WO2004080914A1 - Wärmesenke mit hoher wärmeleitfähigkeit - Google Patents
Wärmesenke mit hoher wärmeleitfähigkeit Download PDFInfo
- Publication number
- WO2004080914A1 WO2004080914A1 PCT/AT2004/000018 AT2004000018W WO2004080914A1 WO 2004080914 A1 WO2004080914 A1 WO 2004080914A1 AT 2004000018 W AT2004000018 W AT 2004000018W WO 2004080914 A1 WO2004080914 A1 WO 2004080914A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- silicon
- component according
- volume
- diamond
- composite material
- Prior art date
Links
Classifications
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
-
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/653—Processes involving a melting step
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
-
- 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
-
- 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
- H01L23/3732—Diamonds
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/402—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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/407—Copper
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/408—Noble metals
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/427—Diamond
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/604—Pressing at temperatures other than sintering temperatures
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/608—Green bodies or pre-forms with well-defined density
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
-
- 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
Definitions
- the invention relates to a component as a heat sink made of a composite material with a diamond content of 40-90% by volume, with an average size of the diamond grains of 5 to 300 ⁇ m, and a method for its production.
- Heat sinks are widely used in the manufacture of electronic components.
- the semiconductor components and a mechanically stable casing are the essential components of an electronic package.
- the terms substrate, heat spreader or carrier plate are often used for the heat sink.
- the semiconductor component consists, for example, of single-crystal silicon or gallium arsenide. This is connected to the heat sink, and soldering methods are usually used as the joining technique.
- the heat sink has the function of dissipating the heat generated during the operation of the semiconductor component.
- Semiconductor components with particularly high heat development are, for example, LDMOS (laterally diffused metal oxide semi-conductor), laser diodes, CPU (central processing unit), MPU (microprocessor unit) or HFAD (high frequency amplify device).
- LDMOS laterally diffused metal oxide semi-conductor
- laser diodes laser diodes
- CPU central processing unit
- MPU microprocessor unit
- HFAD high frequency amplify device
- the geometric designs of the heat sink
- Semiconductor materials are low compared to other materials and are used in the literature for silicon with 2.1 x 10 "6 K “ 1 to 4.1 x 10 "6 K “ 1 and for gallium arsenide with 5, 6 x 10 "6 K “ 1 to 5.8 x 10 "6 K “ 1 specified.
- Ceramic materials, composite materials or plastics are usually used for the encapsulation. Examples of ceramic materials are Al 2 0 3 with a Expansion coefficient of 6.5 x 10 "6 K “ 1 or aluminum nitride with an expansion coefficient of 4.5 x 10 "6 K “ 1 .
- Tensions can arise during the manufacture of the package, namely during the cooling phase from the soldering temperature to the room temperature. However, temperature fluctuations also occur during operation of the package, which range, for example, from -50 ° C to 200 ° C and can lead to thermomechanical stresses in the package.
- Single-phase metallic materials do not sufficiently meet the required property profile, since the materials with high thermal conductivity also have a high coefficient of thermal expansion. Therefore, in order to meet the requirement profile, composite materials or material composites are used for the production of the substrate.
- Usual tungsten-copper and Mo-copper composite materials or composite materials such as are described for example in EP 0 100 232, US 4 950 554 and US 5 493 153 have a thermal conductivity at room temperature of 170 to 250 W / (mK) a coefficient of thermal expansion of 6.5 x 10 "6 to 9.0 x 10 " 6 K "1 , which is no longer sufficient for many applications.
- Heat sinks were also of interest to diamond or composite materials or composite materials containing diamond. This is the thermal conductivity of diamond at 1,000 to 2,000 W / (mK), whereby the content of nitrogen and boron atoms on lattice sites is particularly important for quality.
- EP 0521 405 describes a heat sink which has a polycrystalline diamond layer on the side facing the semiconductor chip.
- the lack of plastic deformability of the diamond layer can lead to cracks in the diamond layer as soon as it cools down from the coating temperature.
