WO2011121863A1 - Élément à couche mince piézoélectrique, procédé de production de celui-ci et dispositif à couche mince piézoélectrique - Google Patents

Élément à couche mince piézoélectrique, procédé de production de celui-ci et dispositif à couche mince piézoélectrique Download PDF

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WO2011121863A1
WO2011121863A1 PCT/JP2010/073006 JP2010073006W WO2011121863A1 WO 2011121863 A1 WO2011121863 A1 WO 2011121863A1 JP 2010073006 W JP2010073006 W JP 2010073006W WO 2011121863 A1 WO2011121863 A1 WO 2011121863A1
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thin film
piezoelectric thin
component
substrate
piezoelectric
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PCT/JP2010/073006
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English (en)
Japanese (ja)
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和史 末永
憲治 柴田
秀樹 佐藤
明 野本
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日立電線株式会社
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Priority claimed from JP2010075161A external-priority patent/JP5035378B2/ja
Application filed by 日立電線株式会社 filed Critical 日立電線株式会社
Priority to DE112010005432.0T priority Critical patent/DE112010005432B9/de
Priority to CN201080065779.5A priority patent/CN102823007B/zh
Publication of WO2011121863A1 publication Critical patent/WO2011121863A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/088—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or Pb and B representing a refractory or rare earth metal
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
    • C30B23/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • C30B29/22—Complex oxides
    • C30B29/30—Niobates; Vanadates; Tantalates
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/02—Details
    • H03H9/02007—Details of bulk acoustic wave devices
    • H03H9/02015—Characteristics of piezoelectric layers, e.g. cutting angles
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/02—Details
    • H03H9/02007—Details of bulk acoustic wave devices
    • H03H9/02086—Means for compensation or elimination of undesirable effects
    • H03H9/02094—Means for compensation or elimination of undesirable effects of adherence
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/02—Details
    • H03H9/02535—Details of surface acoustic wave devices
    • H03H9/02543—Characteristics of substrate, e.g. cutting angles
    • H03H9/02574—Characteristics of substrate, e.g. cutting angles of combined substrates, multilayered substrates, piezoelectrical layers on not-piezoelectrical substrate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/07—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base
    • H10N30/074—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing
    • H10N30/076—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by depositing piezoelectric or electrostrictive layers, e.g. aerosol or screen printing by vapour phase deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
    • H—ELECTRICITY
    • H03—ELECTRONIC CIRCUITRY
    • H03H—IMPEDANCE NETWORKS, e.g. RESONANT CIRCUITS; RESONATORS
    • H03H9/00—Networks comprising electromechanical or electro-acoustic devices; Electromechanical resonators
    • H03H9/15—Constructional features of resonators consisting of piezoelectric or electrostrictive material
    • H03H9/17—Constructional features of resonators consisting of piezoelectric or electrostrictive material having a single resonator
    • H03H9/171—Constructional features of resonators consisting of piezoelectric or electrostrictive material having a single resonator implemented with thin-film techniques, i.e. of the film bulk acoustic resonator [FBAR] type

Definitions

  • the present invention relates to a piezoelectric thin film element and a piezoelectric thin film device using a lithium potassium sodium niobate film or the like.
  • Piezoelectric materials are processed into various piezoelectric elements according to various purposes. In particular, they are widely used as functional electronic parts such as actuators that generate deformation by applying voltage and conversely sensors that generate voltage from deformation of the element. ing.
  • a piezoelectric material used for actuators and sensors a lead-based dielectric material having a large piezoelectric characteristic, particularly a Pb (Zr 1-x Ti x ) O 3 -based perovskite ferroelectric material called PZT is used. And is usually formed by sintering oxides composed of individual elements.
  • LKNN lithium potassium sodium niobate
  • Patent Document 1 a PZT thin film formed by an RF sputtering method has been put into practical use as a head actuator for a high-definition high-speed inkjet printer or a small and low-priced gyro sensor (for example, see Patent Document 1 and Non-Patent Document 1).
  • a piezoelectric thin film element using a LKNN piezoelectric thin film that does not use lead has been proposed (see, for example, Patent Document 2).
  • Patent Document 2 In the prior art (for example, Patent Document 2), detailed studies have not been made on the orientation of the piezoelectric thin film, and it has not been possible to stably realize a piezoelectric thin film element exhibiting a high piezoelectric constant.
  • An object of the present invention is to provide a piezoelectric thin film element and a piezoelectric thin film device with improved piezoelectric characteristics.
  • the piezoelectric thin film laminate in which the piezoelectric thin film represented by 1) and the upper electrode are arranged, the piezoelectric thin film has a pseudo-cubic, tetragonal or orthorhombic crystal structure, or at least one of them coexists.
  • (001) component and (111) component as the components of the oriented crystal axis that are preferentially oriented to a specific axis of two or less of the crystal axes.
  • the volume fraction of the (001) component when the sum of both is 100%, the volume fraction of the (001) component is in the range of 60% to 100%, and the volume fraction of the (111) component is 0% to 40%.
  • a piezoelectric thin film element in the range is provided.
  • the volume fraction of the (001) component is preferably in the range of 70% or more and 100% or less where the crystallinity is high, and the volume fraction of the (111) component is in the range of 0% or more and 30% or less. Is preferred.
  • the piezoelectric thin film is preferably in a state where the (001) component and the (111) component coexist, and the volume fraction of the (111) component is more preferably greater than 1%.
  • the piezoelectric thin film has a texture composed of particles having a columnar structure.
  • a part of the piezoelectric thin film may include an ABO 3 crystal layer, an ABO 3 amorphous layer, or a mixed layer in which ABO 3 crystal and amorphous are mixed.
  • A is one or more elements selected from Li, Na, K, La, Sr, Nd, Ba, and Bi
  • B is Zr, Ti, Mn, Mg, Nb, Sn, Sb, One or more elements selected from Ta and In, and O is oxygen.
  • the piezoelectric thin film may have a strain in a direction parallel to the substrate surface.
  • the strain may have a tensile stress state or a compressive stress state in a direction parallel to the substrate surface.
