JP5906610B2 - Thin film manufacturing apparatus and thin film manufacturing method - Google Patents

Description

  The present invention relates to a thin film manufacturing apparatus and a thin film manufacturing method using an ink jet method, and more particularly to a thin film manufacturing apparatus and a thin film manufacturing method suitable for forming an electromechanical conversion film. Furthermore, the present invention relates to a liquid discharge head and an ink jet printer using the electromechanical conversion element.

  As a technique for increasing the density of a liquid discharge head using an electromechanical transducer (piezoelectric element), a technique using MEMS (micro electro mechanical system) is disclosed as disclosed in Patent Document 1 and the like. That is, by applying semiconductor device manufacturing technology and finely forming the actuator and the liquid flow path, the nozzle density can be increased, so that the head can be miniaturized and highly integrated.

  In a liquid discharge head employing such MEMS technology, an electrode and an electromechanical conversion film (piezoelectric body) formed by thin film formation technology are patterned on a diaphragm formed by thin film technology by photolithography to perform electromechanical conversion. An actuator can be formed by forming an element.

The following methods are known for forming an electromechanical transducer.
That is, various vacuum film formation methods (for example, sputtering method, MO-CVD method (chemical vapor deposition method using metal organic compound), vacuum deposition method, ion plating method), sol-gel method, water on the lower electrode An electromechanical conversion film is deposited by a well-known film forming technique such as a thermal synthesis method, an AD (aerosol deposition) method, or a coating / pyrolysis method (MOD), and then an upper electrode is formed. The electrode is patterned, and similarly, the electromechanical conversion film and the lower electrode are patterned to form an electromechanical conversion element.

  Among these, regarding the sol-gel method, for example, a technique of forming an electromechanical conversion element by applying a precursor of lead zirconate titanate (PZT) to a base material by an ink jet method and baking is already known. This method is advantageous in terms of the environment because the PZT precursor can be selectively applied to a desired region and the consumption of lead-containing PZT precursor can be suppressed.

  However, the ink-jet method is a method of applying a liquid using a plurality of nozzles and non-contact means, and the pattern formation accuracy is several μm to several tens due to the positional variation of the relative movement means between the carriage on which the liquid discharge head is mounted and the substrate. Since a variation of about 10 μm occurs, the shape of the electromechanical conversion element varies, which causes a problem in the electrical characteristics of the electromechanical conversion element.

  As a method for solving this problem, an area having a difference in surface energy consisting of a lyophilic area and a lyophobic area is formed by patterning on the surface of the substrate, and a functional ink is formed on the lyophilic area by an inkjet method There is a technique in which an electromechanical conversion film is formed in a predetermined pattern by dropping (for example, a PZT precursor).

  As one of the patterning methods, a technique called micro contact printing (μCP) method is already known. This technology uses a PDMS (polydimethylsiloxane) resin having a thickness on the order of millimeters to micrometers, with a concavo-convex pattern on the order of nanometers to micrometers, as a printing plate, and to a functional ink (PZT precursor). Using a solution (organic molecule-containing solution) having liquid repellency (or lyophilicity), a high-resolution liquid repellency (or lyophilic) pattern is printed by a contact method (Patent Document 2). , 3).

  Alternatively, as another patterning method, a technique using a phenomenon in which alkanethiol self-aligns on a specific metal is known (see Non-Patent Document 1). That is, alkanethiol is formed as a self-assembled monolayer (SAM) on a platinum group metal (eg, Pt) film, and this SAM film is etched into a predetermined pattern by a well-known photolithography technique. Thus, a liquid-phobic (liquid-repellent) region composed of a patterned SAM film and a lyophilic region composed of Pt are formed for the functional ink (PZT precursor).

  Here, since the functional ink of the PZT precursor has a limited solvent for dissolving the PZT precursor, it is necessary to devise a discharge waveform in order to stably discharge from the liquid discharge head. However, there is a limit to stable ejection by optimizing the ejection waveform, and a droplet called a mist with a small volume and a slow speed is generated after the main droplet during ink ejection. This mist may be pushed back to the liquid discharge head side by an air flow accompanying the stage movement, and the mist may adhere to the vicinity of the nozzle. In addition, if a fine droplet that could not be ejected downward by ejection adheres to the edge of the nozzle, the PZT precursor solution is a sol-gel solution, and after a while it hydrolyzes and gels, causing ejection bend and speed deviation. Become. Furthermore, when micro droplets accumulate near the nozzle, the nozzle may be clogged. In this way, normal ejection cannot be performed, which causes a pattern defect.

  At this time, various techniques for wiping the ink by appropriately pressing a blade-shaped wipe member against the nozzle surface against ink adhesion to the nozzle in the liquid ejection head have been proposed (Patent Documents 4 to 6). ), But the problem has not been fully resolved.

  The present invention has been made in view of the above problems in the prior art, and an object of the present invention is to provide a thin film manufacturing apparatus using an inkjet method having functional ink ejection stability. Another object of the present invention is to provide a thin film manufacturing method using the thin film manufacturing apparatus, an electromechanical conversion element manufactured by the thin film manufacturing method, a liquid discharge head, and an ink jet printer.

The present invention provided to solve the above problems includes a stage for holding a substrate, and a liquid ejection head that is disposed opposite to the stage and that ejects functional ink from a nozzle by an ink jet method and applies the functional ink onto the substrate. A liquid discharge application mechanism that discharges the functional ink onto the substrate by relatively moving the stage and / or the liquid discharge head, and applying the ink in an arbitrary pattern, and the functional ink on the substrate A heating mechanism section that heats and crystallizes to form a functional thin film, and the stage in the liquid discharge application mechanism section has the nozzle on a scanning path when the functional ink of the liquid discharge head is applied. have a wiping blade rubbing with the wiping blade arrangement on both end sides of the scanning direction in the scanning path of the liquid ejecting head on the stage Be one that is a thin film manufacturing apparatus, characterized in that the blade plate shape having the same length as the width perpendicular to the scanning direction of at least the substrate.

  According to the thin film manufacturing apparatus of the present invention, the stage has a wiping blade that slides on the scanning path when the functional ink of the liquid ejection head is applied. Alternatively, the nozzle wiping process is performed for each scan of the liquid ejection head, so that the ejection stability of the functional ink can be ensured.

It is a perspective view which shows the structural example of the liquid discharge application | coating mechanism part used for the thin film manufacturing apparatus which concerns on this invention. It is sectional drawing which shows the structure of the IJ head used for the liquid discharge application | coating mechanism part of FIG. It is a perspective view which shows the structural example 1 of the wiping blade used by this invention. It is sectional drawing which shows the structure (1) of the wiping process in the liquid discharge application | coating mechanism part of FIG. It is sectional drawing which shows the structure (2) of the wiping process in the liquid discharge application | coating mechanism part of FIG. It is sectional drawing which shows the structure (3) of the wiping process in the liquid discharge application | coating mechanism part of FIG. It is sectional drawing which shows the structure (4) of the wiping process in the liquid discharge application | coating mechanism part of FIG. It is sectional drawing which shows the structure (5) of the wiping process in the liquid discharge application | coating mechanism part of FIG. FIG. 7 is a cross-sectional view illustrating another example of the arrangement of wiping blades in the liquid discharge application mechanism unit of FIG. 1. It is a perspective view which shows the structural example 2 of the wiping blade used by this invention. It is a perspective view which shows the structural example 3 of the wiping blade used by this invention. It is a perspective view which shows the structural example 4 of the wiping blade used by this invention. It is a perspective view which shows the structural example 5 of the wiping blade used by this invention. It is explanatory drawing of the patterning method of a SAM film. It is the schematic which shows the procedure which forms a functional thin film using the thin film manufacturing apparatus of this invention. It is a PE hysteresis curve which shows the performance example of the electromechanical conversion film of this invention. It is a manufacturing process figure of the electromechanical conversion element in the liquid discharge head of this invention. FIG. 3 is a perspective view illustrating a configuration of a liquid discharge head according to the present invention. FIG. 3 is a schematic cross-sectional view illustrating a configuration in a width direction of the liquid discharge head according to the present invention. It is an external view of a liquid cartridge using the liquid discharge head of the present invention. 1 is an external view of an inkjet printer according to the present invention. It is sectional drawing which shows the structure of the mechanism part of the inkjet printer of FIG.

