WO2021090759A1 - Graphene-containing carbonaceous member/ceramic assembly and copper/graphene-containing carbonaceous member/ceramic assembly - Google Patents

Graphene-containing carbonaceous member/ceramic assembly and copper/graphene-containing carbonaceous member/ceramic assembly Download PDF

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Publication number
WO2021090759A1
WO2021090759A1 PCT/JP2020/040652 JP2020040652W WO2021090759A1 WO 2021090759 A1 WO2021090759 A1 WO 2021090759A1 JP 2020040652 W JP2020040652 W JP 2020040652W WO 2021090759 A1 WO2021090759 A1 WO 2021090759A1
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Prior art keywords
graphene
layer
containing carbonaceous
copper
active metal
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PCT/JP2020/040652
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French (fr)
Japanese (ja)
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東洋 大橋
晶 櫻井
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三菱マテリアル株式会社
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Priority claimed from JP2020179736A external-priority patent/JP2021075452A/en
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Publication of WO2021090759A1 publication Critical patent/WO2021090759A1/en

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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
    • 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
    • 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

Definitions

  • the present invention relates to a graphene-containing carbonaceous member / ceramics joint having a structure in which a graphene-containing carbonaceous member containing a graphene aggregate and a ceramics member made of nitrogen-containing ceramics are joined, and the graphene-containing carbonaceous member /
  • the present invention relates to a copper / graphene-containing carbonaceous member / ceramics joint in which a copper member made of copper or a copper alloy is bonded to a ceramics joint.
  • the graphene-containing carbonaceous member containing the graphene aggregate is excellent in thermal conductivity, it is particularly suitable as a member constituting a heat radiating member, a heat conductive member, and the like.
  • a heat radiating member a heat conductive member, and the like.
  • an insulating layer made of ceramics or the like on the surface of the graphene-containing carbonaceous member containing the graphene aggregate described above, it can be used as an insulating substrate.
  • Patent Document 1 a structure in which graphene sheets are laminated along the first direction and an intermediate member (ceramics) joined to the end face of the structure in the second direction intersecting the first direction.
  • an intermediate member for example, ceramics
  • an insert material containing at least titanium is disclosed.
  • a cold cycle may be applied under the usage environment.
  • it may be used in a harsh environment such as an engine room, and a cold cycle under severe conditions with a large temperature difference may be loaded.
  • Patent Document 1 described above an intermediate made of ceramics and a graphene structure are joined via an insert material containing titanium, but depending on the joining conditions, the intermediate made of ceramics and graphene are joined. It was not possible to firmly join the structure of the above, and there was a risk of peeling when a cold cycle under severe conditions was applied.
  • the present invention has been made in view of the above-mentioned circumstances, and the ceramic member and the graphene-containing carbonaceous member containing a graphene aggregate are firmly bonded to each other, and peeling occurs even when a cold cycle load is applied.
  • the graphene-containing carbonaceous member / ceramics joint of one aspect of the present invention (hereinafter, "graphene-containing carbonaceous member / ceramics joint of the present invention"). ) Is a graphene-containing carbonaceous member / ceramics joint having a structure in which a graphene-containing carbonaceous member containing a graphene aggregate and a ceramics member made of ceramics containing nitrogen are joined, and the graphene-containing carbon is said.
  • an active metal nitride layer is formed on the joint surface of the ceramic member, and the thickness of the active metal nitride layer is within the range of 0.05 ⁇ m or more and 2 ⁇ m or less. It is characterized by being done.
  • an active metal nitride layer is formed on the joint surface of the ceramics member at the joint interface between the graphene-containing carbonaceous member and the ceramic member made of nitrogen-containing ceramics. Since the thickness of this active metal nitride layer is 0.05 ⁇ m or more, the joint surface of the ceramic member is sufficiently reacted by the active metal, and the graphene-containing carbonaceous member and the ceramic member are separated from each other. It is possible to firmly join.
  • the thickness of the active metal nitride layer is limited to 2 ⁇ m or less, it is possible to suppress the occurrence of cracks in the active metal nitride layer under a cold cycle load, and it is possible to improve the cold cycle reliability.
  • an active metal compound layer is formed on the bonding surface of the graphene-containing carbonaceous member at the bonding interface between the graphene-containing carbonaceous member and the ceramics member. It is preferably formed so that the thickness of the active metal compound layer is in the range of 0.05 ⁇ m or more and 3 ⁇ m or less. In this case, at the bonding interface between the graphene-containing carbonaceous member and the ceramic member, an active metal compound layer is formed on the bonding surface of the graphene-containing carbonaceous member, and the thickness of the active metal compound layer is 0.05 ⁇ m.
  • the joint surface of the graphene-containing carbonaceous member is sufficiently reacted by the active metal, and the graphene-containing carbonaceous member and the ceramic member can be joined more firmly. Further, since the thickness of the active metal compound layer is limited to 3 ⁇ m or less, it is possible to suppress the occurrence of cracks in the active metal compound layer when loaded with a cold cycle, and it is possible to improve the reliability of the cold cycle.
  • the graphene-containing carbonaceous member / ceramics joint of the present invention at the bonding interface between the graphene-containing carbonaceous member and the ceramics member, Ag is sandwiched between the active metal nitride layer and the active metal compound layer. It is preferable that an alloy layer containing Cu and Cu is formed, and the thickness of the alloy layer is within the range of 1 ⁇ m or more and 20 ⁇ m or less. In this case, the above-mentioned alloy layer is formed by the sufficient reaction of Ag and Cu contained in the bonding material, and the thickness of the alloy layer is 1 ⁇ m or more. The bonding strength with the ceramic member can be further improved. Further, since the thickness of the alloy layer is limited to 20 ⁇ m or less, it is possible to suppress the occurrence of cracks in the alloy layer when a cold cycle load is applied, and it is possible to improve the reliability of the cold cycle.
  • the graphene-containing carbonaceous member contains a graphene aggregate formed by depositing single-layer or multi-layer graphene and flat graphite particles, and is flat. It is preferable that the graphite particles having a shape are laminated with the graphene aggregate as a binder so that the basal surfaces thereof fold over, and the basal surfaces of the flat graphite particles are oriented in one direction. In this case, it is possible to further improve the heat conduction characteristics of the graphene-containing carbonaceous member.
  • the copper / graphene-containing carbonaceous member / ceramics joint (hereinafter, referred to as “copper / graphene-containing carbonaceous member / ceramics joint” of the present invention), which is another aspect of the present invention, is made of copper or a copper alloy.
  • the graphene-containing carbonaceous member of the carbon-containing member / ceramics joint is bonded to the copper member.
  • the graphene-containing carbonaceous member / ceramics joint of the graphene-containing carbonaceous member / ceramics joint has the graphene-containing carbonaceous member and the copper member bonded to each other. It will be excellent in reliability. Further, the graphene-containing carbonaceous member is protected by the copper member, and the occurrence of cracks in the graphene-containing carbonaceous member can be suppressed.
  • an active metal compound is formed on the bonding surface of the graphene-containing carbonaceous member at the bonding interface between the graphene-containing carbonaceous member and the copper member. It is preferable that the layer is formed and the thickness of the active metal compound layer is within the range of 0.05 ⁇ m or more and 3 ⁇ m or less. In this case, at the bonding interface between the graphene-containing carbonaceous member and the copper member, an active metal compound layer is formed on the bonding surface of the graphene-containing carbonaceous member, and the thickness of the active metal compound layer is 0.05 ⁇ m.
  • the joint surface of the graphene-containing carbonaceous member is sufficiently reacted by the active metal, and the graphene-containing carbonaceous member and the copper member can be joined more firmly. Further, since the thickness of the active metal compound layer is limited to 3 ⁇ m or less, it is possible to suppress the occurrence of cracks in the active metal compound layer when loaded with a cold cycle, and it is possible to improve the reliability of the cold cycle.
  • an Ag is formed between the copper member and the active metal compound layer.
  • an alloy layer containing Cu is formed and the thickness of the alloy layer is within the range of 1 ⁇ m or more and 20 ⁇ m or less.
  • the above-mentioned alloy layer is formed by the sufficient reaction of Ag and Cu contained in the bonding material, and the thickness of the alloy layer is 1 ⁇ m or more.
  • the bonding strength with the copper member can be further improved. Further, since the thickness of the alloy layer is limited to 20 ⁇ m or less, it is possible to suppress the occurrence of cracks in the alloy layer when a cold cycle load is applied, and it is possible to improve the reliability of the cold cycle.
  • the ceramic member and the graphene-containing carbonaceous member containing the graphene aggregate are firmly bonded to each other, no peeling occurs even under a cold cycle load, and graphene having excellent cold cycle reliability. It is possible to provide a carbonaceous member / ceramics joint containing carbonene and a copper / graphene-containing carbonic member / ceramics joint in which a copper member made of copper or a copper alloy is bonded to the graphene-containing carbonaceous member / ceramics joint. It will be possible.
  • the graphene-containing carbonaceous member / ceramics joint in the present embodiment is an insulating substrate 20 having a structure in which a graphene-containing carbonaceous member containing a graphene aggregate and ceramics containing nitrogen are joined.
  • the power module 1 shown in FIG. 1 includes an insulating circuit board 10, a semiconductor element 3 bonded to one surface side (upper side in FIG. 1) of the insulating circuit board 10 via a solder layer 2, and an insulating circuit board 10. It is provided with a heat sink 31 arranged on the other surface side (lower side in FIG. 1).
  • the insulating circuit board 10 is arranged on the insulating layer, the circuit layer 12 disposed on one surface of the insulating layer (upper surface in FIG. 1), and the other surface of the insulating layer (lower surface in FIG. 1). It includes a metal layer 13.
  • the insulating layer prevents electrical connection between the circuit layer 12 and the metal layer 13, and is composed of the insulating substrate 20 of the present embodiment.
  • the circuit layer 12 is formed by joining a metal plate having excellent conductivity to one surface of an insulating layer (insulating substrate 20).