  • the piezoelectric thin film may be in an unstrained state having no internal stress.
  • the piezoelectric thin film may have a strain that is perpendicular or parallel to the substrate surface or non-uniform in both directions.
  • the lower electrode layer is preferably an electrode layer having a laminated structure including Pt or an alloy containing Pt as a main component, or an electrode layer containing Pt as a main component.
  • the lower electrode layer may be an electrode layer having a stacked structure including a layer of a compound of Ru, Ir, Sn, In or the same oxide or an element contained in the piezoelectric thin film.
  • the upper electrode layer is preferably an electrode layer having a laminated structure including Pt or an alloy containing Pt as a main component or an electrode layer containing Pt as a main component.
  • the upper electrode layer may be an electrode layer of a laminated structure including an electrode layer of a compound of Ru, Ir, Sn, In or the same oxide or an element contained in the piezoelectric thin film.
  • the lower electrode layer is preferably a single layer or a laminated electrode layer preferentially oriented in the direction perpendicular to the substrate surface in terms of crystal orientation.
  • the substrate is selected from Si substrate, MgO substrate, ZnO substrate, SrTiO 3 substrate, SrRuO 3 substrate, glass substrate, quartz glass substrate, GaAs substrate, GaN substrate, sapphire substrate, Ge substrate, and stainless steel substrate. It is good also as a kind of board
  • the substrate is preferably a Si substrate.
  • the piezoelectric thin film laminate in which the piezoelectric thin film represented by The piezoelectric thin film has a pseudo-cubic, tetragonal, or orthorhombic crystal structure, or a state in which at least one of them coexists, and has priority over a specific axis of two or less of those crystal axes.
  • the (001) component and the (111) component which are components of the preferentially oriented crystal axis, are in a coexistence state, and in the ratio of the (001) component and the (111) component, both
  • the total volume of the piezoelectric thin film is such that the volume fraction of the (001) component is in the range of more than 60% and less than 100%, and the volume fraction of the (111) component is in the range of less than 40%.
  • the underlayer may be used LaNiO 3 and NaNbO 3, may be used Pt thin film is preferentially oriented in the (111).
  • a piezoelectric thin film device including the above-described piezoelectric thin film element and a voltage applying unit or a voltage detecting unit.
  • a piezoelectric thin film element and a piezoelectric thin film device having excellent piezoelectric characteristics can be provided.
  • FIG. 4 is a characteristic diagram of the KNN piezoelectric thin film (KNN-1) of Example 1 of the present invention, where (a) is an example of a measurement result by a two-dimensional X-ray detector, and (b) is in the ⁇ axis direction in (110) diffraction. Accordingly, the X-ray reflection profile is derived from (111) and (001) obtained by integration calculation.
  • FIG. 4 is a characteristic diagram of the KNN piezoelectric thin film (KNN-1) of Example 1 of the present invention, where (a) is an example of a measurement result by a two-dimensional X-ray detector, and (b) is in the ⁇ axis direction in (110) diffraction. Accordingly, the X-ray reflection profile is derived from (111) and (001) obtained by integration calculation.
  • FIG. 1 is a measurement result example of wide area reciprocal lattice mapping
  • FIG. 4 is a characteristic diagram of the KNN piezoelectric thin film (KNN-1) of Example
  • Example 4 is a characteristic diagram of the KNN piezoelectric thin film (KNN-2) of Example 1 of the present invention, where (a) is an example of a measurement result by a two-dimensional X-ray detector, and (b) is in the ⁇ -axis direction in (110) diffraction. Accordingly, the X-ray reflection profile is derived from (111) and (001) obtained by integration calculation. It is a characteristic view of Example 1 of this invention, (a) is a stereographic projection figure of a polar figure, (b) is the graph which converted the stereographic projection figure of the polar figure into the orthogonal coordinate.
  • Example 2 is a polar figure of Example 2 of the present invention, where (a) is a model of a (110) polar figure with (001) orientation as a pole, and (b) is a (110) polar figure with (111) orientation as a pole.
  • Model. It is a figure which shows the characteristic of the X-ray-diffraction profile of Example 2 of this invention, Comprising: (a) is the example which performed fitting analysis with respect to the measurement result of the X-ray-diffraction profile shown in FIG.6 and FIG.7, (b). These are examples of analysis results of volume fractions (001) and (111) in consideration of correction coefficients for the integrated intensity obtained by the fitting analysis of FIG.
  • FIG. 10 is a correlation diagram between the volume fraction of the (111) orientation component of the piezoelectric thin film and the variation (%) of the piezoelectric constant in the wafer surface in the substrate (wafer) with the piezoelectric thin film using the piezoelectric thin film of Example 5 of the present invention.
  • It is a schematic block diagram of the piezoelectric thin film device of one Embodiment of this invention. It is a cross-sectional schematic diagram of the filter device using the piezoelectric thin film of this invention.
  • the present inventor has developed a piezoelectric thin film element exhibiting a high piezoelectric constant by quantitatively and precisely controlling crystal orientation that has not been studied in the prior art in a lead-free piezoelectric thin film that is a basic part of the piezoelectric element. And the knowledge that a piezoelectric device can be realized. Unless the crystal orientation of the piezoelectric thin film is managed and controlled, a high piezoelectric constant cannot be obtained, and the crystal orientation varies depending on the film forming location, so that the piezoelectric constant becomes non-uniform in the device.
  • the electrodes, the piezoelectric thin film, and the like, which are constituent materials, are appropriately selected, and the film forming conditions such as the film forming temperature of the piezoelectric thin film are controlled so that the piezoelectric thin film is preferentially oriented.
  • the film forming conditions such as the film forming temperature of the piezoelectric thin film are controlled so that the piezoelectric thin film is preferentially oriented.
  • the piezoelectric thin film element of the present embodiment includes a substrate, an oxide film formed on the surface of the substrate, a lower electrode layer formed on the oxide film, and a piezoelectric thin film formed on the lower electrode layer. , And an upper electrode layer formed thereon.
