Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
• • 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
• • 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
• • 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
  • H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
• • 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
  • H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
• • 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
  • H10N30/01—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
  • H10N30/077—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 liquid phase deposition
  • H10N30/078—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 liquid phase deposition by sol-gel 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
  • H10N30/20—Piezoelectric or electrostrictive devices with electrical input and mechanical output, e.g. functioning as actuators or vibrators
• • 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
  • H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure
• • 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
• • 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
  • H10N30/87—Electrodes or interconnections, e.g. leads or terminals
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials

Definitions

• the present invention relates to crystals, laminated structures, electronic devices, electronic equipment, and manufacturing methods thereof.
• shape memory materials also referred to as superelastic materials
• shape memory phenomena or superelasticity phenomena also referred to as pseudoelastic phenomena
• shape-memory materials include shape-memory alloys (SMA) and shape-memory polymers (SMP).
• SMA shape-memory alloys
• SMP shape-memory polymers
• Nitinol which is an alloy of nickel and titanium, is known as SMA (Patent Document 1). Nitinol has excellent shape memory effect and superelastic properties, and is used in medical guide wires, eyeglasses, and the like.
• a polyurethane-based shape memory polymer having an ionic component or a mesogenic component 2) a polyethylene terephthalate-polyethylene oxide (PET-PEO) block copolymer crosslinked with maleic anhydride, and the like are known.
• PET-PEO polyethylene terephthalate-polyethylene oxide
• An object of the present invention is to provide a crystal with excellent shape memory characteristics and corrosion resistance, a laminated structure, an electronic device, an electronic equipment, including the crystal, and a manufacturing method that can obtain these with industrial advantage.
• the present inventors formed at least a compound film on a crystal substrate, then laminated an epitaxial film containing a crystalline compound, and further, directly or on the epitaxial film,
• the epitaxial film is formed by using a compound element in the compound film.
• a regular transformation matching the lattice constant of the second epitaxial film occurs without dislocation or slip deformation, and a shape memory phenomenon or superelasticity phenomenon is exhibited even though the epitaxial film is made of oxide.
• such an epitaxial film is a novel shape memory material that can solve the above-described conventional problems at once.
• the inventors of the present invention conducted further studies and completed the present invention.
• the present invention relates to the following inventions.
• the crystalline metal compound contains 50 atomic % or more of Hf and/or Zr among the constituent metals, and 0.1 atomic % of one or more metals selected from Al, Ti, Y and Ce.
• [5] The crystal according to any one of [1] to [4], which has a transformation temperature of 350°C to 1000°C.
• [6] The crystal according to any one of [1] to [5], which is a film-like shape memory material.
• a method for manufacturing a laminated structure comprising forming at least a compound film on a crystalline substrate and then laminating an epitaxial film containing a crystalline compound, wherein lamination of the epitaxial film is performed by removing a compound element in the compound film. and forming the epitaxial film using a crystal that exhibits superelasticity of 10% or more when deformed at a transformation temperature or higher. .
• [12] A method for manufacturing a piezoelectric element using a laminated structure, wherein the laminated structure is the laminated structure according to [9] or [10].
• An electronic device comprising a laminated structure, wherein the laminated structure is the laminated structure according to [9] or [10].
• An electronic equipment including an electronic device wherein the electronic device is the electronic device according to [14] or [15].
• [17] A method of manufacturing an electronic device using a laminated structure or an electronic device, wherein the laminated structure is the laminated structure according to [9] or [10], and the electronic device comprises the [ 14] or a method of manufacturing an electronic device, wherein the electronic device is the electronic device according to [15].
• [18] A system including an electronic device, wherein the electronic device is the electronic device described in [16] above. [19] between the crystal substrate and the epitaxial film, an amorphous thin film containing metals constituting the epitaxial film and/or the crystal substrate and/or embedded in a part of the crystal substrate, and The laminated structure according to the above [9], which has an embedded layer containing the constituent metal.
• the shape memory material, the laminated structure, the electronic device, and the electronic equipment of the present invention include an epitaxial film having excellent corrosion resistance. There is an effect that the electronic device and the electronic equipment can be industrially advantageously obtained.
