JP2013065633A - Manufacturing method of electromechanical conversion film, manufacturing method of electromechanical conversion element, electromechanical conversion element manufactured by that manufacturing method, liquid droplet ejection head and liquid droplet ejection device - Google Patents

Abstract

An electromechanical conversion film having a desired pattern can be formed.
A bank forming solution 15 including a part of a component of a PZT precursor solution 17 is selectively applied to a predetermined portion on a first electrode of a substrate 11 by a droplet discharge head 14, thereby The bank film 16 formed so as to surround a predetermined portion on the first electrode rises toward the periphery of the predetermined portion. Then, the bank film 16 is dried to form a bank. A droplet of the PZT precursor solution 17 containing the raw material for forming the electromechanical conversion film 18 is applied to the predetermined portion surrounded by the bank by discharging it from the nozzle of the droplet discharge head 14.
[Selection] Figure 1

Description

  The present invention relates to an electromechanical conversion film manufacturing method, an electromechanical conversion element manufacturing method, an electromechanical conversion element manufactured by the manufacturing method, a droplet discharge head, and a droplet discharge apparatus.

  Conventionally, an electromechanical conversion element configured such that an electromechanical conversion film is sandwiched between electrodes includes, for example, a liquid discharge head that discharges ink droplets, and forms an image by adhering ink droplets to a sheet while conveying a medium. Used in an ink jet recording apparatus. The medium here is also referred to as “paper”, but the material is not limited, and a recording medium, a recording medium, a transfer material, a recording paper, and the like are also used synonymously. The image forming apparatus means an apparatus for forming an image by discharging a liquid onto a medium such as paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics. The image formation is not only giving an image having a meaning such as a character or a figure to the medium but also giving an image having no meaning such as a pattern to the medium (simply ejecting a droplet). Also means. The ink is not limited to so-called ink, and is not particularly limited as long as it becomes liquid when ejected. For example, the ink is a generic term for liquids including DNA samples, resists, pattern materials, and the like. Use.

  The inkjet recording apparatus mainly includes a nozzle that ejects ink droplets, a discharge chamber that communicates with the nozzle, a liquid chamber that is referred to as a pressurized liquid chamber, a pressure chamber, an ink flow path, and the like, and ink in the liquid chamber. And pressure generating means for discharging. 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. The electromechanical conversion layer is formed by performing the process of forming the electromechanical conversion film a plurality of times. As the electromechanical conversion film, lead zirconate titanate (PZT) ceramics or the like is used, and these are generally referred to as metal composite oxides because they are mainly composed of a plurality of metal oxides.

  As a method for producing this electromechanical conversion film, there are a sputtering method, a sol-gel method, a CVD method, a laser ablation method, and the like. Of these, the sol-gel method for forming a film by the steps of sol coating, drying, degreasing, and baking is the method. Excellent controllability of the crystalline state. As a method for producing an electromechanical conversion film using this sol-gel method, one described in Patent Document 1 is known. In the manufacturing method of Patent Document 1, the coating liquid is applied to a predetermined portion on a platinum (Pt) electrode by 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 patterned by dripping. And the film | membrane of the said coating liquid dripped on the electrode is dried, the film | membrane of the dried coating liquid is thermally decomposed and crystallized, and the electromechanical conversion film | membrane is formed.

  However, in the manufacturing method of Patent Document 1, since the viscosity of the coating solution is low, the coating solution dropped on the platinum (Pt) electrode spreads on the electrode. For this reason, the desired pattern of the electromechanical conversion film has collapsed.

  The present invention has been made in view of the above problems, and its object is to provide an electromechanical conversion film manufacturing method capable of forming an electromechanical conversion film having a desired pattern, an electromechanical conversion element manufacturing method, To provide an electromechanical conversion element, a droplet discharge head, and a droplet discharge device manufactured by a manufacturing method.

