JP5939457B2 - Method for manufacturing electromechanical transducer and method for manufacturing droplet discharge head - Google Patents

Description

The present invention relates to a manufacturing method and a manufacturing method of the droplet discharge head of electrical mechanical conversion element.

  Conventionally, an electromechanical conversion element configured to sandwich an electromechanical conversion film between electrodes has been used in, for example, an ink jet recording apparatus. Inkjet recording devices have many advantages such as extremely low noise, high-speed printing, and the ability to use plain paper that is free of ink and inexpensive, so printers, facsimiles, copiers, etc. Widely deployed as an image recording apparatus or an image forming apparatus. The droplet discharge device used in this ink jet recording apparatus mainly includes a nozzle that discharges ink droplets, a discharge chamber that communicates with the nozzle, a pressurized liquid chamber, a pressure chamber, a liquid chamber that refers to an ink flow path, and the like, And pressure generating means for discharging ink in the liquid chamber. As this pressure generating means, there is known a piezo-type pressure generating means for discharging ink droplets by deforming and displacing a vibration plate forming the wall surface of the discharge chamber using an electromechanical conversion element such as a piezoelectric element. . The electromechanical conversion element used for this piezo-type pressure generating means is formed by laminating a lower electrode (first electrode), an electromechanical conversion layer, and an upper electrode (second electrode). Individual piezoelectric elements are arranged to generate ink discharge pressure in each pressure chamber. As the electromechanical conversion layer, lead zirconate titanate (PZT) ceramics or the like is used, and these are generally referred to as metal composite oxides because they are composed mainly of a plurality of metal oxides.

  Here, as a conventional method for manufacturing an electromechanical conversion film, a droplet discharge method in which a droplet of a coating liquid containing a raw material for forming an electromechanical conversion film is discharged from a nozzle is applied to a predetermined portion on a lower electrode. A manufacturing method using a liquid coating method for coating a coating liquid is known (see, for example, Patent Documents 1 and 2). In this droplet discharge method, it is possible to discharge and apply droplets of the coating liquid containing the raw material with high resolution. However, the coating liquid applied on the surface of the lower electrode is very small in amount, so that the drying is fast. Also, at the end portion in the coating region, the vapor concentration of the solvent evaporated from the coating liquid is low, so that the drying is fast. Such a difference in the drying speed of the coating liquid becomes a factor that causes unevenness of the film thickness of the electromechanical conversion film, and causes a problem in the electric characteristics of the electromechanical conversion element.

  Therefore, Patent Document 3 proposes a method of manufacturing an electromechanical conversion film that can solve the above-described problems. The manufacturing method disclosed in Patent Document 3 includes a first step in which surface modification is partially performed on a substrate to be a first electrode, and a composite of metal in a predetermined portion of the first electrode subjected to surface modification. A second step of applying an oxide sol-gel solution, a third step of drying, pyrolyzing and crystallizing the applied sol-gel solution to form an electromechanical conversion film; a first step; a second step; , A fourth step of sequentially repeating the third step to obtain a desired film thickness, and a fifth step of disposing the second electrode so as to sandwich the substrate of the first electrode and the electromechanical conversion film. . In Patent Document 3, as a first step of performing the partial surface modification, a film made of a thiol compound having excellent chemical reactivity with a noble metal (for example, platinum) used as the first electrode is provided. A process of partially removing the thiol compound after being formed on the first electrode by photolithography etching or ultraviolet irradiation through a mask is disclosed. The part from which the thiol compound is removed becomes a hydrophilic part having hydrophilicity with respect to the coating liquid, and the part that remains without the thiol compound being removed is a hydrophobic part having hydrophobicity (water repellency) with respect to the coating liquid. It becomes. Therefore, an electromechanical conversion film having a predetermined pattern and film thickness can be formed by applying the coating liquid only to a predetermined pattern portion from which the thiol compound is removed. In particular, when a droplet discharge method is used for applying the coating liquid, when the droplet of the coating liquid is discharged and adhered to a part of the hydrophilic portion of the predetermined pattern from which the thiol compound is removed, the liquid of the coating liquid is used. The droplet spreads only to the hydrophilic portion, and a coating liquid having a predetermined pattern is formed. Therefore, an electromechanical conversion film having a desired pattern can be easily formed.

  However, when surface modification using a thiol compound as described in the cited document 3 is performed, the cost may increase as shown below. That is, since the thiol compound is excellent in chemical reactivity with a noble metal (for example, platinum) used as the first electrode (lower electrode), it is chemically adsorbed on the surface of the first electrode made of the noble metal, Moreover, the chemisorbed thiol compound is relatively stable and resistant to ultraviolet light. Therefore, in the first surface modification step of partially modifying the surface of the first electrode on which the electromechanical conversion film is not formed, the thiol compound film formed on the first electrode is partially coated. However, it is necessary to use a high-cost method or apparatus for removing the thiol compound film with certainty, because a relatively inexpensive apparatus or method using ultraviolet irradiation cannot be used. For example, when the first electrode is an electrode made of platinum, in order to partially remove the thiol compound film chemically adsorbed on the platinum electrode, a resist pattern is formed by photolithography and the resist pattern is interposed. Etching of the thiol compound film and the surface portion of the platinum electrode and resist ashing are required, resulting in high costs. Further, in the case where the first electrode is an electrode made of a conductive oxide, a thiol compound is not adsorbed on the conductive oxide, so that a platinum film is interposed between the conductive oxide electrode and the thiol compound. It is possible to make it. In this case, when the thiol compound film is partially removed, the underlying platinum film must also be partially removed to expose the surface of the conductive oxide electrode. Therefore, the formation of the resist pattern by photolithography, the etching of the thiol compound film and the surface portion of the platinum electrode via the resist pattern, and the resist ashing are also required, resulting in high cost.

The present invention has been made in view of the above problems, an object of a desired pattern and electromechanical conversion film vapor collector Ru can be easily formed a transducer of thickness while reducing the manufacturing cost it is to provide a manufacturing method of preparation and the droplet discharge head element.

