JP2003188431A - Piezo-electric device, ink jet head and method for manufacturing them and ink jet recording device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To reduce variations in properties of a piezo-electric device and improve a withstand voltage and the reliability of the piezo-electric device by forming a PZT piezo-electric thin film which is superior in its crystallizability and (001) crystal orientation. <P>SOLUTION: An adhesion layer 12 is laid on a board 11 of the piezo-electric device. A first orientation control layer 13 made of an oxide thin film of a (100) orientation NaCl type crystal structure is laid on the layer 12. A first electrode layer 14 made of a (100) orientation Pt thin-film is laid on the first orientation control layer 13. A second orientation control layer 15 is formed on the layer 14 with its main component of titanate containing excluding Zr. A piezo-electric layer 16 made of a PZT thin-film is laid on the second orientation control layer 15. A second electrode layer 17 is laid on the layer 16. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric element having an electromechanical conversion function, an ink jet head using the piezoelectric element, a method of manufacturing the same, and an ink jet recording apparatus having the ink jet head as a printing means.

[0002]

2. Description of the Related Art Piezoelectric materials are materials that convert mechanical energy into electrical energy or convert electrical energy into mechanical energy. As a typical piezoelectric material, lead zirconate titanate (Pb (Zr, Ti) O ₃ ) having a perovskite crystal structure (hereinafter, referred to as
"PZT"). In PZT, the largest piezoelectric displacement is obtained in the <001> direction (c-axis direction) in the case of tetragonal PZT, and <in the case of rhombohedral PZT.
The largest piezoelectric displacement is obtained in the 111> direction. However, many piezoelectric materials are polycrystalline bodies composed of aggregates of crystal grains, and the crystal axes of the respective crystal grains are oriented in random directions. Therefore, the spontaneous polarization Ps is also randomly arranged.

By the way, with the recent miniaturization of electronic devices, there has been a strong demand for miniaturization of piezoelectric elements. In order to meet the demand, piezoelectric elements are being used in the form of thin films that have a significantly smaller volume than the sintered bodies that have been widely used in the past. Is becoming popular. For example, in the case of tetragonal PZT, spontaneous polarization Ps
Since it is oriented in the c-axis direction, in order to achieve high piezoelectric characteristics even if the film is thinned, the c of the crystal that constitutes the PZT thin film should be used.
The axis must be aligned perpendicular to the substrate surface. In order to realize this, conventionally, NaCl cut out so that the crystal orientation (100) plane appears on the surface.
Using a single-crystal substrate made of magnesium oxide (MgO) having a type crystal structure, a (100) -oriented Pt electrode thin film is formed as a lower electrode, and c is formed in a direction perpendicular to the surface.
An axially oriented PZT thin film was formed at a temperature of 600 to 700 ° C. (for example, J. Appl. Phys. Vol.65, No. 4 (15
Feb. 1989) pp.1666-1670, JP-A-10-209517.
Issue). At this time, as a base layer of the PZT film, a piezoelectric layer having a film thickness of 0.1 μm and made of PbTiO ₃ or (P, La) TiO ₃ without Zr is formed on the (100) Pt electrode, and the film thickness is formed thereon. By forming the PZT film of 2.5 μm, it becomes difficult to form a layer having low crystallinity made of Zr oxide at the initial stage of formation of the PZT film, and P having a higher crystallinity is formed.
A ZT film is obtained.

However, in the above method, M is used as the base substrate.
Since the gO single crystal is used, there is a problem that the piezoelectric element becomes expensive and the inkjet head using the piezoelectric element becomes expensive. Also, the substrate material is MgO
There was also a drawback that it was limited to one type of single crystal.

As a method for solving the above problems, expensive M
An inexpensive glass substrate or Si substrate is used instead of the gO single crystal substrate, and a plasma CVD method is used on it (100)
MgO thin film of NaCl type crystal structure with preferential orientation, NiO
It has been proposed that a thin film or a CoO thin film be formed as an orientation control layer, and a (001) preferentially oriented PZT film be formed thereon by a sputtering method (Patent Publication: 28343).
55).

[0006]

However, when the above-mentioned piezoelectric element is industrially mass-produced, there are problems in variations in piezoelectric characteristics, withstand voltage, reliability, and yield. This is because the piezoelectric element described above is a PZ with (001) preferential orientation.
In order to form a T film on inexpensive glass or Si substrate,
A (100) MgO thin film, a NiO thin film and a CoO thin film are used as the orientation control layer. These orientation control layers are manufactured by the plasma CVD method. Using this method, the (10
0) An oriented film can be obtained, and all the thin films are polycrystalline (for example, Jpn.J.Appl.Phys.32 (1993) L1448). That is, since the grain boundaries exist on the surface of the thin film, the crystals are more likely to be disturbed in the initial stage of forming the PZT film than in the case of forming on the single-crystal MgO substrate. It becomes easy to form a layer having low crystallinity. This problem is due to the (100) of the NaCl type crystal structure.
PZT on the alignment film via a (100) -oriented Pt electrode film
Even when a film is formed, the (100) -oriented Pt electrode film has a polycrystalline structure, and therefore occurs similarly. As a result, PZT
Variations in the (001) orientation and crystallinity of the piezoelectric film tend to occur, causing problems in the variation of piezoelectric characteristics, withstand voltage, and reliability. Furthermore, since the oxide thin film having the NaCl type crystal structure such as the MgO film described above has a problem in adhesion to a glass substrate, a Si substrate, or the like, film peeling may occur during manufacturing, which reduces the yield of piezoelectric elements. It was the cause.

Further, the ink jet head and the ink jet type recording apparatus using the above-mentioned piezoelectric element have a problem in variation in ink ejection capability and durability due to variation in piezoelectric characteristics and reliability.

The present invention is intended to solve such a conventional problem and is to provide a piezoelectric element having improved piezoelectric characteristics, withstand voltage, reliability and yield, an ink jet head, a method for manufacturing the same, and an ink jet head type ink jet head. The purpose is to provide a recording device.

[0009]

In order to provide an understanding of the present invention, a detailed description will be given below based on the embodiments, but the following contents are not intended to intentionally limit the scope of the claims. Absent.

In order to achieve the above object, the piezoelectric element according to claim 1 of the present invention is provided with an adhesion layer on a substrate, and the first orientation control of a (100) oriented NaCl type oxide thin film is provided on the adhesion layer. A layer is provided, a first electrode layer is provided on the first orientation control layer, and (001) or (10) is provided on the first electrode layer.
0) A second orientation control layer of an oriented perovskite oxide thin film is provided, and a piezoelectric layer of a (001) or (100) oriented perovskite oxide thin film is provided on the second orientation control layer. A second electrode layer is provided on the layer.

As described above, by forming the (100) oriented NaCl-type or spinel-type oxide thin film which is the first orientation control layer on the substrate through the adhesion layer, the substrate and the first orientation control layer are formed. It is possible to improve the adhesion to the (100) oriented NaCl-type oxide thin film, and to eliminate the peeling of the film during manufacturing. Further, Zr is not contained between the first electrode and the piezoelectric layer (001) or (10
0) Oriented perovskite type lead titanate as a main component,
Second, oxide thin film containing lead in excess of stoichiometric composition
By providing the orientation control layer of (0), the crystallinity of the oxide thin film of the perovskite type crystal structure which is the piezoelectric layer and (00
It is possible to improve the 1) or (100) orientation. In particular, since the second orientation control layer containing lead titanate as a main component contains an excessive amount of lead, it can be easily formed on the (100) oriented polycrystalline film such as Pt which is the first electrode layer. The crystallinity is excellent and a (001) or (100) oriented film can be obtained. As a result, variations in piezoelectric characteristics, withstand voltage,
The reliability can be improved. Since the piezoelectric element is used by applying an electric field in the direction perpendicular to the surface of the PZT film, particularly in the tetragonal perovskite type PZT film, the electric field direction and the <001> polarization axis direction are parallel to each other due to the (001) orientation. Therefore, large piezoelectric characteristics can be obtained. Further, since the polarization axis is parallel to the applied electric field, the rotation of polarization due to the applied electric field does not occur, so that variations in piezoelectric characteristics and reliability are also improved. In the rhombohedral perovskite PZT film, the polarization axis is <111>. Therefore, in the (100) oriented PZT film, an angle of about 54 ° is generated between the electric field direction and the polarization axis direction (for example, Appl .P
hys.Lett.76 (2000) 1617), by improving the crystallinity and (100) orientation, the polarization can always maintain a constant angle of about 54 ° with respect to voltage application. Since the rotation of polarization due to the application of an electric field does not occur, variations in piezoelectric characteristics and reliability are improved (for example, non-oriented PZT).
In the case of a film, polarization is oriented in various directions.When an electric field is applied, the polarization axis tends to be oriented in the direction parallel to the electric field. There are problems with reliability due to changes). Further, in any of the tetragonal system and the rhombohedral system, since the low crystallinity layer of Zr oxide is not formed in the initial stage of forming the PZT film, the withstand voltage is also improved.

The method of manufacturing a piezoelectric element according to claim 2 is
In the piezoelectric element having the above structure, the adhesion layer, the first electrode layer,
The second alignment control layer, the piezoelectric layer, and the second electrode layer are formed by a sputtering method, and the first alignment control layer is formed by a plasma CVD method.

