CN108110134B - Preparation method of multi-orientation oxide piezoelectric film and piezoelectric film - Google Patents
Preparation method of multi-orientation oxide piezoelectric film and piezoelectric film Download PDFInfo
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- CN108110134B CN108110134B CN201711442075.5A CN201711442075A CN108110134B CN 108110134 B CN108110134 B CN 108110134B CN 201711442075 A CN201711442075 A CN 201711442075A CN 108110134 B CN108110134 B CN 108110134B
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- 229910052759 nickel Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
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- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
- C04B35/491—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
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Abstract
The invention discloses a preparation method of a multi-orientation oxide piezoelectric film and the piezoelectric film, wherein the method comprises the steps of spin-coating a sol-gel solution of the prepared oxide on a substrate, then carrying out heating treatment at 90-330 ℃ to form an amorphous solid layer on the coating, coating photoresist on the surface of the amorphous solid layer, carrying out patterning treatment, then putting a structural material into plasma treatment equipment for surface treatment, removing the photoresist, and finally carrying out high-temperature treatment at 600-750 ℃ on the amorphous solid layer of the oxide after the surface treatment to crystallize the amorphous solid layer of the oxide to obtain a finished piezoelectric film; the method is easy to realize, and the prepared piezoelectric film has good stability and high integration level.
Description
Technical Field
The invention relates to the technical field of piezoelectric materials and preparation thereof, in particular to a preparation method of a multi-orientation oxide piezoelectric film and the piezoelectric film.
Background
Lead zirconate titanate (PZT) thin film materials having a perovskite crystal structure are widely used as a piezoelectric material in the fields of sensors, micro-actuators, memories, and the like.
PZT with different crystal orientations has different characteristics and different suitable application fields. For example, (111) oriented PZT has a large remanent polarization Pr, suitable for ferroelectric memory (FRAM) fabrication; the (100) -oriented PZT has a large dielectric constant and is suitable for the fabrication of Dynamic Random Access Memory (DRAM).
When FRAM and DRAM are required to be integrated together as the integration degree of electronic devices increases, the FRAM and DRAM are separately manufactured on different wafers and then integrated together by a conventional manufacturing method, which is complicated in process and results in low system integration.
Japanese laid-open patent publication 2015-146389 discloses a method of subjecting different regions to different heat treatment processes using a local heating method, thereby realizing piezoelectric thin films having different crystal orientations on the same substrate; however, because the crystallization temperature of the oxide piezoelectric thin film material is relatively high, the local part is heated to the crystallizable temperature according to the heat conduction principle, and the manufacture of peripheral devices is not influenced, the devices must be kept above a certain distance, which inevitably reduces the integration level of the devices; in addition, local heating may cause uneven stress distribution within the substrate, thereby compromising the stability of various devices.
It is seen that improvements and enhancements to the prior art are needed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a multi-orientation oxide piezoelectric film and the piezoelectric film, and aims to overcome the defect that piezoelectric films with different orientations are prepared on one substrate in the prior art and realize the preparation of the multi-orientation piezoelectric film with good stability and high integration degree on one substrate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a multi-orientation oxide piezoelectric film comprises the following steps:
A. forming an amorphous solid layer of the oxide on a substrate;
B. forming a patterned mask on the surface of the amorphous solid layer of the oxide formed in the step A, partially covering the surface of the amorphous solid layer, then carrying out plasma surface treatment on the material, and removing the patterned mask on the surface of the amorphous solid layer after the surface treatment is finished;
C. and C, heating the amorphous solid layer of the oxide treated in the step B to obtain the multi-orientation crystallized oxide piezoelectric film.
In the method for manufacturing a multi-orientation oxide piezoelectric thin film, the main crystal orientation of the piezoelectric thin film in the uncovered area in the step B is (111), and the strength of the 111) crystal orientation of the piezoelectric thin film in the uncovered area accounts for 50% or more of the total of the strengths of the various crystal orientations.