In order to achieve the above object, the invention of claim 1 includes an electrode forming step of forming a first electrode made of a platinum group metal on a substrate, and before performing an oxygen plasma treatment on the surface of the first electrode. a processing step, wherein after a first partially forming a film of the silane coupling agent to the surface of the electrode, the first surface of the surface modified by removing a film of the silane coupling agent partially A reforming step, and a first coating step of selectively applying a coating solution containing a PZT precursor solution for forming an electromechanical conversion film containing a metal oxide to a predetermined portion on the first electrode. A drying step of drying a film of the coating liquid applied on the first electrode, a crystallization step of forming a PZT film that thermally decomposes and crystallizes the dried film of the coating liquid, and the crystal The substrate that has undergone the conversion step contains a thiol compound The surface modification step after the second time for forming the thiol film of the thiol compound on the surface where the PZT film is not formed on the first electrode, and the thiol film are absent. Applying the coating solution only on the surface of the hydrophilic PZT film, and coating the exposed surface of the hydrophobic first electrode on which the thiol film is formed without coating the coating solution; comprising a times subsequent coating step, and the second and subsequent surface modification step and the second and subsequent coating step and the drying step and the crystallization step, repeatedly a plurality of times in this order execution Thus, an electromechanical conversion film is formed on the first electrode, and a second electrode is formed on the electromechanical conversion film .

In the present invention, a surface modification step for partially modifying the surface of the first electrode and a coating liquid containing a raw material for forming the electromechanical conversion film are selected as predetermined portions on the first electrode. A coating process for applying the film, a drying process for drying the film of the coating liquid applied on the first electrode, and a crystallization process for thermally decomposing and crystallizing the dried film of the coating liquid. Among these four steps, at least the surface modification step, the coating step, and the drying step can be repeated a plurality of times in that order to form an electromechanical conversion film having a predetermined pattern and film thickness.
Further, the first surface modification step repeated a plurality of times is a step of partially removing the silane coupling agent film after forming the silane coupling agent film on the first electrode. This silane coupling agent film can be adsorbed to the first electrode regardless of whether the material of the first electrode is organic or inorganic, and can be partially removed by irradiation with ultraviolet rays. Accordingly, it is possible to maintain the adsorptivity with the first electrode and the hydrophobicity (water repellency) with respect to the coating liquid and prevent the coating liquid from being reliably applied to the portion where the silane coupling agent film is desired to remain. . On the other hand, the part where the film of the silane coupling agent is to be removed can be easily removed by using a relatively inexpensive apparatus or method using ultraviolet irradiation to make the coating liquid hydrophilic, and the coating liquid can be reliably applied. Can be done.
Therefore, according to the present invention, it is possible to easily form an electromechanical conversion film having a desired pattern and thickness while reducing the manufacturing cost.

(A)-(D) are explanatory drawings which show an example of the 1st surface modification process in the manufacturing method of the electromechanical conversion element accompanied with formation of the electromechanical conversion film which concerns on one Embodiment of this invention. (A), (b) and (c) are the results of XPS analysis in which the surface of platinum (Pt) after performing oxygen plasma treatment for 1 minute, 3 minutes and 5 minutes, respectively, was analyzed by X-ray photoelectron spectroscopy. Graph showing. (A ')-(D') is explanatory drawing which shows the other example of the surface modification process of the 1st time in the manufacturing method of the electromechanical conversion element accompanying formation of the electromechanical conversion film which concerns on this embodiment. In (D) to (F) and (D ′) to (F ′), the first surface modification step in the method for manufacturing an electromechanical conversion element involving the formation of an electromechanical conversion film according to this embodiment is completed. Explanatory drawing which shows an example of a back process. The graph which shows the XPS analysis result of the surface of platinum (Pt) after the heat processing of a 2nd heating process (pyrolysis process). The graph which shows the relationship between the time of oxidation plasma processing, the ratio of the platinum oxide after the oxygen plasma processing obtained from the XPS analysis result, and the contact angle of the pure water measured on the silane coupling agent film. The graph which shows an example of the PE hysteresis curve of the PZT film | membrane produced in the Example. Explanatory drawing which shows an example of the droplet discharge apparatus which can be used for the manufacturing method of the electromechanical conversion element accompanied with formation of the electromechanical conversion film which concerns on other embodiment of this invention. The schematic block diagram which shows one structural example of the liquid discharge head comprised using the electromechanical conversion element (PZT element) manufactured with the manufacturing method of this embodiment. FIG. 10 is a schematic configuration diagram illustrating a configuration example in which a plurality of liquid ejection heads of FIG. 9 are arranged. FIG. 3 is a schematic configuration diagram illustrating a configuration example of an image forming apparatus as a droplet discharge device that can use an electromechanical conversion element manufactured by the manufacturing method of the present embodiment. FIG. 2 is a schematic perspective view of the image forming apparatus.

  Hereinafter, embodiments of the present invention will be described. In the present embodiment, an electromechanical conversion element having an electromechanical conversion film made of a transverse vibration (bend mode) type piezoelectric material using deformation of the piezoelectric constant d31 will be described as an example. The present invention can be applied without being limited to the electromechanical conversion film.

When the electromechanical conversion film is a PZT film, a PZT precursor solution synthesized using lead acetate trihydrate, isopropoxide titanium, and normal butoxide zirconium as starting materials can be used. The crystal water of lead acetate is dissolved in methoxyethanol and then dehydrated. The amount of lead is 10 mol% excess relative to the stoichiometric composition. This is to prevent crystallinity deterioration due to so-called lead loss during heat treatment. It is possible to synthesize PZT precursor solution by dissolving isopropoxide titanium and normal butoxide zirconium in methoxyethanol, proceeding with alcohol exchange reaction and esterification reaction, and uniformly mixing with methoxyethanol solution in which lead acetate is dissolved. it can. The PZT concentration of the PZT precursor solution is, for example, 0.1 mol / liter.
The PZT precursor solution in the case where the electromechanical conversion film is a PZT film is prepared by dissolving lead acetate, zirconium alkoxide, and titanium alkoxide compounds described in Non-Patent Document 1 as starting materials and dissolving them in methoxyethanol as a common solvent. Alternatively, a uniform solution may be obtained.
The PZT precursor solution is also called “sol-gel solution”.

PZT is a solid solution of lead zirconate (PbZrO ₃ ) and lead titanate (PbTiO ₃ ), and the characteristics differ depending on the ratio. In general, the composition exhibiting excellent piezoelectric characteristics has a ratio of PbZrO ₃ and PbTiO ₃ of 53:47. When expressed by a chemical formula, Pb (Zr0.53, Ti0.47) O ₃ , generally PZT (53/47) It is indicated. The starting materials for lead acetate, zirconium alkoxide and titanium alkoxide compounds are weighed according to this chemical formula. Since the metal alkoxide compound is easily hydrolyzed by moisture in the atmosphere, an appropriate amount of a stabilizer such as acetylacetone, acetic acid or diethanolamine may be added to the precursor solution as a stabilizer.

