US20030091846A1 - Granular thin magnetic film and method of manufacturing the film, laminated magnetic film, magnetic part, and electronic device - Google Patents
Granular thin magnetic film and method of manufacturing the film, laminated magnetic film, magnetic part, and electronic device Download PDFInfo
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- US20030091846A1 US20030091846A1 US10/221,869 US22186902A US2003091846A1 US 20030091846 A1 US20030091846 A1 US 20030091846A1 US 22186902 A US22186902 A US 22186902A US 2003091846 A1 US2003091846 A1 US 2003091846A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/30—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE]
- H01F41/301—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE] for applying ultrathin or granular layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/007—Thin magnetic films, e.g. of one-domain structure ultrathin or granular films
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
- H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
- H01F10/12—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being metals or alloys
- H01F10/13—Amorphous metallic alloys, e.g. glassy metals
- H01F10/138—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/32—Spin-exchange-coupled multilayers, e.g. nanostructured superlattices
- H01F10/3227—Exchange coupling via one or more magnetisable ultrathin or granular films
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/18—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by cathode sputtering
- H01F41/183—Sputtering targets therefor
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F10/00—Thin magnetic films, e.g. of one-domain structure
- H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
- H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
- H01F10/12—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being metals or alloys
- H01F10/13—Amorphous metallic alloys, e.g. glassy metals
- H01F10/132—Amorphous metallic alloys, e.g. glassy metals containing cobalt
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
- Y10T428/12618—Plural oxides
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31826—Of natural rubber
- Y10T428/3183—Next to second layer of natural rubber
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- 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
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/32—Composite [nonstructural laminate] of inorganic material having metal-compound-containing layer and having defined magnetic layer
Definitions
- the present invention relates to a granular magnetic thin film in which magnetic grains are scattered in an insulating material and a method of making the same, a multilayered magnetic film, magnetic components and electronic equipment and more particularly to improvements in and relating to the magnetic properties in high frequency bands.
- Typical of such materials as expected for use in such high frequency bands is a nano-granular magnetic thin film of the type in which the grains of a magnetic material are included in an insulating material.
- the nano-granular magnetic thin film has a structure in which the magnetic grains of the order of a nano-scale (nm, 10 ⁇ 9 m) are enclosed by the grain boundaries of the insulating material.
- Japanese Laid-Open Patent Publication No. 9-82522 proposes a magnetic film designed to obtain an uniaxial magnetic anisotropy of a proper magnitude and a permeability having excellent high frequency characteristics including a high electric resistance and a high degree of saturation magnetization.
- Japanese Laid-Open Patent Publication No. 10-270246 proposes a magnetic film designed to obtain excellent soft magnetic properties in high frequency bands including an anisotropic magnetic field of over 20 oersted (Oe), an electric specific resistance value of 50 ⁇ cm or over and a saturation magnetic flux density of 16 kG or over.
- nano-granular magnetic thin films employing CoFe alloy attract a notice in that they have a structure in which the magnetic grains of CoFe alloy crystals are enclosed by the grain boundaries of the insulating material composed of a ceramic and both a high saturation magnetization and a high electric specific resistance coexist with each other.
- nano-granular films are relatively high in resistivity than metallic magnetic films due to the structure in which the magnetic grains are enclosed by the insulating material, it cannot be said that they are sufficiently high in resistivity as compared with oxide magnetic material such as ferrite.
- oxide magnetic material such as ferrite.
- the above-mentioned multilayered magnetic film is such that while the resistivity is increased by the introduction of the insulating layers, capacitors are formed within the magnetic film because of its multilayered structure thus causing a loss due to a displacement current.
- the thickness of the insulating layers is relatively large ranging from 100 nm to several ⁇ m so that there is a disadvantage of decreasing the magnetic coupling between the magnetic grains holding the insulating layers therebetween thus eventually failing to ensure adequate magnetic properties.
- the present invention has stemmed from the noticing of the foregoing deficiencies, and it is an object of the present invention to provide a magnetic thin film utilizing a granular film and having excellent high frequency characteristics, a method of producing the same, and a multilayered magnetic film and magnetic components and electronic equipment utilizing the same.
- the present invention consists in a granular magnetic thin film in which an insulating material is present around grain boundaries so as to enclose magnetic grains and which is characterized in the following:
- the thickness of the insulating material (the spacing between the magnetic grains) is between 0.5 nm and 1.5 nm, or
- the production method of the granular magnetic thin film according to the present invention is characterized by the steps of preparing a magnetic metal target and an insulating material target, respectively, and sputtering the targets simultaneously in a nonoxidizing atmosphere, thereby forming on a substrate a thin film in which the insulating material is present around grain boundaries so as to enclose magnetic grains.
- a nano-granular magnetic thin film of the present invention is characterized in that the film is formed by utilizing the following:
- the size of the magnetic grains is less than 10 nm (100 ⁇ ).
- the thickness of the insulating material or the spacing between the magnetic grains should preferably be between 0.5 nm (5 ⁇ ) and 1.5 nm (15 ⁇ ).