In the preparation method of the multi-orientation oxide piezoelectric film, the plasma surface treatment in the step B is carried out under vacuum or atmospheric conditions.
In the preparation method of the multi-orientation oxide piezoelectric film, the crystal thickness of the piezoelectric film is 20-200 nm.
In the preparation method of the multi-orientation oxide piezoelectric film, the preparation method further comprises the following steps: and D, taking the piezoelectric film processed in the step C as a substrate, and increasing the film thickness of the piezoelectric film through epitaxial deposition, wherein the crystal orientation distribution in the thickened piezoelectric film is the same as that of the oxide piezoelectric film obtained in the step C.
In the method for manufacturing the multi-orientation oxide piezoelectric film, the oxide piezoelectric film takes more than two of Pb, Zr, Ti, Ba, Bi, Fe, Sn and Sr as main components.
A multi-orientation piezoelectric film is an oxide piezoelectric film which takes lead, zirconium and titanium as main components and comprises at least one of lanthanum, niobium, manganese, iron, calcium, cadmium, strontium and germanium.
In the multi-orientation piezoelectric film, the base material of the piezoelectric film comprises one of silicon chip, gallium arsenide, gallium nitride, iron, copper, nickel, aluminum, titanium, magnesium oxide, aluminum oxide and polyimide.
Has the advantages that:
the invention provides a preparation method of a multi-orientation oxide piezoelectric film and the piezoelectric film, wherein the method comprises the steps of coating photoresist on the surface of a film intermediate body heated at a low temperature for graphical processing, and then carrying out plasma processing and high-temperature processing, so that crystal areas with different orientations can be obtained after the same piezoelectric film is processed at the same temperature; the formed piezoelectric film has the advantages of no phenomenon of uneven stress distribution, good stability and high integration level.
Drawings
Fig. 1 is a flow chart of a method for preparing the multi-orientation oxide piezoelectric film provided by the invention.
FIG. 2 is a flow chart of a method for increasing the film thickness of the multi-orientation oxide piezoelectric thin film.
FIG. 3 is an XRD pattern of the plasma treated area of the multi-oriented lead zirconate titanate piezoelectric film.
FIG. 4 is an XRD pattern of the non-plasma treated region of the multi-oriented lead zirconate titanate piezoelectric film.
Detailed Description
The present invention provides a method for preparing a multi-orientation oxide piezoelectric film and a piezoelectric film, and in order to make the purpose, technical scheme and effect of the present invention clearer and clearer, the present invention is further described in detail below by referring to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the present invention provides a method for preparing a multi-oriented oxide piezoelectric film, comprising the following steps:
A. an amorphous solid layer is formed on a substrate. In this embodiment, a sol-gel solution as the precursor of the oxide piezoelectric thin film is spin-coated on a substrate by a spin coating method; heating the coating at 80-350 ℃ to form an amorphous solid layer on the coating; the heating process can substantially remove the main solvent and partially remove the organic matter from the coating, so that the coating forms an amorphous solid layer;
B. and C, forming a patterned covering on the surface of the amorphous solid layer formed after heating in the step A. In the example, the patterned covering is formed by coating photoresist on the surface of the amorphous solid layer and carrying out patterning treatment, and the treated material is put into plasma treatment equipment for plasma surface treatment; in the embodiment, the amorphous solid layer is subjected to plasma surface treatment for 90-110W for 8-20 s; and removing the residual photoresist on the surface by using acetone.
C. And C, heating the amorphous solid layer processed in the step B to change the amorphous solid layer into a crystal, and obtaining a finished piezoelectric film. In this embodiment, the amorphous solid layer after the plasma treatment is heated at 400-750 ℃ for 1-10 min to become a crystal.
In the method, the patterned covering is formed by patterning the photoresist, and a metal mask can be used as the patterned covering; under the condition of low precision requirement, the processing method adopting the metal mask is simple, and the process cost and time can be reduced.