  Examples of composite oxides other than PZT include barium titanate. In this case, it is also possible to prepare a barium titanate precursor solution by dissolving barium alkoxide and a titanium alkoxide compound in a common solvent. is there.

These materials are described by the general formula ABO ₃ and correspond to composite oxides containing A = Pb, Ba, Sr, B = Ti, Zr, Sn, Ni, Zn, Mg, and Nb as main components. Specific examples thereof include (Pb1-x, Ba) (Zr, Ti) O ₃ and (Pb1-x, Sr) (Zr, Ti) O ₃ . These are cases where Pb of the A site is partially replaced with Ba or Sr. Such substitution is possible with a divalent element, and the effect thereof has an effect of reducing characteristic deterioration due to evaporation of lead during heat treatment.

  In addition, when obtaining a patterned PZT film as an electromechanical conversion film on the surface of the first electrode on the base substrate, the solution is applied by a solution coating method such as spin coating or a droplet discharge method. A coated PZT film can be obtained by forming a coating film by coating and applying heat treatments such as solvent drying, thermal decomposition, and crystallization. Since transformation from a coating film to a crystallized film involves volume shrinkage, it is necessary to adjust the precursor concentration so that a film thickness of 100 [nm] or less can be obtained in one step in order to obtain a crack-free film. is there. The precursor concentration is preferably adjusted so as to be optimized from the relationship between the film formation area of the electromechanical conversion film and the coating amount of the PZT precursor solution. Further, when used as an electromechanical conversion element of a droplet discharge device, the thickness of the PZT film is required to be 1 [μm] to 2 [μm]. In order to obtain this film thickness, the process is repeated ten times or more.

  Further, in the case of forming a patterned electromechanical conversion layer by the sol-gel method, the PZT precursor solution in which the wettability of the electrode surface of the base substrate is controlled is separately applied. As a method for controlling the wettability of the electrode surface of the base substrate, there is a method using a self-assembled monolayer (SAM), which is disclosed in Non-Patent Document 2, for example. It utilizes the phenomenon that a material such as alkanethiol self-aligns on a specific metal, etc. Typical materials for the SAM film include a thiol compound such as alkanethiol and a silane coupling agent. Each of the thiol compound and the silane coupling agent has the following characteristics and needs to be used properly depending on the application.

<Thiol compound>
・ The thiol group reacts with the precious metal and chemisorbs.
・ The adsorbed material is relatively stable.
-UV resistance (resistance to ultraviolet light).
・ There is a deterioration phenomenon due to moisture absorption.
・ Film thickness is on the order of submicrons.

<Silane coupling agent>
-It has reactive functional groups and hydrolyzable groups, and can be adsorbed on both organic and inorganic substances.
A silane coupling agent having a reactive group such as a chlorosilane group or an alkoxysilane group on the hydrolyzable group side is adsorbed by a reaction with a hydroxy group on the inorganic surface.
When the inorganic substance is adsorbed with a hydrolyzable group and the reactive functional group contains an alkyl group or fluorine, it exhibits water repellency.
・ For example, the hydrolyzable group is trichlorosilane, trimethoxysilane, triethoxysilane, and the reactive functional group is a combination of octyl, octadecyl, and fluoro. Show.
Particularly, UV-sensitive silane coupling agents such as phenyltrichlorosilane and octadecyltrimethoxysilane exhibit water repellency when formed on the substrate surface, but they are substituted with substituents or C—C bonds, C—H by UV irradiation. Bonds are decomposed, silanol groups are formed on the substrate surface, and the substrate surface becomes hydrophilic.

  In this embodiment, the wettability of the electrode surface of the base substrate is controlled by using the characteristics that the thiol compound is adsorbed only to the noble metal and the silane coupling agent is UV-decomposed (decomposed by ultraviolet rays), Patterning of the hydrophobic region (water repellent region) and the hydrophilic region with respect to the PZT precursor solution is performed.

The material used as the lower electrode, which is the first electrode, has heat resistance and hydroxyl group adsorption, and forms a monomolecular film of a thiol compound (hereinafter referred to as “thiol film”) by reaction with alkanethiol. The metal to be selected is selected.
Although copper and silver can form a thiol film on the surface, they cannot be used because these metals are altered by heat treatment at 500 [° C.] or higher in the atmosphere.
Although gold satisfies both the heat resistance and the hydroxyl group adsorptivity, it cannot be used because it adversely affects the crystallization of the laminated PZT film.

  Examples of the material used as the lower electrode (first electrode) of this embodiment include platinum, rhodium, ruthenium, iridium single metals, and alloy materials with other platinum group elements mainly composed of platinum such as platinum-rhodium. It is valid. Hereinafter, these single metals and alloy materials are referred to as “platinum group metals”.

  When a thiol film is formed on the surface of the platinum group metal on the substrate, the alkyl group is arranged on the SAM film, so that it becomes hydrophobic. This SAM film can be patterned using a photoresist by, for example, well-known photolithography etching. Since the patterned SAM film remains even after the resist is peeled off, this portion is hydrophobic. On the other hand, the portion from which the SAM film has been removed is hydrophilic because the platinum surface is exposed. Using this surface energy contrast, the PZT precursor solution can be applied separately. In the present embodiment, after the SAM film is selectively formed in a region where the PZT precursor solution is not applied, the PZT precursor solution is selectively applied by a solution coating method such as spin coating, or the PZT precursor solution. The PZT precursor solution is selectively applied by coating (inkjet coating) by a droplet discharge method that can reduce the amount of consumption.

  The vibration plate disposed on the silicon substrate may be a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a film obtained by stacking these films with a thickness of several microns. Further, a ceramic film such as an aluminum oxide film or a zirconia film in consideration of a difference in thermal expansion may be used. These materials are insulators.

  In addition, since the lower electrode is electrically connected as a common electrode for inputting a signal to the electromechanical transducer, an insulating material is used as a diaphragm located below the lower electrode, and insulation treatment is performed if it is a conductor. Will be used. When this diaphragm is formed of a silicon-based insulating film, a thermal oxide film or a CVD deposited film can be used. Moreover, when forming a diaphragm with a metal oxide film, it can form into a film by sputtering method.

  When a lower electrode made of a platinum group metal is disposed on the diaphragm, it is preferable to provide an adhesion layer between the lower electrode and the electromechanical conversion film in order to increase the adhesion of the electromechanical conversion film. As the material of this adhesion layer, titanium, tantalum, titanium oxide, tantalum oxide, titanium nitride, tantalum nitride, and a laminated film thereof are effective. On the other hand, when the lower electrode made of a conductive oxide film is disposed on the diaphragm, the diaphragm is the same oxide (silicon oxide). Sufficient adhesion of the conversion film can be obtained.