Thus, the first orientation control layer (1
00) Plasma CV for forming oriented NaCl-type oxide thin film
By using the D method, a (100) -oriented NaCl-type oxide thin film can be obtained regardless of the types of the base substrate and the adhesion layer, so that it is not necessary to use an expensive MgO single crystal substrate, and an inexpensive glass substrate or Si substrate. Can be used. In addition, by forming the second orientation control layer containing lead titanate as a main component and the piezoelectric layer containing lead zirconate titanate as a main component by a sputtering method, it is possible to obtain a crystallinity free from cracks at low temperature. The above oxide thin film having a good perovskite type crystal structure can be obtained.

Further, in the piezoelectric element and the method for manufacturing the piezoelectric element of the present invention, the adhesion layer is made of titanium, tantalum,
It is desirable to be at least one selected from the group consisting of iron, cobalt, nickel and chromium.

Further, in the piezoelectric element and the method for manufacturing the piezoelectric element of the present invention, the first orientation control layer comprises magnesium oxide, nickel oxide, cobalt oxide, iron oxide preferentially oriented to (100) having a NaCl type crystal structure. It is desirable that at least one selected from the group consisting of titanium oxides.

Further, in the piezoelectric element and the method for manufacturing a piezoelectric element of the present invention, the second orientation control layer comprises lead titanate preferentially oriented to (001) or (100) having a perovskite type crystal structure, and magnesium or calcium. , Strontium, barium, lanthanum, niobium, manganese, zinc, and aluminum are added in an amount of more than 0 and 25 mol% or less, and the lead content is higher than that of the stoichiometric composition. An excess of more than 5 and 30 mol% or less is desirable.

Further, in the piezoelectric element and the method for manufacturing the piezoelectric element of the present invention, the piezoelectric layer is (001) or (1
It is preferable to use lead zirconate titanate having a perovskite crystal structure preferentially oriented to (00).

According to a third aspect of the present invention, there is provided an ink jet head in which an adhesion layer is provided on a substrate, a first orientation control layer is provided on the adhesion layer, and a first electrode layer is provided on the first orientation control layer. A piezoelectric element, in which a second orientation control layer is provided on the first electrode layer, a piezoelectric layer is provided on the second orientation control layer, and a second electrode layer is provided on the piezoelectric layer. And a vibrating layer is provided on the second electrode layer of the piezoelectric element, and the vibrating layer and the pressure chamber for ejecting ink are joined to form the substrate, the adhesion layer and the first orientation control layer. It is characterized by being removed.

As a result, it is possible to realize an ink jet head having less variation in ink ejection capacity and excellent durability.

According to a fourth aspect of the present invention, there is provided an ink jet head manufacturing method, wherein an adhesion layer, a first orientation control layer, and
The first electrode layer, the second orientation control layer, the piezoelectric layer, and the second
Forming an electrode layer, forming a vibrating layer on the second electrode layer, joining a pressure chamber for ejecting ink onto the vibrating layer, the substrate, the adhesion layer, And a method for manufacturing an inkjet head, which comprises a step of removing the first orientation control layer, the adhesion layer, the first electrode layer, the second orientation control layer, the piezoelectric layer, and the second electrode layer. Is formed by a sputtering method, and the first orientation control layer is formed by a plasma CVD method.

As a result, it is possible to manufacture an ink jet head having less variation in ink ejection capacity and excellent durability.

Further, in the ink jet head according to the present invention, a vibrating layer is provided on the other surface of the pressure chamber substrate having a pressure chamber for ejecting ink on one surface, and the vibrating layer is adhered to the vibrating layer. A layer, a first orientation control layer is provided on the adhesion layer, a first electrode layer is provided on the first orientation control layer, and a second orientation control layer is provided on the first electrode layer. It is characterized in that a piezoelectric layer is provided on the second orientation control layer, and a second electrode layer is provided on the piezoelectric layer.

As a result, it is possible to realize an ink jet head having excellent durability and less variation in ink ejection capacity.

According to a sixth aspect of the present invention, there is provided a method of manufacturing an ink jet head, wherein a step of forming a vibrating layer on one surface of the substrate, an adhesion layer, a first orientation control layer, a first electrode layer, A method for manufacturing an ink jet head, comprising: a step of forming an alignment control layer, a piezoelectric layer, and a second electrode layer, and a step of etching the substrate to form a pressure chamber. A layer, a first electrode layer, a second orientation control layer, a piezoelectric layer, and a second electrode layer are formed by a sputtering method, and the first orientation control layer is formed by a plasma CVD method. To do.

As a result, it is possible to manufacture an ink jet head which has little variation in ink ejection capacity and is excellent in durability.

An ink jet recording apparatus according to a seventh aspect of the invention is an ink jet head according to the third or fifth aspect, a moving means for moving the ink jet head in the width direction, and a direction substantially perpendicular to the width direction. And a moving means for moving the recording medium.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings.

(Embodiment 1) FIG. 1 is a sectional view of a piezoelectric element according to the present embodiment. In FIG.
It is a substrate made of 0.3 mm φ4 inch silicon (Si) wafer, and a thickness of 0.02 μm made of titanium (Ti) on it.
Adhesion layer 12 is formed. In addition, Na on the adhesion layer 12
A first orientation control layer 13 made of magnesium oxide (MgO) having a NaCl type crystal structure in which a (100) plane having a Cl type crystal structure thickness of 0.4 μm is preferentially oriented is formed. A first electrode layer 14 made of platinum (Pt) having a thickness of 0.2 μm and having a (100) plane preferentially oriented is formed on the first orientation control layer 13.
Furthermore, 10 mol% of lanthanum (La) having a thickness of 0.02 μm was added on the first electrode layer 14, and lead was added from the stoichiometric composition to 2%.
A second orientation control layer 15 made of lead titanate containing an excess of 0 mol% is formed. The orientation control layer 15 has a perovskite structure in which the (001) plane is preferentially oriented. A piezoelectric layer 16 made of lead zirconate titanate having a thickness of 3 μm is formed on the second orientation control layer 15. This piezoelectric layer 16 has a perovskite structure in which the (001) plane is preferentially oriented, and its composition is a composition (Zr / Ti = 52/48) near the boundary between the tetragonal crystal and the rhombohedral crystal (morphotropic phase boundary). Is.
A second Pt layer with a thickness of 0.2 μm is formed on the piezoelectric layer.
Electrode layers are formed.

The adhesion layer 12 is used to improve the adhesion between the substrate 11 and the base layer 13. The adhesion layer is not limited to Ti and may be tantalum, iron, cobalt, nickel, chromium or a compound thereof. The film thickness is 0.005 to 1 μm
It should be in the range of.

The first orientation control layer 13 is used for orienting Pt, which is the first electrode layer, to (100), and is not limited to magnesium oxide, but is a NaCl type that exhibits (100) orientation. The oxide may be nickel oxide, cobalt oxide, iron oxide, titanium oxide or a compound thereof. The film thickness may be in the range of 0.05 to 0.5 μm.
This is because when the film thickness is 0.05 μm or less, sufficient crystallinity and (100) orientation cannot be obtained. Again 2
This is because if the thickness is more than μm, the surface irregularities become large and the formation of the first electrode layer is adversely affected.

Further, in the first orientation control layer, (10
0) The orientation rate α1 may be 90% or more. Where α1
Is defined by α1 = I (100) / ΣI (hkl).

ΣI (hkl) is Cu in the X-ray diffraction method.
-NaCl at 2θ of 10-70 ° when using Kα rays
The sum of all diffraction intensities of the oxide thin film, specifically (11
1) Sum of diffraction peak intensities from (200) and (220). Further, I (100) is the intensity of the diffraction peak from (200).

The first electrode layer 13 has not only a role as an electrode, but also a role of (001) orienting the second orientation control layer to (001) or (100) orientation. , Pt, but may be palladium, iridium, rhodium or a compound thereof. The film thickness may be in the range of 0.05 to 2 μm.

The second orientation control layer 15 improves the crystallinity and the (001) or (100) orientation of the piezoelectric layer 16. Therefore, Zr is not contained and lead has a composition that is in excess of the stoichiometric composition. The second orientation control layer is not limited to a perovskite-type oxide in which lead titanate contains lanthanum in an amount of 10 mol% and lead is present in an excess of 20 mol% with respect to the stoichiometric composition, and in addition to lanthanum, magnesium, calcium, strontium, barium, etc. , Niobium, Manganese, Zinc, Aluminum, and lead excess 5-30mo
It should be l%. At this time, when the lead excess amount is 5 mol% or less or exceeds 30 mol%, the (001) or (100) orientation with good crystallinity is formed on the polycrystalline (100) Pt film as the first electrode layer. It is difficult to obtain the second orientation control layer containing lead titanate as a main component. The film thickness is 0.005-0.2.
It may be in the range of μm. (001) or (100)
The degree of orientation α2 may be 80% or more in any case. Here, α2 is the diffraction peak intensity from (001) or (100) and the total diffraction peak intensity of the perovskite oxide thin film at 2θ of 10 to 70 ° when Cu-Kα ray is used in the X-ray diffraction method. It is the ratio with the sum of. However, since (002) and (200) are equivalent to (001) and (100), they are not included in the peak intensity.

