US20130320813A1 - Dielectric device - Google Patents
Dielectric device Download PDFInfo
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- US20130320813A1 US20130320813A1 US13/487,530 US201213487530A US2013320813A1 US 20130320813 A1 US20130320813 A1 US 20130320813A1 US 201213487530 A US201213487530 A US 201213487530A US 2013320813 A1 US2013320813 A1 US 2013320813A1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
-
- 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
-
- 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
- H10N30/877—Conductive materials
-
- 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
- H10N30/071—Mounting of piezoelectric or electrostrictive parts together with semiconductor elements, or other circuit elements, on a common 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
- H10N30/072—Forming of piezoelectric or electrostrictive parts or bodies on an electrical element or another base by laminating or bonding of piezoelectric or electrostrictive bodies
-
- 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
- H10N30/09—Forming piezoelectric or electrostrictive materials
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10D1/00—Resistors, capacitors or inductors
- H10D1/60—Capacitors
- H10D1/68—Capacitors having no potential barriers
- H10D1/682—Capacitors having no potential barriers having dielectrics comprising perovskite structures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/42—Piezoelectric device making
Definitions
- the present invention relates to a dielectric device.
- Patent Literatures 1 to 5 There are conventionally known dielectric devices having a dielectric film and a pair of electrode films laid on both sides of the dielectric film, as disclosed in Patent Literatures 1 to 5.
- the present invention has been accomplished in view of these problems and provides a dielectric device capable of readily achieving improvement in crystallinity of the dielectric and lower cost.
- a dielectric device comprises: a first electrode film having a non-oriented or amorphous structure; a dielectric film provided on the first electrode film and having a preferentially oriented structure; and a second electrode film provided on the dielectric film and having a non-oriented or amorphous structure.
- the “preferentially oriented structure” refers to a structure such that in the result of X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 50% of a total of intensities of all peaks.
- the “non-oriented structure” refers to a structure such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal plane is less than 50% of a total of intensities of all peaks.
- the “amorphous structure” refers to a structure such that in X-ray diffraction measurement, no peak is observed to be ascribed to a crystal lattice plane.
- the dielectric film is preferably (001), (101), or (110) preferentially oriented.
- the two electrode films can be composed of an elemental metal or can also be composed of an alloy containing two or more metals, and they may contain an element other than metals, without inhibiting the characteristics including electrical conductivity.
- the two electrode films can have their respective compositions different from each other, but they preferably have the same composition.
- the dielectric may be a piezoelectric material or may be a paraelectric, pyroelectric, or ferroelectric material. Among others, the piezoelectric material is preferable.
- an oxidation-reduction potential of every metal element forming the first and second electrode films is preferably higher than that of every metal element forming the dielectric film. This makes the dielectric film chemically and electrically stable, without being reduced by the electrode films, thereby to further improve the lifetime and reliability of the dielectric device.
- the first and second electrode films are preferably composed of a metal selected from Al, Ti, Zr, Ta, Cr, Co, and Ni or composed of an alloy containing metals selected therefrom.
- a metal selected from Al, Ti, Zr, Ta, Cr, Co, and Ni or composed of an alloy containing metals selected therefrom.
- the dielectric device has the dielectric film composed of only a metal element or metal elements having a sufficiently low oxidation-reduction potential, when the constituent elements of the two electrode films are selected from the aforementioned metal elements, interfaces between the electrode films and the dielectric film become chemically and electrically stable, thereby to further improve the lifetime and reliability of the dielectric device.
- One principal surface of the dielectric film can be in contact with the first electrode film and the other principal surface of the dielectric film can be in contact with the second electrode film.
- the dielectric device preferably further comprises an intermediate film composed of a metal selected from Al, Ti, Zr, Ta, Cr, Co, and Ni, between at least one electrode film and the dielectric film, for the purpose of improvement in adhesion between the two films.
- An oxidation-reduction potential of the metal forming this intermediate film is preferably lower than that of any one of metal elements forming the dielectric film.
- the intermediate film can be in contact with the electrode film and the dielectric film.
- an electroconductive oxide film composed of an electroconductive oxide may be provided between the electrode film and the dielectric film, preferably between the intermediate film and the dielectric film, for the purpose of preventing characteristic degradation of this device.
- This configuration makes the dielectric film less likely to be reduced by the electrode film, thereby to further improve the device in degradation of characteristics.
- the intermediate film or the electroconductive oxide film can be in contact with the dielectric film.
- the dielectric device can further comprise a metal film having a preferentially oriented structure, between the second electrode film and the dielectric film, and the metal film can be in contact with the second electrode film and the dielectric film.
- the crystallinity of the dielectric film in the dielectric device can be readily improved and it becomes feasible to achieve replacement of materials of the two electrode films with inexpensive materials and increase in throughput of deposition process.
- Sections (a) to (d) in FIG. 1 are schematic sectional views of dielectric devices according to embodiments of the present invention.
- FIG. 2 is a table showing oxidation-reduction potentials of metals.
- Sections (a) to (g) in FIG. 3 are schematic sectional views showing methods for manufacturing the dielectric devices in FIG. 1 .
- FIG. 4 is a schematic sectional view of a dielectric device in Comparative Example 1.
- FIG. 5 is a drawing showing a relation of thickness of underlying Pt film versus degree of orientation of dielectric film.
- a dielectric device 100 A according to an embodiment of the present invention will be described with reference to (a) in FIG. 1 .
- the dielectric device 100 A is disposed on a resin layer 7 which is laid on a support substrate 5 , and has a first electrode film 4 , a dielectric film 3 , a metal film 2 , and a second electrode film 8 in the order named.
- the dielectric film 3 has a preferentially oriented structure.
- the “preferentially oriented structure” refers to a structure such that in the result of X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 50% of a total of intensities of all peaks.
- the dielectric film 3 is preferably one such that in the result of X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 80% of a total of intensities of all peaks.
- the dielectric film 3 is preferably (001), (101), or (110) preferentially oriented. This configuration allows the dielectric film 3 to be a dielectric body with excellent characteristics.
- piezoelectric film When a piezoelectric film is used as the dielectric film 3 , examples of piezoelectric film preferably applicable include films of KNN or equivalently (K,Na)NbO 3 , LN or equivalently LiNbO 3 , AlN, and so on. Other applicable materials for the dielectric film 3 include MgO, STO or equivalently SrTiO 3 , BTO or equivalently BaTiO 3 , and so on.
- the thickness of the dielectric film 3 is normally in the range of about 1000 nm to 4000 nm.
- the first electrode film 4 is laid on a bottom surface of the dielectric film 3
- the second electrode film 8 is laid on a top surface of the dielectric film 3 .
- Each of the first electrode film 4 and the second electrode film 8 has a non-oriented or amorphous structure. Both of the two electrode films may have the amorphous structure; or, both of the electrode films may have the non-oriented structure; or, one electrode film may have the non-oriented structure while the other electrode film has the amorphous structure.
- non-oriented structure refers to a structure such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal plane is less than 50% of a total of intensities of all peaks.
- the electrode films 4 , 8 are preferably those such that an intensity of a peak ascribed to a certain crystal lattice plane is not more than 10% of a total of intensities of all peaks.