  In order to achieve the above object, the invention of claim 1 is a coating step of selectively applying a coating solution containing a raw material for forming an electromechanical conversion film to a predetermined portion on a first electrode; In the method for producing an electromechanical conversion film, the method includes a drying step of drying a film of the coating liquid applied onto one electrode, and a crystallization step of thermally decomposing and crystallizing the dried film of the coating liquid. In the coating step, a bank film forming solution containing a part of the components of the coating solution is applied to a predetermined portion on the first electrode, and the bank film forming solution is predetermined on the first electrode by the coffee stain phenomenon. A bank film forming step of forming a bank film so as to flow toward the periphery of the portion and rise at the periphery to surround a predetermined portion on the first electrode; and drying the bank film along the periphery of the predetermined portion Bank formation worker to form a bank And performing the solution coating step and the bank forming step, coating the coating liquid on the inner side surrounded by the formed bank, performing the drying step and the crystallization step, and performing the electromechanical conversion. A film is manufactured.

  In the present invention, when the droplet of the coating liquid containing the raw material for forming the electromechanical conversion film is ejected from the nozzle and selectively applied to a predetermined portion on the first electrode, After the bank film is formed, a predetermined portion on the first electrode is surrounded by the bank formed in the back formation step. By applying the coating liquid to a predetermined portion on the inner first electrode surrounded by the bank, the coating liquid is prevented from spreading and the coating liquid is applied only to the predetermined portion on the first electrode. Thereby, an electromechanical conversion film having a desired pattern can be formed.

  According to the present invention, there is an effect that an electromechanical conversion film having a desired pattern can be formed.

It is process sectional drawing which shows the manufacturing process of the electromechanical conversion film which concerns on one Embodiment of this invention. It is a characteristic view which shows an example of the PE hysteresis curve of the PZT film | membrane produced in the Example. 1 is a perspective view showing a configuration of a droplet discharge coating apparatus equipped with a droplet discharge head according to an embodiment. It is explanatory drawing which shows each mode of the contact angle of the pure water in the electrode exposure surface which removed the SAM film, and the surface where the SAM film has been arrange | positioned. It is a schematic block diagram which shows the example of 1 structure of the liquid discharge head comprised using the electromechanical conversion element manufactured with the manufacturing method of this embodiment. FIG. 6 is a schematic configuration diagram illustrating a configuration example in which a plurality of liquid ejection heads of FIG. 5 are arranged. It is a schematic block diagram which shows one structural example of the droplet discharge apparatus which can use the electromechanical conversion element manufactured with the manufacturing method of this embodiment. It is a perspective view which shows one structural example of a droplet discharge apparatus.

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

  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 synthesized by the above method was used.

  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.

  Further, when obtaining a patterned PZT film as an electromechanical conversion film on the surface of the first electrode on the base substrate, a coating film is formed by applying the above solution as a coating liquid by a droplet discharge method. A patterned PZT film can be obtained by performing heat treatments of solvent drying, thermal decomposition, and crystallization. Since transformation from the coating film to the crystallized film involves volume shrinkage, it is preferable to obtain a film thickness of 100 [nm] or less in one step in order to obtain a crack-free film. And it is preferable to adjust so that a precursor density | concentration may be optimized from the relationship between the film-forming area of an electromechanical conversion film, and the application quantity of a 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 base substrate is controlled is separately applied. This utilizes the phenomenon of alkanethiol self-arranged on a specific metal shown in Non-Patent Document 2, and first, a SAM (Self assembled monolayer) film of thiol on the surface of the platinum group metal of the substrate. Form. Since the alkyl group is arranged on the SAM film, 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, as shown below, the droplet discharge method can reduce the consumption of the PZT precursor solution. The PZT precursor solution is selectively applied by coating (inkjet coating).