The Zr / Ti composition in the piezoelectric layer 16 is
Not limited to Zr / Ti = 52/48, Zr / Ti = 30/70 to 70/30 may be used. In addition, the piezoelectric layer 16 (001) or (100)
The degree of orientation α3 is the degree of orientation α of (001) or (100).
3 may be 90% or more in any case. Here, α3 is the diffraction peak intensity from (001) or (100) of the perovskite-type oxide thin film at 2θ of 10 to 70 ° when Cu-Kα ray is used in the X-ray diffraction method, like α2. And the total intensity of all diffraction peaks. The film thickness may be in the range of 0.1 to 5.0 μm.

Example 1 Next, a method of manufacturing the piezoelectric element having the structure shown in FIG. 1 of the present invention will be described.

Of the layers having the structure shown in FIG. 1, an adhesion layer,
The first electrode layer, the second orientation control layer, the piezoelectric layer, and the second electrode layer were formed by the sputtering method, and the first orientation control layer was formed by the plasma CVD method.

First, the adhesion layer was formed by using a Ti target, heating the substrate at 400 ° C., applying a high-frequency power of 100 W, and argon gas of 1 Pa for 1 minute.

Next, the first orientation control layer was formed by the plasma CVD method. Magnesium acetylacetonate (Mg (C ₅ H ₇ O ₂ ) ₂ ) was used as the starting material, vaporization temperature 210 ° C, carrier gas (nitrogen) flow rate 100 (SCCM), reaction gas (oxygen) flow rate 1000 (SCCM), vacuum It was fabricated at 400 W for 45 minutes in high frequency (13.56 MHz) plasma under the conditions of 10 Pa and a substrate temperature of 500 ° C.

Subsequently, the first electrode layer was formed by the sputtering method. Using a Pt target, the substrate was heated to 600 ° C. and formed in argon gas of 1 Pa at a high frequency power of 200 W for 12 minutes.

The second orientation control layer has 20 m of lead lanthanum titanate (Pb0.9La0.1TiO3) and lead oxide (PbO) as the target.
Using a sintered body target prepared by adding ol% excess, at a substrate temperature of 600 ° C, in a mixed atmosphere of argon and oxygen (gas volume ratio Ar: O2 = 19: 1), vacuum degree 0.8Pa, high frequency power 300W
It was made for 12 minutes under the conditions of.

The piezoelectric layer uses a lead zirconate titanate (Zr / Ti = 52/48) sintered target as a target, and the substrate temperature is 630 ° C. in a mixed atmosphere of argon and oxygen (gas volume: Ratio Ar: O2 = 9: 1), vacuum degree of 0.3 Pa, and high frequency power of 250 W were prepared for 3 hours to obtain sample A1. No crack or peeling of the film was observed in Sample A1.

The crystal orientation and film composition of the piezoelectric layer were investigated using sample A1. From the analysis by the X-ray diffraction method, the obtained piezoelectric layer 16 had a (100) oriented rhombohedral perovskite type crystal structure. No diffraction peak was observed from the planes other than (100). As a result of composition analysis by X-ray microanalyzer, the composition of the PZT film was the same as the target composition, and the Zr / Ti ratio was 52/48.

Next, the crystal orientation of the first orientation control layer 13,
Further, in order to investigate the crystalline orientation and the film composition of the second orientation control layer 15, the adhesion layer is formed on the Si substrate 11 by the above-mentioned film forming method.
12, sample A2 formed up to the first orientation control layer 13,
And an adhesion layer 12, a first orientation control layer 13, on the Si substrate 11,
A sample A3 having the first electrode layer 14 and the second alignment control layer 15 formed was prepared.

As a result of analysis by the X-ray diffraction method, the MgO thin film of the first orientation control layer in Sample A2 was
It showed a (100) oriented NaCl type crystal structure. (10
No diffraction peak was seen from the planes other than 0). Further, the lead titanate thin film to which lanthanum was added as the second orientation control layer in Sample A3 exhibited a (100) oriented perovskite type crystal structure. No diffraction peak was observed from the planes other than (100). Furthermore, sample A3
As a result of performing a composition analysis of the second orientation control layer on the X-ray microanalyzer using
Lanthanum was added at 10 mol% and Pb was contained in excess of 20 mol%.

Next, using sample A1, 100 cantilevers cut into 15 mm × 2 mm by dicing were manufactured,
A Pt upper electrode (second electrode layer) having a thickness of 0.1 μm was formed by a sputtering method (room temperature), and the piezoelectric characteristic d31 was measured (JP 2001-2105A).
2) was performed. The average piezoelectric constant of 100 cantilevers was -126 pC / N, and the variation was σ = 3
%Met.

Further, a piezoelectric element (sample A4) formed on a φ4 inch Si wafer by the above manufacturing method was prepared,
65 Pt films of 1 mm square and 0.1 μm thickness were formed as the upper electrode by a sputtering method using a metal mask at 10 mm intervals,
Each upper electrode (second electrode layer) and lower electrode (first electrode)
A voltage was applied to the electrode layer) to measure the withstand voltage of the piezoelectric element. Note that the withstand voltage value is a current value of 1μ due to voltage application.
The value is A. As a result, the average withstand voltage is 123V.
The variation was σ = 5%.

No film peeling or cracks were found in any of the above piezoelectric elements.

(Comparative Example 1) FIG. 2 is a sectional view of a conventional piezoelectric element. In the figure, the substrate 21 is a substrate made of a φ4 inch silicon (Si) wafer having a thickness of 0.3 mm, on which a NaCl type crystal structure having a NaCl type crystal structure with a thickness of 0.4 μm is preferentially oriented to a (100) plane. A first orientation control layer 22 made of magnesium oxide (MgO) having a crystal structure is formed. A first electrode layer 23 made of platinum (Pt) having a thickness of 0.2 μm and having a (100) plane preferentially oriented is formed on the first orientation control layer 22. Further, a piezoelectric layer 24 made of lead zirconate titanate having a thickness of 3 μm is formed on the first electrode layer 23.
The piezoelectric layer 24 has a perovskite type crystal structure,
The composition is a composition (Zr / Ti = 52/48) in the vicinity of the boundary between the tetragonal crystal and the rhombohedral crystal (the morphotropic phase boundary). A second electrode layer 25 made of Pt and having a thickness of 0.2 μm is formed on the piezoelectric layer 24. Compared with the piezoelectric element of the present invention shown in FIG. 1, the adhesive layer 12 and the second orientation control layer 15 are not provided.

Adhesion layers 22 and 10 made of Ti on the Si substrate
0) The first orientation control layer 23, the first electrode layer 24, the piezoelectric layer 24, and the second electrode layer 25 made of an oriented MgO film were all manufactured by the same method and under the same conditions as in Example 1. And sample B1
And

The crystal orientation and film composition of the piezoelectric layer were investigated using sample B1. From the analysis by the X-ray diffraction method, the obtained piezoelectric layer 24 had a perovskite type crystal structure, but diffraction peaks from (110) and (111) were observed in addition to (100). (100) Degree of orientation α2 = 65
%Met.

As a result of composition analysis by X-ray microanalyzer, the composition of the PZT film was the same as the target composition, and the Zr / Ti ratio was 52/48.

Next, the crystal orientation of the first orientation control layer 13,
The first orientation control layer 22 is formed on the Si substrate 21 by the film formation method described above.
A sample B2 having the above was formed. As a result of analysis by the X-ray diffraction method, the MgO thin film of the first orientation control layer in sample B2 showed a (100) oriented NaCl type crystal structure. No diffraction peak was observed from the planes other than (100).

Next, using sample B1, 100 cantilevers cut out to a size of 15 mm × 2 mm by dicing were prepared, and a Pt upper electrode (second electrode layer) having a thickness of 0.1 μm was formed by a sputtering method (room temperature). , Measurement of piezoelectric characteristic d31 (JP 2001-21
The same method as 052) was performed. It should be noted that cracks were not observed in the 60 manufactured elements, but film peeling was observed between the Si substrate 21 and the first orientation control layer in 8 samples. The average value of the piezoelectric constants of 42 cantilevers without film peeling was -72 pC / N, and the variation was σ = 12%.

Further, a piezoelectric element (Sample B3) formed on a φ4 inch Si wafer was produced by the above-mentioned manufacturing method,
65 Pt films of 1 mm square and 0.1 μm thickness were formed as the upper electrode by a sputtering method using a metal mask at 10 mm intervals,
Each upper electrode (second electrode layer) and lower electrode (first electrode)
A voltage was applied to the electrode layer) to measure the withstand voltage of the piezoelectric element. Note that the withstand voltage value is a current value of 1μ due to voltage application.
The value is A. As a result, the average withstand voltage is 78V,
The variation was σ = 16%.

Comparative Example 2 In the piezoelectric element having the structure shown in FIG. 1, lead lanthanum titanate (Pb0.
A piezoelectric element was manufactured under the same manufacturing conditions as in Example 1 except that a sintered body of 9La0.1TiO3) was used, and this was designated as sample C1.
That is, in Comparative Example 2, unlike Example 1, lead oxide (PbO) was not excessively added when the second orientation control layer was formed.

The crystal orientation and film composition of the piezoelectric layer were investigated using sample C1. From the analysis by the X-ray diffraction method, the obtained piezoelectric layer showed a rhombohedral perovskite type crystal structure, but in addition to (100), (111) and (11
A diffraction peak from 0) was also seen. (100) Degree of orientation α
3 = 75%. As a result of composition analysis by X-ray microanalyzer, the composition of the PZT film was the same as the target composition, and the Zr / Ti ratio was 52/48.

