi: Fe: Mn = 100: 95: 5, Ba: Ti = 100: 100, and BFM: BT = 75: 25. Here BFM-BT has the general formula (Bi, Ba) (Fe, Ti, Mn) is represented by _{O z, Bi: Fe: Mn} : Ba: Ti = 75: 71.25: 3.75: 25: 25 It becomes. BFM represents the number of moles of Bi, that is, the total number of moles of Fe and Mn, and BT represents the number of moles of Ba, that is, the number of moles of Ti.
As a solvent, a mixture of octane and xylene was used.
To the above solution, 2-dimethylaminoethanol (DMAE) was added so as to be 10 vol% of the total amount to prepare the precursor solution of Example 1, and diethanolamine was added so as to be 10 vol% of the total amount. Then, the precursor solution of Example 2 was prepared, and n-octanol was added so as to be 10 vol% of the total amount to prepare the precursor solution of Comparative Example 1. The raw material solution to which nothing was added was used as the precursor solution of Comparative Example 2.

(BFM-BT thin film production)
Each precursor solution was spin-coated on a Pt / TiO _x / SiO ₂ / Si substrate at 3000 rpm (application process), heated to dry (drying process), and further heated to degrease (degreasing process). These steps were repeated 8 times to form 8 layers, and crystallized by a heat treatment at 800 ° C. for 5 minutes with a lamp heat treatment apparatus (RTA method) to form a BFM-BT piezoelectric thin film.

Table 1 shows the film thickness of each BFM-BT thin film.

表２に示すように、実施例１，２のｐＨは７．２及び８．０であり、いずれも弱塩基性であった。一方、比較例１，２のｐＨは６．０及び５．３であり、いずれも弱酸性であった。 (PH of each BFM-BT precursor solution)
Table 2 shows the pH when each precursor solution is a 50-fold diluted aqueous solution.

As shown in Table 2, the pH of Examples 1 and 2 was 7.2 and 8.0, and both were weakly basic. On the other hand, the pH of Comparative Examples 1 and 2 was 6.0 and 5.3, both of which were weakly acidic.

(Evaluation of BFM-BT thin film)
When the appearance of each BFM-BT thin film was confirmed by a dark field image, in Examples 1 and 2, a relatively smooth appearance was shown, but in Comparative Example 1, a protrusion-like appearance abnormality appeared as a white spot. In Example 2, a crack-like appearance abnormality appeared as a white line. When the surface of each BFM-BT thin film was observed by SEM (scanning electron microscope), the BFM-BT thin film of Examples 1 and 2 had a grain boundary as compared with the BFM-BT thin film of Comparative Examples 1 and 2. An unclear and smooth thin film surface was shown. When the surface of each BFM-BT thin film was scratched and the shape of the scratch was evaluated, the shape of the scratch could be evaluated in Examples 1 and 2, while the shape of the scratch was compared in Comparative Examples 1 and 2. Could not be evaluated. It is known from the evaluation with other materials that the surface of the thin film needs to be smooth in order to evaluate the shape of the scratch. From this, it can be obtained from the precursor solution having a pH ≧ 7 in the case of an aqueous solution. It can be seen that the surface smoothness of the piezoelectric layer is improved. The smooth surface leads to suppression of leakage current of the piezoelectric layer.

  Moreover, when the X-ray diffraction chart was calculated | required by X-ray diffraction wide angle method (XRD) about each BFM-BT thin film, it turned out that all are preferentially oriented to (110) plane, and there was no big difference.

Further, for each BFM-BT thin film, a Pt thin film having a film thickness of 100 nm was formed by DC sputtering, and heat treatment was performed in oxygen at 775 ° C. for 5 minutes by a lamp heat treatment apparatus (RTA method) to produce a BFM-BT capacitor. . For each BFM-BT capacitor, a triangular wave with a frequency of 1 kHz is applied in an atmosphere of room temperature using an FCE manufactured by Toyo Corporation, and the relationship between the polarization amount P (μC / cm ² ) and the electric field E (kV / cm) (P− E curve).

