JP5909933B2 - Oxide conductive thin film processing method, electronic device manufacturing method, and droplet discharge head manufacturing method - Google Patents

Description

  The present invention relates to a method for processing an oxide conductive thin film, an electronic device manufactured using the processing method, a droplet discharge head, and a droplet discharge apparatus, and more particularly to a piezoelectric actuator obtained by using this processing method. It relates to electronic devices.

By using PbTiO ₃ (PZT) for the piezoelectric film and inserting SrRuO ₃ (SRO) at the interface with the lower Pt electrode, the (111) orientation of the PZT film and the stabilization of the interface can be realized. It is well known to improve the fatigue resistance of manufactured electronic devices. (For example, refer to Patent Document 1.) This is because the SRO film has the same perovskite crystal structure as PZT, and the presence of the SRO film is the diffusion of mutual components at the interface between the PZT film and the Pt film. It is said to suppress formation.

Here, the ideal SRO is Sr: Ru: O = 1: 1: 3 conductive oxide.
However, Non-Patent Document 1 shows that the surface state of SRO varies greatly depending on heat treatment, dry etching conditions, and the like. Usually, the surface of the processed SRO becomes Sr rich.
The change in the surface composition of the SRO film affects the piezoelectric film formed on the SRO film, and particularly has a large effect on a thin piezoelectric film.
Further, when SRO is provided as an electrode, when Sr / Ru> 1, the composition approaches SrO, so that the electric conductivity is not exhibited. In the worst case, a high-resistance perovskite oxide film that cannot be used as an electrode is formed. Will be formed.

The present invention has been made in view of the above problems in the prior art, and an object thereof is to provide a method for treating an oxide conductive thin film having a desired surface composition.
It is another object of the present invention to provide an electronic device, a droplet discharge head, and a droplet discharge apparatus manufactured using the oxide conductive thin film processing method.

In order to solve the above-described problems, a method for treating an oxide conductive thin film according to the present invention is a treatment of a SrRuO ₃ type oxide conductive thin film with a mixed liquid of ethanol and pure water, and a volume ratio of ethanol in the mixed liquid. Is 25% or less, and the atomic ratio Sr / Ru of the surface of the SrRuO ₃ type oxide conductive thin film is made close to a stoichiometric ratio of 1/1 .
In order to solve the above problems, an electronic device manufacturing method according to the present invention includes (a) a step of forming a SrRuO ₃ type oxide conductive thin film, and (b) a step of forming the SrRuO ₃ type oxide conductive thin film. Treated with a mixed solution of ethanol and pure water, the volume ratio of ethanol in the mixed solution is 25% or less, and the atomic ratio Sr / Ru of the surface of the SrRuO ₃ type oxide conductive thin film in terms of the stoichiometric ratio . a step closer to a 1/1, laminating an oxide piezoelectric layer on the SrRuO ₃ type conductive oxide thin film as part of (c) the lower electrode or the lower electrode, (d) said oxide piezoelectric And a step of laminating the upper electrode on the body layer.

  According to the present invention, a method for treating an oxide conductive thin film having a desired surface composition is provided, and a high-performance electronic device, a droplet discharge head, and a high-performance electronic device manufactured using the method for treating an oxide conductive thin film A droplet discharge device can be provided.

It is a figure which shows the flow which produces the sample of a SRO film | membrane. (A) It is a graph which shows the relationship between atomic ratio of Sr / Ru, and processing time. (B) It is a graph which shows the relationship between the atomic ratio of Sr / Ru, and the volume ratio of ethanol of a liquid mixture. It is a figure which shows the one part flow in one Embodiment of the manufacturing method of the electronic device which concerns on this invention. (A) It is the schematic which shows the structure in one Embodiment of the droplet discharge head concerning this invention. (B) It is the schematic which shows the structure in other embodiment of the droplet discharge head which concerns on this invention. 1 is a perspective view showing a configuration of a droplet discharge device equipped with a droplet discharge head according to the present invention. 1 is a side view showing a configuration of a droplet discharge device equipped with a droplet discharge head according to the present invention.

In the method for treating an oxide conductive thin film according to the present invention, the ABO ₃ type oxide conductive thin film represented by the general formula ABO ₃ is treated with a liquid containing at least water, and the surface of the ABO ₃ type oxide conductive thin film is treated. The atomic ratio A / B is close to the stoichiometric ratio.

