JP2013225671A - Thin film manufacturing device, electromechanical conversion element, liquid discharge head, image forming apparatus and thin film manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin film manufacturing device which is configured to obtain a functional film including an electromechanical conversion film by repeating the same process multiple (many) times and capable of efficiently manufacturing a thin film with target film thickness.SOLUTION: A thin film manufacturing device 50 comprises: an ink jet head 67 as liquid discharge means which forms coating patterns in a plurality of locations by discharging a functional ink multiple times for each of the plurality of locations on a substrate 1; a laser irradiation device 71 as heating and crystallizing means which obtains thin film patterns in the plurality of locations by heating and crystallizing the coating patterns in the plurality of locations each time the functional ink is discharged among the multiple times; film thickness measuring means 73 which measures film thickness of the thin film patterns in all the locations after multiple times of heating and crystallizing; and a control section 75 as correction means which corrects the amount of the functional ink to be discharged from the ink jet head 67 to each of the locations on the substrate 1 so as to obtain target film thickness on the basis of a result of measuring film thickness of the thin film patterns in all the locations by the film thickness measuring means 73.

Description

  The present invention relates to a thin film manufacturing apparatus, an electromechanical conversion element, a liquid discharge head, an image forming apparatus, and a thin film manufacturing method, and more specifically, an ink jet recording apparatus used as an image forming apparatus, a printer, a facsimile, a copying machine, or a plotter. Or an electro-mechanical conversion element to be a piezoelectric element of a liquid discharge head provided in an image forming apparatus such as a multi-function machine having a plurality of functions, and a thin film manufacturing apparatus and a thin film manufacturing apparatus for an electro-mechanical conversion film constituting the element Regarding the method.

  Nozzles for ejecting ink droplets and pressures at which the nozzles communicate with ink jet recording apparatuses and liquid ejection heads used as image forming apparatuses such as printers, facsimiles, copiers, plotters, etc., or multifunction devices having a plurality of these functions A chamber having a chamber and an electro-mechanical conversion element such as a piezoelectric element that pressurizes ink in the pressure chamber is known.

  The electro-mechanical conversion element has, for example, a structure in which an electro-mechanical conversion film and an upper electrode are stacked on a lower electrode. The electro-mechanical conversion film that is a thin film can be produced by, for example, a sputtering method, an MOCVD method, a vacuum deposition method, an ion plating method, a sol-gel method, an aerosol deposition method, or the like.

  A method for producing an electromechanical conversion film using a sol-gel method has been proposed (see, for example, Patent Document 1). Incidentally, in Patent Document 1, (1) surface modification is performed by applying a surface modification liquid in advance to the region other than the portion where the electro-mechanical conversion film on the first electrode is provided by an inkjet method. And (2) applying a sol-gel solution containing a piezoelectric precursor to the portion where the electro-mechanical conversion film, which is a non-surface modified region on the first electrode, is provided by an inkjet method. And (3) heat-treating the sol-gel liquid coating film applied to the site where the electro-mechanical conversion film is provided, and forming an electro-mechanical conversion film patterned ( Thin film) is disclosed.

  Since the precursor coating film of the electromechanical conversion film is thin, it cannot be formed in a predetermined film thickness by a single treatment. Therefore, by repeating the steps (1) to (3) as many times as necessary (usually many times), a precursor coating film of the electro-mechanical conversion film is laminated, and the electro-mechanical conversion film having a predetermined thickness is obtained. Is to manufacture.

  On the other hand, a discharge amount control method of an ink jet printer is known (for example, see Patent Document 2). Incidentally, Patent Document 2 discloses a film forming step of forming a film on an object to be coated by discharging ink from the print head having a plurality of nozzles in the coating width direction onto the object to be coated with ink non-absorbability. Measure the film thickness of the film formed on the coating object in the film forming process in relation to the ink discharge position of each nozzle along the coating width direction to detect variations in the ink discharge amount from each nozzle. The variation in the ink discharge amount from each nozzle based on the difference between the film thickness measurement step to be performed and the film thickness at the ink discharge position of each nozzle measured in the film thickness measurement step and the target film thickness. The ejection amount correction process for increasing / decreasing the correction is performed for a plurality of print heads arranged adjacently along the nozzle arrangement direction, and the ejection amount correcting process is performed to increase / decrease the ink ejection amount of each nozzle. The correction data, be memorized for each of the plurality of print heads is disclosed that.

  However, the technique relating to the discharge amount control method (or control device) described in Patent Document 2 is efficient when applied to a technique for obtaining an electro-mechanical conversion film by repeating the same process as in Patent Document 1, for example. There is a problem that it is difficult to manufacture a thin film.

  That is, in the method for producing the electro-mechanical conversion film (thin film) in the technique described in Patent Document 1, the electro-mechanical conversion film having a desired film thickness is obtained by repeatedly performing the steps (1) to (3). Although it is obtained, the excessive film thickness portion with respect to the target film thickness of the electromechanical conversion film is hardly produced by repeating the steps (1) to (3) a few times. In other words, the technique described in Patent Document 1 is configured to obtain an electro-mechanical conversion film having a target film thickness by performing each of the steps (1) to (3) a plurality of (many) times. ) It is inefficient from the viewpoint of productivity to measure the film thickness for each of the steps (1) to (3) repeated.

  Therefore, the present invention has been made in view of the above-described circumstances and problems, and a functional film including an electro-mechanical conversion film is obtained by repeating the same process as in Patent Document 1 a plurality of times (many times). The main object of the thin film manufacturing apparatus is to realize and provide a thin film manufacturing apparatus capable of efficiently manufacturing a thin film with a target film thickness.

In order to solve the above-described problems and achieve the above-described object, the present invention adopts the following characteristic means / invention specific items (hereinafter referred to as “configuration”).
The present invention relates to a liquid ejecting unit that ejects a functional ink a plurality of times at a plurality of locations on a film formation target to form a coating film pattern at the plurality of locations, and the coating film pattern at the plurality of locations. And a heating and crystallization unit that heats and crystallizes each time the ink is ejected a plurality of times to obtain a thin film pattern at the plurality of locations.

  According to the present invention, a thin film having a target film thickness can be efficiently produced with the above configuration.

FIG. 3 is a cross-sectional view (part 1) illustrating a liquid ejection head using an electro-mechanical conversion element. FIG. 6 is a cross-sectional view (part 2) illustrating a liquid ejection head using an electro-mechanical conversion element. It is a perspective view which illustrates the thin film manufacturing apparatus concerning a 1st embodiment. (A)-(c) is typical sectional drawing (the 1) which illustrates the thin film manufacturing process which concerns on 1st Embodiment at the time of patterning a SAM film | membrane by a respectively different method. FIG. 5 is a schematic cross-sectional view (part 2) illustrating the thin film manufacturing process according to the first embodiment. (A), (b) is typical sectional drawing (the 3) which illustrates the thin film manufacturing process which concerns on 1st Embodiment. (A) is a schematic diagram illustrating the functional ink application in the thin film manufacturing process according to the first embodiment (part 4), and (b) is a schematic diagram illustrating the same film thickness measurement. (Part 4). It is a flowchart which illustrates the process from functional ink application | coating of the thin film manufacturing process which concerns on 1st Embodiment to completion | finish of functional film film-forming. It is a schematic partial cross-sectional front view of the mechanism part of the inkjet recording device which concerns on 2nd Embodiment. FIG. 10 is a perspective view showing the recording apparatus of FIG. 9 in a transparent manner. (A) is the photograph which measured the contact angle of water in the SAM film formation site | part, (b), respectively in the SAM film removal site | part. 3 is a graph showing a PE hysteresis curve of the electrical-converting element obtained in Example 1. FIG. (A) is a figure which illustrates many thin film patterns formed on the board | substrate of Example 2, (b) is a figure which expands and illustrates the same thin film pattern. It is a graph of Example 3 which shows the measurement result of the displacement amount of the electromechanical conversion element obtained in Example 1. (A) is an actuator part of an electro-mechanical conversion element according to a comparative example formed by a spin method, and (b) is an actuator part of an electro-mechanical conversion element according to Example 1 formed by an ink-jet method. These are explanatory drawings of Example 3 which show the mode of a deformation | transformation of the one-side half, respectively. 6 is a graph showing a half on one side of a film thickness distribution of an electro-mechanical conversion film (PZT film) in Example 3. FIG. 17 is a graph and a formula for explaining an example of a film thickness distribution shape in FIG. 16. FIG.

  Hereinafter, embodiments (hereinafter referred to as “embodiments”) and examples of the present invention will be described in detail with reference to the drawings. In the embodiment and each example, components such as members and components having the same function or shape are given the same reference numerals as much as possible to avoid duplicate explanation. Note that the contents described in the embodiments and examples are only one form and one example, and the scope of the present invention is not limited thereto.

