JP2013135164A - Thin film manufacturing device, thin-film manufacturing method, droplet discharge head, and ink jet recording device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin film manufacturing device and a thin-film manufacturing method, capable of suitably performing a heating treatment corresponding to a film thickness of a thin film to be heated.SOLUTION: The thin film manufacturing device comprises: liquid discharge means which discharges a liquid on an object to be deposited and forms a coated film; imaging means which captures an image of the coated film; color depth conversion means which converts a color of an image captured by the imaging means to a color depth; film thickness calculation means which calculates a film thickness from the color depth; irradiation power calculation means which calculates an irradiation power corresponding to the film thickness calculated by the film thickness calculation means; and laser irradiation means which irradiates the coated film with a laser beam with the irradiation power calculated by the irradiation power calculation means and heats and crystallizes the coated film.

Description

  The present invention relates to a thin film manufacturing apparatus, a thin film manufacturing method, a droplet discharge head, and an inkjet recording apparatus including the droplet discharge head.

  2. Related Art An ink jet recording apparatus and a liquid ejection head used as an image recording apparatus or an image forming apparatus such as a printer, a facsimile machine, a copying apparatus, etc., a nozzle for ejecting ink droplets, a pressure chamber communicating with the nozzle, and ink in the pressure chamber A device having an electromechanical conversion element such as a piezoelectric element for pressing is known.

  The electromechanical conversion element has, for example, a structure in which an electromechanical conversion film and an upper electrode are stacked on a lower electrode. The electromechanical conversion film which 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.

  Here, a method for manufacturing an electromechanical conversion film using a sol-gel method will be described as an example. First, a hydrophobic film pattern is formed on the lower electrode (step 1). The portion of the lower electrode where the hydrophobic film pattern is not formed is hydrophilic. Next, a precursor coating film of the electromechanical conversion film is formed only on the hydrophilic part (the part where the hydrophobic film pattern is not formed) on the lower electrode, and heat treatment is performed (step 2). By this heat treatment, the pattern of the hydrophobic film disappears.

  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 Step 1 and Step 2 as many times as necessary, the precursor coating film of the electromechanical conversion film is laminated to produce an electromechanical conversion film having a predetermined film thickness.

  However, in the method for producing an electromechanical conversion film, Step 1 and Step 2 are repeated as many times as necessary. Therefore, the film thickness of the precursor coating film to be heat-treated is different each time (the more the number of repetitions, the larger the film thickness. Thicken). Therefore, even if heat treatment was performed under the same conditions in step 2, there was a problem that heating to the same temperature was not possible due to the difference in light absorption due to the difference in the film thickness of the precursor coating film.

  The present invention has been made in view of the above points, and it is an object to provide a thin film manufacturing apparatus and a thin film manufacturing method capable of performing a suitable heat treatment corresponding to the thickness of a thin film to be heated. And

  The thin film manufacturing apparatus includes a liquid discharge unit that discharges liquid onto a film formation target to form a coating film, an imaging unit that images the coating film, and a color depth of an image captured by the imaging unit. Color depth conversion means for conversion, film thickness calculation means for calculating the film thickness of the coating film from the color depth, and irradiation power calculation means for calculating the irradiation power corresponding to the film thickness calculated by the film thickness calculation means And laser irradiation means for irradiating the coating film with laser light with the irradiation power calculated by the irradiation power calculation means and heating the coating film for crystallization.

  ADVANTAGE OF THE INVENTION According to this invention, the thin film manufacturing apparatus and thin film manufacturing method which can perform the suitable heat processing corresponding to the film thickness of the thin film used as heating object can be provided.

FIG. 6 is a cross-sectional view illustrating a liquid discharge head using an electromechanical conversion element (part 1); FIG. 6 is a cross-sectional view (part 2) illustrating a liquid discharge head using an electromechanical conversion element. It is a perspective view which illustrates the thin film manufacturing apparatus concerning a 1st embodiment. It is FIG. (The 1) which illustrates the thin film manufacturing process which concerns on this Embodiment. It is a figure (the 2) which illustrates the thin film manufacturing process which concerns on this Embodiment. It is FIG. (The 3) which illustrates the thin film manufacturing process which concerns on this Embodiment. It is FIG. (The 4) which illustrates the thin film manufacturing process which concerns on this Embodiment. It is FIG. (The 5) which illustrates the thin film manufacturing process which concerns on this Embodiment. It is a figure which illustrates the relationship between color depth and a film thickness. It is a figure which illustrates the relationship between a film thickness and a light absorption rate. It is a figure which illustrates the pattern of the functional ink recognized with the camera. It is a perspective view which illustrates an inkjet recording device. It is a side view which illustrates the mechanism part of an inkjet recording device. It is the photograph which measured the contact angle of water in the SAM film formation site. It is the photograph which measured the contact angle of water in the SAM film removal site | part. It is a graph which shows the PE hysteresis curve of the electromechanical conversion element produced in the present Example.

  Hereinafter, embodiments for carrying out the invention will be described with reference to the drawings. In the drawings, the same components are denoted by the same reference numerals, and redundant description may be omitted.

<First Embodiment>
[Thin film]
First, an electromechanical conversion film constituting an electromechanical conversion element will be described as an example of a thin film manufactured by the thin film manufacturing apparatus and the thin film manufacturing method according to the first embodiment. Needless to say, the thin film that can be manufactured by the thin film manufacturing apparatus and the thin film manufacturing method according to the first embodiment is not limited to the electromechanical conversion film.

  The electromechanical transducer is used, for example, as a component part of a liquid discharge head used in an ink jet recording apparatus. FIG. 1 is a cross-sectional view illustrating a liquid discharge head using an electromechanical transducer.