Next, a method for processing an oxide conductive thin film according to the present invention, an electronic device manufactured using the processing method, a droplet discharge head, and a droplet discharge apparatus will be described in detail.
Although the embodiments described below are preferred embodiments of the present invention, various technically preferable limitations are attached thereto, but the scope of the present invention is intended to limit the present invention in the following description. Unless otherwise described, the present invention is not limited to these embodiments.

<ABO _3- type oxide conductive thin film>
The method for treating an oxide conductive thin film according to the present invention uses an ABO ₃ type oxide conductive thin film as an object to be treated.

The ABO ₃ type oxide conductive thin film is a composite oxide represented by the general formula ABO ₃ , wherein A contains one or more selected from Sr, Ba, Ca and La, and B is selected from Ru, Co and Ni. It is preferable that each contains at least one of the above. Further, it is particularly preferable that A includes Sr and B includes Ru.

The ABO ₃ type oxide conductive thin film may be formed by a well-known and usual method, but any one of CVD (Chemical Vapor Deposition) method, PVD (Physical Vapor Deposition) method, and CSD (Chemical Solution Deposition) method. It is preferable to form by the method chosen from these.

<Treatment with liquid>
In the method for treating an oxide conductive thin film according to the present invention, the ABO ₃ type oxide conductive thin film is treated with a liquid. This liquid contains at least water, and is preferably a mixed liquid of pure water and an organic solvent, or pure water.
The organic solvent preferably contains at least one alcohol. Preferable specific examples of alcohols include alcohols having 1 to 6 carbon atoms, and ethanol is particularly preferable.

  When a mixed liquid of pure water and an organic solvent is used, the volume ratio of pure water is preferably 50% or more, more preferably 75% or more.

Further, by treating the ABO ₃ type oxide conductive thin film with the liquid containing water as described above, the desired atomic ratio A / B of the surface of the ABO ₃ type oxide conductive thin film is brought close to the stoichiometric ratio. An ABO ₃ type oxide conductive thin film having characteristics can be obtained.
Here, the stoichiometric ratio for the atomic ratio A / B is 1/1.
Moreover, the atomic ratio A / B of the surface of the ABO ₃ type oxide conductive thin film after being treated with the liquid is preferably 0.5 or more, more preferably closer to 1.

  The treatment time with the liquid is preferably 1 second or longer, more preferably 5 seconds or longer. If it is less than 1 second, the treatment becomes insufficient, and A / B becomes larger than the stoichiometric ratio of 1, which is not preferable because desired characteristics cannot be obtained.

<Electronic device>
The electronic device according to the present invention includes an ABO ₃ type oxide conductive thin film 4 as a lower electrode or a part of the lower electrode, and an oxide piezoelectric layer 5 laminated on the ABO ₃ type oxide conductive thin film 4. And the upper electrode 6 laminated on the oxide piezoelectric layer 5, and the ABO ₃ type oxide conductive thin film 4 is processed by the above oxide conductive thin film processing method. It is characterized by being.

・ Lower electrode (4)
In the electronic device according to the present invention, the ABO ₃ type oxide conductive thin film 4 is used as a lower electrode or a part of the lower electrode.

As a metal material constituting the portion other than the ABO ₃ type oxide conductive thin film 4 in the lower electrode, platinum having high heat resistance and low reactivity has been conventionally used. In some cases, it cannot be said that the lead used has a sufficient barrier property. Therefore, in addition to platinum, a laminated body of a platinum group element such as iridium or platinum-rhodium, an alloy film thereof, and the ABO ₃ type oxide conductive thin film can be used as a lower electrode.
For example, the lower electrode can be formed by first laminating a metal material and then laminating an ABO ₃ type oxide conductive thin film. In addition, when using platinum, since adhesion to the substrate (especially SiO ₂ ) as a base is poor, Ti, TiO ₂ , Ta, Ta ₂ O ₅ , Ta ₃ N _5, etc. are laminated first. Is preferred.

  The thickness of the lower electrode is preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm.