  • a metal plate constituting the circuit layer 12 a copper plate made of copper or a copper alloy, specifically, a rolled plate of oxygen-free copper is used.
  • a circuit pattern is formed in the circuit layer 12, and one surface (upper surface in FIG. 1) is a mounting surface on which the semiconductor element 3 is mounted.
  • the thickness of the metal plate (copper plate) to be the circuit layer 12 is set within the range of 0.1 mm or more and 1.0 mm or less, and in the present embodiment, it is set to 0.6 mm.
  • the method of joining the metal plate (copper plate) to be the circuit layer 12 and the insulating substrate 20 is not particularly limited, and can be joined using an active metal brazing material or the like.
  • the metal layer 13 is formed by joining a metal plate having excellent thermal conductivity to the other surface of the insulating layer (insulating substrate 20).
  • a metal plate constituting the metal layer 13 a copper plate made of copper or a copper alloy, specifically, a rolled plate of oxygen-free copper is used.
  • the thickness of the metal plate (copper plate) to be the metal layer 13 is set within the range of 0.1 mm or more and 1.0 mm or less, and in the present embodiment, it is set to 0.6 mm.
  • the method of joining the metal plate (copper plate) to be the metal layer 13 and the insulating substrate 20 is not particularly limited, and can be joined using an active metal brazing material or the like.
  • the heat sink 31 is for cooling the above-mentioned insulating circuit board 10, and has a structure in which a plurality of flow paths 32 for flowing a cooling medium (for example, cooling water) are provided.
  • the heat sink 31 is preferably made of a material having good thermal conductivity, for example, aluminum or aluminum alloy, copper or copper alloy, and in this embodiment, it is made of 2N aluminum having a purity of 99 mass% or more. There is.
  • the metal layer 13 of the insulating circuit board 10 and the heat sink 31 are joined by a solid phase diffusion joining method.
  • the semiconductor element 3 is made of a semiconductor material such as Si or SiC.
  • the semiconductor element 3 is mounted on the circuit layer 12 via, for example, a solder layer 2 made of a Sn—Ag-based, Sn—In-based, or Sn—Ag—Cu-based solder material.
  • the insulating substrate 20 of the present embodiment constituting the insulating layer is a carbon plate made of a ceramic plate 25 made of nitrogen-containing ceramics and a graphene-containing carbonaceous member containing a graphene aggregate.
  • the structure is such that 21 and 21 are laminated, and carbon plates 21 are bonded to both main surfaces of the ceramic plate 25, respectively.
  • Examples of the nitrogen-containing ceramics constituting the ceramic plate 25 include aluminum nitride (AlN) and silicon nitride (Si 3 N 4 ).
  • the lower limit of the thickness of the ceramic plate 25 is preferably 100 ⁇ m or more, and more preferably 250 ⁇ m or more.
  • the upper limit of the thickness of the ceramic plate 25 is preferably 1500 ⁇ m or less, and more preferably 1000 ⁇ m or less.
  • the graphene-containing carbonaceous member constituting the carbon plate 21 contains graphene aggregates formed by depositing single-layer or multi-layer graphene and flat graphite particles so that the flat graphite particles fold their basal surfaces.
  • the graphene aggregate has a laminated structure as a binder.
  • the flat graphite particles have a basal surface on which a carbon hexagonal network surface appears and an edge surface on which an end portion of the carbon hexagonal network surface appears.
  • the flat graphite particles scaly graphite, scaly graphite, earthy graphite, flaky graphite, kiss graphite, pyrolytic graphite, highly oriented pyrolytic graphite and the like can be used.
  • the average particle size of the graphite particles as seen from the basal surface is preferably in the range of 10 ⁇ m or more and 1000 ⁇ m or less, and more preferably in the range of 50 ⁇ m or more and 800 ⁇ m or less.
  • the thickness of the graphite particles is preferably in the range of 1 ⁇ m or more and 50 ⁇ m or less, and more preferably in the range of 1 ⁇ m or more and 20 ⁇ m or less.
  • the orientation of the graphite particles is appropriately adjusted.
  • the thickness of the graphite particles within the range of 1/1000 to 1/2 of the particle size seen from the basal surface, excellent thermal conductivity and orientation of the graphite particles are appropriately adjusted.
  • the graphene aggregate is a deposit of single-layer or multi-layer graphene, and the number of layers of the multi-layer graphene is, for example, 100 layers or less, preferably 50 layers or less.
  • This graphene aggregate can be produced, for example, by dropping a graphene dispersion in which single-layer or multi-layer graphene is dispersed in a solvent containing lower alcohol or water onto a filter paper and depositing the graphene while separating the solvent. It is possible.
  • the average particle size of the graphene aggregate is preferably in the range of 1 ⁇ m or more and 1000 ⁇ m or less. By keeping the average particle size of the graphene aggregate within the above range, the thermal conductivity is improved.
  • the thickness of the graphene aggregate is preferably in the range of 0.05 ⁇ m or more and less than 50 ⁇ m. By keeping the thickness of the graphene aggregate within the above range, the strength of the carbonaceous member is ensured.
  • the thickness of the carbon plate 21 is preferably in the range of 0.5 mm or more and 5 mm or less.
  • FIGS. 3A and 3B show observational photographs of the interface between the carbon plate 21 made of a graphene-containing carbonaceous member and the ceramic plate 25, and FIG. 4 shows a carbon plate 21 made of a graphene-containing carbonaceous member and a ceramic plate.
  • the schematic diagram of the junction interface with 25 is shown.
  • the upper black portion is the carbon plate 21 (graphene-containing carbonaceous member)
  • the gray portion located below the carbon plate 21 is the ceramic plate 25.
  • an active metal nitride layer 41 is formed on the bonding surface of the ceramic plate 25.
  • an active metal compound layer 42 containing one or two types of active metal oxide and active metal carbide is formed on the bonding surface of the carbon plate 21.
  • an alloy layer 43 containing Ag and Cu is formed between the active metal nitride layer 41 and the active metal compound layer 42. That is, in the present embodiment, the bonding interface 40 has a structure in which the active metal nitride layer 41, the alloy layer 43, and the active metal compound layer 42 are laminated in this order from the ceramic plate 25 side.
  • the active metal nitride layer 41 is formed by reacting the active metal contained in the bonding material interposed between the carbon plate 21 and the ceramic plate 25 with nitrogen contained in the ceramic plate 25 at the time of bonding. is there.
  • the active metal constituting the active metal nitride layer 41 for example, one kind or two or more kinds selected from Ti, Zr, Hf, and Nb can be used.
  • the active metal is Ti
  • the active metal nitride layer 41 is made of titanium nitride (Ti—N).
  • the thickness t1 of the active metal nitride layer 41 is set within the range of 0.05 ⁇ m or more and 2 ⁇ m or less.
  • the lower limit of the thickness t1 of the active metal nitride layer 41 is more preferably 0.1 ⁇ m or more, and more preferably 0.2 ⁇ m or more.
  • the upper limit of the thickness t1 of the active metal nitride layer 41 is more preferably 1 ⁇ m or less, and more preferably 0.7 ⁇ m or less.
  • the active metal compound layer 42 is formed by reacting the active metal contained in the bonding material interposed between the carbon plate 21 and the ceramic plate 25 at the time of bonding with oxygen and carbon.
  • the active metal is Ti
  • the active metal compound layer 42 contains one or two types of titanium oxide (Ti—O) and titanium carbide (Ti—C). It is supposed to be.
  • the thickness t2 of the active metal compound layer 42 is 0.05 ⁇ m or more, the reaction between the bonding material and the carbon plate 21 is promoted, and the bonding strength of the carbon plate 21 is sufficiently secured.
  • the thickness t2 of the active metal compound layer 42 is 3 ⁇ m or less, it is possible to suppress the occurrence of cracks in the active metal compound layer 42 when the active metal compound layer 42 is loaded. Therefore, in the present embodiment, the thickness t2 of the active metal compound layer 42 is preferably in the range of 0.05 ⁇ m or more and 3 ⁇ m or less.
  • the lower limit of the thickness t2 of the active metal compound layer 42 is more preferably 0.1 ⁇ m or more, and more preferably 0.2 ⁇ m or more.
  • the upper limit of the thickness t2 of the active metal compound layer 42 is more preferably 2 ⁇ m or less, and more preferably 1.8 ⁇ m or less.
  • the alloy layer 43 is formed by reacting Ag and Cu contained in the bonding material interposed between the carbon plate 21 and the ceramic plate 25 at the time of bonding.
  • the alloy layer 43 contains Ag in the range of 30 mass% or more and 70 mass% or less, and Cu in the range of 15 mass% or more and 45 mass% or less.
  • the thickness t3 of the alloy layer 43 is 1 ⁇ m or more, the reaction of the bonding material is sufficiently promoted, and the bonding strength between the carbon plate 21 and the ceramic plate 25 is sufficiently secured.
  • the thickness t3 of the alloy layer 43 is 20 ⁇ m or less, it is possible to suppress the occurrence of cracks in the alloy layer 43 during a cold cycle load. Therefore, in the present embodiment, the thickness t3 of the alloy layer 43 is preferably in the range of 1 ⁇ m or more and 20 ⁇ m or less.
  • the lower limit of the thickness t3 of the alloy layer 43 is more preferably 2 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the upper limit of the thickness t3 of the alloy layer 43 is more preferably 10 ⁇ m or less, and more preferably 8 ⁇ m or less.
  • Carbon plate forming step S01 First, the above-mentioned flat graphite particles and graphene aggregates are weighed so as to have a predetermined blending ratio, and these are mixed by an existing mixing device such as a ball mill. A molded product is obtained by filling the obtained mixture in a mold having a predetermined shape and pressurizing the mixture. In addition, heating may be carried out at the time of pressurization. Then, the obtained molded product is cut out to obtain a carbon plate 21.
  • the pressure at the time of molding is preferably in the range of 20 MPa or more and 1000 MPa or less, and more preferably in the range of 100 MPa or more and 300 MPa or less. Further, the temperature at the time of molding is preferably in the range of 50 ° C. or higher and 300 ° C. or lower. Further, the pressurizing time is preferably in the range of 0.5 minutes or more and 10 minutes or less.
