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WO2010116802A1 - Elément piézoélectrique - Google Patents

Elément piézoélectrique Download PDF

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Publication number
WO2010116802A1
WO2010116802A1 PCT/JP2010/052697 JP2010052697W WO2010116802A1 WO 2010116802 A1 WO2010116802 A1 WO 2010116802A1 JP 2010052697 W JP2010052697 W JP 2010052697W WO 2010116802 A1 WO2010116802 A1 WO 2010116802A1
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layer
elastic modulus
piezoelectric
substrate
piezoelectric element
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Japanese (ja)
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昌宣 鶴子
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Brother Industries Ltd
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Brother Industries Ltd
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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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/048—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material with layers graded in composition or physical properties
    • 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
    • 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
    • H10N30/079—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 using intermediate layers, e.g. for growth control
    • 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
    • H10N30/706—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings characterised by the underlying bases, e.g. substrates
    • H10N30/708—Intermediate layers, e.g. barrier, adhesion or growth control buffer layers

Definitions

  • the present invention relates to a piezoelectric element having a thin film formed by an aerosol deposition method as a piezoelectric film.
  • the aerosol deposition method has attracted attention as a method for forming a piezoelectric film in a piezoelectric actuator used in an inkjet printer or the like.
  • an aerosol composed of ceramic fine particles dispersed in a gas is sprayed from a nozzle and sprayed onto the substrate surface at a high speed to pulverize and deposit the fine particles on the substrate to form a ceramic thin film.
  • It is a membrane method.
  • This method uses the normal temperature impact solidification phenomenon caused by the induction of the mechanochemical reaction caused by the release of the local impact energy generated by the collision of ceramic fine particles with the substrate surface. Is a film formation technique that acts as a reaction energy during film formation.
  • the annealing treatment is intended to improve the piezoelectric characteristics and the like of the thin film by heating the thin film formed by the aerosol deposition method and growing crystal grains inside the thin film. It is known that Fe and Cr in stainless steel are diffused into the piezoelectric layer by this annealing treatment, and the piezoelectric characteristics are deteriorated. In order to prevent this, the above-mentioned diffusion is prevented by providing a diffusion prevention layer made of an insulating ceramic material, a metal material, a conductive oxide, etc. between the stainless steel substrate and the piezoelectric layer. It is proposed in Document 1.
  • An object of the present invention is to provide a piezoelectric element that can suppress the occurrence of film peeling and short circuit and can improve the piezoelectric characteristics.
  • a piezoelectric element is a piezoelectric element having a three-layer structure in which a substrate, a single diffusion prevention layer, and a piezoelectric layer are laminated in this order,
  • Each of the prevention layer and the piezoelectric layer is a film formed by an aerosol deposition method, and the elastic modulus of the diffusion prevention layer is less than the elastic modulus of the substrate and more than the elastic modulus of the piezoelectric layer. It is characterized by that.
  • the piezoelectric element according to the first aspect wherein the diffusion preventing layer is made of material particles having a smaller elastic modulus as the film thickness by the aerosol deposition method is larger.
  • a piezoelectric element according to a third invention is characterized in that, in the first or second invention, the diffusion preventing layer is made of zirconia to which alumina is added.
  • a piezoelectric element according to a fourth invention is characterized in that, in the first or second invention, the diffusion preventing layer is composed of lead zirconate titanate.
  • a piezoelectric element of a fifth invention is characterized in that, in the first or second invention, the diffusion preventing layer is made of zirconia having a thickness of 5 ⁇ m or more.
  • the elastic modulus of the substrate ⁇ the elastic modulus of the diffusion preventing layer ⁇ the elastic modulus of the piezoelectric film, so that the elastic modulus gap between the films in the multilayer piezoelectric element is reduced. Can do. Therefore, it is possible to suppress the occurrence of film peeling or short circuit and improve the piezoelectric characteristics.
  • the film forming apparatus shown in FIG. 1 includes an aerosol generator 1 for generating aerosol by dispersing material particles in a carrier gas, and an internal structure. And a chamber 2 for carrying out the membrane.