・ Oxide piezoelectric layer (electromechanical conversion film) 5
The oxide piezoelectric layer 5 is not limited, but a PZT (lead zirconate titanate) film is preferably used.
PZT is a solid solution of lead zirconate (PbZrO ₃ ) and titanic acid (PbTiO ₃ ), and the characteristics differ depending on the ratio. In general, the composition exhibiting excellent piezoelectric characteristics has a ratio of PbZrO ₃ and PbTiO ₃ of 53:47. When expressed by a chemical formula, it is represented by Pb (Zr0.53, Ti0.47) O ₃ , , PZT (53/47).
Examples of complex oxides other than PZT include barium titanate. In this case, it is also possible to prepare a barium titanate precursor solution by using a barium alkoxide compound and a titanium alkoxide compound as starting materials and dissolving them in a common solvent.

These materials correspond to composite oxides described by the general formula CDO ₃ (C = Pb, Ba, Sr, D = Ti, Zr, Sn, Ni, Zn, Mg, Nb as main components).
Specific examples thereof include (Pb _1-x Ba _x ) (Zr, Ti) O ₃ , (Pb _1-x Sr _x ) (Zr, Ti) O _{3, and the} like. Substituted with part Ba or Sr. Such substitution is possible with a divalent element, and the effect thereof has an effect of reducing characteristic deterioration due to evaporation of lead during heat treatment.

  As a method for producing the oxide piezoelectric layer 5, it can be produced by a spin coater using a sputtering method or a Sol-gel method (sol-gel process). In that case, since patterning is required, a desired pattern is obtained by photolithography etching or the like.

  When a PZT film is produced as the oxide piezoelectric layer 5 by the Sol-gel method, a compound such as lead acetate, zirconium alkoxide, or titanium alkoxide is used as a starting material, and these are uniformly dissolved in methoxyethanol, which is a common solvent. A PTZ precursor solution can be prepared. Since the metal alkoxide compound is easily hydrolyzed by moisture in the atmosphere, an appropriate amount of a stabilizer such as acetylacetone, acetic acid or diethanolamine may be added to the precursor solution as a stabilizer.

When a PZT film is formed on the entire surface of the underlying substrate, a PTZ precursor solution is used to form a coating film by a solution coating method such as spin coating, and each heat treatment of solvent drying, thermal decomposition, and crystallization is performed. Can be achieved. Since the transformation from the coating film to the crystallized film involves volume shrinkage, it is necessary to adjust the concentration of the precursor solution so that a film thickness of 100 nm or less can be obtained in one step in order to obtain a crack-free film.
In addition, a PZT film patterned by an inkjet method can be produced.

  The film thickness of the oxide piezoelectric layer 5 is preferably 0.5 μm to 5 μm, more preferably 1 μm to 2 μm. If the film thickness is less than 0.5 μm, sufficient displacement cannot be generated, and if the film thickness exceeds 5 μm, many layers are required to obtain a desired film thickness, which increases the number of processes. There is a problem that the process time becomes long.

-Upper electrode 6
Similar to the lower electrode, in the electronic device according to the present invention, the ABO ₃ type oxide conductive thin film is used as the upper electrode.

Further, platinum having high heat resistance and low reactivity has been conventionally used as a metal material, but it may not be said that it has sufficient barrier properties against lead. Therefore, in the same manner as the above lower electrode, besides platinum, platinum group elements such as iridium and platinum-rhodium, alloy films thereof, Ag alloys, Cu, Al, Au, and the above ABO ₃ type oxide conductive thin film The laminate can be used as the upper electrode.

  The film thickness of the upper electrode 6 is preferably 0.05 to 1 μm, and more preferably 0.1 to 0.5 μm.

  As a method for producing the upper electrode 6, it can be produced by a spin coater using a sputtering method or a Sol-gel method. In that case, since patterning is required, a desired pattern is obtained by a photolithography etching method or the like.

  In addition, a patterned film can also be obtained by using a process of partially modifying the surface of the underlying surface by an inkjet method.

<Method for manufacturing electronic device>
An electronic device manufacturing method according to the present invention includes the following steps (a) to (d).
(A) Step of forming an ABO ₃ type oxide conductive thin film 4 represented by the general formula ABO ₃ (b) The ABO ₃ type oxide conductive thin film 4 is treated with a liquid containing at least water, and the ABO ₃ type Step (c) for bringing the atomic ratio A / B of the surface of the oxide conductive thin film 4 close to the stoichiometric ratio (c) The ABO ₃ type oxide conductive thin film 4 as the lower electrode or a part of the lower electrode has an oxide piezoelectric body Step (d) of laminating layer 5 Step of laminating upper electrode 6 on oxide piezoelectric layer 5

<Droplet ejection head, droplet ejection device>
The droplet discharge head and the droplet discharge apparatus according to the present invention include the above-described electronic device, and other known configurations can be employed as they are.

