JP2013065637A - Thin film manufacturing device and thin film manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thin film manufacturing device which manufactures a thin film using a laser as a heat treatment method and can calculate and control optimum laser conditions.SOLUTION: A thin film manufacturing device for manufacturing a thin film on a substrate comprises: coating means for coating a functional ink on a substrate in a prescribed pattern; one or two or more laser light sources for crystallizing the coated functional ink by heating; an X-ray diffraction device which measures a crystal state of the functional ink; a recording unit which records information of the crystal state of the functional ink measured by the X-ray diffraction device; and a control unit which controls laser irradiation conditions of the laser light source. The control unit controls adjustment of the laser irradiation conditions of the laser light source on the basis of the information (recorded in the recording unit) of the crystal state of the functional ink laser-irradiated in advance by the laser light source.

Description

  The present invention relates to a thin film manufacturing apparatus and a thin film manufacturing method.

  Devices such as a vibration sensor, a piezoelectric speaker, and various driving devices include an electromechanical conversion element in which thin films such as an electromechanical conversion film are stacked. In the driving device, for example, a liquid discharge head of an ink jet recording apparatus includes a nozzle that discharges ink droplets, a pressurizing chamber that communicates with the nozzle, and an electromechanical conversion element such as a piezoelectric element. Ink droplets are ejected from the nozzles by pressurizing the ink.

  Examples of a method for producing the electromechanical conversion film include a spin coating method. In this method, a uniform electromechanical conversion film is formed by applying a sol-gel solution having a precursor of an electromechanical conversion film component to the entire surface of the substrate by spin coating and heat-treating (drying, pyrolysis, crystallization). Is the method.

  As a heat treatment method for the precursor, a method of heating using a halogen lamp, infrared rays or laser is generally known. Among these, a method of heating using a laser irradiation apparatus that is excellent in energy conversion efficiency, has a fast tact time, and is capable of rapid heating / cooling is widely used (for example, Patent Document 1).

  However, it is difficult to control laser conditions (for example, laser output) with a method of heating using a laser irradiation apparatus such as Patent Document 1. For example, if the laser output is too large, the electromechanical conversion film may crack. On the other hand, if the laser output is too small, the solvent of the precursor may not be completely evaporated, or the electromechanical conversion film may not be completely crystallized, and the function of the electromechanical conversion element may be deteriorated. Furthermore, since the light absorption rate of the precursor is changed according to the phase state and film thickness of the precursor, it is necessary to control the laser conditions according to the phase state and film thickness of the precursor.

  Accordingly, an object of the present invention is to provide a thin film manufacturing apparatus for manufacturing a thin film using a laser as a heat treatment method, and capable of calculating and controlling optimum laser conditions.

According to the present invention,
Application means for applying functional ink in a predetermined pattern on the substrate;
One or more laser light sources for heating and crystallizing the applied functional ink;
An X-ray diffractometer for measuring the crystalline state of the functional ink;
A recording unit that records information on the crystalline state of the functional ink measured by the X-ray diffractometer;
A control device for controlling laser irradiation conditions of the laser light source;
Have
The control unit performs control so as to adjust the laser irradiation condition of the laser light source based on information on the crystal state of the functional ink recorded in the recording unit and laser-irradiated by the laser light source in advance. ,
A thin film manufacturing apparatus for forming a thin film on a substrate is provided.

  ADVANTAGE OF THE INVENTION According to this invention, it is a thin film manufacturing apparatus which manufactures a thin film using a laser as a heat processing method, Comprising: The thin film manufacturing apparatus which can calculate and control optimal laser conditions can be provided.

FIG. 1 is a schematic diagram illustrating an example of the structure of the liquid ejection head. FIG. 2 is a schematic diagram showing an example of the patterning process of the SAM film. FIG. 3 is a flowchart for explaining an example of the thin film manufacturing method according to the present invention. FIG. 4 is a diagram illustrating an example of an XRD measurement result before crystallization by laser irradiation. FIG. 5 is a diagram illustrating an example of an XRD measurement result after crystallization by laser irradiation. FIG. 6 is a schematic view showing a configuration example of a thin film manufacturing apparatus according to the present invention. FIG. 7 is a schematic view for explaining the thin film manufacturing method according to the present invention. FIG. 8 is another schematic diagram for explaining the thin film manufacturing method according to the present invention. FIG. 9 is a schematic diagram illustrating a structure of a liquid discharge head having a plurality of electromechanical transducer elements. FIG. 10 is a schematic view showing an example of an ink jet recording apparatus equipped with the liquid discharge head according to the present invention. FIG. 11 is a schematic view showing an example of an ink jet recording apparatus equipped with a liquid discharge head according to the present invention.