[Thin film manufacturing equipment]
Below, the structure of the thin film manufacturing apparatus which concerns on this invention is demonstrated.
First, a thin film manufacturing apparatus according to the present invention includes a stage that holds a substrate, and a liquid ejection head that is disposed opposite to the stage and that ejects functional ink from a nozzle by an ink jet method and applies the functional ink onto the substrate. A liquid discharge application mechanism that discharges the functional ink onto the substrate by applying relative movement of the stage and / or the liquid discharge head, and heats the functional ink on the substrate. A heating mechanism section that is crystallized into a functional thin film, and a stage in the liquid discharge application mechanism section slides on the scanning path when the functional ink of the liquid discharge head is applied. It has a wiping blade for rubbing.
In addition, as a means for heating the functional ink in the heating mechanism section, a heating means such as a hot plate, an oven, a halogen lamp, a xenon lamp, an infrared lamp, or a laser irradiation means such as a YAG laser, a CO ₂ laser, an Ar laser, etc. Is used.
Here, since the thin film manufacturing apparatus of the present invention is characterized by the liquid discharge application mechanism unit, the liquid discharge application mechanism unit will be described below.

FIG. 1 is a perspective view showing a configuration example of a liquid discharge coating mechanism used in a thin film manufacturing apparatus according to the present invention.
As shown in FIG. 1, the liquid discharge application mechanism is a so-called inkjet coating apparatus, which is a base 200 as a base of the apparatus, and is installed on the base 200, and a Y-axis drive that moves the stage 203 in the Y-axis direction. Means 201, a stage 203 that is installed on the Y-axis driving means 201, holds the substrate 202 on the Y-axis driving means 201, and has a wiping blade 212; and a liquid that is disposed on the stage 203 so as to eject functional ink. A discharge head (hereinafter referred to as IJ head) 208, a Z-axis drive unit 211 that supports the IJ head 208 via the head base 206 and moves it in the Z-axis direction, an IJ head 208, the head base 206, and the Z-axis drive unit 211. X-axis drive means 205 that supports the X-axis and moves in the X-axis direction, and an X-axis support member 20 that supports the X-axis drive means 205 And, equipped with a.

  Here, as shown in FIG. 2, the IJ head 208 is filled with a diaphragm 540, an electromechanical transducer 501 that is a piezoelectric element provided on the diaphragm 540 via an adhesion layer 500d, and functional ink. Pressure chamber (also referred to as individual liquid chamber) 21 and a nozzle plate 504 provided with nozzles 505 corresponding to the pressure chambers 506, which are droplet discharge holes for discharging functional ink.

  The pressure chamber 506 is a space surrounded by the vibration plate 540, the wall surface (partition wall portion) of the pressure chamber substrate 503, and the nozzle plate 504.

  In addition, an electromechanical conversion element 501 in which an adhesion layer 500d, a lower electrode 500a, an electromechanical conversion film 500b that is a piezoelectric body, and an upper electrode 500c are stacked is formed on the side of the diaphragm 540 opposite to the pressure chamber 506. ing. A plate surface of the pressure chamber 506 facing the vibration plate 540 is a nozzle plate 504.

  In the IJ head 208 configured as described above, in a state where each pressure chamber 506 is filled with a liquid, for example, functional ink, a recording ink is generated by an oscillation circuit based on predetermined pattern data from a control unit (not shown). A pulse voltage is applied to the upper electrode 500c corresponding to the nozzle 505 that is desired to discharge the ink. By applying this voltage pulse, the electromechanical conversion film 500b is contracted in the direction parallel to the diaphragm 540 by the electrostrictive effect, so that the diaphragm 540 becomes convex toward the pressure chamber 506 side. Will be bent. As a result, the pressure in the pressure chamber 506 increases rapidly, and the functional ink is ejected from the nozzle 505 communicating with the pressure chamber 506. At this time, several tens to several hundreds of droplets are continuously ejected from the nozzle 505. Next, after applying the pulse voltage, the contracted electromechanical conversion film 500b returns to its original position, so that the flexed diaphragm 540 returns to its original position, and the functional ink is transferred from the common liquid chamber 533 (described later) to the pressure chamber. 506 is supplied. By repeating the above operation control, the IJ head 208 can continuously eject functional ink droplets. The functional ink is supplied to the IJ head 208 from an ink tank (not shown) via the ink supply pipe 210.

  The stage 203 has an adsorbing unit that adsorbs and holds the substrate 202 on the main surface of the stage 203 using vacuum, static electricity, or the like.

  The stage 203 has a wiping blade 212 that slides on the nozzle 505 on the scanning path of the IJ head 208 when the functional ink is applied. The wiping blade 212 is preferably arranged on one end side or both end sides in the scanning direction on the scanning path of the IJ head 208 on the stage 203. In FIG. 1, the wiping blade 212 is arranged on the stage 203 near the movement start position and the movement end position when the IJ head 208 moves and scans in the Y-axis direction during coating. The arrangement of the stage 203 and the stage 203 moves without changing. The wiping blade 212 is a flat blade having at least the same width as the width of the substrate 202 (the length in the X-axis direction), and the Z-axis direction (the main axis of the stage 203) with the longitudinal direction as the X-axis direction. (Vertical direction to the surface). At this time, the height of the wiping blade 212 in the Z-axis direction is such that the tip thereof slightly contacts the nozzle surface of the nozzle plate 504 of the IJ head 208 (the main surface facing the substrate 202). In addition, at least a tip portion of the wiping blade 212 in the Z-axis direction, that is, a portion that slides on the nozzle 505 has flexibility.

  Thereby, at the time of scanning for applying functional ink, one of the two wiping blades 212 rubs against the nozzle surface of the nozzle plate 504 of the IJ head 208 when the IJ head 208 starts scanning in the Y-axis direction. A wiping process is performed, and at the end of scanning of the IJ head 208 in the Y-axis direction, the other of the two wiping blades 212 slides on the nozzle surface of the nozzle plate 504 of the IJ head 208 to perform the wiping process.

  The wiping process is a process in which the wiping blade 212 is rubbed against the nozzle surface of the nozzle plate 504 of the IJ head 208 to wipe away the functional ink attached to the nozzle 505 and its vicinity.

FIG. 3 shows a configuration example 1 of the wiping blade 212.
As shown in FIG. 3, the wiping blade 212 includes a flat plate-shaped support member 213, and a nozzle contact portion 214 that is fixed to one end surface of the support member 213 and has a tip that contacts the nozzle surface of the nozzle plate 504. Has been.

  Of these, the support member 213 is made of metal, ceramic, or the like used for the stage 203, and has such a rigidity that the nozzle contact portion 214 is not deformed even if it slides on the nozzle plate 504.