Hereinafter, in the present invention, the “image forming apparatus” of the liquid discharge recording method forms an image by landing droplets on a medium such as paper, thread, fiber, fabric, leather, metal, plastic, glass, wood, ceramics, etc. Means the device to perform. In addition, “image formation” not only applies an image having a meaning such as a character or a figure to a medium but also applies an image having no meaning such as a pattern to the medium (simply applying a droplet to the medium). It also means to land on.
“Droplets” are not limited to inks, but include those called recording liquids, fixing processing liquids, resins, liquids, etc., and are droplets that are finely granulated to enable image formation. It is used as a generic term for droplets as all liquids that can be formed, that is, functional solutions (hereinafter referred to as “functional inks”). The term “recording medium” does not limit the material to paper, but also includes OHP sheets, cloth, etc., and means that the droplets adhere to it, and can be used as a recording medium, recording paper, recording paper, etc. It is used as a general term for anything from thin paper to thick paper, postcards, envelopes, or simply paper. Further, the image is not limited to a two-dimensional image, and includes a three-dimensional image.

The present invention is also directed to a liquid discharge head, also called a droplet discharge head, and an image forming apparatus using the liquid discharge head. The image forming apparatus is generally called an ink jet recording apparatus. Hereinafter, the image forming apparatus is called an ink jet recording apparatus.
This ink jet recording apparatus has many advantages such as extremely low noise, high-speed printing, and the ability to use plain paper, which is an inexpensive recording medium with a high degree of ink freedom. Therefore, it is widely deployed as an image recording apparatus or an image forming apparatus such as a printer, a facsimile machine, a copying apparatus, a multi-function machine having a plurality of image forming functions as described above.

  A droplet discharge device or a liquid discharge head used in an ink jet recording apparatus is also referred to as a nozzle that discharges ink droplets and a liquid chamber (discharge chamber, pressurized liquid chamber, pressure chamber, ink flow path, or the like) that communicates with the nozzle. And pressure generating means for discharging ink in the liquid chamber.

  As the pressure generating means, an ink droplet is ejected by deforming and displacing the diaphragm forming the wall surface of the liquid chamber using an electro-mechanical conversion element such as a piezoelectric element constituted by an electro-mechanical conversion film or the like. A piezo-type, bubble that generates bubbles by boiling the ink film using an electrothermal conversion element such as a heating resistor (meaning that it is placed at a fixed position) in the liquid chamber and ejects ink droplets There is a type (thermal type).

  The electro-mechanical conversion element converts an electrical input into a mechanical deformation, and is composed of a pair of upper and lower electrodes that execute the electrical input, and a film (piezoelectric layer) such as a piezoelectric body between them. It has a laminated structure. As the piezoelectric body, lead zirconate titanate (hereinafter abbreviated as “PZT”) ceramics or the like is used, and these are generally referred to as metal composite oxides because they have a plurality of metal oxides as main components.

Further longitudinal vibration type utilizing d ₃₃ direction of deformation to those of the piezoelectric type, horizontal vibration utilizing d ₃₁ direction of deformation (bend mode) type, even there is a shear mode type or the like using a shear deformation. Recently, a thin film actuator in which a liquid chamber and a piezo element are directly formed on a Si substrate has been devised due to advances in semiconductor processes and micro electro mechanical systems (hereinafter abbreviated as “MEMS”).
Electrical functions as a pressure generating means according to the present invention - mechanical conversion element is a transverse vibration (bend mode) type utilizing d ₃₁ direction of deformation.

(First embodiment)
(Thin film)
First, an electro-mechanical conversion film constituting an electro-mechanical conversion element will be described as an example of a thin film / thin film pattern manufactured by the thin film manufacturing apparatus and the thin film manufacturing method according to the first embodiment. In addition, it cannot be overemphasized that the thin film which can be manufactured with the thin film manufacturing apparatus and thin film manufacturing method which concern on 1st Embodiment is not limited to an electromechanical conversion film.

  The electro-mechanical conversion element is used as, for example, a component of an ink jet head as an example of a liquid discharge head used in an ink jet recording apparatus. First, the liquid discharge head 9 will be described with reference to FIGS. 1 and 2. FIG. 1 is a somewhat schematic cross-sectional view of a single liquid discharge head 9, and FIG. 2 is a somewhat schematic cross-sectional view of a configuration example in which a plurality of liquid discharge heads 9 are arranged. FIG. In both figures, illustration of liquid supply means, flow paths, and fluid resistance is omitted for simplification of the figures.

  The liquid discharge head 9 illustrated in FIG. 1 includes a nozzle plate 10, a liquid chamber substrate 20, a vibration plate 30, and an electromechanical conversion element 40. The nozzle plate 10 is formed with nozzles 11 that eject ink droplets. The nozzle plate 10, the liquid chamber substrate 20, and the vibration plate 30 form a pressure chamber 21 (also referred to as a liquid chamber, an ink flow path, a pressurized liquid chamber, a discharge chamber, etc.) that communicates with the nozzle 11. The diaphragm 30 forms part of the wall surface of the ink flow path and the pressure chamber 21. The pressure chamber 21 is formed as a space by disposing the pressure chamber substrate 20 on the nozzle plate 10.

  The electro-mechanical conversion element 40 includes an adhesion layer 41, a lower electrode 42 (also referred to as a platinum group electrode), an electro-mechanical conversion film 43, and an upper electrode 44, and ink ( It functions as a pressure generating means for pressurizing and discharging (not shown). The electro-mechanical conversion element 40 includes an electro-mechanical conversion film 43 having a specific film thickness formed by a thin film manufacturing apparatus and a thin film manufacturing method described later.

  In the electromechanical conversion element 40, an adhesion layer 41, which is also referred to as an oxide electrode, is formed on the vibration plate 30, and a lower electrode 42 serving as a first electrode is formed on the adhesion layer 41. An electro-mechanical conversion film 43 is formed on the lower electrode 42, and an upper electrode 44 serving as a second electrode is formed on the electro-mechanical conversion film 43. That is, the electromechanical conversion film 43 is interposed (meaning that it is provided between the members) between the lower electrode 42 serving as the first electrode and the upper electrode 44 serving as the second electrode.

The adhesion layer 41 is a layer made of, for example, Ti, TiO ₂ , TiN, Ta, Ta ₂ O ₅ , Ta ₃ N ₅ or the like, and has a function of improving the adhesion between the lower electrode 42 and the diaphragm 30. However, the adhesion layer 41 is not an essential component of the electro-mechanical conversion element 40.

In the electro-mechanical conversion element 40, when a voltage is applied between the lower electrode 42 and the upper electrode 44 (meaning that a voltage is applied), the electro-mechanical conversion film 43 is mechanically displaced. Electrical - along with the mechanical displacement of the transducer layer 43, deformation displacement in the vibration plate 30, for example, laterally disposed on the nozzle plate 10 and the opposite side constituting the walls of the pressure chambers 21 (d ₃₁ direction), the pressure chamber The ink in 21 is pressurized. Thereby, ink droplets as an example of functional ink can be ejected from the nozzle 11.

The actuator portion 35 is a drive portion that is actually deformed and displaced when a voltage is applied between the lower electrode 42 and the upper electrode 44, and a PZT film as an electro-mechanical conversion film 43 from the diaphragm 30 as a substrate. The laminated structure part to the upper electrode 44 comprised on both sides is shown. As will be described later, the actuator part 35 has a rigidity and a film thickness that gradually increase from the end part of the actuator part 35 in the cross section in the short direction of the actuator part 35 toward the center part thereof. More specifically, the actuator portion 35 has a substantially meniscus convex lens shape with the convex portion facing the upper electrode 44.
The above-described electro-mechanical conversion film 43 having a substantially meniscus convex lens shape is produced by a thin film production apparatus and a thin film production method described later (when a sol-gel solution (PZT precursor solution) is applied by an inkjet method as a droplet discharge method) ) On the outer peripheral surface. In the film shape produced by spin coating or the like using a sol-gel solution (PZT solution), the film shape has a substantially flat plate thickness.

  As shown in FIG. 2, a plurality of liquid discharge heads 9 can be arranged in parallel to form a liquid discharge head.

As a material of the electromechanical conversion film 43, for example, PZT can be used. PZT is a solid solution of lead zirconate (PbZrO ₃ ) and lead titanate (PbTiO ₃ ). For example, the ratio of PbZrO ₃ and PbTiO ₃ is 53:47, and the chemical formula indicates Pb (Zr _0.53 , Ti _0.47 ) O ₃ , PZT generally indicated as PZT (53/47), etc. Can be used. The characteristics of PZT vary depending on the ratio of PbZrO ₃ and PbTiO ₃ .

When PZT is used as the electro-mechanical conversion film 43, lead acetate, a zirconium alkoxide compound, and a titanium alkoxide compound are used as starting materials and dissolved in methoxyethanol as a common solvent to prepare a PZT precursor solution. The mixing amount of the lead acetate, zirconium alkoxide compound, and titanium alkoxide compound can be appropriately selected by those skilled in the art depending on the desired composition of PZT (ratio of PbZrO ₃ and PbTiO ₃ ).

  Note that the metal alkoxide compound is easily decomposed by moisture in the atmosphere. Therefore, stabilizers such as acetylacetone, acetic acid and diethanolamine may be added to the PZT precursor solution as stabilizers.

  As a material of the electromechanical conversion film 43, for example, barium titanate or the like may be used. In this case, it is possible to prepare a barium titanate precursor solution by using barium alkoxide and a titanium alkoxide compound as starting materials and dissolving them in a common solvent.