Drawing 1 (A)-(D) is an explanatory view showing an example of the 1st surface modification process in a manufacturing method of an electromechanical conversion element accompanied with formation of an electromechanical conversion film concerning one embodiment of the present invention. .
First, a thermal oxide film (film thickness: 1 [μm]) is formed on the surface of a substrate 11 made of a silicon wafer shown in FIG. 1A, and a titanium film (film thickness: 50 [nm]) is sputtered as an adhesion layer. The film is formed. Subsequently, a platinum film (thickness: 200 [nm]) made of a platinum group metal is formed by sputtering as the lower electrode. Here, in order to perform hydrophobic treatment (water repellent treatment) on the platinum film, a solution having a concentration of 0.01 [mol / liter] using phenyltrichlorosilane as a silane coupling agent (solvent: ethanol) Create and prepare. Hereinafter, a solution composed of the silane coupling agent is referred to as “SAM solution”, and hydrophobic treatment (water repellent treatment) using the silane coupling agent is referred to as “silane coupling agent treatment”.

  Next, an oxygen plasma treatment is performed as a pretreatment prior to the silane coupling agent treatment using the SAM solution on the platinum film as the lower electrode. In the case of the PE mode (chemical treatment), this oxygen plasma treatment requires a high-frequency output power (RF Power) to be set to 200 [W] or more and a treatment time of 5 minutes or more. This is because platinum is a chemically stable substance and therefore it is necessary to give sufficient energy.

  2 (a), 2 (b) and 2 (c) respectively show the surface of platinum (Pt) after performing the oxygen plasma treatment for 1 minute, 3 minutes and 5 minutes, respectively, by X-ray photoelectron spectroscopy (XPS). It is a graph which shows the XPS analysis result analyzed by X-ray Photoelectron Spectroscopy. The horizontal axis in the figure is the binding energy [eV] of the inner electrons of the target atom (platinum) calculated from the energy of the irradiated X-ray and the photoelectron, and the vertical axis is observed per unit time (1 second). The number of photoelectrons [counts / sec]. As shown in FIGS. 2A and 2B, when the time of the oxygen plasma treatment is 1 minute and 3 minutes, the increase in the measurement count value in the energy range corresponding to platinum oxide (PtOx or the like) is small. It can be seen that platinum is hardly oxidized. On the other hand, when the oxygen plasma treatment time is 5 minutes as shown in FIG. 2 (c), the measured count value in the energy range corresponding to platinum oxide (PtOx, etc.) greatly increases, and platinum is oxidized. You can see that

  In addition, although oxygen plasma processing was used as pre-processing of a silane coupling agent process, the same result is also obtained by processing using a surface processing apparatus (for example, an atmospheric pressure plasma apparatus, a UV ozone apparatus, etc.).

  After the above pretreatment, a silane coupling agent treatment is performed. More specifically, for example, the substrate 11 is immersed in the SAM solution for 5 minutes, and then the substrate 11 is washed with ethanol and dried. The hydrophobicity (water repellency) after the silane coupling agent treatment can be evaluated by measuring the contact angle of pure water. When the contact angle of pure water on a silane coupling agent monomolecular film (hereinafter referred to as “silane coupling agent film”) 12 was measured, it was 105 °, indicating hydrophobicity (water repellency). On the other hand, when the contact angle of pure water on the platinum sputtered film before the silane coupling agent treatment was measured, it was 5 ° or less (complete wetting). As described above, it was found that the silane coupling agent treatment for modifying the hydrophilicity on the platinum sputtered film to hydrophobic (water repellency) was performed by immersion in the SAM solution.

  Next, the hydrophobic region (water repellent region) and the hydrophilic region are patterned on the substrate 11 (see FIG. 1B) on which the silane coupling agent film 12 is formed by the silane coupling agent treatment. 1 is an example in which the silane coupling agent film 12 is partially removed by ultraviolet irradiation through the metal mask 13 (see FIG. 1C). By irradiating ultraviolet rays through the metal mask 13, as shown in FIG. 1D, the silane coupling agent film 12 remains in the unexposed area, and the silane coupling agent film 12 disappears in the exposed area. In this exposure, ultraviolet rays are irradiated for an irradiation time of, for example, 5 seconds or more. When the contact angle of pure water with respect to the area | region where the silane coupling agent film | membrane 12 was removed by ultraviolet exposure was measured, it was 5 degrees or less, and it became a hydrophilic area | region (complete wetting). Such a hydrophilic region means that the silane coupling agent film 12 was decomposed and disappeared from the surface of the platinum film on the substrate 11. By patterning the silane coupling agent film 12 as described above, the hydrophobic region (water repellent region) and the hydrophilic region can be patterned on the substrate 11.

  FIGS. 3A to 3D are explanatory views showing another example of the first surface modification step in the method for manufacturing an electromechanical conversion element involving the formation of an electromechanical conversion film according to the present embodiment. is there. The example of FIG. 3 is an example in which photolithography etching is used for patterning a hydrophobic region (water repellent region) and a hydrophilic region. In this example, the same pretreatment and silane coupling agent treatment as in FIG. 1 are performed (see FIGS. 3A 'and 3B'). Thereafter, a photoresist (for example, a photoresist manufactured by Tokyo Ohka Co., Ltd., TSMR8800) is formed by spin coating, and a resist pattern 14 is formed by ordinary photolithography (see FIG. 3C ′), and oxygen plasma treatment is performed. Then, the exposed portion of the silane coupling agent film 12 is partially removed. The residual resist remaining after the patterning process of the silane coupling agent film 12 is dissolved and removed with, for example, acetone (see FIG. 3 (D ′)).

  In addition, when the contact angle of water was evaluated in the same manner as described above in the case of performing the surface modification step of FIG. 3, the surface of the hydrophilic region from which the silane coupling agent film 12 was removed was 5 ° or less (completely wetted). )Met. On the other hand, the region covered with the resist, that is, the surface of the hydrophobic region where the silane coupling agent film 12 remains, was 92.4 °. As described above, it was confirmed that the silane coupling agent film 12 was patterned.

4 (D) to (F) and (D ′) to (F ′) show the first surface modification step in the method of manufacturing an electromechanical transducer element that involves the formation of an electromechanical transducer film according to this embodiment. It is explanatory drawing which shows an example of the process after complete | finishing.
After the first surface modification step using the silane coupling agent shown in FIG. 4D is completed, an electromechanical conversion film is formed on the substrate on which the water-repellent / hydrophilic region is patterned. In this embodiment, a PZT (53/47) film is formed as the electromechanical conversion film.

