WO2006030676A1 - アルミニウム-炭化珪素質複合体 - Google Patents
アルミニウム-炭化珪素質複合体 Download PDFInfo
- Publication number
- WO2006030676A1 WO2006030676A1 PCT/JP2005/016453 JP2005016453W WO2006030676A1 WO 2006030676 A1 WO2006030676 A1 WO 2006030676A1 JP 2005016453 W JP2005016453 W JP 2005016453W WO 2006030676 A1 WO2006030676 A1 WO 2006030676A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aluminum
- silicon carbide
- heat dissipation
- carbide composite
- circuit board
- Prior art date
Links
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 90
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 40
- 230000017525 heat dissipation Effects 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 27
- 239000000835 fiber Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 13
- 238000005242 forging Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 7
- 239000012798 spherical particle Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 241001676573 Minium Species 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 24
- 230000005855 radiation Effects 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 22
- 238000000137 annealing Methods 0.000 description 21
- 238000003754 machining Methods 0.000 description 19
- 238000005470 impregnation Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000010304 firing Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- -1 for example Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
-
- 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
-
- 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
-
- 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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/515—Other specific metals
- C04B41/5155—Aluminium
-
- 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
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
-
- 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
- H01L23/13—Mountings, e.g. non-detachable insulating substrates characterised by the shape
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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
- H01L23/142—Metallic substrates having insulating layers
-
- 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
-
- 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
- H01L23/3733—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon having a heterogeneous or anisotropic structure, e.g. powder or fibres in a matrix, wire mesh, porous structures
-
- 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
- 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
-
- 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
- H05K1/0284—Details of three-dimensional rigid printed circuit boards
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0116—Porous, e.g. foam
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09009—Substrate related
- H05K2201/09018—Rigid curved substrate
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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
- Y10T428/12007—Component of composite having metal continuous phase interengaged with nonmetal continuous phase
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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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249955—Void-containing component partially impregnated with adjacent component
- Y10T428/249956—Void-containing component is inorganic
- Y10T428/249957—Inorganic impregnant
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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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
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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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249971—Preformed hollow element-containing
- Y10T428/249974—Metal- or silicon-containing element
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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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249986—Void-containing component contains also a solid fiber or solid particle
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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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
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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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
- Y10T428/24999—Inorganic
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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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
Definitions
- the present invention relates to an aluminum silicon carbide based composite suitable as a base plate of a circuit board.
- the major axis in the present invention represents a diagonal line when the flat plate shape is a rectangle, a diameter when the flat plate is a circle, a major axis when the shape is an ellipse, and a longest axis when the shape is any other shape. .
- a ceramic circuit board in which a copper or aluminum metal circuit is formed on the surface of a ceramic substrate such as an aluminum nitride substrate or a silicon nitride substrate having high insulation and high thermal conductivity is manufactured, and on the back surface thereof.
- a substrate on which a copper or aluminum base plate is formed as a heat sink is used as a power module substrate, for example.
- a typical heat dissipation structure of a conventional ceramic circuit board is obtained by soldering a base board to a ceramic circuit board, and copper and aluminum are generally used as a base board.
- copper and aluminum are generally used as a base board.
- this structure for example, when the heat load is strong, cracks due to the difference in thermal expansion coefficient between the base plate and the ceramic circuit board occur in the solder layer, resulting in insufficient heat dissipation. There were problems such as malfunctioning or damage of semiconductors on the circuit.
- the base plate is often joined to a heat radiating fin, a heat radiating unit or the like, and the shape and warpage of the joint are also important.
- a base plate is joined to a heat radiating fin, a heat radiating unit or the like, it is generally screwed using a hole provided at the peripheral edge of the base plate, but if the base plate has minute irregularities, the base plate Between the heat sink and the heat dissipation fin or heat dissipation unit There is a gap, and even if high thermal conductivity thermal grease is applied, heat transfer may be reduced. As a result, there is a problem that the heat radiation performance of the entire module composed of the ceramic circuit board, the base plate, the heat radiation fin, the heat radiation unit, and the like is lowered.