  The present invention can be applied to an apparatus for manufacturing a thin film such as an electromechanical conversion element film, a liquid discharge head including the manufactured electromechanical conversion film, and an image forming apparatus such as an ink jet recording apparatus including the liquid discharge head.

  The ink jet recording apparatus usually has extremely low noise and can perform high-speed printing. Further, the ink jet recording apparatus has many advantages such as a high degree of freedom of ink and the use of inexpensive plain paper. Therefore, it is widely used as an image recording apparatus or an image forming apparatus such as a printer, a facsimile machine, and a copying apparatus.

FIG. 1 is a schematic diagram showing an example of the structure of the liquid discharge head. A droplet discharge head 10 used in an ink jet recording apparatus includes a nozzle 11 that discharges ink droplets and a pressure chamber 21 (an ink channel, a pressurized liquid chamber, a pressurized chamber, a discharge chamber, a liquid chamber, etc.) that communicates with the nozzle. And an electromechanical transducer 40 that pressurizes the ink in the pressurizing chamber, and a diaphragm 30 that forms the wall surface of the ink flow path. The electromechanical conversion element 40 includes an upper electrode 44, an electromechanical conversion film 43, and a lower electrode 42, and the pressure chamber includes the pressure chamber substrate 20, the vibration plate 30, and the nozzle plate 10. In response to the energy generated by the energy generating means, 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 to eject ink droplets from the nozzles. In order to improve the adhesion between the lower electrode 42 and the diaphragm 30, an adhesion layer 41 such as Ti, TiO ₂ , TiN, Ta, Ta ₂ O ₅ , Ta ₃ N ₅ or the like is formed on the diaphragm 30. May be provided.

[Electromechanical conversion film]
In this embodiment, PZT is mainly used as the material of the electromechanical conversion film. 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 Pb (Zr _0.53 , Ti _0.47 ) O ₃ in the chemical formula, 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, 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.

Examples of composite oxides other than PZT include barium titanate. In this case, it is also possible to prepare a barium titanate precursor solution by dissolving barium alkoxide and a titanium alkoxide compound in a common solvent. is there. These materials are described by the general formula ABO ₃ and correspond to composite oxides containing A = Pb, Ba, Sr B = Ti, Zr, Sn, Ni, Zn, Mg, and Nb as main components. 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.

[Lower electrode]
As a material for the lower electrode, a metal having high heat resistance and forming a SAM film by reaction with alkanethiol described 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 are used. An alloy material or the like 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 .

  As a method for producing the lower electrode, it can be produced by a method such as a sputtering method or a vacuum film forming method such as vacuum deposition.

[Diaphragm]
The lower electrode is electrically connected as a common electrode for inputting a signal to the electromechanical transducer, and therefore, the diaphragm under the insulator can be an insulator or a conductor subjected to insulation treatment.

  As a specific material of the diaphragm, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a film in which these films are stacked having a thickness of about several microns can be used. In addition, a ceramic film such as an aluminum oxide film or a zirconia film in consideration of a difference in thermal expansion can also be used.

  As a method for forming the diaphragm, for example, the silicon-based insulating film can be obtained by CVD or thermal oxidation treatment of the silicon-based film. The metal oxide film can be formed by a sputtering method or the like.

[Thin film manufacturing method]
A method for producing a thin film such as an electromechanical conversion film according to the present invention will be described with reference to the drawings.

<< SAM film patterning method >>
First, a substrate surface treating method for producing an electromechanical conversion film will be described.

  FIG. 2 is a schematic diagram showing an example of a patterning process of a SAM (Self Assembled Monolayer) film on a substrate.

  FIG. 2A shows a substrate 1 that is a lower electrode, for example. In the present embodiment, platinum (Pt) is used as the lower electrode.

  The substrate 1 is dipped using a SAM material made of alkanethiol or the like (FIG. 2B). Thereby, the SAM material reacts on the surface of the substrate 1 and the SAM film 2 adheres, and the surface of the substrate 1 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 substrate 1 is taken out, and excess molecules are washed by substitution with a solvent and dried.

  Next, a photoresist 3 is patterned by known photolithography (FIG. 2C). Thereafter, the SAM film is removed by dry etching, the photoresist 3 is removed, and the patterning of the SAM film is completed (FIG. 2D).

  In addition, a photoresist pattern is first formed from the state of FIG. 2A (FIG. 2B ′), SAM treatment is performed (FIG. 2C ″), and the resist is removed to remove the SAM. The film 2 may be patterned.