FIG. 1 is a process cross-sectional view illustrating a manufacturing process of an electromechanical transducer including formation of an electromechanical transducer film according to an embodiment of the present invention. A platinum electrode made of a platinum group metal (not shown) as a first electrode excellent in reactivity with thiol is formed on the surface (upper surface) of the substrate 11 shown in FIG. Yes. A SAM film 12 is formed on the surface of the platinum electrode of the substrate 11 as shown in FIG. The SAM film 12 can be obtained by dipping the substrate 11 in an alkanethiol solution and making it self-align. In this example, an alkanethiol solution obtained by dissolving alkanethiol molecules of CH ₃ (CH ₂ ) -SH in a general organic solvent (alcohol, acetone, toluene, etc.) at a predetermined concentration (for example, several mol / l) is used. Using. After immersing the substrate 11 in this alkanethiol solution and taking it out after a predetermined time, the SAM film 12 can be formed on the surface of the platinum electrode by replacing and washing excess molecules with a solvent and drying. Next, as shown in (c) of the figure, a photoresist 13 is patterned by photolithography, and dry etching (for example, oxygen plasma irradiation or UV light irradiation) is performed as shown in (d) of the figure. Then, the SAM film 12 is removed, and the photoresist 13 used for processing is removed, and the patterning of the SAM film 12 is completed. The SAM film 12 thus formed has a contact angle with respect to pure water of, for example, 92 degrees and exhibits hydrophobicity. On the other hand, the surface of the platinum electrode of the substrate 11 exposed by removing the SAM film 12 has a contact angle with pure water of, for example, 54 degrees and is hydrophilic. Even if the patterned SAM film of FIG. 1D is obtained by forming a photoresist pattern at the pattern position of the electromechanical conversion film on the substrate 11 and performing SAM treatment and removing the photoresist pattern. Good. Further, as shown in FIG. 1B, after the SAM film 12 is formed, the SAM film 12 remains in the unexposed area by irradiating ultraviolet rays through the mask, and the SAM film 12 remains in the exposed area. By disappearing, the patterned SAM film of FIG. 1D may be obtained.

  Next, after the step (d) of FIG. 1 is performed, a droplet discharge method, specifically, is applied to the surface of the platinum electrode of the substrate 11 exposed by removing the patterned SAM film 12 from the back forming solution 15. Specifically, it was applied by the droplet discharge head 14 (see (e) of FIG. 1). In a method other than the droplet discharge method, a dispenser method is used to apply a fixed amount. The bank forming solution 15 is a solution having the same composition as that of the PZT precursor solution but having a different solvent. The bank forming solution 15 is added with a solvent having a surface tension and a viscosity that forms a height necessary for forming the bank. The composition of this solvent varies depending on the desired bank height. Then, in the applied coating film of the bank forming solution 15, the coffee stain phenomenon occurs due to the surface energy difference between the lyophobic liquid and the lyophilic liquid, and the bank film 16 is formed. The coffee stain phenomenon is a phenomenon that occurs when a droplet in which a solute is dissolved in a solvent is dried. That is, the outer edge of the liquid film spread on the substrate, that is, the amount of evaporation at the peripheral portion is larger than that at other portions, so that the liquid flows toward the peripheral portion to compensate for it, and as a result, the peripheral portion rises after drying. This is a phenomenon in which a film is formed. Then, the bank film 16 is subjected to drying, organic matter decomposition, and crystallization treatment (see FIG. 1F). At this time, the height (thickness) of the bank film 16 was about 250 [nm]. Then, the PZT precursor solution 17 is applied in the bank by the droplet discharge head 14 (see (g) of FIG. 1). Thereafter, the coating process shown in FIG. 1G was repeated three times to obtain an electromechanical conversion film 15 having a thickness of 250 [nm], and then crystallization heat treatment (temperature 700 ° C.) was performed by RTA (rapid heat treatment). (See (h) in FIG. 1). The obtained electromechanical conversion film 18 did not have defects such as cracks.

  Further, SAM treatment is performed to form the SAM film 12 on the surface of the platinum electrode of the substrate 11 other than the electromechanical conversion film 18 (see (i) in FIG. 1). Then, the back forming solution 15 is applied to the electromechanical conversion film 18 by the droplet discharge head 14 to form the bank film 16 on the electromechanical conversion film 18 (see (j) of FIG. 1). The bank film 16 is subjected to drying, organic matter decomposition, and crystallization treatment (see (k) in FIG. 1). Then, the electromechanical conversion film 18 is obtained by applying the PZT precursor solution 17 by the droplet discharge head 14 in the bank, heat treatment of solvent drying, thermal decomposition, and crystallization ((l) in FIG. 1). (See (m)). The steps (j) to (m) in FIG. 1 are repeated until the electromechanical conversion film 18 has a desired thickness (see (n) in FIG. 1).