• FIG. 4 is a diagram schematically showing an example of another preferred embodiment of the laminated structure of the present invention. It is a figure which shows typically an example of the oxide film formation process in the suitable manufacturing method of the laminated structure of this invention. It is a figure which shows typically an example of the epitaxial film formation process in the suitable manufacturing method of the laminated structure of this invention.
• 1 shows a cross-sectional STEM image observed in an example. 1 shows a cross-sectional STEM image observed in an example. The STEM image observed in the Example is shown. The STEM image observed in the Example is shown.
• FIG. 1 is a diagram schematically showing a preferred example of an embodiment of a MEMS transducer in the present invention
• FIG. FIG. 10 is a diagram schematically showing an example of a cross-sectional view of a part of a wafer provided with piezoelectric actuators as a preferred application example to the fluid ejection device of the present invention.
• 1 shows a cross-sectional STEM image observed in an example.
• (b) shows a bright field (BF) STEM image of (a). It is a figure which shows the XRD measurement result which shows the symmetry of the crystal
• FIG. 1 is a diagram schematically showing a film forming apparatus preferably used in Examples; 1 shows a cross-sectional STEM image measured in an example. The STEM image measured in the example is shown. FIG. 4 shows an STEM image of a buried layer measured in an example. FIG.
• the crystal of the present invention is a crystal made of a crystalline metal compound, preferably a crystalline metal oxide, and is characterized by exhibiting superelasticity of 10% or more by being deformed at a temperature equal to or higher than the transformation temperature.
• the crystalline compound is not particularly limited, and may be a known crystalline compound.
• the crystalline compound is preferably a metal compound, and the metal of the metal compound may also be a known metal. you can Examples of the metal include metals containing d-block elements of the periodic table.
• the compounds of the metal compounds may also be known compounds, and the compounds in the crystalline compounds include, for example, oxides, nitrides, oxynitrides, sulfides, oxysulfides, borides, oxyborides, and carbides. , oxycarbides, borocarbides, boronitrides, borosulfides, carbonitrides, carbosulfides or carboborides. It is preferable because it can improve the stress relaxation and warp reduction in the buffer layer and further improve the electrical properties (especially the interface between the conductor layer and the insulating layer).
• the crystalline compound is preferably a crystalline oxide
• the compound film is preferably an oxide film
• the compound element is oxygen.
• the crystalline compound is preferably a crystalline nitride
• the compound film is preferably a nitride film
• the compound element is nitrogen.
• the crystal may be a single crystal or a polycrystal, but is preferably a single crystal in the present invention.
• the crystal is preferably a film-like shape memory material.
• Shape memory material usually refers to a material that, even if deformed at a temperature lower than a predetermined temperature, recovers its original shape before deformation by heating to a predetermined temperature or higher. Any material that partially or entirely deforms above its transformation temperature and recovers its shape may be used, including superelastic materials having superelastic properties.
• the superelastic property means that even if the shape memory material is deformed (including bending, tension, compression, etc.) at a working temperature equal to or higher than its transformation temperature, it recovers its original shape by unloading.
• the shape memory material is preferably a shape memory material having a transformation temperature of 350°C or higher, more preferably 350°C to 1000°C, more preferably 350°C to 750°C. is most preferred.
• the crystal is a single-layer crystal film including a first crystal face and a second crystal face opposite to the first crystal face, and the first crystal face is the first crystal face.
• the crystal plane is regularly transformed so as to have a constant lattice constant different from that of crystal plane 2, and it is more preferable that the transformation is a transformation that deforms the shape into a mountain-and-valley structure.
• the angles formed by the mutually adjacent peaks and bottoms of the mountain-and-valley structure are different from each other, and the difference in lattice constant between the first crystal plane and the second crystal plane is 0.5. It is also preferably in the range of 1% to 20%.
• the crystal film According to such a preferable range, it can be suitably used as a more excellent buffer layer, and the adhesion between the crystal film and a crystal film having a different composition provided on the substrate or the crystal film by crystal growth. And not only can the crystallinity of the crystalline film be improved, but also the properties of the crystalline film or the like as a functional film can be improved.