  Furthermore, the SAM film 2 in the exposed portion is removed by irradiating the substrate surface with ultraviolet light or oxygen plasma through the photomask 4 from the state of FIG. 2B (FIG. 2C ′). Then, the SAM film 2 may be patterned.

  Note that the surface of the region where the SAM film remains after patterning is hydrophobic. On the other hand, in the region where the SAM film is removed by dry etching or the like and the surface is an electrode material, the surface becomes hydrophilic. Using this surface energy contrast, the PZT precursor liquid described in detail below can be applied separately.

<Method for forming electromechanical conversion film>
Next, a method for manufacturing a thin film such as an electromechanical conversion film on a surface-treated substrate will be described with reference to the drawings. FIG. 3 shows a flow chart for explaining an example of the thin film manufacturing method according to the present invention.

  The electromechanical conversion film is obtained by using a PZT precursor solution to form a coating film by a solution coating method such as a spin coating method or an ink jet method, and performing a heat treatment such as solvent drying, thermal decomposition, or crystallization. . Since the transformation from the coating film to the crystallized film is accompanied by volume shrinkage, the precursor solution concentration is adjusted so that a film thickness of 100 nm or less can be obtained in one step in order to obtain a crack-free film.

  Moreover, when using a PZT film | membrane as an electromechanical conversion element of a liquid discharge apparatus, it is requested | required that the film thickness of a PZT film | membrane should be 1 micrometer-2 micrometers. Therefore, the desired film thickness is usually obtained by repeating the coating and heat treatment steps.

  As shown in FIG. 3, first, a functional ink (for example, PZT precursor solution) is uniformly applied on a substrate by an inkjet method (or spin coating method) using an inkjet head (step 1 (S1)). ). At this time, due to the contrast of the surface energy, the application region of the functional ink is only a hydrophilic region. By discharging the PZT precursor solution only to the area of the new water surface, the amount of the solution to be applied can be reduced as compared with a process such as a spin coating method, and the process can be simplified.

  Next, heat treatment is performed until the applied functional ink film is completely crystallized (step 2 (S2)). The heat treatment referred to here includes a step of drying a solvent component contained in the sol-gel liquid film, a step of thermally decomposing the dried sol-gel liquid film, and a step of crystallizing the pyrolyzed sol-gel liquid film. . Thereby, the PZT precursor solution is crystallized to become a PZT film. As the heating means, an oven, a rapid thermal annealing (RTA) apparatus, or the like can be usually used. In this embodiment, a laser apparatus 400 (manufactured by Dias) is used.

  Next, the crystallinity of the functional ink film is measured by an X-ray diffractometer (XRD) (step 3 (S3)). The XRD apparatus is not particularly limited, and for example, Bruker Ax's D8 Discover with Vantec 2000 can be used. When this device is used, the output is 45 kV, 100 mA, the X-ray irradiation area is φ50 μ, the shaft angle (2θ) is set to 20 to 50 degrees, and the angle resolution is 0.02 degrees. It is possible to measure at approximately 10 minutes per frame.

  FIG. 4 and FIG. 5 show examples of XRD measurement results before and after crystallization by laser irradiation, respectively. Crystallinity changes before and after crystallization, and a characteristic peak is observed in each.

  Next, the target value of the target crystal peak is set ((Step 4 (S4))). That is, a target value of intensity (Intensity) value is set for a crystal peak corresponding to a predetermined orientation. A specific example is given here. For example, when emphasizing the crystallinity of the (110) orientation of the PZT film, the (110) orientation has a crystal peak of approximately 31 degrees at 2θ. Therefore, in the present embodiment, the intensity value of about 31 degrees of 2θ is set to be 700 or more, for example.

  The strength value depends on the thickness of the PZT film, and the strength value usually increases as the PZT film is thicker. The intensity value also greatly depends on the measurement region. When the XRD measurement region is substantially the same as the PZT film pattern shape region or the XRD measurement region is narrower, the measurement noise is smaller and the intensity value can be measured more efficiently. The PZT film is overcoated as described later. Therefore, a person skilled in the art can appropriately set a target according to the number of layers of overcoating. At this time, the crystallinity measurement of XRD is usually performed in real time during laser irradiation, and is about several milliseconds to several tens of milliseconds. When the measurement time is short, the X-ray dose entering the light receiving element is reduced and the intensity is measured low. For this reason, it is preferable to set the pre-measurement in step 3 to the same measurement time as the real-time measurement (several milliseconds to several tens of milliseconds).