  6 and 7 show the hysteresis characteristics of each BFM-BT capacitor. 6A shows the first embodiment, FIG. 6B shows the second embodiment, FIG. 7A shows the first comparative example, and FIG. 7B shows the second comparative example. As shown in FIGS. 6 and 7, there was no significant difference between the hysteresis characteristics.

[Examples 3 and 4 and Comparative Example 3]
(Preparation of BFM-BT precursor solution)
As in Examples 1 and 2, 2-ethylhexanoate was used as a precursor material for each metal element, and the molar ratio of the dissolved metal was Bi: Fe: Mn = 100: 95: 5, Ba: Ti = 100. : 100 and BFM: BT = 75: 25. That is, Bi: Fe: Mn: Ba: Ti = 75: 71.25: 3.75: 25: 25. As a solvent, a mixture of octane and xylene was used.
The precursor solution of Example 3 was prepared by adding DMAE so as to be 3 vol%, 10 vol%, and 30 vol% of the total amount of the above solutions, respectively, and 3 vol%, 10 vol%, and 30 vol% of the total amount, respectively. Then, 2-diethylaminoethanol (DEAE) was added so that a precursor solution of Example 4 was produced. The raw material solution to which nothing was added was used as the precursor solution of Comparative Example 3.

(BFM-BT thin film production)
Each precursor solution was spin-coated on a Pt / TiO _x / SiO ₂ / Si substrate at 3000 rpm, dried at 180 ° C., degreased at 350 ° C., and further 750 ° C. for 5 minutes with a lamp heat treatment apparatus (RTA method). It was crystallized by heat treatment. Then, spin coating at 3000 rpm (application process), drying at 180 ° C. (drying process), then degreasing at 350 ° C. (degreasing process), and repeating these processes three times, a lamp heat treatment apparatus (RTA method) And crystallized by heat treatment at 750 ° C. for 5 minutes (firing step). The BFM-BT thin film of 10 layers was formed on the substrate by repeating the combination of “the combination of the coating process, the drying process and the degreasing process three times” and the “firing process” three times.

表３に示すように、実施例３，４の前駆体溶液の５０倍希釈水溶液は、いずれもｐＨ≧７であった。また、有機アミンの添加量が多くなるほどｐＨが大きくなった。一方、比較例３のｐＨは５．３であり、弱酸性であった。 Table 3 shows the pH when each precursor solution is a 50-fold diluted aqueous solution.

As shown in Table 3, the 50-fold diluted aqueous solutions of the precursor solutions of Examples 3 and 4 all had pH ≧ 7. Further, the pH increased as the amount of organic amine added increased. On the other hand, the pH of Comparative Example 3 was 5.3, which was weakly acidic.

(Measurement of leakage current)
Further, for each BFM-BT thin film, a Pt thin film having a film thickness of 100 nm was formed by DC sputtering, and heat treatment was performed in oxygen at 750 ° C. for 5 minutes using a lamp heat treatment apparatus (RTA method), thereby producing a BFM-BT capacitor. . About each BFM-BT capacitor, leak current (IV characteristic) was measured twice using 4140B made by Agilent, and twice under the condition of +500 kV / cm and twice under the condition of -500 kV / cm.

FIG. 1B shows the measurement results of the leakage current of Example 3 and Comparative Example 3, and FIG. 1C shows the measurement results of the leakage current of Example 4 and Comparative Example 3. Here, the horizontal axis represents the organic amine addition amount (%), the vertical axis represents the leakage current (A / cm ² ), the organic amine addition amount 0% corresponds to Comparative Example 3, and the organic amine addition amount 3 to 30%. Corresponds to Examples 3 and 4.