Moreover, after repeating the surface modification process, the coating process, the drying process, and the thermal decomposition process four times, a crystallization treatment was performed. As a result, the thickness of the PZT film reached 1000 [nm] without causing defects such as cracks. An electromechanical conversion film having a desired film thickness can be easily formed by applying a fixed amount of the PZT precursor solution at a time and repeating a series of steps. An electromechanical conversion element was formed by sputtering an upper electrode (second electrode) made of platinum on the patterned PZT film, and the electrical characteristics and electromechanical conversion ability (piezoelectric constant) were evaluated. As a result, a hysteresis curve of P (polarization) -E (electric field strength) in FIG. 2 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. Further, it is desirable that the film thickness of the bank film excluding the bank is smaller than the film thickness of the bank. The influence of the back-forming solution that contacts the first electrode, for example, poor connection can be reduced. Further, it is desirable that the film thickness of the bank is substantially the same as the film thickness of the electromechanical conversion film after the crystallization process. Leakage of the PZT precursor solution applied in the bank can be avoided.

  Furthermore, by using PT (lead titanate) or PZ (lead zirconate) instead of PZT as the bank forming solution, it is possible to suppress composition fluctuations due to differences in decomposition rates that occur in high temperature processes such as organic matter decomposition and crystallization. It is possible to suppress a decrease in breakdown voltage due to a composition shift at the end of the mechanical conversion film. Further, by performing crystallization treatment with a laser, damage due to heat outside the pattern, for example, accumulation of thermal stress and diffusion of each layer of the substrate can be reduced.

  FIG. 3 is a perspective view showing the configuration of a droplet discharge coating apparatus equipped with the droplet discharge head of this embodiment. According to the droplet discharge coating apparatus 60 shown in FIG. 3 equipped with the droplet discharge head 200 of the present embodiment, the Y-axis driving means 62 is installed on the gantry 61, and the substrate 63 (see FIG. 1 is mounted so that it can be driven in the Y-axis direction. The stage 64 is provided with suction means such as vacuum and static electricity (not shown), and the substrate 63 is fixed. An X-axis driving means 66 is attached to the X-axis support member 65, and a head base 68 mounted on the Z-axis driving means 67 is attached to the X-axis support member 65, so that it can move in the X-axis direction. ing. A liquid droplet ejection head 69 for ejecting liquid is mounted on the head base 68. Liquid (PZT precursor solution) is supplied to the droplet discharge head 69 from a liquid tank (not shown) through a supply pipe 70.

  Here, the solution used was lead acetate trihydrate, isopropoxide titanium, and normal butoxide zirconium as starting materials. Crystal water of lead acetate was dissolved in methoxyethanol and then dehydrated. The lead amount is 10 mol% excess relative to the stoichiometric composition. This is to prevent crystallinity deterioration due to so-called lead loss during heat treatment. PZT precursor solution was synthesized by dissolving isopropoxide titanium and normal butoxide zirconium in methoxyethanol, proceeding with alcohol exchange reaction and esterification reaction, and mixing with methoxyethanol solution in which lead acetate was dissolved. The PZT concentration was 0.1 [mol / l].

  Furthermore, when the lower electrode (first electrode) was formed from a sample on which an iridium metal or platinum film was disposed, the contact angle of pure water on the electrode exposed surface from which the SAM film 12 was removed was 5 ° or less in all samples. It was (completely wet) (see FIG. 4A). On the other hand, the contact angle of pure water on the surface where the SAM film 12 was placed was about 90 ° in all samples (see FIG. 4B).

  FIG. 5 is a schematic configuration diagram showing a configuration example of a droplet discharge head configured using an electromechanical transducer (PZT element) manufactured by the above manufacturing method. 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, and a predetermined on the lower electrode (first electrode) 42 is formed. The electromechanical conversion element (PZT element) 43 and the upper electrode 44 having the same performance as that of bulk ceramics can be patterned and formed on the portion by the simple manufacturing method described above. 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 droplet discharge heads 50 shown in FIG. 5 can be arranged as shown in FIG.