  Referring to FIG. 1, the droplet discharge head 1 includes a nozzle plate 10, a pressure 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 pressure chamber substrate 20, and the vibration plate 30 may be referred to as a pressure chamber 21 (an ink channel, a pressurized liquid chamber, a pressurized chamber, a discharge chamber, a liquid chamber, or the like) that communicates with the nozzle 11. ) Is formed. The diaphragm 30 forms part of the wall surface of the ink flow path.

The electromechanical conversion element 40 includes an adhesion layer 41, a lower electrode 42, an electromechanical conversion film 43, and an upper electrode 44, and has a function of pressurizing ink in the pressure chamber 21. 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 electromechanical conversion element 40.

  In the electromechanical conversion element 40, when a voltage is applied between the lower electrode 42 and the upper electrode 44, the electromechanical conversion film 43 is mechanically displaced. Along with the mechanical displacement of the electromechanical conversion film 43, the vibration plate 30 is deformed and displaced, for example, in the lateral direction (d31 direction), and pressurizes the ink in the pressure chamber 21. Thereby, ink droplets can be ejected from the nozzle 11.

  As shown in FIG. 2, a plurality of droplet discharge heads 1 can be arranged in parallel to form the droplet discharge head 2.

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 electromechanical 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 use by laminating 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 electromechanical transducer 40, the diaphragm 30 under the lower electrode 42 can use an insulator or a conductor whose surface is insulated.

  As a specific material of the diaphragm 30, for example, silicon can be used. In addition, as a specific material for insulating the surface of the vibration plate 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 laminated. A film or the like can be used. In consideration of the 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.

[Thin film manufacturing equipment]
Next, the structure of the thin film manufacturing apparatus according to the first embodiment will be described. FIG. 3 is a perspective view illustrating the thin film manufacturing apparatus according to the first embodiment. Referring to FIG. 3, in the thin film manufacturing apparatus 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 5 is mounted is installed so as to be driven in the Y-axis direction.

  The stage 62 is usually accompanied by a suction means (not shown) using vacuum or static electricity, so that the substrate 5 can be fixed. In addition, a driving means (not shown) that rotates around the Z axis is mounted on the stage 62, and the inkjet head 67, the continuous irradiation laser apparatus 71, the pulse irradiation laser apparatus 72, and the imaging means 73 described later are relative to the substrate 5. It is also possible to adopt a configuration that can correct the tilt.

  An X-axis support member 64 for supporting the X-axis drive means 63 is installed on the gantry 60. The X-axis drive means 63 is provided with a Z-axis drive means 65, and a head base 66 is mounted on the Z-axis drive means 65 so as to be movable in the X-axis and Z-axis directions.

  The Z-axis drive unit 65 can control the distance between an inkjet head 67 and a substrate 5 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).

  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 continuous irradiation laser device 71, a pulse irradiation laser device 72, and an imaging unit 73 are attached to the support member 70. The Z-axis drive unit 69 can control the distance between the substrate 5 and the continuous irradiation laser device 71, the pulse irradiation laser device 72, and the imaging unit 73. As the imaging unit 73, for example, a CCD camera or the like can be used.

  In FIG. 3, the stage 62 has one axis of freedom in the Y direction, and the inkjet head 67, the continuous irradiation laser device 71, the pulse irradiation laser device 72, and the imaging unit 73 have one axis of freedom in the X direction. However, the present invention is not limited to this configuration. For example, the stage 62 may have two-axis freedom in the X and Y directions, and the inkjet head 67, the continuous irradiation laser device 71, the pulse irradiation laser device 72, and the imaging unit 73 may be fixed. Further, the stage 62 has a single axis freedom in the Y direction, and the inkjet head 67, the continuous irradiation laser device 71, the pulse irradiation laser device 72, and the imaging means 73 are arranged in a line in the Y axis direction. good.

  Alternatively, the substrate 5 may be fixed, and the inkjet head 67, the continuous irradiation laser device 71, the pulse irradiation laser device 72, and the imaging unit 73 may have a biaxial degree of freedom in the X and Y directions. The X axis and the Y axis need not be orthogonal as long as one plane can be expressed by the X axis and Y axis vectors. For example, the X axis vector and the Y axis vector have angles of 30 degrees, 45 degrees, and 60 degrees. You may do it.

  The thin film manufacturing apparatus 3 has an apparatus control unit (not shown) and can control the functional ink ejection conditions of the inkjet head 67 and the laser irradiation conditions of the continuous irradiation laser apparatus 71 and the pulse irradiation laser apparatus 72.

  The device control unit includes, for example, a CPU, a ROM, a RAM, a nonvolatile memory, a main memory, and the like. Various functions of the device control unit are read by the control program recorded in the ROM and the like and executed by the CPU. It is realized by doing. However, part or all of the apparatus control unit may be realized only by hardware.

  The device control unit may be physically configured by a plurality of devices. In a recording unit such as a RAM or a non-volatile memory, it is possible to record the crystalline state of the functional ink, the optimal laser irradiation conditions, and the like. For example, the color depth conversion unit, the film thickness calculation unit, the irradiation power calculation unit, the shape determination unit, and the like according to the present invention can be realized by the apparatus control unit.

[Thin film manufacturing method]
Next, the thin film manufacturing method according to the first embodiment will be described. Here, the example which manufactures the electromechanical conversion film | membrane 43 shown in FIG. 1 as a thin film is shown.

[SAM film patterning]
First, as shown in FIG. 4, a SAM (Self Assembled Monolayer) film 50 having a predetermined pattern is formed on the surface of the lower electrode 42. Specifically, in the step shown in FIG. 4A, for example, a substrate to be the lower electrode 42 is prepared. As the lower electrode 42, for example, platinum (Pt) can be used.