  • the above-mentioned carbon plates 21 are laminated on both main surfaces of the ceramic plate 25 via a bonding material.
  • a bonding material a material containing Ag, Cu, and an active metal (Ti in this embodiment) is used.
  • the bonding material may be in the form of a paste or in the form of a foil. Further, for example, a Cu—Ag alloy and an active metal may be laminated.
  • a material having a composition containing Cu in the range of 18 mass% or more and 34 mass% or less, Ti in the range of 0.3 mass% or more and 7 mass% or less, and the balance being Ag and unavoidable impurities is used as the bonding material. There is.
  • the ceramic plate 25 and the carbon plate 21 laminated via the bonding material are pressed in the laminating direction, heated, and then cooled to join the ceramic plate 25 and the carbon plate 21.
  • the heating temperature is preferably in the range of 790 ° C. or higher and 900 ° C. or lower.
  • the holding time at the heating temperature is preferably in the range of 20 minutes or more and 180 minutes or less.
  • the pressurizing pressure is preferably in the range of 0.1 MPa or more and 3.5 MPa or less.
  • the atmosphere is preferably a non-oxidizing atmosphere such as a reduced pressure atmosphere or a nitrogen gas atmosphere.
  • the active metal (Ti in the present embodiment) contained in the joining material reacts with nitrogen contained in the ceramic plate 25 to form the active metal nitride layer 41 on the joining surface of the ceramic plate 25.
  • the active metal (Ti in this embodiment) contained in the bonding material reacts with oxygen and carbon to form the active metal compound layer 42 on the bonding surface of the carbon plate 21.
  • the reaction between Cu and Ag contained in the bonding material forms an alloy layer 43 between the active metal nitride layer 41 and the active metal compound layer 42.
  • the graphene-containing carbonaceous member / ceramics joint (insulating substrate 20) of the present embodiment will be manufactured.
  • the carbon plate 21 made of the graphene-containing carbonaceous member and the ceramic plate 25 made of nitrogen-containing ceramics In the bonding interface 40 of the above, an active metal nitride layer 41 is formed on the bonding surface of the ceramic plate 25, and the thickness of the active metal nitride layer 41 is 0.05 ⁇ m or more, and thus is included in the bonding material.
  • the active metal Ti in this embodiment reacts sufficiently with the ceramic plate 25, and the carbon plate 21 and the ceramic plate 25 can be firmly bonded to each other.
  • the thickness of the active metal nitride layer 41 is limited to 2 ⁇ m or less, it is possible to suppress the occurrence of cracks in the active metal nitride layer under a cold cycle load, and it is possible to improve the cold cycle reliability. ..
  • the active metal compound layer 42 is formed on the joint surface of the carbon plate 21 at the joint interface 40 between the carbon plate 21 and the ceramic plate 25, and the thickness of the active metal compound layer 42 is 0.05 ⁇ m or more. If so, the joint surface of the carbon plate 21 made of the active metal (Ti in this embodiment) and the graphene-containing carbonaceous member contained in the joint material is sufficiently reacted, and the carbon plate 21 and the ceramic plate are sufficiently reacted. The bonding strength with 25 can be further improved. On the other hand, when the thickness of the active metal compound layer 42 is limited to 3 ⁇ m or less, it is possible to suppress the occurrence of cracks in the active metal compound layer 42 when the active metal compound layer 42 is loaded.
  • the thickness of the alloy layer 43 is 1 ⁇ m or more. Ag and Cu contained in the bonding material are sufficiently reacted with each other, and the bonding strength between the carbon plate 21 and the ceramic plate 25 can be further improved.
  • the thickness of the alloy layer 43 is limited to 20 ⁇ m or less, it is possible to suppress the occurrence of cracks in the alloy layer 43 during a cold cycle load.
  • the graphene-containing carbonaceous member constituting the carbon plate 21 contains graphene aggregates formed by depositing single-layer or multi-layer graphene and flat-shaped graphite particles, and the flat-shaped graphite particles.
  • the carbon plate 21 graphene is used. It is possible to further improve the heat conduction characteristics of the graphite-containing member).
  • the copper / graphene-containing carbonaceous member / ceramics joint in the present embodiment has a structure in which a copper member made of copper or a copper alloy, a graphene-containing carbonaceous member containing a graphene aggregate, and nitrogen-containing ceramics are joined. Insulated circuit board 110.
  • the power module 101 shown in FIG. 6 includes an insulating circuit board 110, a semiconductor element 3 bonded to one surface side (upper side in FIG. 6) of the insulating circuit board 110 via a solder layer 2, and an insulating circuit board 110. It is provided with a heat sink 31 arranged on the other surface side (lower side in FIG. 6).
  • the heat sink 31 is for cooling the above-mentioned insulating circuit board 10, and has a structure in which a plurality of flow paths 32 for flowing a cooling medium (for example, cooling water) are provided.
  • the heat sink 31 is preferably made of a material having good thermal conductivity, for example, aluminum or aluminum alloy, copper or copper alloy, and in this embodiment, it is made of 2N aluminum having a purity of 99 mass% or more. There is.
  • the metal layer 13 of the insulating circuit board 10 and the heat sink 31 are joined by a solid phase diffusion joining method.
  • the semiconductor element 3 is made of a semiconductor material such as Si or SiC.
  • the semiconductor element 3 is mounted on the circuit layer 12 via, for example, a solder layer 2 made of a Sn—Ag-based, Sn—In-based, or Sn—Ag—Cu-based solder material.
  • the copper / graphene-containing carbonaceous member / ceramics joint (insulating circuit substrate 110) of the present embodiment is the insulating substrate 20 made of the graphene-containing carbonaceous member / ceramics joint of the first embodiment and the insulating substrate. It includes a circuit layer 112 disposed on one surface (upper surface in FIG. 6) of 20 and a metal layer 113 arranged on the other surface (lower surface in FIG. 6) of the insulating substrate 20.
  • the circuit layer 112 is formed by joining a copper plate having excellent conductivity to one surface of the insulating substrate 20.
  • an oxygen-free copper rolled plate is used as the copper plate constituting the circuit layer 112.
  • the thickness of the copper plate (copper plate) to be the circuit layer 112 is set within the range of 0.1 mm or more and 1.0 mm or less, and in this embodiment, it is set to 0.6 mm.
  • the size of the circuit layer 112 is equal to or larger than that of the carbon plate 21.
  • the metal layer 113 is formed by joining a copper plate having excellent thermal conductivity to the other surface of the insulating substrate 20.
  • an oxygen-free copper rolled plate is used as the copper plate constituting the metal layer 113.
  • the thickness of the copper plate (copper plate) to be the metal layer 113 is set within the range of 0.1 mm or more and 1.0 mm or less, and in the present embodiment, it is set to 0.6 mm.
  • the size of the metal layer 113 is equal to or larger than that of the carbon plate 21.
  • FIG. 7 shows a schematic view of the bonding interface between the carbon plate 21 made of a graphene-containing carbonaceous member and the circuit layer 112 (metal layer 113).
  • the active metal oxide and the active metal carbide are formed on the bonding surface of the carbon plate 21.
  • An active metal compound layer 142 containing one or two of the above is formed.
  • an alloy layer 143 containing Ag and Cu is formed between the circuit layer 112 (metal layer 113) and the active metal compound layer 142. That is, in the present embodiment, the bonding interface 140 has a structure in which the alloy layer 143 and the active metal compound layer 142 are laminated in this order from the circuit layer 112 (metal layer 113) side.
  • the active metal compound layer 142 is formed by reacting the active metal contained in the bonding material interposed between the carbon plate 21 and the copper plate with oxygen and carbon at the time of bonding.
  • the active metal is Ti
  • the active metal compound layer 142 contains one or two types of titanium oxide (Ti—O) and titanium carbide (Ti—C). Has been done.
  • the thickness t12 of the active metal compound layer 142 is 0.05 ⁇ m or more, the reaction between the bonding material and the carbon plate 21 is promoted, and the bonding strength of the carbon plate 21 is sufficiently secured.
  • the thickness t12 of the active metal compound layer 142 is 3 ⁇ m or less, it is possible to suppress the occurrence of cracks in the active metal compound layer 142 during a cold cycle load. Therefore, in the present embodiment, the thickness t2 of the active metal compound layer 142 is preferably in the range of 0.05 ⁇ m or more and 3 ⁇ m or less.
  • the lower limit of the thickness t12 of the active metal compound layer 142 is more preferably 0.1 ⁇ m or more, and more preferably 0.2 ⁇ m or more.
  • the upper limit of the thickness t12 of the active metal compound layer 142 is more preferably 2 ⁇ m or less, and more preferably 1.8 ⁇ m or less.
  • the alloy layer 143 is formed by reacting Ag and Cu contained in the bonding material interposed between the carbon plate 21 and the copper plate at the time of bonding.
  • the alloy layer 143 contains Ag in the range of 30 mass% or more and 70 mass% or less, and Cu in the range of 15 mass% or more and 45 mass% or less.
  • the thickness t13 of the alloy layer 143 is 1 ⁇ m or more, the reaction of the bonding material is sufficiently promoted, and the bonding strength between the carbon plate 21, the circuit layer 112, and the metal layer 113 is sufficiently secured. ..
  • the thickness t13 of the alloy layer 143 is 20 ⁇ m or less, it is possible to suppress the occurrence of cracks in the alloy layer 143 during a cold cycle load. Therefore, in the present embodiment, the thickness t13 of the alloy layer 143 is preferably in the range of 1 ⁇ m or more and 20 ⁇ m or less.
  • the lower limit of the thickness t13 of the alloy layer 143 is more preferably 2 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • the upper limit of the thickness t13 of the alloy layer 143 is more preferably 10 ⁇ m or less, and more preferably 8 ⁇ m or less.