- the “amorphous structure” refers to a structure such that in X-ray diffraction measurement no peak is observed to be attributed to a crystal lattice plane.
- the electrode films 4 , 8 are composed of a metal element or metal elements and there are no particular restrictions on the metal element or metal elements, which can be selected from a wide variety of elemental metals and alloys.
- an oxidation-reduction potential of every metal forming the electrode films 4 , 8 is preferably higher than that of every metal element forming the dielectric film 3 .
- an oxidation-reduction reaction is remarkably suppressed between the dielectric film 3 and the electrode films 4 , 8 to reduce time degradation of the dielectric film 3 due to the battery effect, so as to enhance the reliability of the device.
- the material of each of the electrode films 4 , 8 preferably has a melting point sufficiently higher than heat loads applied in subsequent processes.
- the electrode films 4 , 8 to be employed are preferably films composed of a metal selected from Zr, Ta, Cr, Fe, Co, Ni, and Cu having the oxidation-reduction potentials higher than that of Ti (oxidation-reduction potential: ⁇ 1.63 V or higher), or films composed of any one of alloys of these metals.
- the electrode films 4 , 8 to be employed are preferably films composed of a metal selected from Ta, Cr, Fe, Co, Ni, and Cu having the oxidation-reduction potentials higher than that of Nb (oxidation-reduction potential: ⁇ 1.099 V), or films composed of any one of alloys of these metals.
- the metal films to be used are preferably films composed of a metal selected from Al, Ti, Zr, Ta, Cr, Fe, Co, Ni, and Cu having the oxidation-reduction potentials higher than that of Mg (oxidation-reduction potential: ⁇ 2.356 V), or films composed of any one of alloys of these metals; particularly, it is possible to adopt even Al and Ti.
- the material to be selected can be an electrode material (e.g., Cu or the like) having the oxidation-reduction potential higher than that of Pb (oxidation-reduction potential: ⁇ 1.126 V).
- the material of the electrode films 4 , 8 to be employed can be any one of materials with a relatively low melting point other than Pt, Ir, Pd, and Rh having high melting points.
- alloy materials to be used for the electrode films 4 , 8 include Al—Cu alloys, Ti—Al—Cr alloys, and Ni—Cr alloys and it is particularly preferable to use one of the Al—Cu alloys, for the reasons of low electric resistance and low power consumption.
- the electrode film materials of the electrode films 4 , 8 are preferably the same material. Since the materials of the electrode films 4 , 8 can be selected from the wide selection range of metals or alloys, inexpensive materials can also be used as long as the conditions including the resistance to process temperatures are satisfied.
- the thicknesses of the electrode films 4 , 8 can be determined in the range of 100 nm to 200 nm.
- the metal film 2 is provided between the second electrode film 8 and the dielectric film 3 and the metal film 2 is in contact with the dielectric film 3 and the second electrode film 4 .
- the metal film 2 has a preferentially oriented structure; that is, the metal film 2 has a structure such that in X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 50% of a total of intensities of all peaks.
- the metal film 2 is preferably one such that in X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 80% of a total of intensities of all peaks.
- the thickness of the metal film 2 is selected so as to enhance the crystallinity of the dielectric film 3 epitaxially grown in contact with the metal film 2 .
- the thickness of the metal film 2 is preferably in the range of 20 nm to 70 nm (cf. FIG. 5 ). In this small thickness range, it is difficult for the metal film 2 alone to function as a lower electrode film of the dielectric device 100 A.
- a metal forming the metal film 2 can be selected from metals (including alloys) having the a-axis lattice constant smaller than that of the dielectric film 3 and having thermal resistance to temperature during deposition of the dielectric film, and it is preferable to select Pt or Rh.
- a dielectric device 100 B according to an embodiment of the present invention will be described with reference to (b) in FIG. 1 .
- This dielectric device 100 B is different from the dielectric device 100 A in that the dielectric device 100 B does not have the metal film 2 and therefore the electrode film 8 and the dielectric film 3 are in direct contact. Furthermore, there is no other film between the dielectric film 3 and the electrode film 8 , as in the first embodiment.
- a dielectric device 100 C according to an embodiment of the present invention will be described with reference to (c) in FIG. 1 .
- This dielectric device 100 C is different from the dielectric device 100 B in that intermediate films 9 composed of a metal having the oxidation-reduction potential lower than that of any one of metal elements forming the dielectric film 3 are provided, one between the electrode film 8 and the dielectric film 3 and the other between the electrode film 4 and the dielectric film 3 .
- the dielectric film 3 is potassium sodium niobate: (K,Na)NbO 3
- a standard is Nb (oxidation-reduction potential: ⁇ 1.099 V) having the highest oxidation-reduction potential among the three elements except for oxygen.
- the electrode films 8 , 4 metal films composed of Cr (oxidation-reduction potential: ⁇ 0.74 V) and/or Ni (oxidation-reduction potential: ⁇ 0.257 V) having the oxidation-reduction potential higher than Nb.
- metal films composed of Ti (oxidation-reduction potential: ⁇ 1.63 V) having the oxidation-reduction potential lower than Nb can be used as the intermediate films 9 .
- the dielectric film 3 is magnesium oxide
- a standard is Mg (oxidation-reduction potential: ⁇ 2.356 V).
- metal films composed of Al oxidation-reduction potential: ⁇ 1.676 V
- Ti oxidation-reduction potential: ⁇ 1.63 V
- Metal films composed of Sr oxidation-reduction potential: ⁇ 2.89 V
- the intermediate films 9 are preferably composed of any element selected from Al, Ti, Zr, Ta, Cr, Co, and Ni.
- the thicknesses of the intermediate films 9 are preferably in the range of 2 nm to 5 nm, from the viewpoint of minimizing the oxidation-reduction reaction with the dielectric film 3 while enhancing the adhesion strength between the dielectric film 3 and the electrode films 4 , 8 .
- the film thicknesses of more than 5 nm can degrade the characteristics of the dielectric film, and the thicknesses of less than 2 nm can lead to insufficient function as an adhesion layer.
- the intermediate films 9 may have a preferentially oriented structure or may have a non-oriented or amorphous structure, but they preferably have the non-oriented or amorphous structure.
- the preferentially oriented, non-oriented, and amorphous structures all are as described above.
- the intermediate films 9 are preferably those such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal plane is not more than 10% of a total of intensities of all peaks.
- the dielectric film 3 is composed of potassium sodium niobate and when the intermediate films 9 are composed of Ti, the surfaces of the dielectric film 3 can be reduced because the oxidation-reduction potential of Ti: ⁇ 1.63 V is lower than that of Nb: ⁇ 1.099 V. Therefore, the thicknesses of the intermediate films 9 are preferably not too large while being enough to enhance adhesion.
- the presence of the intermediate films 9 makes it easier to improve the adhesion strength between the two electrode films 4 , 8 and the dielectric film 3 .
- a dielectric device 100 D according to an embodiment of the present invention will be described with reference to (d) in FIG. 1 .
- This dielectric device 100 D is different from the dielectric device 100 C in that electroconductive oxide films 10 are provided respectively between the dielectric film 3 and the intermediate films 9 . It is also possible to employ a single electroconductive oxide film 10 , and it can be located anywhere between the electrode film 4 , 8 and the dielectric film 3 .