• the crystal film preferably contains one or more d-block elements, and a metal oxide containing one or more metals selected from d-block elements of the periodic table. It is also preferred to include objects.
• the metal oxide is not particularly limited as long as it does not interfere with the object of the present invention, but it is a metal oxide containing one or more metals selected from Groups 3, 4 and 13 of the periodic table. and more preferably a metal oxide containing one or more metals selected from Group 4 of the periodic table. More specifically, the metal oxide is preferably a crystalline metal oxide, preferably containing Hf and/or Zr, more preferably containing Hf.
• the crystalline metal oxide may contain metals other than Hf and Zr, and when the crystalline metal oxide contains the other metals, the crystalline oxide is , the constituent metals preferably contain 50 atomic % or more of Hf and/or Zr, and 0.1 atomic % to 50 atomic % of one or more metals selected from Al, Ti, Y and Ce. Within such a preferred range, the crystals exhibiting superelasticity of 10% or more can be obtained more easily. In addition, in the present invention, when it is within such a preferable range, crystal growth can be made easier and of higher quality, especially as a buffer layer.
• the crystal structure of the crystal film is not particularly limited, it preferably has a cubic crystal structure.
• the crystal film is preferably a single crystal film containing a crystalline oxide, and is also preferably an epitaxial film.
• a laminated structure of the present invention includes at least an epitaxial film, wherein the epitaxial film contains crystals exhibiting superelasticity of 10% or more by deformation at a transformation temperature or higher.
• the method for producing the laminated structure is not particularly limited, but is a method for producing a laminated structure in which at least a compound film is formed on a crystal substrate and then an epitaxial film containing a crystalline oxide is laminated, wherein the epitaxial film is is performed by forming the epitaxial film using a compound element in the compound film, and the epitaxial film containing crystals exhibiting superelasticity of 10% or more by being deformed at a transformation temperature or higher is formed.
• a method of producing is preferable, and such a production method is also included in the present invention.
• FIG. 1 shows a preferred example of the laminated structure.
• an epitaxial layer 3 is laminated on a crystal substrate 1 using an oxide film 2.
• a second epitaxial layer 4 is laminated thereon.
• film and “layer” may be interchanged depending on the case or situation.
• oxides are mentioned as suitable examples of the laminated structure, the present invention is not limited to these suitable examples, and various compounds such as nitrides are also suitable for the present invention. can be applied. For example, as shown in FIG.
• the laminated structure is formed by forming an oxide film 2 of the crystal substrate 1 on the crystal substrate 1, and then using oxygen in the oxide film 2 to obtain a structure as shown in FIG. It can be easily manufactured by forming an epitaxial film 3 made of a crystalline oxide on a crystal substrate 1 and then forming the second epitaxial film on the epitaxial film 3 .
• the laminated structure may have the oxide film 2 on the crystal substrate 1. However, when the epitaxial film 3 is formed, all the oxygen in the oxide film 2 is taken in and the oxidization occurs. The membrane 2 may disappear. Each of them will be described in more detail below, but the present invention is not limited to these specific examples.
• the crystalline substrate (hereinafter also simply referred to as "substrate”) is not particularly limited as long as it does not interfere with the object of the present invention, such as a substrate material, and may be a known crystalline substrate. It may be an organic compound or an inorganic compound.
• the crystal substrate preferably contains an inorganic compound.
• the substrate preferably has crystals on part or all of its surface, and is preferably a crystal substrate having crystals on all or part of its main surface on the crystal growth side. More preferably, it is most preferably a crystal substrate having crystals on the entire main surface on the crystal growth side.
• the crystal is not particularly limited as long as it does not interfere with the object of the present invention, and the crystal structure etc.
• the cubic system, tetragonal system, trigonal system, hexagonal system, orthorhombic system or monoclinic system It is preferably a crystal of the system, and more preferably a crystal oriented in (100) or (200).
• the crystal substrate may have an off-angle, and examples of the off-angle include an off-angle of 0.2° to 12.0°.