  • the copper / graphene-containing carbonaceous member / ceramics joint (insulated circuit board 110) of the present embodiment is, for example, the graphene-containing carbonic member / ceramics joint (insulated substrate 20) described in the first embodiment. ), It can be manufactured by joining a copper plate to the surface of the carbon plate 21. Alternatively, when the ceramic plate 25 and the carbon plate 21 are joined to produce a graphene-containing carbonaceous member / ceramics joint (insulating substrate 20), the carbon plate 21 and the copper plate may be joined at the same time. In either case, the carbon plate 21 and the copper plate are joined by laminating the copper plate on the surface of the carbon plate 21 via a bonding material and heating while pressurizing in the stacking direction.
  • the bonding material a material containing Ag, Cu, and an active metal (Ti in this embodiment) is used.
  • the bonding material may be in the form of a paste or in the form of a foil. Further, for example, a Cu—Ag alloy and an active metal may be laminated.
  • the heating temperature is preferably in the range of 790 ° C. or higher and 900 ° C. or lower.
  • the holding time at the heating temperature is preferably in the range of 20 minutes or more and 180 minutes or less.
  • the pressurizing pressure is preferably in the range of 0.1 MPa or more and 3.5 MPa or less.
  • the atmosphere is preferably a non-oxidizing atmosphere such as a reduced pressure atmosphere or a nitrogen gas atmosphere.
  • the active metal (Ti in this embodiment) reacts with oxygen and carbon to act on the bonding surface of the carbon plate 21.
  • the metal compound layer 142 is formed. Further, the reaction between Cu and Ag contained in the bonding material forms an alloy layer 143 between the copper plate and the active metal compound layer 142.
  • the graphene-containing carbonaceous member / ceramics joint (insulated circuit board 110) of the present embodiment having the above-described configuration
  • the graphene-containing carbonaceous member / ceramics joint (insulated circuit board 110) of the first embodiment Since the carbon plate 21 of the insulating substrate 20), the circuit layer 112, and the metal layer 113 are bonded to each other, the reliability of the thermal cycle is excellent. Further, the carbon plate 21 is protected by the circuit layer 112 and the metal layer 113, and the occurrence of cracks in the carbon plate 21 can be suppressed.
  • the size of the circuit layer 112 and the metal layer 113 is equal to or larger than that of the carbon plate 21, the occurrence of cracks in the carbon plate 21 can be further suppressed.
  • the active metal compound layer 142 is formed on the bonding surface of the carbon plate 21, and the thickness t12 of the active metal compound layer 142. Since the value is 0.05 ⁇ m or more, the bonding surface of the carbon plate 21 is sufficiently reacted by the active metal, and the carbon plate 21, the circuit layer 112, and the metal layer 113 can be bonded more firmly. Become. Further, since the thickness t12 of the active metal compound layer 142 is limited to 3 ⁇ m or less, it is possible to suppress the occurrence of cracks in the active metal compound layer 142 when loaded with a cold cycle, and it is possible to improve the reliability of the cold cycle.
  • an alloy layer 143 containing Ag and Cu is formed between the circuit layer 112, the metal layer 113, and the active metal compound layer 142.
  • the bonding strength between the carbon plate 21, the circuit layer 112, and the metal layer 113 can be further improved.
  • the thickness of the alloy layer 143 is limited to 20 ⁇ m or less, it is possible to suppress the occurrence of cracks in the alloy layer 143 when a cold cycle load is applied, and it is possible to improve the cold cycle reliability.
  • a semiconductor element (power semiconductor element) is mounted on the circuit layer of the insulated circuit board to form a power module, but the present embodiment is not limited to this.
  • an LED element may be mounted on an insulated circuit board to form an LED module
  • a thermoelectric element may be mounted on a circuit layer of an insulated circuit board to form a thermoelectric module.
  • the insulating substrate 20 of the present embodiment is applied as the insulating layer of the insulating circuit board 10, but the present invention is not limited to this.
  • the method of using the graphene-containing carbonaceous member / ceramic joint of the present invention is not particularly limited.
  • the copper plate has been described as an example of the metal plate to be bonded to the insulating substrate 20, but the present invention is not limited to this, and other metal plates such as an aluminum plate may be used. ..
  • the flat graphite particles and the graphene aggregate are mixed at a predetermined blending ratio, mixed, and heated by pressurization to form the flat graphite particles on the basal surface thereof.
  • a molded body having a structure in which graphene aggregates were laminated as a binder was obtained so as to be folded over.
  • the obtained molded product was cut out to obtain a carbon plate (40 mm ⁇ 40 mm ⁇ thickness 1.5 mm) as a graphene-containing carbonaceous member.
  • the above-mentioned carbon plate is placed on both sides of the ceramic plate (40 mm ⁇ 40 mm ⁇ thickness 0.32 mm) shown in Table 1 via a bonding material (thickness 20 ⁇ m) having a composition of Ag-28 mass% Cu-3 mass% Ti. After laminating, the carbon plate and the ceramic plate were joined under the conditions shown in Table 1. Then, the bonding interface between the carbon plate and the ceramic plate was observed, and the thickness of the active metal nitride layer or the thickness of the active metal compound layer was confirmed.
  • an observation sample is taken from the central part of the graphene-containing carbonaceous member / ceramics junction, and the junction interface is measured using a scanning transmission electron microscope (FEI TitanChemiSTEM (with EDS detector)) at a magnification of 40,000. Observation is performed under the condition of double acceleration voltage of 200 kV, mapping is performed using energy dispersive X-ray analysis method (NSS7 manufactured by Thermo Scientific Co., Ltd.), and in the case of an active metal nitride layer, the region where the active metal and N overlap.
  • FEI TitanChemiSTEM with EDS detector
  • the active metal compound layer In the case of the active metal compound layer, the area of the region where the active metal exists is measured, and the value divided by the width of the measurement field (length: (2.3 ⁇ m ⁇ width: 3 ⁇ m)) is obtained. Was taken as the thickness of the active metal nitride layer or the active metal compound layer.
  • a cross-sectional observation sample near the junction interface of the graphene-containing carbonaceous member / ceramics junction was collected, and EPMA (JXA-8530F manufactured by JEOL Ltd., acceleration voltage: 15 kV, spot diameter: EPMA mapping was obtained using (1 ⁇ m or less), and the area of Ag within the range of 30 mass% or more and 70 mass% or less and Cu within the range of 15 mass% or more and 45 mass% or less was regarded as an alloy layer, and the area was measured.
  • the value obtained by dividing by the width dimension of (: 90 ⁇ m ⁇ width: 120 ⁇ m) was obtained, and the average value of the five visual fields was taken as the thickness of the alloy layer.
  • measurement points a total of 5 points were observed, which are the region of the center point of the insulated circuit board and the region of four vertices of a 20 mm ⁇ 20 mm quadrangle centered on that point.
  • the obtained conjugate was subjected to 2000 cycles of cooling and heating at ⁇ 40 ° C. ⁇ 5 minutes ⁇ ⁇ 150 ° C. ⁇ 5 minutes. Then, the bonding ratio at the interface between the carbon plate and the copper plate was evaluated using an ultrasonic flaw detector (FineSAT200 manufactured by Hitachi Power Solutions, Ltd.) and calculated from the following formula.
  • the initial joining area is the area to be joined before joining.
  • the peeling is shown by the white part in the joint, and the area of this white part is defined as the peeling area.
  • (Joining ratio) ⁇ (Initial joining area)-(Non-joining area) ⁇ / (Initial joining area) x 100
  • Comparative Example 1 in which the thickness of the active metal nitride layer was 2.20 ⁇ m and the thickness of the active metal compound layer was 3.30 ⁇ m, the bonding ratio after the thermal cycle test was as low as 75%.
  • Comparative Example 2 in which the thickness of the active metal nitride layer was 0.03 ⁇ m and the thickness of the active metal compound layer was 0.03 ⁇ m, the bonding ratio after the thermal cycle test was as low as 72%.
  • Example 1-10 of the present invention in which the thickness of the active metal nitride layer was in the range of 0.05 ⁇ m or more and 2 ⁇ m or less, the bonding ratio after the thermal cycle test was 80% or more, and the cold heat was obtained. It had excellent cycle reliability.
  • Example 2 The graphene-containing carbonaceous member / ceramics joints of Examples 3, 4, 6 and 10 of the present invention described above were prepared, and a bonding material having a composition of Ag-28 mass% Cu-3 mass% Ti was prepared on the surface of the carbon plate (thickness).
  • cracks in the carbon plate were evaluated by observing with a microscope (Digital Microscope VHX-7000 manufactured by KEYENCE CORPORATION). From the side surface of the copper / graphene-containing carbonaceous member / ceramics joint, observe the carbon plates bonded to both sides of the ceramic plate at a magnification that allows them to be seen, and the length is 2/3 or more of the thickness of the carbon plate. The case where the number of cracks was 15 or less was evaluated as " ⁇ ", and the case where the number of cracks exceeded 15 was evaluated as "x”. The length of the crack was defined as the length along the crack, and the longest length was defined as the crack when branched in the middle.
  • Copper / graphene-containing carbonaceous member / ceramic joint of Invention Examples 13, 14, 16 and 20 formed by joining a copper plate to the graphene-containing carbonaceous member / ceramic joint of Invention Examples 3, 4, 6 and 10. In each case, the occurrence of cracks in the carbon plate (graphene-containing carbonaceous member) could be suppressed.
  • Example 3 A carbon plate (40 mm ⁇ 40 mm ⁇ thickness 1.5 mm) to be a graphene-containing carbonaceous member was obtained by the same procedure as in Example 1. The above-mentioned carbon plate is placed on both sides of the ceramic plate (40 mm ⁇ 40 mm ⁇ thickness 0.32 mm) shown in Table 3 via a bonding material (thickness 20 ⁇ m) having a composition of Ag-28 mass% Cu-3 mass% Ti. Laminated. Further, a copper plate (40 mm ⁇ 40 mm ⁇ thickness 0.) Made of rolled oxygen-free copper is interposed on the surface of the carbon plate via a bonding material (thickness 20 ⁇ m) having a composition of Ag-28 mass% Cu-3 mass% Ti. 8 mm) was laminated. Then, under the conditions shown in Table 3, the ceramic plate, the carbon plate, and the copper plate were simultaneously bonded to obtain a copper / graphene-containing carbonaceous member / ceramic bonded body.