  The PZT precursor solution as a coating solution used for forming the electromechanical conversion film is synthesized using, for example, lead acetate trihydrate, isopropoxide titanium, or isopropoxide zirconium as a starting material. Crystal water of lead acetate was dissolved in methoxyethanol and then dehydrated. In addition, lead acetate makes the lead amount 10 [mol%] excess with respect to the stoichiometric composition. This is to prevent crystallinity deterioration due to so-called lead loss during heat treatment. Isopropoxide titanium and isopropoxide zirconium are dissolved in methoxyethanol, alcohol exchange reaction and esterification reaction are advanced, and a PZT precursor solution is synthesized by mixing with the methoxyethanol solution in which the lead acetate is dissolved. The concentration of the PZT precursor in the PZT precursor solution is, for example, 0.1 [mol / liter]. Here, the film thickness obtained by film formation by one application of the PZT precursor solution is preferably, for example, 100 [nm], and the concentration of the PZT precursor is the relationship between the film formation area and the application amount of the PZT precursor solution. It is optimized from. Therefore, the concentration of the PZT precursor in the PZT precursor solution is not limited to 0.1 [mole / liter] exemplified above.

  The PZT precursor solution 15 is applied to the surface of the platinum film on the substrate 11 (see FIG. 4D) on which the hydrophobic region and the hydrophilic region have been patterned by the silane coupling agent treatment, for example, by spin coating. Is done. Here, on the silane coupling agent film 12 in the hydrophobic region, the coating film of the PZT precursor solution 15 is not formed by the centrifugal force action during spinning, and the coating film of the PZT precursor solution 15 is formed only in the hydrophilic region. (See FIG. 4E).

  Next, heat treatment is performed at a predetermined drying temperature (for example, 120 [° C.]) as a first heating step (drying step), and then, predetermined heat for thermally decomposing organic matter as a second heating step (thermal decomposition step). Heat treatment is performed at a decomposition temperature (for example, 500 [° C.]). Thereby, as shown in FIG. 4F, a PZT film 16 as an electromechanical conversion film having a predetermined film thickness (for example, 90 [nm]) can be obtained. At this time, the contact angle of water on the surface where the silane coupling agent film 12 was formed and was a hydrophobic region was 5 ° or less. This means that the silane coupling agent film 12 was decomposed by the heat treatment at the thermal decomposition temperature (for example, 500 [° C.]) in the second heating step (thermal decomposition step). Further, as shown in FIG. 5, the platinum oxide oxidized in the above-described pretreatment (oxygen plasma treatment) is reduced to platinum by the heat treatment in the second heating step (pyrolysis step). Was obtained from XPS analysis.

  The effect of the oxygen plasma treatment performed in the pretreatment described above is mainly due to four control factors: (1) treatment time, (2) high frequency output power (RF Power), (3) distance between electrodes, (4) Varies with oxygen flow rate. FIG. 6 is a graph showing the results of examining the effect of the oxygen plasma treatment while changing the conditions (1 minute, 3 minutes, and 5 minutes) that are the easiest to handle as control factors. The vertical axis on the left side corresponding to the data of the symbol ■ in FIG. 6 is the ratio [atm%] of platinum oxide after the oxygen plasma treatment obtained from the XPS analysis result. Also, the vertical axis on the right side corresponding to the data marked with ● is the contact angle of pure water measured on the silane coupling agent film after the silane coupling agent treatment after the oxygen plasma treatment. From the results of FIG. 6, the longer the time of the oxygen plasma treatment, the higher the ratio of platinum oxide and the larger the contact angle of pure water on the silane coupling agent film, that is, on the silane coupling agent film. It turns out that the hydrophobicity of increases.

In the second and subsequent surface modification steps to the PZT film formation step shown in FIGS. 4D 'to 4', a water repellent treatment using a thiol compound in the surface modification step for patterning the hydrophobic region and the hydrophilic region. To implement. The process of repeating the water-repellent treatment (hereinafter referred to as “thiol treatment”) using this thiol compound and the formation of the PZT film can be simplified as in the following steps (1) to (3).
(1) A thiol film using a thiol compound cannot be formed on an oxide thin film. Therefore, as shown in FIG. 4D ′, the thiol film 17 is formed only on the surface where the PZT film 16 is not formed in the first surface modification process to the PZT film formation process, that is, the surface where the platinum film is exposed. Is formed.
(2) In the second and subsequent coating steps of the PZT precursor solution 15, as shown in FIG. 4E ′, the PZT precursor solution 15 is coated only on the surface of the hydrophilic PZT film 16 without the thiol film 17. The PZT precursor solution 15 is not applied to the exposed surface of the hydrophobic platinum film on which the thiol film 17 is formed. After the PZT precursor solution 15 is separately applied, the above-described heat treatment (drying and pyrolysis) is performed, so that the PZT film 18 having a thick film thickness is formed as shown in FIG. Is formed.
(3) The second and subsequent surface modification steps to PZT film formation steps shown in FIGS. 4D ′ to F ′ are repeated until a desired film thickness is obtained.
Through the steps (1) to (3), a PZT film having a thickness of about 5 [μm] can be formed.

In more specific examples of the second and subsequent surface modification steps to the PZT film formation step, a PZT film could be formed as described below.
First, the surface of the substrate 11 after the first and subsequent surface modification steps to the PZT film forming step is washed with isopropyl alcohol, and then the substrate 11 is immersed in a SAM solution using a thiol compound. A film (SAM film) was formed. Here, since the contact angle of pure water on the PZT film 16 is about 92.0 °, no thiol film is formed. On the other hand, on the surface portion where the platinum film without the PZT film 16 is exposed, the contact angle of pure water is 5 ° or less (complete wetting), and the thiol film thus formed is formed. Is done. And after patterning of this thiol film | membrane, the coating film of the following PZT precursor solution 15 was formed only in the surface part with the PZT film | membrane 16 by apply | coating the PZT precursor solution 15 with a spin coat method. Thereafter, the above-mentioned heat treatment (drying at 120 [° C.] and thermal decomposition at 500 [° C.]) was carried out, whereby the PZT film 18 that had been overcoated twice was formed. The film thickness of the twice coated PZT film 18 was 180 [nm].