- the multilayered magnetic film of the present invention is a multilayered magnetic film made by alternately laminating magnetic layers each composed of a granular film including magnetic grains enclosed by an insulating material and insulating layers and it is characterized in that the thicknesses of the magnetic layers and the insulating layers are predetermined such that the growth of the magnetic grains is prevented by the insulating layers.
- the magnetic layer is composed of a CoFeAlO film and the insulating layer is composed of an Al 2 O 3 film. More specifically, it features that if WM represents the thickness of the magnetic layer and WI represents the thickness of the insulating layer, any one of the following relations is satisfied,
- the magnetic layer is composed of a CoFeSiO film and the insulating layer is composed of an SiO 2 film. More specifically, if WM represents the thickness of the magnetic layer and WI represents the thickness of the insulating layer, the following relations are satisfied,
- the magnetic components of the present invention each has a feature of employing the foregoing granular thin film(s) or multilayered magnetic film(s) as its magnetic material.
- One of their primary forms features that it is formed with oxidation preventive films for preventing oxidation of the magnetic metal in the granular magnetic film or multilayered magnetic film.
- the electronic equipment of the present invention have a feature of employing such magnetic component(s).
- FIG. 1 is a diagram showing the construction of a nano-granular magnetic thin film according to Embodiment 1 of the present invention.
- FIG. 2 illustrates graphs showing exemplary measurements of the metal grain spectral of the magnetic thin film according to the above-mentioned embodiment by an X-ray photoelectron spectroscopy.
- FIG. 3 is a graph showing an exemplary measurement by a single turn coil method of the frequency characteristics of the permeability in the magnetic thin film of the above-mentioned embodiment.
- FIG. 4 is a photograph showing an exemplary TEM observation image of the magnetic thin film according to the above embodiment.
- FIG. 5 is a principal sectional perspective view showing a thin film inductor according to Embodiment 2 of the present invention.
- FIG. 6 is a graph showing an exemplary measurement of the frequency characteristics of the inductance in the above thin film inductor.
- FIG. 7 is a principal sectional perspective view of a thin film inductor according to Embodiment 3 of the present invention.
- FIG. 8 is a principal sectional view showing the basic construction of a multilayered magnetic film according to the present invention.
- FIG. 9 is a series of graphs showing the frequency characteristics of the permeability in exemplary forms of the above multilayered magnetic film and comparative examples.
- FIG. 10 illustrates graphs each showing the relation between the resistivity and the thickness of the magnetic layers in the above embodiment.
- FIG. 11 illustrates graphs each showing the relation between the real part of the permeability and the thickness of the magnetic layers in the above embodiment.
- FIG. 12 illustrates graphs each showing the relation between the resistivity and the thickness of the insulating layers in the above embodiment.
- FIG. 13 illustrates graphs each showing the relation between the real part of the permeability and the thickness of the insulating layers in the above embodiment.
- FIG. 14 illustrates graphs respectively showing the inductance frequency characteristics of a thin film inductor utilizing the multilayered magnetic film(s) of the above embodiment and a comparative example.
- FIG. 15 is a perspective view showing an exemplary embodiment of the magnetic components and electronic equipment of the present invention.
- FIG. 16 is a circuit diagram showing an exemplary equivalent circuit of an MMIC to which the present invention is applied.
- FIG. 17 illustrates graphs showing other exemplary measurements of the metal grain spectral in the magnetic thin film of Embodiment 1 by the X-ray photoelectron spectroscopy.
- the present embodiment is an embodiment of a nano-granular magnetic thin film and its production method.
- a description will be first made of a case in which a CoFeAlO nano-granular film is formed by means of a dual-target simultaneous nonreactive sputtering using a CoFe alloy target and an Al 2 O 3 target.
- the production conditions of the samples produced are as follows. Differing from the conventional film forming methods, the method of this embodiment features that no oxygen is supplied during the film formation. Also, a rare gas such as argon is used as a sputtering gas.
- Substrate temperature 20° C.
- Substrate Si single crystal substrate
- FIG. 1 shows the construction of the sample magnetic thin film produced and magnetic grains 12 composed of CoFe alloy are scattered in an insulating material 10 composed of Al 2 O 3 .
- the insulating material 10 is present around the grain boundaries so as to enclose the magnetic grains 12 .
- FIG. 2 shows the measurement results of the samples produced according to the XPS (X-ray photoelectron spectroscopy).
- the abscissa represents the bound energy and the ordinate represents the intensity.
- the XPS measurement is conducted by using MgK ⁇ -rays and the sample is irradiated with X-rays generated at an applied current of 5 mA and an applied voltage of 12 kV.
- FIG. 2(A) shows the measurement of 2p orbital electrons of Al. As shown in the Figure, only the peak of Al 2 O 3 or an oxide is measured and it is possible to presume that Al 2 O 3 in the sample acts effectively as an insulating material.
- FIG. 2(B) shows the measurement made with respect to 2p orbital electrons of Co and FIG. 2(C) shows the measurement of 2p orbital electrons of Fe.
- FIG. 2(C) shows the measurement of 2p orbital electrons of Fe.