- the electroconductive oxide films 10 provide an effect to suppress the oxidation-reduction reaction between the intermediate films 9 and the dielectric film 3 .
- the electroconductive oxide is preferably an oxide containing one metal element having the oxidation-reduction potential higher than every metal element forming the dielectric film 3 and containing a metal element having the oxidation-reduction potential lower than the metal element forming the intermediate films 9 .
- Examples of such electroconductive oxides include SRO (SrRuO 3 ), ITO (In 2 O 3 —SnO 2 ), and so on.
- the thicknesses of the electroconductive oxide films 10 are, for example, in the range of about 5 nm to 20 nm.
- the electroconductive oxide films 10 can be formed, for example, by sputtering.
- the electroconductive oxide films 10 may have a preferentially oriented structure or may have a non-oriented or amorphous structure, but they preferably have the non-oriented or amorphous structure.
- the preferentially oriented, non-oriented, and amorphous structures all are as described above.
- the intermediate films 9 are preferably those such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal plane is not more than 10% of a total of intensities of all peaks.
- the two principal surfaces of the dielectric film 3 both are in contact with the film having the non-oriented or amorphous structure, and an underlying film, which was used in epitaxial growth of the dielectric film 3 , is removed.
- a substrate 1 is prepared, as shown in (a) in FIG. 3 .
- substrate 1 are substrates of single-crystal Si, sapphire, magnesium oxide, and so on, and a single-crystal Si substrate is suitably applicable, particularly, in the case where a piezoelectric film of PZT or the like is formed thereon.
- a metal film 2 with a preferentially oriented structure to serve as an underlying film for dielectric film 3 is formed on the substrate 1 .
- the metal film 2 is obtained, for example, by evaporation, sputtering, or the like in such a manner that a metal material is epitaxially grown on the substrate 1 , under the condition that the substrate 1 is kept at high temperature.
- the metal material is sputtered in a state in which the Si substrate 1 is heated at about 400-600° C., the metal film 2 having structure corresponding to the surface orientation of the Si substrate 1 can be obtained.
- a dielectric film 3 having a preferentially oriented structure is formed on the metal film 2 .
- the dielectric film 3 can be obtained by sputtering or the like in such a manner that a dielectric material is epitaxially grown on the underlying layer, under the condition that the underlying layer, i.e., the substrate 1 and metal film 2 , is kept at high temperature.
- the Si substrate 1 and metal film 2 are preferably heated at about 400-600° C.
- an electrode film 4 having a non-oriented or amorphous structure is formed on the dielectric film 3 .
- the electrode film 4 is obtained by depositing a metal material on the dielectric film 3 , without epitaxial growth. Specifically, it may be deposited at low temperature by sputtering, evaporation, or the like. It can be formed at a high deposition rate in a short time.
- the substrate 1 and the dielectric film 3 are preferably kept at a temperature in the range of room temperature to 200° C.
- the electrode film 4 is bonded to a support substrate 5 by resin layer 7 .
- An example of the support substrate 5 is a polycrystalline silicon substrate.
- the resin layer 7 include epoxy resin and silicone resin, and the epoxy resin is preferably applicable, particularly, in terms of rigidity.
- the bonding may be implemented, for example, by a method of applying an adhesive in the thickness of about 2000-5000 nm onto the support substrate 5 and the electrode film 4 by spin coating and then stacking and bonding them in vacuum.
- the substrate 1 is removed from the metal film 2 .
- the removal of the substrate 1 can be implemented by a method such as CMP (chemical mechanical polishing) or RIE (reactive ion etching).
- CMP chemical mechanical polishing
- RIE reactive ion etching
- an electrode film 8 having a non-oriented or amorphous structure is formed on the metal film 2 .
- the electrode film 8 may be formed by the same method as the electrode film 4 . This completes the dielectric device 100 A having the electrode films 4 , 8 and the dielectric film 3 .
- the dielectric device 100 A can be patterned on the support substrate 5 . If necessary, a protecting film to protect the dielectric device 100 A may be formed. Furthermore, if necessary, the dielectric device 100 A can be singulated; or, it may be singulated after the dielectric device 100 A is peeled off from the support substrate 5 ; or, it may be singulated by cutting the dielectric device 100 A together with the support substrate 5 .
- the dielectric device 100 A with the electrode films 4 , 8 above and below the dielectric film 3 can be obtained in the manner as described above.
- the dielectric device 100 B can be manufactured by also removing the metal film 2 as well as the substrate 1 , in (f) in FIG. 3 .
- the dielectric device 100 C can be manufactured by forming the intermediate film 9 , before the formation of each of the electrode films 4 , 8 in the process of the dielectric device 100 B described above.
- the intermediate films may be formed by sputtering or the like.
- the intermediate films do not have to be formed by epitaxial growth.
- the dielectric device 100 D can be manufactured by forming the electroconductive oxide film 10 and intermediate film 9 in this order, before formation of each of the electrode films 4 , 8 in the process of the dielectric device 100 B described above.
- the electroconductive oxide films 10 can be formed by sputtering or the like.
- the electroconductive oxide films do not have to be formed by epitaxial growth.
- the deposition time is remarkably reduced from the conventional time of 10 to 20 minutes per layer.
- Manufacturing cost of dielectric device is significantly improved by synergistic effect of the process throughput improvement and the reduction in material cost of the electrode films 4 , 8 .
- the dielectric devices of the present invention can be manufactured by the above-described methods, they have the effects as described below. Namely, since the dielectric film 3 can be epitaxially grown on the thin metal film 2 , the dielectric film 3 is readily provided with high crystallinity. Furthermore, since the electrode films 4 , 8 can be formed respectively above and below the dielectric film 3 thereafter, degrees of freedom increase for selection of the material of the two electrode films 4 , 8 and a forming rate is increased considerably. Therefore, it becomes feasible to achieve improvement in reliability of the dielectric device and reduction of cost.
- the thin metal film 2 may or may not remain in the dielectric device eventually.
- a Pt film was epitaxially grown in the thickness of 50 nm on the surface orientation of the Si substrate 1 by sputtering to obtain a (100) preferentially oriented metal film 2 on the Si substrate 1 .
- a growth rate of the Pt film was 0.2 nm/sec.
- a potassium sodium niobate (KNN) film was epitaxially grown as dielectric film 3 in the thickness of 2000 nm on the metal film 2 by sputtering to obtain a (110) preferentially oriented dielectric film 3 .
- an Ni film was deposited in the thickness of 200 nm on the dielectric film 3 by sputtering to obtain an amorphous electrode film 4 .
- the electrode film 4 was bonded to an Si support substrate 5 by an epoxy resin layer 7 .
- the Si substrate 1 was removed from the metal film 2 by an etching process based on RIE.
- an Ni film was formed in the thickness of 200 nm on the metal film 2 by sputtering at room temperature to obtain an amorphous electrode film 8 .
- a deposition rate of the electrode film 8 was 2 nm/sec.
- a dielectric device 100 B was obtained in the same manner as in Example 1, except that the metal film 2 was also etched in addition to the Si substrate 1 in the removal of the Si substrate 1 .
- a dielectric device 100 C was obtained in the same manner as in Example 2, except that intermediate films 9 of a non-oriented structure composed of Ti were provided in the thickness of 5 nm between the dielectric film 3 and the two electrode films 4 , 8 by sputtering.