  • This piezoelectric thin film is an ABO 3 type oxide having a perovskite structure, and as its composition, the A site is one or more selected from Li, Na, K, La, Sr, Nd, Ba, and Bi.
  • the B site is one or more elements selected from Zr, Ti, Mn, Mg, Nb, Sn, Sb, Ta, and In, and O is oxygen.
  • the substrate is selected from Si substrate, MgO substrate, ZnO substrate, SrTiO 3 substrate, SrRuO 3 substrate, glass substrate, quartz glass substrate, GaAs substrate, GaN substrate, sapphire substrate, Ge substrate, stainless steel substrate and the like. Any one kind of board
  • substrate is mentioned.
  • an Si substrate that is inexpensive and has an industrial record is desirable.
  • the oxide film formed on the surface of the substrate examples include a thermal oxide film formed by thermal oxidation and a Si oxide film formed by a CVD (Chemical Vapor Deposition) method.
  • a lower electrode layer such as a Pt electrode may be formed directly on an oxide substrate such as quartz glass (SiO 2 ), MgO, SrTiO 3 , or SrRuO 3 without forming the oxide film.
  • the lower electrode layer is preferably an electrode layer including an electrode layer made of Pt or an alloy containing Pt as a main component, or an electrode layer having a structure in which these layers are stacked. Further, the lower electrode layer is preferably formed to be oriented on the (111) plane, and the adhesion between the substrate and the electrode layer made of Pt or an alloy containing Pt as a main component is close to the substrate. An adhesive layer may be provided to increase the resistance.
  • the Pt thin film oriented in the (111) plane also functions as an underlayer for the piezoelectric thin film.
  • the LKNN thin film may be doped with a predetermined amount of Ta, V, or the like.
  • the piezoelectric thin film is formed using an RF sputtering method, an ion beam sputtering method, a CVD method, or the like. In this embodiment, an RF sputtering method is employed.
  • the piezoelectric characteristics of the LKNN film in the (001) preferential orientation state differ depending on the film formation location or production lot. The reason is that a small change in the (001) orientation of the piezoelectric thin film was not found, and further (110), (111) and (210) orientations including (001) were not analyzed in detail. This is because it is difficult to perform crystal growth by strictly controlling the orientation of each crystal plane.
  • the crystal orientation is generally (001) preferential orientation by a simple X-ray diffraction method known as 2 ⁇ / ⁇ scan, which is generally known. Since the positions other than the diffraction angle axis ( ⁇ ) are fixed, the actual crystal orientation cannot be evaluated.
  • [Crystal orientation of lower electrode layer] (Crystal orientation of Pt thin film) Therefore, first, in order to strictly manage and control the crystal orientation of the LKNN film, in order to stably realize the crystallinity of the Pt thin film of the lower electrode, which is the initial crystal growth surface of the piezoelectric thin film.
  • the film forming gas and the degree of vacuum were optimized.
  • the film forming conditions first, the film forming temperature was studied, and it was found that the film forming range of 100 to 500 ° C. corresponds to the optimum temperature range as the condition for the (111) preferential orientation.
  • Ar gas, a mixed gas of Ar and O 2 , or a gas in which at least one inert gas such as He, Ne, Kr, or N 2 is mixed is used.
  • the surface roughness of the Pt lower electrode can be reduced and controlled to a size of several nanometers.
  • the film thickness of the Pt lower electrode layer is precisely controlled to reduce the surface unevenness of the Pt lower electrode layer, and the polycrystalline Pt lower electrode layer is controlled to have uniform crystal grain size. It was also possible to form.
  • the lower electrode layer is an electrode layer having a single layer structure or a laminated structure preferentially oriented in the direction perpendicular to the substrate surface in terms of crystal orientation.
  • the lower electrode layer may be not only Pt but also an alloy containing Pt as a main component, or Pt or a thin film containing Pt as a main component (Pt thin film).
  • a layer of a compound with Au, Ru, Ir, Sn, In or the same oxide or an element contained in the piezoelectric thin film may be included. Even in these cases, the crystallinity of the lower electrode thin film, which is the base of the LKNN thin film, can be stably realized by optimizing the film forming temperature and film forming gas as in the case of the Pt thin film.
  • the crystal orientation of the piezoelectric thin film changes depending on the manufacturing conditions. Further, the internal stress (strain) of the piezoelectric thin film changes to compressive stress or tensile stress. In some cases, there is no stress, that is, no strain
  • crystals such as Si, MgO, ZnO, SrTiO 3 , SrRuO 3 , glass, quartz glass, GaAs, GaN, sapphire, Ge, and stainless steel, or amorphous or Those composites and the like are desirable.
  • the crystal orientation of the LKNN film is compared in detail. We recommended the selection of a substrate that can strictly control the preferred orientation.
  • the film formation temperature of the LKNN film itself the type of sputtering operation gas, the operation gas pressure, the degree of vacuum, the input power, and the composition.
  • the heat treatment after the film may be achieved by finding and optimizing the production conditions of the piezoelectric thin film having crystal orientation that improves the piezoelectric characteristics. By carefully examining manufacturing conditions, evaluation, and management methods in accordance with each device and in various environments, these conditions are (001) or (111) preferential orientation, or both coexist and give priority.
  • An oriented pseudo cubic LKNN thin film can be formed with good reproducibility.
  • the (001) orientation component and the (111) orientation component are deposited so as to fall within a certain range. Set precisely so that the temperature is always constant.
  • heat radiation by an infrared lamp or heat conduction by heater heating through a heat transfer plate was used to set the temperature within an optimal temperature range for the crystal orientation component ratio.
  • the sputtering structure power, the pressure of the gas introduced into the film forming apparatus and the magnitude of the flow rate are determined to be optimum values, or by selecting an appropriate gas type, Various alignment components including (001) and (111) orientations are strictly controlled, and an effect that a LKNN film exhibiting a high piezoelectric constant can be obtained stably and reproducibly can be expected.
  • sputtering film formation is performed by plasma using a mixed gas of Ar and O 2 , or a gas in which at least one inert gas such as Ar gas, He, Ne, Kr, or N 2 is mixed.