  • Example 2 the bonding interface between the carbon plate and the ceramic plate was observed, and the thickness of the active metal nitride layer or the thickness of the active metal compound layer was confirmed. In addition, the bonding interface between the carbon plate and the copper plate was observed to confirm the thickness of the active metal compound layer. Further, as in Example 2, cracks in the carbon plate (graphene-containing carbonaceous member) were evaluated by observation with a microscope.
  • the ceramic member and the graphene-containing carbonaceous member containing the graphene aggregate are firmly bonded to each other, and peeling does not occur even under a cold cycle load. It was confirmed that it is possible to provide a graphene-containing carbonaceous member / ceramics joint having excellent cycle reliability and a copper / graphene-containing carbonaceous member / ceramics joint.
  • the ceramics member and the graphene-containing carbonaceous member containing the graphene aggregate are firmly bonded to each other, and peeling does not occur even under a cold cycle load, and the graphene-containing carbonaceous member / ceramics having excellent thermal cycle reliability. It is possible to provide a joint body and a copper / graphene-containing carbonaceous member / ceramics joint body in which a copper member made of copper or a copper alloy is bonded to the graphene-containing carbonaceous member / ceramics joint body.

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Abstract

Disclosed is a graphene-containing carbonaceous member/ceramic assembly having a structure wherein a graphene-containing carbonaceous member (21) containing a graphene aggregate and a ceramic member (25) made of a ceramic containing nitrogen are joined together. At a joining interface (40) between the graphene-containing carbonaceous member (21) and the ceramic member (25), an active metal nitride layer (41) is formed on the joining surface of the ceramic member (25), and the thickness of the active metal nitride layer is within a range from 0.05 µm to 2 µm.

Description

グラフェン含有炭素質部材／セラミックス接合体、および、銅／グラフェン含有炭素質部材／セラミックス接合体Graphene-containing carbonaceous member / ceramics joint and copper / graphene-containing carbonaceous member / ceramics joint
　この発明は、グラフェン集合体を含有するグラフェン含有炭素質部材と窒素を含むセラミックスからなるセラミックス部材とが接合された構造のグラフェン含有炭素質部材／セラミックス接合体、および、このグラフェン含有炭素質部材／セラミックス接合体に銅又は銅合金からなる銅部材が接合された銅／グラフェン含有炭素質部材／セラミックス接合体に関するものである。
　本願は、２０１９年１１月５日に日本に出願された特願２０１９－２００７２４号及び２０２０年１０月２７日に日本に出願された特願２０２０－１７９７３６号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a graphene-containing carbonaceous member / ceramics joint having a structure in which a graphene-containing carbonaceous member containing a graphene aggregate and a ceramics member made of nitrogen-containing ceramics are joined, and the graphene-containing carbonaceous member / The present invention relates to a copper / graphene-containing carbonaceous member / ceramics joint in which a copper member made of copper or a copper alloy is bonded to a ceramics joint.
This application claims priority based on Japanese Patent Application No. 2019-290724 filed in Japan on November 5, 2019 and Japanese Patent Application No. 2020-179736 filed in Japan on October 27, 2020. Is used here.
　グラフェン集合体を含有するグラフェン含有炭素質部材は、熱伝導性に優れていることから、放熱部材及び熱伝導部材等を構成する部材として特に適している。
　例えば、上述のグラフェン集合体を含有するグラフェン含有炭素質部材の表面にセラミックス等からなる絶縁層を形成することにより、絶縁基板として使用することが可能となる。 Since the graphene-containing carbonaceous member containing the graphene aggregate is excellent in thermal conductivity, it is particularly suitable as a member constituting a heat radiating member, a heat conductive member, and the like.
For example, by forming an insulating layer made of ceramics or the like on the surface of the graphene-containing carbonaceous member containing the graphene aggregate described above, it can be used as an insulating substrate.
　ここで、例えば特許文献１には、第１方向に沿ってグラフェンシートが積層された構造体と、第１方向と交差する第２方向における上記構造体の端面に接合される中間部材（セラミックス）と、を有し、この中間部材（例えばセラミックス）が、少なくともチタンを含むインサート材を介して、上記端面に加圧接合された異方性熱伝導素子が開示されている。 Here, for example, in Patent Document 1, a structure in which graphene sheets are laminated along the first direction and an intermediate member (ceramics) joined to the end face of the structure in the second direction intersecting the first direction. Disclosed is an anisotropic heat conductive element in which an intermediate member (for example, ceramics) is pressure-bonded to the end face via an insert material containing at least titanium.
日本国特開２０１２－２３８７３３号公報（Ａ）Japanese Patent Application Laid-Open No. 2012-238733 (A)
　ところで、上述の絶縁基板においては、使用環境下において冷熱サイクルが負荷されることがある。特に、最近では、エンジンルーム等の過酷な環境下で使用されることがあり、温度差が大きな厳しい条件の冷熱サイクルが負荷されることがある。
　ここで、上述の特許文献１においては、セラミックスからなる中間体とグラフェンの構造体とを、チタンを含むインサート材を介して接合しているが、接合条件によっては、セラミックスからなる中間体とグラフェンの構造体とを強固に接合することができず、厳しい条件の冷熱サイクルが負荷された際に剥離が生じるおそれがあった。 By the way, in the above-mentioned insulating substrate, a cold cycle may be applied under the usage environment. In particular, recently, it may be used in a harsh environment such as an engine room, and a cold cycle under severe conditions with a large temperature difference may be loaded.
Here, in Patent Document 1 described above, an intermediate made of ceramics and a graphene structure are joined via an insert material containing titanium, but depending on the joining conditions, the intermediate made of ceramics and graphene are joined. It was not possible to firmly join the structure of the above, and there was a risk of peeling when a cold cycle under severe conditions was applied.
　この発明は、前述した事情に鑑みてなされたものであって、セラミックス部材とグラフェン集合体を含有するグラフェン含有炭素質部材とが強固に接合されており、冷熱サイクル負荷時においても剥離が生じることがなく、冷熱サイクル信頼性に優れたグラフェン含有炭素質部材／セラミックス接合体、および、このグラフェン含有炭素質部材／セラミックス接合体に銅又は銅合金からなる銅部材が接合された銅／グラフェン含有炭素質部材／セラミックス接合体を提供することを目的とする。 The present invention has been made in view of the above-mentioned circumstances, and the ceramic member and the graphene-containing carbonaceous member containing a graphene aggregate are firmly bonded to each other, and peeling occurs even when a cold cycle load is applied. Graphene-containing carbonaceous member / ceramics joint with excellent thermal cycle reliability, and copper / graphene-containing carbon in which a copper member made of copper or a copper alloy is bonded to the graphene-containing carbonaceous member / ceramics joint. It is an object of the present invention to provide a quality member / ceramics joint.
　このような課題を解決して、前記目的を達成するために、本発明の一態様のグラフェン含有炭素質部材／セラミックス接合体（以下、「本発明のグラフェン含有炭素質部材／セラミックス接合体」と称する。）は、グラフェン集合体を含有するグラフェン含有炭素質部材と、窒素を含むセラミックスからなるセラミックス部材とが接合された構造のグラフェン含有炭素質部材／セラミックス接合体であって、前記グラフェン含有炭素質部材と前記セラミックス部材との接合界面において、前記セラミックス部材の接合面に活性金属窒化物層が形成されており、この活性金属窒化物層の厚さが０．０５μｍ以上２μｍ以下の範囲内とされていることを特徴としている。 In order to solve such a problem and achieve the above object, the graphene-containing carbonaceous member / ceramics joint of one aspect of the present invention (hereinafter, "graphene-containing carbonaceous member / ceramics joint of the present invention"). ) Is a graphene-containing carbonaceous member / ceramics joint having a structure in which a graphene-containing carbonaceous member containing a graphene aggregate and a ceramics member made of ceramics containing nitrogen are joined, and the graphene-containing carbon is said. At the joint interface between the quality member and the ceramic member, an active metal nitride layer is formed on the joint surface of the ceramic member, and the thickness of the active metal nitride layer is within the range of 0.05 μm or more and 2 μm or less. It is characterized by being done.
　この構成のグラフェン含有炭素質部材／セラミックス接合体においては、前記グラフェン含有炭素質部材と窒素を含むセラミックスからなるセラミックス部材との接合界面において、前記セラミックス部材の接合面に活性金属窒化物層が形成されており、この活性金属窒化物層の厚さが０．０５μｍ以上とされているので、活性金属によってセラミックス部材の接合面が十分に反応しており、グラフェン含有炭素質部材とセラミックス部材とを強固に接合することが可能となる。
　また、活性金属窒化物層の厚さが２μｍ以下に制限されているので、冷熱サイクル負荷時において活性金属窒化物層にクラックが生じることを抑制でき、冷熱サイクル信頼性を向上させることができる。 In the graphene-containing carbonaceous member / ceramics joint having this configuration, an active metal nitride layer is formed on the joint surface of the ceramics member at the joint interface between the graphene-containing carbonaceous member and the ceramic member made of nitrogen-containing ceramics. Since the thickness of this active metal nitride layer is 0.05 μm or more, the joint surface of the ceramic member is sufficiently reacted by the active metal, and the graphene-containing carbonaceous member and the ceramic member are separated from each other. It is possible to firmly join.
Further, since the thickness of the active metal nitride layer is limited to 2 μm or less, it is possible to suppress the occurrence of cracks in the active metal nitride layer under a cold cycle load, and it is possible to improve the cold cycle reliability.