- the dielectric device 100 C was improved in adhesion of the dielectric film 3 to the electrode film 4 and the electrode film 8 .
- a dielectric device 100 D was obtained in the same manner as in Example 3, except that electroconductive oxide films 10 of a non-oriented structure composed of SrRuO 3 were provided in the thickness of 20 nm respectively between the intermediate films 9 and the dielectric film 3 by sputtering.
- the present example suppressed the oxidation-reduction reaction between the intermediate films 9 and the dielectric film 3 while enhancing the adhesion between the electrode films 4 , 8 and the dielectric film 3 , thereby achieving high reliability of the device thanks to the chemical stability of the dielectric film 3 .
- a dielectric device 100 A′ was obtained in the same manner as in Example 1, except that an (Al) 50 —(Cu) 50 alloy was used as a material for the electrode films 4 , 8 .
- a Pt film was epitaxially grown in the thickness of 200 nm on the surface orientation of the Si substrate 1 by sputtering to obtain a (100) preferentially oriented electrode film 8 ′ on the Si substrate 1 .
- a growth rate at this time was 0.2 nm/sec.
- a potassium sodium niobate (KNN) film was epitaxially grown as dielectric film 3 in the thickness of 2000 nm on the electrode film 8 ′ by sputtering to obtain a (110) preferentially oriented dielectric film 3 .
- a Pt film was deposited in the thickness of 200 nm on the dielectric film 3 by sputtering to obtain a non-oriented electrode film 4 .
- the electrode film 4 was bonded to an Si support substrate 5 by an epoxy resin layer 7 .
- the Si substrate 1 was removed from the electrode film 8 ′ by an etching process based on RIE.
- the configuration of the resultant device is shown in FIG. 4 .
- Example 1 A comparison was made between the crystallinities of the dielectric films in the dielectric devices of Example 1 and Comparative Example 1.
- the measurement was conducted by X-ray diffractometry, using a diffractometer ATX-E of Rigaku Corporation as a measuring device and the Out-of-Plane method as a measuring method. Percentages of the peak intensity of (110) orientation to the overall peak intensity were measured under this condition; the percentage in Example 1 was found to be 92% and the percentage in Comparative Example 1 was found to be 61%.
- the deposition times of the electrode film 8 and the electrode film 8 ′ were one minute and forty seconds and about seventeen minutes, respectively.
- the orientation of the dielectric film 3 deposited thereon was measured every time by X-ray diffractometry (XRD) with the aforementioned diffractometer.
- the epitaxial metal film 2 was formed by DC sputtering under the conditions of surface orientation of single-crystal Si substrate 1 : (100), composition of metal film 2 : Pt (20-200 nm) film, substrate temperature during deposition: 400° C., gas pressure: 0.10 Pa, and input power: 150 W.
- the deposition rate was 0.2 nm/sec.
- the dielectric film 3 was formed on the metal film 2 by DC sputtering under the conditions of composition of dielectric film 3 : potassium sodium niobate, substrate temperature: 550° C., gas pressure: 0.15 Pa, and input power: 700 W.
- the film thickness was 2000 nm.
- a percentage of the peak intensity ascribed to (110), which is the preferential orientation of the dielectric, to the overall peak intensity was measured by X-ray diffractometry. The measurement result is shown in FIG. 5 .
- the dielectric film demonstrated high crystallinity in the range in which the thickness of the metal film 2 was from 20 nm to 70 nm.
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Abstract
A dielectric device has a first electrode film having a non-oriented or amorphous structure, a dielectric film provided on the first electrode film and having a preferentially oriented structure, and a second electrode film provided on the dielectric film and having a non-oriented or amorphous structure.
Description
- 1. Field of the Invention
- The present invention relates to a dielectric device.
- 2. Related Background Art
- There are conventionally known dielectric devices having a dielectric film and a pair of electrode films laid on both sides of the dielectric film, as disclosed in
Patent Literatures 1 to 5. - Patent Literature 1: Japanese Patent Application Laid-open No. 2010-103194
- Patent Literature 2: Japanese Patent Application Laid-open No. 2009-094449
- Patent Literature 3: Japanese Patent Application Laid-open No. 2008-211385
- Patent Literature 4: Japanese Patent Application Laid-open No. 2007-277606
- Patent Literature 5: Japanese Patent Application Laid-open No. 2006-286911
- In the case of the conventional dielectric devices, however, it is not easy to enhance the crystallinity of the dielectric and manufacturing cost thereof is also high. The present invention has been accomplished in view of these problems and provides a dielectric device capable of readily achieving improvement in crystallinity of the dielectric and lower cost.
- A dielectric device according to the present invention comprises: a first electrode film having a non-oriented or amorphous structure; a dielectric film provided on the first electrode film and having a preferentially oriented structure; and a second electrode film provided on the dielectric film and having a non-oriented or amorphous structure.
- In the present invention the “preferentially oriented structure” refers to a structure such that in the result of X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 50% of a total of intensities of all peaks. The “non-oriented structure” refers to a structure such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal plane is less than 50% of a total of intensities of all peaks. The “amorphous structure” refers to a structure such that in X-ray diffraction measurement, no peak is observed to be ascribed to a crystal lattice plane.
- In the present invention, the dielectric film is preferably (001), (101), or (110) preferentially oriented.
- In the present invention the two electrode films can be composed of an elemental metal or can also be composed of an alloy containing two or more metals, and they may contain an element other than metals, without inhibiting the characteristics including electrical conductivity. The two electrode films can have their respective compositions different from each other, but they preferably have the same composition.
- In the present invention the dielectric may be a piezoelectric material or may be a paraelectric, pyroelectric, or ferroelectric material. Among others, the piezoelectric material is preferable.
- In the present invention, an oxidation-reduction potential of every metal element forming the first and second electrode films is preferably higher than that of every metal element forming the dielectric film. This makes the dielectric film chemically and electrically stable, without being reduced by the electrode films, thereby to further improve the lifetime and reliability of the dielectric device.
- The first and second electrode films are preferably composed of a metal selected from Al, Ti, Zr, Ta, Cr, Co, and Ni or composed of an alloy containing metals selected therefrom. Particularly, in cases where the dielectric device has the dielectric film composed of only a metal element or metal elements having a sufficiently low oxidation-reduction potential, when the constituent elements of the two electrode films are selected from the aforementioned metal elements, interfaces between the electrode films and the dielectric film become chemically and electrically stable, thereby to further improve the lifetime and reliability of the dielectric device.
- One principal surface of the dielectric film can be in contact with the first electrode film and the other principal surface of the dielectric film can be in contact with the second electrode film.
- In the present invention, the dielectric device preferably further comprises an intermediate film composed of a metal selected from Al, Ti, Zr, Ta, Cr, Co, and Ni, between at least one electrode film and the dielectric film, for the purpose of improvement in adhesion between the two films. An oxidation-reduction potential of the metal forming this intermediate film is preferably lower than that of any one of metal elements forming the dielectric film.
- The intermediate film can be in contact with the electrode film and the dielectric film.