- US Pat. No. 5,273,790 describes a diamond composite material with a thermal conductivity> 1,700 W / (m.K), in which loose, shaped diamond particles are converted from the gas phase into a stable shaped body by means of subsequent diamond deposition.
- the diamond composite produced in this way is too expensive for commercial use in mass parts.
- WO 99/12866 describes a method for producing a
- Diamond-silicon carbide composite material described It is manufactured by infiltrating a diamond skeleton with silicon or a silicon alloy. Due to the high melting point of silicon and the resulting high infiltration temperature, diamond is partly converted into carbon or subsequently into silicon carbide. Due to the high brittleness, the mechanical workability of this material is extremely problematic and complex, so that this composite material has not yet been used for heat sinks.
- US 4902652 describes a method for producing a sintered diamond material.
- An element from the group of transition metals from groups 4a, 5a and 6a, boron and silicon is deposited on diamond powder by means of physical exposure processes.
- the coated diamond grains are then connected to one another by means of a solid phase sintering process. It is disadvantageous that the resulting product has a high porosity and a coefficient of thermal expansion that is too low for many applications.
- No. 5,045,972 describes a composite material in which, in addition to diamond grains with a size of 1 to 50 ⁇ m, there is a metallic matrix which consists of aluminum, magnesium, copper, silver or their alloys. The disadvantage here is that the metallic matrix is only poorly bonded to the diamond grains, so that the thermal conductivity and mechanical integrity are insufficient to this extent.
- the metal carbides are the carbides of the metals of the 4a to 6a groups of the periodic table. Particular emphasis is given to EP 0 859 408 TiC, ZrC and HfC. Ag, Cu, Au and Al are mentioned as particularly advantageous filler metals. It is disadvantageous that the metal carbides have a low thermal conductivity, which for TiC, ZrC, HfC, VC, NbC and TaC is in the range from 10 to 65 W / (m.K). Another disadvantage is that the metals of the 4a to 6a groups of the periodic table have a solubility in the filler metal, such as silver, whereby the thermal conductivity of the metal phase is greatly reduced.
- EP 0 898 310 describes a heat sink which consists of diamond grains, a metal or a metal alloy of high thermal conductivity from the group Cu, Ag, Au, Al, Mg and Zn and a metal carbide of the metals of groups 4a, 5a and Cr, the Metal carbides cover at least 25% of the surface of the diamond grains.
- the process speed and the degree of integration of the semiconductor components have increased significantly, which has also led to an increase in heat development in the package.
- Optimal heat management is therefore an increasingly important criterion.
- the thermal conductivity of the materials described above is no longer sufficient for a large number of applications, or their production is too expensive for widespread use.
- the availability of improved, inexpensive heat sinks is a prerequisite for further optimization of semiconductor components.
- the component according to the invention has excellent adhesive strength between the diamond grains and the phase rich in Ag, Au or Al due to the silicon-carbon compound formed in between. A thickness of this is sufficient to achieve this connection
- Silicon-carbon compound in the nanometer range or a degree of coverage of> 60 percent.
- the degree of coverage is to be understood as the proportion of the diamond grain surface which is covered with the silicon-carbon compound. According to these premises, this corresponds to a volume content of the silicon-carbon compound of> 0.005 percent.
- silicon carbide In contrast to metal carbides, silicon carbide has a very high thermal conductivity of around 250 W / (mK). Since the solubility of Si in Ag, Au and Al is very low at room temperature, the very high thermal conductivity of these metals in the pure state is only slightly deteriorated. Alloys of Ag, Au or Al with Cu or Ni also have a sufficiently high thermal conductivity, which is deteriorated to a not unacceptably high degree by low, dissolved Si components. Furthermore, the machinability is sufficient due to the very ductile Ag, Au or Al structural components. For a cost-effective representation, it is also advantageous that the diamond content can be reduced due to the high thermal conductivity of the Ag, Au or Al-rich structural components.