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. The specific description is expressed as (Pb _1-x , Ba) (Zr, Ti) O ₃ , (Pb _1-x , Sr) (Zr, Ti) O ₃ , which is the same as Pb of the A site. This is a case where the part Ba or Sr is substituted. 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.

  As the material of the lower electrode 42, a metal having high heat resistance and forming a SAM film by reaction with alkanethiol shown below can be used. Specifically, platinum group metals such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) and platinum (Pt) having low reactivity, and these platinum group metals An alloy material containing can be used.

Moreover, after producing these metal layers, it is also possible to laminate | stack and use a conductive oxide layer. As the conductive oxide, specifically, there is a composite oxide described by the chemical formula ABO ₃ and having A = Sr, Ba, Ca, La, B = Ru, Co, Ni as main components, and SrRuO ₃ And CaRuO ₃ , (Sr _1-x Ca _x ) O ₃ which is a solid solution thereof, LaNiO ₃ and SrCoO ₃ , and further, (La, Sr) (Ni _1-y Co _y ) O ₃ which is a solid solution thereof. (Y may be 1). Other oxide materials include IrO ₂ and RuO ₂ .

  The lower electrode 42 can be produced by a method such as a vacuum film forming method such as sputtering or vacuum deposition. Since the lower electrode 42 is electrically connected as a common electrode when a signal is input to the electro-mechanical conversion element 40, the diaphragm 30 (corresponding to the substrate 1 shown in FIG. A conductor whose body or surface is insulated can be used.

  As a specific material of the diaphragm 30, for example, silicon (Si) can be used. In addition, as a specific material for insulating the surface of the diaphragm 30, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film having a thickness of about several hundred nm to several μm, or a stack of these films is stacked. A film or the like can be used. In consideration of a difference in thermal expansion, a ceramic film such as an aluminum oxide film or a zirconia film may be used. The silicon-based insulating film that insulates the surface of the diaphragm 30 can be formed by a CVD method, a thermal oxidation process of silicon, or the like. Further, a metal oxide film such as an aluminum oxide film for insulating the surface of the vibration plate 30 can be formed by a sputtering method or the like.

  According to the present embodiment, the electro-mechanical conversion element 40 can be formed with a simple manufacturing process and performance equivalent to that of bulk ceramics, and etching removal from the back surface for forming the pressure chamber 21 thereafter. The liquid discharge head 9 can be configured by joining the nozzle plate 10 having the nozzles 11.

  The liquid discharge head 9 has been described as an example of use of the electro-mechanical conversion element 40. However, the liquid discharge head including the electro-mechanical conversion element of the present invention is not limited to the liquid discharge head 9 described above, but a micropump, super It can also be used in applications such as sonic motors, acceleration sensors, two-axis scanners for projectors, and infusion pumps.

(Thin film manufacturing equipment)
With reference to FIG. 3, the structure of the thin film manufacturing apparatus which concerns on 1st Embodiment is demonstrated. FIG. 3 is an external perspective view of the thin film manufacturing apparatus showing the first embodiment.
In the thin film manufacturing apparatus 50 shown in FIG. 3, Y-axis driving means 61 is installed on the gantry 60. On the Y-axis driving means 61, a stage 62 on which the substrate 1 is mounted is installed so as to be driven in the Y-axis direction.

  The stage 62 is usually provided with a suction means (not shown) using vacuum or static electricity, whereby the substrate 1 can be fixed. In addition, a driving means (not shown) that rotates around the Z axis is mounted on the stage 62, and the relative inclination between the inkjet head 67, the laser irradiation device 71, the film thickness measuring means 73, which will be described later, and the substrate 1 can be corrected. It is good also as a structure.

  An X-axis support member 64 for supporting the X-axis drive means 63 is installed on the gantry 60. The X-axis drive unit 63 is provided with a Z-axis drive unit 65. Further, a head base 66 is mounted on the Z-axis driving means 65 and is configured to move in the X-axis and Z-axis directions.

The Z-axis driving unit 65 can control the distance between an inkjet head 67 and a substrate 1 described later. On the head base 66, an ink jet head 67 that discharges functional ink (for example, PZT precursor solution) is mounted. Functional ink is supplied to the inkjet head 67 from each ink tank 68 via an ink supply pipe (not shown).
The inkjet head 67 ejects a functional ink (for example, PZT precursor solution) a plurality of times at a plurality of locations on the substrate 1 as an example of a film formation target, and a coating film (for example, a PZT precursor coating) at a plurality of locations. It functions as a liquid discharge means for forming a (film) pattern.

Other Z-axis drive means 69 is attached to the X-axis drive means 63, and a support member 70 is attached to the Z-axis drive means 69. A laser irradiation device 71 and a film thickness measuring unit 73 are attached to the support member 70. The Z-axis driving unit 69 can control the distance between the laser irradiation device 71 and the film thickness measuring unit 73 and the substrate 1.
The laser irradiation device 71 functions as a heat crystallization unit that heat-crystallizes the functional ink. The film thickness measuring means 73 has a function of measuring the film thickness of a thin film (for example, PZT film) pattern after heat crystallization by a laser irradiation device 71 a plurality of times (hereinafter, referred to as “multiple times because it is usually many times”). Have
As the film thickness measuring means 73, for example, a contact type surface roughness meter or a non-contact type can be used, and a specific configuration example will be described later.

In the thin film manufacturing apparatus 50 of FIG. 3, the stage 62 has a uniaxial degree of freedom in the Y direction, and the inkjet head 67, the laser irradiation device 71, and the film thickness measuring unit 73 have a uniaxial degree of freedom in the X direction. Although the structure which has is shown, it is not limited to this form. For example, the stage 62 may have a biaxial degree of freedom in the X and Y directions, and the inkjet head 67, the laser irradiation device 71, and the film thickness measuring unit 73 may be fixed.
Further, the stage 62 may have a uniaxial degree of freedom in the Y direction, and the inkjet head 67, the laser irradiation device 71, and the film thickness measuring unit 73 may be arranged in a line in the Y axis direction.

  Alternatively, the substrate 1 may be fixed, and the inkjet head 67, the laser irradiation device 71, and the film thickness measuring unit 73 may have a biaxial degree of freedom in the X and Y directions. Furthermore, the X axis and the Y axis need not be orthogonal if one plane can be expressed by the X axis and the Y axis vector. For example, the X axis vector and the Y axis vector have angles of 30 degrees, 45 degrees, and 60 degrees. You may have.

  In the present embodiment, functional ink is heated and crystallized by a single laser irradiation device 71, but the present invention is not limited to this. That is, a continuous irradiation laser device functioning as a heating means (laser light capable of thermally decomposing functional ink by keeping the temperature of the lower electrode 42 below 500 ° C. without losing the SAM film described later. ) And a pulse irradiation laser device that functions as a heat crystallization means (irradiates a laser beam with a temperature of about 700 ° C. for thermal decomposition). You may make it comprise.

  The thin film manufacturing apparatus 50 includes a control unit 75 shown in FIG. 7, and discharges functional ink of the inkjet head 67, laser irradiation conditions of the laser irradiation apparatus 71, measurement conditions of the film thickness measuring unit 73, and Y-axis driving. Each drive source of the means 61, the X-axis drive means 63, the Z-axis drive means 65 and 69, etc. can be controlled. The control unit 75 is connected to a personal computer 76 as a computer for giving necessary instructions from the user to the control unit 75 and grasping the state of the control target elements including the control unit 75.

  The controller 75 includes, for example, a CPU, ROM, RAM, nonvolatile memory, main memory, and the like. Various functions of the control unit 75 are realized by reading a control program recorded in a ROM or the like into the main memory and executing it by the CPU. However, a part or all of the control unit 75 may be realized only by hardware.

  Further, the control unit 75 may be physically configured by a plurality of devices. In a recording unit such as a RAM or a non-volatile memory, the crystalline state of the functional ink, the film thickness data as the film thickness measurement result, the optimum laser irradiation condition, or the like can be recorded. For example, the correction means according to the present invention can be realized by the control unit 75. It is also possible to give a part or all of the control unit 75 to the personal computer 76.

(Thin film manufacturing method)
Next, the thin film manufacturing method according to the first embodiment will be described. Here, an example of manufacturing the electro-mechanical conversion film (also referred to as a piezoelectric layer) 43 shown in FIG. 1 as a thin film will be described.

(Formation of electro-mechanical conversion film by sol-gel method)
Hereinafter, formation of the electromechanical conversion film by the sol-gel method will be described.
When the electromechanical conversion film is PZT, as described above, lead acetate, zirconium alkoxide, and titanium alkoxide compound are used as starting materials, and dissolved in methoxyethanol as a common solvent to obtain a uniform solution. This uniform solution is also called a PZT precursor solution or sol-gel solution as an example of functional ink.

When a PZT film is obtained on the entire surface of the underlying substrate, a coating film is formed by a solution coating method such as a spin coating method, and each of the solvent drying, thermal decomposition (also referred to as “heating”) and crystallization heat treatment is performed. It is obtained with. Since the transformation from the coating film to the 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.
When used as an electro-mechanical conversion element (piezoelectric element) of a liquid discharge head, the thickness of the PZT film is required to be 1 to 2 μm. In order to obtain this film thickness by the above method, the above steps are repeated ten times.