  The nozzle contact portion 214 is made of a flexible silicone resin, a rubber material, or the like, and has a thickness that decreases toward the tip in the Z-axis direction so that the cross-sectional shape in the YZ plane is a convex shape. As a result, the tip of the wiping blade 212 (nozzle contact portion 214) can be brought into contact with the nozzle surface of the nozzle plate 504 of the IJ head 208 with equal pressure, and the functional ink adhering to the nozzle plate 504 is efficiently wiped off. It becomes possible to do.

  With the liquid discharge application mechanism having the above-described configuration, it is possible to apply functional ink in a predetermined pattern to the substrate 202 disposed opposite to the IJ head 208. At this time, a wiping process in which the wiping blade 212 slides on the nozzle 505 is performed at the start and end of the scan for each scan in the Y-axis direction of the IJ head 208.

Specifically, the processing is performed as follows when functional ink is applied (FIGS. 4 to 8).
(S11) After the IJ head 208 is moved in the Z-axis direction by the Z-axis driving unit 211 and the distance from the substrate 202 is adjusted, the stage 203 is moved in the Y-axis direction by Y-axis driving unit 201 (for example, Y ( (+) Direction, rightward in FIG. 4) starts to move (FIG. 4).
(S12) Immediately after the stage 203 starts to move in the Y-axis direction (Y (+) direction), one of the two wiping blades 212 (the right side in FIG. 5) rubs against the nozzle surface of the nozzle plate 504 in the IJ head 208. Then, a wiping process is performed (FIG. 5). Note that before the ink is ejected, depending on the functional ink, if the IJ head 208 is left unattended, the nozzle surface may be slightly wetted by the functional ink in the pressure chamber 506, and this functional ink is wiped off by this wiping process.
(S13) Further, while the stage 203 moves in the Y-axis direction (Y (+) direction), the functional ink 209 is ejected from the IJ head 208 based on the input pattern and is moved to a predetermined position on the substrate 202 that moves together with the stage 203. Application is performed (FIG. 6). At this time, as described above, the functional ink adheres to the nozzle 505 and the vicinity thereof on the nozzle surface.
(S14) Immediately before the end of the movement of the stage 203 in the Y-axis direction (Y (+) direction), the other of the two wiping blades 212 (left side in FIG. 7) rubs against the nozzle surface of the nozzle plate 504 in the IJ head 208. Then, a wiping process is performed (FIG. 7). Further, the stage 203 moves in the Y-axis direction (Y (+) direction), and one scan in the Y-axis direction is completed (FIG. 8).
(S15) Then, when one scanning in the Y-axis direction is completed, the I-J head 208 is moved to the next Y-axis direction scanning position in the X-axis direction by the X-axis driving unit 205.
(S16) Steps S11 to S15 are performed. In this case, the stage 203 moves in the reverse direction (Y (−) direction) in the Y-axis direction.

  The above steps S11 to S16 are repeated until the input pattern is applied, and the functional ink having a predetermined pattern is applied to the substrate 202. Depending on the pattern to be applied at this time, scanning is usually performed several tens of times. The Y-axis direction scanning may be any configuration as long as it moves relatively between the IJ head 208 and the stage 203. Here, an example in which the IJ head 208 is fixed and the stage 203 is moved. Although shown, the stage 203 may be fixed and the IJ head 208 may be moved.

  As described above, at the time of applying functional ink, the nozzle 505 and the nozzles in the vicinity of the nozzle 505 are scanned before and after one scan without performing special scan control of the IJ head 208 every time the IJ head 208 scans in the Y-axis direction. Since the functional ink adhering to the plate 504 is wiped off, nozzle clogging can be prevented, ejection stability of the functional ink can be ensured, and a functional ink coating film having a desired pattern can be formed. Become. Note that in a conventional liquid discharge application mechanism unit that does not have the wiping blade 212, the greater the number of scans during application, the greater the amount and area of functional ink that adheres to the nozzle surface, resulting in a coating pattern defect. It becomes easy.

  Further, here, the configuration in which the wiping blades 212 are provided on both end sides of the stage 203 has been described, but as shown in FIG. 9, one end side in the scanning direction in the scanning path of the IJ head 208 on the stage 203 (FIG. The wiping blade 212 may be arranged only on the left side in FIG. Whether the wiping blade 212 is arranged on both ends or one end of the stage 203 may be determined in consideration of the stability of the functional ink and the application pattern.

In addition, the wiping blade 212 preferably has a solvent supply unit that supplies a solvent for the functional ink to a portion that slides on the nozzle 505. When a functional ink that is easily dried, such as a PZT precursor, is used, if it adheres to the nozzle 505, nozzle clogging tends to occur. Therefore, if a solvent of functional ink, for example, 1-propanol or ethanol, is supplied to the portion (the tip of the nozzle contact portion 214) of the wiping blade 212 that slides on the nozzle 505 by the solvent supply means, as described above. Since the solvent is supplied to the nozzle 505 when the tip of the nozzle contact portion 214 rubs against the nozzle 505, the functional ink adhering to the nozzle 505 can be prevented from drying and solidifying, and the removal can be facilitated. It becomes possible to prevent nozzle clogging.
Examples thereof are shown in FIGS.

FIG. 10 is a perspective view showing a configuration example 2 of the wiping blade 212.
As shown in FIG. 10, a solvent supply tube 215 that passes through the inside of the wiping blade 212 is provided from the bottom of the support member 213 to the tip of the nozzle contact portion 214, and at the center in the longitudinal direction (X-axis direction) of the nozzle contact portion 214. It has a structure for supplying a solvent.

FIG. 11 is a perspective view showing a configuration example 3 of the wiping blade 212.
As shown in FIG. 11, a solvent supply tube 215 that passes through the nozzle contact portion 214 from the longitudinal end (X-axis direction) end of the nozzle contact portion 214 to the tip of the nozzle contact portion 214 is provided. The solvent is supplied to the central portion in the longitudinal direction (X-axis direction).

FIG. 12 is a perspective view showing a configuration example 4 of the wiping blade 212.
As shown in FIG. 12, a groove 214a extending in the longitudinal direction (X-axis direction) of the nozzle contact portion 214 is provided at the tip of the nozzle contact portion 214 (the portion of the wiping blade 212 that slides on the nozzle 505). The solvent supply tube 215 shown in FIG. 10 or FIG. 11 is connected.

  As a result, the solvent supplied from the solvent supply tube 215 is stored in the groove 214a, and the solvent can be stably supplied to the nozzle 505 when the tip of the nozzle contact portion 214 rubs against the nozzle 505. In addition, nozzle clogging can be prevented.

  In FIG. 12, the groove 214a is provided on a part of the flat surface of the tip portion of the nozzle contact portion 214. However, as shown in FIG. 13, the solvent is applied to the entire flat surface of the tip portion of the nozzle contact portion 214. A groove 214a ′ for storage may be provided.

  Further, the solvent supplied from the solvent supply tube 215 may be used not only for the wiping process of the nozzle 505 but also for cleaning the wiping blade 212 itself. Since many functional inks are easily solidified, the wiping blade 212 can be kept clean by supplying the solvent immediately after the wiping process to wash away the functional ink adhering to the wiping blade 212.