  As a specific example of the orientation, in the case of (100) orientation, it is preferable to set the target value of the intensity value for the crystal peak around 23 to 25 degrees at 2θ. In the case of (111) orientation, it is preferable to set the target value of the intensity value for the crystal peak at 38 to 40 degrees at 2θ. A plurality of orientations for setting the target value may be selected. In that case, if the intensity ratio of the crystal peaks of each orientation is known, the target may be set by setting the target values of the plurality of intensity peaks to substantially the same ratio as the ratio.

  Furthermore, the target crystal peak has a peak width with respect to the 2θ axis, for example, a peak of about 31 degrees in FIG. Therefore, a condition relating to the peak width such that the peak width is narrowed to, for example, 30.5 degrees to 31.5 degrees may be added to the target value setting conditions. In general, the narrower the peak width, the better the crystallinity (for example, in the case of PZT, a perovskite structure), and the excellent characteristics as an electromechanical conversion element. Conversely, the wider the peak width, the worse the crystallinity (for example, in the case of PZT, a pyrochlore structure), and the characteristics as an electromechanical conversion element tend to deteriorate.

  In the next step 5 (S5), range information such as a target angle at 2θ and a target value of the intensity of the corresponding crystal peak is recorded in a recording unit to be described later. Next, functional ink (for example, PZT precursor solution) is uniformly applied on the substrate by an ink jet method (or spin coat method) using the ink jet head 300 (step 6 (S6)). In the heating process, when the SAM film disappears, the SAM film is formed every time the functional ink is applied later. From the second time on, the SAM film is not formed on the oxide film, and the photolithography process is not necessary. In the second and subsequent processes, when it is desired to reduce the consumption of the PZT precursor solution, a PZT pattern is formed by an ink jet method or letterpress printing. The patterning by this method can be preferably formed until the film thickness of the PZT film is usually about 5 μm.

  Thereafter, the applied PZT film is laser-heated (step 7 (S7)). Further, the crystallinity of the PZT film is measured by XRD, compared with the target value of the intensity of the crystal peak recorded in step 5 in real time, and laser heating is continued until an equivalent crystallinity is obtained (step 8 (S8)). .

  An example of a method for measuring crystallinity at high speed and with high accuracy in real-time measurement will be described below. For example, by arraying the light receiving elements within the required 2θ range, it is possible to perform measurement with higher accuracy and higher speed than the method of driving a single light receiving element at a certain angle. In addition, high-precision and high-speed measurement can be realized by limiting the 2θ range to be measured. As described above, when the target orientation is determined, information on the angle range of 2θ corresponding to the orientation is required. Therefore, high-precision and high-speed measurement is possible by measuring only a predetermined angle.

  Examples of parameters that can be adjusted (changed) according to laser heating conditions include laser power, laser irradiation time, and number of times of laser irradiation. Laser power is usually adjustable in real time by changing the input voltage that controls the power of the laser controller. For example, in the case of a continuous irradiation type laser, the laser irradiation time can be adjusted by changing the moving speed of the stage holding the substrate. In the case of a pulse laser, it can be adjusted by changing the emission time. Furthermore, the number of times of laser irradiation can irradiate the same pattern a plurality of times by conveying the substrate a plurality of times under laser irradiation. Thus, by changing the laser heating conditions in real time, a PZT pattern film having good quality and uniform characteristics can be manufactured. In addition, as described above, the XRD measurement area is substantially the same as the laser irradiation area (that is, the pattern shape area of the PZT film), or the XRD measurement area is smaller, the noise during measurement is smaller. Higher precision control is possible.

Note that it is preferable to perform the heating (evaporation) process using a laser in an atmosphere having an O ₂ concentration of 50% or more because a higher-quality film can be formed. By performing in an atmosphere having an O ₂ concentration of 50% or more, C is easily removed from the film when the chemical bond of the organic compound is broken. At this time, C bonds with O _{2 in} the atmosphere and escapes. Further, in a crystallization process using a laser, it is preferable to perform in an atmosphere having an N ₂ concentration of 50% or more because a film with higher quality can be formed. By performing the N ₂ concentration in an atmosphere having a concentration of 50% or more, it is possible to reduce Pb in the film at the time of crystallization from bonding and desorption with O _{2 in the} atmosphere. This effect is achieved by setting the N ₂ concentration to 50% or more in order to lower the O ₂ concentration of the atmosphere.

  In the above process, an electromechanical conversion film having a thickness of 100 nm or less can be obtained in a single process. When the electromechanical conversion film is used as an electromechanical conversion element of a liquid ejection device, 1 μm to 2 μm is required. Therefore, the above steps 1 to 8 are repeated until the target film thickness is reached.