  • LKNN piezoelectric thin film For the formation of the LKNN piezoelectric thin film, a ceramic target of (Na x K y Li z ) NbO 3 0 ⁇ x ⁇ 1.0, 0 ⁇ y ⁇ 1.0, 0 ⁇ z ⁇ 0.2 may be used. Furthermore, the same effect can be expected by changing the density of the sputtering target material according to the above situation. Further, even after film formation, the internal stress of the piezoelectric thin film can be controlled by performing a heat treatment in oxygen, an inert gas, a mixed gas of both, or in the air or in vacuum.
  • the LKNN film thus obtained has a texture composed of crystal grains having a columnar structure. Further, when the lower electrode layer is formed to be oriented in the (111) plane, the piezoelectric thin film layer is preferentially oriented in a predetermined direction with respect to the lower electrode layer.
  • the piezoelectric thin film layer is preferably in a state where at least one of (001) preferentially oriented crystal grains, (110) preferentially oriented crystal grains, and (111) preferentially oriented crystal grains coexist. By realizing such a state of crystal orientation, it is possible to improve piezoelectric characteristics by controlling internal stress.
  • the piezoelectric thin film constituting the piezoelectric thin film element of Example 1 has a pseudo-cubic, tetragonal or orthorhombic crystal structure, or a state in which at least one of these crystal structures coexists.
  • the piezoelectric thin film is preferentially oriented in a specific axis of two or less of these crystal axes.
  • the piezoelectric thin film has a volume fraction of the (001) component of 60 when the sum of the (001) component and the (111) component is 100% as the component of the oriented crystal axis.
  • the volume fraction of the (111) component is in the range of 0 to 40%.
  • the volume fraction of the (001) component of the piezoelectric thin film described above is in the range of 60 to 100%, or the volume fraction of the (111) component is in the range of 0 to 40%. It can be realized by controlling the film forming conditions of the piezoelectric thin film, for example, the film forming temperature. (FIG. 13 of Example 4)
  • the piezoelectric thin film By controlling the component ratio (volume fraction) of the crystal orientation of the piezoelectric thin film, the piezoelectric thin film has a strain in a tensile stress state in a direction parallel to the substrate surface, or in a direction parallel to the substrate surface. It can be made to have a strain in a compressive stress state. Further, by controlling the volume fraction, the piezoelectric thin film can be brought into an unstrained state having no internal stress. In addition, by controlling the volume fraction, the piezoelectric thin film can be made to have a strain that is perpendicular or parallel to the substrate surface or non-uniform in both directions. By controlling the volume fraction of the piezoelectric thin film in this way, the internal stress of the piezoelectric thin film can be controlled, and a piezoelectric thin film having a desired internal stress can be obtained. (FIGS. 13 and 14 of Example 4)
  • piezoelectric thin film device By forming the upper electrode layer 15 on the piezoelectric thin film layer on the substrate with the piezoelectric thin film of the above embodiment, a piezoelectric thin film element exhibiting a high piezoelectric constant can be produced.
  • the piezoelectric thin film devices such as various actuators and sensors can be manufactured by processing the substrate into a thin film or by providing the voltage application unit (voltage detection unit) 16.
  • a filter device using surface acoustic waves can be manufactured.
  • the lower electrode (Pt thin film) mainly functions as a base layer.
  • the upper electrode layer formed on the piezoelectric thin film or the patterned electrode having a predetermined pattern is Pt or an alloy containing Pt as a main component, or an electrode layer containing Pt as a main component, like the lower electrode layer. It is preferable that the electrode layer has a laminated structure including Alternatively, it may be an electrode layer of a laminated structure including an electrode layer of a compound with Ru, Ir, Sn, In or the same oxide or an element contained in the piezoelectric thin film.
  • the present invention has one or more of the following effects.
  • the LKNN piezoelectric thin film has a pseudo-cubic, tetragonal or orthorhombic crystal structure, or a state in which at least one of these crystal structures coexists. And is preferentially oriented to a specific axis of two or less of the crystal axes, and as a component of the oriented crystal axis, the ratio of the (001) component to the (111) component When the sum of the two is 100%, the volume fraction of the (001) component is in the range of 60 to 100%, and the volume fraction of the (111) component is in the range of 0 to 40%. Accordingly, it is possible to prevent the crystal orientation from becoming random and the piezoelectric constant from being lowered due to an increase in internal strain.
  • the piezoelectric thin film, electrode, substrate, and adhesive layer, which are constituent materials, are appropriately selected and the production conditions of the material are optimized.
  • the piezoelectric properties can be improved by precisely measuring the crystal orientation degree of the obtained piezoelectric thin film and quantifying it accurately, and strictly controlling the atomic level structure of the piezoelectric thin film.
  • a high-performance piezoelectric thin film device can be realized, and at the same time, the manufacturing yield of the device can be improved.
  • the (001) preferentially oriented crystal grains and the (111) preferentially oriented crystal grains coexist, thereby causing internal stress.
  • Piezoelectric characteristics can be improved by control.
  • the mechanical strength of the piezoelectric thin film is improved, and a piezoelectric thin film having excellent processability can be provided.
  • a Pt electrode, a Pt alloy, or Ru, Ir, or the like having controlled crystal orientation is used as the lower electrode of the piezoelectric thin film element.
  • a compound of oxide or Pt and an element contained in the piezoelectric thin film it is possible to control the crystal orientation of the piezoelectric thin film formed on the upper portion with high accuracy and to improve the environmental resistance as an element.
  • the substrate is not only Si but also MgO substrate, ZnO substrate, SrTiO 3 substrate, SrRuO 3 substrate, glass substrate, quartz glass substrate,
  • MgO substrate MgO substrate
  • ZnO substrate ZnO substrate
  • SrTiO 3 substrate SrRuO 3 substrate
  • glass substrate quartz glass substrate
  • a piezoelectric thin film having good piezoelectric characteristics can be realized according to the present embodiment, and the piezoelectric thin film element having high yield and high quality can be realized. Can be obtained.
  • the piezoelectric thin film element includes a thin film that does not use lead, the environmental load is reduced by mounting the piezoelectric thin film element.
