WO2012067263A1 - 積層体および積層体の製造方法 - Google Patents
積層体および積層体の製造方法 Download PDFInfo
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- WO2012067263A1 WO2012067263A1 PCT/JP2011/077115 JP2011077115W WO2012067263A1 WO 2012067263 A1 WO2012067263 A1 WO 2012067263A1 JP 2011077115 W JP2011077115 W JP 2011077115W WO 2012067263 A1 WO2012067263 A1 WO 2012067263A1
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/11—Printed elements for providing electric connections to or between printed circuits
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/001—Interlayers, transition pieces for metallurgical bonding of workpieces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B18/00—Layered products essentially comprising ceramics, e.g. refractory products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/02—Coating starting from inorganic powder by application of pressure only
- C23C24/04—Impact or kinetic deposition of particles
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00844—Uses not provided for elsewhere in C04B2111/00 for electronic applications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/15—Ceramic or glass substrates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3735—Laminates or multilayers, e.g. direct bond copper ceramic substrates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0058—Laminating printed circuit boards onto other substrates, e.g. metallic substrates
- H05K3/0061—Laminating printed circuit boards onto other substrates, e.g. metallic substrates onto a metallic substrate, e.g. a heat sink
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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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer
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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
Definitions
- the present invention relates to a laminate used between electric circuit boards and the like, and a method for producing the laminate.
- the power module has a temperature adjusting unit (cooling unit or heating unit) in which a moving path of a heat medium for cooling or heating is formed via an insulating substrate as a base material.
- a temperature adjusting unit cooling unit or heating unit
- a laminated body in which a metal film is formed on the surface of a ceramic base material that is an insulating substrate is used for the temperature adjustment unit.
- the heat generated from the chip (transistor) stacked on the surface of the insulating substrate where the temperature control part is not formed is transferred to the metal film and dissipated to the outside.
- Module cooling can be performed.
- a circuit pattern with a metal film is formed between the insulating substrate and the chip, and a laminated body in which the metal film is formed on the surface of the ceramic substrate is also used in this portion.
- the method for forming a metal film on the surface of the ceramic substrate include a thermal spraying method and a cold spray method.
- the thermal spraying method is a method in which a coating is formed by spraying a thermal spray material that is melted or heated to a state close to the base material.
- the cold spray method powder of a material to be a film is sprayed from a laver nozzle together with an inert gas having a melting point or a softening point or less, and the material to be a film is a base material in a solid state.
- a film is formed on the surface of the base material by colliding with the substrate (for example, see Patent Document 1).
- the cold spray method has a lower temperature than the thermal spraying method, so that the influence of thermal stress is mitigated, so that a metal film having no phase transformation and suppressing oxidation can be obtained.
- both the base material and the material to be the film are metals
- the powder that becomes the film collides with the base material plastic deformation occurs between the powder and the base material, and an anchor effect can be obtained.
- the oxide film of each other is destroyed, metal bonding occurs between the new surfaces, and the effect of obtaining a laminate with high adhesion strength is also expected. Yes.
- the present invention has been made in view of the above, and in the case of producing a laminate in which a metal film is formed on a ceramic substrate using a cold spray method, the adhesion strength between the ceramic and the metal film is high. It aims at providing a high laminated body and a manufacturing method of this laminated body.
- a laminate according to the present invention includes an insulating ceramic base material, a main component metal layer containing a metal, and a metal or an oxide or hydride of a metal. Having an active component layer, an intermediate layer formed on the surface of the ceramic substrate, and a metal-containing powder on the surface of the intermediate layer are accelerated together with a gas and sprayed in the solid state on the surface And a metal film formed by being deposited.
- the laminate according to the present invention is characterized in that, in the above invention, the intermediate layer is formed by heat treatment in a vacuum.
- the active component layer includes at least one selected from the group consisting of a metal selected from titanium, zirconium, hafnium, and germanium, or a metal hydride. It is characterized by that.