- Particularly advantageous contents of silicon carbide and phase rich in Ag, Au or Al are 0.1 to 7% by volume or 7 to 30% by volume.
- Tests have shown that diamond powders can be processed in a wide range of grain sizes. In addition to natural diamonds, cheaper synthetic diamonds can also be processed. Excellent processing results have also been achieved with the common coated diamond grades. This means that the cheapest variety can be used. For non-cost-critical applications with extremely high demands on thermal conductivity, it is favorable to use a diamond fraction with an average grain size in the range from 50 to 150 ⁇ m. Furthermore, the highest thermal conductivity values can be achieved by using Ag at a content of 20 to 30 vol.%.
- the components are advantageously coated with Ni, Cu, Au or Ag or an alloy of these metals and subsequently soldered to a ceramic frame, for example Al 2 O 3 or AIN.
- a ceramic frame for example Al 2 O 3 or AIN.
- a wide variety of processes can be used for the production. It is possible to compact silicon powder coated with silicon carbide with Ag, Au or Al under temperature and pressure. This can be done, for example, in hot presses or hot isostatic presses. Infiltration has proven to be particularly advantageous.
- a precursor or intermediate is produced which can contain a binder in addition to diamond powder. Binders which pyrolyze to a high degree under the influence of temperature are particularly advantageous. Advantageous binder contents are 1 to 20% by weight. Diamond powder and binder are mixed in conventional mixers or mills.
- shaping which can be carried out by pouring into a mold or with pressure support, for example by pressing or metal powder injection molding.
- the intermediate substance is subsequently heated to a temperature at which the binder at least partially pyrolyzes.
- the pyrolysis of the binder can also take place during the heating up in the infiltration process.
- the infiltration process can be pressure-free or pressure-supported. The latter is commonly referred to as squezze casting.
- a foil made of an Ag-Si, Au-Si or Al-Si alloy with an Si content of ⁇ 50% by weight is advantageously used as the infiltration material.
- the liquidus temperature of the respective alloy is not higher than 1200 ° C, advantageously not higher than 1000 ° C, since otherwise excessive diamond components will decompose.
- Films with a eutectic composition are particularly suitable for infiltration.
- the composite material according to the invention can also be used as a heat sink in other areas of application, for example in the field of aerospace or engine construction. The invention is explained in more detail below by means of production examples.
- Natural diamond powder of quality IIA (Micron + SND from Element Six GmbH) with an average grain size of 40 - 80 ⁇ m was mixed with 7% by volume of a binder based on epoxy resin.
- the precursor or intermediate thus produced was pressed by means of die presses at a pressure of 200 MPa to a plate measuring 35 mm x 35 mm x 5 mm.
- the pore content of the plate was approximately 15% by volume.
- this plate was covered with a foil made of an eutectic Ag-Si alloy, the Si content being 11 atomic% and heated to a temperature of 860 ° C. in a vacuum oven for infiltration, the holding time being 15 minutes scam.
- the volume contents of the phases present were determined by means of quantitative metallography.
- the value for silicon carbide was about 2% by volume, the silicon carbide largely enveloping the diamond grains evenly. Due to the thin layer thickness of this silicon carbide coating, the modification of the silicon carbide phase could not be determined.
- the structure consists of an Ag-rich phase with embedded Si precipitates, which have formed through the eutectic conversion.
- the volume fraction of the Ag-rich phase was approximately 12%, that of Si approximately 1%.
- no other constituents could be detected by means of EDX, so that, based on the detection limit, it can be assumed that the Ag content is greater than 99 atom%.
- Thermal expansion coefficients were processed by laser and EDM. An average value of 450 W / (mK) was measured for the thermal conductivity at room temperature. The determination of the coefficient of thermal expansion gave an average value of 8.5 10 "6 K " 1 .