(Formation of patterned electro-mechanical conversion film by sol-gel method)
The formation of a patterned electro-mechanical conversion film by the sol-gel method will be described.
(1) First, the PZT precursor solution with controlled wettability of the base substrate is applied separately. This is a phenomenon of self-arrangement on a specific metal of alkanethiol.
(2) A self-assembled monomolecular film (Self-assembled Monolayer: hereinafter abbreviated as “SAM film”) is formed as a liquid repellent film with thiol on a platinum group metal.
(3) Pt (platinum) is used for the lower electrode as the first electrode, and the entire surface is subjected to SAM treatment. Since an alkyl group is arranged on the SAM film, it becomes hydrophobic (water repellency).
(4) The SAM film is patterned by known photolithography etching.
(5) Since the patterned SAM film remains even after the resist is peeled off, this portion becomes hydrophobic. On the other hand, the portion from which the SAM film is removed becomes hydrophilic because it is a platinum surface.
The processing steps (1) to (5) are also referred to as a surface modification step in which the surface modification is partially performed on the lower electrode as the first electrode.

(6) The PZT precursor solution is applied separately using the surface energy contrast. Due to the contrast of the surface energy, the coated area is only a hydrophilic area.
Depending on the degree of contrast, the PZT precursor solution may be applied separately in a pattern even when applied over the entire surface by spin coating. Doctor blade coating or dip coating may be used. When it is desired to reduce the consumption of the PZT precursor solution, coating by an ink jet method may be used. Similarly, letterpress printing is also possible.

(SAM film patterning)
With reference to FIG. 4, the process of patterning the SAM film using alkanethiol by three kinds of methods will be described. FIG. 4A, FIG. 4B, and FIG. 4C are schematic cross-sectional views showing steps in patterning the SAM film using alkanethiol by different methods. A to D, A1 to D1, and A2 to D2 shown in the left horizontal direction of FIG. 4A, FIG. 4B, and FIG. 4C indicate the progression order of the steps shown in the above drawings.

As shown in FIGS. 4A, 4B, and 4C, it goes without saying that the outermost surface of the substrate 1 is a portion corresponding to a part of the lower electrode 42 shown in FIG. It is assumed that 1 is platinum excellent in reactivity with thiol (common to steps A, A1, and A2).
Only in A of FIG. 4A and D of FIG. 5, the lower electrode 42 becomes a part corresponding to a part of the substrate 1 by adding parentheses and adding the reference numeral 42 of the lower electrode. Shall be shown.

Alkanethiol has different reactivity and hydrophobicity (water repellency) depending on the molecular chain length. Usually, a molecule having ₆ to ₁₈ carbon atoms (C _{6 to} C ₁₈ ) is converted into a common organic solvent such as alcohol, acetone or toluene. It is prepared by dissolving in etc. Usually, the concentration of alkanethiol is about several moles / liter. After immersing the substrate 1 in this solution and taking it out after a predetermined time, the SAM film 2 can be formed on the platinum surface of the lower electrode 42 on the substrate 1 by replacing and washing the excess molecules with a solvent and drying. (See B process in FIG. 4A and B2 process in FIG. 4C). Hereinafter, forming the SAM film 2 on the platinum surface of the lower electrode 42 on the substrate 1 is also referred to as “SAM treatment”.

  In step C of FIG. 4A, the photoresist layer 3 is patterned by photolithography in order to remove the SAM film 2 where the PZT precursor is to be formed and to protect the SAM film 2 where necessary. Then, the SAM film 2 is removed by dry etching, the resist used for processing is removed, and the patterning of the SAM film 2 is completed. As a result, the SAM film 2 having a predetermined pattern is formed on the surface of the lower electrode 42 on the substrate 1 (see step D in the figure).

  The region where the SAM film 2 is formed on the surface of the lower electrode 42 on the substrate 1 is hydrophobic. On the other hand, the region where the surface of the lower electrode 42 is exposed after the SAM film 2 is removed becomes hydrophilic. By utilizing this surface energy contrast, it becomes possible to coat the PZT precursor solution described in detail below.

  On the other hand, in the B1 step of FIG. 4B, the pattern of the photoresist layer 3 is first formed on the portion where the PZT precursor is to be formed, and then the SAM film 2 is patterned. In the state after the SAM treatment, the SAM film 2 is not formed on the photoresist layer 3 (see step C1 in FIG. 1), and the patterning of the SAM film 2 is completed when the photoresist layer 3 is removed.

  In the B2 process of FIG. 4C, the SAM film 2 is formed on the platinum surface of the lower electrode 42 on the substrate 1 through the same process as the B process of FIG. By irradiating with ultraviolet rays (UV light exposure), the unexposed SAM film 2 remains and the exposed SAM film 2 disappears. As a result, the SAM film 2 having a predetermined pattern is formed on the surface of the lower electrode 42 on the substrate 1.

(Formation of electro-mechanical conversion film)
Next, the PZT film 7 to be the electro-mechanical conversion film 43 is formed on the surface of the lower electrode 42 on the substrate 1. In order to show that the PZT film 7 corresponds to an electro-mechanical conversion film 43 as an example of a functional film, parentheses are added to F, D ′, E ′, and F ′ in FIG. The reference numeral 43 of the mechanical conversion film is also shown.
After the step D in FIG. 4 (a), the step D1 in FIG. 4 (b), and the step D2 in FIG. 4 (c), the PZT precursor solution described above is applied to the SAM film as shown in step E in FIG. The process of apply | coating to the hydrophilic part 5 made into 2 patterning is performed. As shown in step E of FIG. 5, a PZT precursor solution is applied to the patterned hydrophilic portion 5 by a selected ink jet method to form a patterned PZT precursor coating film 6.
Thereafter, heat treatment is performed according to a normal sol-gel process. The heat treatment temperature of the patterned PZT precursor coating 6 is such that the SAM film 2 disappears by high temperature treatment such as organic combustion temperature: 500 ° C., PZT crystallization temperature: 700 ° C., and only the PZT film 7 is formed on the platinum surface of the substrate 1. Is formed (see step F in FIG. 5).

  The second and subsequent steps can be simplified for the following reasons (see steps D ′, E ′, and F ′ in FIG. 5). The SAM film is not formed on the oxide thin film. For this reason, the SAM film 2 is formed only on the PZT film-free (exposed) platinum film by the first process that does not require the photolithography process or the exposure process (see the D ′ process in FIG. 5). .

  Conventional patterning of SAM film and patterning of functional color material (color filter, polymer organic EL, nano metal wiring) using the same have been completed by one SAM treatment and subsequent functional color material arrangement. However, in the sol-gel method, the film thickness that can be formed at a time is small, so it is necessary to repeat the film a plurality of times. Each time, the process of forming the patterned SAM film by photolithography and etching becomes complicated. The present invention can be realized for the first time only by a combination in which an SAM film cannot be formed as an electro-mechanical conversion element and a lower electrode are constituent elements and a SAM film can be formed on the lower electrode.

After the SAM treatment is performed on the first pattern-formed sample, the PZT precursor solution is applied separately (formation of the patterned PZT precursor coating film 6) and heat treatment is performed. The above steps D ′, E ′, and F ′ of FIG. 5 are repeated until a desired film thickness is obtained. Patterning by this method can form ceramics up to a thickness of 5 μm.
In addition, after the coating process, the processes so far include drying, thermal decomposition (hereinafter, also referred to as “heating”), crystallization, and crystallization of the sol-gel solution (PZT precursor solution) partially applied in the coating process. This corresponds to a crystallization step (hereinafter also referred to as “heating / crystallization step”).

With reference to FIGS. 6 and 7, the formation of the electro-mechanical conversion film 43 will be described from another viewpoint. As shown in FIGS. 6 and 7, an electromechanical conversion film 43 is formed on the surface of the lower electrode 42. 6 and 7, the number of patterns of the SAM film 2 is increased from two to three as compared with those shown in FIGS. 4 and 5, and the lower electrode 42 is formed in FIGS. 4 and 5. Corresponding to the substrate 1 shown, the reference numeral 1 is shown with parentheses.
In the steps shown in FIGS. 6A and 7A, the lower electrode 42 (see FIG. 3) having a predetermined pattern of the SAM film 2 formed on the stage 62 of the thin film manufacturing apparatus 50 shown in FIG. (Corresponding to the substrate 1) is placed. Then, the position, inclination, and the like of the lower electrode 42 are aligned using a known alignment device (CCD camera, CMOS camera, or the like).

  Then, the inkjet head 67 is driven on the X axis, the stage 62 on which the lower electrode 42 is mounted is driven on the Y axis, and the inkjet head 67 is disposed on the stage 62. At this time, as shown in FIG. 7A, the film thickness measuring means 73 is separated upward from the lower electrode 42 and occupies the initial position in the Z axis. Then, the functional ink 43a (corresponding to the PZT precursor solution in FIG. 5) is ejected from the inkjet head 67 to a region (hydrophilic region) where the SAM film 2 is not present on the surface of the lower electrode. At this time, due to the contrast of the surface energy, the functional ink 43a spreads wet only in the region where the SAM film 2 does not exist (hydrophilic region).