  • the aerosol generator 1 stores a predetermined amount of material particles (for example, particles having a particle size of about 0.5 ⁇ m to 5.0 ⁇ m) and introduces a carrier gas.
  • the aerosol generator 1 generates a winding gas when the carrier gas is introduced. Further, the aerosol generator 1 applies vibration to the material particles from the lower part by an ultrasonic vibration apparatus or a flow stirring using a part of the carrier gas. As a result, the material particles are dispersed in the carrier gas, and aerosol is generated.
  • the carrier gas for example, an inert gas such as helium or argon, nitrogen, air, oxygen, or the like can be used.
  • One end of an aerosol supply pipe 3 is inserted in the upper part of the aerosol generator 1.
  • the other end of the aerosol supply pipe 3 is disposed inside the chamber 2 and is connected to an injection nozzle 4.
  • the chamber 2 is connected with a mechanical booster pump and a rotary pump, and these pumps depressurize the inside of the chamber 2. As a result, the internal pressure of the chamber 2 becomes lower than the internal pressure of the aerosol generator 1. Due to the differential pressure between the chamber 2 and the aerosol generator 1, the aerosol generated in the aerosol generator 1 is sucked into the aerosol supply pipe 3 and supplied to the injection nozzle 4.
  • the cavity inside the injection nozzle 4 has such a shape that the cross-sectional area decreases as it travels inside.
  • the aerosol that has entered the inside of the injection nozzle 4 from the introduction opening of the injection nozzle 4 is accelerated and sprayed from the injection opening of the injection nozzle 4 onto the substrate 7 as an aerosol flow 5 at a high speed.
  • the material particles that collide with the surface of the substrate 7 are crushed and deposited to form a thin film.
  • a substrate holder 6 for mounting the substrate 7 on the lower surface is disposed above the injection opening of the injection nozzle 4.
  • the substrate holder 6 has a rectangular plate shape.
  • the substrate holder 6 is suspended from the ceiling of the chamber 2 in a horizontal posture by the driving device 8.
  • the driving device 8 drives the substrate holder 6 in the left-right direction in FIG. By this driving in the left-right direction, scanning film formation on the substrate 7 is performed. By this scanning film formation, a thin film is formed in a predetermined wide range of the substrate 7.
  • the substrate 7 that is a film formation target includes a stainless steel substrate, but is not limited thereto, and may be a substrate composed of other metals, silicon, semiconductor, resin, or the like.
  • the piezoelectric element 100 shown in FIG. 2 is an example of a form used as a piezoelectric actuator.
  • a single diffusion prevention layer 12 that is not a plurality of layers is laminated on a substrate 7.
  • a lower electrode 15 is formed on the diffusion prevention layer 12.
  • a piezoelectric layer 13 made of a piezoelectric material that contributes to deformation of the piezoelectric actuator is laminated on the lower electrode 15.
  • An upper electrode 16 is laminated on the piezoelectric layer 13.
  • the piezoelectric element 100 has a three-layer structure in which the substrate 7, the diffusion prevention layer 12 and the piezoelectric layer 13 are laminated, and the lower electrode 15 is formed between the diffusion prevention layer 12 and the piezoelectric layer 13. In addition, an upper electrode 16 is formed on the piezoelectric layer 13.
  • the diffusion prevention layer 12 and the piezoelectric layer 13 are respectively formed on the substrate 7 by the aerosol deposition method described above.
  • the lower electrode 15 is provided over the entire surface of the diffusion prevention layer 12 at the interface between the diffusion prevention layer 12 and the piezoelectric layer 13.
  • the lower electrode 15 is used as a ground electrode that is grounded and always has a ground potential.
  • the upper electrode 16 is configured as an electrode pattern on the upper surface of the piezoelectric layer 13 by a plurality of independent regions.
  • the upper electrode 16 has a lead portion connected to each individual region, and is connected to the drive circuit IC via the lead portion.
  • the upper electrode 16 is used as a drive electrode to which a ground potential or a potential different from the ground potential is selectively applied by the drive circuit IC.
  • the lower electrode 15 and the upper electrode 16 are made of a metal such as Au or Pt, for example.