Next, in order to investigate the crystalline orientation and the film composition of the second orientation control layer, the adhesion layer, the first orientation control layer and the first electrode layer were formed on the Si substrate by the above-mentioned film forming method. , Sample C2 including the second alignment control layer was prepared.

As a result of analysis by the X-ray diffraction method, the lead titanate thin film to which the lanthanum was added as the second orientation control layer in the sample C2 showed a perovskite type crystal structure. But (111) and (110) other than (100)
The diffraction peak from was also seen. (100) Degree of orientation α2 =
It was 72%. Furthermore, as a result of performing a composition analysis of the second orientation control layer on the X-ray microanalyzer using the sample C2, it was the same as the target composition and the lanthanum was 10%.
Mol% was added and Pb was not included in excess.

Next, using the sample C1, 100 cantilevers cut out to a size of 15 mm × 2 mm by dicing were prepared, and a Pt upper electrode (second electrode layer) having a thickness of 0.1 μm was formed by the sputtering method (room temperature). , Measurement of piezoelectric characteristic d31 (JP 2001-21
The same method as 052) was performed. The average piezoelectric constant of the 60 cantilevers produced was -90 pC / N, and the variation was σ =
It was 96%.

Further, a piezoelectric element (sample C3) formed on a φ4 inch Si wafer was manufactured by the above manufacturing method,
65 Pt films of 1 mm square and 0.1 μm thickness were formed as the upper electrode by a sputtering method using a metal mask at 10 mm intervals,
Each upper electrode (second electrode layer) and lower electrode (first electrode)
A voltage was applied to the electrode layer) to measure the withstand voltage of the piezoelectric element. Note that the withstand voltage value is a current value of 1μ due to voltage application.
The value is A. As a result, the average withstand voltage is 92V,
The variation was σ = 12%.

No film peeling or cracks were found in any of the above piezoelectric elements.

(Embodiment 2) The piezoelectric element of the present embodiment is shown in FIG.
In the configuration shown in, the substrate is made of stainless steel (SUS30
4) using nickel (film thickness 0.02 μm) for the adhesion layer, first
Of nickel oxide (0.2 μm) in the first orientation control layer, Pt (0.2 μm) in the first electrode layer, magnesium and lanthanum in the second orientation control layer, and lead from a stoichiometric composition of 10
Lead titanate (0.04 μm) containing excess mol%, lead zirconate titanate (Zr / Ti = 40/60, thickness 2.
6 μm) Pt (film thickness 0.1 μm) is used for the second electrode layer.

First, the adhesion layer was formed by using a Ni target and applying a high-frequency power of 200 W while heating the substrate at 600 ° C. in an argon gas of 0.8 Pa for 2 minutes.

Next, the first orientation control layer was formed by the plasma CVD method. Nickel acetylacetonate (Ni (C ₅ H ₇ O ₂ ) ₂ ) was used as the starting material, vaporization temperature 190 ° C, carrier gas (nitrogen) flow rate 100 (SCCM), reaction gas (oxygen) flow rate 100
Fabrication was performed for 30 minutes in a high frequency (13.56 MHz) plasma under the conditions of 0 (SCCM), a vacuum degree of 10 Pa, and a substrate temperature of 450 ° C.

Subsequently, the first electrode layer was formed by the sputtering method. Using a Pt target, the substrate was heated to 600 ° C. and formed in argon gas of 1 Pa at a high frequency power of 200 W for 12 minutes.

For the orientation control layer, a sintered body target prepared by adding 20 mol% of lead oxide (PbO) in excess to lead titanate containing 2 mol% and 10 mol% of magnesium and lanthanum, respectively, was used as a substrate. At a temperature of 600 ℃, in a mixed atmosphere of argon and oxygen (gas volume ratio Ar: O2 = 19: 1),
It was manufactured for 20 minutes under the conditions of a vacuum degree of 0.8 Pa and a high frequency power of 300 W.

The piezoelectric layer uses a lead zirconate titanate (Zr / Ti = 40/60) sintered target as a target, and the substrate temperature is 580 ° C. in a mixed atmosphere of argon and oxygen (gas volume: The ratio Ar: O2 = 9.5: 0.5), the degree of vacuum was 0.3 Pa, and the high frequency power was 250 W, and the sample was manufactured for 3 hours to obtain sample D1.
No crack or film peeling was observed in sample D1.

The crystal orientation and film composition of the piezoelectric layer were investigated using sample D1. From the analysis by the X-ray diffraction method, the obtained piezoelectric layer 16 had a (001) oriented tetragonal perovskite type crystal structure. No diffraction peak was observed from the planes other than (001). As a result of composition analysis by X-ray microanalyzer, the composition of the PZT film was the same as the target composition, and the Zr / Ti ratio was 40/60.

Next, in order to investigate the crystal orientation of the first orientation control layer and the crystal orientation and film composition of the second orientation control layer, the adhesion layer on the Si substrate, First
Sample D2 formed up to the orientation control layer of Si and Si
A sample D3 was prepared in which the adhesion layer, the first alignment control layer, the first electrode layer, and the second alignment control layer were formed on the substrate.

As a result of analysis by the X-ray diffraction method, the NiO thin film of the first orientation control layer in sample D2 was
It showed a (100) oriented NaCl type crystal structure. (10
No diffraction peak was seen from the planes other than 0). In addition, the lead titanate thin film added with magnesium and lanthanum in the second orientation control layer in sample D3 is (00
1) It showed an oriented perovskite type crystal structure. (0
No diffraction peak was observed from the planes other than 01). Further, as a result of performing a composition analysis of the second orientation control layer by an X-ray microanalyzer using the sample D3, the same as the target composition was obtained, 2 mol% of lanthanum was added in an amount of 10 mol% of magnesium, and Pb was 10 It was contained in excess of mol%.

Next, using sample D1, 100 cantilevers cut out into 15 mm × 2 mm by dicing were prepared,
A Pt upper electrode (second electrode layer) having a thickness of 0.1 μm was formed by a sputtering method (room temperature), and the piezoelectric characteristic d31 was measured (JP 2001-2105A).
2) was performed. The average piezoelectric constant of the 60 cantilevers produced was -131pC / N, and the variation was σ = 2
%Met.

Further, a piezoelectric element (Sample A4) formed on a φ4 inch Si wafer was manufactured by the above manufacturing method,
65 Pt films of 1 mm square and 0.1 μm thickness were formed as the upper electrode by a sputtering method using a metal mask at 10 mm intervals,
Each upper electrode (second electrode layer) and lower electrode (first electrode)
A voltage was applied to the electrode layer) to measure the withstand voltage of the piezoelectric element. Note that the withstand voltage value is a current value of 1μ due to voltage application.
The value is A. As a result, the average withstand voltage is 133V.
The variation was σ = 4%.

No film peeling or cracks were found in any of the above piezoelectric elements.

(Embodiment 3) The piezoelectric element of the present embodiment is shown in FIG.
In the structure shown in FIG. 2, barium borosilicate glass is used for the substrate, tantalum (film thickness 0.01 μm) is used for the adhesion layer, and cobalt oxide-titanium oxide (0.5 μm) is used for the first orientation control layer.
Pt (0.2 μm) was added to the second electrode layer, manganese and lanthanum were added to the second orientation control layer, and lead was added from the stoichiometric composition to 1
Lead titanate (0.03 μm) containing 5 mol% excess, lead zirconate titanate (Zr / Ti = 60/40, film thickness in piezoelectric layer)
3.0 μm) Pt (film thickness 0.1 μm) is used for the second electrode layer.

First, for the adhesion layer, a Ta target is used,
While heating the substrate to 300 ° C., a high frequency power of 90 W was applied, and the substrate was formed in an argon gas of 1.0 Pa for 2 minutes.

Next, the first orientation control layer was formed by the plasma CVD method. Cobalt acetylacetonate (Co (C ₅ H ₇ O ₂ ) ₂ ) and titanium tetraisopropoxide (Ti (OC ₃ H ₇ ) ₄ ) were used as starting materials, and the vaporization temperature was 170 ° C.
And 60 ℃, carrier gas (nitrogen) flow rate of 100 each
(SCCM) and 30 (SCCM), reaction gas (oxygen) flow rate 500 (S
CCM), the degree of vacuum is 14 Pa, and the substrate temperature is 300 ° C., and the film is formed in high frequency (13.56 MHz) plasma for 45 minutes.

Subsequently, the first electrode layer was formed by the sputtering method. Using a Pt target, the substrate was heated to 600 ° C. and formed in argon gas of 1 Pa at a high frequency power of 200 W for 12 minutes.

For the orientation control layer, a sintered body target prepared by adding lead oxide (PbO) in excess of 15 mol% to lead titanate containing 2 mol% and 10 mol% of manganese and lanthanum, respectively, was used as a substrate. At a temperature of 610 ° C., in a mixed atmosphere of argon and oxygen (gas volume ratio Ar: O2 = 19: 1), a vacuum degree of 0.8 Pa and a high frequency power of 300 W were used for 20 minutes.