- Example 3 synthetic diamond powder of Micron + MDA quality from Element Six GmbH and an average grain size of 40 - 80 ⁇ m was processed. Processing was carried out as described in Example 1. The average thermal conductivity at room temperature of the composite material produced in this way was 410 W / (mK), the average coefficient of thermal expansion 9.0 10 "6 K " 1 .
- Example 3 The average thermal conductivity at room temperature of the composite material produced in this way was 410 W / (mK), the average coefficient of thermal expansion 9.0 10 "6 K " 1 .
- Example 4 Synthetic diamond powder of the Micron + MDA quality from Element Six GmbH with an average grain fraction of 40-80 ⁇ m was processed in accordance with Example 3, but without a holding phase being carried out at about 400 ° C. for 15 minutes while cooling from the infiltration temperature.
- the average thermal conductivity at room temperature of the composite material produced in this way was 440 W / (mK), the average coefficient of thermal expansion 8.5 10 "6 K " 1 .
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04703308.9A EP1601630B1 (de) | 2003-03-11 | 2004-01-20 | Wärmesenke mit hoher wärmeleitfähigkeit |
US10/548,725 US8575051B2 (en) | 2003-03-11 | 2004-01-20 | Heat sink having a high thermal conductivity |
JP2006503938A JP4880447B2 (ja) | 2003-03-11 | 2004-01-20 | 高熱伝導率のヒートシンク |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0016403U AT7382U1 (de) | 2003-03-11 | 2003-03-11 | Wärmesenke mit hoher wärmeleitfähigkeit |
ATGM164/2003 | 2003-03-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004080914A1 true WO2004080914A1 (de) | 2004-09-23 |
Family
ID=32967982
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AT2004/000017 WO2004080913A1 (de) | 2003-03-11 | 2004-01-20 | Verfahren zur herstellung eines verbundwerkstoffes |
PCT/AT2004/000018 WO2004080914A1 (de) | 2003-03-11 | 2004-01-20 | Wärmesenke mit hoher wärmeleitfähigkeit |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/AT2004/000017 WO2004080913A1 (de) | 2003-03-11 | 2004-01-20 | Verfahren zur herstellung eines verbundwerkstoffes |
Country Status (6)
Country | Link |
---|---|
US (2) | US20060157884A1 (de) |
EP (2) | EP1601630B1 (de) |
JP (2) | JP4880447B2 (de) |
CN (1) | CN100400467C (de) |
AT (1) | AT7382U1 (de) |
WO (2) | WO2004080913A1 (de) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006245568A (ja) * | 2005-03-02 | 2006-09-14 | Mitac Technology Corp | 半導体チップ冷却システム及び冷却装置構造と製造方法 |
US7427807B2 (en) | 2005-02-18 | 2008-09-23 | Mitac Technology Corp. | Chip heat dissipation structure and manufacturing method |
US7504148B2 (en) | 2005-03-03 | 2009-03-17 | Mitac Technology Corp | Printed circuit board structure and manufacturing method thereof |
US8575625B2 (en) | 2010-02-08 | 2013-11-05 | A.L.M.T. Corp. | Semiconductor element mounting member, method of producing the same, and semiconductor device |
WO2019201588A1 (de) * | 2018-04-18 | 2019-10-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | WERKSTOFF BESTEHEND AUS EINEM DREIDIMENSIONALEN GERÜST, DAS MIT SiC ODER SiC UND Si3N4 GEBILDET IST UND EINER EDELMETALLLEGIERUNG, IN DER SILICIUM ENTHALTEN IST, GEBILDET, SOWIE EIN VERFAHREN ZU SEINER HERSTELLUNG |