The second and subsequent surface modification steps to the PZT film formation step (thiol treatment → selective application of the PZT precursor solution 15 → 120 [° C.] drying → 500 [° C.] thermal decomposition) are repeated 6 times, 540 [nm After crystallization heat treatment (temperature 700 [° C.]), RTA (rapid heat treatment) was performed. As a result, no defects such as cracks occurred in the PZT film.
Further, the second and subsequent surface modification steps to the PZT film formation step (thiol treatment → selective application of the PZT precursor solution 15 → 120 [° C.] drying → 500 [° C.] thermal decomposition) are repeated 6 times to obtain crystals. The heat treatment (temperature 700 [° C]) was performed. As a result, the PZT film did not have defects such as cracks, and the thickness of the PZT film reached 1000 [nm].

An upper electrode (platinum) was formed on the patterned PZT film having a thickness of 1000 [nm], and electrical characteristics and electro-mechanical conversion ability (piezoelectric constant) were evaluated. As a result, a hysteresis curve of P (polarization) -E (electric field strength) in FIG. 7 is obtained. The relative permittivity of the PZT film is 1220, the dielectric loss is 0.02, and the residual polarization is 19.3 [μC / cm ^2. The coercive electric field was 36.5 [kV / cm], and it was found that the coercive electric field had the same characteristics as a normal ceramic sintered body. In addition, the electromechanical conversion ability was calculated by measuring the amount of deformation by applying an electric field with a laser Doppler vibrometer and fitting it by simulation. The piezoelectric constant d31 was −120 [pm / V], which was also the same value as the ceramic sintered body. This value is a characteristic value that can be sufficiently designed as a piezoelectric element for use in a liquid discharge head.

  On the other hand, an attempt was made to further increase the thickness of the PZT film without disposing the upper electrode (second electrode) made of platinum. That is, the surface modification step, the coating step, the drying step (temperature 120 [° C]) and the thermal decomposition step (temperature 500 [° C]) were repeated 6 times and the subsequent crystallization treatment was repeated 10 times. As a result, a patterned PZT film having a total film thickness of 5 [μm] could be obtained without defects such as cracks.

  In addition, in the example of six repetitions of the above-described second and subsequent surface modification steps to the PZT film formation step, a case where thiol treatment, selective application of the PZT precursor solution 15, drying, and thermal decomposition are repeated a plurality of times is shown. However, the thiol treatment and the selective application and drying of the PZT precursor solution 15 may be repeated a plurality of times. In this case, after repeating the thiol treatment and the selective application and drying of the PZT precursor solution 15 a plurality of times, the thermal decomposition treatment and the crystallization treatment are performed.

FIG. 8 is an explanatory diagram showing an example of a droplet discharge device that can be used in a method for manufacturing an electromechanical transducer element that involves the formation of an electromechanical transducer film according to another embodiment of the present invention. In the present embodiment, the droplet discharge apparatus shown in FIG. 8 is used to form the upper electrode (second electrode) made of platinum, and only necessary portions on the PZT film 16 formed on the lower electrode 11a of the substrate 11 are used. Then, a liquid (platinum ink) 251 containing a platinum material was applied with a platinum ink discharge head 250 as a liquid discharge head and dried. Other steps were performed in the same manner as the embodiment described with reference to FIGS. When applying a platinum ink containing a platinum material, the application area was defined using the contact angle contrast in the same manner as when the PZT precursor solution 15 was applied. Since it is necessary to apply the upper electrode to a region smaller than the pattern of the PZT film 16 in order to prevent a short circuit, it is necessary to provide a water repellent part (hydrophobic surface) also on the PZT film 16. Therefore, in this embodiment, the above-described silane coupling agent treatment was performed, and the silane coupling agent film 12 was formed on the entire substrate 11. Then, using the metal mask, the part which does not form platinum was irradiated with ultraviolet rays, and the silane coupling agent film 12 was patterned. After that, the liquid discharge head 250 discharges the platinum ink droplets 251 containing the platinum material for application, and after the landing platinum ink is dried at 120 [° C.], the final 250 [° C.] is applied. Sintered with. The film thickness of the upper electrode (second electrode) made of platinum after firing was 0.5 [μm], and the specific resistance (volume resistivity) was 5 × 10 ⁻⁶ [Ωcm].

  FIG. 9 is a schematic configuration diagram illustrating a configuration example of the liquid discharge head 50 configured using the electromechanical transducer (PZT element) manufactured by the manufacturing method of the above embodiment. In the illustrated example, a diaphragm 30, an adhesion layer 41, and a lower electrode (first electrode) 42 are stacked on a silicon substrate 20 serving as a liquid chamber substrate in which a liquid chamber (pressure chamber) 20a is formed. Electromechanical transducer elements (PZT elements) 43 and upper electrodes 44 having performance equivalent to that of bulk ceramics can be patterned and formed on predetermined portions on the electrodes (first electrodes) 42 by the above simple manufacturing method. it can. Thereafter, the liquid chamber 21 is formed from the back surface (the lower surface in the drawing) of the silicon substrate 20 by an etching removal process, and the nozzle plate 22 having the nozzle holes 21 is joined, whereby the liquid discharge head 50 can be manufactured. In the figure, descriptions of the liquid supply means, the flow path, and the fluid resistance are omitted. Further, a plurality of the liquid discharge heads 50 in FIG. 8 can be arranged as shown in FIG.