[Thin film manufacturing method]
Next, the thin film manufacturing method according to the present invention will be described.
The thin film manufacturing method according to the present invention is a thin film manufacturing method for forming a functional thin film on a substrate using the above-described thin film manufacturing apparatus of the present invention, and relatively scanning the stage and / or the liquid discharge head. However, an ink jet coating process in which functional ink is ejected from the liquid ejection head and applied in an arbitrary pattern on the substrate, and a heating process in which the functional ink on the substrate is heated and crystallized to form a functional thin film. The inkjet coating step includes a wiping process in which the wiping blade rubs against the nozzle at the start of scanning and / or at the end of scanning for each scanning of the stage and / or liquid ejection head. It is what.
Here, it is preferable that the ink jet coating step is to coat the functional ink on a substrate on which a pattern including a liquid repellent portion and a lyophilic portion is formed.
The functional thin film includes a lower electrode 500a, an electromechanical conversion film 500b, an upper electrode 500c, and the like which will be described later.

Details of the thin film manufacturing method of the present invention will be described below.
(I) Patterning of SAM film FIG. 14 shows a patterning method of the SAM film. Here, three methods are shown in FIGS. 14 (a), (b), and (c).

(Patterning method 1)
(S21) First, the substrate 202 is prepared. Here, for example, a substrate 202 having an adhesion layer 500d made of Pt having excellent reactivity with thiol on the surface of the vibration plate 540 is used as the substrate 202 (FIG. 14A1).
(S22) A uniform SAM film 300 is formed on the surface of the substrate 202 using a functional solution (FIG. 14 (a2)).

The functional solution used here is an organic molecule-containing solution for imparting liquid repellency or lyophilicity to the substrate 202. For example, an alkanethiol represented by C _n H _{2n + 1} SH (n = 6 to 18). A liquid repellent material such as a compound or a fluoroalkylthiol compound represented by C _n F _{2n + 1} (CH ₂ ) ₂ SH can be used. Further, the material type or concentration can be appropriately selected according to desired liquid repellency or reactivity to the surface of the substrate 202. These compounds are made into a functional solution by dissolving in an organic solvent such as alcohol, acetone, toluene, and xylene.

  The SAM film 300 is formed by immersing the substrate 202 in this functional solution for a predetermined time, and after removing the substrate 202, cleaning the excess molecules with a solvent and drying.

(S23) Next, a photoresist 300p is patterned by a conventionally known photolithography technique (FIG. 14 (a3)).
(S24) The exposed SAM film 300 is removed from the material surface in Step S23 by dry etching with oxygen plasma or the like, and then the photoresist 300p is removed to remove the liquid repellent portion (liquid repellent region) 301, lyophilic liquid. A SAM film 300 having a predetermined pattern composed of a portion (lyophilic region) 302 is obtained (FIG. 14 (a4)). Here, the region where the SAM film 300 remains is the lyophobic portion 301, and the region where the SAM film 300 is removed is the lyophilic portion 302.

(Patterning method 2)
(S31) First, the substrate 202 is prepared. Here, for example, a substrate 202 formed with an adhesion layer 500d made of Pt having excellent reactivity with thiol on the surface of the diaphragm 540 is used as the substrate 202 (FIG. 14B1).
(S32) A mask layer 300r having a predetermined pattern is formed on the surface of the substrate 202 (FIG. 14B2). The mask layer 300r may be formed from a photoresist film by a conventionally known photolithography technique.
(S33) The SAM film 300 is formed on the surface of the substrate 202 using a functional solution (FIG. 14 (b3)). At this time, the SAM film 300 is formed on the surface of the substrate 202 exposed from the mask layer 300r.
(S34) The mask layer 300r is removed to obtain a SAM film 300 having a predetermined pattern including a liquid repellent part (liquid repellent area) 301 and a lyophilic part (lyophilic area) 302 (FIG. 14 (b4)).

(Patterning method 3)
(S41) First, the substrate 202 is prepared. Here, for example, a substrate 202 having an adhesion layer 500d made of Pt having excellent reactivity with thiol on the surface of the diaphragm 540 is used as the substrate 202 (FIG. 14 (c1)).
(S42) Similar to the patterning method 1, a uniform SAM film 300 is formed on the surface of the substrate 202 using a functional solution (FIG. 14C2).
(S43) A photomask 300m is arranged on the surface of the material in step S42, and ultraviolet rays are exposed from above (300 (c3)). As a result, the exposed portion of the SAM film 300 disappears and the unexposed portion of the SAM film 300 remains, and has a predetermined pattern consisting of a liquid repellent portion (liquid repellent region) 301 and a lyophilic portion (lyophilic region) 302. The SAM film 300 is obtained (FIG. 14 (c4)).

  In the present invention, any of the above three patterning methods may be used. Alternatively, the SAM film 300 having a predetermined pattern including a desired liquid repellent part (liquid repellent area) 301 and a lyophilic part (lyophilic area) 302 may be formed by a micro contact printing method. In the substrate 202 obtained by this step, for example, in a region where the SAM film 300 remains, the contact angle with respect to pure water is 92 degrees, indicating hydrophobicity (water repellency), the SAM film 300 is removed, and the adhesion layer 500d. In the exposed region, the contact angle with pure water is 54 degrees, indicating hydrophilicity.

(Ii) Formation of functional thin film In the formation of a functional thin film using the thin film production apparatus of the present invention, there is a limit to the thickness of the thin film obtained by a single film formation. It is preferable to form a functional thin film having a predetermined thickness by repeating and laminating.

FIG. 15 shows a procedure for forming a functional thin film using the thin film manufacturing apparatus of the present invention.
(S51) A substrate 202 on which a SAM film 300 having a predetermined pattern composed of the liquid repellent part 301 and the lyophilic part 302 is formed is prepared (FIG. 15 (1)).

(S52) The functional ink 209 is discharged from the IJ head 208 to the lyophilic portion 302 using the liquid discharge coating mechanism portion in the thin film manufacturing apparatus of the present invention to form the coating film 401 (FIG. 15 (2)). At this time, the functional ink 209 spreads with good wettability in the lyophilic portion 302 and is repelled by the liquid repellent portion 301, so that the coating film 401 having the pattern of the lyophilic portion 302 is formed.

  For the functional ink 209, for example, a PZT precursor solution is used. For preparing this PZT precursor solution, for example, lead acetate trihydrate, isopropoxide titanium, and normal butoxide zirconium are used as starting materials. First, crystal water of lead acetate is dissolved in methoxyethanol and then dehydrated. In addition, with respect to lead acetate, in order to prevent crystallinity deterioration due to so-called lead loss during heat treatment, the lead content is weighed so that it is excessive by about 10 mol% with respect to the stoichiometric composition. Subsequently, isopropoxide titanium and normal butoxide zirconium are dissolved in methoxyethanol, alcohol exchange reaction and esterification reaction are advanced, and a PZT precursor solution is synthesized by mixing with the methoxyethanol solution in which lead acetate is dissolved.

  The PZT concentration in this PZT precursor solution is optimized from the relationship between the film formation area and the amount of applied precursor, but the film thickness of the coating film 401 formed by one application is preferably about 100 nm. 1 mol / l. In the following description of FIG. 15, the case where this PZT precursor solution is used will be described.

(S53) A first heat treatment (for example, heating at 120 ° C.) for solvent drying is performed on the coating film 401, and then a thermal decomposition treatment (heating at 500 ° C.) of the organic substance is performed to form the first PZT film. A functional thin film 500 is formed (FIG. 15 (3)). The film thickness at this time is 90 nm.