In the piezoelectric layer, a lead zirconate titanate (Zr / Ti = 60/40) sintered target was used as a target, and the substrate temperature was 640 ° C. in a mixed atmosphere of argon and oxygen (gas volume: The ratio Ar: O2 = 9.5: 0.5), the degree of vacuum was 0.3 Pa, and the high frequency power was 250 W, and the sample was manufactured for 3 hours to obtain sample E1. No crack or film peeling was observed in sample E1.

The crystal orientation and film composition of the piezoelectric layer were investigated using sample E1. From the analysis by the X-ray diffraction method, the obtained piezoelectric layer showed a (100) oriented rhombohedral perovskite type crystal structure. No diffraction peak was observed from the planes other than (100). As a result of composition analysis by X-ray microanalyzer, the composition of the PZT film was the same as the target composition and the Zr / Ti ratio was 60/40.

Next, in order to investigate the crystal orientation and the film composition of the first orientation control layer and the second orientation control layer, the adhesion layer and the first orientation control layer were formed on the Si substrate by the above-mentioned film forming method. Up to sample E2 and adhesion layer on Si substrate,
A sample E3 having the first alignment control layer, the first electrode layer, and the second alignment control layer formed was prepared.

As a result of analysis by the X-ray diffraction method, the cobalt oxide-titanium oxide thin film of the first orientation control layer in sample E2 showed a (100) oriented NaCl type crystal structure. No diffraction peak was observed from the planes other than (100). As a result of composition analysis of the first orientation control layer by X-ray microanalyzer, it was Ti / Co = 20/80. In addition, the lead titanate thin film to which manganese and lanthanum were added in the second orientation control layer in Sample E3 exhibited a (100) oriented perovskite type crystal structure. No diffraction peak was observed from the planes other than (100). Further, as a result of performing a composition analysis of the second orientation control layer with an X-ray microanalyzer using Sample E3, the same as the target composition, 2 mol% of manganese and 15 mol% of lanthanum were added, and Pb was 15 It was contained in excess of mol%.

Next, using the sample E1, 100 cantilevers cut out to a size of 15 mm × 2 mm by dicing were prepared, and a Pt upper electrode (second electrode layer) having a thickness of 0.1 μm was formed by the sputtering method (room temperature). , Measurement of piezoelectric characteristic d31 (JP 2001-21
The same method as 052) was performed. The average piezoelectric constant of the 60 cantilevers produced was -121 pC / N, and the variation was σ
= 3%.

Further, a piezoelectric element (Sample E4) formed on a φ4 inch Si wafer was manufactured by the above manufacturing method,
65 Pt films of 1 mm square and 0.1 μm thickness were formed as the upper electrode by a sputtering method using a metal mask at 10 mm intervals,
Each upper electrode (second electrode layer) and lower electrode (first electrode)
A voltage was applied to the electrode layer) to measure the withstand voltage of the piezoelectric element. Note that the withstand voltage value is a current value of 1μ due to voltage application.
The value is A. As a result, the average withstand voltage is 118V.
The variation was σ = 5%.

No film peeling or cracking was observed in any of the above piezoelectric elements.

(Embodiment 2) FIG. 3 shows the overall construction of an ink jet head according to an embodiment of the present invention, and FIG. 4 shows the construction of the essential parts thereof. 3 and 4, A is a pressure chamber component, and the pressure chamber opening 101 is formed.
B is an actuator portion arranged so as to cover the upper end opening surface of the pressure chamber opening portion 101, and C is an ink liquid flow path component arranged so as to cover the lower end opening surface of the pressure chamber opening portion 101. . Pressure chamber opening 1 of the pressure chamber component A
The pressure chamber 102 is partitioned by the actuator section B and the ink liquid flow path component C which are located above and below it. In the actuator section B, the pressure chamber 102
The individual electrode 103 located above is disposed. As can be seen from FIG. 3, the pressure chambers 102 and the individual electrodes 103 are arranged in a zigzag pattern. In the ink liquid flow path component C, a common liquid chamber 105 shared by the pressure chambers 102 arranged in the ink liquid supply direction, a supply port 106 communicating the common liquid chamber 105 with the pressure chamber 102, and the pressure chamber An ink flow path 107 through which the ink liquid in 102 flows out is formed. D is a nozzle plate, and the ink flow path 10
A nozzle hole 108 communicating with 7 is formed. Also,
In FIG. 3, E is an IC chip, which supplies a voltage to the large number of individual electrodes 103 via the bonding wires BW.

Next, the structure of the actuator section B will be described with reference to FIG. In the figure, the actuator section B shows a cross-sectional view in a direction orthogonal to the ink liquid supply direction shown in FIG. In the figure, a pressure chamber component A having four pressure chambers 102 arranged in the orthogonal direction is drawn for reference. The actuator section B includes an individual electrode 103 located above each pressure chamber 102, a second piezoelectric thin film 110 located immediately below the individual electrode 103, and a vibration that is displaced and vibrated by the piezoelectric effect of the piezoelectric thin film 110. And a plate 111. Further, the actuator portion B is the diaphragm 1
11 and a common electrode 112 arranged between each piezoelectric thin film 110 and a partition wall 1 partitioning each pressure chamber 102 from each other.
It has a vertical wall 113 located above 02a. Common electrode 1
Reference numeral 12 also serves as an adhesion layer that strengthens the adhesion between the vibration plate 111 and each piezoelectric thin film 110. In the figure,
Reference numeral 114 denotes an adhesive that bonds the pressure chamber component A and the actuator portion B together. Each of the vertical walls 113 has the adhesive 11
4 when a part of the adhesive 114 is attached to the partition wall 10
The adhesive 114 does not adhere to the vibrating plate 111 even when it protrudes to the outside of the 2a, so that the vibrating plate 111 can be displaced and vibrated as desired, so that the upper surface of the pressure chamber 102 and the vibrating plate 111 are not separated. Has the role of expanding the distance from the bottom surface.

Next, a method for manufacturing an ink jet head excluding the IC chip E of FIG. 3, that is, an ink jet head including the pressure chamber component A, the actuator section B, the ink flow channel component C and the nozzle plate D shown in FIG. 6 to 10 will be described.

In FIG. 6A, an adhesion layer 121, a first alignment control layer 221, a first electrode layer (individual electrode material) 321, and a second alignment control layer 12 are sequentially formed on a substrate 120.
2, piezoelectric layer 222, second electrode layer (common electrode material) 1
23, the diaphragm 124, and the intermediate layer material 125 for the vertical wall 113 of FIG. 5 are deposited and laminated. The substrate 120 is, for example, a Si substrate. For example, Ti is used for the adhesion layer 121, and NaCl is used for the first orientation control layer 211.
A (100) oriented MgO thin film having a type crystal structure, the first electrode layer (individual electrode material) 321 contains, for example, Pt, and the second orientation control layer 122 contains, for example, 10 mol% of lanthanum.
In addition, a lead titanate layer containing 10% excess of lead from the stoichiometric composition, for example, lead zirconate titanate (PZT) is used for the piezoelectric layer 222, and Ti (titanium) is used for the second electrode layer 123. The diaphragm 124 is made of Cr (chrome), and the intermediate layer material 125 is made of Ti, for example.

As the substrate 120, a Si substrate cut into 18 mm square was used. The substrate is not limited to Si,
A glass substrate, a metal substrate, or a ceramic substrate may be used. Also, the substrate size is not limited to 18 mm square, for example, S
A wafer of φ2 to 10 inches may be used as long as it is an i substrate.

The adhesion layer 121 was formed by using a Ti target, applying 100 W of high frequency power while heating the substrate at 400 ° C., and in argon gas of 1 Pa for 1 minute. The film thickness is
It was 0.02 μm. The adhesion layer 121 is not limited to Ti and may be tantalum, iron, cobalt, nickel, chromium, or a compound thereof. The film thickness may be in the range of 0.005 to 0.2 μm.

The first orientation control layer 211 was formed by the plasma CVD method. Magnesium acetylacetonate (Mg (C ₅ H ₇ O ₂ ) ₂ ) was used as the starting material, vaporization temperature 210 ° C, carrier gas (nitrogen) flow rate 100 (SCCM), reaction gas (oxygen) flow rate 1000 (SCCM), vacuum It was fabricated at 400 W for 45 minutes in high frequency (13.56 MHz) plasma under the conditions of 10 Pa and a substrate temperature of 500 ° C. The film thickness was 0.4 μm. Here, the first orientation control layer 211 changes the Pt of the first electrode layer 321 to (100).
The present invention is not limited to magnesium oxide and may be nickel oxide, cobalt oxide, iron oxide, titanium oxide, or their compounds, which are NaCl type oxides exhibiting (100) orientation. The film thickness is 0.05 to 2
It may be μm.

The first electrode layer 321 was formed by a sputtering method. Using a Pt target, the substrate was heated to 600 ° C. and formed in argon gas of 1 Pa at a high frequency power of 200 W for 12 minutes. The film thickness was 0.2 μm. First electrode layer 406
Not only plays a role as an electrode, but also makes the second orientation control layer have (001) or (1) orientation by (100) orientation.
(00) also plays a role of orientation, and not only Pt but also palladium, iridium, rhodium or a compound thereof may be used. The film thickness may be 0.1 to 0.5 μm.