- FIG. 17 shows the measurement results by the XPS of magnetic thin film samples produced, as other examples, by the dual-target simultaneous nonreactive sputtering using a CoFe alloy target and an SiO 2 target.
- the abscissa represents the bound energy and the ordinate represents the intensity.
- the manufacturing conditions of the samples are the same as in the case of the previously mentioned CoFeAlO nano-granular film and no oxygen is supplied during film formation.
- the XPS measuring conditions are the same.
- FIG. 17(A) shows the measurement result of 2s orbital electrons of Si.
- SiO 2 the peak of SiO 2
- no peak of Si is observed.
- Si is present in the state of SiO 2 and it is presumed that it effectively functions as an insulating material.
- the 2p orbit is used for the analysis of Si, in the present case the 2p orbit overlaps with the 3s orbit of Co and therefore the 2s orbit is employed.
- the peak of SiO 2 is observed in the result of the 1s orbit of O (oxygen) shown in FIG. 17(B), showing that Si is present in the form of SiO 2 .
- FIG. 17(C) shows the result of the measurement of 2p orbital electrons of Co (cobalt)
- FIG. 17(D) shows the measurement result of 2p orbital electrons of Fe (iron).
- FIG. 3 shows the measurement results of the frequency characteristics of the permeability measured by the single-turn coil method made on the samples of CoFeAlO nano-granular film among the samples manufactured in the forgoing manner.
- the abscissa represents the frequency and the ordinate represents the permeability. Note that the both axes use the logarithmic scale.
- the value of the real part ⁇ ′ of the permeability is on the order of 300 and it increases more or less with increase in the frequency, showing that a sufficiently large value is ensured for each of the measured frequencies.
- the imaginary part ⁇ ′′ of the permeability shows a value of less than 50 until the frequency reaches 2 GHz and thus it will be seen that in the present embodiment the resonant frequency of the magnetic thin film is over 2 GHz.
- FIG. 4 shows an observation image of the manufactured sample by the TEM (transmission electron microscopy). From reference to the Figure it will be seen that the sample has a structure in which crystalline phases (magnetic grains) composed of CoFe and having a grain size of about 10 nm (100 ⁇ ) are enclosed by an amorphous layer (insulating layer) composed of Al 2 O 3 and having a thickness of about 1 nm (10 ⁇ ). In this case, if the thickness of the insulating material (corresponding to the spacing or distance between the magnetic grains 12 ) becomes less than 0.5 nm (5 ⁇ ), the electric specific resistance is decreased and the eddy current loss is increased, eventually making the sample unsuitable for practical applications.
- amorphous layer insulating layer
- the thickness of the insulating material 10 when the thickness of the insulating material 10 becomes greater than 1.5 nm (15 ⁇ ), the exchange interaction between the magnetic grains 12 decreases and thus the soft magnetic properties are deteriorated.
- the thickness of the insulating material 10 should preferably be in the range from 0.5 nm to 1.5 nm. Particularly, the thickness of the insulating material 10 should preferably be between 0.8 nm and 1.2 nm from the standpoint of optimization of the permeability.
- Embodiment 2 is one directed to a thin film inductor produced by mounting the previously mentioned nano-granular magnetic thin film.
- FIG. 5 shows its perspective view and the principal parts of the device are shown in section.
- a polyimide insulating layer 22 is first applied to the thickness of 7 ⁇ m to the principal surface of an Si substrate 20 of 400 ⁇ m in thickness by a suitable method such as a spin coater.
- a magnetic thin film 24 of CoFeAlO according to the previously mentioned Embodiment 1 is formed to the thickness of 0.5 ⁇ m on the insulating layer 22 by the combination of a multi-target simultaneous sputtering and a nonreactive sputtering.
- a protective film (passivation film) 26 of Al 2 O 3 is formed to the thickness of 0.1 ⁇ m on the magnetic thin film 24 by a suitable method such as sputtering.
- a polyimide insulating layer 28 is again formed to the thickness of 7 ⁇ m on the protective film 26 by a suitable method such as a spin coater.
- An electrode 30 which is a conductor for carrying electric current, is formed in a spiral form of 3 ⁇ m thick on the insulating layer 28 by using Al, for example.
- the insulating layers 22 and 28 are provided to reduce the capacitance components between them and the magnetic thin film 24 . As the actual components, however, the insulating layers 22 and 28 may be reduced in thickness in order to positively form capacitance components.
- FIG. 6 shows the measurement results of inductance frequency characteristics of a thin film inductor made by trial manufacture as well as the characteristics of an inductor without a magnetic thin film.
- the abscissa represents the frequency and the ordinate represents the inductance.
- the abscissa takes the form of a logarithmic scale and symbol E indicates the power of 10 on both of the abscissa and ordinate. For instance, “E ⁇ 09” represents “10 ⁇ 9 ”.
- Embodiment 3 is one of more preferred forms of Embodiment 2 such that oxidation preventive films 23 and 25 are provided on the top and back surfaces of the magnetic thin film 24 as shown in FIG. 7.
- the present invention features that the magnetic metal of the magnetic thin film 24 is nonoxidizable.