　ここで、本発明のグラフェン含有炭素質部材／セラミックス接合体においては、前記グラフェン含有炭素質部材と前記セラミックス部材との接合界面において、前記グラフェン含有炭素質部材の接合面に、活性金属化合物層が形成されており、前記活性金属化合物層の厚さが０．０５μｍ以上３μｍ以下の範囲内とされていることが好ましい。
　この場合、前記グラフェン含有炭素質部材と前記セラミックス部材との接合界面において、前記グラフェン含有炭素質部材の接合面に、活性金属化合物層が形成され、前記活性金属化合物層の厚さが０．０５μｍ以上とされているので、活性金属によってグラフェン含有炭素質部材の接合面が十分に反応しており、グラフェン含有炭素質部材とセラミックス部材とをさらに強固に接合することが可能となる。また、前記活性金属化合物層の厚さが３μｍ以下に制限されているので、冷熱サイクル負荷時において活性金属化合物層にクラックが生じることを抑制でき、冷熱サイクル信頼性を向上させることができる。 Here, in the graphene-containing carbonaceous member / ceramics joint of the present invention, an active metal compound layer is formed on the bonding surface of the graphene-containing carbonaceous member at the bonding interface between the graphene-containing carbonaceous member and the ceramics member. It is preferably formed so that the thickness of the active metal compound layer is in the range of 0.05 μm or more and 3 μm or less.
In this case, at the bonding interface between the graphene-containing carbonaceous member and the ceramic member, an active metal compound layer is formed on the bonding surface of the graphene-containing carbonaceous member, and the thickness of the active metal compound layer is 0.05 μm. As described above, the joint surface of the graphene-containing carbonaceous member is sufficiently reacted by the active metal, and the graphene-containing carbonaceous member and the ceramic member can be joined more firmly. Further, since the thickness of the active metal compound layer is limited to 3 μm or less, it is possible to suppress the occurrence of cracks in the active metal compound layer when loaded with a cold cycle, and it is possible to improve the reliability of the cold cycle.
　さらに、本発明のグラフェン含有炭素質部材／セラミックス接合体においては、前記グラフェン含有炭素質部材と前記セラミックス部材との接合界面において、前記活性金属窒化物層と前記活性金属化合物層の間に、ＡｇとＣｕを含む合金層が形成されており、前記合金層の厚さが１μｍ以上２０μｍ以下の範囲内とされていることが好ましい。
　この場合、接合材に含まれるＡｇとＣｕが十分に反応することで上述の合金層が形成されており、前記合金層の厚さが１μｍ以上とされているので、前記グラフェン含有炭素質部材と前記セラミックス部材との接合強度をさらに向上させることができる。また、前記合金層の厚さが２０μｍ以下に制限されているので、冷熱サイクル負荷時において前記合金層にクラックが生じることを抑制でき、冷熱サイクル信頼性を向上させることができる。 Further, in the graphene-containing carbonaceous member / ceramics joint of the present invention, at the bonding interface between the graphene-containing carbonaceous member and the ceramics member, Ag is sandwiched between the active metal nitride layer and the active metal compound layer. It is preferable that an alloy layer containing Cu and Cu is formed, and the thickness of the alloy layer is within the range of 1 μm or more and 20 μm or less.
In this case, the above-mentioned alloy layer is formed by the sufficient reaction of Ag and Cu contained in the bonding material, and the thickness of the alloy layer is 1 μm or more. The bonding strength with the ceramic member can be further improved. Further, since the thickness of the alloy layer is limited to 20 μm or less, it is possible to suppress the occurrence of cracks in the alloy layer when a cold cycle load is applied, and it is possible to improve the reliability of the cold cycle.
　さらに、本発明のグラフェン含有炭素質部材／セラミックス接合体においては、前記グラフェン含有炭素質部材は、単層又は多層のグラフェンが堆積してなるグラフェン集合体と扁平形状の黒鉛粒子とを含み、扁平形状の前記黒鉛粒子が、そのベーサル面が折り重なるように前記グラフェン集合体をバインダーとして積層され、扁平形状の前記黒鉛粒子のベーサル面が一方向に向けて配向した構造とされていることが好ましい。
　この場合、グラフェン含有炭素質部材における熱伝導特性をさらに向上させることが可能となる。 Further, in the graphene-containing carbonaceous member / ceramics joint of the present invention, the graphene-containing carbonaceous member contains a graphene aggregate formed by depositing single-layer or multi-layer graphene and flat graphite particles, and is flat. It is preferable that the graphite particles having a shape are laminated with the graphene aggregate as a binder so that the basal surfaces thereof fold over, and the basal surfaces of the flat graphite particles are oriented in one direction.
In this case, it is possible to further improve the heat conduction characteristics of the graphene-containing carbonaceous member.
　また、本発明の他態様である銅／グラフェン含有炭素質部材／セラミックス接合体（以下、「本発明の銅／グラフェン含有炭素質部材／セラミックス接合体」と称する）は、銅又は銅合金からなる銅部材と、グラフェン集合体を含有するグラフェン含有炭素質部材と、窒素を含むセラミックスからなるセラミックス部材とが接合された構造の銅／グラフェン含有炭素質部材／セラミックス接合体であって、上述のグラフェン含有炭素質部材／セラミックス接合体の前記グラフェン含有炭素質部材と前記銅部材とが接合されていることを特徴としている。 Further, the copper / graphene-containing carbonaceous member / ceramics joint (hereinafter, referred to as “copper / graphene-containing carbonaceous member / ceramics joint” of the present invention), which is another aspect of the present invention, is made of copper or a copper alloy. A copper / graphene-containing carbonaceous member / ceramics joint having a structure in which a copper member, a graphene-containing carbonaceous member containing a graphene aggregate, and a ceramics member made of nitrogen-containing ceramics are joined, and the graphene is described above. The graphene-containing carbonaceous member of the carbon-containing member / ceramics joint is bonded to the copper member.
　この構成の銅／グラフェン含有炭素質部材／セラミックス接合体によれば、上述のグラフェン含有炭素質部材／セラミックス接合体の前記グラフェン含有炭素質部材と前記銅部材とが接合されているので、冷熱サイクル信頼性に優れることになる。また、銅部材によってグラフェン含有炭素質部材が保護され、前記グラフェン含有炭素質部材におけるひび割れの発生を抑制することができる。 According to the copper / graphene-containing carbonaceous member / ceramics joint having this configuration, the graphene-containing carbonaceous member / ceramics joint of the graphene-containing carbonaceous member / ceramics joint has the graphene-containing carbonaceous member and the copper member bonded to each other. It will be excellent in reliability. Further, the graphene-containing carbonaceous member is protected by the copper member, and the occurrence of cracks in the graphene-containing carbonaceous member can be suppressed.
　ここで、本発明の銅／グラフェン含有炭素質部材／セラミックス接合体においては、前記グラフェン含有炭素質部材と前記銅部材との接合界面において、前記グラフェン含有炭素質部材の接合面に、活性金属化合物層が形成されており、前記活性金属化合物層の厚さが０．０５μｍ以上３μｍ以下の範囲内とされていることが好ましい。
　この場合、前記グラフェン含有炭素質部材と前記銅部材との接合界面において、前記グラフェン含有炭素質部材の接合面に、活性金属化合物層が形成され、前記活性金属化合物層の厚さが０．０５μｍ以上とされているので、活性金属によってグラフェン含有炭素質部材の接合面が十分に反応しており、グラフェン含有炭素質部材と銅部材とをさらに強固に接合することが可能となる。また、前記活性金属化合物層の厚さが３μｍ以下に制限されているので、冷熱サイクル負荷時において活性金属化合物層にクラックが生じることを抑制でき、冷熱サイクル信頼性を向上させることができる。 Here, in the copper / graphene-containing carbonaceous member / ceramics joint of the present invention, an active metal compound is formed on the bonding surface of the graphene-containing carbonaceous member at the bonding interface between the graphene-containing carbonaceous member and the copper member. It is preferable that the layer is formed and the thickness of the active metal compound layer is within the range of 0.05 μm or more and 3 μm or less.
In this case, at the bonding interface between the graphene-containing carbonaceous member and the copper member, an active metal compound layer is formed on the bonding surface of the graphene-containing carbonaceous member, and the thickness of the active metal compound layer is 0.05 μm. As described above, the joint surface of the graphene-containing carbonaceous member is sufficiently reacted by the active metal, and the graphene-containing carbonaceous member and the copper member can be joined more firmly. Further, since the thickness of the active metal compound layer is limited to 3 μm or less, it is possible to suppress the occurrence of cracks in the active metal compound layer when loaded with a cold cycle, and it is possible to improve the reliability of the cold cycle.
　また、本発明の銅／グラフェン含有炭素質部材／セラミックス接合体においては、前記グラフェン含有炭素質部材と前記銅部材との接合界面において、前記銅部材と前記活性金属化合物層の間に、ＡｇとＣｕを含む合金層が形成されており、前記合金層の厚さが１μｍ以上２０μｍ以下の範囲内とされていることが好ましい。
　この場合、接合材に含まれるＡｇとＣｕが十分に反応することで上述の合金層が形成されており、前記合金層の厚さが１μｍ以上とされているので、前記グラフェン含有炭素質部材と前記銅部材との接合強度をさらに向上させることができる。また、前記合金層の厚さが２０μｍ以下に制限されているので、冷熱サイクル負荷時において前記合金層にクラックが生じることを抑制でき、冷熱サイクル信頼性を向上させることができる。 Further, in the copper / graphene-containing carbonaceous member / ceramics joint of the present invention, at the bonding interface between the graphene-containing carbonaceous member and the copper member, an Ag is formed between the copper member and the active metal compound layer. It is preferable that an alloy layer containing Cu is formed and the thickness of the alloy layer is within the range of 1 μm or more and 20 μm or less.
In this case, the above-mentioned alloy layer is formed by the sufficient reaction of Ag and Cu contained in the bonding material, and the thickness of the alloy layer is 1 μm or more. The bonding strength with the copper member can be further improved. Further, since the thickness of the alloy layer is limited to 20 μm or less, it is possible to suppress the occurrence of cracks in the alloy layer when a cold cycle load is applied, and it is possible to improve the reliability of the cold cycle.