  • a small system device such as a high-performance small motor, sensor, and actuator, for example, a micro-electro-mechanical system (MEMS) or the like can be realized.
  • MEMS micro-electro-mechanical system
  • a filter device having good filter characteristics using surface acoustic waves can be realized.
  • the lead-free piezoelectric thin film corresponding to the basic portion of the piezoelectric element since crystal orientation is controlled and managed quantitatively and precisely, a lead-free device having a long life and a high piezoelectric constant can be stably produced. Further, since the crystal orientation in the element does not vary depending on the site, the piezoelectric constant of the piezoelectric thin film formed on the substrate becomes uniform, and the manufacturing yield is improved.
  • the piezoelectric properties of piezoelectric thin film elements and piezoelectric thin film devices can be improved and stabilized by stably controlling the crystal orientation of these piezoelectric thin films. Therefore, it becomes possible to provide a high-performance micro device at a low cost.
  • a piezoelectric thin film element having excellent piezoelectric characteristics in which an atomic level structure of a piezoelectric thin film such as LKNN is controlled with high accuracy. And a piezoelectric thin film device can be obtained.
  • FIG. 1 is a sectional view showing an outline of a substrate with a piezoelectric thin film.
  • an adhesive layer 2 is formed on a Si substrate 1 having an oxide film, and a lower electrode layer 3 and a KNN piezoelectric thin film layer 4 having a perovskite structure are sequentially formed on the adhesive layer 2. An element was produced.
  • the piezoelectric thin film layer 4 is a pseudo cubic crystal, a tetragonal crystal or an orthorhombic crystal as a crystal system, and at least a part thereof may be a composition of ABO 3 crystal or amorphous or a mixture of both.
  • A is one or more elements selected from Li, Na, K, La, Sr, Nd, Ba, and Bi
  • B is Zr, Ti, Mn, Mg, Nb, Sn, Sb.
  • One or more elements selected from Ta, In, and O is oxygen.
  • a Pt thin film or an Au thin film may be used.
  • a Pt alloy, an alloy containing Ir, or Ru may be used, or a stacked structure thereof may be used.
  • a thermal oxide film was formed on the surface of a 4-inch circular Si substrate 1, and a lower electrode layer 3 was formed thereon.
  • the thermal oxide film was provided with a thickness of 150 nm.
  • the lower electrode layer 3 is composed of a Ti film having a thickness of 2 nm formed as the adhesive layer 2 and a Pt thin film having a thickness of 100 nm formed as an electrode layer on the Ti film.
  • a sputtering method was used to form this electrode layer.
  • a metal target is used as the sputtering target 12 shown in FIG. 19, the sputtering input power during film formation is 100 W, and 100% Ar gas is used as the sputtering gas.
  • the substrate temperature was set to 350 ° C. to form a thin film made of polycrystalline thin film Pt.
  • a KNN thin film was formed as the piezoelectric thin film layer 4 on the lower electrode layer.
  • the KNN thin film was also formed by sputtering.
  • the KNN thin film was formed by sputtering film formation using a substrate temperature of 700 ° C. to 730 ° C. and plasma with a 5: 5 mixed gas of Ar and O 2 .
  • Film formation was performed until the film thickness reached 3 ⁇ m.
  • heat treatment was performed in the air after film formation. Note that a self-revolving furnace was used for sputtering, and the distance between the substrate and the target during sputtering (hereinafter, the distance between TSs) was 50 mm.
  • the structure was composed of a columnar structure.
  • the Pt thin film of Example 1 formed by heating the substrate was a substrate as shown in the X-ray diffraction pattern (2 ⁇ / ⁇ scan measurement) of FIG. It was found that a thin film oriented in the (111) plane was formed in a direction perpendicular to the surface.
  • the produced KNN thin film was found to be a polycrystalline thin film having a pseudo cubic perovskite crystal structure shown in FIG. did. Further, as can be seen from the X-ray diffraction pattern of FIG. 2, since only the diffraction peaks of (001), (002), and (003) can be confirmed, the KNN piezoelectric thin film is preferentially oriented to (001). I was able to expect.
  • Example 1 for a KNN piezoelectric thin film whose crystal orientation was intentionally controlled, a pole figure was measured in order to evaluate the orientation of the KNN thin film in detail and precisely.
  • Pole figure is a stereo projection of the spread of poles on a specific lattice plane, and is an analysis method that can evaluate the state of orientation of a polycrystal in detail.
  • Citation Example 1 Science Electric Co., Ltd., X-ray diffraction manual, revised 4th edition, (Science Electric Co., Ltd. 1986)
  • Citation Example 2 written by Karity Tsuji, new edition X-ray diffraction theory, ( See Agne, 1980)).
  • priority orientation can be clarified by the above polar figure measurement.
  • a substance including a thin film
  • each crystal particle is “preferentially oriented” in a certain direction
  • a local distribution of X-ray reflection such as spot-like or ring-shaped Debye ring, can always be found.
  • Example 1 In the structural analysis of the piezoelectric thin film element of Example 1, “D8DDISCOVER with Hi Star” manufactured by Bruker AXS, which is a high-power X-ray diffractometer equipped with a two-dimensional detector having a large X-ray detection area, VANTEC2000 (registered trademark) "was used. In this example, a pole figure having (110) as a pole of the KNN thin film was measured.
  • FIG. 4 shows a conceptual diagram of the measurement arrangement of the pole figure performed in this example. This is a method called the Schultz reflection method.
  • the X-ray detector used is often the 0th order, it is necessary to simultaneously scan the ⁇ ( ⁇ ) axis and the ⁇ ( ⁇ ) axis shown in FIG. It took a long time.
  • a large-area two-dimensional detector D8 DISCOVER with Hi Star, VANTEC2000 (registered trademark)
  • VANTEC2000 registered trademark
  • FIG. 5 shows the analysis result of the wide area reciprocal lattice point map in the piezoelectric thin film of Example 1.
  • the horizontal axis is the X-ray diffraction angle of 2 ⁇ / ⁇
  • the vertical axis is the ⁇ axis perpendicular to the diffraction angle axis (2 ⁇ / ⁇ ) shown in FIG.