(S54) Subsequently, as an iterative process, after the object is washed with isopropyl alcohol, the SAM film 300 is formed by the immersion process in the functional solution similar to FIG. 14 (a2) (FIG. 15 (4)). In the second and subsequent immersion treatments, the SAM film 300 is not formed on the functional thin film 500 that is an oxide film, and thus includes the liquid repellent part 301 and the lyophilic part 302 without performing a pattern forming process by photolithography. A SAM film 300 having a predetermined pattern is obtained. The contact angle at this time was 92 degrees on the SAM film 300 and 34 degrees on the PZT film with respect to pure water.

(S55) The functional ink 209 is ejected from the IJ head 208 onto the functional thin film 500, which is the first PZT film, using the liquid ejection coating mechanism in the thin film manufacturing apparatus of the present invention, thereby forming the coating film 401. (FIG. 15 (5)).

(S56) Further, the coating film 401 is subjected to a second heat treatment for drying the solvent (for example, heating at 120 ° C.), followed by a thermal decomposition treatment of organic matter, and a functional thin film 500 that is a PZT film laminated. Is formed (FIG. 15 (6)). The film thickness at this time is 180 nm.

  Steps S54 to S56 are further repeated 4 times (by a total of 6 treatments) to obtain a functional thin film 500 having a thickness of 540 nm, and then crystallization heat treatment (heating at 700 ° C.) is performed by RTA (rapid heat treatment). . At this time, defects such as cracks did not occur in the functional thin film 500.

  Next, steps S54 to S56 are further repeated six times to perform a crystallization heat treatment (heating at 700 ° C.). At this time, the film thickness of the functional thin film 500 was 1000 nm, and defects such as cracks did not occur in the film.

Here, an upper electrode (platinum) was formed on the functional thin film 500, which is a patterned PZT film, and the electrical characteristics and electromechanical conversion ability (piezoelectric constant) were evaluated.
As a result, the functional thin film 500 has a relative dielectric constant of 1220, a dielectric loss of 0.02, a remanent polarization of 19.3 μC / cm ² and a coercive electric field of 36.5 kV / cm, which is the same as that of a normal ceramic sintered body. The characteristics were shown.

  FIG. 16 shows a PE hysteresis curve. The electromechanical conversion ability was calculated from the amount of deformation by applying an electric field measured with a laser Doppler vibrometer and adjusted 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 liquid discharge head.

  For the functional thin film 500 having a thickness of 1000 nm, an attempt was made to further increase the thickness without arranging the upper electrode. That is, when the process of steps S54 to S56 is repeated 6 times and the process of crystallization heat treatment (heating at 700 ° C.) is repeated 10 times, the functional thin film 500 of the patterned PZT film having a thickness of 5 μm has defects such as cracks. Obtained without.

[Electromechanical transducer and liquid discharge head]
Next, the electromechanical transducer according to the present invention will be described.
The electromechanical conversion element according to the present invention is an electromechanical conversion element having an electromechanical conversion film manufactured by the above-described thin film manufacturing method of the present invention, wherein the functional ink is a ferroelectric precursor ink. The first electrode as the substrate, the second electrode disposed opposite to the first electrode, and the electromechanical conversion sandwiched between the first electrode and the second electrode And a film.
The second electrode is preferably manufactured by the thin film manufacturing method of the present invention.

Referring to FIG. 17, a case will be described in which the lower electrode 500a, the electromechanical conversion film 500b, and the upper electrode 500c are all formed in the electromechanical conversion element 501 by the thin film manufacturing method of the present invention.
(S61) First, the diaphragm 540 having the adhesion layer 500d is used (the adhesion layer 500d is not shown), and the desired lyophobic part 301a and lyophilic part 302a are formed on the surface by the SAM film patterning method described above. A patterned SAM film 300 is formed (FIG. 17A1).
(S62) Next, the electrode material-containing solution 401a, which is functional ink, is selectively applied from the IJ head 208 to the lyophilic portion 302a using the liquid discharge application mechanism portion in the thin film manufacturing apparatus of the present invention (FIG. 17). (A2)). The electrode material-containing solution 401a applied to the lyophilic portion 302a spreads wet with respect to the lyophilic portion 302a due to the surface energy difference on the vibration plate 540 (adhesion layer 500d) and spreads wet with respect to the lyophobic portion 301a. Therefore, high-resolution patterning can be performed. Here, as the electrode material-containing solution 401a, a solution in which platinum fine particles are dispersed in an ethanol solvent is used. However, platinum-based metal fine particles such as palladium, rhodium, ruthenium, and iridium are placed in an organic solvent such as alcohol. A dispersed fine metal particle dispersion or a so-called sol-gel solution in which a metal organic compound such as a metal alkoxide is dissolved and dispersed in a solvent by a sol-gel method may be used.
(S63) Next, energy is applied to the electrode material-containing solution 401a on the diaphragm 540 (adhesion layer 500d) using the energy applying means 700 to form the lower electrode 500a (FIG. 17A3). Here, as the energy applying means 700, a hot plate or an oven is used, but a heating means such as a halogen lamp, a xenon lamp or an infrared lamp, or a laser irradiation means such as a YAG laser, a CO ₂ laser or an Ar laser is used. May be.
As described above, steps S61 to S63 are performed a plurality of times until the film of the lower electrode 500a has a desired film thickness.

Note that the lower electrode 500a may be formed by a sputtering method. In this case, the SAM film 300 having a pattern including a desired liquid-repellent part 301a and a lyophilic part 302a is formed on the vibration plate 540, which is a silicon wafer with a thermal oxide film, on which an adhesion layer 500d made of Ti is disposed, as in step S61. Then, any one of Pt, an electrode material of other platinum group elements (ruthenium, iridium, rhodium) or a platinum group alloy (platinum-rhodium (rhodium concentration 15 wt%)) is formed by sputtering. Alternatively, as the lower electrode 500a, an iridium oxide film and an iridium metal may be stacked to form a sputtering film.
In the vibration plate 540 on which the adhesion layer 500d made of Ti is formed, the water contact angle of the lyophilic portion 302a (the SAM film 300 removal portion) is 5 ° or less (completely wet), and the liquid repellent portion 301a (the SAM film placement portion). ) Showed 90.0 ° in all samples.

(S71) Next, on the surface of the diaphragm 540 where the lower electrode 500a is formed, the SAM film 300 having a pattern including a desired liquid repellent part 301b and a lyophilic part 302b is formed on the surface by the SAM film patterning method described above. (FIG. 17 (B1)).
(S72) Next, the PJT precursor solution 401b, which is functional ink, is selectively applied from the IJ head 208 to the lyophilic portion 302b (lower electrode 500a) using the liquid discharge coating mechanism in the thin film manufacturing apparatus of the present invention. Apply (FIG. 17 (B2)). Here, as the PZT precursor solution 401b, a piezoelectric material formed by a sol-gel method, specifically, lead acetate, isopropoxide zirconium, isopropoxide titanium as described above is used as a starting material, and a common solvent is used. A lead zirconate titanate (PZT) -based material dissolved in methoxyethanol is used.
(S73) Next, energy is applied to the PZT precursor solution 401b on the lower electrode 500a using the energy applying means 700 to form the electromechanical conversion film 500b (FIG. 17 (B3)).
As described above, the processes of steps S71 to S73 are performed a plurality of times until the thin film of the electromechanical conversion film 500b has a desired film thickness.