  FIG. 7 is a schematic configuration diagram showing a configuration example of a droplet discharge device that can use the electromechanical conversion element manufactured by the above manufacturing method. FIG. 8 is a schematic perspective view of the droplet discharge device. The droplet discharge apparatus of the present invention shown in both figures is equipped with a droplet discharge head including the electromechanical conversion element manufactured by the above-described method for manufacturing an electromechanical conversion element of the present invention. An ink jet recording apparatus 100 as an example of the droplet discharge apparatus of the present invention shown in both figures mainly includes a carriage 101 that can move in the main scanning direction inside the recording apparatus main body, and the present invention mounted on the carriage 101. The printing mechanism unit 104 is configured to include a recording head 102 including an inkjet head, which is an example of a liquid droplet ejection head manufactured as described above, and 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. In order to move and scan the carriage 101 in the main scanning direction, 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, and the timing belt 104 is moved to the carriage 101. The carriage 101 is reciprocally driven by forward and reverse rotations 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.

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 bank film forming solution having the same composition as that of the coating solution but having a different solvent is applied to a predetermined portion on the first electrode, and the bank film forming solution is directed toward the periphery of the predetermined portion on the first electrode by the coffee stain phenomenon. A bank film forming step of forming a bank film so as to flow and flow up at the periphery and surround a predetermined portion on the first electrode; and a bank formation step of drying the bank film to form a bank on the periphery of the predetermined portion; The solution applying step and the bank forming step are performed, the coating solution is applied to the inner side surrounded by the formed bank, the drying step and the crystallization step are performed, and the electromechanical conversion film is manufactured. According to this, as described in the above embodiment, the bank forming solution 15 containing a part of the components of the PZT precursor solution is selected as a predetermined portion on the first electrode of the substrate 11 by the droplet discharge head 14. The bank film 16 is formed on the peripheral edge of the predetermined portion by applying it, and dried to form a bank. Then, droplets of the PZT precursor solution 17 containing the raw material for forming the electromechanical conversion film are ejected from the nozzles of the droplet ejection head 14 and applied to the predetermined portion surrounded by the bank. As a result, the PZT precursor solution 17 is applied to only a predetermined portion on the first electrode of the substrate 11 while the wetting and spreading is suppressed by the bank. Therefore, an electromechanical conversion film having a desired pattern can be formed.
(Aspect B)
In (Aspect A), the coating process is repeated to form an electromechanical conversion film having a desired film thickness. According to this, as described in the above embodiment, the PZT precursor solution 17 applied on the first electrode of the substrate 11 does not wet and spread except for a predetermined portion surrounded by the bank film 16, so that the predetermined film Thickness is obtained. Thereafter, the coating process is repeated several times to obtain a desired film thickness. Thereby, by quantifying the coating amount in the coating process, an electromechanical film having a desired film pressure can be easily formed by the number of repetitions of the coating process.
(Aspect C)
In (Aspect A), the film thickness of the bank film excluding the bank is smaller than the film thickness of the bank. According to this, as described in the above embodiment, the influence of the back forming solution 15 in contact with the first electrode, for example, connection failure can be reduced.
(Aspect D)
In any one of (Aspect A) to (Aspect C), the thickness of the bank is substantially the same as the thickness of the electromechanical conversion film after the crystallization step. According to this, as described in the above embodiment, the leakage of the PZT precursor solution 17 applied in the bank can be avoided.
(Aspect E)
In any one of (Aspect A) to (Aspect D), the coating solution and the bank film forming solution are applied by a droplet discharge method or a dispenser method. According to this, as described in the above embodiment, the application amounts of the bank forming solution 15 and the PZT precursor solution 17 are quantified using the droplet discharge head 14. Thereby, an electromechanical film having a desired film pressure can be easily formed.
(Aspect F)
After the electromechanical conversion film having a predetermined thickness was formed on the first electrode by the method for manufacturing the electromechanical conversion film according to any one of (Aspect A) to (Espect E), the electromechanical conversion film was formed on the first electrode. A second electrode arranging step of arranging the second electrode so as to sandwich the electromechanical conversion film; According to this, as described in the above embodiment, after forming the electromechanical conversion film having a predetermined thickness on the first electrode, the electromechanical conversion film formed on the first electrode By disposing the second electrode so as to be sandwiched, a high-quality electromechanical transducer can be manufactured.
(Aspect G)
An electromechanical transducer is produced by the method for producing an electromechanical transducer of (Aspect F). According to this, as explained about the above-mentioned embodiment, a high quality electromechanical transducer can be manufactured.
(Aspect H)
The electromechanical transducer of (Aspect G) is provided. According to this, as described in the above embodiment, a high-quality liquid droplet ejection head can be manufactured.
(Aspect I)
The droplet discharge head of (Aspect H) is provided. According to this, as described in the above embodiment, it is possible to provide a droplet discharge device that can prevent discharge failure and maintain stable discharge performance.