  In the first embodiment, the above method was repeated to manufacture a piezoelectric element made of PZT having a thickness of about 1 to 2 μm. In this embodiment, the laser irradiation area is 1000 μm × 50 μm, the laser wavelength is 980 nm, the laser beam profile is top hat (flat), and the substrate scanning speed is 100 mm / s. At this time, an optimum laser power was observed in the vicinity of 20 to 40 W, and was initially set. In the first embodiment, a film having a thickness of about 70 nm is formed per layer, and the above method is repeated approximately 28 to 29 times to form a film having a thickness of approximately 2 μm. Usually, the absolute value of Intensity increases as the film thickness increases. Therefore, the target value of Intensity was gradually increased. At this time, the intensity of the obtained film thickness is considered to change linearly with respect to the film thickness, and the target value of the intensity was set (specifically, the intensity is approximately 500 when one layer is 70 nm, approximately 2 μm. Intensity was 1E6 (1 million to 10 million) or more at the time of film thickness). In other embodiments, the target value of Intensity is set in the same procedure.

  The functional ink film (electromechanical conversion film) produced under the above laser heating conditions had no cracks and good crystallinity. Moreover, the piezoelectric element characteristics of the obtained electromechanical conversion film were also good.

  As specific piezoelectric element characteristics of the obtained electromechanical conversion film, the relative dielectric constant was 1000 or more, and the piezoelectric strain constant (d31 direction) was 100 pm / V or more. Further, the crystal orientation of the film having a thickness of 2 μm was mainly (111) orientation, and the Intensity in the range of 38 ° to 40 ° at 2θ was 1E6 (1 million to 10 million) or more. In addition, it also has (100) orientation, and the intensity in the range of 23 to 25 degrees at 2θ was 1E4 (10,000 to 100,000) or more.

[Thin film manufacturing equipment]
Next, a thin film manufacturing apparatus capable of carrying out the thin film manufacturing method of the present invention will be described with reference to the drawings.

<< First Embodiment >>
Next, the apparatus structure of the thin film manufacturing apparatus for enforcing the electromechanical conversion film forming method will be described. FIG. 6 is a schematic view showing a configuration example of a thin film manufacturing apparatus according to the present invention. FIG. 7 shows a schematic diagram for explaining the thin film manufacturing method according to the present invention, and FIG. 8 shows another schematic diagram for explaining the thin film manufacturing method according to the present invention. Note that directions such as the X-axis direction, the Y-axis direction, and the Z-axis in the present invention are for explanation, and do not limit the present invention.

  In the thin film manufacturing apparatus according to the present invention, a Y-axis driving unit 201 is installed on a gantry 700. On the Y-axis driving means 201, a stage 203 on which the substrate 1 is mounted is installed so as to be driven in the Y-axis direction. The stage 203 is usually accompanied by a suction means (not shown) using vacuum or static electricity, so that the substrate 1 can be fixed. Further, the stage 203 may be provided with a driving means (not shown) that rotates around the Z axis so that the relative inclination between an inkjet coating apparatus or a laser irradiation system (to be described later) and the substrate can be corrected.

  An X-axis support member 704 for supporting the X-axis drive unit 705 is installed on the gantry 700. The X-axis drive means 705 is provided with a Z-axis drive means 711, and a head base 706 is attached on the Z-axis drive means 711 so that it can move in the X-axis and Z-axis directions. The Z-axis driving unit 711 can control the distance between the inkjet coating apparatus or the laser irradiation system and the substrate. On the head base 706, an ink jet (IJ) head 300 for discharging functional ink (for example, PZT precursor solution) is mounted. Functional ink is supplied to the inkjet head 300 from each ink tank 707 through an ink supply pipe (not shown).

  To the X-axis driving means 705, another Z-axis driving means 711 ′ is attached, and a laser and XRD support member 708 is attached. To the XRD support member 708, a laser light source 400 (and 500 or 600 depending on the embodiment), an X-ray tube 602, and an X-ray light receiving element 603 are attached. The X-ray tube 602 and the X-ray light receiving element 603 are installed on member position adjusting mechanisms 709 and 709 ′, respectively. As shown in FIG. 7, the X-ray 604 irradiated from the X-ray tube 602 at an angle 606 is applied to the functional ink 402 which has been evaporated and thermally decomposed, and the reflected X-ray 605 is detected by the X-ray light receiving element. (See S3 and S8 in FIG. 3). The member position adjustment mechanism 709 is an adjustment mechanism that can adjust the positions and angles of the X-ray tube 602 and the X-ray light receiving element 603. The laser light sources 400, 500, and 600 can also adjust the relative positions and angles of the X-ray tube 602 and the X-ray light receiving element 603 by an adjusting mechanism (not shown).