- a base plate with a convex warp is used in advance so that there is no gap as much as possible between the base plate and the heat radiating fin.
- This warpage is usually obtained by using a jig having a predetermined shape and applying pressure to the base plate under heating.
- the warpage obtained by this method has a large amount of warpage and a shape.
- quality was not stable because it was not constant.
- the aluminum layer means a metal layer mainly composed of aluminum such as an aluminum alloy layer.
- the base plate manufactured using the above method tends to have a thick central portion of the aluminum layer after machining. For this reason, if the ceramic circuit board is soldered when assembling the power module, the shape of the central part of the heat dissipation surface may be distorted depending on the layout of the ceramic circuit board, creating a gap between the heat dissipation fins and sufficient heat dissipation. In some cases, the characteristics could not be exhibited.
- an aluminum plate having a melting point higher than that of the aluminum alloy used during impregnation and a high purity may be used.
- a difference in local color tone was caused by the reaction between high-purity aluminum and an aluminum layer having a low melting point.
- the present invention has been made in view of the above situation, and an object thereof is a ceramic circuit. It is to provide an aluminum monocarbide composite suitable as a base plate for a substrate
- a flat silicon carbide porous body is impregnated with a metal containing aluminum as a main component, both main surfaces have aluminum layers made of a metal containing aluminum as a main component, and one main surface is a circuit board.
- the heat-dissipating surface of the silicon carbide-based porous material is formed or machined into a convex warp shape, and the main component is aluminum.
- Aluminum-silicon carbide composite characterized in that after impregnation with metal, the aluminum layer on the heat dissipation surface is further machined to form a warp
- the average thickness of the aluminum layer on the circuit board bonding surface is 0.:! To 0.3 mm, the difference in thickness between the aluminum layers in the circuit board bonding surface is within 0.1 mm, and the aluminum on both main surfaces
- an aluminum layer made of a metal containing aluminum as a main component 5 to 40% by mass of one or more of fibers, spherical particles and crushed particles containing alumina or silica as a main component is contained.
- the amount of change in the amount of warpage in the major axis direction of the heat dissipation surface before and after heat treatment for removing processing strain is 30 ⁇ m or less per 200 mm.
- Aluminum carbide composite is 30 ⁇ m or less per 200 mm.
- the aluminum silicon carbide composite of the present invention is characterized by low thermal expansion and high thermal conductivity.
- Have One main surface of a flat plate-like silicon carbide porous body is formed or machined in advance into a convex shape before impregnation with an aluminum alloy, and after impregnation with the aluminum alloy, the surface aluminum layer is further machined.
- the heat dissipation after soldering to the ceramic circuit board is better. Ceramics that can be easily processed into a predetermined shape and that can prevent the occurrence of local color unevenness with little distortion on the heat-dissipating surface, especially for mounting semiconductor components that require high reliability. It is suitable as a base board for circuit boards.
- FIG. 1 is a perspective view of an embodiment of an aluminum silicon carbide composite of the present invention.
- FIG. 2 is a cross-sectional view taken along line AA in FIG.
- the methods for producing metal-ceramic composites can be broadly classified into two types: impregnation and powder metallurgy.
- the powder metallurgy method has not been obtained in terms of characteristics such as thermal conductivity, and what is actually commercialized is the impregnation method.
- various methods of impregnation including a method performed at normal pressure and a method performed under high pressure (high pressure forging method).
- High pressure forging methods include molten metal forging and die casting.
- a method suitable for the present invention is a high-pressure forging method in which impregnation is performed under high pressure, and either a molten metal forging method or a die casting method can be used, but a molten metal forging method is more preferable.
- the high-pressure forging method is a method in which a ceramic porous body (hereinafter referred to as a preform) is loaded into a high-pressure vessel and impregnated with a molten aluminum alloy at a high pressure to obtain a composite.
- SiC preform silicon carbide porous body
- SiC preform silicon carbide porous body
- SiC preform silicon carbide porous body
- it can be produced by a known method without any particular limitation.
