JP3722262B2 - Method for manufacturing piezoelectric thin film element, method for manufacturing ink jet recording head, and ink jet printer - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a manufacturing technique of a piezoelectric thin film element, and more particularly to a manufacturing technique of a piezoelectric thin film element in which a degreasing process temperature of a piezoelectric film precursor is performed in a low temperature environment.
[0002]
[Prior art]
The ink jet recording head includes a piezoelectric thin film element that functions as a drive source for ink ejection. Piezoelectric thin film elements are elements exhibiting an electromechanical conversion function, and ceramics having a perovskite crystal structure exhibit many of these effects, and are therefore used as materials for piezoelectric films. The piezoelectric thin film element includes a piezoelectric film, and an upper electrode and a lower electrode that sandwich the piezoelectric film.
[0003]
The piezoelectric film generally used is a two-component system mainly composed of lead zirconate titanate (hereinafter sometimes referred to as “PZT”), or a third component of PZT in this two-component system. It has a three-component composition with the addition of As a method for forming this piezoelectric film, a sol-gel method is known. In the sol-gel method, a hydroxide hydrate complex (sol) of a metal component of a PZT-based piezoelectric film is applied / dried / degreased on a lower electrode to obtain a piezoelectric film precursor (gel). In this method, a body film precursor is heated and fired to adjust an inorganic oxide (piezoelectric film). According to this method, since the precursor of the PZT-based piezoelectric film can be formed by repeating coating / drying / degreasing several times until the desired thickness is obtained, the composition control is excellent, and the thickness of the piezoelectric film It is suitable for adjustment. Patterning using a photoetching process is also possible, and application to an ink jet recording head has been put into practical use. For example, when a PZT film having a thickness of about 1 μm is formed by a sol-gel method, several steps of spin coating the sol of the PZT film and drying / degreasing are performed, and then an alkaline aqueous solution is used as a treatment liquid. The piezoelectric film precursor was crystallized by hydrothermal treatment.
[0004]
[Problems to be solved by the invention]
However, in the conventional manufacturing method, it is possible to perform the hydrothermal treatment temperature at 200 ° C. or lower, whereas the temperature of the degreasing process by the heat treatment is set to around 350 ° C. Therefore, it was not possible to realize the production in a low temperature environment (200 ° C. or less). When the temperature in the manufacturing process is high, the residual stress generated inside the film increases, and cracks may occur in the manufacturing process. In addition, the ink discharge speed and the ink discharge amount may become unstable due to fluctuations in the piezoelectric characteristics of the piezoelectric thin film element.
[0005]
Therefore, an object of the present invention is to provide a method for manufacturing a piezoelectric thin film element that can set the temperature environment in the degreasing process of the piezoelectric film precursor to a low temperature and can set the entire manufacturing process to a low temperature. Another object of the present invention is to provide an ink jet recording head manufacturing method capable of setting the temperature of the entire manufacturing process in a low temperature environment, and an ink jet printer provided with the ink jet recording head obtained by this manufacturing method.
[0006]
[Means for Solving the Problems]
The method for manufacturing a piezoelectric thin film element according to the present invention includes a step of forming a lower electrode and a hydration complex of a metal component hydroxide capable of forming a piezoelectric film, that is, a sol is applied on the lower electrode and degreased. a piezoelectric film precursor deposition step of forming a piezoelectric film precursor is treated, the degreasing step of removing part of the residual organic matter of said piezoelectric film precursor by irradiation with ultraviolet rays, the piezoelectric member by hydrothermal treatment A crystallization step of crystallizing the film precursor to obtain a piezoelectric film; and a step of forming an upper electrode on the piezoelectric film .
[0007]
By providing such a manufacturing process, the degreasing process by ultraviolet irradiation can be performed at room temperature, and the upper limit of the entire manufacturing process temperature of the piezoelectric thin film element is not more than the temperature required for hydrothermal treatment (for example, 200 ° C.). The temperature of the manufacturing process can be reduced. Moreover, it is preferable that the wavelength of the ultraviolet rays irradiated in the degreasing step is 100 nm to 350 nm. Part of the residual organic matter in the amorphous piezoelectric film precursor can be removed by ultraviolet irradiation.