- the magnetic metal of the magnetic thin film 24 combines with the oxygen and moisture in the air and it is oxidized, thus lowering the saturation magnetization and thereby deteriorating the magnetic properties as a whole.
- Conducting a treatment tending to heat the magnetic thin film 24 has the effect of advancing the oxidation of the magnetic metal.
- the magnetic metal in the magnetic thin film 24 is prevented from being oxidized by forming the oxidation preventive films 23 and 25 on the top and back surfaces of the magnetic thin film 24 .
- Suitable materials for the oxidation preventive films 23 and 25 include, for example, Al 2 O 3 film and SiO 2 film.
- the oxidation preventive films are provided on the top and back surfaces of the magnetic thin film 24 , it is possible to provide the oxidation preventive film only one or the other of the two surfaces, particularly that surface tending to contact with oxygen.
- the protective film 26 also functions as an oxidation preventive film. Thus, it is possible to provide at least one of the oxidation preventive film 25 and the protective film 26 or their order of the lamination may be reversed.
- Embodiment 4 of the present invention will be described. While the above-mentioned Embodiments 1 to 3 have been described as applied to the granular magnetic thin film of the single layer structure, the present embodiment will be described as applied to a multilayered magnetic film formed by laminating magnetic layers and insulating layers (the same applies to the below-mentioned embodiments). The basic construction of the multilayered magnetic film of the present embodiment will be described first with reference to FIG. 8.
- FIG. 8 is a principal sectional view of a multilayered magnetic film or multilayered granular film 50 .
- the multilayered magnetic film 50 has a multilayered structure formed by alternately laminating a plurality of magnetic layers 52 each composed of a granular thin film in which an insulating material 58 and nonoxidizable-metal magnetic grains (nonoxidizable magnetic grains) 56 are separately coexist and insulating layers 54 of a metal oxide.
- an oxidation preventive film 60 is provided on each of the top and back surfaces of the film 50 . If the vacuum is broken during the manufacturing process, O 2 and H 2 O are deposited on the surface of the multilayered magnetic film 50 . When a heat treatment or the like is performed in this condition, there is the danger of causing oxidation of the magnetic grains 56 in the magnetic layers 52 . If the magnetic grains 56 are oxidized, the magnetic properties of the multilayered magnetic film 50 are deteriorated on the whole, particularly the saturation magnetization is deteriorated. In order to prevent such oxidation of the magnetic grains 56 , the oxidation preventive films 60 are formed.
- the oxidation preventive films 60 may each be composed of the insulating material 58 formed to be relatively large in thickness.
- the oxidation preventive film 60 may be provided on each of the top and back surfaces of the multilayered film as shown in the Figure or alternatively it may be provided on either one of the two sides, particularly on the top surface side tending to contact with the outside air.
- the magnetic layers 52 of the multilayered magnetic film 50 are each formed of CoFeAlO film, whereas the insulating layers 54 are each formed of Al 2 O 3 film.
- an Si substrate is prepared and a multilayered film (0.5 ⁇ m in film thickness) of the CoFeAlO films and the Al 2 O 3 films is formed on the substrate by using the said targets alternately under the film forming conditions of ⁇ circle over (1) ⁇ a sputtering gas pressure of 0.42 Pa and ⁇ circle over (2) ⁇ a substrate temperature of 20° C.
- FIG. 9(A) shows the frequency characteristics of permeability in a sample of the multilayered CoFeAlO/Al 2 O 3 film or the multilayered magnetic film 50 manufactured in the previously mentioned way
- FIG. 9(B) shows the frequency characteristics of a CoFeAlO single-layer film by way of comparative example.
- the abscissa represents the frequency (Hz)
- the ordinate represents the permeability (both are in the form of logarithms).
- the real part ⁇ 1′ of the permeability of the CoFeAlO/Al 2 O 3 multilayered film is on the order of 70 to 100.
- the real part ⁇ 2′ of the permeability of the CoFeAlO single-layer film is on the order of 300 to 400.
- a comparison between the two shows that the permeability real part of the CoFeAlO/Al 2 O 3 multilayered film of the present embodiment is reduced to 1 ⁇ 3 to 1 ⁇ 4 as compared with the CoFeAlO single-layer film.
- the thickness WM of the magnetic layer 52 (CoFeAlO film) will be examined. Note that the thicknesses of the magnetic layer 52 and the insulating layer 54 have been measured by mean of a crystal vibrator.
- FIG. 10(A) shows the relation between the resistivity and the thickness WM of the magnetic layer 52 , with the abscissa showing the thickness WM ( ⁇ ) of the magnetic layer 52 and the ordinate showing the resistivity ( ⁇ cm).
- FIG. 11(A) shows the relation between the real part of permeability and the thickness WM of the magnetic film 52 at 1 GHz, with the abscissa representing the thickness WM ( ⁇ ) of the magnetic layer 52 and the ordinate representing the real part of permeability. In either of the cases, the thickness WI of the insulating layer 54 is fixed at 4 ⁇ .
- the resistance value increases and it abruptly rises with the thickness WM of less than 10 ⁇ as shown in FIG. 10(A).