The second orientation control layer 122 is composed of lead lanthanum titanate (Pb0.9La0.1TiO3) and lead oxide (Pb).
O) was added in an excess of 20 mol%, and a sintered target was prepared at a substrate temperature of 600 ° C in a mixed atmosphere of argon and oxygen (gas volume ratio Ar: O2 = 19: 1), vacuum degree 0.8 Pa, high frequency. Fabrication was performed for 12 minutes under the condition of electric power of 300W. The film thickness was 0.02 μm. The second orientation control layer 122 contains 10 mol% of lanthanum in lead titanate, and the lead content is 20 mol from the stoichiometric composition.
In addition to lanthanum, magnesium, calcium, strontium, barium, niobium, manganese, zinc, and aluminum may be included, and the lead excess amount may be 5 to 30 mol%. Further, the film thickness may be 0.005 to 0.2 μm.

For the piezoelectric layer 222, a lead zirconate titanate (Zr / Ti = 52/48) sintered target was used as a target, and the substrate temperature was 630 ° C. in a mixed atmosphere of argon and oxygen (gas volume ratio). Ar: O2 = 9: 1), vacuum degree of 0.3 Pa, and high frequency power of 250 W were prepared for 3 hours. The film thickness was 3 μm. The Zr / Ti composition in the piezoelectric layer 222 is Zr / Ti.
Not limited to = 52/48, Zr / Ti = 30/70 to 70/30 may be used. The film thickness may be 1 to 5 μm.

The second electrode layer 123 was formed by using a Ti target at a room temperature and a high frequency power of 200 W in an argon gas of 1 Pa.
Formed for 0 minutes. The film thickness was 0.2 μm. The second electrode layer is not limited to Ti and may be any conductive material. Further, the film thickness may be 0.1 to 0.4 μm.

The vibrating plate 124 is a Cr target, and a high frequency power of 200 W in argon gas of 1 Pa at room temperature is used.
Formed for hours. The film thickness was 3 μm. Further, the diaphragm material is not limited to Cr, but silicon dioxide, aluminum oxide, zirconium oxide, silicon nitride, tungsten,
Tantalum may be used. The film thickness may be 2 to 5 μm. Not only chromium but also nickel, aluminum, tantalum, tungsten, silicon and oxides or nitrides thereof may be used.

As the intermediate layer material 125, a Ti target was used, and a high frequency power of 200 W was applied in an argon gas of 1 Pa at room temperature.
Formed for hours. The film thickness was 5 μm. Further, the material of the intermediate layer is not limited to Ti, but may be any conductive metal such as Cr.
The film thickness may be 3 to 10 μm.

On the other hand, in FIG. 6B, the pressure chamber component A
To form. The pressure chamber component A is the Si substrate 120.
It is formed using a silicon substrate 130 of the same size as, for example, a 4-inch wafer. Specifically, first, the plurality of pressure chamber openings 1 are patterned on the silicon substrate (for pressure chamber) 130. In this patterning, as can be seen from FIG. 2B, a partition wall 102 that partitions each of the four pressure chamber openings 101 into one group is formed.
b is set to a thickness width that is approximately twice the width of the partition wall 102a that partitions the pressure chamber opening 101 in each set. Then, the patterned silicon substrate 130 is processed by chemical etching or dry etching,
Four pressure chamber openings 101 are formed in each set to obtain a pressure chamber component A.

After that, the silicon substrate (for film formation) 120 after the film formation and the pressure chamber component A are bonded with an adhesive. The formation of this adhesive is by electrodeposition. That is, first,
As shown in FIG. 6C, an adhesive 114 is attached by electrodeposition to the upper surfaces of the partition walls 102a and 102b of the pressure chamber as the adhesive surface on the pressure chamber component A side. Specifically, although not shown, a thin Ni film of several hundred Å that is thin enough to transmit light is formed on the upper surfaces of the partition walls 102a and 102b as a base electrode film by a sputtering method. Then, the patterned adhesive resin agent 114 is formed. At this time, as the electrodeposition liquid, a solution in which 0 to 50 parts by weight of pure water is added to an acrylic resin-based water dispersion liquid and well mixed by stirring is used. The thickness of the Ni thin film is set to be small enough to allow light to pass therethrough in order to easily visually confirm that the adhesive resin is completely attached to the silicon substrate (for pressure chamber) 130.
According to the experiment, the electrodeposition conditions were a liquid temperature of about 25 ° C and a DC voltage of 3
0V and energization time of 60 seconds are suitable, under this condition about 3
Acrylic resin of 10μm is silicon substrate (for pressure chamber)
It was electrodeposited on 130 Ni thin film.

Then, as shown in FIG. 7A, the laminated Si substrates (for film formation) 120 and the pressure chamber component A are formed.
And are bonded using the electrodeposited adhesive 114. This adhesion is performed by using the intermediate layer material 125 formed on the substrate (for film formation) 120 as the substrate-side adhesion surface. Further, the Si substrate (for film formation) 120 has a size of 18 mm, and the Si substrate 130 for forming the pressure chamber component A is as large as φ4 inch size. Therefore, as shown in FIG. Of S
The i substrate (for film formation) 120 is attached to one pressure chamber component A. As shown in FIG. 7 (a), this attachment is performed for each Si
It is performed in a state in which the center of the substrate (for film formation) 120 is positioned so as to be located at the center of the thick partition wall 2b of the pressure chamber component. After this attachment, the pressure chamber component A is pressed and closely adhered to the Si substrate (for film formation) 120 side to enhance the liquid tightness of the adhesion between the two. Further, the bonded Si substrate (for film formation) 1
20 and the pressure chamber component A are gradually heated in a heating furnace to completely cure the adhesive 114. Subsequently, plasma treatment is performed to remove the protruding pieces of the adhesive 114.

In FIG. 7A, the Si substrate (for film formation) 120 after film formation is adhered to the pressure chamber member A, but the Si substrate (pressure) at the stage where the pressure chamber opening 101 is not formed. The chamber) 130 may be adhered to the Si substrate (for film formation) 120 after the film formation.

Thereafter, as shown in FIG. 7B, the intermediate layer 125 is etched by using the partition walls 102a and 102b of the pressure chamber component A as a mask, and the partition walls 102a and 102a are removed.
A vertical wall 113 continuous with 102b is formed. Next, as shown in FIG. 8A, the Si substrate (for film formation) 120, the adhesion layer 121, and the first orientation control layer 211 are removed by etching.

Subsequently, as shown in FIG. 8B, the first electrode layer (individual electrode material) 321 located above the pressure chamber component A is etched by using photolithography technique to be individually etched. The electrode 103 is formed. Furthermore,
As shown in FIG. 9A, the second alignment control layer 122 and the piezoelectric layer 222 are etched by using a photolithography technique, and the second alignment control layer 122 and the piezoelectric layer 222 are formed immediately below the individual electrodes 103. Piezoelectric thin film 1 including piezoelectric layer 222
Form 10. The individual electrodes 103 and the piezoelectric thin film 110 are located above each of the pressure chambers 102, and the centers of the individual electrodes 103 and the piezoelectric elements 110 in the width direction are
The pressure chamber 2 is formed so as to coincide with the center of the corresponding pressure chamber 2 in the width direction with high accuracy. As described above, after the individual electrodes 103 and the piezoelectric thin film 110 are individualized for each pressure chamber 102, as shown in FIG.
As shown in (b), the silicon substrate (for pressure chamber) 130
Is cut at the part of the partition wall 102b of each thickness, and four sets of pressure chamber parts A having four pressure chambers 102 and actuator parts B fixed to the upper surface thereof are completed.

Subsequently, in FIG. 10A, the common liquid chamber 105, the supply port 106 and the ink flow path 107 are formed in the ink liquid flow path component C, and the nozzle hole 1 is formed in the nozzle plate D.
08 is formed. After the nozzle hole 108 is formed, a water repellent agent is poured into the nozzle hole 108, and the adhesive used for bonding the ink liquid flow path component C and the nozzle plate D in the next step is supposed to flow into the nozzle hole 108 in advance. Take measures to suppress it. Next, as shown in FIG. 7B, the ink liquid flow path component C and the nozzle plate D are bonded together using an adhesive agent 130.

Thereafter, as shown in FIG. 7C, an adhesive (not shown) is transferred to the lower end surface of the pressure chamber part A or the upper end surface of the ink liquid flow path part C, and the pressure chamber part A and the ink are transferred. The alignment adjustment with the liquid flow path component C is performed, and the both are bonded with the adhesive. As described above, the ink jet head having the pressure chamber part A, the actuator part B, the ink liquid flow path part C and the nozzle plate D is completed as shown in FIG.

When a predetermined amount of voltage was applied to the obtained ink jet head and the displacement amount of the actuator part was measured, the displacement variation was σ = 2%. Also the frequency
Even when an AC voltage of 20 kHz and 20 V was applied for 10 days, there was no defect in ink ejection and the ejection ability did not decrease.

Using the same manufacturing method as above, the piezoelectric layer 222 was formed without the adhesion layer 121 and the second orientation control layer 122, and an ink jet head was manufactured. Similarly to the inkjet head of the present invention, when a predetermined amount of voltage was applied and the displacement amount of the actuator portion was measured, the displacement variation was σ = 6%. Also, if an AC voltage with a frequency of 20kHz and 20V is applied for 10 days, it will be about 3
Ink ejection failure occurred in 0% of the actuators.