[0008]
The method for manufacturing a piezoelectric thin film element according to the present invention includes a step of forming a lower electrode and a hydration complex of a metal component hydroxide capable of forming a piezoelectric film, that is, a sol is applied on the lower electrode and degreased. a piezoelectric film precursor deposition step of forming a piezoelectric film precursor is treated, the degreasing step of removing part of the residual organic matter of said piezoelectric film precursor by an alkali aqueous solution treatment of certain conditions, water A crystallization step of crystallizing the piezoelectric film precursor by heat treatment to obtain a piezoelectric film; and a step of forming an upper electrode on the piezoelectric film .
[0009]
By performing the degreasing step by a treatment using an alkaline aqueous solution, a part of the residual organic matter in the amorphous piezoelectric film precursor can be removed. In this case, the alkaline aqueous solution treatment in the degreasing step is preferably performed under atmospheric pressure. In addition, the alkaline aqueous solution treatment in the degreasing step is performed at room temperature or higher and 80 ° C. or lower, and the treatment liquid is adjusted to a concentration of 0.05M or higher and 0.5M or lower, barium hydroxide aqueous solution, potassium hydroxide aqueous solution, lead hydroxide aqueous solution. Or these mixed aqueous solution is preferable. By setting the degreasing temperature to 80 ° C. or lower, it is possible to reduce the temperature of the manufacturing process of the piezoelectric thin film element.
[0010]
In the piezoelectric film precursor film forming step, it is preferable that a sol containing an organic metal is applied on the lower electrode, dried and degreased to form an amorphous piezoelectric film precursor. The piezoelectric film is composed of lead titanate (PbTiO ₃ ), lead zirconate titanate (Pb (Zr, Ti) O ₃ ), lead zirconate (PbZrO ₃ ), lead lanthanum titanate ((Pb, La ), TiO ₃ ), lead lanthanum zirconate titanate ((Pb, La) (Zr, Ti) O ₃ ) or lead magnesium niobate zirconium titanate (Pb (Zr, Ti) (Mg, Nb) O ₃ ) Among them, any piezoelectric ceramic is preferable.
[0011]
The method of manufacturing an ink jet recording head of the present invention includes a step of forming a diaphragm film on one surface of a substrate and a step of manufacturing a piezoelectric thin film element on the diaphragm film by the method of manufacturing a piezoelectric thin film element of the present invention. And a step of processing the substrate and forming a pressurizing chamber at a location where the displacement of the diaphragm film due to driving of the piezoelectric thin film element can be transmitted. The ink jet printer of the present invention includes an ink jet recording head manufactured by the manufacturing method of the present invention.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Embodiment 1 of the Invention
Hereinafter, the present embodiment will be described with reference to the drawings. FIG. 1 shows a configuration diagram of an ink jet printer. The ink jet printer mainly includes an ink jet recording head 100, a main body 102, a tray 103, and a head driving mechanism 106. The ink jet recording head 100 includes a total of four ink cartridges 101 of yellow, magenta, cyan, and black, and is configured to be capable of full color printing. The inkjet printer includes a CPU, a memory, an interface circuit, and the like inside, and receives print data from each client connected to the network via a connector. The CPU buffers the print data in the memory and develops the print image described in the page description language at a predetermined address. The CPU controls the ink ejection timing of the ink jet recording head 100 and the scanning of the head driving mechanism 106 based on the print image. Further, the main body 102 includes a tray 103 on the back surface, and an auto sheet feeder (automatic continuous paper feeding mechanism) 105 inside the main body 102 to automatically feed out the paper 107 and discharge the paper 107 from the front discharge port 104. .