• the "off angle" refers to the angle formed between the substrate surface and the crystal growth plane.
• the shape of the substrate is not particularly limited as long as it is plate-like and serves as a support for the epitaxial film. It may be an insulator substrate or a semiconductor substrate.
• the substrate is preferably a Si substrate, more preferably a crystalline Si substrate, and (100) Most preferably, the crystalline Si substrate is oriented.
• the substrate material include, in addition to the Si substrate, one or more metals belonging to Groups 3 to 15 of the periodic table, oxides of these metals, and the like.
• the shape of the substrate is not particularly limited. , octagon, octagon, etc.), and various shapes can be suitably used. Further, in the present invention, a substrate having a large area can be used, and by using such a substrate having a large area, the area of the epitaxial film can be increased.
• the crystal substrate preferably has a flat surface, but the crystal substrate having unevenness on part or all of the surface also affects the quality of the crystal growth of the epitaxial film. It is preferable because it can be made better.
• the crystal substrate having the uneven shape may be formed on a part or the whole of the surface with an uneven portion composed of concave portions or convex portions. It is not limited, and may be an uneven portion made up of projections, an uneven portion made up of recesses, or an uneven portion made up of both projections and recesses. Further, the uneven portion may be formed from regular protrusions or recesses, or may be formed from irregular protrusions or recesses.
• the irregularities are preferably formed periodically, and more preferably patterned periodically and regularly.
• the shape of the uneven portion is not particularly limited, and examples thereof include stripes, dots, meshes, and random shapes. In the present invention, the shape of dots or stripes is preferable, and the shape of dots is more preferable. . Further, when the uneven portion is patterned periodically and regularly, the pattern shape of the uneven portion is a polygonal shape such as a triangle, a quadrangle (for example, a square, a rectangle, or a trapezoid), a pentagon, or a hexagon, A shape such as circular or elliptical is preferred.
• the lattice shape of the dots is preferably a lattice shape such as a square lattice, an orthorhombic lattice, a triangular lattice, or a hexagonal lattice. is more preferred.
• the cross-sectional shape of the concave portion or convex portion of the uneven portion is not particularly limited, but may be, for example, a U-shape, a U-shape, an inverted U-shape, a wave shape, a triangle, a quadrangle (e.g., a square, a rectangle, a trapezoid, etc.). ), polygons such as pentagons or hexagons.
• the thickness of the crystal substrate is not particularly limited, it is preferably 50 to 2000 ⁇ m, more preferably 100 to 1000 ⁇ m.
• the oxide film is not particularly limited as long as it is an oxide film capable of incorporating oxygen atoms into the epitaxial film, and usually contains an oxide material.
• the oxidizing material is not particularly limited as long as it does not interfere with the object of the present invention, and may be any known oxidizing material. Examples of the oxidizing material include oxides of metals or metalloids.
• the oxide film preferably contains an oxidizing material of the crystal substrate, and examples of such an oxide film include a thermal oxide film and a natural oxide film of the crystal substrate. Further, in the present invention, the oxide film may be a sacrificial layer that partially or entirely disappears or is destroyed when oxygen atoms are incorporated.
• the oxide film may be patterned, for example, may be patterned in stripes, dots, meshes, or random.
• the thickness of the oxide film is not particularly limited, it is preferably more than 1 nm and less than 100 nm.
• the epitaxial layer preferably includes an epitaxial film in which oxygen atoms in the oxide film are incorporated.
• the term "epitaxial film in which oxygen atoms in the oxide film are incorporated” means that oxygen atoms in the oxide film are taken away by the epitaxial film during crystal growth of the epitaxial film.
• the epitaxial film is not particularly limited as long as it is an epitaxial film crystal-grown by incorporating oxygen atoms in the oxide film, but in the present invention, it preferably contains a metal or a metal oxide.
• Suitable metals include, for example, one or more metals belonging to the d-block of the periodic table.
• Suitable examples of the metal oxides include oxides of one or more metals belonging to the d-block of the periodic table.
• the epitaxial film preferably contains a dielectric. Moreover, in the present invention, the epitaxial film preferably contains a neutron absorbing material.