  Next, in the step shown in FIG. 4B, the lower electrode 42 is immersed in a SAM material made of alkanethiol or the like. Thereby, the SAM material reacts on the surface of the lower electrode 42 and the SAM film 50 adheres, and the surface of the lower electrode 42 can be made water repellent. Although alkanethiol has different reactivity and hydrophobicity (water repellency) depending on the molecular chain length, it is usually prepared by dissolving a molecule having 6 to 18 carbon atoms in an organic solvent such as alcohol, acetone or toluene. Usually, the concentration of alkanethiol is about several moles / liter. After a predetermined time, the lower electrode 42 is taken out, and excess molecules are replaced with a solvent and dried.

  Next, in a step shown in FIG. 4C, a photoresist 51 having an opening 51x is formed on the SAM film 50 formed on the surface of the lower electrode 42 by a known photolithography method. Next, in the step shown in FIG. 4D, the SAM film 50 exposed in the opening 51x is removed by dry etching or the like, and the photoresist 51 is further removed. As a result, the SAM film 50 having a predetermined pattern is formed on the surface of the lower electrode 42.

  The region where the SAM film 50 is formed on the surface of the lower electrode 42 is hydrophobic. On the other hand, the region where the surface of the lower electrode 42 is exposed after the SAM film 50 is removed becomes hydrophilic. By utilizing this surface energy contrast, it becomes possible to coat the PZT precursor solution described in detail below.

  After the step shown in FIG. 4A, a photoresist 53 is formed on the surface of the lower electrode 42 as in the step shown in FIG. 5A, and the SAM treatment is performed as in the step shown in FIG. And the photoresist 53 may be removed as in the step shown in FIG. Thereby, a SAM film 50 having a predetermined pattern is formed on the surface of the lower electrode 42 as in the step shown in FIG.

  4B, after the process shown in FIG. 6A, the surface of the lower electrode 42 is irradiated with ultraviolet light, oxygen plasma, or the like through the photomask 54 having the opening 54x. The SAM film 50 in the exposed portion (in the opening 54x) may be removed as in the step shown in FIG. Thereby, a SAM film 50 having a predetermined pattern is formed on the surface of the lower electrode 42 as in the step shown in FIG.

[Formation of electromechanical conversion film]
Next, as shown in FIGS. 7 and 8, an electromechanical conversion film 43 is formed on the surface of the lower electrode 42. Specifically, in the process shown in FIG. 7A, a lower electrode 42 (corresponding to the substrate 5 in FIG. 3) having a SAM film 50 of a predetermined pattern formed on the surface is provided on the stage 62 of the thin film manufacturing apparatus 3. Place. 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. Then, the functional ink 43a is ejected from the inkjet head 67 to a region (hydrophilic region) on the surface of the lower electrode 42 where the SAM film 50 does not exist. 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 50 does not exist (hydrophilic region).

  As described above, the functional ink 43a is formed only in the region where the SAM film 50 does not exist (hydrophilic region) by utilizing the contrast of the surface energy. In addition, the process can be simplified and the process can be simplified. As the functional ink 43a, for example, a PZT precursor solution can be used.

  Next, in the step shown in FIG. 7B, the continuous irradiation laser device 71 is driven on the X axis, and if necessary, the stage 62 on which the lower electrode 42 is mounted is driven on the Y axis. A continuous irradiation laser device 71 is arranged on the top. Then, the continuous irradiation laser device 71 irradiates the functional ink 43a wetted and spread in the step shown in FIG. The functional ink 43a irradiated with the laser light 71x is vaporized and thermally decomposed into the functional ink 43b thermally decomposed. For example, a semiconductor laser device or a YAG laser device can be used as the continuous irradiation laser device 71.

  The wavelength of the laser beam 71x is preferably 400 nm or more (for example, about 400 nm to 10000 nm), which is a region where the light absorption rate of the substrate including the lower electrode 42 is relatively high. More specifically, the functional ink 43a almost transmits laser light 71x having a wavelength of 400 nm or more and hardly absorbs it. Therefore, the functional ink 43a is not directly heated, the substrate including the lower electrode 42 (platinum or the like) on which the functional ink 43a is mounted is heated, and the functional ink 43a is indirectly heated accordingly. Therefore, it is preferable that the wavelength of the laser beam 71x is 400 nm or more, which is a region where the light absorption rate of the lower electrode 42 is relatively high.

  If the direct heating method is used, temperature unevenness may occur in the irradiated portion due to unevenness of the beam profile of the laser beam. However, by using the indirect heating method, the functional ink 43a is uniformly distributed within the irradiation surface. Can be heated.

  In the above description, the functional ink 43a is formed on the lower electrode 42, but the adhesion layer 41 made of titanium or the like and the lower electrode 42 made of platinum or the like are laminated on the vibration plate 30 made of silicon. In some cases, the functional ink 43 a is formed on the formed lower electrode 42. Even in such a case, it is preferable that the wavelength of the laser beam 71x is 400 nm or more, which is a region where the light absorption rate of silicon, titanium, and platinum is relatively high.

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

  The moving speed of the lower electrode 42 can be about 10 mm / s to 1000 mm / s, and the power of the laser light 71x can be about several watts to several tens of watts. The beam diameter of the laser beam 71x can be about several tens of μm to several hundreds of μm, and the beam profile can be a general Gaussian profile.

  The laser beam 71x is also applied to the SAM film 50, and the SAM film 50 is also heated. The SAM film 50 may disappear when the temperature is 500 ° C. or higher. However, when the laser light 71x is set as the above setting condition, the temperature of the lower electrode 42 remains at 500 ° C. or lower, so the SAM film 50 disappears. do not do.

  Next, in the step shown in FIG. 8A, the imaging means 73 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, An imaging means 73 is arranged. Then, the pattern of the functional ink 43b thermally decomposed in the process shown in FIG. Note that the imaging unit 73 is preferably configured to be able to image the entire area of the functional ink 43b at a time.