- SiC raw material silicon carbide
- SiC silicon carbide
- press molding, extrusion molding, squeeze molding, and the like can be used without any limitation, and a shape-retaining binder can be used in combination as required.
- the convex warped shape of one main surface of the SiC preform which is one of the features of the present invention, is formed by molding or machining.
- molding and machining methods There are no particular restrictions on the molding and machining methods, but in the above-described SiC preform manufacturing method, when forming a mixture in which a binder is added to SiC powder, a method using a mold added with a shape, or firing Any method of later machining one major surface to form a convex shape can be used.
- Examples of a method for obtaining an aluminum silicon carbide composite by impregnating a SiC preform with an aluminum alloy include the following methods. After the SiC preform is stored in the mold, both main surfaces of the mold are in direct contact with one or more of fibers, spherical particles, and crushed particles mainly composed of alumina or silica. Placed in a single block.
- As the aluminum alloy AC4C, AC4CH, ADC 12 or the like is preferably used. After preheating the block at about 500 to 650 ° C, place one or more in a high-pressure vessel, and add molten aluminum alloy at a pressure of 30 MPa or more as quickly as possible to prevent the temperature of the block from decreasing.
- an aluminum silicon carbide composite having an aluminum layer on both main surfaces can be obtained.
- annealing may be performed for the purpose of removing distortion during impregnation.
- Important characteristics of the aluminum-silicon carbide composite obtained by impregnating the silicon carbide based porous material of the present invention with aluminum or an alloy thereof are thermal conductivity and thermal expansion coefficient.
- a higher SiC content in the silicon carbide porous body is preferable because the thermal conductivity is high and the thermal expansion coefficient is small, but if the content is high, the aluminum alloy may not be sufficiently impregnated.
- the strength of the SiC preform is preferably 3 MPa or more in bending strength to prevent cracking during handling and impregnation.
- the SiC preform is obtained by degreasing and firing a molded body of a mixture obtained by adding a binder to the SiC powder. If the firing temperature is 800 ° C or higher, a SiC preform with a bending strength of 3 MPa or more, which is related to the firing atmosphere, can be obtained. However, in an oxidizing atmosphere, firing at a temperature exceeding 1100 ° C promotes the oxidation of SiC and may decrease the thermal conductivity of the aluminum-silicon carbide composite. In the atmosphere, it is preferable to fire at a temperature of 1100 ° C or lower. The firing time is appropriately determined according to the conditions such as the size of the SiC preform, the amount charged into the firing furnace, and the firing atmosphere.
- the SiC preform according to the present invention is formed into a predetermined shape at the time of molding, a force for drying one sheet at a time, and using a spacer such as carbon having a shape equal to the shape of the preform between the SiC preforms.
- a spacer such as carbon having a shape equal to the shape of the preform between the SiC preforms.
- the aluminum alloy in the aluminum-silicon carbide composite of the present invention preferably has a melting point as low as possible in order to sufficiently penetrate into the voids of the preform when impregnated.
- Such aluminum alloys for example, silicon 7 to 25 mass 0/0 containing the aluminum Niumu alloy.
- metal components other than aluminum, silicon, and magnesium in the aluminum alloy there is no particular limitation as long as the characteristics do not change extremely, for example, copper may be included.
- one or more of fibers, spherical particles, and crushed particles mainly composed of alumina or silica are used in the stacking step. It is preferable to place it in direct contact with the surface of the SiC preform. As a result, there is an advantage that the workability is improved when the shape is added so that the color after impregnation is almost impossible as long as an aluminum layer having a predetermined thickness can be formed.
- the content of the material composed of one or more of fibers mainly composed of alumina or silica, spherical particles, and crushed particles is based on the mass of the aluminum monocarbide composite.
- the amount is preferably 5 to 40% by mass, particularly preferably 10 to 20% by mass. If the content is less than 5% by mass, it may be difficult to control the thickness of the aluminum layers on both main surfaces, and the warped shape may change greatly due to the annealing treatment after processing. On the other hand, if the content exceeds 40% by mass, the aluminum alloy layer becomes too hard and general machining becomes difficult.