- It is believed that a requisite minimum oxidation-reduction reaction occurs between the intermediate film and the dielectric film, so as to improve adhesion between the films. However, if the oxidation-reduction reaction is promoted too much, a composition balance of the dielectric film will be lost, so as to cause degradation of the piezoelectric property and other properties in some cases; therefore, there is, naturally, an upper limit to the film thickness of the intermediate film.
- When the dielectric device comprises the intermediate film, an electroconductive oxide film composed of an electroconductive oxide may be provided between the electrode film and the dielectric film, preferably between the intermediate film and the dielectric film, for the purpose of preventing characteristic degradation of this device. This configuration makes the dielectric film less likely to be reduced by the electrode film, thereby to further improve the device in degradation of characteristics.
- The intermediate film or the electroconductive oxide film can be in contact with the dielectric film.
- The dielectric device can further comprise a metal film having a preferentially oriented structure, between the second electrode film and the dielectric film, and the metal film can be in contact with the second electrode film and the dielectric film.
- According to the present invention, the crystallinity of the dielectric film in the dielectric device can be readily improved and it becomes feasible to achieve replacement of materials of the two electrode films with inexpensive materials and increase in throughput of deposition process.
- Sections (a) to (d) in
FIG. 1 are schematic sectional views of dielectric devices according to embodiments of the present invention. -
FIG. 2 is a table showing oxidation-reduction potentials of metals. - Sections (a) to (g) in
FIG. 3 are schematic sectional views showing methods for manufacturing the dielectric devices inFIG. 1 . -
FIG. 4 is a schematic sectional view of a dielectric device in Comparative Example 1. -
FIG. 5 is a drawing showing a relation of thickness of underlying Pt film versus degree of orientation of dielectric film. - Embodiments of the present invention will be described below in detail with reference to the drawings.
- (Dielectric Device 100A)
- A
dielectric device 100A according to an embodiment of the present invention will be described with reference to (a) inFIG. 1 . Thedielectric device 100A is disposed on aresin layer 7 which is laid on asupport substrate 5, and has afirst electrode film 4, adielectric film 3, ametal film 2, and asecond electrode film 8 in the order named. - (Dielectric Film 3)
- The
dielectric film 3 has a preferentially oriented structure. The “preferentially oriented structure” refers to a structure such that in the result of X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 50% of a total of intensities of all peaks. Thedielectric film 3 is preferably one such that in the result of X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 80% of a total of intensities of all peaks. - The
dielectric film 3 is preferably (001), (101), or (110) preferentially oriented. This configuration allows thedielectric film 3 to be a dielectric body with excellent characteristics. - When a piezoelectric film is used as the
dielectric film 3, examples of piezoelectric film preferably applicable include films of KNN or equivalently (K,Na)NbO3, LN or equivalently LiNbO3, AlN, and so on. Other applicable materials for thedielectric film 3 include MgO, STO or equivalently SrTiO3, BTO or equivalently BaTiO3, and so on. - There are no particular restrictions on the thickness of the
dielectric film 3, but the thickness is normally in the range of about 1000 nm to 4000 nm. - (Electrode Films 4, 8)
- The
first electrode film 4 is laid on a bottom surface of thedielectric film 3, while thesecond electrode film 8 is laid on a top surface of thedielectric film 3. Each of thefirst electrode film 4 and thesecond electrode film 8 has a non-oriented or amorphous structure. Both of the two electrode films may have the amorphous structure; or, both of the electrode films may have the non-oriented structure; or, one electrode film may have the non-oriented structure while the other electrode film has the amorphous structure. - The “non-oriented structure” refers to a structure such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal plane is less than 50% of a total of intensities of all peaks. The
4, 8 are preferably those such that an intensity of a peak ascribed to a certain crystal lattice plane is not more than 10% of a total of intensities of all peaks. The “amorphous structure” refers to a structure such that in X-ray diffraction measurement no peak is observed to be attributed to a crystal lattice plane.electrode films - The
4, 8 are composed of a metal element or metal elements and there are no particular restrictions on the metal element or metal elements, which can be selected from a wide variety of elemental metals and alloys.electrode films - In terms of improvement in reliability to prevent degradation of characteristics due to the battery effect, however, an oxidation-reduction potential of every metal forming the
4, 8 is preferably higher than that of every metal element forming theelectrode films dielectric film 3. When this condition is met, an oxidation-reduction reaction is remarkably suppressed between thedielectric film 3 and the 4, 8 to reduce time degradation of theelectrode films dielectric film 3 due to the battery effect, so as to enhance the reliability of the device. The material of each of the 4, 8 preferably has a melting point sufficiently higher than heat loads applied in subsequent processes.electrode films - For example, when the
dielectric film 3 is composed of barium titanate, the 4, 8 to be employed are preferably films composed of a metal selected from Zr, Ta, Cr, Fe, Co, Ni, and Cu having the oxidation-reduction potentials higher than that of Ti (oxidation-reduction potential: −1.63 V or higher), or films composed of any one of alloys of these metals.electrode films - For example, when the
dielectric film 3 is composed of potassium sodium niobate (KNN), the 4, 8 to be employed are preferably films composed of a metal selected from Ta, Cr, Fe, Co, Ni, and Cu having the oxidation-reduction potentials higher than that of Nb (oxidation-reduction potential: −1.099 V), or films composed of any one of alloys of these metals.electrode films - When the
dielectric film 3 is composed of magnesium oxide, the metal films to be used are preferably films composed of a metal selected from Al, Ti, Zr, Ta, Cr, Fe, Co, Ni, and Cu having the oxidation-reduction potentials higher than that of Mg (oxidation-reduction potential: −2.356 V), or films composed of any one of alloys of these metals; particularly, it is possible to adopt even Al and Ti. - When the
dielectric film 3 is composed of PZT (lead zirconate titanate), the material to be selected can be an electrode material (e.g., Cu or the like) having the oxidation-reduction potential higher than that of Pb (oxidation-reduction potential: −1.126 V). - As described above, the material of the
4, 8 to be employed can be any one of materials with a relatively low melting point other than Pt, Ir, Pd, and Rh having high melting points.electrode films - Examples of alloy materials to be used for the
4, 8 include Al—Cu alloys, Ti—Al—Cr alloys, and Ni—Cr alloys and it is particularly preferable to use one of the Al—Cu alloys, for the reasons of low electric resistance and low power consumption.electrode films - The electrode film materials of the
4, 8 are preferably the same material. Since the materials of theelectrode films 4, 8 can be selected from the wide selection range of metals or alloys, inexpensive materials can also be used as long as the conditions including the resistance to process temperatures are satisfied.electrode films - There are no particular restrictions on the thicknesses of the
4, 8, but they can be determined in the range of 100 nm to 200 nm.electrode films - (Metal Film 2)
- The
metal film 2 is provided between thesecond electrode film 8 and thedielectric film 3 and themetal film 2 is in contact with thedielectric film 3 and thesecond electrode film 4. Themetal film 2 has a preferentially oriented structure; that is, themetal film 2 has a structure such that in X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 50% of a total of intensities of all peaks. Themetal film 2 is preferably one such that in X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 80% of a total of intensities of all peaks. The thickness of themetal film 2 is selected so as to enhance the crystallinity of thedielectric film 3 epitaxially grown in contact with themetal film 2. - For example, when the