After the plasma treatment, the unmasked surface region is subjected to the plasma treatment, the masked surface region is not subjected to the ionization treatment, the regions can form different crystal orientations in the heating process, and the plasma treated region can form crystals with the (111) orientation as the main crystal, in the embodiment, the PZT piezoelectric material is adopted, and the XRD pattern of the PZT piezoelectric material is shown in fig. 3; the regions that were not plasma treated formed predominantly (100) oriented crystals with an XRD pattern as shown in fig. 4; in the X-ray diffraction results of fig. 3 and 4, i (xyz)/∑ i (hkl) >50%, where i (xyz) is a certain specified crystal orientation intensity in the XRD results, and Σ i (hkl) is the sum of the various crystal orientation intensities.
In the method, each area of the piezoelectric film is subjected to the same heating process, and the phenomenon of uneven stress distribution caused by uneven heating can not be generated; the sizes of the crystal areas with different orientations are determined by the photoetching patterns, so that the precision is high and the integration level is good.
Specifically, the crystal thickness of the piezoelectric film is 20-200 nm; the thickness of the piezoelectric film formed by one-step forming by adopting the method is generally not more than 200nm, and the thickness of the piezoelectric film can be increased according to the requirement in practical application.
As shown in fig. 2, further, the piezoelectric thin film processed in step C is used as a substrate, and the thickness of the piezoelectric thin film is increased by epitaxial deposition, and the distribution of crystal orientation in the thickened piezoelectric thin film is the same as that of the oxide piezoelectric thin film obtained in step C; because the crystal orientation of the first piezoelectric film layer can determine the crystal orientation of the subsequent film, the piezoelectric film can not be subjected to plasma surface treatment when the thickness of the piezoelectric film is increased; in addition, in order to obtain a piezoelectric thin film having a relatively large thickness, a thick film of a PZT oxide having a (111) crystal orientation can be obtained by a physical deposition method such as magnetron sputtering on a substrate of a crystalline thin film of a PZT oxide after plasma treatment.
Specifically, the PZT sol-gel solution is a mixed solution with lead acetate, zirconium n-propoxide and n-butyl titanate as raw materials and dimethoxyethanol as a common solvent, wherein the concentration of components forming PZT solid is 0.1-1.2M/L; lead acetate, zirconium propanol and titanium isopropoxide can also be used as raw materials for the PZT sol-gel solution, and carboxylic acid glacial acetic acid is used as a solvent; lead acetate, 1-butanol zirconium salt and tetraisopropyl titanate can also be used as raw materials, and n-butanol is used as a solvent.
Preferably, the concentration of the lead zirconate titanate in the sol-gel of the lead zirconate titanate is 0.1 to 0.5 mol/L.
Preferably, the substrate is a substrate which takes a silicon wafer as a base and is sequentially provided with a silicon dioxide layer, a titanium layer and a platinum layer; the invention uses SiO2The structure between the substrate Si and the lower metal motor Pt is/Ti, and SiN, TiOx and Al can be selected2O3One or a combination of MgO, SiNO, or the like as a structure between the base and the lower electrode; the method of the present invention is also applicable to Ir, Rh, Ru, Pd, Ti, etc. as the lower metal electrode.
Preferably, the thickness of the silicon chip in the substrate is 600-700 mu m, the thickness of the silicon dioxide layer is 400-600 nm, the thickness of the titanium layer is 15-25nm, and the thickness of the platinum layer is 80-120 nm; more preferably, the silicon wafer has a thickness of 650 μm, the silicon dioxide layer has a thickness of 500nm, the titanium layer has a thickness of 20nm, and the platinum layer has a thickness of 100 nm; the thickness of each layer of material of the substrate is kept, so that the piezoelectric film has good conductivity, and the stability meeting the use requirement is achieved.
Specifically, the structural material in the step C is subjected to surface treatment in an atmospheric plasma treatment device under vacuum or atmospheric conditions; in this embodiment, the sample is placed in the plasma apparatus, and the sample and the apparatus are in a relatively static state, but the sample and the apparatus may also be in a relatively moving state, for example, a strip plasma generating device is adopted, so that the sample passes through the surface of the sample at a certain speed to process the surface of the sample, and the processing effect can be controlled by adjusting the speed, the strip width, the generating power, the distance between the sample and the device, and the like. The atmospheric plasma treatment method is preferably adopted in the embodiment, and in practical application, the treatment method can also be carried out under vacuum conditions, such as a low vacuum environment of 3 mTorr.