- the thickness WM of the magnetic layer 52 is less than the grain size of the magnetic grains 56 .
- the grain growth of the magnetic grains 56 held between the insulating layers 54 is restricted.
- minimizing the size of the magnetic grains 56 has the effect of reducing the crystalline magnetic anisotropy and increasing the exchange interaction between the magnetic grains 56 , with the resulting advantage from the soft magnetic property point of view.
- the thickness WM of the magnetic layer 52 exceeds 100 ⁇ , the extent of increase in resistivity is decreased. This is considered due to the fact that if the thickness WM of the magnetic layer 52 exceeds 100 ⁇ , there is the effect of causing the grain growth of the magnetic grains 56 in the magnetic layer 52 so that the effect of the reduced grain size is reduced and the increase in resistivity is decreased.
- the thickness WM of the magnetic layers 52 reaches 150 ⁇ , it is no longer possible to confirm any eminent difference over the CoFeAlO single-layer film having a resistivity of 80 ⁇ cm (not shown).
- the thickness WM of the magnetic layers 52 is selected 130 ⁇ or less, preferably 100 ⁇ or less.
- the permeability decreases with reduction in the thickness WM of the magnetic layers 52 .
- the thickness WM is 5 ⁇ or less, the magnetic grains 56 are isolated so that a super paramagnetic behavior is exhibited and they fail practically to function as magnetic films.
- the thickness WM of the magnetic layers 52 should be in such range that satisfies 5 ⁇ WM ⁇ 130 ⁇ , more preferably 10 ⁇ WM ⁇ 100 ⁇ .
- FIG. 12(A) shows the relation between the resistivity and the thickness WI of the insulating layer 54 , with the abscissa representing the thickness WI ( ⁇ ) of the insulating layer 54 and the ordinate representing the resistivity ( ⁇ cm).
- FIG. 13(A) shows the relation between the real part of permeability and the thickness WI ( ⁇ )of the insulating layer 54 at 1 GHz, with the abscissa representing the thickness WI ( ⁇ ) of the insulating layer 54 and the ordinate representing the real part of permeability.
- the thickness WM of the magnetic layer 52 is fixed at 50 ⁇ .
- the resistivity of the CoFeAlO single-layer film is 80 ⁇ cm
- the resistivity is increased greatly with increase in the thickness WI of the insulating layer 54 and thus it is possible to confirm that a higher resistance is produced by the introduction of the insulating layer 54 .
- the value of the permeability real part is decreased with increase in the thickness WI of the insulating layer 54 . This is due to the fact that increasing the thickness WI of the insulating layer 54 has the effect of decreasing the exchange interaction between the magnetic grains 52 holding the insulating layer 54 therebetween and its effect is increased if the thickness WI exceeds 10 ⁇ .
- the magnetic layer 52 fails to effectively function as a magnetic film when the thickness WI is 15 ⁇ .
- a preferred range for the thickness WI of the insulating layer 54 should be WI ⁇ 10 ⁇ , preferably 5 ⁇ WI ⁇ 8 ⁇ .
- the thickness WM of the magnetic layer 52 is selected to fall in a range that satisfies 5 ⁇ WM ⁇ 130 ⁇ , preferably 10 ⁇ WM ⁇ 100 ⁇
- the thickness WI of the insulating layer 14 is selected to fall in a range that satisfies WI ⁇ 10 ⁇ , preferably 5 ⁇ WI ⁇ 8 ⁇
- a plurality of these layers are laminated to produce the multilayered magnetic film 50 , thereby obtaining the following effects:
- FIG. 14(A) shows the frequency characteristics of the inductance LA of the thin film inductor composed of the multilayered film and the frequency characteristics of the inductance LB of an inductor manufactured by using a single layer film by way of comparative example for the purposes of comparison.
- the abscissa represents the frequency (Hz) and the ordinate represents the inductance (nH).
- the reduced imaginary part of the permeability due to the multilayered structure also has an effective action on the reduction of loss.
- the magnetic material film increased in resistance due to the multilayered structure as a magnetic core material, it is possible to obtain a thin film inductor well suited for use in high frequency bands.
- Embodiment 6 of the present invention will now be described with reference to FIGS. 9 to FIG. 13.
- the multilayered structure of the present embodiment is also the same as in FIG. 8.
- the magnetic layers 52 are each composed of CoFeSiO film and the insulating layers 54 are each composed of SiO 2 film.
- an Si substrate of 400 ⁇ m thick is prepared and the targets are alternately sputtered onto its surface ( 100 ) under the film forming conditions including ⁇ circle over (1) ⁇ sputtering gas pressure of 0.42 Pa and ⁇ circle over (2) ⁇ substrate temperature of 20° C., thereby forming a multilayered film (film thickness of 0.5 ⁇ m) of the CoFeSiO films and SiO 2 films.
- FIG. 9(C) shows the frequency characteristics of the permeability in a sample of the multilayered magnetic film 50 or the CoFeSiO/SiO 2 mltilayered film produced in the foregoing manner
- FIG. 9(D) shows the frequency characteristics of the CoFeSiO single-layer film or the comparative device.