- the annealing treatment for the purpose of removing strain when the SiC preform is impregnated with the SiC preform is preferably performed at a temperature of 400 to 550 ° C for 10 minutes or more. If the annealing temperature is less than 400 ° C, the distortion inside the composite may not be fully released, and the warpage may change greatly in the annealing process after machining. On the other hand, if the annealing temperature exceeds 550 ° C, the aluminum alloy used for impregnation may melt.
- the annealing time is less than 10 minutes, even if the annealing temperature is 400 to 550 ° C, the distortion inside the composite will not be released sufficiently, and warping will occur in the annealing process to remove the processing distortion after machining. May change significantly.
- the thickness of the aluminum layer provided on the surface of the silicon carbide based composite may be equal when both main surfaces are machined, but only on the heat radiating surface side. When processing, it is better to thicken the aluminum layer on the heat-dissipating surface side in advance so that the thickness of the aluminum layer on both main surfaces does not differ greatly after processing.
- the average thickness of the aluminum layer on the circuit board bonding surface is 0.:! To 0.3 mm.
- the difference between the average thicknesses of the aluminum layers on both main surfaces is preferably S, and the average thickness of the thicker aluminum layer is 40. /. Is preferably within.
- the machining blade will hit the SiC preform structure in the aluminum-silicon carbide composite during machining and cause chipping.
- the SiC preform structure in the aluminum-silicon carbide composite may be exposed and cause plating defects.
- the average thickness of the aluminum layer on the circuit board bonding surface exceeds 0.3 mm, the shape of the heat dissipation surface becomes distorted after the ceramic circuit board is soldered, and there is a sufficient gap between the heat dissipation fins. The heat dissipation characteristics may not be obtained.
- the thermal conductivity will decrease or the annealing treatment to remove the subsequent processing strain will occur. At this time, the amount of warpage may change due to the difference in thermal expansion coefficient between the aluminum layers on both main surfaces.
- the thickness difference of the aluminum layer in the circuit board bonding surface is preferably within 0.1 mm, particularly preferably within 0.05 mm. If the thickness difference of the aluminum layer in the circuit board bonding surface is greater than 0.1 mm, the warpage may change greatly during the subsequent annealing process when machined. Furthermore, a difference in thermal expansion between the thickest part and the thinnest part may cause cracks due to heat from the mounted element.
- Warpage formation of the heat radiating surface or the circuit board bonding surface is preferably performed by machining such as a lathe.
- the work piece is fixed to a lathe by screwing using a hole or the like provided in the peripheral portion of the work piece.
- the aluminum layer on the surface of the aluminum carbide silicon composite is machined, it is possible to obtain an ideal spherical heat radiating surface, which has good heat radiating characteristics and stress relaxation properties.
- a silicon carbide composite can be obtained.
- the thickness of the aluminum layer on the heat dissipation surface side is increased in advance, only the heat dissipation surface is processed and the difference in the average thickness of the aluminum layers on both main surfaces is preferably within 40% of the average thickness of the aluminum layer on the heat dissipation surface, especially It is preferable to adjust within 30%.
- the sum of the average thicknesses of the aluminum layers on both main surfaces after machining is preferably 1.0 mm or less, particularly preferably 0.6 mm or less. If the sum of the average thicknesses of the aluminum layers on both main surfaces exceeds 1. Omm, the thermal expansion coefficient of the entire aluminum monosilicon carbide composite increases, and when a thermal load force S is applied after mounting the semiconductor parts, aluminum silicon carbide is applied. Cracks caused by the difference in thermal expansion coefficient between the plastic composite and the ceramic circuit board As a result, there is a risk that the semiconductor will malfunction or break due to insufficient heat dissipation.
- the amount of warpage of the heat dissipation surface of the aluminum-silicon carbide composite after machining is preferably about 10 to 400 ⁇ m, more preferably about 100 to 300 ⁇ m per 200 mm on the long axis. It is preferable to process it.