- the laminate according to the present invention is characterized in that, in the above invention, the main component metal layer includes at least one selected from the group consisting of gold, silver, copper, aluminum, and nickel.
- the laminate according to the present invention is characterized in that, in the above invention, the intermediate layer is formed by heat treatment in the atmosphere.
- the active component layer is formed of a group consisting of oxide, hydride of titanium, zirconium, hafnium, germanium, boron, silicon, aluminum, chromium, indium, or metal. It includes at least one type selected.
- the laminate according to the present invention is characterized in that, in the above invention, the main component metal layer includes at least one of gold and silver.
- the manufacturing method of the laminated body concerning this invention is a manufacturing method of the laminated body which manufactures the laminated body by which the metal film was formed on the surface of the ceramic base material, Comprising: Alternatively, a brazing material disposing step of disposing a brazing material containing a metal oxide or hydride, and heat treating the ceramic substrate on which the brazing material is disposed in the brazing material disposing step, thereby forming the intermediate layer.
- An intermediate layer forming step to be formed; and a powder containing a metal is accelerated together with a gas on the surface of the intermediate layer formed by the intermediate layer forming step, and sprayed and deposited on the surface in a solid state.
- a metal film forming step of forming the metal film is a manufacturing method of the laminated body which manufactures the laminated body by which the metal film was formed on the surface of the ceramic base material, Comprising: Alternatively, a brazing material disposing step of disposing a brazing material containing a metal oxide or hydride, and heat
- the method for manufacturing a laminate according to the present invention is characterized in that, in the above invention, the intermediate layer forming step is performed in a vacuum.
- the method for manufacturing a laminate according to the present invention is characterized in that, in the above invention, the intermediate layer forming step is performed in the atmosphere.
- the laminate and the method for producing a laminate according to the present invention include forming an intermediate layer including a main component metal layer and an active component layer between a ceramic substrate and a metal coating, and the main component metal layer with respect to the metal coating. Since the active ingredient layer is bonded to the ceramic substrate, the adhesion strength between the ceramic and the metal coating is reduced when the metal film is formed on the ceramic substrate using the cold spray method. There exists an effect that a laminated body with high can be obtained.
- FIG. 1 is a schematic diagram showing a configuration of a power module according to an embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing a configuration of a main part of the power module shown in FIG.
- FIG. 3 is a cross-sectional view schematically showing a configuration of a main part of the power module according to the embodiment of the present invention.
- FIG. 4 is a cross-sectional view schematically showing a configuration of a main part of the power module according to the embodiment of the present invention.
- FIG. 5 is a schematic diagram showing an outline of a cold spray apparatus used for manufacturing the power module according to the embodiment of the present invention.
- FIG. 6 is a schematic diagram showing an example of the configuration of a conventional power module that does not use the cold spray method.
- FIG. 1 is a schematic diagram showing a configuration of a power module according to an embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing a configuration of a main part of the power module shown in FIG.
- FIG. 7 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 1 of the present invention.
- FIG. 8 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 1 of the present invention.
- FIG. 9 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 1 of the present invention.
- FIG. 10 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 1 of the present invention.
- FIG. 11 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 1 of the present invention.
- FIG. 12 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 13 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 14 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 15 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 16 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 17 is a schematic diagram illustrating a schematic configuration of an evaluation apparatus that performs adhesion strength evaluation.
- FIG. 18 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 2 of the present invention.
- FIG. 19 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 3 of the present invention.
- FIG. 20 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 3 of the present invention.
- FIG. 21 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 22 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG. FIG.
- FIG. 23 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 24 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 25 is a diagram showing a cross-sectional element distribution analysis result for the cross-section reflected electron image shown in FIG.
- FIG. 26 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Example 4 of the present invention.
- FIG. 27 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Comparative Example 1 of the present invention.
- FIG. 28 is a diagram showing a cross-sectional backscattered electron image of the multilayer body according to Comparative Example 2 of the present invention.
- FIG. 1 is a schematic diagram showing a configuration of a power module according to an embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing a configuration of a main part of the power module shown in FIG.