[0013]
Next, an exploded perspective view of the ink jet recording head is shown in FIG. Here, a type in which a common ink passage is provided in the pressure chamber substrate is shown. As shown in the figure, the ink jet recording head includes a pressurizing chamber substrate 1, a nozzle plate 2, and a base 3. The pressurizing chamber substrate 1 is separated into each after the silicon single crystal substrate is etched. The pressurizing chamber substrate 1 is provided with a plurality of strip-shaped pressurizing chambers 10 and includes a common passage 12 for supplying ink to all the pressurizing chambers 10. The pressurizing chambers 10 are separated by side walls 11. A piezoelectric thin film element is provided on the substrate 3 side of the pressurizing chamber substrate 1. Further, the wiring from each piezoelectric thin film element is converged on the wiring substrate 4 which is a flexible cable and connected to an external circuit of the base 3. The nozzle plate 2 is bonded to the pressurizing chamber substrate 1. A nozzle 21 for ejecting ink droplets is formed at a position corresponding to the pressurizing chamber 10 in the nozzle plate 2. The pitch between the nozzles 21 is appropriately set according to the printing accuracy, and for example, a resolution of 400 dpi or the like is set. The base 3 is made of plastic, metal or the like and serves as a mounting base for the pressurizing chamber substrate 1.
[0014]
Next, the principle of ink ejection will be described with reference to FIG. FIG. 2 is a cross-sectional view of the main part of the ink jet recording head. This figure shows a cross-sectional shape of the main part cut along a plane perpendicular to the longitudinal direction of the pressurizing chamber. In the figure, the same structure as that of FIG. 2 is indicated by the same symbol, and the description thereof is omitted. A piezoelectric thin film element 5 is formed on a substrate 1 composed of a silicon single crystal substrate via a diaphragm film 20. The piezoelectric thin film element 5 includes a piezoelectric film 40 sandwiched between an upper electrode 50 and a lower electrode 30. In the figure, the case where the lower electrode 30 is used as a common electrode of each piezoelectric thin film element is shown. By applying a desired voltage to the piezoelectric thin film element 5, the piezoelectric film 40 is deformed, and the ink filled in the pressurizing chamber 10 is pressurized via the diaphragm film 20. Then, the ink filled in the pressurizing chamber 10 is ejected from the nozzle 21 and attached to a predetermined recording paper, thereby enabling printing or the like.
[0015]
Next, a method for manufacturing an ink jet recording head will be described together with a method for manufacturing a piezoelectric thin film element. FIG. 3 is a sectional view of the manufacturing process of the ink jet recording head, and FIGS. 3A to 3D are common to the method of manufacturing the piezoelectric thin film element. As shown in FIGS. 4A and 4B, the diaphragm film 20, the lower electrode 30, and the piezoelectric film precursors 41 to 44 are sequentially formed on the substrate 1. For example, a silicon single crystal substrate having a thickness of 220 μm is used as the substrate 1. When an ink jet recording head is used for a line printer, a long and thin silicon single crystal substrate is used, and its thickness is, for example, about 200 μm so that the height of the side wall does not become too high. A diaphragm film 20 made of silicon dioxide having a thickness of 1.0 μm is formed by a thermal oxidation method. In this step, high temperature treatment is performed in an oxygen atmosphere containing oxygen or water vapor. The diaphragm film 20 has a function of transmitting the deformation of the piezoelectric thin film element to the pressurizing chamber and increasing the ink pressure in the pressurizing chamber. The film is not limited to a silicon dioxide film, and may be a zirconium oxide film, a tantalum oxide film, a silicon nitride film, or an aluminum oxide film. Further, the diaphragm itself may be eliminated and the lower electrode itself may also serve as a diaphragm film. The film formation of the diaphragm film 20 is not limited to the thermal oxidation method, and may be a CVD method.