As shown in FIGS. 1B and 1C, the leakage currents of Examples 3 and 4 were smaller than the leakage current of Comparative Example 3. The BFM-BT thin films of Examples 3 and 4 contain a perovskite oxide obtained by crystallizing a precursor solution having a pH of 7 or higher when containing Bi, Ba, Fe, and Ti as an aqueous solution. It can be seen that a piezoelectric element having such a piezoelectric layer has a leakage current suppressed when compared with a piezoelectric element having a perovskite oxide obtained by crystallizing an acidic precursor solution when an aqueous solution is used.
Further, the leakage current of Comparative Example 3 has a large variation, while the leakage currents of Examples 3 and 4 have a small variation. As described above, a piezoelectric element having a perovskite oxide obtained by crystallizing a precursor solution having a pH of 7 or more in an aqueous solution containing at least Bi, Ba, Fe, and Ti has an acidic precursor in an aqueous solution. It can be seen that there is less variation in performance than a piezoelectric element having a perovskite oxide obtained by crystallizing a body solution, and the reliability of the piezoelectric element is improved.

(Measurement of crack area ratio)
About the surface of each BFM-BT thin film, the area (pixel area) of the crack which exists in a predetermined area was measured, and the area relative value which made the crack area of the comparative example 3 1 was calculated | required.

  FIG. 8 shows the pixel area ratio of the crack with respect to the DEAE addition amount as an example of the result. Here, the horizontal axis represents the DEAE addition amount (%), the vertical axis represents the pixel area ratio, the DEAE addition amount of 0% corresponds to Comparative Example 3, and the DEAE addition amount of 3 to 30% corresponds to Example 4.

As shown in FIG. 8, the crack area of Example 4 was smaller than the crack area of Comparative Example 3. Therefore, it can be seen that cracks are suppressed in the piezoelectric layer obtained from the precursor solution having a pH ≧ 7 when an aqueous solution is used. A small crack area leads to suppression of leakage current of the piezoelectric layer.
In addition, it can be seen that the piezoelectric layer obtained from the precursor solution having the organic amine addition amount of 3 to 10% is suppressed in cracking than the piezoelectric layer obtained from the precursor solution having the organic amine addition amount of 30%. Therefore, it turns out that the more preferable quantity of the amine added to a precursor solution is 3-10 vol%.

(Other evaluation)
When X-ray diffraction charts were obtained for each BFM-BT thin film by the X-ray diffraction wide angle method (XRD), it was found that all were preferentially oriented in the (110) plane, and there was no significant difference.

For each BFM-BT capacitor, a triangular wave with a frequency of 1 kHz is applied in an atmosphere of room temperature using an FCE manufactured by Toyo Corporation, and the relationship between the polarization amount P (μC / cm ² ) and the electric field E (kV / cm) (P− E curve). Here, FIG. 9 (a) is a comparative example 3, FIG. 9 (b) is an example with 3% DMAE added, FIG. 9 (c) is an example with 10% DMAE added, and FIG. 9 (d) is an example with 30% DMAE added. For example, FIG. 9 (e) shows an example with 3% DEAE added, FIG. 9 (f) shows an example with 10% DEAE added, and FIG. 9 (g) shows an example with 30% DEAE added. As shown in FIG. 9, there was no significant difference between the hysteresis characteristics.

(5) Application and others:
Various modifications can be considered for the present invention.
In the above-described embodiment, an individual piezoelectric body is provided for each pressure generation chamber. However, a common piezoelectric body may be provided for a plurality of pressure generation chambers, and an individual electrode may be provided for each pressure generation chamber.
In the above-described embodiment, a part of the reservoir is formed on the flow path forming substrate. However, the reservoir may be formed on a member different from the flow path forming substrate.
In the above-described embodiment, the upper side of the piezoelectric element is covered with the piezoelectric element holding unit, but the upper side of the piezoelectric element can be opened to the atmosphere.
In the embodiment described above, the pressure generating chamber is provided on the opposite side of the piezoelectric element with the diaphragm interposed therebetween, but it is also possible to provide the pressure generating chamber on the piezoelectric element side. For example, if a space surrounded by fixed plates and piezoelectric elements is formed, this space can be used as a pressure generating chamber.