- the power module 1 includes a ceramic substrate 10 which is an insulating substrate, a copper circuit 20 laminated on the ceramic substrate 10, a chip 30 laminated on the copper circuit 20 and fixed by solder C1, and aluminum or the like.
- the cooling fin 40 is made of a metal film and laminated on a surface different from the copper circuit 20 of the ceramic substrate 10.
- the ceramic substrate 10 has a substantially plate shape and is made of an insulating member.
- the insulating member include oxides such as alumina, magnesia, zirconia, steatite, forsterite, mullite, titania, silica, sialon, aluminum nitride, silicon nitride, silicon carbide, and the like.
- the copper circuit 20 forms a circuit pattern on the surface of the ceramic substrate 10 for transmitting an electrical signal to the stacked chips 30 and the like by patterning using copper.
- the chip 30 is realized by a semiconductor element such as a diode, a transistor, or an IGBT (insulated gate bipolar transistor). A plurality of chips 30 are provided on the ceramic substrate 10 in accordance with the purpose of use.
- the cooling fin 40 is a metal film laminated on the surface of the ceramic substrate 10 by a cold spray method described later.
- the metal film include copper, copper alloy, aluminum, aluminum alloy, silver, and silver alloy. The heat generated from the chip 30 is released to the outside through the ceramic substrate 10 by the metal film.
- An intermediate layer 50 as shown in FIG. 2 is formed between the ceramic substrate 10 and the cooling fin 40.
- the intermediate layer 50 includes a main component metal layer 51 formed on the cooling fin 40 side and an active component layer 52 formed on the ceramic substrate 10 side.
- the main component metal layer 51 is formed using any of aluminum, nickel, copper, silver, and gold.
- the main component metal layer 51 is laminated by metal bonding with the cooling fin 40 on a surface different from the contact surface with the active component layer 52.
- the active component layer 52 is formed using any of titanium, zirconium, hafnium, germanium, boron, silicon, aluminum, chromium, indium, vanadium, molybdenum, tungsten, manganese, or an oxide or hydride thereof.
- the active component layer 52 is laminated by being covalently bonded to the ceramic substrate 10 on a surface different from the contact surface with the main component metal layer 51.
- FIGS. 3 and 4 are cross-sectional views schematically showing the formation of the intermediate layer in the power module.
- FIG. 5 is a schematic diagram showing an outline of a cold spray apparatus used for forming a metal film.
- a brazing material used as the intermediate layer 50 is applied to one surface of the ceramic substrate 10 by a screen printing method.
- the brazing material includes a metal or alloy used as a main component metal layer, and a metal or metal oxide used as an active component layer, a hydride, etc., and a paste in which an organic solvent and an organic binder are mixed. Eggplant.
- the intermediate layer 50 After the application of the brazing material as the intermediate layer 50, it is kept in a vacuum of 800 to 1000 ° C. or in the atmosphere for 1 hour. After holding for 1 hour, the intermediate layer 50 is separated into the main component metal layer 51 and the active component layer 52 as shown in FIG.
- the main component metal layer and the active component layer held in vacuum include gold, silver, copper, aluminum, and nickel as materials used for the main component metal layer.
- the material used for the metal include titanium, zirconium, hafnium, germanium, and hydrides thereof.
- the main component metal layer and active component layer held in the atmosphere include gold and silver as materials used for the main component metal layer, and titanium, zirconium, hafnium, germanium, boron as materials used for the active component layer. , Silicon, aluminum, chromium, indium, vanadium, molybdenum, tungsten, manganese, or an oxide or hydride thereof.
- any metal that does not oxidize even when dissolved in the atmosphere can be applied to the main component metal layer held in the atmosphere.
- nitrides, carbonides and hydrides of silicon, calcium, titanium and zirconium can be used for the active component layer held in the atmosphere. Any combination of the above-described main component metal layer and active component layer is applicable.