(S81) Next, on the surface of the diaphragm 540 where the lower electrode 500a and the electromechanical conversion film 500b are formed, the pattern of the desired lyophobic part 301c and lyophilic part 302c is formed on the surface by the SAM film patterning method described above. A SAM film 300 is formed (FIG. 17C1).
The upper electrode 500c needs to be coated with an electrode material-containing solution 401c in a region smaller than the pattern region of the electromechanical conversion film 500b in order to prevent a short circuit. Therefore, as shown in FIG. 17C1, a liquid repellent portion 301c is also formed on the electromechanical conversion film 500b.
(S82) Next, the electrode material-containing solution 401c, which is functional ink, is selected from the IJ head 208 as the lyophilic part 302c (electromechanical conversion film 500b) using the liquid discharge coating mechanism in the thin film manufacturing apparatus of the present invention. (Fig. 17 (C2)). Here, the electrode material-containing solution 401c and the electrode material-containing solution 401a described above are the same material.
(S83) Next, energy (120 ° C. heating for drying and 250 ° C. heating for sintering) is added to the electrode material-containing solution 401c on the electromechanical conversion film 500b using the energy applying means 700. The upper electrode 500c is formed (FIG. 17 (C3)).
As described above, the processes of steps S81 to S83 are performed a plurality of times until the film of the upper electrode 500c has a desired film thickness. For example, the film thickness of the upper electrode 500c made of Pt is 0.5 μm, and the specific resistance is 5 × 10 ⁻⁶ Ω · cm.

  As described above, the lower electrode 500a and the electromechanical conversion film 500b are formed on the diaphragm 540 (adhesion layer 500d) by the steps S61 to S63, S71 to S73, and S81 to S83 using the thin film manufacturing method of the present invention. As a result, the electromechanical conversion element 501 including the upper electrode 500c can be accurately formed without causing a pattern defect, and the liquid discharge head 1 having stable discharge performance can be obtained.

Next, the configuration of the liquid discharge head according to the present invention will be described.
The liquid discharge head according to the present invention includes the electromechanical transducer 501 according to the present invention described above.

  FIG. 18 is an exploded perspective view showing a part of the liquid discharge head according to the present invention in cross section. A schematic cross-sectional configuration in the width direction of the liquid discharge head according to the present invention is as shown in FIG. 2 shows a single pressure chamber 506, the liquid discharge head is partitioned by the partition walls of the pressure chamber substrate 503 as shown in FIG. 19, so that the pressure chambers 506 are arranged in the left-right direction. Take.

  The liquid discharge head 1 includes a nozzle plate 504 having a nozzle 505 that is a droplet discharge hole for discharging ink, a plurality of pressure chambers 506, a vibration plate 540, and an electromechanical conversion element 501. A laminated structure in which three substrates, a pressure chamber substrate 503 having a flexible printed circuit board (FPC) 573 on which a driving circuit for driving is mounted, and a holding substrate 572 provided with an electromechanical transducer protection space 574 are stacked. It has become.

  In the pressure chamber substrate 503, a vibration plate 540 is formed of a laminated film on a Si substrate. The diaphragm 540 in this embodiment is obtained by depositing a silicon oxide film, a silicon active film, and a silicon oxide film on one side of a Si substrate using an SOI substrate. Further, a plurality of electromechanical transducers 501 are provided thereon, a pressure chamber 506 corresponding to each of the plurality of electromechanical transducers 501, and a fluid resistance unit (supply) for supplying liquid to the pressure chamber 506 Path) 532 and a common liquid chamber 533 are formed.

  The nozzle plate 504 is a nickel substrate formed to a thickness of 20 μm using, for example, a nickel high-speed electroforming method, and nozzles 505 provided to communicate with the pressure chambers 506 in correspondence with the pressure chambers 506 respectively. Have.

  The holding substrate 572 forms an electromechanical conversion element protection space 574 for preventing the electromechanical conversion element 501 from being protected and displaced, and an ink supply portion 533a for supplying ink as droplets to the common liquid chamber 533 from the outside. Substrate.

  As shown in FIG. 2, the liquid ejection head 1 includes a diaphragm 540 formed on a Si substrate, and a lower electrode 500a, an electromechanical conversion film 500b, and an upper electrode 500c stacked in this order on the diaphragm 540. The electromechanical conversion element 501 is provided, and a droplet is ejected from a nozzle 505 which is a liquid droplet ejection hole provided in the substrate surface portion of the nozzle plate 504 using a piezoelectric actuator including the electromechanical conversion element 501 and the vibration plate 540. It is what is discharged.

  Here, the nozzle plate 504 is configured by forming the nozzle 505 on a metal or an inorganic material such as SUS, Ni, or Si, or a resin material such as PI (polyimide). The pressure chamber substrate 503 is joined by the joining means.

  The pressure chamber substrate 503 is made of a Si substrate that is an easily processable material having the required mechanical strength and chemical resistance. In the case of using a Si substrate, a so-called semiconductor process can be used for processing by photolithography and etching, so that the liquid chamber arrangement can be highly integrated.

The diaphragm 540 needs to be made of a material that is elastically deformed within a range of displacement by the electromechanical transducer 501. As a material, a thin film of an inorganic material or an organic material is used, but it is preferable to use an inorganic material in consideration of adhesion with an electrode. As the inorganic material, any material such as a metal, an alloy, a semiconductor, or a dielectric can be used. Material can be selected as the best from the machining process, in the case of using Si in the pressure chamber substrate _{503, SiO 2, Si 3 N} 4, it is preferable to use a polycrystalline Si. In general, a Si thermal oxide film is often used. Moreover, by using these laminated films, it is possible to adopt a structure that cancels out residual stress. In addition, dielectric materials such as SiO ₂ and Si ₃ N ₄ are chemically stable and can prevent the vibration plate 540 from being broken due to corrosion caused by ink even when it comes into contact with the ejected ink. Furthermore, since these thin film deposition techniques are established in the semiconductor process, a stable diaphragm 540 can be obtained.

The thickness of the diaphragm 540 is preferably optimized from the rigidity of the material and the formation method, but when the above-described inorganic material (SiO ₂ , Si ₃ N ₄ ) is used, the thickness may be in the range of 1 to 5 μm. preferable. For example, first, an insulator to be the vibration plate 540 is formed on the Si substrate, and then a cavity to be a liquid chamber such as the pressure chamber 506 is formed by etching and then polished to a necessary thickness. In the etching, the insulating layer becomes a stop layer.

  The lower electrode 500a is a common electrode in the plurality of electromechanical transducers 501 and is connected to a common electrode wiring (not shown).

The lower electrode 500a is, for example, a (111) crystal-oriented thin film for controlling the orientation of the electromechanical conversion film 500b, and any conductive material can be used as a material for the lower electrode 500a. it can. As the conductive material, a metal, an alloy, a conductive compound, or the like can be used, but it is preferable to use an electrode material having high heat resistance by a method for forming the electromechanical conversion film 500b. Usually, the electromechanical conversion film 500b needs to be crystallized after film formation. When a general piezoelectric material lead zirconate titanate (PZT) is used, the crystallization process temperature is 500 ° C. to 800 ° C. It is common to become. Therefore, the material used for the electromechanical conversion element needs to have a high melting point and a highly stable material that does not form a compound with the adjacent diaphragm 540 or the piezoelectric material at a high temperature. As these materials, it is preferable to use a metal having low reactivity and high melting point such as Pt, Ir, Pd, Au, or an alloy thereof. Of these, lead zirconate titanate (PZT), which is a typical material constituting the electromechanical conversion film 500b, and Pt, which is a noble metal that has a lattice constant close to and is not easily oxidized, are most frequently used. Further, a compound conductive material having high temperature stability may be used. Any compound oxide can be used as these compound conductive materials. For _{example, IrO 2, RuO 2, SrO} , SrRuO 3, CaRuO 3, BaRuO 3, and the like _{(Sr x Ca 1-x)} a platinum group such as RuO ₃ metal-containing conductive oxide or LaNiO _3.