dielectric film 3 is a piezoelectric film, the thickness of themetal film 2 is preferably in the range of 20 nm to 70 nm (cf.FIG. 5 ). In this small thickness range, it is difficult for themetal film 2 alone to function as a lower electrode film of thedielectric device 100A. A metal forming themetal film 2 can be selected from metals (including alloys) having the a-axis lattice constant smaller than that of thedielectric film 3 and having thermal resistance to temperature during deposition of the dielectric film, and it is preferable to select Pt or Rh. - There is the
metal film 2 remaining between thedielectric film 3 and theelectrode film 8, while there is no other film between thedielectric film 3 and theelectrode film 4. - (
Dielectric Device 100B) - A
dielectric device 100B according to an embodiment of the present invention will be described with reference to (b) inFIG. 1 . Thisdielectric device 100B is different from thedielectric device 100A in that thedielectric device 100B does not have themetal film 2 and therefore theelectrode film 8 and thedielectric film 3 are in direct contact. Furthermore, there is no other film between thedielectric film 3 and theelectrode film 8, as in the first embodiment. - (
Dielectric Device 100C) - A
dielectric device 100C according to an embodiment of the present invention will be described with reference to (c) inFIG. 1 . Thisdielectric device 100C is different from thedielectric device 100B in thatintermediate films 9 composed of a metal having the oxidation-reduction potential lower than that of any one of metal elements forming thedielectric film 3 are provided, one between theelectrode film 8 and thedielectric film 3 and the other between theelectrode film 4 and thedielectric film 3. - For example, when the
dielectric film 3 is potassium sodium niobate: (K,Na)NbO3, a standard is Nb (oxidation-reduction potential: −1.099 V) having the highest oxidation-reduction potential among the three elements except for oxygen. As described above, it is preferable to use as the 8, 4, metal films composed of Cr (oxidation-reduction potential: −0.74 V) and/or Ni (oxidation-reduction potential: −0.257 V) having the oxidation-reduction potential higher than Nb. Then, metal films composed of Ti (oxidation-reduction potential: −1.63 V) having the oxidation-reduction potential lower than Nb can be used as theelectrode films intermediate films 9. - When the
dielectric film 3 is magnesium oxide, a standard is Mg (oxidation-reduction potential: −2.356 V). As described previously, it is preferable to use as the 4, 8, metal films composed of Al (oxidation-reduction potential: −1.676 V) and/or Ti (oxidation-reduction potential: −1.63 V). Metal films composed of Sr (oxidation-reduction potential: −2.89 V) can be used as theelectrode films intermediate films 9. - The
intermediate films 9 are preferably composed of any element selected from Al, Ti, Zr, Ta, Cr, Co, and Ni. - The thicknesses of the
intermediate films 9 are preferably in the range of 2 nm to 5 nm, from the viewpoint of minimizing the oxidation-reduction reaction with thedielectric film 3 while enhancing the adhesion strength between thedielectric film 3 and the 4, 8. The film thicknesses of more than 5 nm can degrade the characteristics of the dielectric film, and the thicknesses of less than 2 nm can lead to insufficient function as an adhesion layer. Theelectrode films intermediate films 9 may have a preferentially oriented structure or may have a non-oriented or amorphous structure, but they preferably have the non-oriented or amorphous structure. The preferentially oriented, non-oriented, and amorphous structures all are as described above. Theintermediate films 9 are preferably those such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal plane is not more than 10% of a total of intensities of all peaks. - For example, when the
dielectric film 3 is composed of potassium sodium niobate and when theintermediate films 9 are composed of Ti, the surfaces of thedielectric film 3 can be reduced because the oxidation-reduction potential of Ti: −1.63 V is lower than that of Nb: −1.099 V. Therefore, the thicknesses of theintermediate films 9 are preferably not too large while being enough to enhance adhesion. - Even if the metal element forming the
4, 8 has the oxidation-reduction potential higher than every metal element forming theelectrode films dielectric film 3, the presence of theintermediate films 9 makes it easier to improve the adhesion strength between the two 4, 8 and theelectrode films dielectric film 3. - (
Dielectric Device 100D) - A
dielectric device 100D according to an embodiment of the present invention will be described with reference to (d) inFIG. 1 . Thisdielectric device 100D is different from thedielectric device 100C in thatelectroconductive oxide films 10 are provided respectively between thedielectric film 3 and theintermediate films 9. It is also possible to employ a singleelectroconductive oxide film 10, and it can be located anywhere between the 4, 8 and theelectrode film dielectric film 3. - The
electroconductive oxide films 10 provide an effect to suppress the oxidation-reduction reaction between theintermediate films 9 and thedielectric film 3. The electroconductive oxide is preferably an oxide containing one metal element having the oxidation-reduction potential higher than every metal element forming thedielectric film 3 and containing a metal element having the oxidation-reduction potential lower than the metal element forming theintermediate films 9. Examples of such electroconductive oxides include SRO (SrRuO3), ITO (In2O3—SnO2), and so on. - The thicknesses of the
electroconductive oxide films 10 are, for example, in the range of about 5 nm to 20 nm. Theelectroconductive oxide films 10 can be formed, for example, by sputtering. - The
electroconductive oxide films 10 may have a preferentially oriented structure or may have a non-oriented or amorphous structure, but they preferably have the non-oriented or amorphous structure. The preferentially oriented, non-oriented, and amorphous structures all are as described above. Theintermediate films 9 are preferably those such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal plane is not more than 10% of a total of intensities of all peaks. - In the
dielectric devices 100B-100D, the two principal surfaces of thedielectric film 3 both are in contact with the film having the non-oriented or amorphous structure, and an underlying film, which was used in epitaxial growth of thedielectric film 3, is removed. - (Methods for Manufacturing Dielectric Devices)
- Methods for manufacturing the above-described
dielectric devices 100A-100D will be described below with reference toFIG. 3 . - First, a
substrate 1 is prepared, as shown in (a) inFIG. 3 . Examples ofsubstrate 1 are substrates of single-crystal Si, sapphire, magnesium oxide, and so on, and a single-crystal Si substrate is suitably applicable, particularly, in the case where a piezoelectric film of PZT or the like is formed thereon. - Next, as shown in (b) in
FIG. 3 , ametal film 2 with a preferentially oriented structure to serve as an underlying film fordielectric film 3 is formed on thesubstrate 1. Themetal film 2 is obtained, for example, by evaporation, sputtering, or the like in such a manner that a metal material is epitaxially grown on thesubstrate 1, under the condition that thesubstrate 1 is kept at high temperature. For example, when the metal material is sputtered in a state in which theSi substrate 1 is heated at about 400-600° C., themetal film 2 having structure corresponding to the surface orientation of theSi substrate 1 can be obtained. - Next, as shown in (c) in
FIG. 3 , adielectric film 3 having a preferentially oriented structure is formed on themetal film 2. Thedielectric film 3 can be obtained by sputtering or the like in such a manner that a dielectric material is epitaxially grown on the underlying layer, under the condition that the underlying layer, i.e., thesubstrate 1 andmetal film 2, is kept at high temperature. TheSi substrate 1 andmetal film 2 are preferably heated at about 400-600° C. - Next, as shown in (d) in