CN111304481A (zh) * | 2020-02-11 | 2020-06-19 | 中南大学 | 一种金刚石-金属复合材料的熔渗制备工艺及金刚石-金属复合材料 |
Families Citing this family (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004056734A1 (de) * | 2004-11-24 | 2006-06-01 | Vatcharachai Buanatra | Diamantenformkörper |
TWI268755B (en) * | 2005-03-21 | 2006-12-11 | Mitac Tech Corporation | Chip heat dissipation system and manufacturing method and structure of heat exchange device thereof |
US8637127B2 (en) | 2005-06-27 | 2014-01-28 | Kennametal Inc. | Composite article with coolant channels and tool fabrication method |
US8236074B1 (en) | 2006-10-10 | 2012-08-07 | Us Synthetic Corporation | Superabrasive elements, methods of manufacturing, and drill bits including same |
US9017438B1 (en) | 2006-10-10 | 2015-04-28 | Us Synthetic Corporation | Polycrystalline diamond compact including a polycrystalline diamond table with a thermally-stable region having at least one low-carbon-solubility material and applications therefor |
CN101522930B (zh) | 2006-10-25 | 2012-07-18 | Tdy工业公司 | 具有改进的抗热开裂性的制品 |
US8080074B2 (en) | 2006-11-20 | 2011-12-20 | Us Synthetic Corporation | Polycrystalline diamond compacts, and related methods and applications |
US8034136B2 (en) | 2006-11-20 | 2011-10-11 | Us Synthetic Corporation | Methods of fabricating superabrasive articles |
WO2009006163A2 (en) * | 2007-06-29 | 2009-01-08 | Itt Manufacturing Enterprises, Inc. | Thermally conductive structural composite material and method |
SE532992C2 (sv) * | 2007-11-08 | 2010-06-08 | Alfa Laval Corp Ab | Förfarande för framställning av en diamantkomposit, grönkropp, diamantkomposit samt användning av diamantkompositen |
EP2065734A1 (de) * | 2007-11-30 | 2009-06-03 | Plansee Se | Spiegel zur Laserbearbeitung |
US8999025B1 (en) | 2008-03-03 | 2015-04-07 | Us Synthetic Corporation | Methods of fabricating a polycrystalline diamond body with a sintering aid/infiltrant at least saturated with non-diamond carbon and resultant products such as compacts |
US20090236087A1 (en) * | 2008-03-19 | 2009-09-24 | Yamaha Corporation | Heat exchange device |
US8790439B2 (en) | 2008-06-02 | 2014-07-29 | Kennametal Inc. | Composite sintered powder metal articles |
US8297382B2 (en) | 2008-10-03 | 2012-10-30 | Us Synthetic Corporation | Polycrystalline diamond compacts, method of fabricating same, and various applications |
JP2010109081A (ja) * | 2008-10-29 | 2010-05-13 | Denki Kagaku Kogyo Kk | Led発光素子用金属基複合材料基板及びそれを用いたled発光素子 |
CN102030556B (zh) * | 2010-11-11 | 2012-10-31 | 北京科技大学 | 一种金刚石/碳化硅陶瓷基复合材料的制备方法 |
US10309158B2 (en) | 2010-12-07 | 2019-06-04 | Us Synthetic Corporation | Method of partially infiltrating an at least partially leached polycrystalline diamond table and resultant polycrystalline diamond compacts |
US9027675B1 (en) | 2011-02-15 | 2015-05-12 | Us Synthetic Corporation | Polycrystalline diamond compact including a polycrystalline diamond table containing aluminum carbide therein and applications therefor |