[0016]
Next, the lower electrode 30 is formed on the diaphragm film 20. For example, titanium is formed on the diaphragm film 20 with a film thickness of 100 nm by sputtering to obtain the lower electrode 30. Further, when the lower electrode 30 is platinum, an adhesion layer (not shown) such as titanium or chromium may be interposed in order to improve the adhesion between the diaphragm film 20 and the lower electrode 30. For the adhesion layer, for example, titanium may be formed to a thickness of 50 nm by sputtering.
[0017]
Next, the piezoelectric film precursors 41 to 44 are formed on the lower electrode 30. A piezoelectric ceramic having piezoelectric characteristics is used as the piezoelectric film. For example, a PZT piezoelectric material or a material obtained by adding a metal oxide such as niobic acid, nickel or magnesium to this system is suitable as the piezoelectric film. Specifically, lead titanate (PbTiO ₃ ), lead zirconate titanate (Pb (Zr, Ti) O ₃ : PZT), lead zirconate (PbZrO ₃ ), lead lanthanum titanate ((Pb, La), TiO ₃ ), lead lanthanum zirconate titanate ((Pb, La) (Zr, Ti) O ₃ ), or lead magnesium niobate zirconium titanate (Pb (Zr, Ti) (Mg, Nb) O ₃ : PZT— PMN) and the like are preferable.
[0018]
In the present embodiment, a case where Pb (Zr _0.56 Ti _0.44 ) O ₃ is used as the composition of the piezoelectric film and the piezoelectric film precursors 41 to 44 are formed by the sol-gel method will be described. When forming a film by the sol-gel method, a metal component hydroxide hydration complex capable of forming a piezoelectric film, that is, a sol is applied on the lower electrode and degreased to obtain a piezoelectric film precursor, This piezoelectric film precursor is crystallized by hydrothermal treatment to obtain an inorganic oxide (piezoelectric film). Specifically, a PZT-based piezoelectric film precursor in an amorphous state in which the molar mixing ratio of lead zirconate and lead titanate is 56%: 44% has a final film thickness of 0.4 μm. The film is formed by repeatedly applying / drying / degreasing a desired number of times. First, a sol to be applied on the lower electrode 30 is prepared. For example, 2-n-butoxyethanol is used as a main solvent, and titanium tetraisopropoxide and tetra-n-propoxyzirconium are mixed with this and stirred at room temperature for 20 minutes. Then add diethanolamine and stir for another 20 minutes at room temperature. Add lead acetate and heat to 80 ° C. The mixture is stirred for 20 minutes in the heated state, and then naturally cooled to room temperature. In this step, a sol is obtained. This sol is spin-coated on the lower electrode 30 to a thickness of 0.1 μm. In order to make the sol film uniform, spin coating is first performed at 500 rpm for 30 seconds, then at 1500 rpm for 30 seconds, and finally at 500 rpm for 10 seconds. At this stage, each metal atom constituting the piezoelectric film is dispersed as an organometallic complex. After applying the sol to the lower electrode 30, for example, it is dried at 180 ° C. for 10 minutes.
[0019]
Next, at room temperature, ultraviolet rays having a wavelength of 100 nm to 350 nm, particularly preferably ultraviolet rays having a wavelength of 180 nm are irradiated for 10 minutes, and the organic substance in the film is partially removed to degrease the piezoelectric film precursor. Drying / degreasing is performed each time the sol is applied. FIG. 5B shows a degreasing process for the piezoelectric film precursor 44. The amount of residual organic substances in the piezoelectric film precursor obtained in the degreasing process by ultraviolet irradiation may be larger than the residual organic substances in the piezoelectric film precursor obtained in the conventional degreasing process (heat treatment at around 350 ° C.). confirmed. When the amount of organic matter remaining in the film increases, the gap in the piezoelectric film precursor increases, so that in the hydrothermal treatment process described later, the treatment liquid can penetrate into the film and further promote crystallization. . Piezoelectric film precursors 41, 42, 43, and 44 are laminated by repeating sol coating / drying / degreasing four times. In this way, the piezoelectric film precursor can be multi-layered to increase the thickness while preventing the generation of cracks. In addition to the sol-gel method described above, the piezoelectric film precursor is formed by RF sputtering, ion beam sputtering, MOD (Metal Organic Decomposition Process), electron beam evaporation, or the like. You can also.