- the main component metal layer and the active component layer include at least one of the listed metals or oxides or hydrides. It is also possible to use an alloy mainly composed of any of the listed metals.
- the intermediate layer 50 is separated into the main component metal layer 51 and the active component layer 52, and the cold spray method is used on the exposed surface of the main component metal layer 51 with the main component metal layer 51 exposed to the outside.
- Film formation by the cold spray method is performed by a cold spray apparatus 60 shown in FIG.
- the cold spray device 60 contains a gas heater 61 that heats the compressed gas, a powder supply device 62 that contains a powder material to be sprayed on the sprayed material, and supplies the powder material to the spray gun 64, and a compressed gas heated by the spray gun 64. And a gas nozzle 63 for injecting the mixed material powder onto the substrate.
- the compressed gas helium, nitrogen, air or the like is used.
- the supplied compressed gas is supplied to the gas heater 61 and the powder supply device 62 by valves 65 and 66, respectively.
- the compressed gas supplied to the gas heater 61 is heated to, for example, 50 to 700 ° C. and then supplied to the spray gun 64. More preferably, the compressed gas is heated so that the upper limit temperature of the thermal spray material powder sprayed onto the main component metal layer 51 of the intermediate layer 50 laminated on the ceramic substrate 10 is kept below the melting point of the metal material. This is because the oxidation of the metal material can be suppressed by keeping the heating temperature of the powder material below the melting point of the metal material.
- the compressed gas supplied to the powder supply device 62 supplies, for example, material powder having a particle size of about 10 to 100 ⁇ m in the powder supply device 62 to the spray gun 64 so as to have a predetermined discharge amount.
- the heated compressed gas is made a supersonic flow (about 340 m / s or more) by a gas nozzle 63 having a tapered and wide shape.
- the powder material supplied to the spray gun 64 is accelerated by the injection of the compressed gas into the supersonic flow, and collides with the substrate at a high speed in the solid state to form a film.
- the apparatus is not limited to the cold spray apparatus 60 of FIG. 5 as long as the apparatus can form a film by colliding the material powder with the base material in a solid state.
- a metal film (cooling fin 40) as shown in FIGS. 1 and 2 is formed by the cold spray device 60 described above.
- the brazing material used is described as a paste in which an organic solvent and an organic binder are mixed, the metal or alloy used as the main component metal layer and the metal or metal oxidation used as the active component layer As long as it contains a product, hydride, etc., it may be a foil.
- the laminated body according to the above-described embodiment it is possible to obtain a laminated body having high adhesion strength as compared with a laminated body obtained by a conventional cold spray method. Thereby, it becomes possible to form a laminate having a thick metal film.
- an intermediate layer in the ceramic base material to be used it is possible to use any oxide, nitride, or carbide, so that the selectivity of the ceramic base material to be used can be increased.
- FIG. 6 is a schematic diagram showing an example of the configuration of a conventional power module that does not use the cold spray method.
- the power module 100 includes a copper circuit 20 bonded to a ceramic base material 10 that is an insulating substrate by an adhesive layer C1 such as a sealing material, and is laminated on the copper circuit 20 and is soldered by a solder C2.
- the cooling fin 40 is bonded to the ceramic substrate 10 through the copper substrate 82 and the thermal compound 83.
- the laminated body according to the present invention can have a thin layer structure with a simple structure as compared with the conventional laminated body as shown in FIG. Moreover, even if the laminated body has the same thickness, the area occupied by the main components such as the cooling fins can be increased, and the design width of the laminated body can be widened.
- the metal film has been described as a cooling fin that dissipates heat generated from the chip.
- the metal film may be provided to heat a layer laminated on a ceramic substrate such as a chip via the metal film.
- intermediate layer has been described as being provided between the ceramic substrate and the metal film as the cooling fin, it may be provided between the ceramic substrate and the copper circuit.