11 Substrate 12 SAM Film 13 Photoresist 14 Droplet Discharge Head 15 Bank Formation Solution 16 Bank Film 17 PZT Precursor Solution 18 Electromechanical Conversion Film 100 Inkjet Recording Device

JP 2008-187302 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 (9)

(Claims 1 and 5 on the notification form)
A coating step of selectively applying a coating liquid containing a raw material for forming an electromechanical conversion film to a predetermined portion on the first electrode, and drying for drying the film of the coating liquid coated on the first electrode In a method for producing an electromechanical conversion film, comprising: a step; and a crystallization step of thermally decomposing and crystallizing the dried coating solution film,
In the coating step, a bank film forming solution containing a part of the components of the coating solution is applied to a predetermined portion on the first electrode, and the bank film forming solution is applied to the first electrode by a coffee stain phenomenon. A bank film forming step of forming a bank film so as to flow toward the periphery of the predetermined portion and rise at the periphery and surround the predetermined portion on the first electrode; and drying the bank film along the periphery of the predetermined portion A bank forming step of forming a bank
Performing the solution coating step and the bank forming step, applying the coating solution to the inside surrounded by the formed bank, and performing the drying step and the crystallization step to manufacture the electromechanical conversion film. A method for producing an electromechanical conversion film characterized by (Claim 1 of the notification form)
In the manufacturing method of the electromechanical conversion film according to claim 1,
The method of manufacturing an electromechanical conversion film, wherein the coating process is repeated to manufacture the electromechanical conversion film having a desired film thickness. (Claim 2 of the notification form)
In the manufacturing method of the electromechanical conversion film according to claim 1,
The method of manufacturing an electromechanical conversion film, wherein a thickness of the bank film excluding the bank is smaller than a thickness of the bank. (Claim 3 of the notification form)
In the manufacturing method of the electromechanical conversion film according to any one of claims 1 to 3,
The method of manufacturing an electromechanical conversion film, wherein the bank has a film thickness substantially the same as the film thickness of the electromechanical conversion film after the crystallization step. (Claim 6 of the notification form)
In the manufacturing method of the electromechanical conversion film according to any one of claims 1 to 4,
The method for producing an electromechanical conversion film, wherein the coating solution and the bank film forming solution are applied by a droplet discharge method or a dispenser method. A method for manufacturing an electromechanical transducer, comprising:
An electromechanical conversion film having a predetermined thickness is formed on the first electrode by the method for manufacturing an electromechanical conversion film according to any one of claims 1 to 5, and then the electric formed on the first electrode. A method of manufacturing an electromechanical conversion element, comprising a second electrode arrangement step of arranging a second electrode so as to sandwich a mechanical conversion film.   An electromechanical transducer produced by the method for producing an electromechanical transducer according to claim 6. (Claim 8 of the notification form)
A droplet discharge head comprising the electromechanical conversion element according to claim 7. (Claim 9 of the notification form)
A droplet discharge apparatus comprising the droplet discharge head according to claim 8.

(Comment to the inventor: The electromechanical conversion element according to claims 6 and 7 having the first and second electrodes is provided in the droplet discharge head, so the electromechanical conversion element was claimed. In addition, claims 4 and 7 of the Invention Notification Form cannot be found technically in comparison to other claims that have been claimed, and the principle that the total number of claims in your company specification guidelines is 10 or less. (Please note that if you make a claim, please indicate.)