- the amount of warp on the heat dissipation surface is less than 10 zm, a gap will be created between the heat dissipation surface and the heat dissipation fin in the subsequent module assembly process, and even if high thermal conductivity heat dissipation grease is applied, As a result, the conductivity may decrease, and as a result, the heat dissipation of a module composed of a ceramic circuit board, a base plate, heat dissipation fins, and the like may decrease.
- the amount of warpage exceeds 400 ⁇ , cracks may occur in the aluminum-silicon carbide composite or ceramic circuit board during screwing when joining to the radiating fin.
- the amount of warpage on the major axis of the circuit board surface is preferably 200 to 200 ⁇ m, particularly preferably -100 to 100 / m, per 200 mm. If the warpage on the major axis of the circuit board surface is out of the above range, the thickness of the solder at the time of circuit board bonding will not be constant, and a ceramic circuit board, aluminum silicon carbide, where voids are likely to occur when soldered There is a case where the heat dissipation of the module composed of the composite material and the heat radiation fin is lowered.
- the annealing treatment for removing the processing strain is preferably performed at a temperature of 400 ° C to 550 ° C for 10 minutes or more. Even if the annealing temperature is less than 400 ° C, or even if the annealing temperature is 400 ° C to 550 ° C, if the annealing time is less than 10 minutes, the distortion inside the composite is not fully released and the subsequent The warpage may change significantly during the circuit board soldering process. In addition, if the annealing temperature exceeds 550 ° C, the impregnated aluminum alloy may melt.
- the difference in warpage on the major axis of the heat dissipation surface before and after annealing is preferably about 30 x m or less, more preferably about 20 x m or less per 200 mm. If the difference in warpage exceeds 30 ⁇ m, a gap will be created between the aluminum-silicon carbide composite and the heat release fin during the module assembly process, and even if high thermal conductivity heat dissipation grease is applied, heat transfer will occur. Conductivity may be reduced.
- the aluminum silicon carbide based composite according to the present invention has good heat dissipation characteristics and stress relaxation properties.
- it is suitable as a base plate interposed between a ceramic circuit board and a heat radiating component such as a heat radiating fin.
- the aluminum-silicon carbide based composite according to the present invention has an aluminum layer on both main surfaces, and the heat dissipation surface can be formed into an ideal spherical shape.
- the contact between the base plate and the heat radiating parts such as the heat radiating fins is improved, and the module is composed of the ceramic circuit board, the base plate, and the heat radiating fins. There is an effect that the heat dissipation characteristic of the is excellent.
- the aluminum silicon carbide based composite of the present invention has a thermal conductivity of 180 W / mK or more, particularly 200 W / m or more, and a thermal expansion coefficient of 10 X 10_6 / K or less, in particular 8.5. X 10 " 6 / ⁇ or less can be reached. In addition to the above effects, it has high thermal conductivity and low expansion coefficient equivalent to that of semiconductor components and ceramic circuit boards. Furthermore, the module using it has excellent heat dissipation characteristics, and it is difficult to be deformed even if it is subjected to temperature changes.
- SiC powder ⁇ (manufactured by Taiheiyo Random: NG_220, average particle size: 60 zm) 70 g
- SiC powder B (manufactured by Yakushima Electric: GC_1000F, average particle size: 10 ⁇ m) 30 g
- silica sol (Nissan Kagakusha) (Manufactured by SNOWTEX) 10 g was collected and mixed with a stirrer / mixer for 30 minutes, and then press-molded into a flat plate with dimensions of 185 mm long x 135 mm wide x 5. Omm in pressure lOMPa.
- the obtained compact was fired in the atmosphere at 900 ° C for 2 hours to obtain a SiC preform with a relative density of 65%, and then the main surface of the SiC preform was warped at 200 ⁇ m per 200 mm by a lathe. It was processed into a convex spherical shape so that the thickness of the central part was 4.6 mm.