US9016406B2 (en) | 2011-09-22 | 2015-04-28 | Kennametal Inc. | Cutting inserts for earth-boring bits |
US20130291445A1 (en) * | 2012-05-01 | 2013-11-07 | Sigma Innovation Technology Inc. | Diamond abrasive grain and electroplated tool having the same |
JP5350553B1 (ja) | 2013-04-26 | 2013-11-27 | 冨士ダイス株式会社 | 耐熱性の優れたCu−ダイヤモンド基固相焼結体を用いた放熱板、その放熱板を用いたエレクトロニクス用デバイス、および耐熱性の優れたCu−ダイヤモンド基固相焼結体を用いた放熱板の製造方法 |
CN103496215B (zh) * | 2013-09-25 | 2015-07-29 | 华南理工大学 | 一种嵌入式组合热沉及其制备方法 |
US9992917B2 (en) | 2014-03-10 | 2018-06-05 | Vulcan GMS | 3-D printing method for producing tungsten-based shielding parts |
JP5807935B1 (ja) * | 2014-10-09 | 2015-11-10 | 株式会社半導体熱研究所 | 放熱基板と、それを使用した半導体用モジュール |
CN104370546B (zh) * | 2014-10-28 | 2016-02-17 | 倪娟形 | 一种散热器连接件用高导热性陶瓷及其制备方法 |
US10074589B2 (en) | 2016-04-14 | 2018-09-11 | Hamilton Sundstrand Corporation | Embedding diamond and other ceramic media into metal substrates to form thermal interface materials |
JP6645586B2 (ja) * | 2016-09-06 | 2020-02-14 | 株式会社Ihi | セラミックス基複合材の製造方法 |
CN107034377A (zh) * | 2017-03-14 | 2017-08-11 | 刘金财 | 一种镍金包覆的镶嵌金刚石铜的高密度密度板及其制备方法 |
CN111170317B (zh) * | 2018-11-12 | 2022-02-22 | 有研工程技术研究院有限公司 | 一种石墨烯改性金刚石/铜复合材料的制备方法 |
JP7233991B2 (ja) * | 2019-03-18 | 2023-03-07 | Dowaメタルテック株式会社 | 複合めっき材およびその製造方法 |
US20220186347A1 (en) * | 2019-03-29 | 2022-06-16 | Sumitomo Electric Industries, Ltd. | Composite material |
US20230167528A1 (en) * | 2020-04-09 | 2023-06-01 | Sumitomo Electric Industries, Ltd. | Composite material, heat sink and semiconductor device |
CN112195384A (zh) * | 2020-10-26 | 2021-01-08 | 河南飞孟金刚石工业有限公司 | 一种低成本金刚石高导热材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4735655A (en) * | 1985-10-04 | 1988-04-05 | D. Swarovski & Co. | Sintered abrasive material |
EP0475575A1 (de) * | 1990-08-27 | 1992-03-18 | The Standard Oil Company | Metall-Matrix-Verbundkörper mit hoher Wärmeleitfähigkeit |
EP0691413A2 (de) * | 1993-04-06 | 1996-01-10 | Sumitomo Electric Industries, Ltd. | Diamantversärktes Verbundmaterial und Verfahren zu dessen Herstellung |
US6039641A (en) * | 1997-04-04 | 2000-03-21 | Sung; Chien-Min | Brazed diamond tools by infiltration |
US6179886B1 (en) * | 1997-09-05 | 2001-01-30 | Ambler Technologies, Inc. | Method for producing abrasive grains and the composite abrasive grains produced by same |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2543820C2 (de) * | 1975-10-01 | 1984-10-31 | Hoechst Ag, 6230 Frankfurt | Verfahren zur Herstellung von Flachdruckformen mittels Laserstrahlen |
IE47393B1 (en) * | 1977-09-12 | 1984-03-07 | De Beers Ind Diamond | Abrasive materials |
JPS5946050A (ja) * | 1982-09-09 | 1984-03-15 | Narumi China Corp | 半導体用セラミツクパツケ−ジ |
ZA894689B (en) * | 1988-11-30 | 1990-09-26 | Gen Electric | Silicon infiltrated porous polycrystalline diamond compacts and their fabrications |
US6003221A (en) * | 1991-04-08 | 1999-12-21 | Aluminum Company Of America | Metal matrix composites containing electrical insulators |
US5505750A (en) * | 1994-06-22 | 1996-04-09 | Norton Company | Infiltrant for metal bonded abrasive articles |