FIG. 11 is a schematic configuration diagram showing a configuration example of an image forming apparatus which is an example of a droplet discharge device that can use an electromechanical transducer manufactured by the above manufacturing method. FIG. 12 is a schematic perspective view of the image forming apparatus. The illustrated image forming apparatus is an example of an ink jet recording apparatus 100 equipped with a droplet discharge head including an electromechanical conversion element manufactured by the above-described electromechanical conversion element manufacturing method according to the present embodiment.
An ink jet recording apparatus 100 mainly includes a carriage 101 that can move in the main scanning direction inside the recording apparatus main body, and an ink jet head that is an example of a droplet discharge head that is mounted on the carriage 101 and is manufactured by implementing the present invention. And a printing mechanism unit 104 including an ink cartridge 103 that supplies ink to the recording head 102. In addition, a sheet feeding cassette 106 capable of stacking a large number of sheets 105 can be detachably attached to the lower part of the apparatus main body from the front side, and a manual feed tray 107 for manually feeding sheets 105 is provided. The paper 105 fed from the paper feed cassette 106 or the manual feed tray 107 can be taken in, and a required image is recorded by the printing mechanism 104, and then discharged to a paper discharge tray 108 mounted on the rear side. Make paper. The printing mechanism unit 104 holds a carriage 101 slidably in the main scanning direction by a main guide rod 109 and a sub guide rod 110 which are guide members horizontally mounted on left and right side plates (not shown). (Y), cyan (C), magenta (M), and black (Bk) ink droplets are ejected from a recording head 102, which is an example of a droplet ejection head according to the present invention that ejects ink droplets of each color. Outlets (nozzles) are arranged in a direction crossing the main scanning direction, and are mounted with the ink droplet ejection direction facing downward. In addition, each ink cartridge 103 for supplying ink of each color to the recording head 102 is replaceably mounted on the carriage 101. The ink cartridge 103 has an air port that communicates with the atmosphere upward, a supply port that supplies ink to the recording head 102 below, and a porous body filled with ink inside. The ink supplied to the recording head 102 by the force is maintained at a slight negative pressure. Further, although the heads of the respective colors are used here as the recording heads 102, a single head having nozzles for ejecting ink droplets of the respective colors may be used. Here, the carriage 101 is slidably fitted to the main guide rod 109 on the rear side (downstream side in the paper conveyance direction), and is slidably mounted on the sub guide rod 110 on the front side (upstream side in the paper conveyance direction). doing. Then, in order to move and scan the carriage 101 in the main scanning direction, as shown in FIG. 12, a timing belt 114 is stretched between a driving pulley 112 and a driven pulley 113 that are rotationally driven by a main scanning motor 111. The timing belt 114 is fixed to the carriage 101, and the carriage 101 is reciprocated by forward and reverse rotation of the main scanning motor 111.

  On the other hand, in order to convey the paper 105 set in the paper feed cassette 106 to the lower side of the recording head 102, the paper feed roller 115 and the friction pad 116 for separating and feeding the paper 105 from the paper feed cassette 106 and the paper 105 are guided. A guide member 117 that rotates, a conveyance roller 118 that reverses and conveys the fed paper 105, a conveyance roller 119 that is pressed against the peripheral surface of the conveyance roller 118, and a feeding angle of the sheet 105 from the conveyance roller 118. A tip roller 120 is provided. The transport roller 118 is rotationally driven by a sub-scanning motor 121 through a gear train. A printing receiving member 122 is provided as a paper guide member that guides the paper 105 fed from the transport roller 118 on the lower side of the recording head 102 corresponding to the movement range of the carriage 101 in the main scanning direction. A conveyance roller 123 and a spur 124 that are rotationally driven to send the paper 105 in the paper discharge direction are provided on the downstream side of the printing receiving member 122 in the paper conveyance direction, and the paper 105 is further delivered to the paper discharge tray 108. A roller 125 and a spur 126, and guide members 127 and 128 that form a paper discharge path are disposed. At the time of recording, the recording head 102 is driven in accordance with the image signal while moving the carriage 101, thereby ejecting ink onto the stopped paper 105 to record one line. Record the line. Upon receiving a recording end signal or a signal that the trailing edge of the paper 105 has reached the recording area, the recording operation is terminated and the paper 105 is discharged. Further, a recovery device 129 for recovering the ejection failure of the recording head 102 is disposed at a position outside the recording area on the right end side in the movement direction of the carriage 101. The recovery device 129 includes a cap unit, a suction unit, and a cleaning unit. The carriage 101 is moved to the recovery device 129 side during printing standby, and the recording head 102 is capped by the capping means, and the ejection port portion is kept in a wet state to prevent ejection failure due to ink drying. Further, by ejecting ink that is not related to recording during recording or the like, the ink viscosity of all the ejection ports is made constant and stable ejection performance is maintained.

  In addition, this invention is not limited to the said embodiment and Example, It cannot be overemphasized that various deformation | transformation and substitution are possible if it is description in a claim.