- the obtained SiC preform was placed in a steel frame of 185mm in length X 13 5mm in width X 5.2mm in height with a pouring gate through which molten metal can flow, and 185mm in length on the spherical surface (heat dissipation surface).
- X side 135mm X thickness 0.4mm alumina fiber Teanaka Paper Co., Ltd., purity 97%, sheet-like form
- mm alumina fibers Teanaka Paper Industries, Inc., purity 97%, sheet-like form
- An integrated product sandwiched between carbon-coated SUS plates on both sides was preheated to 600 ° C in an electric furnace. Next, it is placed in a pre-heated press mold with an inner diameter of 300 mm, and a molten aluminum alloy containing 12% by mass of silicon and 0.5% by mass of magnesium is poured into it and applied at a pressure of lOOMPa for 20 minutes.
- the SiC preform was impregnated with an aluminum alloy. After cooling to room temperature, the steel frame, etc. is cut with a wet band saw, the sandwiched US plate is peeled off, and then annealed at a temperature of 530 ° C for 3 hours to remove strain during impregnation. An aluminum monocarbide composite was obtained.
- machining holes having a diameter of 8 mm are provided at the four corners of the edge of the aluminum silicon carbide composite, and screws are secured to the lathe jig using the machining holes, so that the thickness of the aluminum layer is 0.4 mm.
- the surface was warped with 200 ⁇ per 200 mm and processed into a spherical shape.
- the grinding amount was set to an average thickness of 5. Omm by performing an average 200 / im grinding so that the average thicknesses of the aluminum layers on both main surfaces after processing were equal.
- an annealing process was performed for 3 hours at a temperature of 530 ° C using a pine furnace, and the processing distortion was removed.
- the shape of the SiC preform is a flat shape of length 185mm x width 135mm x thickness 5 ⁇ Omm, with alumina fibers on both sides of the SiC preform.
- An aluminum-silicon carbide composite was produced in the same manner as in Example 1 except that the preform and the aluminum silicon carbide composite were not machined.
- spherical aluminum molds with a spherical shape of 250 ⁇ m per 250 mm are placed above and below the obtained aluminum-silicon carbide composite, heated in the atmosphere at a temperature of 530 ° C for 10 minutes, and further at a pressure of 5 MPa. The pressure was applied for 10 minutes, and warping was performed so that a warp of 200 ⁇ m per 200 mm was applied. After the warping, annealing was performed at a temperature of 530 ° C for 3 hours.
- Example 1 The aluminum-silicon carbide composite obtained in Example 1 and Comparative Example 1 was cut along a diagonal, and the aluminum layers (A1 layer) on the respective main surfaces (hereinafter referred to as main surface 1 and main surface 2). 20 points were measured at equal intervals along the diagonal, and the average value was calculated.
- a thermal expansion coefficient of 25-250 ° C was measured with a thermal dilatometer (Seiko Denshi Kogyo Co., Ltd .; TMA300), and thermal conductivity at 25 ° C was measured with a laser flash method (manufactured by Rigaku Corporation); LFZT CM—8510B).
- a contour shape measuring machine manufactured by Tokyo Seimitsu Co., Ltd .; contour record 1600D-22 was used, and for each of the 20 test specimens, in Example 1, on the diagonal line of the heat dissipation surface after machining and annealing.
- the amount of warpage per 200 mm was measured in Comparative Example 1, and the amount of warpage per 200 mm on the diagonal of the heat dissipation surface after warping and annealing was measured. Furthermore, in order to know the variation, the average and standard deviation of the difference in warpage values on the two diagonals were calculated. The results are shown in Tables 1 and 2.
- the thickness of the alumina fiber on the planar surface was changed to 0.1 mm so that the average thickness of the aluminum layer was 100 / im, and after impregnating the aluminum alloy, the spherical surface was ground by 300 ⁇ (Example 2), aluminum The thickness of the alumina fiber on the planar surface was changed to 0.3 mm so that the average thickness of the layer was 300 ⁇ 300 ⁇ , and after impregnating the aluminum alloy, the spherical surface was ground at 100 / im (Example 3), The thickness of the alumina fiber on the plane surface was changed to 0.05 mm so that the average thickness of the aluminum layer was 50 / m, and after impregnating the aluminum alloy, the spherical surface was ground 350 ⁇ m (Example 4), The thickness of the alumina fiber on the plane-shaped surface was changed to 0.35 mm so that the average thickness of the aluminum layer was 350 ⁇ m, and the spherical-shaped surface was subjected to 50 xm polishing IJ (
- the difference in thickness of the aluminum layer is 100 ⁇ m.