  By installing a plurality of Z-axis driving means 711 (711 ′), a plurality of laser light sources and inkjet heads can be easily installed.

  FIG. 6 shows a configuration in which the substrate 1 has one axis of freedom in the Y direction and the inkjet head 300 and the laser light sources 400, 500, and 600 have one axis of freedom in the X direction. The present invention is not limited in this respect. For example, the substrate 1 may have a biaxial degree of freedom in the X and Y directions, and the inkjet head 300 and the laser light sources 400, 500, and 600 may be fixed. Alternatively, the substrate 1 may be fixed, and the inkjet head 300 and the laser light sources 400, 500, and 600 may have a biaxial degree of freedom in the X and Y directions. In addition, the X axis and the Y axis do not need to 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 do it.

  As the laser light sources 400, 500, and 600, a continuous irradiation laser device such as a semiconductor laser or a YAG laser or a pulse irradiation laser device can be used. The configuration of the laser device will be described in detail below.

  The thin film manufacturing apparatus according to the present invention includes an apparatus control unit (not shown) and controls the functional ink ejection conditions of the inkjet head 300 and the laser irradiation conditions of the laser light sources 400, 500, and 600. In addition, the apparatus control unit has a recording unit (not shown), and the crystal state of the functional ink and the optimum laser irradiation conditions described in detail above are recorded.

<< Second Embodiment >>
In the second embodiment, the continuous irradiation laser device 400 is disposed as the laser light source 400 and the pulse irradiation laser device 500 is disposed as the laser light source 500 in the first embodiment.

  As shown on the left side of FIG. 8, the functional inks 301 and 302 that have landed on the hydrophilic portion on the substrate 1 spread out with time. Thereafter, by driving the stage to the Y axis and / or the X axis, the substrate on which the functional ink is patterned is laser-heated by the method shown in FIG. At this time, the stage 203 is driven to the Y axis and / or the X axis, and the laser beam 401 is irradiated to the functional ink pattern by the continuous irradiation laser device 400 (see the center of FIG. 8). The irradiated functional ink is vaporized and thermally decomposed to become thermally decomposed functional ink 402. As the continuous irradiation laser 400, a semiconductor laser or a YAG laser can be usually used.

  As specific laser heating conditions, the wavelength was 400 nm to 10000 nm, the substrate moving speed was 10 mm / s to 1000 mm / s, and the laser power was in the range of several W to several tens W. Note that the laser beam emitted by the continuous irradiation laser device 400 also irradiates the region where the SAM film exists. However, the SAM film does not disappear because the substrate temperature remains below 500 ° C. under the above set conditions. Thereafter, the thermally decomposed functional ink 402 film is irradiated with laser light 501 using the pulse irradiation laser apparatus 500 to crystallize the functional ink (see the right side of FIG. 8). The crystallized functional ink 502 is, for example, a PZT film used as an electromechanical conversion film. As the pulse irradiation laser device 500, a semiconductor fiber coupling laser device, a semiconductor laser stack device, or the like can be used. The laser heating conditions are selected so as to meet the crystallinity target value setting in step 4 as described above with reference to FIG.

  Specifically, the laser power was adjusted from several W to several tens W, the laser irradiation time was several μs to several hundreds μs, and the light emission frequency was adjusted by the functional ink pattern and the moving speed of the substrate. For example, when the pattern interval is 100 μm and the substrate moving speed is 100 mm / s, the emission frequency of the pulse laser is 1 kHz. By moving the substrate during pulsed laser emission, for example, when the irradiation time is 100 μsec and the substrate moving speed is 100 mm / s, the range of 10 μm laser irradiation is expanded. Therefore, it is preferable not to irradiate the SAM film region by controlling the irradiation timing according to the pattern shape in consideration of the range of laser irradiation.

<< Third Embodiment >>
In the second embodiment described above, the continuous irradiation laser device 400 and the pulse irradiation laser device 500 are configured as separate devices. In the third embodiment, a pulse irradiation laser device such as a normal semiconductor fiber coupling laser device or a semiconductor laser stack device is used to provide the functions of both a pulse laser device and a continuous irradiation laser device. Thus, the process from solvent evaporation, thermal decomposition, and crystallization of the functional ink can be performed with one laser device. In addition, with the configuration as in the present embodiment, 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.