  • the feature of the piezoelectric element 100 of this embodiment is that the elastic modulus value of the substrate 7 is configured to be equal to or larger than the elastic modulus value of the diffusion prevention layer 12. Further, the elastic modulus of the diffusion preventing layer 12 is configured to be equal to or greater than the elastic modulus of the piezoelectric layer 13. By setting it as this structure, the elastic-modulus gap between each layer can be made small.
  • the elastic modulus of each film can be measured by a nanoindentation method. Specifically, it is a value measured using an ultra-fine indentation hardness tester: ENT-1100a manufactured by Elionix Co., with an indentation load of 5 mN.
  • the elastic modulus here is a value measured after forming each layer and before annealing.
  • the piezoelectric characteristics were evaluated by calculating the value of the piezoelectric constant -d31 indicating the ease of deformation in the thickness direction on the electrode surface when a voltage was applied.
  • This piezoelectric constant ⁇ d31 can be calculated by an operation such as measuring the displacement of the piezoelectric actuator.
  • the diffusion prevention layer 12 is formed on the surface of the substrate 7 by the above-described aerosol deposition method.
  • material particles having a smaller elastic modulus as the deposition thickness by the aerosol deposition method is thicker are used as the material constituting the material particles when the diffusion prevention layer 12 is formed.
  • the detailed material configuration of the material particles will be described later.
  • the elastic modulus of the diffusion preventing layer 12 is set by the aerosol deposition method so as to be equal to or lower than that of the substrate 7 and equal to or higher than that of the piezoelectric layer 13. It can be easily done by adjusting the thickness at the time.
  • the powder on the surface is removed, and the lower electrode 15 is formed on the surface of the diffusion preventing layer 12 by vapor deposition or sputtering, or by applying and drying a paste containing metal particles. Film.
  • a stress release annealing process is performed by heating at a relatively low temperature (about 500 ° C.). The stress release annealing treatment is performed for the purpose of heating the thin film formed by the aerosol deposition method to remove the film forming gas and moisture mixed in the film and releasing the residual stress of the thin film. .
  • the piezoelectric layer 13 is again formed on the surface of the lower electrode 15 by the aerosol deposition method.
  • material particles for forming the piezoelectric layer 13 piezoelectric materials such as barium titanate, lead titanate, lead magnesium niobate, lead nickel niobate, lead zinc niobate and the like can be used.
  • a grain growth annealing process is performed by heating at a relatively high temperature (about 800 to 900 ° C.) in order to remove the powder on the surface and grow crystal grains of the piezoelectric layer. .
  • the grain growth annealing treatment is intended to improve crystal characteristics of the thin film by heating the piezoelectric layer 13 formed by the aerosol deposition method to achieve growth of crystal grains in the thin film and correction of lattice defects. It is a process performed in.
  • the piezoelectric layer 13 formed by the aerosol deposition method has a large change in elastic modulus in the vicinity of the interface due to the grain growth annealing process.
  • problems such as film peeling can be avoided by employing the layer configuration of the present embodiment having the above-described elastic modulus relationship.
  • the upper electrode 16 is formed on the surface of the piezoelectric layer 13.
  • masking is performed and a vapor deposition method or a sputtering method is performed.
  • a metal layer may be formed on the entire surface of the piezoelectric layer 13 by vapor deposition or sputtering, and then formed into a predetermined pattern using photolithography etching.
  • the upper electrode 16 may be formed by screen printing directly on the surface of the piezoelectric layer 13.
  • the piezoelectric element 100 according to the present embodiment is completed.
  • the piezoelectric element 100 has a three-layer structure including the substrate 7, the diffusion prevention layer 12, and the piezoelectric layer 13 except for the upper electrode 16 and the lower electrode 15. Constitute. Furthermore, their elastic modulus is The elastic modulus of the substrate 7 ⁇ the elastic modulus of the diffusion preventing layer 12 ⁇ the elastic modulus of the piezoelectric layer 13 is configured. The reason for this configuration is to reduce the elastic modulus gap between the films.