• the neutron absorbing material may be a known neutron absorbing material. The properties of the film can be made more excellent. As the neutron absorber, for example, hafnium (Hf) is preferred.
• the epitaxial layer may be composed of one or more types of epitaxial films, and in the present invention, the epitaxial layer preferably contains two or more types of epitaxial films. More specifically, for example, it is preferable that a second epitaxial film having a composition different from that of the epitaxial film is laminated directly or via another layer on the epitaxial film.
• the interface between the epitaxial layer (hereinafter also referred to as "first epitaxial layer”) and the second epitaxial layer is formed at the interface between the epitaxial layer and the second epitaxial layer.
• the first epitaxial layer can be regularly transformed so as to have substantially the same lattice constant as the second epitaxial layer.
• Preferred examples of the regular transformation mode include transformation in which the shape is transformed into a ridge-and-valley structure. Preferably they are different and more preferably each said angle is in the range of 30° to 45°.
• the epitaxial layer normally has a first crystal face and a second crystal face, but the transformation causes a lattice constant difference between the first crystal face and the second crystal face.
• the lattice constant difference between the first crystal plane and the second crystal plane is in the range of 0.1% to 20%.
• the lattice constant difference between the first epitaxial layer and the second epitaxial layer is 0.0. It can be easily realized to be within the range of 1% to 20%.
• the epitaxial film is a dielectric and the second epitaxial film is an electrode.
• the second epitaxial layer is made of a single-crystal film of a conductive metal, a defect-free film having a large area can be easily obtained. It is also possible to improve the characteristics of the device and the like.
• the conductive metal is not particularly limited as long as it does not interfere with the object of the present invention, and examples thereof include gold, silver, platinum, palladium, silver-palladium, copper, nickel, or alloys thereof. preferably contains platinum.
• a defect-free single crystal film can be obtained as an electrode preferably in an area of 100 nm 2 or more, more preferably in an area of 1000 nm 2 or more. can be easily obtained. Also, a single crystal film having a thickness of preferably 100 nm or more can be easily obtained as an electrode.
• a third epitaxial film having a composition different from that of the epitaxial film and the second epitaxial film and/or directly or via another layer is formed on the second epitaxial film.
• a fourth epitaxial film is preferably laminated.
• FIG. 2 shows a preferred example of a laminated structure in which the third epitaxial layer 5 and the fourth epitaxial layer 6 are laminated on the second epitaxial layer 4 .
• a first epitaxial layer 3 is laminated on a crystal substrate 1 using an oxide film, and a second epitaxial layer 4 is laminated on the first epitaxial layer 3.
• a third epitaxial layer 5 is laminated on the second epitaxial layer 4
• a fourth epitaxial layer 6 is laminated on the third epitaxial layer 5 .
• the third epitaxial film in the third epitaxial layer is preferably dielectric, semiconductor or conductor, more preferably dielectric, and most preferably piezoelectric.
• the fourth epitaxial film in the fourth epitaxial layer is preferably a dielectric, a semiconductor or a conductor, more preferably a dielectric, and most preferably a piezoelectric.
• the thickness of each of the epitaxial films is not particularly limited, but is preferably 10 nm to 100 ⁇ m, more preferably 50 nm to 30 ⁇ m.
• the laminated structure is a laminated structure manufacturing method in which an epitaxial layer is laminated on a crystal substrate with at least an oxide film interposed therebetween. It can be easily obtained by forming an epitaxial film using When the temperature is in the range of 350° C. to 700° C., the oxygen atoms in the oxide film can be easily taken into the epitaxial film to grow the crystal.
• the epitaxial film it is preferable to form the epitaxial film by using oxygen gas after using oxygen atoms in the oxide film for the lamination. etc. will be superior. Further, by forming a film in this manner, a laminated structure in which an epitaxial layer is laminated on a crystal substrate, wherein the epitaxial layer and/or the crystal substrate are provided between the crystal substrate and the epitaxial layer. and/or one or more embedded layers embedded in a part of the crystal substrate and containing the constituent metals. In the present invention, it is preferable that the layered structure has both the amorphous layer and the buried layer, because the functionality of the epitaxial film can be further improved.