A multi-orientation piezoelectric film is an oxide piezoelectric film which takes lead, zirconium and titanium as main components and comprises at least one of lanthanum, niobium, manganese, iron, calcium, cadmium, strontium and germanium; the piezoelectric thin film in this embodiment preferably contains lead, zirconium, and titanium as main components, and at least one of lanthanum, niobium, manganese, iron, calcium, cadmium, strontium, and germanium as an auxiliary component; the same applies to oxide piezoelectric materials containing elements such as Ba, Bi, Zr, Ti, Fe, Mg, Na, and K, such as BaTiO3 and BiFeO 3.
Further, the base material of the piezoelectric film comprises one of a silicon wafer, gallium arsenide, gallium nitride, iron, copper, nickel, aluminum, titanium, magnesium oxide, aluminum oxide and polyimide; in this embodiment, a silicon wafer is preferably used as a base material, a platinum electrode is used in cooperation, and silicon dioxide and titanium are used as a connecting material of the base material and the electrode, so that a piezoelectric film substrate which is stable, good in conductivity and strong in oxidation resistance is obtained.
The following examples further illustrate the present application using a method of making a lead zirconate titanate piezoelectric film, which is equally applicable to the various materials mentioned above within the scope of the method described.
Example 1
The preparation method of the multi-orientation lead zirconate titanate piezoelectric film comprises the following steps:
taking lead acetate, zirconium n-propoxide and n-butyl titanate as raw materials, taking dimethoxy ethanol as a common solvent, uniformly mixing to prepare a lead zirconate titanate sol-gel solution, wherein the concentration of components forming PZT solid is 0.3M/L, and spin-coating the sol-gel solution on a substrate by using a spin-coating method; the substrate is formed by sequentially forming silicon dioxide, titanium and platinum layers on a silicon wafer, wherein the thickness of the silicon wafer is 650 microns, the thickness of the silicon dioxide is 500nm, the thickness of the Ti is 20nm, and the thickness of the Pt is 100 nm; then heating the sol-gel coating at 125 ℃ for 300s to form an amorphous lead zirconate titanate solid layer; and then coating photoresist on the surface of the formed lead zirconate titanate amorphous solid layer, carrying out patterning treatment, putting the treated structural material into atmospheric plasma treatment equipment, carrying out 100W and 20s surface treatment on the lead zirconate titanate amorphous solid layer, removing the residual photoresist on the surface by using acetone, and carrying out heat treatment on the treated lead zirconate titanate amorphous solid layer at the temperature of 600 ℃ for 5min to obtain the multi-orientation lead zirconate titanate piezoelectric film.
Example 2
The preparation method of the multi-orientation lead zirconate titanate piezoelectric film comprises the following steps:
taking lead acetate, zirconium propanol and titanium isopropoxide as raw materials, taking carboxylic acid glacial acetic acid as a common solvent, uniformly mixing to prepare a lead zirconate titanate sol-gel solution, wherein the concentration of a component forming PZT solid is 0.1M/L, and spin-coating the sol-gel solution on a substrate by using a spin-coating method; the substrate is formed by sequentially forming silicon dioxide, titanium and platinum layers on a silicon wafer, wherein the thickness of the silicon wafer is 600 microns, the thickness of the silicon dioxide is 600nm, the thickness of the Ti is 15nm, and the thickness of the Pt is 120 nm; then heating the sol-gel coating at 180 ℃ for 50s to form an amorphous lead zirconate titanate solid layer; covering and fixing the patterned metal mask plate on the surface of the amorphous lead zirconate titanate solid layer, placing the amorphous lead zirconate titanate solid layer into atmospheric plasma processing equipment, carrying out surface treatment on the amorphous lead zirconate titanate solid layer for 90W and 15s, then removing the metal mask plate, and carrying out heat treatment on the treated amorphous lead zirconate titanate solid layer at the temperature of 400 ℃ for 10min to obtain the multi-orientation lead zirconate titanate piezoelectric film.