　本発明によれば、セラミックス部材とグラフェン集合体を含有するグラフェン含有炭素質部材とが強固に接合されており、冷熱サイクル負荷時においても剥離が生じることがなく、冷熱サイクル信頼性に優れたグラフェン含有炭素質部材／セラミックス接合体、および、このグラフェン含有炭素質部材／セラミックス接合体に銅又は銅合金からなる銅部材が接合された銅／グラフェン含有炭素質部材／セラミックス接合体を提供することが可能となる。 According to the present invention, the ceramic member and the graphene-containing carbonaceous member containing the graphene aggregate are firmly bonded to each other, no peeling occurs even under a cold cycle load, and graphene having excellent cold cycle reliability. It is possible to provide a carbonaceous member / ceramics joint containing carbonene and a copper / graphene-containing carbonic member / ceramics joint in which a copper member made of copper or a copper alloy is bonded to the graphene-containing carbonaceous member / ceramics joint. It will be possible.
本発明の第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板）を用いたパワーモジュールの概略説明図である。It is a schematic explanatory drawing of the power module using the graphene-containing carbonaceous member / ceramics joint (insulating substrate) which is 1st Embodiment of this invention. 本発明の第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板）の概略説明図である。It is a schematic explanatory drawing of the graphene-containing carbonaceous material member / ceramics joint (insulating substrate) which is 1st Embodiment of this invention. 本発明の第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板）のグラフェン含有炭素質部材（炭素板）とセラミックス部材（セラミックス板）の接合界面の観察結果であり、倍率５００倍での観察結果である。It is an observation result of the bonding interface between the graphene-containing carbonaceous member (carbon plate) and the ceramic member (ceramic plate) of the graphene-containing carbonaceous member / ceramics joint (insulating substrate) according to the first embodiment of the present invention, and the magnification is It is an observation result at 500 times. 本発明の第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板）のグラフェン含有炭素質部材（炭素板）とセラミックス部材（セラミックス板）の接合界面の観察結果であり、倍率５０００倍での観察結果である。It is an observation result of the bonding interface between the graphene-containing carbonaceous member (carbon plate) and the ceramic member (ceramic plate) of the graphene-containing carbonaceous member / ceramics joint (insulating substrate) according to the first embodiment of the present invention, and the magnification is It is an observation result at 5000 times. 本発明の第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板）のグラフェン含有炭素質部材とセラミックス部材の接合界面の模式図である。It is a schematic diagram of the bonding interface between the graphene-containing carbonaceous member and the ceramic member of the graphene-containing carbonaceous member / ceramics joint (insulating substrate) according to the first embodiment of the present invention. 本発明の第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板）の製造方法の一例を示すフロー図である。It is a flow chart which shows an example of the manufacturing method of the graphene-containing carbonaceous member / ceramics joint (insulating substrate) which is 1st Embodiment of this invention. 本発明の第２の実施形態である銅／グラフェン含有炭素質部材／セラミックス接合体（絶縁回路基板）の概略説明図である。It is a schematic explanatory drawing of the copper / graphene-containing carbonaceous material member / ceramics joint (insulation circuit board) which is 2nd Embodiment of this invention. 本発明の第２の実施形態である銅／グラフェン含有炭素質部材／セラミックス接合体（絶縁回路基板）の銅部材（回路層および金属層）とグラフェン含有炭素質部材（炭素板）との接合界面の模式図である。The bonding interface between the copper member (circuit layer and metal layer) of the copper / graphene-containing carbonaceous member / ceramics joint (insulating circuit substrate) and the graphene-containing carbonaceous member (carbon plate) according to the second embodiment of the present invention. It is a schematic diagram of.
　以下に、本発明の実施形態について添付した図面を参照して説明する。なお、以下に示す各実施形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。また、以下の説明で用いる図面は、本発明の特徴をわかりやすくするために、便宜上、要部となる部分を拡大して示している場合があり、各構成要素の寸法比率などが実際と同じであるとは限らない。 Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. It should be noted that each of the embodiments shown below is specifically described in order to better understand the gist of the invention, and is not limited to the present invention unless otherwise specified. In addition, the drawings used in the following description may be shown by enlarging the main parts for convenience in order to make the features of the present invention easy to understand, and the dimensional ratios of the respective components are the same as the actual ones. Is not always the case.
　（第１の実施形態）
　まず、図１から図５を参照して本発明の第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体について説明する。
　本実施形態におけるグラフェン含有炭素質部材／セラミックス接合体は、グラフェン集合体を含有するグラフェン含有炭素質部材と窒素を含むセラミックスとを接合した構造の絶縁基板２０とされている。 (First Embodiment)
First, the graphene-containing carbonaceous member / ceramics joint according to the first embodiment of the present invention will be described with reference to FIGS. 1 to 5.
The graphene-containing carbonaceous member / ceramics joint in the present embodiment is an insulating substrate 20 having a structure in which a graphene-containing carbonaceous member containing a graphene aggregate and ceramics containing nitrogen are joined.
　まず、本実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板２０）を用いたパワーモジュールについて説明する。
　図１に示すパワーモジュール１は、絶縁回路基板１０と、この絶縁回路基板１０の一方の面側（図１において上側）にはんだ層２を介して接合された半導体素子３と、絶縁回路基板１０の他方の面側（図１において下側）に配設されたヒートシンク３１とを備えている。 First, a power module using a graphene-containing carbonaceous member / ceramics joint (insulating substrate 20) according to the present embodiment will be described.
The power module 1 shown in FIG. 1 includes an insulating circuit board 10, a semiconductor element 3 bonded to one surface side (upper side in FIG. 1) of the insulating circuit board 10 via a solder layer 2, and an insulating circuit board 10. It is provided with a heat sink 31 arranged on the other surface side (lower side in FIG. 1).
　絶縁回路基板１０は、絶縁層と、この絶縁層の一方の面（図１において上面）に配設された回路層１２と、絶縁層の他方の面（図１において下面）に配設された金属層１３とを備えている。
　絶縁層は、回路層１２と金属層１３との間の電気的接続を防止するものであって、本実施形態である絶縁基板２０で構成されている。 The insulating circuit board 10 is arranged on the insulating layer, the circuit layer 12 disposed on one surface of the insulating layer (upper surface in FIG. 1), and the other surface of the insulating layer (lower surface in FIG. 1). It includes a metal layer 13.
The insulating layer prevents electrical connection between the circuit layer 12 and the metal layer 13, and is composed of the insulating substrate 20 of the present embodiment.
　回路層１２は、絶縁層（絶縁基板２０）の一方の面に、導電性に優れた金属板が接合されることによって形成されている。本実施形態では、回路層１２を構成する金属板として、銅又は銅合金からなる銅板、具体的には無酸素銅の圧延板が用いられている。この回路層１２には、回路パターンが形成されており、その一方の面（図１において上面）が、半導体素子３が搭載される搭載面とされている。
　また、回路層１２となる金属板（銅板）の厚さは０．１ｍｍ以上１．０ｍｍ以下の範囲内に設定されており、本実施形態では、０．６ｍｍに設定されている。
　なお、回路層１２となる金属板（銅板）と絶縁基板２０との接合方法は、特に制限はなく、活性金属ろう材等を用いて接合することができる。 The circuit layer 12 is formed by joining a metal plate having excellent conductivity to one surface of an insulating layer (insulating substrate 20). In the present embodiment, as the metal plate constituting the circuit layer 12, a copper plate made of copper or a copper alloy, specifically, a rolled plate of oxygen-free copper is used. A circuit pattern is formed in the circuit layer 12, and one surface (upper surface in FIG. 1) is a mounting surface on which the semiconductor element 3 is mounted.
Further, the thickness of the metal plate (copper plate) to be the circuit layer 12 is set within the range of 0.1 mm or more and 1.0 mm or less, and in the present embodiment, it is set to 0.6 mm.
The method of joining the metal plate (copper plate) to be the circuit layer 12 and the insulating substrate 20 is not particularly limited, and can be joined using an active metal brazing material or the like.
　金属層１３は、絶縁層（絶縁基板２０）の他方の面に、熱伝導性に優れた金属板が接合されることにより形成されている。本実施形態においては、金属層１３を構成する金属板として、銅又は銅合金からなる銅板、具体的には無酸素銅の圧延板が用いられている。
　また、金属層１３となる金属板（銅板）の厚さは０．１ｍｍ以上１．０ｍｍ以下の範囲内に設定されており、本実施形態では、０．６ｍｍに設定されている。
　なお、金属層１３となる金属板（銅板）と絶縁基板２０との接合方法は、特に制限はなく、活性金属ろう材等を用いて接合することができる。 The metal layer 13 is formed by joining a metal plate having excellent thermal conductivity to the other surface of the insulating layer (insulating substrate 20). In the present embodiment, as the metal plate constituting the metal layer 13, a copper plate made of copper or a copper alloy, specifically, a rolled plate of oxygen-free copper is used.
Further, the thickness of the metal plate (copper plate) to be the metal layer 13 is set within the range of 0.1 mm or more and 1.0 mm or less, and in the present embodiment, it is set to 0.6 mm.
The method of joining the metal plate (copper plate) to be the metal layer 13 and the insulating substrate 20 is not particularly limited, and can be joined using an active metal brazing material or the like.
　ヒートシンク３１は、前述の絶縁回路基板１０を冷却するためのものであり、冷却媒体（例えば冷却水）を流通するための流路３２が複数設けられた構造をなしている。
　このヒートシンク３１は、熱伝導性が良好な材質、例えばアルミニウム又はアルミニウム合金、銅又は銅合金で構成されていることが好ましく、本実施形態においては、純度が９９ｍａｓｓ％以上の２Ｎアルミニウムで構成されている。
　なお、本実施形態では、絶縁回路基板１０の金属層１３とヒートシンク３１は、固相拡散接合法によって接合されている。 The heat sink 31 is for cooling the above-mentioned insulating circuit board 10, and has a structure in which a plurality of flow paths 32 for flowing a cooling medium (for example, cooling water) are provided.