- the abscissa represents the frequency (Hz)
- the ordinate represents the permeability (the both are in the form of logarithms).
- the real part ⁇ 3′ of the permeability of the CoFeSiO/SiO 2 multilayered film is on the order of 200.
- FIG. 9(C) shows the real part ⁇ 3′ of the permeability of the CoFeSiO/SiO 2 multilayered film.
- the real part ⁇ 4′ of the permeability of the CoFeSiO single-layer film is on the order of 30 to 90.
- a comparison between the two shows that the real part of the permeability in the CoFeSiO/SiO 2 multilayered film of the present embodiment is increased to 2 to 7 times as compared with the CoFeSiO single-layer film.
- the imaginary part ⁇ 3′′ of permeability is observed to be greater than in Embodiment 4 shown in FIG. 9(A), it is small enough as compared with FIG. 9(B). Also, it is slightly small as compared with the CoFeSiO single-layer film of FIG. 9(D). Thus, since the imaginary part of permeability is made small in this way, the eddy current loss is greatly decreased even by the multilayered structure of the present embodiment. Further, the resonant frequency of the multilayered magnetic film 50 of the present embodiment is 2 GHz or over and it can be adequately used in high frequency bands.
- FIG. 10(B) shows the relation between the resistivity and the thickness WM of the magnetic layer 12 , with the abscissa representing the thickness WM ( ⁇ ) of the magnetic layer 52 and the ordinate representing the resistivity (m ⁇ cm, logarithmic representation). Also, FIG.
- 11(B) shows the relation between the real part of permeability and the thickness WM of the magnetic layer 52 at 2 GHz, with the abscissa showing the thickness WM ( ⁇ ) of the magnetic layer 52 and the ordinate representing the real part of permeability.
- the thickness WI of the insulating layer 54 is fixed at 10 ⁇ .
- the resistance value increases with decrease in the thickness WM of the magnetic layer 52 and it increases with a large slope when the thickness WM is 45 ⁇ or less.
- the thickness WM of the magnetic layer 52 is less than the grain size of the magnetic grains 56 .
- the grain growth of the magnetic grains 56 held between the insulating layers 54 is restricted.
- a high electric resistance on the whole is obtained by virtue of the electric conduction preventing effect due to the grain boundaries as well as the effect of the introduction of the insulating layers 54 .
- the soft magnetic properties are improved owing to the reduced crystalline magnetic anisotropy and the increased exchange interaction between the magnetic grains 56 which are brought about by the reduced size of the magnetic grains 56 .
- the thickness WM of the magnetic layers 52 exceeds 45 ⁇ , the extent of increase in the permeability is decreased. This is considered to be due to the fact that when the thickness WM of the magnetic layers 52 exceeds 45 ⁇ , the grain growth preventing effect of the insulating layers 54 is reduced so that the effect of the reduced grain size is decreased and the increase in resistivity is decreased. Also, where the thickness WM of the magnetic layers 52 is at least on the order of 90 ⁇ , the resistivity is greater than the resistivity of the CoFeSiO single-layer film which is 0.52 m ⁇ cm (not shown), thereby confirming the effect resulting from the multilayered structure. Therefore, in order to obtain a higher resistivity than in the case of the CoFeSiO single-layer film, the thickness WM of the magnetic layers 52 is selected less than 90 ⁇ .
- the value of permeability becomes maximum when the thickness WM of the magnetic layers 52 is 60 ⁇ .
- the value of permeability is 100 or over when the thickness WM of the magnetic layers 52 is between 50 and 75 ⁇ , and the value of permeability is 50 or over when the thickness WM is between 40 and 90 ⁇ .
- the thickness of the magnetic layers 52 is 40 ⁇ or less, the magnetic grains 56 become excessively small to exhibit a super paramagnetic behavior and this is considered to have an effect on the decrease in permeability.
- the thickness range of the magnetic layers that exhibits super paramagnetic properties is greater than in the case of the CoFeAlO film of the previously mentioned Embodiment 4 is considered to be due to the fact that the volumetric ratio of the magnetic material in the magnetic layers of CoFeSiO films is greater than in those composed of the CoFeAlO films.
- the thickness of the magnetic layers 52 is 90 ⁇ or over, the decrease in permeability is affected by the increase in crystalline magnetic anisotropy due to the increase in grain size of the magnetic grains 56 .
- the advantageous range of thickness of the magnetic layers 52 is from 40 to 90 ⁇ , preferably from 50 to 75 ⁇ .
- ⁇ circle over (2) ⁇ 40 ⁇ WM ⁇ 90 ⁇ , preferably 50 ⁇ WM ⁇ 75 ⁇ is desired from the permeability point of view.
- the thickness WM of the magnetic layers should, on the whole, be in such range that satisfies 40 ⁇ WM ⁇ 90 ⁇ , preferably 50 ⁇ WM ⁇ 75 ⁇ .
- FIG. 12(B) shows the relation between the resistivity and the thickness WI of the insulating layers 54 , with the abscissa representing the thickness WI ( ⁇ ) of the insulating layers 54 and the ordinate representing the resistivity (m ⁇ cm).