• the amorphous layer and the embedded layer each contain a constituent metal of the epitaxial layer, since the crystallinity of the epitaxial film or the like is further improved.
• the constituent metal contains Hf, because stress relaxation and the like can be promoted more and stress relaxation and the like can be realized in multiple stages.
• the thickness of the amorphous thin film is preferably 1 nm to 10 nm because the crystallinity of the epitaxial film can be further improved. can be easily obtained according to the preferred manufacturing method.
• the buried layer has a substantially inverted triangular cross-sectional shape, since the functionality of the epitaxial film can be further improved.
• the film formation means for the epitaxial film is usually preferably used, and the film formation means may be a known film formation means.
• the film forming means is preferably vapor deposition or sputtering, and more preferably vapor deposition.
• the crystal film or laminated structure obtained as described above is suitably used for electronic devices according to a conventional method.
• various electronic devices can be configured by connecting the laminated structure as a piezoelectric element to a power source or an electric/electronic circuit, mounting it on a circuit board, or packaging it.
• the electronic device is preferably a piezoelectric device, and can be used as a piezoelectric device in electronic equipment such as inkjet printer heads, microactuators, gyroscopes, and motion sensors.
• an amplifier and a rectifier circuit are connected and packaged, it can be used for various sensors such as a magnetic sensor. It can also be applied to a memory driven by a constant voltage.
• a power storage device and a rectifying power management circuit are connected, it becomes an energy conversion device (energy harvester) that generates power from external magnetic fields and vibrations.
• the energy conversion device is used by being incorporated into a power supply system, wearable terminal (earphone/hearable device, smart watch, smart glasses (glasses), smart contact lens, cochlear implant, cardiac pacemaker, etc.).
• the laminated structure can be used, for example, in smart glasses, AR headsets, MEMS mirrors for LiDAR systems, piezoelectric MEMS ultrasonic transducers (PMUT) for advanced medicine, piezo heads for commercial and industrial 3D printers, etc. It is preferable to use
• the electronic device is suitably used for electronic equipment according to a conventional method.
• the electronic device can be applied to various electronic devices other than the electronic devices described above.
• Preferable examples include piezoelectric acoustic components, voice reproducing devices, voice recording devices, mobile phones, and various information terminals having such piezoelectric acoustic components.
• the electronic device is also applied to a system according to a conventional method, and examples of such systems include sensor systems and the like.
• Example 1 The crystal growth surface side of the Si substrate (100) is treated with RIE and heated in the presence of oxygen to form a thermal oxide film. A single crystal of crystalline metal oxide was formed on the Si substrate by causing a thermal reaction with oxygen in the oxide film on the substrate. Then, oxygen was flowed, the temperature was lowered, and the pressure was increased, and a single crystal film of a crystalline metal oxide was formed as the crystal by vapor deposition.
• each condition of the vapor deposition method at the time of this film formation was as follows. Evaporation source: Hf, Zr Voltage: 3.5-4.75V Pressure: 3 ⁇ 10 -2 to 6 ⁇ 10 -2 Pa Substrate temperature: 450-700°C
• a metal film of platinum (Pt) was formed as a conductive film on the single-crystal film of the crystalline metal oxide by a sputtering method.
• the conditions at this time are shown below.
• PZT film a Pb(Zr 0.52 Ti 0.48 )O 3 film
• the prepared sol-gel solution was dropped onto the substrate, rotated at 2000 rpm for 1 minute, and the sol-gel solution was spin-coated (applied) onto the substrate to form a film containing the precursor.
• the substrate was placed on a hot plate at a temperature of 150° C., and further placed on a hot plate at a temperature of 350° C. to evaporate the solvent and dry the film.
• This process was repeated five times to laminate five layers under the same conditions, and then heat treated at 650° C. for 3 minutes in an oxygen (O 2 ) atmosphere to oxidize and crystallize the precursor.
• the above process was repeated 10 times to fabricate a Pb(Zr 0.52 Ti 0.48 )O 3 film (PZT film).