  Next, the present invention will be described in more detail with specific examples with reference to the drawings.

(Example 1)
FIG. 1 shows a process for producing a sample.
As shown in FIG. 1A, a thermal oxide film of about 1 μm is formed on a Si (001) substrate 1, and a Ti adhesion layer (50 nm) 2, a Pt film (200 nm) 3 and SrRuO ₃ are formed thereon by sputtering. The (SRO) film (60 nm) 4 is deposited in order.
Next, a pattern as shown in FIG. 1B is formed by using photolithography and dry etching, and then the resist 8 is removed by ashing (acid treatment), and a sample as shown in FIG. 1C. Create

For the sample thus obtained, the surface of the SRO is 5 s, 10 s, 15 s, 30 s, 60 s with pure water, and 5 s, 15 s with a mixture of pure water and ethanol (volume ratio 3: 1). Processed. The treated sample was blown with N ₂ and left to dry for more than 5 hours.
Thereafter, the atomic ratio Sr / Ru on the surface of the SRO pattern was analyzed by XPS (X-ray photoelectron spectroscopy).

  FIG. 2 shows changes in the atomic ratio Sr / Ru on the surface of the sample (SRO pattern) shown in FIG. Curve (A) in FIG. 2 (a) is the result of treatment with pure water, and curve (B) is the result of treatment with a mixture of pure water and ethanol. The dot lines in FIG. 2A indicate the atomic ratio Sr / Ru ratio of the sample surface in FIG. FIG. 2B shows the change in the atomic ratio Sr / Ru on the surface of the SRO pattern treated with 5 s from the volume ratio of ethanol with respect to the mixture of pure water and ethanol.

The atomic ratio Sr / Ru on the surface of the SRO pattern in FIG. 1 (c) before treatment with the liquid was higher than that on the sample surface in FIG. 1 (a). It is conceivable that RuO dissipation from the SRO film occurs during the process from FIG. 1A to FIG.
After treatment with pure water and a mixed solution of pure water and ethanol, the atomic ratio Sr / Ru on the SRO surface decreased.

When processing with pure water, as shown in FIG. 2A, the processing time for achieving the SRO surface with Sr / Ru = 1 is estimated to be only 2 s, and the initial SRO formed by vapor deposition by sputtering is used. The processing time to achieve an SRO surface like a membrane (sample in FIG. 1 (a)) is on the order of 1 s.
When processing for 10 s or longer, the atomic ratio Sr / Ru on the SRO surface gradually decreases with respect to the processing time, but stops at about Sr / Ru≈0.5.
On the other hand, as shown in FIG. 2 (b), when processing with a mixed solution of pure water and ethanol, the ratio of Sr / Ru is gradually reduced with the transition of the processing time. Processing at 15 s achieves the desired SRO surface composition with Sr / Ru≈1.

(Example 2)
A sample on which a pattern as shown in FIG. 1C is formed is treated with a mixed solution of pure water and ethanol (volume ratio 3: 1) for 15 seconds. After drying, the surface of the Pt film was cleaned by heating at 500 ° C. for 1 minute. Next, as shown in FIG. 3A, a self-assembled film (SAM) 8 was formed on the surface of the Pt film with 1H, 1H, 2H, 2H-perfluorodecanethiol (PFDT).

Next, a PZT (lead zirconate titanate) film 5 is formed by an inkjet method as an electro-mechanical conversion film (oxide piezoelectric layer).
In the synthesis of this PZT precursor coating solution, lead acetate trihydrate, isopropoxide titanium, and isopropoxide zirconium were used as starting materials. Crystal water of lead acetate was dissolved in methoxyethanol and then dehydrated.
Note that the lead amount is 10 mol% excess with respect to the stoichiometric composition. This is to prevent crystallinity deterioration due to so-called lead loss during heat treatment.