- the thickness of one end of the alumina fiber on the surface-shaped surface was changed stepwise so that the thickness of one end was 0.15 mm and the thickness of the other end was 0.25 mm (Example 6).
- the thickness of the alumina fiber on the plane surface was changed to 0.11 mm (Example 8), and the thickness of the alumina fiber on the plane surface was changed to 0.1 mm.
- An aluminum-silicon carbide composite was produced, processed, and evaluated in the same manner as in Example 1 except that it was changed to (Example 9). The results are shown in Tables 1 and 2.
- Examples 10 to 16 The content of alumina fiber was 3% by mass (Example 10), the content of alumina fiber was 45% by mass (Example 11), and the content of alumina fiber was 5% by mass (implementation) Example 12), the content of alumina fiber was 40% by mass (Example 13), no alumina fiber was placed on both sides of the SiC preform (Example 14), spherical alumina instead of alumina fiber Particles (Sumitomo Chemical Co., Ltd.
- Example 15 Alumina CB-10 Grade Purity 99.9 /.) Filled with 35% by mass (Example 15) Crush-shaped alumina particles (made by Showa Denko KK) instead of alumina fibers Alumina-silicon carbide composite was prepared and evaluated in the same manner as in Example 1 except that 35% by mass of alumina AL-15-H grade purity 99.9%) was used (Example 16). Went. The results are shown in Tables 1 and 2.
- the surface with the thicker AI layer average thickness is defined as the main surface 1.
- the aluminum-silicon carbide composite of the present invention can be easily processed into a predetermined shape, and can prevent the occurrence of local uneven color appearance with less distortion of the heat release surface.
- it can be suitably used in a wide range as a base plate for ceramic circuit boards on which semiconductor components requiring high reliability are mounted. It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2004-266144 filed on September 14, 2004 are cited here as disclosure of the specification of the present invention. Incorporate.
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Abstract
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EP05782084.7A EP1796164B1 (en) | 2004-09-14 | 2005-09-07 | Aluminum-silicon carbide composite |
JP2006535802A JP4761157B2 (ja) | 2004-09-14 | 2005-09-07 | アルミニウム−炭化珪素質複合体 |
US11/575,262 US7838107B2 (en) | 2004-09-14 | 2005-09-07 | Aluminum-silicon carbide composite |
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US (1) | US7838107B2 (ja) |
EP (1) | EP1796164B1 (ja) |
JP (1) | JP4761157B2 (ja) |
KR (1) | KR101021450B1 (ja) |
CN (1) | CN100472766C (ja) |
TW (1) | TW200618697A (ja) |
WO (1) | WO2006030676A1 (ja) |
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JPWO2016021645A1 (ja) * | 2014-08-06 | 2017-05-25 | デンカ株式会社 | 放熱部品及びその製造方法 |
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KR20070064293A (ko) | 2007-06-20 |
EP1796164B1 (en) | 2020-01-01 |
TWI357788B (ja) | 2012-02-01 |
TW200618697A (en) | 2006-06-01 |
JPWO2006030676A1 (ja) | 2008-05-15 |
CN1977378A (zh) | 2007-06-06 |
JP4761157B2 (ja) | 2011-08-31 |
EP1796164A4 (en) | 2011-11-09 |
US20070248829A1 (en) | 2007-10-25 |
US7838107B2 (en) | 2010-11-23 |
EP1796164A1 (en) | 2007-06-13 |
KR101021450B1 (ko) | 2011-03-15 |
CN100472766C (zh) | 2009-03-25 |
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