  • the diffusion prevention layer 12 when the diffusion prevention layer 12 is provided by the aerosol deposition method as described above, the elastic modulus gap existing between the piezoelectric layer 13 and the diffusion prevention layer 12 and the elastic modulus obtained by the grain growth annealing process described above. Due to the large fluctuation, the inter-membrane stress rapidly increases between the piezoelectric layer 13 and the diffusion preventing layer 12. As a result, after performing the grain growth annealing treatment, film peeling may easily occur at the film interface between the piezoelectric layer 13 and the diffusion prevention layer 12.
  • the elastic modulus of the substrate 7 ⁇ the elastic modulus of the diffusion preventing layer 12 ⁇ the elastic modulus of the piezoelectric film 13 is set.
  • the elastic modulus gap between the films in the piezoelectric element 100 can be reduced. Therefore, it is possible to reduce the stress generated between the layers and make it difficult to generate the interface peeling of the piezoelectric layer 13. Accordingly, the occurrence of film peeling can be suppressed and the yield can be improved. In addition, cracks and pinholes are hardly formed, and occurrence of a short circuit can be suppressed. Further, the piezoelectric characteristics of the piezoelectric element 100 can be improved by reducing the internal stress of the piezoelectric layer 13.
  • each embodiment (3-A) First embodiment and second embodiment stainless steel is provided as a substrate, and alumina is used as a diffusion preventing layer between the piezoelectric layer composed of lead zirconate titanate.
  • the elastic modulus of the substrate is about 260 [GPa]
  • the elastic modulus of the diffusion prevention layer is about 390 [GPa]
  • the elastic modulus of the piezoelectric layer is about 120 [GPa]. Since the elastic modulus protrudes and is large, the elastic modulus gap between the films becomes very large.
  • the diffusion prevention layer 12 is composed of zirconia to which alumina is added so as to exhibit intermediate characteristics between alumina and zirconia.
  • the elastic modulus values of the substrate 7 and the diffusion prevention layer 12 are about 260 [GPa], respectively, and the elastic modulus of the piezoelectric layer 13 is 115. It was found that the difference between the elastic modulus of the diffusion preventing layer 12 and the elastic modulus of the substrate 7 and the piezoelectric layer 13 can be reduced.
  • the diffusion prevention layer 12 by forming the diffusion prevention layer 12 using zirconia to which alumina is added, it is possible to reliably reduce the elastic modulus gap between the films in the multilayer piezoelectric element 100 and to remove the film. Generation
  • production of a short circuit can be suppressed.
  • the diffusion prevention layer 12 is composed of lead zirconate titanate.
  • the value of the elastic modulus of the diffusion preventing layer 12 is about 160 [GPa]
  • the elastic modulus of the piezoelectric layer 13 is 70 [GPa].
  • the value of the elastic modulus of the substrate 7 is about 260 [GPa].
  • the gap in elastic modulus between the films in the multilayer piezoelectric element 100 is reliably reduced, and film peeling or short-circuiting occurs.
  • production can be suppressed and generation
  • the inventors of the present application examined the relationship between the diffusion preventing effect of zirconia used as the diffusion preventing layer 12 and the film thickness, and obtained the results shown in FIG.
  • FIG. 3 it can be seen that Fe and Cr contained in the stainless steel substrate of the substrate 7 are diffused into the diffusion preventing layer 12. However, it can be seen that the diffusion of Fe and Cr is almost completed at a distance of about 1 ⁇ m in the thickness direction after entering the diffusion preventing layer 12 from the substrate 7. In other words, as long as the function as the diffusion preventing layer 12 is obtained, it is found that the thickness of the zirconia layer is sufficient to be about 1 ⁇ m to 2 ⁇ m at most, and it does not make much sense to increase the thickness further.
  • Pt is a component element of the lower electrode 15 and is used to confirm the baseline of composition analysis and the presence or absence of diffusion into the piezoelectric layer 13.
  • the value of the elastic modulus is about 270 [GPa] when the film thickness of zirconia is about 1.6 ⁇ m. Thereafter, the value of the elastic modulus decreases as the film thickness increases, and the film thickness is about 5 ⁇ m.
  • the value of the elastic modulus is about 230 [GPa], and when the film thickness is about 10 ⁇ m, the value of the elastic modulus decreases to about 200 [GPa], which is equal to or less than the standard bulk property of zirconia. After this, even when the film thickness increased, the elastic modulus did not decrease so much, and when the film thickness was about 25 ⁇ m, the value of the elastic modulus was about 190 [GPa].