  Isopropoxide titanium and isopropoxide zirconium were dissolved in methoxyethanol, the alcohol exchange reaction and the esterification reaction were advanced, and the PZT precursor solution was synthesized by mixing with the methoxyethanol solution in which the lead acetate was dissolved. The concentration of the PZT precursor solution was 0.1 mol / l.

  The PZT precursor solution is applied by ejecting this liquid onto the SRO film patterned in the step of FIG. 3B by the inkjet coating apparatus and ejecting the droplet 5 'of the PZT precursor solution from the inkjet head 10. Due to the contact angle contrast, the precursor solution spreads only on the SRO pattern to form a PZT pattern 5 having a desired shape. The film thickness obtained by one film formation is preferably around 100 nm, and the precursor concentration (PZT concentration) is preferably optimized from the relationship between the film formation area and the amount of applied precursor. This was treated as 300 ° C. as the first heating (solvent drying), and then calcined at 500 ° C. to obtain FIG. 3C. The PZT film thickness at this time was 110 nm. The SAM film was decomposed and disappeared from the surface of the Pt film during the heat treatment.

  3A to 3C, the SAM treatment → PZT precursor solution coating → 300 ° C. drying → 500 ° C. pre-baking process is repeated three times to obtain a 330 nm PZT film 5, and then RTA ( A crystallization calcination treatment at 730 ° C. was performed by rapid thermal annealing. Defects such as cracks did not occur in the film. Further, three times of SAM film treatment → 300 ° C. drying → 500 ° C. temporary firing → 730 ° C. crystallization main firing treatment were performed. Defects such as cracks did not occur in the film. As a result of these treatments, the thickness of the PAT film 5 reached 1000 nm.

  Next, an SRO film (200 nm) 6 and a Pt film (100 nm) 7 as an upper electrode were sequentially formed by sputtering to form an electronic device structure as shown in FIG.

  The electronic device thus formed has a small leakage current and an improved fatigue resistance as an actuator.

(Example 3)
FIG. 4 shows a droplet discharge head including an electronic device as shown in FIG. FIG. 4A shows a configuration of a one-nozzle droplet discharge head. FIG. 4B shows a liquid discharge head having a plurality of nozzles in which a plurality of the structures shown in FIG.
First, each member constituting the droplet discharge head shown in FIG. 4 will be described.

<Vibration plate 1c>
The diaphragm 1c disposed on the silicon substrate may be several microns thick, and may be a silicon oxide film, a silicon nitride film, a silicon oxynitride film, or a film in which these films are stacked. Further, a ceramic film such as an aluminum oxide film or a zirconia film in consideration of the thermal expansion difference may be used.
These materials are insulators. Since the lower electrode is electrically connected as a common electrode for inputting a signal to the piezoelectric layer, the diaphragm 1c under the lower electrode is an insulator or a conductor if it is insulated.
As the silicon-based insulating film, a thermal oxide film or a CVD deposited film can be used, and the metal oxide film can be formed by a sputtering method.

<Adhesion layer 2>
When the lower electrode is disposed on these diaphragms 1c, the adhesion layer 2 for increasing the film adhesion is required. Titanium, tantalum, titanium oxide, tantalum oxide, titanium nitride, tantalum nitride, and laminated films thereof are effective as materials that can be used for the adhesion layer 2.

<Pressure chamber 1e, pressure chamber plate (Si substrate) 1b>
The pressure chamber 1e is formed by communicating with a nozzle 1d, and is divided by a pressure chamber plate 1b (which constitutes a side surface), a nozzle plate 1d (which constitutes a lower surface), and a vibration plate 1c (which constitutes an upper surface). And the piezoelectric material layer (electronic device) for pressurizing the liquid in the pressure chamber 1e via the diaphragm 1c is provided.
The pressure chamber plate 1b is composed of a silicon wafer or the like, and is formed by a conventional technique such as etching.

<Nozzle plate 1a, nozzle 1d>
The nozzles 1d are formed in two lines on the nozzle plate 1a in a straight line. The nozzle plate 1a is formed by, for example, Ni electroforming, but is not limited thereto.