  The pattern image of the functional ink 43b picked up by the image pickup means 73 is taken into a device control unit (not shown) of the thin film manufacturing apparatus 3, and the color of the pattern is converted into the color depth. The color of the pattern can be converted into, for example, a color depth of 256 gradations for each of RGB.

  Although the relationship between the color depth and the film thickness varies depending on the range of the film thickness, if the film thickness is about 2 μm as in this embodiment, the color depth of red (R) and the film are as shown in FIG. The relationship with the thickness is almost linear. Therefore, the film thickness can be obtained from the color depth using this relationship. In this embodiment, the relationship between red (R) color depth and film thickness is used. However, the relationship between green (G) color depth and film thickness and blue (B) color depth and film thickness. The relationship between and may be used. It is preferable to obtain the film thickness from the color depth of a color in which the relationship between the color depth and the film thickness is more linear.

  Further, as shown in FIG. 10, the light absorption rate of the laser light changes depending on the film thickness. In FIG. 10, the light absorptance when light with a wavelength of about 1000 nm is irradiated is plotted. In FIG. 10, the solid line is the light absorption rate of the functional ink film from 0 to 1000 μm when baked at 120 ° C. for several minutes on a hot plate, and the rough dotted line is when heated at 500 ° C. for several minutes in an oven. The light absorption rate of the functional ink film is from 0 to 1000 μm, and the fine dotted line is the light absorption rate from 0 to 1000 μm of the functional ink film when heated in an oven at 700 ° C. for several minutes.

  In actual data, the film thickness is measured at a pitch of several tens of μm, and FIG. 10 shows the result of curve fitting. The film thickness can be changed at a pitch of several tens of μm by changing the film formation conditions of the spin pin coat and the ink jet discharge conditions. The temperatures measured in this embodiment are three points of 120 ° C., 500 ° C., and 700 ° C. However, more accurate information can be obtained by acquiring data up to 25 ° C. Needless to say.

  The film thickness of the functional ink film 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. The light absorption rate can be measured using, for example, FTIR, UV-VIS-NIR Spectrometry, or the like. More specifically, for example, IR and UV series of Shimadzu Corporation, Lambda series of PerkinElmer, etc. can be used.

  Based on the relationship of FIG. 9 and FIG. 10, the light absorption rate of the functional ink 43b can be obtained from the color depth of the pattern image of the functional ink 43b. If the light absorptance is obtained, the optimum laser power corresponding to the light absorptance can be calculated. Therefore, the functional ink 43b having the film thickness is irradiated from the color depth of the pattern image of the functional ink 43b. It is possible to obtain the optimum laser power.

  In order to obtain the optimum laser power, first, a reference optimum laser power is determined by prior evaluation. For example, it is assumed that the optimum laser power for heating the functional ink 43b having a thickness of 100 nm to 700 ° C. is 100 W. From FIG. 10, the light absorption rate in this case is about 36%.

  Based on this, the optimum laser power for different film thicknesses can be obtained. For example, the optical absorptance of the functional ink 43b having a thickness of 200 nm is about 82% from FIG. Therefore, about 44 W at 36% / 82% of 100 W is the optimum laser power for heating the functional ink 43 b having a film thickness of 200 nm to 700 ° C.

  Therefore, the relationship between the color depth of the pattern image of the functional ink 43b and the optimum laser power is stored in advance as data in a RAM or a non-volatile memory of the device control unit (not shown). Thereby, in the process shown in FIG. 8A, the apparatus control unit can obtain the optimum laser power to be applied to the functional ink 43b from the pattern image of the functional ink 43b imaged by the imaging means 73. .

  Next, in the step shown in FIG. 8B, the pulse irradiation laser device 72 is driven on the X-axis, and if necessary, the stage 62 on which the lower electrode 42 is mounted is driven on the Y-axis. A pulse irradiation laser device 72 is arranged on the top. Then, in the pulse irradiation laser device 72, only the functional ink 43b thermally decomposed in the process shown in FIG. That is, if the SAM film 50 is irradiated with the laser beam 72x, the temperature of the lower electrode 42 may be 500 ° C. or more, and the SAM film 50 may disappear. Therefore, the SAM film 50 is not irradiated with the laser beam 72x.

  The functional ink 43b irradiated with the laser beam 72x is crystallized to become the functional ink 43c (for example, PZT thin film), and the SAM film 50 remains without disappearing. As the pulse irradiation laser device 72, for example, a semiconductor fiber coupling laser device, a semiconductor laser stack device, or the like can be used.

  The power of the laser beam 72x irradiated in this step is the optimum power obtained in the step shown in FIG. Since the temperature required for the crystallization of the functional ink 43b is about 700 ° C., the optimum power obtained using the data of 700 ° C. in FIG. 10 is irradiated. The optimal power range is about several watts to several tens of watts.

  Further, the irradiation time of the laser beam 72x can be set to several μs to several 100 μs. The emission frequency of the laser beam 72x is preferably adjusted by the pattern of the functional ink 43b and the moving speed of the stage 62. For example, when the pattern interval is 100 μm and the moving speed of the stage 62 is 100 mm / s, the laser beam 72x The emission frequency can be 1 kHz.

  In addition, when the stage 62 moves while the laser beam 72x is emitted, the range in which the laser beam 72x is irradiated is expanded. For example, when the irradiation time is 100 μs and the moving speed of the stage 62 is 100 mm / s, the stage 62 moves while the laser light 72x is emitting, thereby expanding the range of irradiation with the laser light 72x by about 10 μm.

  Therefore, in order to irradiate only the functional ink 43b with the laser beam 72x and not to irradiate the SAM film 50, the laser beam is irradiated at an irradiation timing suitable for the pattern shape of the functional ink 43b in consideration of the irradiation range of the laser beam 72x. 72x needs to emit light.