  In addition, you may perform all the heating processes from solvent evaporation, thermal decomposition, and crystallization using a continuous irradiation type laser. In this case, the device cost is reduced, but the SAM film disappears after the heating process. Therefore, it is necessary to perform a step of forming a SAM film after laser heating.

<< Fourth Embodiment >>
Usually, the shape of the laser irradiation area by laser heating is circular, and the beam profile is Gaussian. Therefore, when the substrate moves in the Y-axis direction and the functional ink is irradiated in a circular laser irradiation area, the actual irradiation time is different 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, in the present embodiment, the laser irradiation area has the same shape as the functional ink pattern or a larger shape. 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 a pulse irradiation laser device and a continuous irradiation laser device into a flat shape or a top hat shape in the irradiation area, it is possible to heat the functional ink more uniformly. Become. The adjustment of the shape of the irradiation area and the beam profile can be mounted on either a continuous irradiation laser device or a pulse irradiation laser device.

  In either case of continuous irradiation laser apparatus or pulse irradiation laser apparatus, if the direction in which the substrate can move simultaneously is one direction, the irradiation area is rectangular, and the inclination of the rectangle and the inclination of the movement direction of the substrate are aligned. It is preferable. With the above-described configuration, the irradiation time in the substrate movement direction is the same in a direction perpendicular to the substrate movement direction (for example, the X-axis direction in FIG. 8). That is, uniform laser heating is possible, and a highly reliable functional ink film can be formed. Further, particularly in a continuous irradiation laser apparatus, the length of the irradiation area in the X-axis direction is the same as the length of the pattern in the X-axis direction, and the length of the irradiation area in the Z-axis is the same as the length of the pattern in the Z-axis direction. This is preferable because the functional ink can be heated more efficiently.

<< 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. For this reason, laser irradiation using an excimer laser cuts the chemical bonds of the respective metal organic compounds and unifies the crystal grain formation method. Thereby, a dense crystal film having a uniform grain size 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 evaporating the solvent with a continuous irradiation laser device, 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 apparatus, the excimer laser is irradiated under irradiation conditions of wavelengths 230 to 280 nm and 100 mJ / cm ² or more, thereby obtaining the characteristics of the functional ink film obtained. Can be improved.

[Inkjet recording apparatus]
An ink jet recording apparatus according to the present invention will be described with reference to the drawings. FIG. 9 shows an example in which a plurality of droplet discharge heads of FIG. 1 are arranged, and FIGS. 10 and 11 are schematic views showing an example of an ink jet recording apparatus equipped with the liquid discharge head according to the present invention.

  10 is a perspective explanatory view of the ink jet recording apparatus, and FIG. 11 is a side explanatory view of a mechanism portion of the ink jet recording apparatus.

  The ink jet recording apparatus according to the present invention includes a carriage 93 that can move in the main scanning direction inside a recording apparatus main body 81, an ink jet recording head 94 that is mounted on the carriage 93, and an ink jet recording head 94 according to an embodiment of the present invention. A printing mechanism 82 including an ink cartridge 95 that supplies ink to the ink is accommodated. A sheet feeding cassette (or a sheet feeding tray) 84 on which a large number of sheets 83 can be stacked can be detachably mounted on the lower part 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). An inkjet recording head 94 according to the present invention for ejecting ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk) is provided on the carriage 93, and a plurality of ink ejection ports (nozzles). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward. Further, the carriage 93 is mounted with replaceable ink cartridges 95 for supplying ink of the respective colors to the ink jet recording head 94.

  The ink cartridge 95 has an air port (not shown) communicating with the air at the upper side, a supply port (not shown) for supplying ink to the inkjet recording head 94 at the lower side, and a porous body (not shown) filled with ink inside. doing. The ink supplied to the inkjet recording head 94 is maintained at a slight negative pressure by the capillary force of the porous body. In addition, although the heads of the respective colors are used here as the ink jet recording head 94, a single head having nozzles for ejecting ink droplets of the respective colors 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.

  The ink jet recording apparatus according to the present invention also reverses 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 that conveys the sheet 83, 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. As a result, the paper 83 set in the paper feed cassette 84 is conveyed to the lower side of the inkjet 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 transport roller 104 corresponding to the movement range of the carriage 93 in the main scanning direction on the lower side of the 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 discharge roller 113 and a spur 114 for sending the paper 83 to the discharge tray 86, and guide members 115 and 116 for forming a discharge path are provided.