FIG. 3 , anelectrode film 4 having a non-oriented or amorphous structure is formed on thedielectric film 3. - The
electrode film 4 is obtained by depositing a metal material on thedielectric film 3, without epitaxial growth. Specifically, it may be deposited at low temperature by sputtering, evaporation, or the like. It can be formed at a high deposition rate in a short time. Thesubstrate 1 and thedielectric film 3 are preferably kept at a temperature in the range of room temperature to 200° C. - Next, as shown in (e) in
FIG. 3 , after the deposition of theelectrode film 4, theelectrode film 4 is bonded to asupport substrate 5 byresin layer 7. - An example of the
support substrate 5 is a polycrystalline silicon substrate. Examples of theresin layer 7 include epoxy resin and silicone resin, and the epoxy resin is preferably applicable, particularly, in terms of rigidity. The bonding may be implemented, for example, by a method of applying an adhesive in the thickness of about 2000-5000 nm onto thesupport substrate 5 and theelectrode film 4 by spin coating and then stacking and bonding them in vacuum. - Next, as shown in (f) in
FIG. 3 , thesubstrate 1 is removed from themetal film 2. The removal of thesubstrate 1 can be implemented by a method such as CMP (chemical mechanical polishing) or RIE (reactive ion etching). After thesubstrate 1 is removed, themetal film 2, which was the underlying film for thedielectric film 3, is exposed as the outermost surface. - Subsequently, as shown in (g) in
FIG. 3 , anelectrode film 8 having a non-oriented or amorphous structure is formed on themetal film 2. Theelectrode film 8 may be formed by the same method as theelectrode film 4. This completes thedielectric device 100A having the 4, 8 and theelectrode films dielectric film 3. - If necessary, the
dielectric device 100A can be patterned on thesupport substrate 5. If necessary, a protecting film to protect thedielectric device 100A may be formed. Furthermore, if necessary, thedielectric device 100A can be singulated; or, it may be singulated after thedielectric device 100A is peeled off from thesupport substrate 5; or, it may be singulated by cutting thedielectric device 100A together with thesupport substrate 5. - The
dielectric device 100A with the 4, 8 above and below theelectrode films dielectric film 3 can be obtained in the manner as described above. - The
dielectric device 100B can be manufactured by also removing themetal film 2 as well as thesubstrate 1, in (f) inFIG. 3 . - The
dielectric device 100C can be manufactured by forming theintermediate film 9, before the formation of each of the 4, 8 in the process of theelectrode films dielectric device 100B described above. The intermediate films may be formed by sputtering or the like. The intermediate films do not have to be formed by epitaxial growth. - The
dielectric device 100D can be manufactured by forming theelectroconductive oxide film 10 andintermediate film 9 in this order, before formation of each of the 4, 8 in the process of theelectrode films dielectric device 100B described above. Theelectroconductive oxide films 10 can be formed by sputtering or the like. The electroconductive oxide films do not have to be formed by epitaxial growth. - In this
dielectric device 100A, since substrate heating and low-rate sputtering are not essential conditions in the deposition of the 4, 8, the deposition time is remarkably reduced from the conventional time of 10 to 20 minutes per layer. Manufacturing cost of dielectric device is significantly improved by synergistic effect of the process throughput improvement and the reduction in material cost of theelectrode films 4, 8.electrode films - Namely, since the dielectric devices of the present invention can be manufactured by the above-described methods, they have the effects as described below. Namely, since the
dielectric film 3 can be epitaxially grown on thethin metal film 2, thedielectric film 3 is readily provided with high crystallinity. Furthermore, since the 4, 8 can be formed respectively above and below theelectrode films dielectric film 3 thereafter, degrees of freedom increase for selection of the material of the two 4, 8 and a forming rate is increased considerably. Therefore, it becomes feasible to achieve improvement in reliability of the dielectric device and reduction of cost. Theelectrode films thin metal film 2 may or may not remain in the dielectric device eventually. - In a state in which an
Si substrate 1 was heated at 400° C., a Pt film was epitaxially grown in the thickness of 50 nm on the surface orientation of theSi substrate 1 by sputtering to obtain a (100) preferentially orientedmetal film 2 on theSi substrate 1. A growth rate of the Pt film was 0.2 nm/sec. Thereafter, in a state in which theSi substrate 1 was heated at 550° C., a potassium sodium niobate (KNN) film was epitaxially grown asdielectric film 3 in the thickness of 2000 nm on themetal film 2 by sputtering to obtain a (110) preferentially orienteddielectric film 3. Subsequently, at room temperature, an Ni film was deposited in the thickness of 200 nm on thedielectric film 3 by sputtering to obtain anamorphous electrode film 4. Thereafter, theelectrode film 4 was bonded to anSi support substrate 5 by anepoxy resin layer 7. Thereafter, theSi substrate 1 was removed from themetal film 2 by an etching process based on RIE. Then an Ni film was formed in the thickness of 200 nm on themetal film 2 by sputtering at room temperature to obtain anamorphous electrode film 8. A deposition rate of theelectrode film 8 was 2 nm/sec. - A
dielectric device 100B was obtained in the same manner as in Example 1, except that themetal film 2 was also etched in addition to theSi substrate 1 in the removal of theSi substrate 1. - A
dielectric device 100C was obtained in the same manner as in Example 2, except thatintermediate films 9 of a non-oriented structure composed of Ti were provided in the thickness of 5 nm between thedielectric film 3 and the two 4, 8 by sputtering. Theelectrode films dielectric device 100C was improved in adhesion of thedielectric film 3 to theelectrode film 4 and theelectrode film 8. - A
dielectric device 100D was obtained in the same manner as in Example 3, except thatelectroconductive oxide films 10 of a non-oriented structure composed of SrRuO3 were provided in the thickness of 20 nm respectively between theintermediate films 9 and thedielectric film 3 by sputtering. The present example suppressed the oxidation-reduction reaction between theintermediate films 9 and thedielectric film 3 while enhancing the adhesion between the 4, 8 and theelectrode films dielectric film 3, thereby achieving high reliability of the device thanks to the chemical stability of thedielectric film 3. - A
dielectric device 100A′ was obtained in the same manner as in Example 1, except that an (Al)50—(Cu)50 alloy was used as a material for the 4, 8.electrode films - In a state in which an
Si substrate 1 was heated at 400° C., a Pt film was epitaxially grown in the thickness of 200 nm on the surface orientation of theSi substrate 1 by sputtering to obtain a (100) preferentially orientedelectrode film 8′ on theSi substrate 1. A growth rate at this time was 0.2 nm/sec. Thereafter, in a state in which theSi substrate 1 was heated at 550° C., a potassium sodium niobate (KNN) film was epitaxially grown asdielectric film 3 in the thickness of 2000 nm on theelectrode film 8′ by sputtering to obtain a (110) preferentially orienteddielectric film 3. Subsequently, at room temperature, a Pt film was deposited in the thickness of 200 nm on thedielectric film 3 by sputtering to obtain anon-oriented electrode film 4. Thereafter, theelectrode film 4 was bonded to anSi support substrate 5 by anepoxy resin layer 7. Thereafter, theSi substrate 1 was removed from theelectrode film 8′ by an etching process based on RIE. The configuration of the resultant device is shown inFIG. 4 . - A comparison was made between the crystallinities of the dielectric films in the dielectric devices of Example 1 and Comparative Example 1. The measurement was conducted by X-ray diffractometry, using a diffractometer ATX-E of Rigaku Corporation as a measuring device and the Out-of-Plane method as a measuring method. Percentages of the peak intensity of (110) orientation to the overall peak intensity were measured under this condition; the percentage in Example 1 was found to be 92% and the percentage in Comparative Example 1 was found to be 61%.