  • a zirconia film thickness of about 1 ⁇ m to 2 ⁇ m is sufficient to obtain the effect as the diffusion preventing layer 12, but there is room for controlling the elastic modulus value to a desired value by further increasing the thickness. . It was found that an effect of reducing the elastic modulus can be obtained by increasing the zirconia film thickness to at least about 5 ⁇ m.
  • the diffusion prevention layer 12 is composed of zirconia having a thickness of 5 ⁇ m or more.
  • the diffusion prevention layer 12 is made of zirconia and has a film thickness of 5 ⁇ m or more, thereby reliably reducing the elastic modulus gap between the films in the multilayer piezoelectric element 100.
  • membrane peeling and a short circuit can be suppressed.
  • the elastic modulus itself of the piezoelectric layer 13 is lowered, it is possible to further prevent film peeling and short circuit.
  • Example 1 Preparation of Substrate A diffusion bonded SUS substrate (head) and an evaluation SUS substrate (elastic modulus measurement) having a width of 15 mm, a depth of 35 mm, and a thickness of 0.4 mm were prepared. Using a nanoindenter, the elastic modulus of the evaluation SUS substrate was measured at a load of 5 mN. The elastic modulus values are shown in FIG.
  • Diffusion Prevention Layer A ZrO 2 (20% Al 2 O 3 added) film is formed as a diffusion prevention layer 12 on these substrates using a film deposition apparatus based on the aerosol deposition method based on the above-described embodiment. did.
  • the aerosol generator 1 was charged with 160 g of ZrO 2 (20% Al 2 O 3 added) powder (TZ-3YS20A manufactured by Tosoh Corporation).
  • the SUS substrate 7 was set on the substrate holder 6 and the portions other than the film formation range were attached with tape.
  • the substrate holder 6 was set on the XY stage of the driving device 8 in the chamber 2 and a reciprocating scan was started.
  • the stage was moved in such a manner that two rows (two sheets) of film formation could be performed in the same batch. That is, the two substrates 7 and 7 are arranged in parallel so as to face the ejection direction of the nozzle 4.
  • (a) the nozzle 4 was brought close to one substrate 7 and faced.
  • the nozzle 4 was moved to the other substrate 7 side substantially at right angles to the jetting direction and opposed to the other substrate 7. Thereafter, (c) it was moved away from the other substrate 7 once. After that, (d) the nozzle 4 was again brought close to the other substrate 7 to face it. (E) The nozzle 4 was moved to the one substrate 7 side substantially at right angles to the ejection direction, and was made to face the one substrate 7. Thereafter, (f) the substrate was moved away from the one substrate 7. Thereafter, the XY stage of the driving device 8 was moved so as to repeat the movements (a) to (f). The chamber 2 was evacuated to an ultimate vacuum pressure of 10 to 20 Pa.
  • Carrier gas was introduced from three systems (flow, crushing, acceleration), and the raw material powder was fluidly stirred.
  • the total flow rate of the carrier gas (the total of the three systems) was adjusted to a predetermined total flow rate, and the flow gas flow rate was set to a constant flow rate while observing the flow state.
  • the aerosol concentration was adjusted to a desired concentration by changing the ratio of the crushing gas and the acceleration gas.
  • spray injection 5 min outside the film formation range
  • aerosol was sprayed onto each SUS substrate for a predetermined film formation time. After the predetermined film formation time was completed, the film formation gas was stopped and the film formation chamber was opened in vacuum.
  • the substrate holder was removed from the XY stage to obtain the SUS substrate 7 on which the diffusion preventing layer 12 was formed.
  • the surface of the SUS substrate 7 on which the diffusion prevention layer 12 was formed was air blown to remove the adhered powder.
  • the film thickness of the diffusion preventing layer 12 on the SUS substrate 7 was measured using a step gauge, it was 0.91 to 2.91 ⁇ m.
  • the elastic modulus of the diffusion prevention layer 12 on the evaluation SUS substrate was measured using a nanoindenter at a load of 5 mN. The elastic modulus values are shown in FIG.