  The pulse irradiation laser device 72 may be a multi-channel one or a single-port one, but a multi-channel one is preferably used. For example, when a plurality of patterns are arranged in parallel as in the example of FIG. 11 described later, each pattern can be irradiated with laser light at a stroke.

  The film thickness of the functional ink 43c (for example, a PZT thin film) crystallized in the process shown in FIG. 8B is about several tens of nm. Since this film thickness is insufficient, after the step shown in FIG. 8B, the steps shown in FIGS. 7A, 7B, 8A, and 8B are further performed. Repeat as many times as necessary. Thereby, the functional ink 43c is laminated, and the functional ink film crystallized with an arbitrary pattern and thickness (for example, about several μm), that is, the electromechanical conversion film 43 is formed on the lower electrode.

  At this time, the film thickness of the functional ink 43c changes (increases) each time each step is repeated, but the functionality is determined from the pattern image of the functional ink 43b imaged by the imaging means 73 in the step shown in FIG. Since the optimum laser power to be applied to the ink 43b is obtained every time, the optimum laser power corresponding to the film thickness of the functional ink 43b can always be applied in the process shown in FIG. 8B.

  As described above, in the first embodiment, the continuous ink laser device 71 irradiates the functional ink 43a with the laser beam 71x and heats the functional ink 43a at a temperature at which the SAM film 50 does not disappear. The functional ink 43b is produced by evaporating the solvent and performing thermal decomposition. Then, the functional ink 43b is irradiated with a laser beam 72x (pulse), heated, and crystallized to produce the functional ink 43c. At this time, in the pulse irradiation laser device 72, since the SAM film 50 is not irradiated with the laser beam 72x, the SAM film 50 remains without disappearing.

  Accordingly, it is not necessary to repeat the steps shown in FIGS. 4 to 6, and only the steps shown in FIGS. 7A, 7 B, 8 A, and 8 B are repeated as many times as necessary. The functional ink 43c can be laminated. That is, a thin film such as an electromechanical conversion film can be manufactured by a simple process.

  Further, in order to obtain the optimum laser power to be applied to the functional ink 43b from the pattern image of the functional ink 43b picked up by the image pickup means 73 in the step shown in FIG. In the process, the optimum laser power corresponding to the film thickness of the functional ink 43b can always be irradiated.

  In the above description, the laser beam was irradiated with the optimum laser power only in the process shown in FIG. This is because the laser beam continuously irradiated in the step shown in FIG. 7 (b) has a larger variation tolerance range than the laser beam irradiated in the pulse shown in FIG. 8 (b). This is because the power setting may be relatively rough.

  However, in the step shown in FIG. 7B, the laser power may be optimized by the same method as the step shown in FIG. In this case, since the temperature required for the evaporation of the solvent of the functional ink 43a is about 120 ° C., first, the optimum power obtained using the data of 120 ° C. in FIG. 10 is irradiated. Further, since the temperature required for the thermal decomposition of the functional ink 43a is about 500 ° C., the optimum power obtained by using the data of 500 ° C. in FIG.

<Second Embodiment>
The shape of the pattern image captured by the imaging unit 73 used in the first embodiment can be measured. Thereby, it can be determined whether the shape of the produced pattern is normal. For example, in FIG. 11, the functional inks 43b ₁ , 43b ₂ , and 43b ₄ indicate normal patterns, and the functional ink 43b ₃ indicates a defective pattern.

  A normal pattern of the functional ink 43b is previously stored as data in a RAM or a non-volatile memory of a device control unit (not shown). Thereby, in the process shown in FIG. 8A, the apparatus control unit detects a defective pattern by comparing, for example, a pattern image of the functional ink 43b imaged by the imaging unit 73 with a normal pattern stored in advance. it can.

<Third Embodiment>
In the first embodiment, the continuous irradiation laser device 71 and the pulse irradiation laser device 72 are used as separate devices. In the third embodiment, an example in which the continuous irradiation laser device 71 and the pulse irradiation laser device 72 are one laser device is shown. Specifically, for example, by using a pulse irradiation laser device such as a semiconductor fiber coupling laser device or a semiconductor laser stack device, one laser device has both functions of a pulse laser device and a continuous irradiation laser device. Can do.

  Thereby, the process from solvent evaporation, thermal decomposition, and crystallization of functional ink can be performed with one laser device. Further, for example, when the stage 62 has a single axis freedom in the Y direction and the inkjet head 67, the continuous irradiation laser device 71, and the pulse irradiation laser device 72 are arranged in a line in the Y axis direction, the stage 62 is continuous. By using the irradiation laser device 71 and the pulse irradiation laser device 72 as a single laser device, the length of the stage driving means in the Y-axis direction can be shortened. For this reason, not only the movement accuracy in the Y-axis direction is improved, but the apparatus becomes compact, so that the cost of the apparatus can be reduced.

<Fourth embodiment>
Usually, the shape of the laser irradiation area by laser heating is circular, and the beam profile is Gaussian. Therefore, when functional ink is irradiated in a circular laser irradiation area, the actual irradiation time differs between the circle center region and the circle end portion. That is, the center of the circle is irradiated for a longer time, and the end of the circle is irradiated for a shorter time. For this reason, it is preferable that the laser irradiation area has the same shape as the functional ink pattern or a shape larger than that. Thereby, the functional ink patterned into a predetermined shape can be heated uniformly.

  Furthermore, for example, by making the beam profile of laser irradiation by the continuous irradiation laser device 71 and the pulse irradiation laser device 72 into a flat shape or a top hat shape in the irradiation area, the functional ink can be heated more uniformly. It becomes. The adjustment of the shape of the irradiation area and the beam profile can be mounted on either the continuous irradiation laser device 71 or the pulse irradiation laser device 72.