  As described above, the functional ink 43a is formed only in the region where the SAM film 2 does not exist (hydrophilic region) by utilizing the contrast of the surface energy, so that the amount of the solution to be applied can be reduced by a process such as a spin coating method. In addition, the process can be simplified and the process can be simplified.

  Next, in the step shown in FIG. 6B, the laser irradiation device 71 is driven on the X axis, and if necessary, the stage 62 on which the lower electrode 42 is placed is driven on the Y axis. A laser irradiation device 71 is disposed on the surface. Then, the laser irradiation device 71 irradiates the functional ink 43a wetted and spread in the step shown in FIG. In the functional ink 43a irradiated with the laser beam 71x, the solvent evaporates and is thermally decomposed, and the SAM film 2 is removed and disappeared. The thermally decomposed functional ink 43a is further crystallized to become an electro-mechanical conversion film 43 as a functional film. As the laser irradiation device 71, for example, a semiconductor laser device, a YAG laser device, or the like can be used.

  As described above, by repeating the steps D ′, E ′, and F ′ in FIG. 5 and the step in FIG. 6 until a desired film thickness (target film thickness) is obtained, functional ink is laminated to form a thin film pattern. can do. That is, a thin film / thin film pattern such as an electro-mechanical conversion film can be manufactured by a simple process.

  Silicon is highly reliable because it has low in-plane unevenness in thickness, crystal characteristics, and thermal characteristics, and is suitable as the substrate 1 (vibrating plate 30) used in this embodiment.

(Measurement of film thickness of electro-mechanical conversion film)
Next, in the step shown in FIG. 7B, the film thickness measuring means 73 is driven along the Z axis, and the film thickness measuring means 73 approaches the lower electrode 42 and occupies a position where the film thickness can be measured. Next, the film thickness measuring unit 73 is driven on the X axis, the stage 62 on which the lower electrode 42 is mounted is driven on the Y axis, and the film thickness measuring unit 73 is disposed on the stage 62. Then, the film thickness measuring means 73 measures the film thickness of the electro-mechanical conversion film 43 that has been thermally decomposed and crystallized in the step shown in FIG. 6B along the Y axis.

  The film thickness measurement result of the electro-mechanical conversion film 43 measured by the film thickness measuring unit 73 is taken into the control unit 75 and necessary calculation processing (for example, from the actually measured film thickness measurement result on the substrate 1). (Including calculation such as obtaining a difference up to the surface of the lower electrode 42) is converted into film thickness data.

  The CPU of the control unit 75 (hereinafter also simply referred to as “control unit 75”) repeats a number of times as described above to form the final plate of all the thin film patterns formed on the substrate 1 at all locations. Measure the film thickness of the thin film pattern, and based on the film thickness measurement results of the thin film pattern at all locations, the functional ink to the thin film pattern at each location from the inkjet head 67 so as to achieve the target thickness It functions as a correction means for correcting the discharge amount 43a.

  Based on the steps D ′, E ′, and F ′ of FIG. 5 and the steps of FIG. 6, the film thickness measurement procedure will be described with reference to the flowchart of FIG. 8. In step S1 of FIG. 8, functional ink is applied on the substrate 1, and then heating and crystallization are performed (step S2). The process from step S1 to step S2 is repeated many times until the target film thickness is approached. For example, when the target film thickness is 2.0 μm, the number of repetitions closest to the target film thickness can be obtained by performing a number of tests and the like.

  In step S3, it is checked whether or not the number of repetitions closest to the target film thickness has been reached. When the number of repetitions closest to the target film thickness is reached (the final plate of the thin film patterns at all locations formed on the substrate 1), the process proceeds to step S4. Here, the control unit 75 measures the film thickness of the thin film patterns at all locations on the final board of the thin film patterns at all locations formed on the substrate 1. That is, information on the thin film patterns at all locations is recorded in the nonvolatile memory RAM, and the film thickness necessary for each thin film pattern is calculated to obtain the target film thickness.

  In step S4, the control unit 75 applies functional ink only to the necessary thin film pattern in the case of NG based on the calculation result of the film thickness necessary for each thin film pattern (step S5), and functions in the case of OK. Finishes the formation of the conductive film.

Further, not only in the above example, in the thin film manufacturing apparatus, when a plurality of liquid ejection heads are used as the liquid ejection means, each liquid ejection head has a ceramic (ferroelectric material) having different concentrations as functional ink. ) Precursor solution may be discharged. When the number of the plurality of liquid discharge heads is two, the concentration of the precursor solution discharged from one liquid discharge head can be reduced to half or less of the concentration of the precursor solution discharged from the other liquid discharge head.
According to this example, when using an inkjet head as a plurality of liquid ejection heads, finer adjustment can be performed by using functional ink having a lower precursor solution concentration.

  In the conventional thin film manufacturing apparatus and thin film manufacturing method, it is inefficient from the viewpoint of productivity to perform film thickness measurement for each of the processes repeated many times. On the other hand, according to this embodiment, the film thickness of the target film thickness is determined based on the film thickness measurement result of the thin film pattern at all locations on the final board of the thin film pattern at all locations formed on the substrate 1. As described above, since the ejection amount of the functional ink 43a from the inkjet head 67 to the thin film pattern at each location is corrected, a thin film with a target film thickness can be efficiently manufactured.

  The film thickness of the electro-mechanical conversion film 43 is not limited to the contact-type roughness meter, and can be measured using, for example, a non-contact shape measuring instrument using light or the like. More specifically, for example, an interferometer NewView series manufactured by Zygo or a shape measurement laser microscope VK series manufactured by Keyence can be used.

(Second Embodiment)
The second embodiment relates to an image forming apparatus according to the present invention.
With reference to FIG. 9 and FIG. 10, an overall configuration of an inkjet recording apparatus 100 as an example of an image forming apparatus according to the present invention will be described. FIG. 9 is a schematic partial cross-sectional front view of the mechanism portion of the ink jet recording apparatus of the present embodiment. FIG. 10 is a perspective view showing the recording apparatus transparently.

The ink jet recording apparatus 100 shown in FIGS. 9 and 10 is an example in which a plurality of liquid ejection heads 9 (see FIG. 2) manufactured by the film thickness manufacturing apparatus 50 of FIG. 3 are mounted.
As shown in FIGS. 9 and 10, the ink jet recording apparatus 100 is a so-called serial type ink jet recording apparatus. The ink jet recording apparatus 100 includes a carriage 101, an ink jet recording head 102 (hereinafter simply referred to as “recording head 102”), and a printing mechanism unit 104. The carriage 101 is configured to be movable in the main scanning direction inside the recording apparatus main body 100A. The recording head 102 is an embodiment of the plurality of liquid ejection heads 9 mounted on the lower side of the carriage 101. The printing mechanism unit 104 includes an ink cartridge 103 that supplies ink to the recording head 102.

  In the lower part of the recording apparatus main body 100A, a paper feed cassette 106 capable of stacking a large number of sheets 105 from the front side on the left side in FIG. 10 is disposed (arranged) so that it can be pulled out and pushed into the recording apparatus main body 100A. Meaning that it is provided). Above the paper feed cassette 106, a manual tray 107 for manually feeding paper is provided so as to be swingable and openable with respect to the recording apparatus main body 100A. The paper 105 fed from the paper feed cassette 106 or the manual feed tray 107 is taken in, and after a required image is recorded by the printing mechanism unit 104, the paper is discharged to a paper discharge tray 108 mounted on the rear side.

  The printing mechanism unit 104 slides the carriage 101 in the main scanning direction by a main guide rod 109 and a sub guide rod 110 which are guide members that are horizontally mounted on left and right side plates (not shown). Hold freely. The carriage 101 has a plurality of ink discharge ports (nozzles) as a recording head 102 according to the present invention for discharging ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). They are arranged in a direction crossing the scanning direction, and are mounted with the ink droplet ejection direction facing downward.

  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 atmosphere port communicating with the atmosphere above, a supply port for supplying ink to the recording head 102 below, and a porous body filled with ink inside. The ink supplied to the recording head 102 is maintained at a slight negative pressure by the capillary force of the porous body. 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 supported on the main guide rod 109 on the rear side (downstream side in the sheet (sheet) conveyance direction) (meaning that it slides in contact) and forward (upstream in the sheet conveyance direction). Side) is slidably mounted on the secondary guide rod 110. The timing belt 104 is fixed to the carriage 101 in order to move and scan the carriage 101 in the main scanning direction. The timing belt 104 is stretched between the drive pulley 112 and the driven pulley 113 that are rotationally driven by the main scanning motor 111 (meaning that the belt is stretched and attached in a tensioned state). The carriage 101 is reciprocated by forward / 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. The guide member 117 to be transported, the transport roller 118 for reversing and transporting the fed paper 105, the transport roller 119 pressed against the peripheral surface of the transport roller 118, and the feed angle of the paper 105 from the transport roller 118 are defined. A tip roller 120 is provided.

  The transport roller 118 is rotationally driven through a gear train by a sub-scanning motor 121 shown in FIG. 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. On the downstream side of the printing receiving member 122 in the sheet conveyance direction, a conveyance roller 123 and a spur 124 that are rotationally driven to send out the sheet 105 in the sheet discharge direction are provided. Further, a paper discharge roller 125 and a spur 126 for sending the paper 105 to the paper discharge tray 108, and guide members 127 and 128 for forming a paper discharge path are provided.