- Example 1 In Example 1, as the intermediate layer 501, a laminate was manufactured using a silver-copper alloy as the main component metal layer 511 and titanium hydride as the active component layer 521. Further, alumina was used as the ceramic substrate 101, and aluminum was used as the metal film 401. Cross-sectional reflected electron images of this laminate are shown in FIGS.
- the cross-sectional reflected electron image in FIG. 7 is a 40-fold electron image
- the cross-sectional reflected electron image in FIG. 8 is a 500-fold electron image
- the main component metal layer 511 and the active component layer 521 of the intermediate layer 501 were formed by applying a brazing material and holding it in a vacuum at 800 ° C. for 1 hour.
- the intermediate layer 501, the ceramic substrate 101, and the metal film 401 are maintained in a joined state without being peeled off.
- the intermediate layer 501 has a main component metal layer 511 formed on the metal film 401 side and an active component layer 521 formed on the ceramic substrate 101 side.
- FIG. 11 is a diagram showing a cross-sectional backscattered electron image (500 times) subjected to elemental analysis.
- 12 to 16 are diagrams showing the results of cross-sectional element distribution analysis for the cross-sectional backscattered electron image shown in FIG.
- the cross-sectional element distribution analysis results shown in FIGS. 12 to 16 are displayed in red as the content of the element to be analyzed increases, and in blue as the content decreases. That is, as the content increases, a reddish color is exhibited.
- FIG. 12 shows the results of cross-sectional element distribution analysis showing the silver content. Silver is used as a silver-copper alloy in the main component metal layer 511, and the intermediate layer 501 is displayed in red.
- FIG. 13 shows the results of cross-sectional element distribution analysis showing the aluminum content.
- Aluminum is used in the metal film 401 and is contained in alumina (aluminum oxide) in the ceramic substrate 101. For this reason, in FIG. 13, the metal film 401 is displayed in red, and the ceramic substrate 101 is displayed in green.
- FIG. 14 shows the results of cross-sectional element distribution analysis showing the copper content. Copper is used as a silver-copper alloy in the main component metal layer 511, and the intermediate layer 501 is displayed in yellow (partially red).
- FIG. 15 shows the results of cross-sectional element distribution analysis showing the titanium content. Titanium is used as the active component layer 521, and the ceramic substrate 101 side of the intermediate layer 501 is displayed in red.
- FIG. 16 shows a cross-sectional element distribution analysis result showing the oxygen content.
- Oxygen is contained in alumina (aluminum oxide) of the ceramic substrate 101, and the ceramic substrate 101 is displayed in red.
- FIG. 17 is a schematic diagram illustrating a schematic configuration of an evaluation apparatus that performs adhesion strength evaluation.
- An evaluation apparatus 70 shown in FIG. 17 includes a sample stage 71 on which a laminate (Examples 1 to 4 and Comparative Examples 1 to 3) composed of at least a ceramic substrate 10 and a cooling fin 40 that is a metal film is placed, and a laminate. And a pin 72 for applying a downward force in the figure.
- the pin 72 is made of aluminum and is in close contact with the laminate by solidifying the adhesive G, which is an epoxy resin.
- the adhesive G was cured by being held at 150 ° C. for 1 hour. Then, the adhesion strength between the ceramic substrate and the metal film was evaluated by pulling the tip 72a of the pin 72 in the direction away from the laminate. The evaluation results of the adhesion strength evaluation are shown in Table 1.
- Example 2 In Example 2, a laminated body was manufactured as the intermediate layer 501 using a silver-copper alloy as the main component metal layer 511 and titanium hydride as the active component layer 521. Further, alumina was used as the ceramic substrate 101, and copper was used as the metal film 402. FIG. 18 shows a cross-sectional backscattered electron image (300 times) of this laminate.
- the main component metal layer 511 and the active component layer 521 of the intermediate layer 501 were formed by applying a brazing material and holding it in a vacuum at 800 ° C. for 1 hour.
- the intermediate layer 501, the ceramic substrate 101, and the metal film 402 are maintained in a joined state without being peeled off. Even when the metal film was not aluminum but copper, a laminate that maintained the bonded state was obtained.