  For example, when the planar shape of the functional ink is rectangular, in any case of the continuous irradiation laser device 71 and the pulse irradiation laser device 72, when the direction in which the stage 62 can move simultaneously is one direction, the irradiation area is rectangular. Preferably there is. The inclination of the rectangle and the inclination of the moving direction of the stage 62 are preferably aligned. That is, it is preferable that the long side or the short side of the functional ink having a rectangular planar shape is parallel to the moving direction of the stage 62.

  With such a configuration, the irradiation time in the moving direction of the stage 62 is the same in a direction perpendicular to the moving direction of the stage 62. That is, uniform laser heating is possible, and a highly reliable functional ink film can be formed.

<Fifth embodiment>
In the fifth embodiment, laser irradiation is performed using an excimer laser before laser heating the functional ink for crystallization. Since the organic compound containing a metal component is decomposed at different temperatures depending on the metal component contained, the method for forming crystal grains differs depending on the material. Therefore, laser irradiation using an excimer laser cuts the chemical bonds of the respective metal organic compounds and unifies the crystal grain formation method.

  Thereby, when a piezoelectric element is produced from functional ink, a dense crystal film having a uniform particle diameter can be formed, and the piezoelectric element characteristics of the obtained crystal film are improved. About the chemical bond cut | disconnected by the excimer laser, it can confirm using an infrared absorption spectrum etc. Specifically, after the solvent is evaporated by the continuous irradiation laser device 71, for example, an excimer laser having a wavelength of 300 nm or less is irradiated.

More specifically, for example, by using a continuous irradiation type KrF excimer laser device, the excimer laser is irradiated under irradiation conditions of a wavelength of 230 to 280 nm and 100 mJ / cm ² or more, thereby obtaining the characteristics of the functional ink film obtained. Can be improved. The same effect can be obtained by irradiating ultraviolet rays using a UV lamp instead of the continuous irradiation type KrF excimer laser device.

<Sixth embodiment>
In the sixth embodiment, an example of an ink jet recording apparatus on which the liquid discharge head 2 (see FIG. 2) manufactured by the thin film manufacturing apparatus 3 is mounted will be described. FIG. 12 is a perspective view illustrating an ink jet recording apparatus. FIG. 13 is a side view illustrating the mechanism unit of the inkjet recording apparatus.

  Referring to FIGS. 12 and 13, the ink jet recording apparatus 4 is an ink jet recording which is an embodiment of a liquid discharge head 2 mounted on a carriage 93 movable in the main scanning direction inside a recording apparatus main body 81. A print mechanism unit 82 including an ink cartridge 95 that supplies ink to the head 94 and the inkjet recording head 94 is accommodated.

  A paper feed cassette 84 (or a paper feed tray) on which a large number of sheets 83 can be stacked can be detachably attached to the lower portion of the recording apparatus main body 81. Further, the manual feed tray 85 for manually feeding the paper 83 can be turned over. The paper 83 fed from the paper feed cassette 84 or the manual feed tray 85 is taken in, and after a required image is recorded by the printing mechanism unit 82, the paper is discharged to a paper discharge tray 86 mounted on the rear side.

  The printing mechanism 82 holds the carriage 93 slidably in the main scanning direction with a main guide rod 91 and a sub guide rod 92 which are guide members horizontally mounted on left and right side plates (not shown). The carriage 93 has an inkjet recording head 94 that ejects ink droplets of yellow (Y), cyan (C), magenta (M), and black (Bk), and a plurality of ink ejection ports (nozzles) in the main scanning direction. They are arranged in the intersecting direction and mounted with the ink droplet ejection direction facing downward. Further, the carriage 93 is mounted with replaceable ink cartridges 95 for supplying ink of each color to the ink jet recording head 94.

  The ink cartridge 95 has an air port (not shown) that communicates with the atmosphere above, an air port (not shown) that supplies ink to the ink jet recording head 94 below, and a porous body (not shown) filled with ink inside. ing. The ink supplied to the inkjet recording head 94 is maintained at a slight negative pressure by the capillary force of the porous body. Further, although the respective color heads are used here as the ink jet recording head 94, one head having nozzles for ejecting ink droplets of each color may be used.

  The carriage 93 is slidably fitted to the main guide rod 91 on the downstream side in the paper conveyance direction, and is slidably mounted on the sub guide rod 92 on the upstream side in the paper conveyance direction. In order to move and scan the carriage 93 in the main scanning direction, a timing belt 100 is stretched between a driving pulley 98 and a driven pulley 99 that are rotationally driven by the main scanning motor 97, so that the main scanning motor 97 is forward / reverse. The carriage 93 is reciprocated by the rotation. The timing belt 100 is fixed to the carriage 93.

  Further, the ink jet recording apparatus 4 reverses and feeds the paper feed roller 101 for separating and feeding the paper 83 from the paper feed cassette 84, the friction pad 102, the guide member 103 for guiding the paper 83, and the fed paper 83. A conveyance roller 104, a conveyance roller 105 that is pressed against the circumferential surface of the conveyance roller 104, and a leading end roller 106 that defines a feeding angle of the sheet 83 from the conveyance roller 104 are provided. As a result, the paper 83 set in the paper feed cassette 84 is conveyed to the lower side of the ink jet recording head 94. The transport roller 104 is rotationally driven by a sub-scanning motor 107 through a gear train.

  The printing receiving member 109 which is a paper guide member guides the paper 83 sent out from the conveying roller 104 corresponding to the movement range of the carriage 93 in the main scanning direction on the lower side of the ink jet recording head 94. On the downstream side of the printing receiving member 109 in the sheet conveyance direction, a conveyance roller 111 and a spur 112 that are rotationally driven to send out the sheet 83 in the sheet discharge direction are provided. Further, a paper discharge roller 113 and a spur 114 for sending the paper 83 to the paper discharge tray 86, and guide members 115 and 116 for forming a paper discharge path are provided.