- FIG. 13(B) shows the relation between the real part of the permeability at 2 GHz and the thickness WI ( ⁇ ) of the insulating layers 54 , with the abscissa representing the thickness WI ( ⁇ ) of the insulating layers 54 and the ordinate representing the permeability real part.
- the thickness WM of the magnetic layers 52 is fixed at 60 ⁇ .
- the resistivity increases practically in proportion to the thickness WI of the insulating layers 54 . Since it is advantageous for the value of resistivity to be as high as possible, it will be seen that the insulating layers 54 should preferably be as thick as possible.
- the value of permeability becomes maximal when the thickness of the insulating layers 54 is 10 ⁇ . It is considered that if the thickness WI of the insulating layers 54 is made greater than 10 ⁇ , the exchange interaction between the magnetic grains adjoining through the insulating layer 54 is decreased to decrease the permeability. Also, the permeability is low when the thickness WI of the insulating layers 54 is 5 ⁇ or less.
- the thickness range differs from that of Embodiment 1 is considered to be due to the difference between the two embodiments with respect to the volumetric ratio of the insulating material in the magnetic layers. Judging from these standpoints, it is considered that the proper range for the thickness WI of the insulating layers 54 is from 5 to 25 ⁇ , preferably from 7 to 20 ⁇ .
- the thickness should preferably be as large as possible from the resistivity point of view.
- the range desired from both the resistivity and permeability points of view should be 5 ⁇ WI ⁇ 25 ⁇ , preferably 7 ⁇ WI ⁇ 25 ⁇ , more preferably 7 ⁇ WI ⁇ 20 ⁇ .
- the range of the thickness WM of the magnetic layers 52 is selected 40 ⁇ WM ⁇ 90 ⁇ , more preferably 50 ⁇ WM ⁇ 75 ⁇
- the range of the thickness WI of the insulating layers 54 is selected 5 ⁇ WI ⁇ 25 ⁇ , preferably 7 ⁇ WI ⁇ 25 ⁇ , more preferably 7 ⁇ WI ⁇ 20 ⁇ , and a plurality each of these layers are laminated to produce a multilayered magnetic film 50 , thereby ensuring the same effects as the previously mentioned Embodiment 4.
- Embodiment 4 it is easier to obtain a structure in which the magnetic grains 56 are enclosed by SiO 2 insulating films and the desired electric conduction preventive effect is ensured by not only the insulating layers but also the grain boundaries, thereby ensuring a higher electric resistance.
- FIG. 14(B) shows a comparison between the frequency characteristics of the inductance LC of the thin film inductor composed of the multilayered film and the frequency characteristics of the inductance LD of an air-core inductor as a comparative example.
- the abscissa represents the frequency (Hz, logarithmic representation) and the ordinate represents the inductance (nH).
- the inductance LC of the present embodiment is higher than the inductance LD of the comparative example in frequency bands lower than 3.5 GHz.
- the inductance of the present embodiment is 7.65 nH which is higher than 6.24 nH of the air-core inductor by 1.41 nH (corresponding to 23% in terms of air-core ratio) and thus the thin film inductor of the present embodiment is satisfactorily applicable to inductors in the GHz bands.
- the inductances of the present embodiment and the comparative example become equal to each other at the frequency of 3.6 GHz, it is considered that the resonant frequency of the present multilayered magnetic material film is 3 GHz or over. From this fact it will be seen that the multilayered magnetic film of Embodiment 6 is much effective as a magnetic core material for an inductor used in high frequency bands.
- FIG. 15 shows an example of an MMIC (monolithic microwave integrated circuit) which is an electronic equipment utilizing the multilayered magnetic film according to the present invention.
- the MMIC is designed for performing signal amplification or modulation/demodulation in the microwave region and it is constructed so that such elements as a transistor, a resistor, a capacitor, an inductor, etc., are combined and integrated in one chip.
- a transistor 102 a transistor 102 , a resistor 104 , an MIM (metal insulator metal) capacitor 106 and a microstrip line 108 are respectively formed on a semiconductor substrate 100 and a spiral inductor 110 is formed as a magnetic component on an interlayer insulating film 112 .
- MIM metal insulator metal
- the spiral inductor 110 of magnetic material loading closed magnetic path construction shown in partially broken form, includes a conductor 114 formed in a spiral pattern so that one end is connected to the microstrip line 108 and the other end is connected to a lead-out electrode 116 . Then, multilayered magnetic films 50 of the previously mentioned construction are formed so as to cover the conductor 114 . An oxidation preventive film 60 is formed on the surface of each multilayered magnetic film 50 .
- FIG. 16 shows an example of an equivalent circuit for a two-stage power amplifier constructed with such MMICs.
- a high frequency signal applied to an input terminal (RF IN) is amplified by a first-stage amplifier mainly composed of a transistor Q 1 and a second-stage amplifier mainly composed of a transistor Q 2 , respectively, and it is generated from an output terminal (RF, OUT).
- the transistors Q 1 and Q 2 are constructed like the transistor 102
- capacitances C 1 to C 12 are constructed like the capacitor 106 .