  The film thickness of the lower electrode 500a can be arbitrarily set depending on the electric resistance required for the electrode, but is preferably in the range of 100 nm to 1 μm.

As a material constituting the electromechanical conversion film 500b, a composite oxide having a perovskite crystal structure and represented by a chemical formula ABO ₃ can be used. Here, the elements at the A site are Pb, Ba, Nb, La, Li, Sr, Bi, Na, K, and the like. In addition, elements of the B site include Cd, Fe, Ti, Ta, Mg, Mo, Ni, Nb, Zr, Zn, W, and Yb. Among these, lead (Pb) is often used for A, and lead zirconate titanate (PZT) in which a mixture of zirconium (Zr) and titanium (Ti) is applied to B is often used. Since this material is excellent in temperature characteristics and piezoelectric characteristics, a highly reliable and highly stable electromechanical transducer element 501 can be obtained. In addition to PZT, barium titanate (BaTiO ₃ ) can be used as an environmental advantage in that lead is not used, the amount of displacement is large, the raw material is inexpensive, and there are many records of use.

  The film thickness of the electromechanical conversion film 500b can be set to an optimum value according to desired characteristics, but is preferably in the range of 0.1 to 5 μm.

  Furthermore, the electromechanical conversion film 500b needs to be formed individually for each pressure chamber 506, and the piezoelectric body width needs to be narrower than the individual liquid chamber width. Accordingly, a portion where the highly mechanical electromechanical conversion film 500b is not formed is formed on the pressure chamber 506, and an area for vibration displacement can be secured. Therefore, the above-described patterning of the electromechanical conversion film 500b (separation for each pressure chamber 506) is important.

  The upper electrode 500c is formed above the electromechanical conversion film 500b formed for each pressure chamber 506. The upper electrode 500c is an individual electrode provided for each of the plurality of electromechanical conversion elements 501, and is connected to individual electrode wiring (not shown). The individual electrode wiring is individually connected to the upper electrode 500c of each of the plurality of electromechanical conversion elements 501 and a drive signal is input to each electromechanical conversion element 501 through a separate electrode wiring from a drive signal input unit (not shown). Is done.

  As a material constituting the upper electrode 500c, any of the same material group as that of the lower electrode 500a can be used. That is, any conductive material can be used as the material of the upper electrode 500c. Examples of the conductive material include metals, alloys, conductive compounds, and the like, but it is preferable to use metals or alloys. At that time, it is necessary to select a material in consideration of adhesion to the electromechanical conversion film 500b. In addition, a material that reacts and interdiffuses with a material such as Pb contained in the piezoelectric material to form an alloy is not preferable. Further, a material that reacts with oxygen or the like contained in the piezoelectric material is not preferable. Therefore, it is preferable to use a stable material with low reactivity. Examples of these materials include Au, Pt, Ir, Pd, alloys thereof, and solid solutions.

  The width of the upper electrode 500c is preferably narrower than the width of the electromechanical conversion film 500b. When the upper electrode 500c is formed up to the end of the electromechanical conversion film 500b, electric field concentration at the end of the electromechanical conversion film 500b may lead to a discharge phenomenon between the lower electrode 500a and the upper electrode 500c. There is a possibility that the reliability of 501 may be significantly impaired.

[Inkjet printers, etc.]
By the way, a liquid tank that supplies a liquid such as ink to the liquid discharge head of the present invention may be integrated into a liquid cartridge.
FIG. 20 is an external view of an ink cartridge that is the liquid cartridge. The ink cartridge 80 is obtained by integrating the liquid discharge head 1 according to the present invention having the nozzle 505 and the like, and an ink tank 82 that is a liquid tank for supplying ink to the liquid discharge head 1. . Thus, when the ink tank 82 is the integrated liquid discharge head 1, the yield and reliability of the ink cartridge 80 can be improved by increasing the accuracy, density, and reliability of the actuator unit. Thus, the cost of the ink cartridge 80 can be reduced.

Next, the ink jet printer according to the present invention will be described.
An ink jet printer according to the present invention is an image forming apparatus that forms an image by ejecting liquid droplets, and includes the above-described liquid discharge head of the present invention or the liquid cartridge that is the integrated liquid discharge head unit of FIG. It is characterized by being.
Here, an ink jet printer which is an image forming apparatus equipped with the liquid discharge head 1 of the present invention will be described as an example with reference to FIGS. FIG. 21 is a perspective explanatory view of the recording apparatus, and FIG. 22 is a side explanatory view of a mechanism portion of the recording apparatus.

  The ink jet printer includes a carriage 98 that can move in the main scanning direction inside the main body of the recording apparatus, a liquid discharge head (recording head) 1 of the present invention mounted on the carriage 98, and an ink cartridge 99 that supplies ink to the liquid discharge head 1. A sheet feeding cassette (or a sheet feeding tray) 93 on which a large number of sheets 92 can be stacked from the front side is detachable in the lower part of the apparatus main body. Can be installed. Further, it has a manual feed tray 94 that is opened to manually feed the paper 92, takes in the paper 92 fed from the paper feed cassette 93 or the manual feed tray 94, and records a required image by the printing mechanism 91. Thereafter, the paper is discharged to a paper discharge tray 95 mounted on the rear side.

  The printing mechanism 91 holds a main guide rod 96, a sub guide rod 97, and a carriage 98, which are guide members horizontally mounted on left and right side plates (not shown), so as to be slidable in the main scanning direction. A liquid discharge head 1 that discharges ink droplets of each color (Y), cyan (C), magenta (M), and black (Bk) is arranged in a direction intersecting the main scanning direction with a plurality of ink discharge ports (nozzles). The ink droplet ejection direction is directed downward. In addition, each ink cartridge 99 for supplying ink of each color to the liquid ejection head 1 is replaceably mounted on the carriage 98.

  The ink cartridge 99 is provided with an air outlet communicating with the atmosphere at the upper side, and a supply port for supplying ink to the liquid ejection head 1 at the lower side, and has a porous body filled with ink inside. The ink supplied to the liquid ejection head 1 is maintained at a slight negative pressure by the capillary force of the material. Further, although the liquid discharge head 1 of each color is used as the liquid discharge head 1, one liquid discharge head having nozzles for discharging ink droplets of each color may be used.

  Here, the carriage 98 is slidably fitted to the main guide rod 96 on the rear side (sheet conveyance downstream side), and the front side (sheet conveyance upstream side) is slidably mounted on the sub guide rod 97. Yes. In order to move and scan the carriage 98 in the main scanning direction, a timing belt 104 is stretched between the driving pulley 102 and the driven pulley 103 that are rotationally driven by the main scanning motor 101, and the timing belt 104 is moved to the carriage 98. The carriage 98 is reciprocally driven by forward and reverse rotations of the main scanning motor 101.

  On the other hand, in order to convey the paper 92 set in the paper feed cassette 93 downward to the liquid ejection head 1, the paper feed roller 105 and the friction pad 106 for separating and feeding the paper 92 from the paper feed cassette 93, and the paper 92 A guide member 107 for guiding, a conveying roller 108 for conveying the fed paper 92 in a reversed manner, a conveying roller 109 pressed against the peripheral surface of the conveying roller 108, and a feeding angle of the paper 92 from the conveying roller 108 are defined. And a leading end roller 110. The conveyance roller 108 is rotationally driven by a sub-scanning motor through a gear train.