  During image recording, the inkjet recording head 94 is driven in accordance with the image signal while moving the carriage 93, thereby ejecting ink onto the stopped paper 83 to record one line and transporting the paper 83 by a predetermined amount. After that, the next line is recorded. Upon receiving a recording end signal or a signal that the trailing end of the paper 83 reaches the recording area, the recording operation is terminated and the paper 83 is discharged.

  A recovery device 117 for recovering defective ejection of the inkjet recording head 94 is provided at a position outside the recording area on the right end side in the movement direction of the carriage 93. The recovery device 117 includes a cap unit, a suction unit, and a cleaning unit. The carriage 93 is moved to the recovery device 117 side during printing standby, and the ink jet recording head 94 is capped by the capping unit, and the ejection port portion is kept in a wet state to prevent ejection failure due to ink drying. Further, by ejecting ink 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 ejection failure occurs, the ejection port of the ink jet recording head 94 is sealed with a capping unit, and bubbles and the like are sucked out from the ejection port with the suction unit through the tube. Also, ink or dust adhering to the ejection port surface is removed by the cleaning means, and the ejection failure is recovered. Further, the sucked ink is discharged to a waste ink reservoir (not shown) installed at the lower part of the main body and absorbed and held by an ink absorber inside the waste ink reservoir.

  Thus, since the inkjet recording head 94 which is one embodiment of the liquid ejection head 2 manufactured by the thin film manufacturing apparatus 3 is mounted in the inkjet recording apparatus 4, there is no ink droplet ejection defect due to vibration plate drive failure. Since stable ink droplet ejection characteristics can be obtained, image quality can be improved.

[Example]
Next, an example of forming a thin film using the thin film manufacturing apparatus 3 will be described. In this example, a thermal oxide film (film thickness 1 μm) was formed on a silicon wafer, 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.

Then, _CH 3 _{(CH 2)} using 6 -SH to alkanethiol, concentration 0.01 mol / l (solvent: isopropyl alcohol) is dipped into the solution, it was subjected to SAM process. Then, after washing and drying with isopropyl alcohol, the process proceeds to a patterning process.

  After the SAM film treatment, when the contact angle of water was measured at the SAM film formation site (on the SAM film), the contact angle of water on the SAM film was 92.2 ° (see FIG. 14). On the other hand, when the contact angle of water was measured on the platinum sputtered film before the SAM treatment, the contact angle of water on the platinum sputtered film was 5 ° or less (complete wetting). From this result, it can be seen that the SAM film treatment was appropriately performed.

  Next, a photoresist made by Tokyo Ohka Co., Ltd. (TSMR8800) was formed by spin coating, a resist pattern was formed by ordinary photolithography, and then an oxygen plasma treatment was performed to remove the exposed SAM film. The residual resist after the treatment was dissolved and removed with acetone, and the same contact angle evaluation was performed. As a result, the contact angle of water at the SAM film removal site was 5 ° or less (complete wetting) (see FIG. 15). That of the covered site showed a value of 92.4 °. From this result, it can be confirmed that the SAM film is appropriately patterned.

  As another type of patterning, a resist pattern was formed in advance with the same resist work, and after the same SAM film treatment, the resist was removed with acetone, and the contact angle was measured. The contact angle on the resist-covered platinum film was 5 ° or less (complete wetting), and that at other sites was 92.0 °, confirming that the SAM film was appropriately patterned.

  As another method, ultraviolet irradiation using a shadow mask was performed. Specifically, irradiation was performed for 10 minutes using vacuum ultraviolet light having a wavelength of 176 nm from an excimer lamp. The contact angle of the irradiated part was 5 ° or less (complete wetting), and that of the unirradiated part was 92.2 °, confirming that the SAM film was appropriately patterned.

  Next, PZT (53/47) was formed as an electromechanical conversion film. In the synthesis of the precursor coating 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 / l.

  The film thickness obtained by a single sol-gel film formation is preferably 100 nm, and the precursor concentration is optimized from the relationship between the film formation area and the amount of applied precursor (thus not limited to 0.1 mol / l). .

  This precursor solution was applied onto the patterned SAM film by the ink jet method (see FIG. 7A). By discharging only the hydrophilic portion without discharging droplets on the SAM film by the ink jet method, a coating film was formed only on the hydrophilic portion due to the contact angle contrast.

  The coating film was heated by irradiating laser light with a continuous irradiation laser device 71 to evaporate the solvent, thereby obtaining a thermally decomposed coating film (see FIG. 7B). Next, the thermally decomposed coating film was imaged by the imaging means 73, and the optimum laser power to be applied to the thermally decomposed coating film was determined from the captured pattern image (see FIG. 8A). Subsequently, with the pulse irradiation laser device 72, only the thermally decomposed coating film was irradiated with laser light and heated to crystallize the thermally decomposed coating film (see FIG. 8B). At this time, the optimum laser power obtained in FIG.

  Liquid droplets were ejected to the same place by the ink jet method, and the process of irradiating laser light with the continuous irradiation laser device 71 and the pulse irradiation laser device 72 was repeated 15 times to perform overcoating to obtain a 500 nm electromechanical conversion film. . No defects such as cracks occurred in the electromechanical conversion film produced at this time.

  The process of ejecting droplets to the same place by the ink jet method and irradiating laser light by the continuous irradiation laser device 71 and the pulse irradiation laser device 72 was repeated 15 times (total 30 times), but the electromechanical conversion film was cracked. Such defects did not occur. The film thickness of the electromechanical conversion film reached 1000 nm.