- In the dielectric devices of Example 1 and Comparative Example 1, the deposition times of the
electrode film 8 and theelectrode film 8′ were one minute and forty seconds and about seventeen minutes, respectively. - With change in film thickness of the
metal film 2 deposited on the single-crystal Si substrate, the orientation of thedielectric film 3 deposited thereon was measured every time by X-ray diffractometry (XRD) with the aforementioned diffractometer. Theepitaxial metal film 2 was formed by DC sputtering under the conditions of surface orientation of single-crystal Si substrate 1: (100), composition of metal film 2: Pt (20-200 nm) film, substrate temperature during deposition: 400° C., gas pressure: 0.10 Pa, and input power: 150 W. The deposition rate was 0.2 nm/sec. - The
dielectric film 3 was formed on themetal film 2 by DC sputtering under the conditions of composition of dielectric film 3: potassium sodium niobate, substrate temperature: 550° C., gas pressure: 0.15 Pa, and input power: 700 W. The film thickness was 2000 nm. For each of samples in which the films up to thedielectric film 3 were deposited, a percentage of the peak intensity ascribed to (110), which is the preferential orientation of the dielectric, to the overall peak intensity was measured by X-ray diffractometry. The measurement result is shown inFIG. 5 . As shown inFIG. 5 , the dielectric film demonstrated high crystallinity in the range in which the thickness of themetal film 2 was from 20 nm to 70 nm.
Claims (17)
1. A dielectric device comprising:
a first electrode film having a non-oriented or amorphous structure;
a dielectric film provided on the first electrode film and having a preferentially oriented structure; and
a second electrode film provided on the dielectric film and having a non-oriented or amorphous structure.
2. The dielectric device according to claim 1 , wherein the dielectric film is (001), (101), or (110) preferentially oriented.
3. The dielectric device according to claim 1 , wherein the dielectric film is a piezoelectric material.
4. The dielectric device according to claim 1 , wherein an oxidation-reduction potential of every metal element forming the first and second electrode films is higher than an oxidation-reduction potential of every metal element forming the dielectric film.
5. The dielectric device according to claim 1 , wherein the first and second electrode films are composed of one selected from Al, Ti, Zr, Ta, Cr, Co, and Ni.
6. The dielectric device according to claim 1 , wherein the first and second electrode films are composed of an alloy containing at least one selected from Al, Ti, Zr, Ta, Cr, Co, and Ni.
7. The dielectric device according to claim 1 , wherein one principal surface of the dielectric film is in contact with the first electrode film and the other principal surface of the dielectric film is in contact with the second electrode film.
8. The dielectric device according to claim 1 , further comprising: an intermediate film composed of an element selected from Al, Ti, Zr, Ta, Cr, Co, and Ni, between the dielectric film and at least one said electrode film.
9. The dielectric device according to claim 8 , wherein the intermediate film is in contact with the electrode film and the dielectric film.
10. The dielectric device according to claim 8 , further comprising an electroconductive oxide film between the dielectric film and at least one said electrode film.
11. The dielectric device according to claim 10 , wherein the intermediate film or the electroconductive oxide film is in contact with the dielectric film.
12. The dielectric device according to claim 1 , further comprising a metal film having a preferentially oriented structure, between the second electrode film and the dielectric film, wherein the metal film is in contact with the second electrode film and the dielectric film.
13. The dielectric device according to claim 1 , wherein thicknesses of the first and second electrode films are in the range of 100 nm to 200 nm.
14. The dielectric device according to claim 1 , wherein the dielectric film is one such that in X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 50% of a total of intensities of all peaks.
15. The dielectric device according to claim 1 , wherein the dielectric film is one such that in X-ray diffraction measurement, an intensity of a peak ascribed to a certain crystal lattice plane is not less than 80% of a total of intensities of all peaks.
16. The dielectric device according to claim 1 , wherein the first electrode film and the second electrode film are films such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal lattice plane is less than 50% of a total of intensities of all peaks.
17. The dielectric device according to claim 1 , wherein the first electrode film and the second electrode film are films such that in X-ray diffraction measurement, an intensity of a peak ascribed to any crystal lattice plane is not more than 10% of a total of intensities of all peaks.
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| US13/487,530 US20130320813A1 (en) | 2012-06-04 | 2012-06-04 | Dielectric device |
| DE112013002782.8T DE112013002782B4 (en) | 2012-06-04 | 2013-05-14 | Method of manufacturing a dielectric device and dielectric device |
| PCT/JP2013/063877 WO2013183428A1 (en) | 2012-06-04 | 2013-05-14 | Dielectric device |
| JP2014554642A JP6065022B2 (en) | 2012-06-04 | 2013-05-14 | Method for manufacturing dielectric device |
| CN201380029575.XA CN104364923B (en) | 2012-06-04 | 2013-05-14 | Dielectric device |
| US15/800,873 US10964879B2 (en) | 2012-06-04 | 2017-11-01 | Method of manufacturing a dielectric device |
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| US15/800,873 Continuation US10964879B2 (en) | 2012-06-04 | 2017-11-01 | Method of manufacturing a dielectric device |
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| US15/800,873 Active 2033-10-10 US10964879B2 (en) | 2012-06-04 | 2017-11-01 | Method of manufacturing a dielectric device |
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| JP (1) | JP6065022B2 (en) |
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| US20140035439A1 (en) * | 2012-08-03 | 2014-02-06 | Tdk Corporation | Piezoelectric device |
| US9136820B2 (en) | 2012-07-31 | 2015-09-15 | Tdk Corporation | Piezoelectric device |
| US12414472B2 (en) | 2019-03-20 | 2025-09-09 | Nitto Denko Corporation | Layered structure, piezoelectric device using the same, and method of manufacturing piezoelectric device |
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| JP6155420B2 (en) * | 2014-08-08 | 2017-07-05 | 株式会社野田スクリーン | Thin film capacitor sheet manufacturing method |
| US11276531B2 (en) * | 2017-05-31 | 2022-03-15 | Tdk Corporation | Thin-film capacitor and method for manufacturing thin-film capacitor |
| JP7035722B2 (en) * | 2018-03-30 | 2022-03-15 | Tdk株式会社 | Capacitors and methods for manufacturing capacitors |
| JP2023029041A (en) * | 2021-08-20 | 2023-03-03 | 株式会社レゾナック | Manufacturing method for laminated body |
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Also Published As
| Publication number | Publication date |
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| JP2015523705A (en) | 2015-08-13 |
| JP6065022B2 (en) | 2017-01-25 |
| US10964879B2 (en) | 2021-03-30 |
| CN104364923A (en) | 2015-02-18 |
| CN104364923B (en) | 2017-09-05 |
| DE112013002782T5 (en) | 2015-02-26 |
| WO2013183428A1 (en) | 2013-12-12 |
| US20180076379A1 (en) | 2018-03-15 |
| DE112013002782B4 (en) | 2020-03-26 |
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