- the adhesion strength evaluation by the evaluation apparatus 70 shown in FIG. 17 was performed.
- the adhesion strength between the ceramic substrate and the metal film was 60 MPa or more, and the result was that the laminate had high adhesion strength.
- Example 3 In Example 3, as the intermediate layer 502, a laminate was prepared by using silver as the main component metal layer, 2% by weight of germanium as the active component layer, and adding 15% by weight of boron. Further, alumina was used as the ceramic substrate 101, and copper was used as the metal film 402. FIG. 19 shows a cross-sectional reflected electron image (300 times) of this laminate.
- the main component metal layer and the active component layer of the intermediate layer 502 were formed by applying a brazing material and holding it in the atmosphere at 850 ° C. for 1 hour.
- the intermediate layer 502, the ceramic substrate 101, and the metal film 402 are maintained in a joined state without being peeled off. Even when the intermediate layer 502 was formed in the air, a laminated body in which the bonded state was maintained was obtained.
- FIG. 20 shows a cross-sectional backscattered electron image (500 times) subjected to elemental analysis.
- 21 to 25 are diagrams showing the results of cross-sectional element distribution analysis on the cross-sectional backscattered electron image shown in FIG.
- the cross-sectional element distribution analysis results shown in FIGS. 21 to 25 are displayed in red as the content of the element to be analyzed increases, and in blue as the content decreases. That is, as the content increases, the color changes from blue to reddish.
- FIG. 21 shows the results of cross-sectional element distribution analysis showing the silver content. Silver is used as a main component metal layer, and the intermediate layer 502 is displayed in red.
- FIG. 22 shows the results of cross-sectional element distribution analysis showing the aluminum content.
- Aluminum is contained in alumina (aluminum oxide) in the ceramic substrate 101, and the ceramic substrate 101 is displayed in green or yellow.
- FIG. 23 is a cross-sectional element distribution analysis result showing the copper content. Copper is used as the metal film 402, and the metal film 402 is displayed in red.
- FIG. 24 is a cross-sectional element distribution analysis result showing the germanium content.
- Germanium is used as an active ingredient layer, and the ceramic substrate 101 side of the intermediate layer 502 is displayed in green.
- the active component layer also contains added boron.
- FIG. 25 shows the result of cross-sectional element distribution analysis showing the oxygen content.
- Oxygen is contained in alumina (aluminum oxide) of the ceramic substrate 101, and the ceramic substrate 101 is displayed in red.
- the intermediate layer 502 is formed in the atmosphere, the oxidized metal portion in the intermediate layer 502 is displayed in green.
- the adhesion strength evaluation by the evaluation apparatus 70 shown in FIG. 17 was performed.
- the adhesion strength between the ceramic substrate and the metal film was 60 MPa or more, and the result was that the laminate had high adhesion strength.
- Example 4 In Example 4, as the intermediate layer 503, silver was used for the main component metal layer, 2 wt% titanium hydride was used for the active component layer, and 0.4 wt% aluminum was added to prepare a laminate. Further, alumina was used as the ceramic substrate 101, and copper was used as the metal film 402. FIG. 26 shows a cross-sectional reflected electron image (500 times) of this laminate. In addition, the main component metal layer 511 and the active component layer 521 of the intermediate layer 503 were formed by applying a brazing material and holding it in the atmosphere at 970 ° C. for 1 hour.
- the intermediate layer 503, the ceramic substrate 101, and the metal film 402 are maintained in a joined state without being peeled off. Even when the metal film was copper instead of aluminum, and the intermediate layer was formed in the atmosphere, a laminate that maintained the bonded state was obtained.
- the adhesion strength evaluation by the evaluation apparatus 70 shown in FIG. 17 was performed.
- the adhesion strength between the ceramic substrate and the metal film was 60 MPa or more, and the result was that the laminate had high adhesion strength.
- Comparative Example 1 As a comparative example for Example 1, a laminate was manufactured by forming a film of aluminum as a metal film 401 by a cold spray method on alumina as a ceramic substrate 101 without forming an intermediate layer.