  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.

  When a discharge failure occurs, the discharge port (nozzle) of the recording head 102 is sealed with a capping unit, and bubbles and the like are sucked out together with ink from the discharge port with a suction unit through a tube. Etc. are removed by the cleaning means, and the ejection failure is recovered. The sucked ink is discharged to a waste ink reservoir (not shown) installed at the lower part of the recording apparatus main body 100A, and is absorbed and held by an ink absorber inside the waste ink reservoir.

  As described above, according to the second embodiment, the inkjet recording apparatus 100 is equipped with the recording heads 102 that are one embodiment of the plurality of liquid ejection heads 9 manufactured by the thin film manufacturing apparatus 50. There is no ink droplet ejection failure due to vibration plate drive failure, stable ink droplet ejection characteristics are obtained, and image quality is improved.

Example 1
Next, Example 1 in which a thin film pattern is formed using the thin film manufacturing apparatus 50 will be described. In Example 1, a thermal oxide film (film thickness 1.0 μm) was formed on a silicon wafer as a substrate, and a titanium film (film thickness 50 nm) was formed by sputtering as an adhesion layer. Subsequently, a platinum film (thickness: 200 nm) was formed by sputtering as the lower electrode.

Next, in step B in FIG. 4 (a) and step B2 in FIG. 4 (c), CH ₃ (CH ₂ ) ₆ —SH is used as the alkanethiol, and the concentration is 0.01 mol / liter (solvent: isopropyl alcohol). ) It was immersed in the solution and subjected to SAM treatment. Thereafter, after washing and drying with isopropyl alcohol, the process proceeds to the patterning process of the SAM film 2.
As shown in the water contact angle measurement photograph in FIG. 11 (a), the water contact angle on the SAM film 2 formation site is 92.2 °. Met. On the other hand, as shown in the water contact angle measurement photograph of FIG. 11 (b), that of the platinum sputtered film before the SAM treatment (which is also the removal site of the SAM film 2) was 5 ° or less (complete wetting). From this result, it was found that the SAM film treatment was performed.

  In step C of FIG. 4A, a photoresist layer 3 is formed by spin coating using a photoresist (TSMR8800) manufactured by Tokyo Ohka Co., Ltd., and a resist pattern is formed by ordinary photolithography, followed by oxygen plasma treatment. Then, the exposed SAM film 2 was removed (see step D in FIG. 4A). The residual resist after the treatment was dissolved and removed with acetone, and a contact angle evaluation similar to that described above was performed. As a result, a hydrophilic portion (hydrophilic region) 5 having a value of 5 ° or less (completely wet) was formed in the removed portion. The SAM film 2 formation site covered by the photoresist layer 3 showed a value of 92.4 °. From this result, it was confirmed that a hydrophobic portion (hydrophobic region) was formed and the SAM film 2 was patterned.

  In the SAM film patterning method shown in FIG. 4B, a resist pattern is formed in advance by the same resist work as described above, and after performing the same SAM treatment, the photoresist layer 3 is removed with acetone (B1 to D1). Step), the contact angle was measured. The hydrophilic part 5 is formed with a contact angle on the platinum film covered with the photoresist layer 3 of 5 ° or less (complete wetting), and the other part (pattern part of the SAM film 2) is 92.0 °. It was confirmed that the SAM film 2 was appropriately patterned by forming a hydrophobic portion having the value of.

In the SAM film patterning method shown in FIG. 4C, the photomask 4 was used for ultraviolet irradiation. The ultraviolet rays used were irradiated with vacuum ultraviolet light having a wavelength of 176 nm from an excimer lamp for 10 minutes. The contact angle of the irradiated part is a value of 5 ° or less (completely wet state), the hydrophilic part 5 is formed, and the non-irradiated part (pattern part of the SAM film 2) is a hydrophobic part having a value of 92.2 °, It was confirmed that the SAM film 2 was appropriately patterned.
Next, PZT (53/47) was formed as an electro-mechanical conversion film. In the synthesis of the precursor coating solution (PZT precursor solution), lead acetate trihydrate, isopropoxide titanium, and isopropoxide zirconium were used 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.

Isopropoxide titanium and isopropoxide zirconium were dissolved in methoxyethanol, the alcohol exchange reaction and the esterification reaction were advanced, and the PZT precursor solution was synthesized by mixing with the methoxyethanol solution in which the lead acetate was dissolved. The PZT concentration was 0.1 mol / liter.
The film thickness obtained by a single sol-gel film formation is preferably 100 nm, and the PZT precursor concentration is optimized from the relationship between the film formation area and the amount of applied precursor (thus, it is not limited to 0.1 mol / liter). ).

  This PZT precursor solution was applied onto the patterned SAM film by the ink jet method (see FIG. 7A). A PZT precursor coating film patterned only on the hydrophilic portion by contrast of the contact angle was obtained by discharging only the hydrophilic portion without discharging droplets on the SAM film (hydrophobic portion) by the inkjet method. . The coating film was heated and crystallized by irradiating a laser with a laser irradiation device 71 to obtain an electro-mechanical conversion film 43 as a PZT film shown in FIG.

By the above-described ink jet method, the process of repeatedly discharging droplets to the same place and irradiating with laser was repeated 15 times to perform overcoating, and a 500 nm electro-mechanical conversion film was obtained. No defects such as cracks occurred in the electro-mechanical conversion film (PZT film) produced at this time.
Further, selective coating of the PZT precursor solution 15 times, laser irradiation was performed, and heating and crystallization treatment were performed (total 30 times). No defects such as cracks occurred in the electro-mechanical conversion film (PZT film). The film thickness of the electro-mechanical conversion film (PZT film) reached 1000 nm. An upper electrode (platinum) was formed on the patterned electro-mechanical conversion film (PZT film) to produce an electro-mechanical conversion element, and the electrical characteristics and electro-mechanical conversion ability (piezoelectric constant) were evaluated. .
The dielectric constant of the electro-mechanical conversion film (PZT film) is 1220, the dielectric loss is 0.02, the remanent polarization is 19.3 μC / cm ² , the coercive electric field is 36.5 kV / cm, and an ordinary ceramic sintered body Has the same characteristics as The PE hysteresis curve obtained at this time is shown in FIG.

The electro-mechanical conversion ability of the electro-mechanical conversion element was calculated from the amount of deformation caused by the application of an electric field measured with a laser Doppler vibrometer and adjusted by simulation. The piezoelectric constant d ₃₁ was −120 pm / V, which was also the same value as the ceramic sintered body. This is a characteristic value that can be sufficiently designed as a liquid discharge head. Note that pm / V is a unit representing how many meters the material extends when a voltage of 1 V (volt) is applied. Here, it indicates that when a voltage of 1 V is applied, the material contracts by 120 pm (picometer).

  As described above, according to the first embodiment, it is possible to minimize damage to the substrate due to heat by performing heating and baking with a laser. Further, the laser irradiation area (shape) may be any shape as long as it is wider than the pattern, but is preferably substantially the same shape. Further, since the amount of energy supplied by the laser is larger than that of other heating / firing processes, tact improvement can be realized at the same time.

Note that an electrode film can be formed in the same manner as the electro-mechanical conversion film by dissolving an oxide such as platinum, SrRuO _3, or LaNiO ₃ in a solvent, applying the ink film by an ink jet method, and irradiating a laser.

(Example 2)
Example 2 relating to film thickness measurement of the electromechanical conversion film will be described. As shown in FIGS. 6 and 7, heating and crystallization are performed after the functional ink is applied in an arbitrary pattern by the inkjet head 67. Here, as shown in FIG. 13, a large number of thin film patterns (hereinafter also simply referred to as “patterns”) of the electro-mechanical conversion film 43 formed on the substrate 1 made of a silicon wafer have the same shape and approximately 1 mm. One dimension (dimension in the longitudinal direction L) × 50 μm (dimension in the film thickness measurement direction (short: sub-scanning direction) B) is defined as one pattern (hereinafter also referred to as “1 bit”), and 400 patterns (400 bits) It is assumed that there are a plurality of chips as one chip.
Here, the thin film pattern means a shape portion in which the electro-mechanical conversion film 43 has an elongated and substantially rectangular shape. Moreover, a coating film pattern means the application | coating and shape part of the functional ink state before a heating and crystallization.

  The above-described steps D ′, E ′, and F ′ of FIG. 5 and the step of FIG. 6 are repeated until the target film thickness is closest. Thereafter, the film thickness of all the bits is measured with a contact-type surface roughness meter as a film thickness measuring means. Although a contact-type roughness meter has been described here, a non-contact type laser microscope may be used. If the functional film is not damaged, the contact type is more advantageous in terms of tact, but if the functional film is soft and may be damaged, a non-contact type roughness meter may be used.