  A printing receiving member 111 that is a sheet guide member is provided to guide the sheet 92 fed from the conveying roller 108 below the liquid discharge head 1 corresponding to the range of movement of the carriage 98 in the main scanning direction. . A conveyance roller 112 and a spur 113 that are rotationally driven to send the paper 92 in the paper discharge direction are provided on the downstream side of the printing receiving member 111 in the paper conveyance direction, and the paper 92 is further discharged to the paper discharge tray 95. A roller 114, a spur 115, and guide members 116 and 117 that form a paper discharge path are disposed.

  During recording by the ink jet printer 90, the liquid ejection head 1 is driven according to the image signal while moving the carriage 98, thereby ejecting ink onto the stopped sheet 92 to record one line, and then After the sheet 92 is conveyed by a predetermined amount, the next line is recorded. Upon receiving a recording end signal or a signal that the trailing edge of the paper 92 reaches the recording area, the recording operation is terminated and the paper 92 is discharged.

  Further, a recovery device 118 for recovering the ejection failure of the liquid ejection head 1 is disposed at a position outside the recording area on the right end side in the movement direction of the carriage 98. The recovery device 118 includes a cap unit, a suction unit, and a cleaning unit. The carriage 98 is moved to the recovery device 118 side during printing standby, and the liquid discharge head 1 is capped by the cap means to keep the discharge port portion in a wet state, thereby preventing discharge failure due to ink drying. Further, by ejecting ink that is not related to recording during recording or the like, the ink viscosity of all the ejection ports is made constant and a stable ejection state is maintained.

  Further, when a discharge failure occurs, the discharge outlet (nozzle) of the liquid discharge head 1 is sealed with the cap means, and bubbles with the ink are sucked out from the discharge port by the suction means through the tube to the discharge port surface. Adhering ink, dust, etc. are 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.

  As described above, since the ink jet printer 90 is equipped with the liquid discharge head 1 of the present invention, there is no ink droplet discharge failure due to a pattern failure of the electromechanical conversion film, stable ink discharge characteristics are obtained, and image quality is improved. Will improve. Although the case where the liquid discharge head 1 is used in the inkjet printer 90 has been described here, the liquid discharge head 1 may be applied to a device that discharges droplets other than ink, for example, a liquid resist for patterning.

  Although the present invention has been described with the embodiments shown in the drawings, the present invention is not limited to the embodiments shown in the drawings, and other embodiments, additions, modifications, deletions, etc. Can be changed within the range that can be conceived, and any embodiment is included in the scope of the present invention as long as the effects and advantages of the present invention are exhibited.

DESCRIPTION OF SYMBOLS 1 Liquid discharge head 80,99 Ink cartridge 82 Ink tank 90 Inkjet printer 91 Printing mechanism part 92 Paper 93 Paper feed cassette 94 Manual feed tray 95 Paper discharge tray 96 Main guide rod 97 Subordinate guide rod 98 Carriage 101 Main scanning motor 102 Drive pulley 103 Drive pulley 104 Timing belt 105 Feed roller 106 Friction pad 107, 116, 117 Guide member 108 Transport roller 109, 112 Transport roller 110 Tip roller 111 Printing receiving member 113, 115 Spur 114 Paper discharge roller 118 Recovery device 200 Mounting base 201 Y Axis driving means 202 Substrate 203 Stage 204 X-axis support member 205 X-axis driving means 206 Head base 208 IJ head 209 Functional ink 210 Ink Supply pipe 211 Z-axis driving means 212 Wiping blade 213 Support member 214 Nozzle contact part 214a, 214a 'groove part 215 Solvent supply tube 300 SAM film 300m Photomask 300p Photoresist 300r Mask layer 301, 301a, 301b, 301c Liquid repellent part 302 , 302a, 302b, 302c, lyophilic part 401, coating 401a, 401c, electrode material-containing solution 401b, PZT precursor solution 500, functional thin film 500a, lower electrode 500b, electromechanical conversion film 500c, upper electrode 500d, adhesion layer 501, electromechanical conversion element 503, pressure chamber Substrate 503a Partition 504 Nozzle plate (head substrate surface)
505 Nozzle 506 Pressure chamber 532 Fluid resistance portion 533 Common liquid chamber 533a Ink supply portion 540 Vibration plate 572 Holding substrate 573 Flexible printed circuit board (FPC)
574 Electromechanical transducer protection space 700 Energy applying means

JP2011-000714A JP 2005-72473 A JP 2009-28947 A JP-A-11-286116 JP 2002-187286 A JP 2010-240543 A

A. Kumar and G. M. Whitesides, Appl. Phys. Lett., 63, 2002 (1993).

Claims (8)

A stage for holding the substrate; and a liquid discharge head that is disposed opposite to the stage and discharges functional ink from the nozzles by an ink jet method to apply the functional ink onto the substrate. The stage and / or the liquid discharge head A liquid discharge application mechanism that discharges functional ink onto the substrate and applies it in an arbitrary pattern;
A heating mechanism unit that heats and crystallizes the functional ink on the substrate to form a functional thin film,
The stage in the liquid discharge application mechanism unit has a wiping blade that rubs against the nozzle on a scanning path when the functional ink of the liquid discharge head is applied.
The wiping blade is disposed on both end sides in the scanning direction in the scanning path of the liquid ejection head on the stage,
A thin-film manufacturing apparatus, wherein the blade is a flat blade having at least the same length as the width in the direction orthogonal to the scanning direction of the substrate.   The thin film manufacturing apparatus according to claim 1, wherein a portion of the wiping blade that slides on the nozzle has flexibility.   The thin film manufacturing apparatus according to claim 1, wherein the wiping blade includes a solvent supply unit that supplies a solvent of the functional ink to a portion that slides on the nozzle. A thin film manufacturing method for forming a functional thin film on a substrate using the thin film manufacturing apparatus according to claim 1,
An inkjet coating process in which functional ink is ejected from the liquid ejection head and coated in an arbitrary pattern on the substrate while relatively scanning the stage and / or the liquid ejection head;
Heating the functional ink on the substrate to crystallize it into a functional thin film,
The inkjet coating step includes a wiping process in which the wiping blade rubs against the nozzle at the start of scanning and / or at the end of scanning for each scanning of the stage and / or liquid discharge head. .   5. The thin film manufacturing method according to claim 4, wherein the ink jet coating step is to coat the functional ink on a substrate on which a pattern including a liquid repellent portion and a lyophilic portion is formed. A manufacturing method of an electro-mechanical transducer having electrical transducer layer,
The electromechanical conversion film is manufactured by the thin film manufacturing method according to claim 4 or 5,
The functional ink is a ferroelectric precursor ink;
A second electrode disposed opposite to the first electrode on the first electrode as the substrate; and the electromechanical conversion film sandwiched between the first electrode and the second electrode; A method for manufacturing an electromechanical transducer, characterized in that Method for manufacturing electromechanical transducer according to claim 6, wherein the second electrode is manufactured by a thin film manufacturing method according to claim 4 or 5. A method of manufacturing a liquid discharge head which Ru provided with electrical transducer,
A method for manufacturing a liquid discharge head , wherein the electromechanical conversion element is manufactured by the method for manufacturing an electromechanical conversion element according to claim 6 .

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