  • the bar graph on the right represents the intensity of X-ray reflection in black and white gradation, and is a measure of the X-ray reflection intensity on the map.
  • FIG. 5A shows the actual analysis result of KNN
  • FIG. 5B shows the result of reciprocal lattice point simulation in the (001) / (111) oriented KNN thin film for comparison.
  • ⁇ represents diffracted X-rays from (001) -oriented KNN
  • ⁇ represents diffracted X-rays from (111) -oriented KNN.
  • the simulation program used at this time is SMAP / for Cross Sectional XRD-RSM provided by Bruker AXS.
  • FIG. 6 shows the actual X-ray diffraction measurement result of the piezoelectric thin film in Example 1.
  • FIG. 6A shows a diffracted X-ray from the sample KNN-1 recorded by an X-ray two-dimensional detector.
  • a black spot-like pattern having an arcuate shape is diffracted X-ray. It corresponds to the reflection of.
  • the direction in which the arc is drawn corresponds to the ⁇ -axis direction, and the arrow in the normal direction relative to the arc corresponds to the direction of 2 ⁇ / ⁇ .
  • the diffracted X-rays at 2 ⁇ / ⁇ of about 32 °, it can be seen that two X-ray reflection spots overlap.
  • the inversion on the left side is X-ray reflection due to the (111) orientation of KNN
  • the spot on the right side is X-ray reflection due to the KNN (001) orientation.
  • the intensity of the reflected X-ray spectrum caused by the (001) and (111) orientations can be expressed by setting the integrated range in a sector shape.
  • the integration in the 2 ⁇ / ⁇ axis direction was performed in the range of 31.4 ° to 32.4 ° in the range of ⁇ axis from 17.5 ° to 72.5 °.
  • FIG. 6 (b) shows the result.
  • the horizontal axis is the ⁇ axis
  • the vertical axis is the X-ray diffraction intensity obtained by the above integration conditions.
  • the respective intensities of the reflected X-ray spectra due to the (001) and (111) orientations can be found.
  • FIG. 7 shows the actual X-ray diffraction measurement result of the piezoelectric thin film in another sample KNN-2 thin film in Example 1. Similar to FIG. 6, it can be seen that two orientation-derived spectra are found. However, the magnitudes of the X-ray intensity due to the (001) orientation and the X-ray intensity due to the (111) orientation are different from the results shown in FIG. 6, and in particular, the intensity due to the (001) orientation and the (111) orientation. It can be seen that a clear difference is found in the ratio.
  • the profile of FIG. 6B and FIG. 7B was calculated using a fitting function, and the X-ray reflection intensity and its ratio were quantified.
  • FIG. 8 shows a measurement result example of the (110) polar figure of the piezoelectric thin film of Example 1.
  • the radial direction is the ⁇ ( ⁇ ) axis and the circumferential direction is the ⁇ ( ⁇ ) axis.
  • a ring (Debye ring) corresponding to the diffraction plane of (001) was observed at an angle from the center of around 45 °.
  • a Debye ring corresponding to the (111) diffraction surface was found near 35.3 °.
  • each Debye ring deviates from the concentric arrangement and is slightly eccentric from the center.
  • a graph of a polar coordinate system having a radial ⁇ ( ⁇ ) axis and a circumferential direction ⁇ ( ⁇ ) axis shown in FIG. was converted into a graph of an orthogonal coordinate system with the ⁇ axis and the vertical axis the ⁇ axis.
  • FIG. 8B shows a graph of ⁇ converted to the orthogonal coordinate system. Based on FIG. 8B, the integrated intensity calculation of each orientation component was performed for the X-ray reflection profile at the position of the ⁇ axis where the angle of ⁇ is maximum (dotted line in FIG. 8B).
  • the integral intensity obtained here is obtained by spectral fitting analysis using a Gauss function, a Lorentz function, and their convolution functions such as Pseudo-Voight function, Pearson function, and Split-Pseudo-Voight function.
  • Example 1 in order to accurately calculate the strength of the orientation component, the ⁇ axis at which the angle ⁇ corresponding to the angle between the (001) orientation direction and the (111) orientation direction is maximized. It has been found that the integrated intensity calculation of each orientation component may be performed for the X-ray reflection profile at the position.
  • FIG. 9 shows the results of a polar figure simulation.
  • FIG. 9A shows a simulation result of a polar figure with (001) as a pole.
  • the correction coefficient is considered to be 4.
  • FIG. 10 shows (001) and (111) orientation components for the piezoelectric thin films of KNN-1 and KNN-2 with different production conditions using the measurement results of FIGS. 6 and 7 shown in Example 1.
  • the result analyzed about ratio is shown.
  • FIG. 10A shows a fitting function applied to the X-ray diffraction profile shown in FIG. A smooth curve is the Pseudo Voight function used as a fitting function in this embodiment. It can be seen that the diffraction profiles due to (111) and (100) are relatively well matched. At this time, the peak position ( ⁇ axis in this embodiment), integrated intensity, and half-value width of each profile are obtained.
  • FIG. 10B shows a table summarizing the analysis results. The integrated intensity given in Example 1 was 298 for the (111) orientation and 2282 for the (001) orientation for KNN-1.
  • FIG. 11 shows a schematic sectional view of the third embodiment.
  • FIG. 19 is a schematic view of an RF sputtering apparatus for producing a KNN thin film.
  • This is a piezoelectric thin film element in which a lower electrode layer 3 and a KNN piezoelectric thin film layer 4 of a perovskite structure are formed on the upper part of an adhesive layer 2 formed on a Si substrate 1 having an oxide film.
  • the polycrystalline piezoelectric thin film has a texture in which columnar crystal grains (columnar crystal grains) are generally aligned in a certain direction.
  • Example 3 when the input power was set to 100 W and the center of the sputtering target 12 shown in FIG. 19 and the center of the substrate 1 were aligned, the KNN piezoelectric thin film 4 was formed.
  • a polycrystalline piezoelectric thin film in which the normal line of the (001) crystal plane almost coincided with the normal direction of the substrate plane could be produced.