What has been described above is merely an example, and the present invention has a specific effect for each of the following modes.
(Aspect A)
A surface modification step for partially modifying the surface of the first electrode and a coating solution containing a raw material for forming an electromechanical conversion film are selectively applied to a predetermined portion on the first electrode. A coating step of drying, a drying step of drying a film of the coating solution applied on the first electrode, and a crystallization step of thermally decomposing and crystallizing the film of the dried coating solution, The surface modification step, the coating step, and the drying step are a method of manufacturing an electromechanical conversion film that is repeated a plurality of times in the order, and the first surface modification step is performed on the first electrode. In this step, after the silane coupling agent film is formed, the silane coupling agent film is partially removed.
According to this, as described in the embodiment, at least the surface modification process, the coating process, and the drying process among the surface modification process, the coating process, the drying process, and the crystallization process are performed in that order. By repeating a plurality of times, an electromechanical conversion film having a predetermined pattern and film thickness can be formed.
Further, the first surface modification step repeated a plurality of times is a step of partially removing the silane coupling agent film after forming the silane coupling agent film on the first electrode. This silane coupling agent film can be adsorbed to the first electrode regardless of whether the material of the first electrode is organic or inorganic, and can be partially removed by irradiation with ultraviolet rays. Accordingly, it is possible to maintain the adsorptivity with the first electrode and the hydrophobicity (water repellency) with respect to the coating liquid and prevent the coating liquid from being reliably applied to the portion where the silane coupling agent film is desired to remain. . On the other hand, the part where the film of the silane coupling agent is to be removed can be easily removed by using a relatively inexpensive apparatus or method using ultraviolet irradiation to make the coating liquid hydrophilic, and the coating liquid can be reliably applied. Can be done.
Therefore, it is possible to easily form an electromechanical conversion film having a desired pattern and film thickness while reducing the manufacturing cost.
(Aspect B)
In the above aspect A, the electromechanical conversion film includes a metal oxide, the first electrode includes a noble metal, and a film of a thiol compound is formed on the first electrode after the second surface modification step. Then, the thiol compound film is partially removed. According to this, as described in the above embodiment, the thiol compound is difficult to wet with respect to the electromechanical conversion film including the metal oxide formed by the first surface modification process, the coating process, and the drying process. It exhibits hydrophobicity and hydrophilicity that is easy to wet with respect to the first electrode containing a noble metal. In the second and subsequent surface modification steps, using the characteristics of this thiol compound, the first electrode in which the electromechanical conversion film is partially formed in the first step is immersed in a liquid containing the thiol compound. The surface modification of a desired pattern becomes possible by the simple operation of doing. That is, the portion where the electromechanical conversion film is formed on the first electrode in the first step does not form a thiol compound film even when immersed in a liquid containing a thiol compound. Can be surely held. On the other hand, the portion where the electromechanical conversion film is not formed in the first step and the first electrode is exposed forms a thiol compound film when immersed in a liquid containing a thiol compound. Sexually can be given. In this way, by immersing in a solution containing a thiol compound, an electromechanical conversion film is not formed in the first step, and a thiol compound film is formed only on a portion where the first electrode is exposed. Thus, it is possible to modify the surface of the desired pattern so as to ensure hydrophobicity with respect to the coating solution.
(Aspect C)
In the above aspect A or aspect B, partial removal of the film of the silane coupling agent is performed by ultraviolet irradiation through a mask or photolithography etching. According to this, as described in the above embodiment, the film of the silane coupling agent is decomposed and partially removed by ultraviolet irradiation through a mask or photolithography etching, and hydrophilicity is removed from the hydrophobic surface. The surface can be reliably changed.
(Aspect D)
In any of the above aspects A to C, the silane coupling agent has a hydrolyzable group and an alkyl group or a fluorine-containing functional group. According to this, as described in the above embodiment, even if the material to be surface-modified is an inorganic material, it can be adsorbed to the surface of the inorganic material by a hydrolyzable group. Furthermore, by having an alkyl group or a fluorine-containing functional group as the reactive functional group, hydrophobicity (water repellency) can be reliably exhibited with respect to the coating solution.
(Aspect E)
In any of the above aspects A to D, a pretreatment step of performing oxygen plasma treatment on the surface of the first electrode before forming the silane coupling agent film in the first surface modification step including. According to this, as described in the above embodiment, the surface of the first electrode is formed by oxidizing the surface of the first electrode by the oxygen plasma treatment and then forming a silane coupling agent film. The effect of changing from hydrophilic to hydrophobic can be enhanced.
(Aspect F)
A method for manufacturing an electromechanical conversion element, wherein a first electrode is formed on a substrate, and the electromechanical conversion is performed on the first electrode by the method for manufacturing an electromechanical conversion film according to any one of aspects A to E. A film is formed, and a second electrode is formed on the electromechanical conversion film. According to this, as described in the above embodiment, it is possible to easily manufacture an electromechanical conversion element having an electromechanical conversion film having a desired pattern and thickness while reducing the manufacturing cost.
(Aspect G)
An electromechanical conversion element, wherein a first electrode, an electromechanical conversion film, and a second electrode are formed on a substrate by the method for manufacturing an electromechanical conversion element of aspect F above. According to this, as described in the above embodiment, it is possible to provide an inexpensive electromechanical conversion element having an electromechanical conversion film having a desired pattern and film thickness that is easily manufactured while reducing the manufacturing cost.
(Aspect H)
A droplet discharge head including the electromechanical conversion element according to the above aspect G. According to this, as described in the above embodiment, an inexpensive liquid in which an electromechanical conversion element having an electromechanical conversion film having a desired pattern and a film thickness, which is easily manufactured while reducing the manufacturing cost, is incorporated. A droplet discharge head can be provided.
(Aspect I)
A liquid droplet ejection apparatus including the liquid droplet ejection head of the above aspect H. According to this, as described in the above embodiment, an inexpensive liquid in which an electromechanical conversion element having an electromechanical conversion film having a desired pattern and a film thickness, which is easily manufactured while reducing the manufacturing cost, is incorporated. A droplet discharge device can be provided. (Aspect J)
An image forming apparatus including the droplet discharge head according to aspect H. According to this, as described in the above embodiment, an inexpensive image in which an electromechanical conversion element having an electromechanical conversion film having a desired pattern and a film thickness that is easily manufactured while reducing the manufacturing cost is incorporated. A forming apparatus can be provided.

11 Substrate 11a Lower electrode 12 Silane coupling agent film (monomolecular film of silane coupling agent)
13 Metal mask 13 Photoresist,
14 resist pattern 15 PZT precursor solution (coating solution)
16 PZT film (electromechanical conversion film)
17 Thiol film (Monomolecular film of thiol compound)
18 Stacked PZT film 19 Upper electrode 20 Silicon substrate 20a Liquid chamber 21 Nozzle hole 22 Nozzle plate 30 Vibrating plate 41 Adhesion layer 42 Lower electrode 43 Electromechanical transducer (PZT element)
44 Upper electrode 50 Liquid discharge head 100 Inkjet recording apparatus 102 Recording head (inkjet head)

JP 2003-297825 A JP 2006-176385 A JP 2011-9726 A

K. D. Budd, S.M. K. Day and D.D. A. Payne, Proc. Brit. Ceram. Soc. 36, 107 (1985) A. Kumar and G.K. M.M. Whitesides, Appl. Phys. Lett. 63, 2002 (1993)

Claims (4)

An electrode forming step of forming a first electrode made of a platinum group metal on a substrate;
A pretreatment step of performing oxygen plasma treatment on the surface of the first electrode;
After forming a film of partially silane coupling agent to the surface of the first electrode, and the first surface modification step of surface modification by removing a film of the silane coupling agent partially ,
A first application step of selectively applying a coating solution containing a PZT precursor solution for forming an electromechanical conversion film containing a metal oxide to a predetermined portion on the first electrode;
A drying step of drying a film of the coating liquid applied on the first electrode;
A crystallization step of forming a PZT film for thermally decomposing and crystallizing the dried coating liquid film ;
By immersing the substrate after the crystallization step in a liquid containing a thiol compound, a thiol film of the thiol compound is formed on the surface of the first electrode where the PZT film is not formed. The second and subsequent surface modification steps;
The coating solution is applied only to the surface of the hydrophilic PZT film without the thiol film, and the coating solution is not applied to the exposed surface of the hydrophobic first electrode on which the thiol film is formed. A coating process for the second and subsequent coatings,
And said second and subsequent surface modification step and the second and subsequent coating step and the drying step and the crystallization step, by executing repeatedly a plurality of times in this order, the first on the electrode electromechanical transducer film is formed, the manufacturing method of electromechanical transducer and forming a second electrode on the electromechanical transducer layer on the. In the manufacturing method of electromechanical transducer of 請 Motomeko 1,
Method for manufacturing electromechanical transducer, characterized in that the partial removal of film of the silane coupling agent is carried out by ultraviolet irradiation or photolithography etching through a mask. In the manufacturing method of electromechanical transducer of claim 1 or 2,
The said silane coupling agent has a hydrolysable group and an alkyl group or a fluorine-containing functional group, The manufacturing method of the electromechanical conversion element characterized by the above-mentioned . Droplets of manufacturing a droplet discharge head by laminating a and 請 Motomeko 1 to any of the substrate where the liquid chamber to the electromechanical conversion element manufactured by the manufacturing method is formed of the electro-mechanical conversion element 3 vibration plate Manufacturing method of the discharge head .

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