  • Piezoelectric Layer A PZT film was formed as the piezoelectric layer 13 on each laminated body after the stress release annealing treatment by the same aerosol deposition method as described above.
  • the piezoelectric material particles used at this time were PZT-LQ powder manufactured by Sakai Chemical Industry.
  • each laminate was air blown to remove the adhered powder.
  • the film thickness of the piezoelectric layer 13 on the SUS substrate 7 was measured using a step gauge, it was 4.56 to 5.51 ⁇ m.
  • the elastic modulus of the piezoelectric layer 13 on the evaluation SUS substrate was measured using a nanoindenter at a load of 5 mN. The elastic modulus values are shown in FIG.
  • the appearance of the PZT film after the above grain growth annealing treatment was observed, and when there was peeling on the entire surface, it was determined that there was film peeling.
  • the presence or absence of film peeling was determined for a large number of samples, and the ratio of the number of samples where film peeling occurred relative to the total number of samples was taken as the rate of film peeling.
  • the value of the film peeling occurrence rate is shown in FIG.
  • a terminal for applying a voltage was connected to the upper electrode 16 and the lower electrode 15 in a portion having no defect determined to be good in electrical evaluation. Then, after heating to 250 ° C. in a heat treatment furnace, a DC voltage corresponding to the film thickness was applied between the terminals under a polarization condition of applying a voltage of 6 kV / cm for 15 minutes. Then, after cooling to 50 ° C., application of DC voltage was stopped, and finally the terminal was removed.
  • Displacement measurement Again, a terminal for voltage application is connected to the upper electrode 16 and the lower electrode 15, and an AC voltage (input waveform: sine wave of 0 to 20 V, frequency 4 kHz) is applied between the terminals.
  • the dynamic displacement of the diffusion bonded SUS substrate which is a vibration plate was measured by a laser Doppler method.
  • Example 2 In the step of forming the diffusion prevention layer 12, ZrO 2 (20% Al 2 O 3 added) powder: Instead of 160 g, PZT powder (PZT-LQ manufactured by Sakai Chemical Industry): 200 g was used. Similarly, a piezoelectric element 100 having a three-layer structure composed of SUS substrate / PZT / PZT was manufactured. The film thickness of the diffusion preventing layer 12 was 1.86 to 1.95 ⁇ m, and the film thickness of the piezoelectric layer 13 was 5.15 to 5.23 ⁇ m. In this example, the piezoelectric constant -d31 was 90 pm / V. As in Example 1, the measured values of the elastic modulus of the SUS substrate 7, the diffusion prevention layer 12, and the piezoelectric layer 13 are shown in FIG. 5, and the values of the film peeling occurrence rate and the defect rate are shown in FIG.
  • Example 1 In the step of forming the diffusion prevention layer 12, 140 g of Al 2 O 3 powder (AL-160SG-4 manufactured by Showa Denko) was used. Otherwise in the same manner as in Example 1 and Example 2 was prepared a piezoelectric element having a three-layer structure composed of SUS substrate / Al 2 O 3 / PZT. The piezoelectric constant -d31 was 21 pm / V. Similarly to the above, the measured values of the elastic modulus of the SUS substrate 7, the diffusion preventing layer 12, and the piezoelectric layer 13 are shown in FIG. 5, and the values of the film peeling occurrence rate and the defect rate are shown in FIG.
  • Example 1 As shown in FIG. 5, the value of the elastic modulus of the diffusion preventing layer 12 decreases to about 260 [GPa], and the elastic modulus of the piezoelectric layer 13 decreases to about 115 [GPa]. For this reason, it can be seen that the difference between the elastic modulus of the diffusion preventing layer 12 and the elastic modulus of the substrate 7 and the piezoelectric layer 13 can be reduced. As a result, the elastic modulus gap between the films can be surely reduced. As a result, as shown in FIG. 6, the rate of film peeling can be suppressed to 16.7%, the rate of short circuit can be reduced to 0%, and the yield can be improved to 83.3%.
  • Example 2 as shown in FIG. 5, the value of the elastic modulus of the diffusion preventing layer 12 is reduced to about 160 [GPa], and the elastic modulus of the piezoelectric layer 13 is reduced to about 70 [GPa].