  • the columnar crystal grains 5 are grown in a direction perpendicular to the substrate.
  • no eccentricity was found in the (001) and (111) debye rings, and they were plotted as if they were arranged concentrically.
  • the ⁇ axis and ⁇ axis of the stereo projection diagram were converted into a graph in which the xy axis was an orthogonal axis, a waveform curve was not seen, and a straight line was obtained.
  • the substrate surface It was confirmed that the normal direction of the crystal plane of the preferentially oriented crystal grains was slightly deviated from the normal direction, and was inclined. At this time, the columnar crystal grains 6 are grown with an inclination with respect to the normal direction of the substrate surface (FIG. 11B).
  • the shift amount is appropriately determined depending on the substrate size to be used and a desired tilt angle. In this example using a 4-inch Si substrate, the shift amount was 10 mm.
  • the angle of the (001) crystal orientation direction is inclined by about 5 ° with respect to the normal direction of the substrate surface, and the angle of the (111) crystal orientation direction is about 0. It was found to be inclined 3 °.
  • Example 4 This will be described with reference to FIGS. As a present example, a result obtained by intentionally changing the volume fraction of the orientation component of (001) and the orientation component of (111) is shown.
  • FIG. 12 shows changes in the integrated intensity of diffraction caused by (111) and (001) with respect to the film formation temperature in the sputtering film formation method. It can be seen that the diffraction intensity due to (001) decreases as the film formation temperature increases. On the other hand, it can be seen that the diffraction intensity due to (111) increases as the film forming temperature increases. Next, using these results, the film formation temperature dependence of the volume fraction in consideration of the correction coefficient shown in Example 2 was examined.
  • FIG. 13 shows changes in the volume fraction of the (111) and (001) orientation components with respect to the film formation temperature of the KNN piezoelectric thin film in the sputtering film formation method.
  • the volume fraction of the (111) orientation component is almost 0, but when it exceeds 650 ° C., the film formation temperature increases ( It can be seen that the volume fraction of the 111) orientation component increases.
  • the (001) orientation component is almost 100% in the range of 550 ° C. to 650 ° C., and almost only the (001) plane. It turns out that it exists in a single orientation state. It can also be seen that if it exceeds 650 ° C., the volume fraction of the (001) orientation component gradually decreases as the film formation temperature rises. This example shows that the ratio of the (111) orientation component and the (001) orientation component can be controlled by changing the film formation temperature.
  • FIG. 14 shows changes in internal stress (strain) with respect to the film formation temperature of the KNN piezoelectric thin film in the sputtering film formation method. It can be seen that as the film forming temperature increases, the compressive stress decreases and changes to an unstrained state without stress. It can be seen that when the film-forming temperature is increased to 700 ° C. to 750 ° C., the state changes from almost no strain to a slightly tensile stress state. Further, Pa is an example of a unit of internal stress in this embodiment.
  • the compressive stress decreases with an increase in the volume fraction of (111). That is, it is shown that the internal stress relaxation of the piezoelectric thin film can be realized by increasing the (111) orientation component ratio of the KNN piezoelectric thin film.
  • the internal stress of the piezoelectric thin film can be controlled by precisely controlling the component ratio (volume fraction) of crystal orientation.
  • the piezoelectric thin film has a volume fraction of the (111) component, the stress of the piezoelectric thin film can be relaxed, and film peeling can be suppressed. Thereby, the mechanical strength of the piezoelectric thin film is improved, and a piezoelectric thin film having excellent processability can be provided.
  • the piezoelectric characteristics can be improved by controlling the internal stress.
  • the mechanical strength of the piezoelectric thin film is improved, and a piezoelectric thin film having excellent processability can be provided.
  • the yield obtained from the substrate with the piezoelectric thin film with the (111) component of less than 1% was less than 70%.
  • the variation of the piezoelectric constant shown here is a relative standard deviation obtained by dividing the standard deviation of the piezoelectric constant measured in the 4-inch wafer plane by the average value. At this time, the value was about 23%. However, when the (111) volume fraction is about 0.2%, the variation varies from 15.3% to 27.1%. Even with the same (111) volume fraction, the value of the variation is different for each wafer. The difference is large, which causes a decrease in yield.
  • FIG. 16 shows the change with respect to (111) integral intensity
  • the horizontal axis represents (111) integrated intensity
  • the vertical axis represents the piezoelectric constant.
  • the piezoelectric constant when an electric field is applied at 6.7 MV / m or 0.67 MV / m is shown.
  • the unit of the piezoelectric constant is an arbitrary unit.
  • d 33 which is a change amount of expansion / contraction perpendicular to the electrode surface (thickness direction), or a direction along the electrode surface.
  • d 31 which is the amount of change in the expansion and contraction of.
  • the piezoelectric constant is an arbitrary unit.
  • numerical values such as the Young's modulus and Poisson's ratio of the piezoelectric layer are necessary, but it is not easy to obtain the numerical values of the Young's modulus and Poisson's ratio of the piezoelectric layer (piezoelectric thin film).
  • the piezoelectric constant was calculated using the estimated values of the Young's modulus and Poisson's ratio of the KNN film known so far.
  • the obtained piezoelectric constant is an estimated value, it was set as a relative arbitrary unit in order to provide objectivity.
  • the values of the Young's modulus and Poisson's ratio of the KNN film used for calculating the piezoelectric constant are estimated values, they are reliable to some extent, and about 80 [arbitrary unit] of the piezoelectric constant is approximately piezoelectric. It can be said that the constant d 31 is 80 [ ⁇ pm / V]. This is common to FIGS. 17 and 18.
  • Table 2 and FIG. 17 which is a graph of Table 2 show the dependency of the piezoelectric characteristics of the KNN piezoelectric thin film on the (111) orientation component ratio.
  • the horizontal axis is the volume fraction of the (111) orientation component, and the vertical axis is the piezoelectric constant.
  • the piezoelectric constant increases as the (111) volume fraction increases in the range where the component of the (111) orientation is 0 to 20% regardless of the magnitude of the applied electric field.