<Production of droplet discharge head>
When producing the pressure chamber on the back surface of the electronic device structure as shown in FIG. 4A, the silicon single crystal substrate is processed using etching. In this case, the etching method is anisotropic. It is common to use reactive etching. Anisotropic etching utilizes the property that the etching rate differs with respect to the plane orientation of the crystal structure. For example, in anisotropic etching immersed in an alkaline solution such as KOH, the (111) plane has an etching rate of about 1/400 compared to the (100) plane.
Thereafter, a nozzle plate having nozzle holes is joined to form a droplet discharge head.
In FIG. 4, descriptions of the liquid supply means, the flow path, and the fluid resistance are omitted.

Example 4
Next, an example of an ink jet recording apparatus (droplet discharge apparatus) equipped with the ink jet head (droplet discharge head) according to the present invention will be described with reference to FIGS. 5 is an explanatory perspective view of the ink jet recording apparatus, and FIG. 6 is an explanatory side view of a mechanism portion of the ink jet recording apparatus.

  The ink jet recording apparatus includes a carriage movable in the main scanning direction inside the recording apparatus main body 81, a recording head 94 including an ink jet head mounted on the carriage according to the present invention, an ink cartridge 95 for supplying ink to the recording head, and the like. A sheet feeding cassette (or a sheet feeding tray) 84 on which a large number of sheets 83 can be stacked from the front side is detachable in the lower portion of the apparatus main body 81. The manual feed tray 85 for manually feeding the paper 83 can be opened, the paper 83 fed from the paper feed cassette 84 or the manual feed tray 85 is taken in, and the printing mechanism section After a required image is recorded by 82, it is discharged to a discharge tray 86 mounted on the rear side.

  The printing mechanism 82 holds a carriage 93 slidably in the main scanning direction by 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). (Y), cyan (C), magenta (M), black (Bk) A head 94 comprising an ink jet head according to the present invention for ejecting ink droplets of each color has a plurality of ink ejection openings (nozzles) as the main scanning direction. They are arranged in the intersecting direction and mounted with the ink droplet ejection direction facing downward. In addition, each ink cartridge 95 for supplying ink of each color to the head 94 is replaceably mounted on the carriage 93.

  The ink cartridge 95 has an air port that communicates with the atmosphere upward, a supply port that supplies ink to the inkjet head below, and a porous body filled with ink inside, and the capillary force of the porous body. Thus, the ink supplied to the inkjet head is maintained at a slight negative pressure. Further, although the heads 94 of the respective colors are used here as the recording heads, a single head having nozzles for ejecting ink droplets of the respective colors may be used.

  Here, the carriage 93 is slidably fitted to the main guide rod 91 on the rear side (downstream side in the paper conveyance direction), and is slidably mounted on the sub guide rod 92 on the front side (upstream side in the paper conveyance direction). doing. 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 a main scanning motor 97, and the timing belt 100 is moved to the carriage 93. The carriage 93 is driven to reciprocate by forward and reverse rotation of the main scanning motor 97.

  On the other hand, in order to convey the paper 83 set in the paper feed cassette 84 to the lower side of the head 94, the paper feed roller 101 and the friction pad 102 for separating and feeding the paper 83 from the paper feed cassette 84 and the paper 83 are guided. A guide member 103, a transport roller 104 that reverses and transports the fed paper 83, a transport roller 105 that is pressed against the peripheral surface of the transport roller 104, and a leading end that defines a feed angle of the paper 83 from the transport roller 104 A roller 106 is provided. The transport roller 104 is rotationally driven by a sub-scanning motor 107 through a gear train.

  A printing receiving member 109 is provided as a paper guide member that guides the paper 83 sent from the transport roller 104 below the recording head 94 in accordance with the movement range of the carriage 93 in the main scanning direction. A conveyance roller 111 and a spur 112 that are rotationally driven to send the paper 83 in the paper discharge direction are provided on the downstream side of the printing receiving member 109 in the paper conveyance direction, and the paper 83 is further delivered to the paper discharge tray 86. A roller 113 and a spur 114, and guide members 115 and 116 that form a paper discharge path are disposed.

  At the time of recording, the recording head 94 is driven according to the image signal while moving the carriage 93, thereby ejecting ink onto the stopped sheet 83 to record one line. Record the line. Upon receiving a recording end signal or a signal that the trailing edge of the paper 83 has reached the recording area, the recording operation is terminated and the paper 83 is discharged.