An upper electrode (platinum) was formed on the patterned electromechanical conversion film to produce an electromechanical conversion element, and electrical characteristics and electromechanical conversion ability (piezoelectric constant) were evaluated. FIG. 16 is a graph showing a PE hysteresis curve of the electromechanical transducer produced in this example. The relative dielectric constant of the electromechanical conversion film is 1220, the dielectric loss is 0.02, the remanent polarization is 19.3 uC / cm ² , and the coercive electric field is 36.5 kV / cm, which is equivalent to that of an ordinary ceramic sintered body. I understood that I have it.

  The electro-mechanical conversion ability of the electromechanical transducer was calculated by measuring the amount of deformation by applying an electric field with a laser Doppler vibrometer and fitting it by simulation. The piezoelectric constant d31 was −120 pm / V, which was also the same value as the ceramic sintered body. This is a characteristic value that can be sufficiently designed as a droplet discharge head.

Note that an electrode film can be formed in the same manner as the electromechanical conversion film by dissolving an oxide such as platinum, SrRuO _3, or LaNiO _{3 in} a solvent, applying the ink by an inkjet method, and irradiating with a laser.

  The preferred embodiments and examples have been described in detail above, but the present invention is not limited to the above-described embodiments and examples, and the above-described embodiments are not deviated from the scope described in the claims. Various modifications and substitutions can be made to the embodiments.

DESCRIPTION OF SYMBOLS 1, 2 Droplet discharge head 3 Thin film manufacturing apparatus 4 Inkjet recording apparatus 5 Substrate 10 Nozzle plate 11 Nozzle 20 Pressure chamber substrate 21 Pressure chamber 30 Vibration plate 40 Electromechanical conversion element 41 Adhesion layer 42 Lower electrode 43 Electromechanical conversion film 43a, _{43b, 43b 1, 43b 2,} 43b 3, 43b 4, 43c functional ink 44 upper electrode 50 SAM film 51 and 53 photoresist 51x, 54x opening 54 photomask 60 gantry 61 Y-axis driving means 62 stage 63 X-axis drive Means 64 X-axis support member 65, 69 Z-axis drive means 66 Head base 67 Inkjet head 68 Ink tank 70 Support member 71 Continuous irradiation laser device 71x, 72x Laser light 72 Pulse irradiation laser device 73 Imaging means 81 Recording device main body 82 Printing mechanism Part 83 paper 84 Paper cassette (or paper tray)
85 Manual feed tray 86 Paper discharge tray 91 Main guide rod 92 Subordinate guide rod 93 Carriage 94 Inkjet recording head 95 Ink cartridge 97 Main scanning motor 98 Drive pulley 99 Driven pulley 100 Timing belt 101 Paper feed roller 102 Friction pad 103 Guide member 104 Transport roller 105 Conveying roller 106 Leading end roller 107 Sub-scanning motor 109 Printing receiving member 111 Conveying roller 112 Spur 113 Paper discharge roller 114 Spur 115, 116 Guide member 117 Recovery device

Japanese translation of PCT publication No. 2002-543429

Claims (14)

A liquid discharge means for discharging a liquid onto a film formation target to form a coating film;
Imaging means for imaging the coating film;
Color depth conversion means for converting the color of the image captured by the imaging means into color depth;
Film thickness calculating means for calculating the film thickness of the coating film from the color depth;
Irradiation power calculation means for calculating irradiation power corresponding to the film thickness calculated by the film thickness calculation means;
A thin film manufacturing apparatus comprising: laser irradiation means for irradiating the coating film with laser light with the irradiation power calculated by the irradiation power calculation means.   The thin film manufacturing apparatus according to claim 1, wherein the laser irradiation unit irradiates the coating film with a pulsed laser beam and heats the coating film to crystallize.   The thin film manufacturing apparatus according to claim 1, further comprising continuous laser irradiation means for continuously irradiating the coating film with laser light with the irradiation power calculated by the irradiation power calculation means, and thermally decomposing the coating film.   The thin film manufacturing apparatus according to any one of claims 1 to 3, wherein the imaging unit is capable of imaging the entire area of the coating film at a time.   The shape determination means which recognizes the shape of the said coating film based on the said image which the said imaging means imaged, and determines whether the said shape is normal is further described in any one of Claim 1 thru | or 4 Thin film manufacturing equipment.   The thin film manufacturing apparatus according to claim 1, wherein the liquid is a ceramic precursor solution. A region forming step of forming a liquid repellent region and a lyophilic region on the surface of the film formation target;
A coating film forming step of discharging a liquid to the lyophilic region to form a coating film;
An imaging step of imaging the coating film;
A color depth conversion step of converting the color of the image captured in the imaging step into a color depth;
A film thickness calculating step for calculating the film thickness of the coating film from the color depth;
An irradiation power calculation step of calculating an irradiation power corresponding to the film thickness calculated in the film thickness calculation step;
A laser irradiation step of irradiating the coating film with laser light with the irradiation power calculated in the irradiation power calculation step.   The thin film manufacturing method according to claim 7, wherein in the laser irradiation step, the coating film is irradiated with pulsed laser light, and the coating film is heated to be crystallized.   The thin film manufacturing method according to claim 7, further comprising a continuous laser irradiation step of continuously irradiating the coating film with laser light with the irradiation power calculated by the irradiation power calculation means and thermally decomposing the coating film.   The thin film manufacturing method according to claim 7, wherein in the imaging step, the entire area of the coating film is imaged at a time.   11. The shape determination step according to claim 7, further comprising a shape determination step of recognizing the shape of the coating film based on the image captured in the imaging step and determining whether or not the shape is normal. Thin film manufacturing method.   The thin film manufacturing method according to claim 7, wherein the liquid is a ceramic precursor solution, and a piezoelectric element is formed from the precursor solution.   A liquid discharge head comprising a piezoelectric element manufactured from the liquid using the thin film manufacturing apparatus according to claim 1.   An ink jet recording apparatus comprising the liquid discharge head according to claim 13.