Here, it is assumed that the target film thickness (for example, 2.0 μm) is a specified film thickness set in advance with a predetermined tolerance of, for example, 2.0 ± 0.1 μm. At this time, the control unit 75 as the correcting means shown in FIG. 7B adjusts the pattern at each location by the inkjet head 67 in accordance with the maximum film thickness value within the tolerance in the film thickness measurement results at all pattern locations. The functional ink has a function of correcting the ejection amount.
As a result of film thickness measurement at all pattern locations, when the maximum film thickness value is 2.1 μm, for example, the film thickness of the pattern at other locations is 2.1 μm in accordance with 2.1 μm. Thus, the ejection amount of functional ink to each location by the inkjet head 67 is corrected. At this time, the ink jet head 67 changes the volume of the functional ink for each pattern at other locations, and discharges the ink so that the maximum film thickness value becomes 2.1 μm. That is, the case where the volume of the functional ink as droplets ejected from the inkjet head 67 is not the same is included (claim 2).

  According to the second embodiment, in the liquid discharge head as a product on which the electro-mechanical conversion element including the electro-mechanical conversion film is mounted, it is possible to suppress the variation width of the applied voltage to be small, thereby reducing the yield. In addition, it is possible to provide a liquid discharge head equipped with an electro-mechanical conversion element having a small variation width.

(Example 3)
In the conventional electro-mechanical conversion element, in order to obtain efficient vibration and deformation displacement, the main purpose is to make the electro-mechanical conversion film such as a piezoelectric body constituting the electro-mechanical conversion element uniform. It was. For this reason, in order to obtain efficient deformation displacement, a full-scale technical proposal on the relationship between the rigidity of the electromechanical conversion element and the film thickness / shape (hereinafter also referred to as “correlation”) is The present situation is not found to the extent that the inventors know.
As described in the present embodiment, the present inventors diligently proceeded with research and studies, and as a substitute characteristic of the displacement amount, which is the electro-mechanical conversion ability of the actuator part of the electromechanical conversion element, the rigidity, the film thickness, A certain correlation is found and proposed with the shape.

The pattern dimension of the electromechanical conversion film 43 finally formed in Example 1 is 1000 × 50 μm as described above, and the displacement amount in the short width direction (short direction: corresponding to the sub-scanning direction) is measured by a laser Doppler meter. FIG. 14 shows the result of measurement in FIG.
In FIG. 14, the horizontal axis indicates the position in the short direction in the actuator portion (see FIGS. 1 and 2) of the electromechanical conversion element, and the vertical axis indicates the amount of displacement of the actuator portion.
In the same figure, (a) is a diagram showing the displacement characteristics of the comparative example, and includes an electro-mechanical conversion film formed by a spin coat method patterned to the same dimensions by the same method as in the first embodiment. -The displacement characteristic of the actuator part of a mechanical transducer is shown. (B) shows the displacement characteristic of the actuator part of the electromechanical conversion element containing the PZT film | membrane formed by the ink jet construction method of Example 1. FIG.

  With reference to FIG. 15, the state of deformation of the third embodiment in the PZT film (electro-mechanical conversion film) of the actuator part of the electromechanical conversion element by analysis will be described in a state in comparison with the comparative example. 15A is a comparative example similar to that described in FIG. 14A: formed by a spin method, and FIG. 15B is the same as that described in FIG. 14B. The state of deformation of one half of each PZT film formed by the construction method is shown. Note that the scale is amplified 50 times in the vertical direction so that the difference in deformation is well understood.

Each white figure shown in the lower side of FIGS. 15A and 15B shows a cross-sectional shape of each of the actuator portions 35 of the electromechanical conversion element when no voltage is applied. As shown also in FIG. 1, the actuator part 35 shows the laminated structure part from the diaphragm 30 as the board | substrate 1 to the upper electrode 44 comprised on both sides of the PZT film | membrane as the electromechanical conversion film | membrane 43, and voltage It represents a drive part that is actually deformed and displaced when the is applied. The X axis is the position in the short (sub-scanning) direction of the PZT film, and the Z axis is the position in the direction in which the actuator unit 35 is deformed and displaced toward the pressure chamber substrate 20 and the pressure chamber 21 (see FIG. 1) when a voltage is applied.・ The amount of displacement is shown respectively.
Since the electro-mechanical conversion film 43 made of the PZT film manufactured by the spin method of the comparative example shown in FIG. 15A is processed by etching, the film thickness is substantially uniform, so the rigidity depends on the location and position. It can be seen that it is substantially constant and hinders deformation of the diaphragm 30 near the end of the electromechanical conversion film 43.

  On the other hand, the electro-mechanical conversion film 43 made of the PZT film formed by the inkjet method of Example 3 shown in FIG. 15B has a substantially meniscus (crescent moon) convex lens shape (the convex is the upper electrode). 44), the film thickness is thin at the end of the PZT film of the actuator unit 35. As a result, the rigidity in the vicinity of the end portion of the actuator portion 35 (PZT film) is lowered, so that the vibration plate 30 in the vicinity of the end portion is greatly deformed by the spin method at the time of deformation, and the maximum in the central portion of the PZT film of the actuator portion 35 The displacement amount was also larger than that of the spin method PZT film, which was found to be consistent with the measurement result of FIG.

  An attempt was made to further increase the film thickness without arranging the upper electrode. That is, crystallization treatment was performed every time pyrolysis annealing was repeated up to 6 times, and when this was repeated 10 times, a patterned PZT film having a thickness of 5 μm was obtained without defects such as cracks.

As described above, the actuator unit 35 in which the electromechanical conversion element obtained in the third embodiment is laminated from the diaphragm 30 as the substrate 1 to the upper electrode 44 as the second electrode is a high-level concept term. It will be as follows. That is, it is expressed as having rigidity that gradually increases from the end portion of the actuator portion 35 toward the central portion thereof in a cross section in the short direction (corresponding to the sub-scanning direction) orthogonal to the longitudinal direction of the actuator portion 35. it can. In this case, in addition to a mountain-shaped curve having the highest center, a triangular curve having the highest center is also included.
More specifically, the actuator portion 35 has a rigidity that gradually increases so as to draw a curved line of the outer peripheral surface of the substantially meniscus convex lens from the end portion of the actuator portion 35 in the cross section in the short direction toward the center portion thereof. It is preferable to make it as follows.

As described above, according to the third embodiment, first, by obtaining an electro-mechanical conversion element having the above-described specific rigidity characteristics, an excellent deformation displacement as an efficient electro-mechanical conversion ability is obtained. Can be obtained.
Second, in Example 3, a surface modification step for partially modifying the surface of the first electrode, and a piezoelectric precursor by a droplet discharge method on the surface-modified first electrode. Coating process for partially applying a sol-gel liquid (PZT precursor solution) containing a PZT precursor as a drying process, and a drying / pyrolysis / crystallization process for drying / pyrolysis / crystallization of the partially applied sol-gel liquid The electro-mechanical conversion film for obtaining a patterned electro-mechanical conversion film by repeatedly performing the coating step and the drying / pyrolysis / crystallization step, and the surface modification is performed , By applying a thiol compound on the first electrode, and then partially removing the thiol compound by photolithography etching. Thereby, generation | occurrence | production of the crack in a heating and crystallization process can be prevented, and the electromechanical conversion film (PZT film | membrane) obtained at the above-mentioned process can have a favorable electrical property.

Next, the film thickness distribution shape of the electro-mechanical conversion film and the outer peripheral surface shape of the electro-mechanical conversion film according to the present invention will be described.
With reference to FIG. 16 and FIG. 17, the thickness distribution shape and outer peripheral surface shape of the PZT film in Example 2 will be described.
FIG. 16 shows the result of the half on one side where the film thickness of the cross section in the short direction in the actuator part of the PZT film finally obtained by the repeated application by the ink jet method as in Example 1 was measured with a surface roughness meter. . The thickness of the PZT film is the thickest at the center of the PZT film, and the film thickness decreases uniformly toward the end. At this time, the maximum film thickness at the center was 1000 nm (1.0 μm).
That is, the thickness distribution shape of the PZT film has a shape characteristic that gradually increases from the end portion of the actuator portion toward the central portion in the cross section in the short direction of the actuator portion, and has a substantially meniscus convex lens shape.

As a result of polynomial approximation of the film thickness distribution, it showed a very good agreement with the approximate expression of the quartic function which is a higher order function of FIG. 17 and the following expressions (1) and (2). As an example of the film thickness distribution shown in FIG. 17, the width of the PZT film in the short side (sub-scanning) direction (both in the + and -X directions) is 50 μm, and the effective range of X (PZT film forming part) is: −25 ≦ X ≦ + 25 μm.
In Equation (1), X represents positive and negative position coordinates toward each end of the PZT film with the center of the cross section of the PZT film being 0, and Y represents the thickness of the PZT film at the X position coordinates (FIG. 17). reference). Coefficients A to E are coefficients that vary as the film thickness changes.
Y = −AX ⁴ + BX ³ −CX ² + DX + E (1)

In order to obtain the above formula (1), the above-described film thickness measurement was performed many times, and polynomial approximation of the film thickness distribution was performed many times, and a specific relationship between the coefficients A to E was found. The results are summarized as follows. In the formula (1), when the range of the coefficient E that is the film thickness E (when X = 0) in the center of the cross section is 0.5 to 5.0 (μm), the coefficient A, the coefficient B, and the coefficient C The coefficient D is in a specific relationship that exists within a range obtained by multiplying the coefficient value of the following expression (2) by 0.9 to 1.1 times.
Y = -3 × 10 ¹⁸ X ⁴ +10 ¹⁴ X ³ −3 × 10 ⁹ X ² + 4520X + 0.996 Formula (2)
In addition, the expressions (1) and (2) can be expressed as an approximate representation of the outer peripheral surface shape of the PZT film, when viewed differently.