- FIG. 27 shows a cross-sectional reflected electron image (2000 times) of this laminate.
- Comparative Example 2 As a comparative example with respect to Example 2, a laminate was manufactured by forming a film of copper as the metal film 402 by a cold spray method on alumina as the ceramic substrate 101 without forming an intermediate layer.
- FIG. 28 shows a cross-sectional reflected electron image (2000 times) of this laminate.
- Comparative Example 3 As a comparative example for Examples 3 and 4, after forming an intermediate layer in the atmosphere (850 ° C., 1 hour) using silver as the ceramic substrate, copper as the metal film was cold-treated. A film was formed by a spray method to produce a laminate. In addition, this comparative example 3 becomes a structure which does not contain an active ingredient layer in an intermediate
- the laminate and the method for producing the laminate according to the present invention are useful when joining a ceramic substrate and a metal film.
Abstract
Description
実施例1では、中間層501として、主成分金属層511に銀−銅合金、活性成分層521に水素化チタンを用いて積層体を作製した。また、セラミックス基材101としてアルミナ、金属皮膜401としてアルミニウムを用いた。この積層体の断面反射電子像を図7~10に示す。図7の断面反射電子像は40倍の電子像、図8の断面反射電子像は500倍の電子像、図9,10の断面反射電子像は2000倍の電子像である。なお、中間層501の主成分金属層511および活性成分層521は、ろう材を塗布後、800℃の真空中で1時間保持することによって形成した。
実施例2では、中間層501として、主成分金属層511に銀−銅合金、活性成分層521に水素化チタンを用いて積層体を作製した。また、セラミックス基材101としてアルミナ、金属皮膜402として銅を用いた。この積層体の断面反射電子像(300倍)を図18に示す。なお、中間層501の主成分金属層511および活性成分層521は、ろう材を塗布後、800℃の真空中で1時間保持することによって形成した。
実施例3では、中間層502として、主成分金属層に銀、活性成分層に2重量%のゲルマニウムを用い、15重量%の硼素を添加して積層体を作製した。また、セラミックス基材101としてアルミナ、金属皮膜402として銅を用いた。この積層体の断面反射電子像(300倍)を図19に示す。なお、中間層502の主成分金属層および活性成分層は、ろう材を塗布後、850℃の大気中で1時間保持することによって形成した。
実施例4では、中間層503として、主成分金属層に銀、活性成分層に2重量%の水素化チタンを用い、0.4重量%のアルミニウムを添加して積層体を作製した。また、セラミックス基材101としてアルミナ、金属皮膜402として銅を用いた。この積層体の断面反射電子像(500倍)を図26に示す。なお、中間層503の主成分金属層511および活性成分層521は、ろう材を塗布後、970℃の大気中で1時間保持することによって形成した。
本実施例1に対する比較例として、セラミックス基材101としてのアルミナに対して、中間層を形成させずに、金属皮膜401としてのアルミニウムをコールドスプレー法によって被膜を形成させて積層体を作製した。この積層体の断面反射電子像(2000倍)を図27に示す。
本実施例2に対する比較例として、セラミックス基材101としてのアルミナに対して、中間層を形成させずに、金属皮膜402としての銅をコールドスプレー法によって皮膜を形成させて積層体を作製した。この積層体の断面反射電子像(2000倍)を図28に示す。
本実施例3,4に対する比較例として、セラミックス基材としてのアルミナに対して、銀を用いて大気中(850℃、1時間)で中間層を形成させた後、金属皮膜としての銅をコールドスプレー法によって皮膜を形成させて積層体を作製した。なお、本比較例3は、中間層に活性成分層を含まない構成となる。
10,101 セラミックス基材
20 銅回路
30 チップ