[0020]
Next, as shown in FIG. 3C, the piezoelectric film precursor is crystallized by hydrothermal treatment. A barium hydroxide aqueous solution (Ba (OH) ₂ ) is prepared as the treatment liquid 6. The concentration of the treatment liquid 6 is about 0.05M to 1M. Since barium hydroxide has less etching on the silicon substrate than potassium hydroxide, there is an advantage that the degree of freedom of the material of the substrate 1 is widened. The treatment liquid 6 is filled in the water tank 7. The piezoelectric film precursors 41 to 44 obtained in the above-described steps are immersed in the water tank 7 together with the substrate 1 to promote crystallization in an autoclave. The temperature of the hydrothermal treatment at this time is set in the range of 120 ° C to 200 ° C. This is because the crystallization is not promoted at a temperature lower than this range, and the piezoelectric film precursor and the substrate 1 are disadvantageously etched at a temperature higher than this range. In particular, a processing temperature of 130 ° C. is suitable. By setting the treatment pressure to 2 atm or more and 10 atm or less, good quality crystals can be obtained. In particular, a processing pressure of 4 atmospheres is suitable. The treatment time is in the range of 30 minutes to 120 minutes, and particularly preferably about 90 minutes. This is because if the treatment time is short, sufficient crystals cannot be obtained, and if the treatment time is longer than necessary, the substrate is etched. The piezoelectric film precursors 41 to 44 can be crystallized by this hydrothermal treatment process. The crystallized piezoelectric film precursors 41 to 44 become the piezoelectric film 40.
[0021]
Next, an upper electrode 50 is formed on the piezoelectric film 40 as shown in FIG. A platinum film of 200 nm is formed on the piezoelectric film 40 to form the upper electrode 50 by using a thin film stacking technique such as an electron beam evaporation method or a sputtering method. The material of the upper electrode 50 is not limited to platinum, but may be iridium, an alloy of platinum and iridium, iridium oxide, aluminum, or the like.
[0022]
Next, as shown in FIG. 5E, the piezoelectric thin film element serving as the ink ejection drive source is separated corresponding to each pressure chamber. A resist (not shown) is spin-coated on the upper electrode 50, exposed and developed in accordance with the position where the pressurizing chamber is to be formed, and patterned. The laminated structure composed of the upper electrode 50 and the piezoelectric film 40 is etched by applying ion milling, dry etching, or the like using this resist as a mask. In this step, the piezoelectric thin film element 5 is separated in accordance with the position where the pressurizing chamber is to be formed.
[0023]
Next, as shown in FIG. 2F, a pressurizing chamber 10 is formed on the substrate 1 and the nozzle plate 2 is joined. The space in which the pressure chamber 10 is formed is etched using anisotropic etching using an active gas such as parallel plate type reactive ion etching. The portion of the substrate left without being etched becomes the side wall 11. After the etching is completed, the nozzle plate 2 is bonded to the substrate 1. At this time, alignment is performed so that each nozzle 21 is arranged corresponding to each space of the pressurizing chamber 10. When the substrate 1 on which the pressurizing chamber 10 is formed is attached to the base 3, an ink jet recording head is completed. In the case where the nozzle plate 2 and the substrate 1 are integrally formed by etching, the nozzle plate 2 joining step is not necessary.