  Further, a recovery device 117 for recovering defective ejection of the head 94 is disposed 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 means, and the ejection port portion is kept in a wet state to prevent ejection failure due to ink drying. Further, by ejecting ink that is not related to recording during recording or the like, the ink viscosity of all the ejection ports is made constant and stable ejection performance is maintained.

  When a discharge failure occurs, the discharge port (nozzle) of the head 94 is sealed with a capping unit, and bubbles and the like are sucked out from the discharge port with the suction unit through the tube. Is removed by the cleaning means to recover the ejection failure. Further, the sucked ink is discharged to a waste ink reservoir (not shown) installed at the lower part of the main body and absorbed and held by an ink absorber inside the waste ink reservoir.

  Thus, since this inkjet recording device (droplet ejection device) is equipped with the inkjet head (droplet ejection head) produced in Example 3, there is no ink droplet ejection failure due to vibration plate drive failure, Stable ink droplet ejection characteristics can be obtained, and image quality can be improved.

  The present invention has been described above with reference to the embodiments. However, the present invention is not limited to these embodiments, and it goes without saying that the present invention can be applied to, for example, a semiconductor memory.

1: Si substrate 2: Adhesion layer 3: Pt layer (part of the lower electrode)
4: SRO layer (part of lower electrode)
5: PZT layer (piezoelectric layer)
5 ′: PZT droplet 6: SRO layer (part of the upper electrode)
7: Pt layer (part of upper electrode)
8: SAM film 8 ': resist 10: inkjet head 1a: nozzle plate 1b: pressure chamber 1c: vibration plate 1d: nozzle 1e: pressure chamber 81: apparatus body 82: printing mechanism 82
83: paper 84: paper feed cassette 85: manual feed tray 86: paper discharge tray 91: main guide rod 92: sub guide rod 93: carriage 94: head 95: ink cartridge 97: main scanning motor 98: drive pulley 99: driven pulley 100: Timing belt 101: Paper feed roller 102: Friction pad 103: Guide member 104: Conveying roller 105: Conveying roller 106: Front roller 107: Sub-scanning motor 109: Printing receiving member 111: Conveying roller 112: Spur 113: Ejection Paper roller 114: spur 115, 116: guide member 117: recovery device

JP 2011-091138 A

Surface layer of SrRuO3 epitaxial thin films under oxidizing and reducing conditions, Journal of Applied Physics, 101, 023701 (2007)

Claims (6)

A SrRuO ₃ type oxide conductive thin film is treated with a mixed liquid of ethanol and pure water,
The volume ratio of ethanol in the mixed solution is 25% or less,
A method for treating an oxide conductive thin film, characterized in that the atomic ratio Sr / Ru of the surface of the SrRuO ₃ type oxide conductive thin film is brought close to a stoichiometric ratio of 1/1 . 2. The oxide conductive thin film treatment according to claim 1, wherein an atomic ratio Sr / Ru of the surface of the SrRuO ₃ type oxide conductive thin film after being treated with the liquid is 0.5 or more. Method. 3. The method for treating an oxide conductive thin film according to claim 1, wherein the time for treating with the liquid is 1 second or longer. The SrRuO ₃ type oxide conductive thin film is formed by a method selected from any one of a CVD (Chemical Vapor Deposition) method, a PVD (Physical Vapor Deposition) method, and a CSD (Chemical Solution Deposition) method. The method for treating an oxide conductive thin film according to any one of claims 1 to 3 . (A) forming a SrRuO ₃ type oxide conductive thin film;
(B) The SrRuO ₃ type oxide conductive thin film is treated with a mixed liquid of ethanol and pure water, and the volume ratio of ethanol in the mixed liquid is 25% or less, and the SrRuO ₃ type oxide conductive thin film Bringing the atomic ratio Sr / Ru of the surface closer to a stoichiometric ratio of 1/1 ;
(C) laminating an oxide piezoelectric layer on the SrRuO ₃ type oxide conductive thin film as a lower electrode or a part of the lower electrode;
(D) laminating an upper electrode on the oxide piezoelectric layer;
The manufacturing method of the electronic device characterized by the above-mentioned. A method of manufacturing a droplet discharge head comprising an electronic device,
A method for manufacturing a droplet discharge head, wherein the electronic device is manufactured by the method for manufacturing an electronic device according to claim 5.

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