As described above, according to the third embodiment, in addition to the effects of the first embodiment, an ideal film thickness distribution shape of the PZT film and an outer peripheral surface shape of the PZT film can be obtained.
In the conventional electro-mechanical conversion element, in order to obtain efficient vibration and deformation displacement, the main purpose is to make the electro-mechanical conversion film such as a piezoelectric body constituting the electro-mechanical conversion element uniform. It was. In view of such a current situation, the present inventors have obtained the rigidity and thickness of the electro-mechanical conversion element / electro-mechanical conversion film in order to obtain an efficient deformation displacement from a viewpoint / idea essentially different from the conventional one. The correlation with the shape is proposed as described above.

  As described above, the present invention has been described with respect to specific embodiments and examples. However, the technology disclosed by the present invention is not limited to those exemplified in the above-described embodiments and examples. . That is, it may be configured by appropriately combining them, and it will be apparent to those skilled in the art that various embodiments, examples, and modifications can be configured within the scope of the present invention according to the necessity and application. It is.

  Although the ink jet recording head 102 that ejects minute ink has been described as an example of the liquid ejecting head using the electro-mechanical conversion element 40 of the first embodiment of the present invention, the present invention is not limited to this. That is, the scope of application of the present invention may be, for example, a liquid discharge head that discharges an arbitrary minute liquid used in accordance with its use instead of ink, and is also applicable to a patterning apparatus using the liquid discharge head. Needless to say, it is applicable.

The image forming apparatus according to the present invention is not limited to the ink jet recording apparatus 100 shown in FIGS. 9 and 10, and can be applied to an image forming apparatus including the ink jet type image forming apparatus of the present invention. That is, for example, the present invention can be applied to an image forming apparatus including an ink jet recording apparatus in a printer, a plotter, a word processor, a facsimile machine, a copying machine, or a multifunction machine having two or more functions.
The application field of the present invention is directly the printing field, particularly the digital printing field, and the image forming apparatus is a digital printing apparatus using a multi-function printer (MFP), a printer used in an office or a personal use. And the above-mentioned MFP. In addition, as an application field, it can be applied to a three-dimensional molding technique using an inkjet technique.
The recording medium is not limited to the paper 105, but includes all recording media capable of forming an image using an inkjet head, such as usable thin paper, thick paper, postcard, envelope, or OHP sheet.

1 substrate 2 SAM film (liquid repellent film)
3 Photoresist layer 4 Photomask 5 Hydrophilic part 6 PZT precursor coating (functional coating)
7 PZT film (functional film)
9 Liquid ejection head 10 Nozzle plate 11 Nozzle 20 Pressure chamber substrate 21 Pressure chamber 30 Vibration plate 40 Electro-mechanical conversion element 41 Adhesion layer 42 Lower electrode (first electrode)
43 Electro-mechanical conversion membrane (functional membrane)
43a Functional ink (functional solution)
44 Upper electrode (second electrode)
50 Thin Film Manufacturing Device 67 Inkjet Head (Liquid Discharge Unit)
71 Laser irradiation device (heating crystallization means)
73 Film thickness measuring means 75 Control unit (correction means)
100 Inkjet head recording apparatus (image forming apparatus)
100A recording apparatus main body 101 carriage 102 ink jet recording head (liquid ejection head)
104 Printing mechanism 105 Paper (recording medium)

JP 2011-108996 A Japanese Patent No. 4364840

Claims (16)

A liquid ejecting unit that ejects the functional ink a plurality of times at a plurality of locations on the film formation target, and forms a coating film pattern at the plurality of locations;
Heat crystallization means for heating and crystallizing the coating film pattern at the plurality of locations for each of the plurality of ejections of the functional ink to obtain a thin film pattern at the plurality of locations;
A thin film manufacturing apparatus comprising: The thin film manufacturing apparatus according to claim 1,
The thin film manufacturing apparatus, wherein the volume of the plurality of droplets ejected from the liquid ejecting means is not the same. The thin film manufacturing apparatus according to claim 1,
Film thickness measuring means for measuring the film thickness of the thin film pattern at all locations after the heat crystallization multiple times,
Correction means for correcting the discharge amount of the functional ink from the liquid discharge means to the respective positions so as to obtain a film thickness of a target film thickness based on the film thickness measurement results of the thin film patterns at all the positions; ,
A thin film manufacturing apparatus comprising: In the thin film manufacturing apparatus according to claim 3,
The target film thickness is a specified film thickness set in advance with a predetermined tolerance,
The thin film manufacturing apparatus, wherein the correction unit corrects the ejection amount of the functional ink to each of the portions in accordance with the maximum film thickness value within the tolerance in the film thickness measurement result. In the thin film manufacturing apparatus according to claim 3 or 4,
The thin film manufacturing apparatus, wherein the film thickness measuring means is a contact type surface roughness meter. In the thin film manufacturing apparatus according to claim 5,
The film thickness measurement by the contact-type surface roughness meter is performed after heating and crystallization of the functional ink. In the thin film manufacturing apparatus according to claim 3 or 4,
The thin film manufacturing apparatus, wherein the film thickness measuring means is a non-contact type. In the thin film manufacturing apparatus according to any one of claims 1 to 7,
The thin film manufacturing apparatus, wherein the functional ink is a ceramic precursor solution. The thin film manufacturing apparatus according to claim 8,
As the liquid ejection means, a plurality of liquid ejection heads are provided,
The thin film manufacturing apparatus, wherein the precursor solutions having different concentrations are discharged from the liquid discharge heads. The thin film manufacturing apparatus according to claim 9, wherein
When the number of the plurality of liquid discharge heads is two, the concentration of the precursor solution discharged from one of the liquid discharge heads is equal to or less than half the concentration of the precursor solution discharged from the other liquid discharge head. A thin film manufacturing apparatus characterized by the above. An electro-mechanical conversion element using an electro-mechanical conversion film as a thin film manufactured by the thin film manufacturing apparatus according to claim 1,
A first electrode is formed on the film formation target, the electro-mechanical conversion film is formed on at least a part of the first electrode, and a second electrode is formed on at least a part of the electro-mechanical conversion film. Is an electro-mechanical conversion element formed,
In the actuator unit in which the film formation target to the second electrode are stacked, the thickness distribution shape of the electro-mechanical conversion film in the cross section of the actuator unit is approximated by a quartic function of the following equation (1). An electro-mechanical conversion element.
Y = −AX ⁴ + BX ³ −CX ² + DX + E (1)
However, in Formula (1), X represents the positive / negative position coordinate which goes to each said edge part which made the said cross-sectional center of the said electromechanical conversion film | membrane 0, and Y represents the said film thickness in a X position coordinate.
In the formula (1), the coefficients A to E are coefficients that vary as the film thickness changes, and the range of the coefficient E that is the film thickness E (when X = 0) in the center of the cross section is 0.5 to 5. When it is 0 (μm), the coefficient A, the coefficient B, the coefficient C, and the coefficient D are in a specific relationship that exists within a range obtained by multiplying the coefficient numerical value of the following expression (2) by 0.9 to 1.1 times, respectively. is there.
Y = -3 × 10 ¹⁸ X ⁴ +10 ¹⁴ X ³ −3 × 10 ⁹ X ² + 4520X + 0.996 Formula (2) The electro-mechanical transducer according to claim 11,
The electro-mechanical conversion film is
A surface modification step for partially modifying the surface on the first electrode, and a sol-gel solution containing a piezoelectric precursor is partially coated on the surface-modified first electrode by a droplet discharge method. The coating step and the drying / pyrolysis / crystallization step for drying, pyrolysis / crystallization of the partially applied sol-gel solution, and repeating the coating step and the drying / pyrolysis / crystallization step. An electro-mechanical conversion element manufactured by a method of manufacturing an electro-mechanical conversion film to obtain a patterned electro-mechanical conversion film. The electro-mechanical transducer according to claim 12,
The electro-mechanical conversion characterized in that the surface modification is performed by applying a thiol compound on the first electrode, and then partially removing the thiol compound by photolithography etching. element.   A liquid discharge head comprising the electro-mechanical conversion element according to claim 11.   An image forming apparatus comprising the liquid discharge head according to claim 14. A surface modification step for partially modifying the surface on a plurality of first electrodes on a film formation target, and a droplet discharge method for each of the plurality of locations on the surface-modified first electrode A coating step of partially applying a sol-gel solution containing a piezoelectric precursor, and a heating / crystallization step of heating / crystallizing the partially applied sol-gel solution, wherein the coating step And in the thin film manufacturing method for repeatedly obtaining the thin film pattern by repeatedly performing the heating and crystallization step,
Based on the film thickness measurement results obtained by measuring the film thickness of the thin film pattern at all locations after the multiple heating and crystallization steps, the sol-gel solution to each location is adjusted so as to have a target thickness. A method for producing a thin film, wherein the coating amount is corrected.

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