[0024]
According to the present embodiment, it is possible to lower the temperature of the degreasing process, which has conventionally been heat-treated at a temperature around 350 ° C., lower than the temperature of the hydrothermal process. That is, since the degreasing process of the piezoelectric film precursor can be performed in a room temperature environment, the temperature of the entire manufacturing process of the piezoelectric thin film element can be set to 200 ° C. or less. As a result, by reducing the temperature of the entire manufacturing process of the piezoelectric thin film element, it is possible to reduce the residual stress generated in the film, thereby preventing the generation of cracks in the manufacturing process, improving the yield, and reducing the manufacturing cost. . In addition, since fluctuations in piezoelectric characteristics of the piezoelectric thin film element can be suppressed, an ink jet recording head using the piezoelectric thin film element manufactured in this embodiment as an ink discharge drive source has an ink discharge speed and an ink discharge amount. Stable characteristics can be provided. Therefore, the ink jet printer provided with this ink jet recording head can stabilize the printing quality. In addition, since the piezoelectric thin film element can be enlarged, a printer capable of printing in a large area such as a line printer can be provided.
[0025]
Moreover, since the degreasing process by ultraviolet irradiation has a relatively large amount of residual organic substances in the piezoelectric film precursor, crystallization of the piezoelectric film precursor by hydrothermal treatment can be promoted. That is, as the amount of organic matter remaining in the film increases, the gap in the piezoelectric film precursor increases, so that the treatment liquid penetrates into the film in the hydrothermal treatment process (piezoelectric film precursor crystallization process). The crystallization can be further promoted by the interaction between the treatment liquid and the piezoelectric film precursor.
[0026]
Embodiment 2 of the Invention
The present embodiment will be described focusing on differences from the first embodiment. During the manufacturing process of the piezoelectric thin film element of the present embodiment, the degreasing process of the piezoelectric film precursor is performed by an alkaline aqueous solution treatment. In this specification, degreasing treatment by alkaline aqueous solution treatment is referred to as alkali degreasing. As a treatment liquid used for alkaline degreasing, an aqueous barium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous lead hydroxide solution or a mixed aqueous solution thereof adjusted to a concentration of 0.05M to 0.5M is used. After applying / drying the piezoelectric film precursor, the piezoelectric film precursor is immersed together with the substrate in a water tank filled with the treatment liquid, and the temperature is set to room temperature to 80 ° C. under atmospheric pressure. Set to about 30 minutes.
[0027]
By the alkali degreasing step, a part of the organic substance in the piezoelectric film precursor is removed, and a relatively large amount of residual organic substance is present in the piezoelectric film precursor. If the amount of organic matter remaining inside the film increases, the gap in the piezoelectric film precursor increases, so that the treatment liquid penetrates into the film in the hydrothermal treatment process (piezoelectric film precursor crystallization process) Crystallization can be further promoted by the interaction between the liquid and the piezoelectric film precursor. In addition, since the alkaline degreasing temperature is set to room temperature to 80 ° C., the residual stress generated inside the film can be reduced by lowering the temperature of the entire manufacturing process of the piezoelectric thin film element (200 ° C. or less). Can prevent cracking, improve yield, and reduce manufacturing costs.
[0028]
The piezoelectric thin film element of the first embodiment or the present embodiment is a micro actuator, filter, delay line, lead selector, tuning fork oscillator, tuning fork clock, transceiver, piezoelectric, as well as an ink discharge drive source for an ink jet recording head. It can be applied to pickups, piezoelectric earphones, piezoelectric microphones, SAW filters, RF modulators, resonators, delay elements, multi-strip couplers, piezoelectric accelerometers, piezoelectric speakers, and the like.
[0029]
【The invention's effect】
According to the method for manufacturing a piezoelectric thin film element of the present invention, the temperature of the entire manufacturing process can be lowered, and the residual stress generated in the film can be reduced, the occurrence of cracks can be prevented, and the manufacturing cost can be reduced.
[0030]
According to the method for manufacturing an ink jet recording head of the present invention, a piezoelectric thin film element with little fluctuation in piezoelectric characteristics can be used as an ink discharge drive source, so that the ink discharge speed and the ink discharge amount can be stabilized. .
[0031]
According to the ink jet printer of the present invention, it is possible to perform high quality printing.
[Brief description of the drawings]
FIG. 1 is a configuration diagram of an ink jet printer.