  At the time of image recording, the recording head 94 is driven in accordance with the image signal while moving the carriage 93 to eject ink onto the stopped paper 83 to record one line, and after the paper 83 is conveyed by a predetermined amount Record the next line. 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 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 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 a discharge failure occurs, the discharge port of the head 94 is sealed by the capping unit, and bubbles and the like are sucked out from the discharge port by 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 into 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.

  In the ink jet recording apparatus according to the present invention, since the ink jet head embodying the present invention is mounted, 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. improves.

DESCRIPTION OF SYMBOLS 1 Substrate 2 SAM film 3 Photoresist 4 Photomask 10 Nozzle plate 11 Nozzle 20 Pressure chamber substrate 21 Pressure chamber 30 Diaphragm 40 Electromechanical conversion element 41 Adhesion layer 42 Lower electrode 43 Electromechanical conversion film 44 Upper electrode 400 Laser source (continuous Irradiation laser device)
500 Laser source (pulse irradiation laser equipment)
600 Laser device 601 Laser light 602 X-ray tube 603 X-ray light receiving element 604 X-ray 605 Reflected X-ray 606 Angle (2θ)
700 Base 704 X-axis support member 705 X-axis drive means 711 Z-axis drive means

Japanese Patent No. 4353145

Claims (13)

Application means for applying functional ink in a predetermined pattern on the substrate;
One or more laser light sources for heating and crystallizing the applied functional ink;
An X-ray diffractometer for measuring the crystalline state of the functional ink;
A recording unit that records information on the crystalline state of the functional ink measured by the X-ray diffractometer;
A control device for controlling laser irradiation conditions of the laser light source;
Have
The control unit performs control so as to adjust the laser irradiation condition of the laser light source based on information on the crystal state of the functional ink recorded in the recording unit and laser-irradiated by the laser light source in advance. ,
A thin film manufacturing apparatus that forms a thin film on a substrate. Applying functional ink in a predetermined pattern on a substrate;
Heating the applied functional ink by laser irradiation with one or more laser light sources to crystallize;
Measuring the crystalline state of the functional ink with an X-ray diffractometer;
Applying the functional ink on the substrate in the predetermined pattern;
Determining the laser irradiation conditions of the laser light source based on the crystalline state of the functional ink obtained by the measuring step, and heat-treating the functional ink;
A thin film manufacturing method for forming a thin film on a substrate. The measurement area for the functional ink by the X-ray diffractometer is:
Same as the pattern area of the functional ink formed on the substrate or the measurement area is narrower,
Same as the irradiation area of the laser irradiation by the laser light source or the measurement area is narrower,
The thin film manufacturing method according to claim 2.   The thin film manufacturing method according to claim 2 or 3, wherein a range of an X-ray irradiation angle by the X-ray diffractometer in the measuring step is an angle corresponding to a predetermined crystal peak of the functional ink.   The said laser irradiation conditions are the thin film manufacturing methods as described in any one of Claims 2 thru | or 4 including any of the irradiation output of the said laser light source, the frequency | count of irradiation, or irradiation time. The heat treatment includes a step of evaporating a solvent in the functional ink, and a step of crystallizing the functional ink,
In the step of evaporating the solvent, laser irradiation is performed using a continuous irradiation laser device,
In the crystallization step, laser irradiation is performed using a pulsed irradiation laser device.
The thin film manufacturing method as described in any one of Claims 2 thru | or 5.   The thin film manufacturing method according to claim 6, wherein a light intensity distribution of the continuous irradiation laser device is a top hat shape. The laser irradiation by the continuous irradiation laser device irradiates while scanning the substrate in one direction,
The irradiation shape of the laser irradiation by the continuous irradiation laser device is such that the width in the one direction is the same as or larger than the width in the one direction of the functional ink,
The irradiation shape of the laser irradiation by the continuous irradiation laser device is such that the width in the depth direction of the substrate is the same as the width in the depth direction of the functional ink or the width in the depth direction of the substrate Greater than,
The thin film manufacturing method according to claim 6 or 7.   The thin film manufacturing method according to claim 6, wherein the pulse irradiation laser device is used in the step of evaporating the solvent.   10. The thin film manufacturing method according to claim 6, wherein a light intensity distribution of the pulse irradiation laser device is a top hat shape. 11.   The irradiation region of laser irradiation by the pulse irradiation laser device is the same as the pattern region of the functional ink formed on the substrate, or the irradiation region is wider. Thin film manufacturing method.   The thin film manufacturing method according to claim 6, wherein an irradiation shape of laser irradiation by the pulse irradiation laser apparatus is a rectangle.   The thin film manufacturing method according to any one of claims 6 to 12, comprising a step of irradiating the functional ink with ultraviolet rays before the crystallization step.

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