  • the elastic modulus of the diffusion preventing layer 12 can be reliably set to an intermediate value between the substrate 7 and the piezoelectric layer 13, and in particular, the elastic modulus value of the piezoelectric layer 13 can be greatly reduced.
  • the elastic modulus gap between the films can be further reliably reduced.
  • FIG. 6 it is possible to completely prevent the film peeling and the short circuit from occurring and to make the yield 100%.
  • Example 3 In the step of forming the diffusion preventing layer 12, ZrO 2 powder (TZ-3YS manufactured by Tosoh): 160 g was used. Otherwise in the same manner as in Example 1 and Example 2, it was manufactured piezoelectric element 100 having a three-layer structure composed of SUS substrate / ZrO 2 / PZT.
  • the film thickness of the diffusion preventing layer 12 is 5.0 ⁇ m or more, and in this example, three types of 5.0 ⁇ m, 9.9 ⁇ m, and 25.0 ⁇ m are used.
  • the piezoelectric constant -d31 was 52 pm / V, 76 pm / V, and 34 pm / V.
  • FIG. 5 the measured values of the elastic modulus of the SUS substrate 7, the diffusion preventing layer 12, and the piezoelectric layer 13 are shown in FIG.
  • Example 2 In the step of forming the diffusion preventing layer 12, the film thickness was 1.6 ⁇ m. Otherwise in the same manner as in Example 3 was prepared a piezoelectric element 100 having a three-layer structure composed of SUS substrate / ZrO 2 / PZT. The piezoelectric constant -d31 was 29 pm / V. Similarly to the above, the measured values of the elastic modulus of the SUS substrate 7, the diffusion preventing layer 12, and the piezoelectric layer 13 are shown in FIG.
  • Example 3 the value of the elastic modulus of the diffusion preventing layer 12 is sufficiently lowered to about 180 to 230 [GPa], which is equal to or less than the standard bulk property of zirconia. Become.
  • the elastic modulus of the diffusion preventing layer 12 can be reliably set to an intermediate value between the elastic modulus of the substrate 7 and the elastic modulus of the piezoelectric layer 13.
  • the elastic modulus of the piezoelectric layer 13 is also greatly reduced to about 40 to 90 [GPa].
  • the elastic modulus gap between the films can be surely reduced, and as in the first and second embodiments, the film peeling rate and the short-circuit rate can be suppressed, and the yield can be improved. .

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Abstract

L'invention concerne un élément piézoélectrique dans lequel la survenue de délaminage du film et de court-circuit est supprimée, et les propriétés piézoélectriques sont améliorées. Une couche de confinement unique (12) et une couche piézoélectrique (13) sont déposées sur un substrat (7) dans l'ordre indiqué, et conjointement au substrat (7) forment un élément piézoélectrique (100) avec une structure à trois couches. La couche de confinement (12) et la couche piézoélectrique (13) sont chacune des films formés par un procédé de dépôt d'aérosol, et le module d'élasticité de la couche de confinement (12) n'est pas supérieur au module d'élasticité du substrat (7) et pas inférieur au module d'élasticité de la couche piézoélectrique (13). La couche de confinement (12) est formée avec de la zircone dopée à l'alumine, du titanate de zirconate de plomb, ou de la zircone avec une épaisseur de film d'au moins 5 μm.
PCT/JP2010/052697 2009-03-30 2010-02-23 Elément piézoélectrique Ceased WO2010116802A1 (fr)

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JP2009080943A JP2010232580A (ja) 2009-03-30 2009-03-30 圧電素子
JP2009-080943 2009-03-30

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WO2017036945A1 (fr) * 2015-08-26 2017-03-09 Ceramtec Gmbh Couche et procédé pour la former
WO2017142090A1 (fr) 2016-02-19 2017-08-24 新日鐵住金株式会社 Stratifié de céramique, substrat isolant de céramique, et procédé de fabrication de stratifié de céramique
WO2018216227A1 (fr) * 2017-05-26 2018-11-29 アドバンストマテリアルテクノロジーズ株式会社 Structure de film et son procédé de fabrication

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