FIG. 2 is an exploded perspective view of an ink jet recording head.
FIG. 3 is a cross-sectional view of an ink jet recording head manufacturing process.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Substrate 10 Pressurizing chamber 20 Diaphragm film 30 Lower electrode 40 Piezoelectric film 50 Upper electrode 100 Inkjet recording head 103 Tray 106 Head drive mechanism

Claims (11)

In a method for manufacturing a piezoelectric thin film element including a piezoelectric film sandwiched between an upper electrode and a lower electrode, a step of forming a lower electrode, and a hydroxide hydrate complex of a metal component capable of forming a piezoelectric film, Applying a sol onto the lower electrode and degreasing to form a piezoelectric film precursor, and partially removing residual organic substances in the piezoelectric film precursor by ultraviolet irradiation. A piezoelectric thin film element comprising: a degreasing step, a crystallization step of crystallizing the piezoelectric film precursor by hydrothermal treatment to obtain a piezoelectric film, and a step of forming an upper electrode on the piezoelectric film. Production method.   The method of manufacturing a piezoelectric thin film element according to claim 1, wherein the degreasing step is performed at room temperature.   2. The method for manufacturing a piezoelectric thin film element according to claim 1, wherein the wavelength of the ultraviolet rays irradiated in the degreasing step is 100 nm to 350 nm. In a method for manufacturing a piezoelectric thin film element including a piezoelectric film sandwiched between an upper electrode and a lower electrode, a step of forming a lower electrode, and a hydroxide hydrate complex of a metal component capable of forming a piezoelectric film, A sol coating on the lower electrode and degreasing to form a piezoelectric film precursor, and a residual film in the piezoelectric film precursor by an alkaline aqueous solution treatment under a predetermined condition. A degreasing process for removing a part of the organic substance, a crystallization process for crystallizing the piezoelectric film precursor by hydrothermal treatment to obtain a piezoelectric film, and a process for forming an upper electrode on the piezoelectric film. A method for manufacturing a piezoelectric thin film element.   The method for producing a piezoelectric thin film element according to claim 4, wherein the alkaline aqueous solution treatment in the degreasing step is performed at room temperature or higher and 80 ° C. or lower.   The method for producing a piezoelectric thin film element according to claim 4, wherein the alkaline aqueous solution treatment in the degreasing step is performed under atmospheric pressure.   The alkaline treatment liquid used in the degreasing step is a barium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a lead hydroxide aqueous solution or a mixed aqueous solution thereof adjusted to a concentration of 0.05M to 0.5M. The method for manufacturing a piezoelectric thin film element according to claim 4.   The piezoelectric film precursor film forming step is a step of applying a sol containing an organic metal to a lower electrode and degreasing to form an amorphous piezoelectric film precursor. Item 8. The method for manufacturing a piezoelectric thin film element according to any one of Items 7 above. The piezoelectric film is composed of lead titanate (PbTiO ₃ ), lead zirconate titanate (Pb (Zr, Ti) O ₃ ), lead zirconate (PbZrO ₃ ), lead lanthanum titanate ((Pb, La) , TiO ₃ ), lead lanthanum zirconate titanate ((Pb, La) (Zr, Ti) O ₃ ) or lead magnesium niobate zirconium titanate (Pb (Zr, Ti) (Mg, Nb) O ₃ ). The method for manufacturing a piezoelectric thin film element according to any one of claims 1 to 8, wherein the piezoelectric ceramic element is any one of the piezoelectric ceramics.   A piezoelectric thin film element is manufactured on the diaphragm film by a step of forming a diaphragm film on one surface of the substrate and a method of manufacturing a piezoelectric thin film element according to any one of claims 1 to 9. And a step of processing the substrate and forming a pressurizing chamber at a location where the displacement of the diaphragm film due to driving of the piezoelectric thin film element can be transmitted.   An inkjet printer comprising an inkjet recording head manufactured by the manufacturing method according to claim 10.

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