US5706999A (en) * | 1995-11-28 | 1998-01-13 | Hughes Electronics | Preparation of a coated metal-matrix composite material |
JP3617232B2 (ja) * | 1997-02-06 | 2005-02-02 | 住友電気工業株式会社 | 半導体用ヒートシンクおよびその製造方法ならびにそれを用いた半導体パッケージ |
JP3893681B2 (ja) | 1997-08-19 | 2007-03-14 | 住友電気工業株式会社 | 半導体用ヒートシンクおよびその製造方法 |
DE19843309A1 (de) * | 1998-09-22 | 2000-03-23 | Asea Brown Boveri | Kurzschlussfestes IGBT Modul |
ATE218520T1 (de) | 1998-09-28 | 2002-06-15 | Frenton Ltd | Verfahren zur herstellung eines diamantkomposits und ein durch dasselbe hergestelltes komposit |
US6933531B1 (en) * | 1999-12-24 | 2005-08-23 | Ngk Insulators, Ltd. | Heat sink material and method of manufacturing the heat sink material |
JP2001339022A (ja) * | 1999-12-24 | 2001-12-07 | Ngk Insulators Ltd | ヒートシンク材及びその製造方法 |
RU2206502C2 (ru) * | 2000-11-21 | 2003-06-20 | Акционерное общество закрытого типа "Карбид" | Композиционный материал |
US7173334B2 (en) * | 2002-10-11 | 2007-02-06 | Chien-Min Sung | Diamond composite heat spreader and associated methods |
-
2003
- 2003-03-11 AT AT0016403U patent/AT7382U1/de not_active IP Right Cessation
-
2004
- 2004-01-20 CN CNB200480006559XA patent/CN100400467C/zh not_active Expired - Lifetime
- 2004-01-20 US US10/548,723 patent/US20060157884A1/en not_active Abandoned
- 2004-01-20 WO PCT/AT2004/000017 patent/WO2004080913A1/de active Application Filing
- 2004-01-20 EP EP04703308.9A patent/EP1601630B1/de not_active Expired - Lifetime
- 2004-01-20 JP JP2006503938A patent/JP4880447B2/ja not_active Expired - Lifetime
- 2004-01-20 WO PCT/AT2004/000018 patent/WO2004080914A1/de active Application Filing
- 2004-01-20 US US10/548,725 patent/US8575051B2/en active Active
- 2004-01-20 JP JP2006503937A patent/JP4995565B2/ja not_active Expired - Lifetime
- 2004-01-20 EP EP04703310A patent/EP1601631A1/de not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4735655A (en) * | 1985-10-04 | 1988-04-05 | D. Swarovski & Co. | Sintered abrasive material |
EP0475575A1 (de) * | 1990-08-27 | 1992-03-18 | The Standard Oil Company | Metall-Matrix-Verbundkörper mit hoher Wärmeleitfähigkeit |
EP0691413A2 (de) * | 1993-04-06 | 1996-01-10 | Sumitomo Electric Industries, Ltd. | Diamantversärktes Verbundmaterial und Verfahren zu dessen Herstellung |
US6039641A (en) * | 1997-04-04 | 2000-03-21 | Sung; Chien-Min | Brazed diamond tools by infiltration |
US6179886B1 (en) * | 1997-09-05 | 2001-01-30 | Ambler Technologies, Inc. | Method for producing abrasive grains and the composite abrasive grains produced by same |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7427807B2 (en) | 2005-02-18 | 2008-09-23 | Mitac Technology Corp. | Chip heat dissipation structure and manufacturing method |
JP2006245568A (ja) * | 2005-03-02 | 2006-09-14 | Mitac Technology Corp | 半導体チップ冷却システム及び冷却装置構造と製造方法 |
US7504148B2 (en) | 2005-03-03 | 2009-03-17 | Mitac Technology Corp | Printed circuit board structure and manufacturing method thereof |
US8575625B2 (en) | 2010-02-08 | 2013-11-05 | A.L.M.T. Corp. | Semiconductor element mounting member, method of producing the same, and semiconductor device |