  The liquid ejected from the fluid ejecting head may be any material that can be ejected from the liquid ejecting head, such as a solution in which a dye or the like is dissolved in a solvent, or a sol in which solid particles such as pigments or metal particles are dispersed in a dispersion medium. Is included. Such fluids include ink, liquid crystal, and the like. The liquid ejecting head includes one that discharges powder or gas. The liquid ejecting head can be mounted on an image recording apparatus such as a printer, a color filter manufacturing apparatus such as a liquid crystal display, an electrode manufacturing apparatus such as an organic EL display, a biochip manufacturing apparatus, and the like.

  The laminated ceramics produced by the production method described above can be suitably used to form ferroelectric thin films for ferroelectric devices, pyroelectric devices, piezoelectric devices, and optical filters. Ferroelectric devices include ferroelectric memory (FeRAM), ferroelectric transistors (FeFET), etc., and pyroelectric devices include temperature sensors, infrared detectors, temperature-electric converters, and the like. Examples of piezoelectric devices include fluid ejection devices, ultrasonic motors, acceleration sensors, and pressure-electric converters. Optical filters include blocking filters for harmful rays such as infrared rays, and photonic crystal effects due to quantum dot formation. And an optical filter using optical interference of a thin film.

As described above, according to the present invention, the performance of the piezoelectric element, the liquid ejecting head, and the liquid ejecting apparatus in which the piezoelectric layer including at least Bi, Ba, Fe, and Ti is formed by the liquid phase method is improved according to various aspects. Technology can be provided.
In addition, the configurations disclosed in the embodiments and modifications described above are mutually replaced, the combinations are changed, the known technology, and the configurations disclosed in the embodiments and modifications described above are mutually connected. It is possible to implement a configuration in which replacement or combination is changed. The present invention includes these configurations and the like.

DESCRIPTION OF SYMBOLS 1 ... Recording head (liquid ejecting head), 2 ... Piezoelectric actuator, 3 ... Piezoelectric element, 10 ... Channel formation substrate, 12 ... Pressure generating chamber, 15 ... Silicon substrate, 16 ... Elastic film (vibration plate), 20 ... Bottom Electrode (first electrode), 30 ... piezoelectric layer (piezoelectric ceramic), 31 ... precursor solution (piezoelectric precursor solution), 40 ... upper electrode (second electrode), 50 ... protective substrate, 60 ... compliance substrate, 65 ... Drive circuit, 70 ... Nozzle plate, 71 ... Nozzle opening, 200 ... Recording apparatus (liquid ejecting apparatus), S1 ... Application step, S2 ... Piezoelectric layer forming step

Claims (7)

A precursor solution containing at least Bi, Ba, Fe and Ti, and a step of applying a precursor solution having a pH of 7 or more when an aqueous solution is formed;
Crystallizing the applied precursor solution to form a piezoelectric ceramic containing a perovskite oxide, and a method for producing the piezoelectric ceramic.   The method for producing a piezoelectric ceramic according to claim 1, wherein the precursor solution contains an amine.   The method for producing a piezoelectric ceramic according to claim 2, wherein the precursor solution contains 3 to 30 vol% of amine.   The method for producing a piezoelectric ceramic according to claim 3, wherein the precursor solution contains 3 to 10 vol% of amine. Forming a piezoelectric ceramic by the method for manufacturing a piezoelectric ceramic according to any one of claims 1 to 4,
And a step of forming an electrode on the piezoelectric ceramic.   A method for manufacturing a liquid jet head, comprising the step of forming a piezoelectric element by the method for manufacturing a piezoelectric element according to claim 5.   A method of manufacturing a liquid ejecting apparatus, comprising the step of forming a liquid ejecting head by the method of manufacturing a liquid ejecting head according to claim 6.

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