(Embodiment 3) FIG. 12 shows a cross section of a main portion of an ink jet head according to an embodiment of the present invention. A pressure chamber 402 is formed on the pressure chamber substrate 401 by etching. The vibration plate 4 is provided on the upper surface of the pressure chamber 402.
03, the adhesion layer 404, the first alignment control layer 405, the first electrode layer 406, the second alignment control layer 407, the piezoelectric layer 408, and the second electrode layer 409. The displacement of the piezoelectric layer causes the ink in the pressure chamber 402 to move to the nozzle 41.
Discharge from 0. Adhesion layer 4 formed on diaphragm 403
04, the first orientation control layer 405, the first electrode 406, the second orientation control layer 407, the piezoelectric layer 408, and the second electrode layer 409 constitute the piezoelectric element of the present invention.

The method of manufacturing the ink jet head of the present invention will be described below with reference to FIG. First, the pressure chamber substrate 401, the vibration plate 403, the adhesion layer 404,
First orientation control layer 405, first electrode layer 406, second orientation control layer 407, piezoelectric layer 408, second electrode layer 40
9 is formed (FIG. 13A).

For the pressure chamber 401, for example, a Si substrate having a diameter of 4 inches and a thickness of 200 μm was used. The thickness of the diaphragm is 1.
An 8 μm silicon dioxide film was used. The diaphragm is manufactured
The sputtering method was used. Using a target of silicon dioxide sintered pair, 300W at room temperature without substrate heating
Was applied for 8 hours in a mixed atmosphere of 0.4 Pa of argon and oxygen (gas volume ratio Ar: O2 = 10: 3). The film thickness was 1.8 μm. The material of the diaphragm 403 is not limited to the silicon dioxide film, and may be nickel, chromium, aluminum, tantalum, tungsten and their oxides, silicon or its nitride, and the like.
Also, the manufacturing method is not limited to sputtering, but thermal CVD
Method, plasma CVD method, sol-gel method, or thermal oxidation treatment of a silicon substrate. The film thickness is 0.5μ
It should be m to 10 μm.

The adhesion layer 404 was formed by using a Ti target, heating the substrate at 400 ° C., applying a high-frequency power of 100 W, and argon gas of 1 Pa for 1 minute. The film thickness was 0.03 μm. Here, the adhesion layer 404 is used to improve the adhesion between the vibration plate 403 and the first orientation control layer 405. The adhesion layer is not limited to Ti, but tantalum,
It may be iron, cobalt, nickel, chromium or a compound thereof. The film thickness may be in the range of 0.005 to 0.1 μm.

The first orientation control layer 405 was formed by the plasma CVD method. Magnesium acetylacetonate (Mg (C ₅ H ₇ O ₂ ) ₂ ) was used as the starting material, vaporization temperature 210 ° C, carrier gas (nitrogen) flow rate 100 (SCCM), reaction gas (oxygen) flow rate 1000 (SCCM), vacuum It was fabricated at 400 W for 45 minutes in high frequency (13.56 MHz) plasma under the conditions of 10 Pa and a substrate temperature of 500 ° C. The film thickness was 0.4 μm. Here, the first orientation control layer 405 has a Pt (10
Not limited to magnesium oxide, it may be nickel oxide, cobalt oxide, iron oxide, titanium oxide or a compound thereof, which is an NaCl type oxide exhibiting (100) orientation. The film thickness is 0.05 ~
It may be in the range of 0.5 μm.

The first electrode layer 406 was formed by a sputtering method. Using a Pt target, the substrate was heated to 600 ° C. and formed in argon gas of 1 Pa at a high frequency power of 200 W for 12 minutes. The film thickness was 0.2 μm. First electrode layer 406
Not only plays a role as an electrode, but also makes the second orientation control layer have (001) or (1) orientation by (100) orientation.
(00) also plays a role of orientation, and not only Pt but also palladium, iridium, rhodium or a compound thereof may be used. The film thickness may be in the range of 0.05 to 0.5 μm.

The second orientation control layer 407 is composed of lead lanthanum titanate (Pb0.9La0.1TiO3) and lead oxide (Pb) as targets.
O) was added in an excess of 20 mol%, and a sintered target was prepared at a substrate temperature of 600 ° C in a mixed atmosphere of argon and oxygen (gas volume ratio Ar: O2 = 19: 1), vacuum degree 0.8 Pa, high frequency. Fabrication was performed for 12 minutes under the condition of electric power of 300W. The film thickness was 0.03 μm. The second orientation control layer 408 contains 10 mol% of lanthanum in lead titanate, and the lead content is 20 mol from the stoichiometric composition.
In addition to lanthanum, magnesium, calcium, strontium, barium, niobium, manganese, zinc, and aluminum may be included, and the lead excess amount may be 5 to 30 mol%. The film thickness may be in the range of 0.005 to 0.2 μm.

For the piezoelectric layer 408, a lead zirconate titanate (Zr / Ti = 52/48) sintered target was used as a target, and the substrate temperature was 630 ° C. in a mixed atmosphere of argon and oxygen (gas volume ratio). Ar: O2 = 9: 1), vacuum degree of 0.3 Pa, and high frequency power of 250 W were prepared for 3 hours. The film thickness was 2.5 μm. The Zr / Ti composition of the piezoelectric layer 408 is Zr
Not limited to / Ti = 52/48, Zr / Ti = 30/70 to 70/30 may be used. The film thickness may be in the range of 0.5 to 5.0 μm.

The second electrode layer 409 is formed by using a Pt target at a room temperature and a high frequency power of 200 W in an argon gas of 1 Pa.
Formed for 0 minutes. The film thickness was 0.2 μm. The second electrode layer 409 is not limited to Pt and may be any conductive material.

Next, a resist is formed on the second electrode layer 409 by spin coating, and exposure / development is performed according to the position where the pressure chamber is to be formed, and patterning is performed.
Then, the second electrode layer 409, the piezoelectric layer 408, the second orientation control layer 407, and the first electrode layer 406 were removed by etching to separate the piezoelectric thin film 411. Etching
It was performed by dry etching using a mixed gas of argon and an organic gas containing a fluorine element.

Next, the pressure chamber was formed by anisotropic dry etching using sulfur hexafluoride gas, organic gas containing elemental fluorine, or mixed gas thereof. An etching mask is formed on the surface of the pressure chamber substrate 401 opposite to the surface on which the piezoelectric thin film 411 is formed, in a portion to be the sidewall 413, and the pressure chamber 402 is formed by anisotropic dry etching (FIG. 13 (b)). ).

Then, the nozzle plate 412 was bonded to the pressure chamber substrate 401 with an adhesive to form an ink jet head. The nozzle 410 can be formed by opening the nozzle plate 412 at a predetermined position by a lithography method, a laser processing method, an electric discharge processing method, or the like. When the nozzle plate 412 is bonded to the pressure chamber substrate 401, the nozzles 410 are aligned so as to be arranged corresponding to the space of the pressure chamber 402.

When a predetermined amount of voltage was applied to the obtained ink jet head and the displacement amount of the actuator portion was measured, the displacement variation was σ = 1.5%. In addition, even when an alternating voltage of 20 V at a frequency of 20 kHz was applied for 10 days, there was no defect in ink ejection and the ejection ability did not decrease.

Further, an ink jet was prepared by the same manufacturing method as described above without the adhesion layer 404 and the second orientation control layer 407. Similarly to the inkjet head of the present invention, when a predetermined amount of voltage was applied and the displacement amount of the actuator part was measured, the displacement variation was σ =
It was 5.5%. When an AC voltage of 20 V at a frequency of 20 kHz was applied for 10 days, defective ink ejection occurred in about 25% of the actuators.

(Embodiment 4) FIG. 12 is a schematic diagram of an ink jet type recording apparatus 27 provided with the ink jet head of the present invention. In the figure, reference numeral 28 is an ink jet head, and ink droplets ejected from the ink jet head 28 are landed on a recording medium 29 such as paper for recording. The ink jet head 28 is mounted on a carriage 31 (moving means) provided on the carriage shaft 30 in the main scanning direction X, and as the carriage 31 reciprocates along the carriage shaft 30, the main scanning direction X. Move back and forth. Further, the ink jet recording apparatus 27 is provided with a plurality of rollers 32 (moving means) for moving the recording medium 29 in the main scanning direction X (width direction) of the ink jet head 28 and in a sub scanning direction Y substantially vertical. . The ink jet type recording apparatus according to the present embodiment has little variation in ejection capacity and high reliability.

In the piezoelectric element and ink jet head of the present invention, lead zirconate titanate was used for the piezoelectric layer. However, the piezoelectric layer is not limited to this, and lead zirconate titanate and Pb (Mg1 / 3Nb3 / 2) are used. It may be a solid solution with O3 or Pb (Zn1 / 3Nb3 / 2) O3.

In addition to the ink jet head and the ink jet recording apparatus, the piezoelectric element of the present invention includes a thin film capacitor, a charge storage capacitor for a non-volatile memory element, various actuators, an infrared sensor, an ultrasonic sensor, a pressure sensor, an acceleration sensor, Angular velocity sensor, flow sensor, shock sensor, piezoelectric transformer,
Piezoelectric ignition element, piezoelectric speaker, piezoelectric microphone,
It can also be applied to piezoelectric filters, piezoelectric pickups, tuning fork oscillators, and delay lines.