WO2019201588A1 (de) * | 2018-04-18 | 2019-10-24 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | WERKSTOFF BESTEHEND AUS EINEM DREIDIMENSIONALEN GERÜST, DAS MIT SiC ODER SiC UND Si3N4 GEBILDET IST UND EINER EDELMETALLLEGIERUNG, IN DER SILICIUM ENTHALTEN IST, GEBILDET, SOWIE EIN VERFAHREN ZU SEINER HERSTELLUNG |
CN111304481A (zh) * | 2020-02-11 | 2020-06-19 | 中南大学 | 一种金刚石-金属复合材料的熔渗制备工艺及金刚石-金属复合材料 |
Also Published As
Publication number | Publication date |
---|---|
US20060130998A1 (en) | 2006-06-22 |
EP1601631A1 (de) | 2005-12-07 |
EP1601630B1 (de) | 2017-12-27 |
AT7382U1 (de) | 2005-02-25 |
CN1759078A (zh) | 2006-04-12 |
US20060157884A1 (en) | 2006-07-20 |
JP4880447B2 (ja) | 2012-02-22 |
JP2006524173A (ja) | 2006-10-26 |
WO2004080913A1 (de) | 2004-09-23 |
US8575051B2 (en) | 2013-11-05 |
EP1601630A1 (de) | 2005-12-07 |
JP2006519928A (ja) | 2006-08-31 |
JP4995565B2 (ja) | 2012-08-08 |
CN100400467C (zh) | 2008-07-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1601630B1 (de) | Wärmesenke mit hoher wärmeleitfähigkeit | |
EP1741137B1 (de) | Wärmesenke aus borhaltigem diamant-kupfer-verbundwerkstoff | |
EP1751320B1 (de) | Verschleissteil aus einem diamanthaltigen verbundwerkstoff | |
DE69912564T2 (de) | Siliziumkarbid-Verbundwerkstoff, Verfahren zu seiner Herstellung und Wärmeableitungsanordnung, die diesen verwendet | |
AT408153B (de) | Metall-matrix-composite- (mmc-) bauteil | |
AT503270B1 (de) | Verbundwerkstoff und verfahren zu seiner herstellung | |
DE60021514T2 (de) | Einen verbundwerkstoff verwendendes halbleiterbauteil oder wärmeableitendes substrat dafür | |
JP2006524173A5 (de) | ||
EP1743047A1 (de) | Trägerplatte für sputtertargets | |
US5605558A (en) | Nitrogenous aluminum-silicon powder metallurgical alloy | |
JP4228444B2 (ja) | 炭化珪素系複合材料およびその製造方法 | |
JP2000141022A (ja) | 炭化珪素質複合体及びその製造方法 | |
JPS59143347A (ja) | 半導体基板材料の製造方法 | |
AT12389U1 (de) | Verbundwerkstoff und verfahren zu dessen herstellung | |
KR20100091348A (ko) | WC-Fe계 초경합금 및 그 제조방법 | |
WO2019201588A1 (de) | WERKSTOFF BESTEHEND AUS EINEM DREIDIMENSIONALEN GERÜST, DAS MIT SiC ODER SiC UND Si3N4 GEBILDET IST UND EINER EDELMETALLLEGIERUNG, IN DER SILICIUM ENTHALTEN IST, GEBILDET, SOWIE EIN VERFAHREN ZU SEINER HERSTELLUNG | |
JPH08176694A (ja) | 半導体装置のヒートシンク用薄肉焼結板材の製造法 | |
JPH04349650A (ja) | 半導体放熱基板材料の製造方法 | |
JPH07179906A (ja) | 窒素化合アルミニウム−シリコン粉末合金およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2004703308 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2006503938 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 90452004 Country of ref document: AT Ref document number: 2004806559X Country of ref document: CN |
|
ENP | Entry into the national phase |
Ref document number: 2006130998 Country of ref document: US Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 10548725 Country of ref document: US |
|
WWP | Wipo information: published in national office |
Ref document number: 2004703308 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 10548725 Country of ref document: US |