• the total film thickness at this time was 10 ⁇ m.
• the obtained laminated structure was a laminated structure including an epitaxial film having good adhesion and crystallinity.
• 5 and 6 show cross-sectional STEM images of the obtained laminated structure. It can be seen from FIG. 6 that a laminated structure of very good quality was obtained. In particular, in FIG. It can be seen that the angles formed by the mutually adjacent peaks and bottoms of the mountain-and-valley structure are different within the range of 30° to 45°.
• 7 and 8 show X-ray crystal lattice images of the conductive film. From FIGS. 7 and 8, it can be seen that the defect-free large-area conductive film exhibits excellent effects in terms of the electrode characteristics and the piezoelectric characteristics of the piezoelectric film laminated thereon.
• a piezoelectric film formed by spin coating has excellent piezoelectric properties.
• rice field crystals of the crystal substrate of the laminated structure, the single crystal film of the crystalline metal oxide, and the conductive film were measured using an X-ray diffraction apparatus.
• FIG. 12 shows the XRD measurement results.
• a (Hf, Zr)O 2 film and a Pt single crystal film having good crystallinity were formed on the Si crystal substrate.
• Example 2 A metal film of platinum (Pt) was formed as a conductive film on the single crystal film of crystalline metal nitride in the same manner as in Example 1, except that nitrogen gas was used instead of oxygen gas. Then, the crystal substrate of the laminated structure, the single crystal film of the crystalline metal nitride, and the conductive film were each measured using an X-ray diffractometer. FIG. 13 shows the XRD measurement results. As is clear from FIG. 13, a (Hf, Zr)N film and a Pt single crystal film having good crystallinity were formed on the Si crystal substrate. It should be noted that the obtained single crystal film of the crystalline metal nitride had good conductivity when measured by a four-probe method.
• FIG. 14 shows the vapor deposition film forming apparatus used in Example 1.
• the film forming apparatus of FIG. At least an Ar source 108 , a reactive gas source 109 , a power source 110 , a substrate holder 111 , a substrate 112 , a cut filter 113 , an ICP ring 114 , a vacuum chamber 115 and a rotating shaft 116 are provided.
• the ICP electrodes 103a and 103b in FIG. 14 have a substantially concave surface shape or a parabolic shape curved toward the center of the substrate 112. As shown in FIG.
• the substrate 112 is locked on the substrate holder 111.
• the rotating shaft 116 is rotated by using the power supply 110 and a rotating mechanism (not shown) to rotate the substrate 112 .
• the substrate 112 is heated by the lamps 107a and 107b, and the inside of the vacuum chamber 115 is evacuated to a vacuum or reduced pressure by a vacuum pump (not shown).
• Ar gas is introduced into the vacuum chamber 115 from the Ar source 108, and the substrate is removed using DC power sources 105a-105b, RF power sources 106a-106b, ICP electrodes 103a-103b, cut filters 104a-104b, and grounds 102a-102h.
• the surface of substrate 112 is cleaned by forming an argon plasma on 112 .
• Ar gas is introduced into the vacuum chamber 115 and the reactive gas is introduced using the reactive gas source 109 .
• the lamps 107a to 107b which are lamp heaters, a crystal growth film of better quality can be formed.
• FIG. 15-17 From FIG. 15, it can be seen that a buried layer 1004 is formed between the crystal substrate 1011 and the epitaxial layer 1001, and amorphous layers 1002 and 1003 are formed. Also, from FIG. 16, it can be seen that the first amorphous layer 1002 on the crystal substrate 1011 contains Si of the crystal substrate and Zr which is a constituent metal of the epitaxial layer 1001 . Moreover, it can be seen that the second amorphous layer contains Si of the crystal substrate and Hf and Zr, which are constituent metals of the epitaxial layer 1001 . Also, from FIG. 17, it can be seen that the buried layer 1004 has a substantially inverted triangular cross-sectional shape and is an oxide containing Hf and Si.
• FIG. 9 shows an embodiment of an acoustic MEMS transducer that constitutes a MEMS microphone in which the laminated structure is preferably used in the present invention.