Example 3
The preparation method of the multi-orientation lead zirconate titanate piezoelectric film comprises the following steps:
taking lead acetate, 1-butanol zirconium salt and tetraisopropyl titanate as raw materials, taking n-butanol as a common solvent, uniformly mixing to prepare a lead zirconate titanate sol-gel solution, wherein the concentration of a component forming PZT solid is 0.2M/L, and spin-coating the sol-gel solution on a substrate by using a spin-coating method; the substrate is formed by sequentially forming silicon dioxide, titanium and platinum layers on a silicon wafer, wherein the thickness of the silicon wafer is 700 mu m, the thickness of the silicon dioxide is 400nm, the thickness of the Ti is 25nm, and the thickness of the Pt is 80 nm; then heating the sol-gel coating at 220 ℃ for 200s to form an amorphous lead zirconate titanate solid layer; and then coating photoresist on the surface of the formed lead zirconate titanate amorphous solid layer, carrying out patterning treatment, putting the treated structural material into atmospheric plasma treatment equipment, carrying out 95W and 13s surface treatment on the lead zirconate titanate amorphous solid layer, removing residual photoresist on the surface by using acetone, and carrying out heat treatment on the treated lead zirconate titanate amorphous solid layer at the temperature of 750 ℃ for 1min to obtain the multi-orientation lead zirconate titanate piezoelectric film.
Example 4
The preparation method of the multi-orientation lead zirconate titanate piezoelectric film comprises the following steps:
taking lead acetate, zirconium n-propoxide and n-butyl titanate as raw materials, taking dimethoxy ethanol as a common solvent, uniformly mixing to prepare a lead zirconate titanate sol-gel solution, wherein the concentration of components forming PZT solid is 0.5M/L, and spin-coating the sol-gel solution on a substrate by using a spin-coating method; the substrate is formed by sequentially forming silicon dioxide, titanium and platinum layers on a silicon wafer, wherein the thickness of the silicon wafer is 630 mu m, the thickness of the silicon dioxide is 450nm, the thickness of the Ti is 18nm, and the thickness of the Pt is 90 nm; then heating the sol-gel coating at 270 ℃ for 100s to form an amorphous lead zirconate titanate solid layer; and then coating photoresist on the surface of the formed lead zirconate titanate amorphous solid layer, carrying out patterning treatment, putting the treated structural material into atmospheric plasma treatment equipment, carrying out 105W and 11s surface treatment on the lead zirconate titanate amorphous solid layer, removing residual photoresist on the surface by using acetone, and carrying out heat treatment on the treated lead zirconate titanate amorphous solid layer at the temperature of 700 ℃ for 3min to obtain the multi-orientation lead zirconate titanate piezoelectric film.
Example 5
The preparation method of the multi-orientation lead zirconate titanate piezoelectric film comprises the following steps:
taking lead acetate, zirconium n-propoxide and n-butyl titanate as raw materials, taking dimethoxy ethanol as a common solvent, uniformly mixing to prepare a lead zirconate titanate sol-gel solution, wherein the concentration of components forming PZT solid is 0.4M/L, and spin-coating the sol-gel solution on a substrate by using a spin-coating method; the substrate is formed by sequentially forming silicon dioxide, titanium and platinum layers on a silicon wafer, wherein the thickness of the silicon wafer is 670 mu m, the thickness of the silicon dioxide is 550nm, the thickness of the Ti is 22nm, and the thickness of the Pt is 110 nm; then heating the sol-gel coating at 330 ℃ for 10s to form an amorphous lead zirconate titanate solid layer; and then coating photoresist on the surface of the formed lead zirconate titanate amorphous solid layer, carrying out patterning treatment, putting the treated structural material into atmospheric plasma treatment equipment, carrying out 110W and 8s surface treatment on the lead zirconate titanate amorphous solid layer, removing residual photoresist on the surface by using acetone, and carrying out heat treatment on the treated lead zirconate titanate amorphous solid layer at the temperature of 500 ℃ for 8min to obtain the multi-orientation lead zirconate titanate piezoelectric film.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.