  • the piezoelectric constant decreases as the volume fraction increases.
  • the value is about half of the maximum value obtained in this example.
  • the volume fraction of (111) in order to secure 50% or more of the maximum piezoelectric constant, it is desirable that the volume fraction of (111) is 40% or more.
  • the volume fraction of (111) in order to improve the piezoelectric characteristics of the piezoelectric material, it is also important to improve the crystallinity, which can be confirmed by an increase in the integrated intensity of X-ray diffraction.
  • the volume fraction of (111) is 30% or less and the degree of crystallinity is high. If an optimum volume fraction is specified after realizing a high degree of crystallinity, higher performance is achieved. A simple piezoelectric thin film can be realized.
  • FIG. 18 in which Table 3 and Table 3 are graphed shows the dependence of the piezoelectric characteristics of the KNN piezoelectric thin film on the (001) orientation component ratio. It can be seen that the dependence of the piezoelectric constant on the (001) volume fraction has an inverse correlation with that of (111). That is, it can be seen that the piezoelectric constant increases as the (001) orientation component increases. However, it can be seen that when the (001) volume fraction is 80% or more, the piezoelectric constant tends to decrease. Further, in the piezoelectric thin film according to the present embodiment, in order to realize a value such that the maximum piezoelectric constant is 50% or more, it is desirable that the volume fraction of (001) is 60% or more. Represents. In this embodiment, it is assumed that the sum of (001) and (111) volume fraction is 100%.
  • the piezoelectric thin film has a pseudo-cubic, tetragonal, or orthorhombic crystal structure, or at least a crystal structure thereof.
  • One of them has a coexistence state, is preferentially oriented to a specific axis of two or less of the crystal axes, and (001) component as a component of the oriented crystal axis;
  • the (111) component ratio when the sum of both is 100%, the volume fraction of the (001) component is in the range of 60 to 100%, or the volume fraction of the (111) component is 0. It has been found that a novel high-performance piezoelectric thin film element can be produced by precisely controlling the crystal orientation so that it is in the range of 40% to 40%.
  • an applied voltage of 6.7 Mv is applied to a piezoelectric thin film element obtained from a substrate with a piezoelectric thin film having a volume fraction of (111) component of 21% and a volume fraction of (001) component of 79%.
  • a piezoelectric constant 87 was obtained.
  • the off-angles of the (001) and (111) crystal planes of the obtained piezoelectric thin film element with respect to the substrate plane are inclined by 3.0 ° with respect to the normal direction of the substrate.
  • the angle of the (111) crystal orientation direction was inclined by 0.5 °.
  • a Si substrate having a thickness of 0.525 mm was prepared as a substrate, and a thermal oxidation treatment was performed on the surface to form an oxide film having a thickness of 200 nm on the surface of the Si substrate.
  • a 2 nm Ti adhesion layer on the thermal oxide film and a 100 nm Pt lower electrode formed with a preferential orientation of (111) on the Ti adhesion layer have a substrate temperature of 350 ° C., input power of 100 W, Ar gas
  • the film was formed under the conditions of 100% atmosphere, pressure 2.5 Pa, film formation time 1 to 3 minutes (Ti adhesion layer), 10 minutes (Pt lower electrode).
  • a KNN piezoelectric film was formed so that The substrate temperature during film formation was 700 ° C., the input power was 100 W, a 5: 5 mixed gas of Ar and O 2 was used, and the pressure was 1.3 Pa. The shift amount between the center of the target and the center of the substrate was 10 mm. Further, after the film formation, annealing treatment was performed at 700 ° C. for 2.0 hours in an air atmosphere.
  • the self-revolution furnace was used for the sputtering device, and the distance between TS was 50 mm.
  • the electrodes, piezoelectric thin films, and the like, which are constituent materials, are appropriately selected, and the film forming conditions such as the film forming temperature of the piezoelectric thin film are controlled to preferentially orient the piezoelectric thin film (001) and (111 )
  • the volume fraction of the component By controlling the volume fraction of the component, good piezoelectric characteristics could be realized.
  • the yield of the element obtained from the substrate with the piezoelectric thin film was 96%, which was a sufficiently high result.

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Abstract

L'invention concerne un élément à couche mince piézoélectrique qui comprend un substrat et, sur celui-ci, au moins une électrode inférieure, une couche mince piézoélectrique représentée par la formule générale (NaxKyLiz)NbO3 (0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 0,2 et x + y + z = 1) et une électrode supérieure, caractérisé en ce que la couche mince piézoélectrique a une structure cristalline de type quasi-cubique, tétragonal ou orthorhombique ou possède un état dans lequel coexistent un ou plusieurs de ces systèmes cristallins, en ce que les grains du cristal sont orientés de préférence sur deux axes cristallographiques spécifiques parmi ces axes et en ce que, par rapport au rapport entre les composants cristallographiques orientés (001) et (111), la proportion en volume des composants (001) est de 60 à 100 % et la proportion en volume des composants (111) est de 0 à 40 %, la somme des deux étant égale à 100 %.
PCT/JP2010/073006 2010-03-29 2010-12-21 Élément à couche mince piézoélectrique, procédé de production de celui-ci et dispositif à couche mince piézoélectrique WO2011121863A1 (fr)

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US20200161533A1 (en) * 2017-07-12 2020-05-21 Sumitomo Chemical Company, Limited Laminated substrate having piezoelectric film, element having piezoelectric film and method for manufacturing this laminated substrate
US11557713B2 (en) * 2017-07-12 2023-01-17 Sumitomo Chemical Company, Limited Laminated substrate having piezoelectric film, element having piezoelectric film and method for manufacturing this laminated substrate
CN112640137A (zh) * 2018-09-12 2021-04-09 Tdk株式会社 介电薄膜、介电薄膜元件、压电致动器、压电传感器、磁头组件、磁头悬臂组件、硬盘驱动器、打印头和喷墨打印装置
CN112640137B (zh) * 2018-09-12 2024-03-12 Tdk株式会社 介电薄膜、介电薄膜元件、压电致动器、和压电传感器

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