[0127]

According to the present invention, the adhesion layer is provided on the substrate, the underlayer is provided on the adhesion layer, and the first layer is formed on the underlayer.
By providing the electrode layer of, the orientation control layer on the first electrode layer, the piezoelectric body on the orientation control layer, and the second electrode layer on the piezoelectric layer. Since the adhesion of each layer and the crystal structure and preferential orientation plane of the piezoelectric layer can be controlled, it has a piezoelectric element with good reproducibility, variation, withstand voltage, and reliability of piezoelectric characteristics even in industrial mass production. Ink jet heads and methods for producing them can be provided. Further, it is possible to provide an ink jet type recording apparatus having a small variation in ejection ability and high reliability.

[Brief description of drawings]

FIG. 1 is a sectional view of a piezoelectric element according to an embodiment of the present invention.

FIG. 2 is a sectional view of a conventional piezoelectric element.

FIG. 3 is a perspective view showing the overall configuration of an inkjet head according to an embodiment of the present invention.

FIG. 4 is an exploded perspective view showing a main part of a pressure chamber part and an actuator part of the inkjet head according to the embodiment of the present invention.

FIG. 5 is a cross-sectional view showing main parts of a pressure chamber component and an actuator section of the inkjet head according to the embodiment of the present invention.

FIG. 6 is a diagram showing a laminating step, a pressure chamber opening forming step, and an adhesive attaching step in the method for manufacturing an inkjet head according to the embodiment of the present invention.

FIG. 7 is a diagram showing a step of adhering a substrate after film formation to a pressure chamber component and a step of forming a vertical wall in the method for manufacturing an inkjet head according to the embodiment of the present invention.

FIG. 8 is a diagram showing a substrate removing step and an individual electrode individualizing step in the inkjet head manufacturing method according to the embodiment of the present invention.

FIG. 9 is a diagram showing a piezoelectric element individualizing step and a cutting step in the method of manufacturing an inkjet head according to the embodiment of the present invention.

FIG. 10 is a diagram showing a method of producing an ink flow path component and a nozzle plate, a step of adhering an ink flow path component and a nozzle plate, a step of forming an actuator part and a pressure component in the method for manufacturing an inkjet head according to the embodiment of the present invention. Figure showing the bonding process and completed inkjet head

FIG. 11 is a diagram showing how the Si substrate on which a film is formed and the Si substrate for forming the pressure chamber are bonded in the method for manufacturing an inkjet head according to the embodiment of the present invention.

FIG. 12 is a sectional view of an actuator portion of the inkjet head according to the embodiment of the present invention.

FIG. 13 is a process sectional view in the method of manufacturing the inkjet head according to the embodiment of the present invention.

FIG. 14 is a schematic configuration diagram of an ink jet recording apparatus.

[Explanation of symbols]

11 board 12 Adhesion layer 13 First Orientation Control Layer 14 First electrode layer 15 Second orientation control layer 16 Piezoelectric layer 17 Second electrode layer 21 board 22 First Orientation Control Layer 23 First electrode layer 24 Piezoelectric layer 25 Second electrode layer 27 Inkjet recording device 28 Ink Jet Head 29 recording media 31 Transportation (Carriage) 32 means of transportation (roller) A pressure chamber parts B actuator C ink flow path parts D nozzle plate E IC chip 101 Opening for pressure chamber 102 pressure chamber 102a, 102b partition wall 103 Distinction electrode 105 common liquid chamber 106 supply port 107 ink flow path 108 nozzle holes 110 Piezoelectric thin film 111 diaphragm 112 common electrode 113 vertical wall 114 adhesive 120 substrates (for film formation) 121 Adhesion layer 122 Second Alignment Control Layer 123 Second electrode layer (common electrode material) 124 diaphragm 125 intermediate layer material 130 Si substrate (for pressure chamber) 221 First orientation control layer 222 Piezoelectric layer 321 First electrode layer (individual electrode material) 401 Pressure chamber substrate 402 Pressure chamber 403 diaphragm 404 adhesion layer 405 First orientation control layer 406 First electrode layer 407 Second orientation control layer 408 Piezoelectric layer 409 Second electrode layer 410 nozzles 411 Piezoelectric thin film 412 nozzle plate

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Jun Tomozawa             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Ryoichi Takayama             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Akiko Kubo             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F-term (reference) 2C057 AF65 AF93 AG42 AG44 AP14                       AP52 AP53 BA04 BA14

Claims (15)

[Claims] 1. An adhesion layer is provided on a substrate, a first orientation control layer is provided on the adhesion layer, and a first electrode layer is provided on the first orientation control layer.
A piezoelectric element in which a second orientation control layer is provided on the electrode layer, the piezoelectric layer is provided on the second orientation control layer, and the second electrode layer is provided on the piezoelectric layer. 2. The method for manufacturing a piezoelectric element according to claim 1, wherein the adhesion layer, the first electrode layer, the second alignment control layer, the piezoelectric layer,
A method of manufacturing a piezoelectric element, comprising forming the second electrode layer by a sputtering method and forming the first orientation control layer by a plasma CVD method. 3. An adhesion layer is provided on a substrate, a first orientation control layer is provided on the adhesion layer, and a first electrode layer is provided on the first orientation control layer.
A second orientation control layer is provided on the electrode layer of, a piezoelectric layer is provided on the second orientation control layer, and a second electrode layer is provided on the piezoelectric layer to form a piezoelectric element. An ink jet formed by providing a vibrating layer on the second electrode layer of the piezoelectric element, joining the vibrating layer and a pressure chamber for ejecting ink, and removing the substrate, the adhesion layer and the first orientation control layer. Ethead. 4. An adhesion layer, a first alignment control layer, and a first alignment control layer on a substrate.
The first electrode layer, the second orientation control layer, the piezoelectric layer, and the second
Forming an electrode layer, forming a vibrating layer on the second electrode layer, joining a pressure chamber for ejecting ink onto the vibrating layer, the substrate, the adhesion layer, And a method for manufacturing an inkjet head, which comprises a step of removing the first orientation control layer, the adhesion layer, the first electrode layer, the second orientation control layer, the piezoelectric layer, and the second electrode layer. Is formed by a sputtering method, and the first orientation control layer is formed by a plasma CVD method. 5. A vibrating layer is provided on the other surface of a pressure chamber substrate having a pressure chamber for ejecting ink on one surface, and an adhesive layer is provided on the vibrating layer. First
Of the first alignment control layer, the first electrode layer is provided on the first alignment control layer, the second alignment control layer is provided on the first electrode layer, and the second alignment control layer is provided on the second alignment control layer. An inkjet head having a structure in which a piezoelectric layer is provided and a second electrode layer is provided on the piezoelectric layer. 6. A step of forming a vibrating layer on one surface of a substrate, an adhesion layer, a first orientation control layer, a first electrode layer, a second orientation control layer, a piezoelectric layer, and A method of manufacturing an inkjet head, comprising: a step of forming a second electrode layer; and a step of etching the substrate to form a pressure chamber, wherein the adhesion layer, the first electrode layer, and the second electrode layer A method for manufacturing an inkjet head, comprising forming an orientation control layer, a piezoelectric layer, and a second electrode layer by a sputtering method, and forming the first orientation control layer by a plasma CVD method. 7. An ink jet head according to claim 3 or 5, a moving means for moving the ink jet head in a width direction, and a movement for moving a recording medium in a direction substantially perpendicular to the width direction. And an ink jet type recording apparatus having a means. 8. The piezoelectric element according to claim 1, wherein the adhesion layer is at least one selected from the group consisting of titanium, tantalum, iron, cobalt, nickel and chromium. 9. The ink jet head according to claim 3, wherein the adhesion layer is at least one selected from the group consisting of titanium, tantalum, iron, cobalt, nickel and chromium. 10. The first orientation control layer is one or more selected from the group consisting of (100) preferentially oriented magnesium oxide, nickel oxide, cobalt oxide, iron oxide and titanium oxide having a NaCl type crystal structure. Item 2. The piezoelectric element according to Item 1. 11. The first orientation control layer is one or more selected from the group consisting of (100) preferentially oriented magnesium oxide, nickel oxide, cobalt oxide, iron oxide and titanium oxide having a NaCl type crystal structure. The ink jet head according to claim 3 or 5. 12. The lead orientation titanate in which the second orientation control layer is preferentially oriented to (001) or (100) having a perovskite type crystal structure, magnesium, calcium, strontium, barium, lanthanum, niobium, manganese, zinc, aluminum. More than 0 over 25 selected from the group of 25
The amount of lead added is 5 mol% or less, and the lead amount is more than 5 and more than 30 mol% in excess as compared with the stoichiometric composition.
The piezoelectric element according to 1. 13. A lead orientation titanate having a (001) or (100) preferential orientation in a perovskite type crystal structure as a second orientation control layer, and magnesium, calcium, strontium, barium, lanthanum, niobium, manganese, zinc, aluminum. Or more than 0 and 25 mol% or less selected from the group of, and the amount of lead is more than 5 and 30 mol% or more in excess as compared with the stoichiometric composition. The inkjet head according to claim 5. 14. The piezoelectric layer is (001) or (10).
The piezoelectric element according to claim 1, which is lead zirconate titanate having a perovskite type crystal structure preferentially oriented in 0). 15. The piezoelectric layer is (001) or (10).
The inkjet head according to claim 3 or 5, which is lead zirconate titanate having a perovskite type crystal structure preferentially oriented in 0).