Claims (8)
1. A preparation method of a multi-orientation oxide piezoelectric film is characterized by comprising the following steps:
A. forming an amorphous solid layer of the oxide on a substrate;
B. forming a patterned mask on the surface of the amorphous solid layer of the oxide formed in the step A, partially covering the surface of the amorphous solid layer, then carrying out plasma surface treatment on the amorphous solid layer after the covering treatment, and removing the patterned mask on the surface of the amorphous solid layer after the surface treatment is finished;
C. and C, heating the amorphous solid layer of the oxide treated in the step B to obtain the multi-orientation crystallized oxide piezoelectric film.
2. The method according to claim 1, wherein the main crystal orientation of the piezoelectric thin film in the uncovered region in the step B is (111), and the intensity of the (111) crystal orientation of the piezoelectric thin film in the uncovered region accounts for 50% or more of the total intensity of the crystal orientations.
3. The method for producing a multi-oriented oxide piezoelectric thin film according to claim 1, wherein the plasma surface treatment in the step B is performed under vacuum or atmospheric conditions.
4. The method for producing a multi-oriented oxide piezoelectric thin film according to claim 1, wherein the crystal thickness of the piezoelectric thin film is 20 to 200 nm.
5. The method of producing a multi-oriented oxide piezoelectric film according to claim 1, further comprising: and D, taking the piezoelectric film processed in the step C as a substrate, and increasing the film thickness of the piezoelectric film through epitaxial deposition, wherein the crystal orientation distribution in the thickened piezoelectric film is the same as that of the oxide piezoelectric film obtained in the step C.
6. The method of manufacturing an oxide piezoelectric thin film according to claim 1, wherein two or more of Pb, Zr, Ti, Ba, Bi, Fe, Sn, Sr are main components of the oxide piezoelectric thin film.
7. A multi-oriented piezoelectric film prepared according to any one of claims 1 to 6, wherein the piezoelectric film is an oxide piezoelectric film containing lead, zirconium and titanium as main components and including at least one of lanthanum, niobium, manganese, iron, calcium, cadmium, strontium and germanium.
8. The multi-orientation piezoelectric film according to claim 7, wherein the base material of the piezoelectric film comprises one of silicon wafer, gallium arsenide, gallium nitride, iron, copper, nickel, aluminum, titanium, magnesium oxide, aluminum oxide, and polyimide.
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| JPH0195575A (en) * | 1987-10-07 | 1989-04-13 | Semiconductor Energy Lab Co Ltd | Formation of oxide superconducting material |
| CN1564876A (en) * | 2001-10-02 | 2005-01-12 | 株式会社先端技术培育*** | Thin metal oxide film and process for producing the same |
| CN103833372A (en) * | 2012-11-20 | 2014-06-04 | 三菱综合材料株式会社 | Method for producing ferroelectric thin film and manufacturing method for composite electric component |
| JP2015146389A (en) * | 2014-02-03 | 2015-08-13 | 株式会社リコー | Oxide crystal film and manufacturing method of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0195575A (en) * | 1987-10-07 | 1989-04-13 | Semiconductor Energy Lab Co Ltd | Formation of oxide superconducting material |
| CN1564876A (en) * | 2001-10-02 | 2005-01-12 | 株式会社先端技术培育*** | Thin metal oxide film and process for producing the same |
| CN103833372A (en) * | 2012-11-20 | 2014-06-04 | 三菱综合材料株式会社 | Method for producing ferroelectric thin film and manufacturing method for composite electric component |
| JP2015146389A (en) * | 2014-02-03 | 2015-08-13 | 株式会社リコー | Oxide crystal film and manufacturing method of the same |
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