• the MEMS transducer can constitute an acoustic emitting device (eg, a speaker, etc.).
• the MEMS microphone composed of acoustic MEMS transducers in FIG. 9 shows a cantilever type MEMS microphone, comprising a Si substrate 21 with two cantilever beams 28 A, 28 B and a cavity 30 .
• Each cantilever beam 28A, 28B is fixed at its respective end to the substrate 21, leaving a gap 9 between the cantilever beams 8A, 8B.
• the cantilever beams 8A and 8B are formed by a laminated structure including, for example, a plurality of piezoelectric layers (PZT films) 26a and 26b, and a plurality of electrode layers, namely Pt films 24a, 24b and 24c and SRO films 25a and 25b. , 25c and 25d.
• a dielectric layer (single crystal film of crystalline oxide) 23 electrically insulates the cantilever beams 8A, 8B from the crystal substrate 21 .
• the dielectric layer (single-crystal film of crystalline oxide) 23 uses a neutron absorbing material (eg, HfO 2 or mixed crystal thereof). It has excellent adhesion and crystallinity to the substrate, and further has excellent piezoelectric properties and durability.
• FIG. 10 shows a printing application in which the laminated structure is preferably used in the present invention, particularly an application example to a fluid ejection device that can be used in the form of an inkjet printhead.
• FIG. 3 shows a cross-sectional view of a portion of a wafer comprising Pt films 34a, 34b and SRO films 35a, 35b and comprising piezoelectric actuators containing a PZT film 36 as the piezoelectric film.
• the wafer of FIG. 10 comprises, in addition to the piezoelectric actuators, a chamber 41 for containing a fluid. Chamber 41 is configured to accept fluid from a tank (not shown) via channel 40 .
• the dielectric layer (single-crystal film of crystalline oxide) 33 uses a neutron absorbing material (eg, HfO 2 or mixed crystal thereof). It has excellent adhesion and crystallinity to the substrate, and further has excellent piezoelectric properties and durability.
• the single-crystal film 33 of crystalline oxide has, for example, a quadrangular shape in a top view (not shown), and such a shape is, for example, a square, a rectangle, a rectangle with rounded corners, or a parallelogram. and so on.
• a Pt film 34a, an SRO film 35a, a piezoelectric film (PZT film) 36, an SRO film 35b, and a Pt film 34b are laminated in this order on the single-crystal film 33 of crystalline oxide to form a piezoelectric actuator.
• the piezoelectric actuator further comprises electrodes 34a and 35a, a piezoelectric film 36, and an insulating film 37 extending over the electrodes 34b and 35b.
• the insulating film 37 comprises a dielectric material used for electrical insulation, which dielectric material may be any known dielectric material, for example a SiO2 layer, a SiN layer or an Al2O3 layer. .
• the thickness of the insulating layer containing the insulating film as a constituent material is not particularly limited, the thickness is preferably between about 10 nm and about 10 ⁇ m.
• Conductive paths 39 are also provided on an insulating layer (insulating film) 37 to contact electrodes 34a and 35a and electrodes 34b and 35b, respectively, to allow selective access during use.
• the conductive path may be made of a known conductive material, and a suitable example of such a conductive material is aluminum (Al).
• the passivation layer 42 is provided on the insulating layer 37 , the electrodes 34 b and 35 b , and the conductive paths 39 .
• the passivation layer 42 may be composed of a dielectric material used for passivation of the piezoelectric actuator, and the dielectric material is not particularly limited, and may be a known dielectric material. Suitable examples of the dielectric material include SiN and SION (silicon oxynitrate). The thickness of the passivation layer is not particularly limited, but is preferably between about 0.1 ⁇ m and about 3 ⁇ m.
• a conductive pad 38 is also provided along the piezoelectric actuator and electrically connected to the conductive path 39 .
• the passivation layer 42 functions as a barrier layer that protects the piezoelectric body from humidity and the like.
• the crystal and laminated structure of the present invention can be applied to various uses, and are particularly suitable for use as buffer layers and substrates for crystal growth. be done.

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