40,401,402 冷却フィン(金属皮膜)
50,501,502,503 中間層
51,511 主成分金属層
52,521 活性成分層
60 コールドスプレー装置
61 ガス加熱器
62 粉末供給装置
63 ガスノズル
64 スプレーガン
70 評価装置
71 試料台
72 ピン
Claims (10)
- 絶縁性のセラミックス基材と、
金属を含む主成分金属層、および金属または金属の酸化物もしくは水素化物からなる活性成分層を有し、前記セラミックス基材の表面に形成される中間層と、
前記中間層の表面に、金属を含む粉体をガスと共に加速し、前記表面に固相状態のままで吹き付けて堆積させることによって形成された金属皮膜と、
を備えたことを特徴とする積層体。 - 前記中間層は、真空中で熱処理されることによって形成されることを特徴とする請求項1に記載の積層体。
- 前記活性成分層は、チタン、ジルコニウム、ハフニウム、ゲルマニウムのいずれかの金属または金属の水素化物からなる群より選択される少なくとも1種類を含むことを特徴とする請求項2に記載の積層体。
- 前記主成分金属層は、金、銀、銅、アルミニウム、ニッケルからなる群より選択される少なくとも1種類を含むことを特徴とする請求項2または3に記載の積層体。
- 前記中間層は、大気中で熱処理されることによって形成されることを特徴とする請求項1に記載の積層体。
- 前記活性成分層は、チタン、ジルコニウム、ハフニウム、ゲルマニウム、硼素、珪素、アルミニウム、クロム、インジウムまたは金属の酸化物もしくは水素化物からなる群より選択される少なくとも1種類を含むことを特徴とする請求項5に記載の積層体。
- 前記主成分金属層は、金または銀のうち少なくとも1種類を含むことを特徴とする請求項5または6に記載の積層体。
- セラミックス基材の表面に金属皮膜が形成された積層体を製造する積層体の製造方法であって、
前記セラミックス基材の表面に対して、金属または金属の酸化物もしくは水素化物を含むろう材を配設するろう材配設ステップと、
前記ろう材配設ステップで前記ろう材が配設された前記セラミックス基材を熱処理することによって中間層を形成させる中間層形成ステップと、
前記中間層形成ステップによって形成された前記中間層の表面に、金属を含む粉体をガスと共に加速し、前記表面に固相状態のままで吹き付けて堆積させることによって前記金属皮膜を形成させる金属皮膜形成ステップと、
を含むことを特徴とする積層体の製造方法。 - 前記中間層形成ステップは、真空中で行うことを特徴とする請求項8に記載の積層体の製造方法。
- 前記中間層形成ステップは、大気中で行うことを特徴とする請求項8に記載の積層体の製造方法。
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EP11842434.0A EP2641997A4 (en) | 2010-11-19 | 2011-11-17 | Laminate and method for producing laminate |
KR1020137012386A KR101513603B1 (ko) | 2010-11-19 | 2011-11-17 | 적층체 및 적층체의 제조 방법 |
CN201180055230.2A CN103282546B (zh) | 2010-11-19 | 2011-11-17 | 层叠体和层叠体的制造方法 |
US13/885,862 US20130236738A1 (en) | 2010-11-19 | 2011-11-17 | Laminate and method for producing laminate |
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EP2732967A1 (en) * | 2011-07-11 | 2014-05-21 | NHK Spring Co., Ltd. | Layered body and manufacturing method for layered body |
EP2732967A4 (en) * | 2011-07-11 | 2015-02-18 | Nhk Spring Co Ltd | LAYER BODY AND MANUFACTURING METHOD FOR LAYER BODY |
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KR20130100338A (ko) | 2013-09-10 |
EP2641997A4 (en) | 2017-12-20 |
KR101513603B1 (ko) | 2015-04-20 |
US20130236738A1 (en) | 2013-09-12 |
EP2641997A1 (en) | 2013-09-25 |
JP2012111982A (ja) | 2012-06-14 |
CN103282546B (zh) | 2016-02-17 |
JP5191527B2 (ja) | 2013-05-08 |
CN103282546A (zh) | 2013-09-04 |
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