- inductances L 1 to L 8 are constructed like the spiral inductor 110
- a resistor R is constructed like the resistor 104 .
- the inductance per unit length of the conductor 114 is increased.
- the length of the conductor 114 can be decreased so that the occupied area of the spiral inductor 110 on the substrate is decreased on the whole.
- the length of the conductor 114 is decreased so that the series resistance is also decreased.
- CoFe alloy is used for the magnetic grains in the foregoing embodiments
- a variety of magnetic metals may be used.
- NiFe and the like may be used.
- oxide ceramic or Al 2 O 3 is used for the insulating material, other amorphous insulating materials may be used.
- MgO, SiO 2 oxides which are stable chemically, e.g., oxides of rare-earth elements and the like are well suited for the purpose.
- the film forming conditions shown in the foregoing embodiments are exemplary conditions and any suitably preset conditions may be used so as to obtain the desired properties. This is also the same with the numbers of lamination layers for the magnetic layers 52 and the insulating layers 54 and the film forming conditions of the multilayered magnetic film 50 .
- the thin film inductor is shown as an example of magnetic components and the MMIC is shown as an exemplary electronic equipment, the present invention may be applied to a variety of magnetic components and equipment which are usable in high frequency bands, e.g., thin film transformer, and it is possible to use them in such equipment as portable telephones.
- the MMIC employing multilayered magnetic films is shown by way of example, it may be replaced with an MMIC using granular magnetic thin films.
- the thickness of the insulating material is set between 0.5 nm and 1.5 nm due to the combination of the multi-target simultaneous sputtering and the nonreactive sputtering, excellent soft magnetic properties are obtained and the eddy current is also restricted to decrease its loss.
- the magnetic films are each composed of CoFeAlO film and the insulating layers are each composed of Al 2 O 3 film, and that the thickness WM of the magnetic layers is selected to fall in a range satisfying 5 ⁇ WM ⁇ 130 ⁇ , preferably 10 ⁇ WM ⁇ 100 ⁇ and the thickness WI of the insulating layers is selected to fall in a range satisfying WI ⁇ 10 ⁇ , preferably 5 ⁇ WI ⁇ 8 ⁇ , there is the effect of ensuring the improved electric resistance and the improved magnetic properties.
- the magnetic layers are each composed of CoFeSiO film and the insulating layers are each composed of SiO 2 film, and that the thickness WM of the magnetic layers is selected to fall in a range satisfying 40 ⁇ WM ⁇ 90 ⁇ , preferably 50 ⁇ WM ⁇ 75 ⁇ , and the thickness WI of the insulating layers is selected to fall in a range satisfying 5 ⁇ WI ⁇ 25 ⁇ , preferably 7 ⁇ WI ⁇ 25 ⁇ , more preferably 7 ⁇ WI ⁇ 20 ⁇ , there is the effect of ensuring the improved electric resistance and the improved magnetic properties.
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US10/842,449 US7060374B2 (en) | 2001-01-18 | 2004-05-11 | Granular magnetic thin film and method for making the same, multilayered magnetic film, magnetic components and electronic equipment |
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US10/842,449 Division US7060374B2 (en) | 2001-01-18 | 2004-05-11 | Granular magnetic thin film and method for making the same, multilayered magnetic film, magnetic components and electronic equipment |
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US10/842,449 Expired - Fee Related US7060374B2 (en) | 2001-01-18 | 2004-05-11 | Granular magnetic thin film and method for making the same, multilayered magnetic film, magnetic components and electronic equipment |
US10/842,473 Expired - Fee Related US7498088B2 (en) | 2001-01-18 | 2004-05-11 | Granular magnetic thin film and method for making the same, multilayered magnetic film, magnetic components and electronic equipment |
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US10/842,473 Expired - Fee Related US7498088B2 (en) | 2001-01-18 | 2004-05-11 | Granular magnetic thin film and method for making the same, multilayered magnetic film, magnetic components and electronic equipment |
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EP (1) | EP1361586A4 (de) |
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WO2005086556A1 (ja) * | 2004-03-08 | 2005-09-15 | Nec Tokin Corporation | 電磁雑音吸収薄膜 |
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US20090002115A1 (en) * | 2004-07-30 | 2009-01-01 | Texas Instruments Incorporated | Method to improve inductance with a high-permeability slotted plate core in an integrated circuit |
US7969274B2 (en) | 2004-07-30 | 2011-06-28 | Texas Instruments Incorporated | Method to improve inductance with a high-permeability slotted plate core in an integrated circuit |
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Also Published As
Publication number | Publication date |
---|---|
EP1361586A4 (de) | 2008-06-11 |
EP1361586A1 (de) | 2003-11-12 |
US20040209098A1 (en) | 2004-10-21 |
JPWO2002058086A1 (ja) | 2004-05-27 |
US20040209111A1 (en) | 2004-10-21 |
US7060374B2 (en) | 2006-06-13 |
JP4758599B2 (ja) | 2011-08-31 |
WO2002058086A1 (en) | 2002-07-25 |
US7498088B2 (en) | 2009-03-03 |
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