The heat sink 31 is preferably made of a material having good thermal conductivity, for example, aluminum or aluminum alloy, copper or copper alloy, and in this embodiment, it is made of 2N aluminum having a purity of 99 mass% or more. There is.
In this embodiment, the metal layer 13 of the insulating circuit board 10 and the heat sink 31 are joined by a solid phase diffusion joining method.
　半導体素子３は、例えばＳｉやＳｉＣ等の半導体材料で構成されている。この半導体素子３は、例えばＳｎ－Ａｇ系、Ｓｎ－Ｉｎ系、若しくはＳｎ－Ａｇ－Ｃｕ系のはんだ材からなるはんだ層２を介して回路層１２上に搭載されている。 The semiconductor element 3 is made of a semiconductor material such as Si or SiC. The semiconductor element 3 is mounted on the circuit layer 12 via, for example, a solder layer 2 made of a Sn—Ag-based, Sn—In-based, or Sn—Ag—Cu-based solder material.
　そして、絶縁層を構成する本実施形態である絶縁基板２０は、図２に示すように、窒素を含むセラミックスからなるセラミックス板２５と、グラフェン集合体を含有するグラフェン含有炭素質部材からなる炭素板２１と、が積層した構造とされており、セラミックス板２５の両主面にそれぞれ炭素板２１が接合されている。 As shown in FIG. 2, the insulating substrate 20 of the present embodiment constituting the insulating layer is a carbon plate made of a ceramic plate 25 made of nitrogen-containing ceramics and a graphene-containing carbonaceous member containing a graphene aggregate. The structure is such that 21 and 21 are laminated, and carbon plates 21 are bonded to both main surfaces of the ceramic plate 25, respectively.
　セラミックス板２５を構成する窒素を含むセラミックスとしては、例えば、窒化アルミニウム（ＡｌＮ）、窒化ケイ素（Ｓｉ３Ｎ４）等が挙げられる。
　このセラミックス板２５の厚さの下限は１００μｍ以上であることが好ましく、２５０μｍ以上であることがさらに好ましい。一方、セラミックス板２５の厚さの上限は１５００μｍ以下であることが好ましく、１０００μｍ以下であることがさらに好ましい。 Examples of the nitrogen-containing ceramics constituting the ceramic plate 25 include aluminum nitride (AlN) and silicon nitride (Si 3 N 4 ).
The lower limit of the thickness of the ceramic plate 25 is preferably 100 μm or more, and more preferably 250 μm or more. On the other hand, the upper limit of the thickness of the ceramic plate 25 is preferably 1500 μm or less, and more preferably 1000 μm or less.
　炭素板２１を構成するグラフェン含有炭素質部材は、単層又は多層のグラフェンが堆積してなるグラフェン集合体と扁平形状の黒鉛粒子とを含み、扁平形状の黒鉛粒子が、そのベーサル面が折り重なるように、グラフェン集合体をバインダーとして積層された構造とされていることが好ましい。 The graphene-containing carbonaceous member constituting the carbon plate 21 contains graphene aggregates formed by depositing single-layer or multi-layer graphene and flat graphite particles so that the flat graphite particles fold their basal surfaces. In addition, it is preferable that the graphene aggregate has a laminated structure as a binder.
　扁平形状の黒鉛粒子は、炭素六角網面が現れるベーサル面と、炭素六角網面の端部が現れるエッジ面と、を有するものである。この扁平形状の黒鉛粒子としては、鱗片状黒鉛、鱗状黒鉛、土状黒鉛、薄片状黒鉛、キッシュグラファイト、熱分解黒鉛、高配向熱分解黒鉛等を用いることができる。
　ここで、黒鉛粒子のベーサル面から見た平均粒径は、１０μｍ以上１０００μｍ以下の範囲内であることが好ましく、５０μｍ以上８００μｍ以下の範囲内であることがさらに好ましい。黒鉛粒子の平均粒径を上述の範囲内とすることで、熱伝導性が向上する。
　さらに、黒鉛粒子の厚さは、１μｍ以上５０μｍ以下の範囲内であることが好ましく、１μｍ以上２０μｍ以下の範囲内であることがさらに好ましい。黒鉛粒子の厚さを上述の範囲内とすることで、黒鉛粒子の配向性が適度に調整される。
　また、黒鉛粒子の厚みがベーサル面から見た粒径の１／１０００～１／２の範囲内とすることによって、優れた熱伝導性と黒鉛粒子の配向性が適度に調整される。 The flat graphite particles have a basal surface on which a carbon hexagonal network surface appears and an edge surface on which an end portion of the carbon hexagonal network surface appears. As the flat graphite particles, scaly graphite, scaly graphite, earthy graphite, flaky graphite, kiss graphite, pyrolytic graphite, highly oriented pyrolytic graphite and the like can be used.
Here, the average particle size of the graphite particles as seen from the basal surface is preferably in the range of 10 μm or more and 1000 μm or less, and more preferably in the range of 50 μm or more and 800 μm or less. By setting the average particle size of the graphite particles within the above range, the thermal conductivity is improved.
Further, the thickness of the graphite particles is preferably in the range of 1 μm or more and 50 μm or less, and more preferably in the range of 1 μm or more and 20 μm or less. By setting the thickness of the graphite particles within the above range, the orientation of the graphite particles is appropriately adjusted.
Further, by setting the thickness of the graphite particles within the range of 1/1000 to 1/2 of the particle size seen from the basal surface, excellent thermal conductivity and orientation of the graphite particles are appropriately adjusted.
　グラフェン集合体は、単層又は多層のグラフェンが堆積したものであり、多層のグラフェンの積層数は、例えば１００層以下、好ましくは５０層以下とされている。このグラフェン集合体は、例えば、単層又は多層のグラフェンが低級アルコールや水を含む溶媒に分散されたグラフェン分散液を、ろ紙上に滴下し、溶媒を分離しながら堆積させることによって製造することが可能である。
　ここで、グラフェン集合体の平均粒径は、１μｍ以上１０００μｍ以下の範囲内であることが好ましい。グラフェン集合体の平均粒径を上述の範囲内とすることで、熱伝導性が向上する。
　さらに、グラフェン集合体の厚さは、０．０５μｍ以上５０μｍ未満の範囲内であることが好ましい。グラフェン集合体の厚さを上述の範囲内とすることで、炭素質部材の強度が確保される。
　なお、炭素板２１の厚さとしては、０．５ｍｍ以上５ｍｍ以下の範囲内であることが好ましい。 The graphene aggregate is a deposit of single-layer or multi-layer graphene, and the number of layers of the multi-layer graphene is, for example, 100 layers or less, preferably 50 layers or less. This graphene aggregate can be produced, for example, by dropping a graphene dispersion in which single-layer or multi-layer graphene is dispersed in a solvent containing lower alcohol or water onto a filter paper and depositing the graphene while separating the solvent. It is possible.
Here, the average particle size of the graphene aggregate is preferably in the range of 1 μm or more and 1000 μm or less. By keeping the average particle size of the graphene aggregate within the above range, the thermal conductivity is improved.
Further, the thickness of the graphene aggregate is preferably in the range of 0.05 μm or more and less than 50 μm. By keeping the thickness of the graphene aggregate within the above range, the strength of the carbonaceous member is ensured.
The thickness of the carbon plate 21 is preferably in the range of 0.5 mm or more and 5 mm or less.
　ここで、図３Ａ及び図３Ｂに、グラフェン含有炭素質部材からなる炭素板２１とセラミックス板２５との接合界面の観察写真を、図４に、グラフェン含有炭素質部材からなる炭素板２１とセラミックス板２５との接合界面の模式図を示す。
　図３Ａ及び図３Ｂにおいて、上方の黒色部が炭素板２１（グラフェン含有炭素質部材）であり、その下方に位置する灰色部がセラミックス板２５である。 Here, FIGS. 3A and 3B show observational photographs of the interface between the carbon plate 21 made of a graphene-containing carbonaceous member and the ceramic plate 25, and FIG. 4 shows a carbon plate 21 made of a graphene-containing carbonaceous member and a ceramic plate. The schematic diagram of the junction interface with 25 is shown.
In FIGS. 3A and 3B, the upper black portion is the carbon plate 21 (graphene-containing carbonaceous member), and the gray portion located below the carbon plate 21 is the ceramic plate 25.
　図３Ａ及び図４に示すように、グラフェン含有炭素質部材からなる炭素板２１とセラミックス板２５との接合界面４０においては、セラミックス板２５の接合面に、活性金属窒化物層４１が形成されている。
　また、図３Ｂ及び図４に示すように、接合界面４０においては、炭素板２１の接合面に、活性金属酸化物及び活性金属炭化物の１種又は２種を含む活性金属化合物層４２が形成されている。
　さらに、図３Ｂ及び図４に示すように、活性金属窒化物層４１と活性金属化合物層４２の間には、ＡｇとＣｕを含有する合金層４３が形成されている。
　すなわち、本実施形態においては、接合界面４０は、セラミックス板２５側から順に、活性金属窒化物層４１、合金層４３、活性金属化合物層４２が積層された構造とされている。 As shown in FIGS. 3A and 4, at the bonding interface 40 between the carbon plate 21 made of a graphene-containing carbonaceous member and the ceramic plate 25, an active metal nitride layer 41 is formed on the bonding surface of the ceramic plate 25. There is.
Further, as shown in FIGS. 3B and 4, at the bonding interface 40, an active metal compound layer 42 containing one or two types of active metal oxide and active metal carbide is formed on the bonding surface of the carbon plate 21. ing.
Further, as shown in FIGS. 3B and 4, an alloy layer 43 containing Ag and Cu is formed between the active metal nitride layer 41 and the active metal compound layer 42.
That is, in the present embodiment, the bonding interface 40 has a structure in which the active metal nitride layer 41, the alloy layer 43, and the active metal compound layer 42 are laminated in this order from the ceramic plate 25 side.
　活性金属窒化物層４１は、接合時において炭素板２１とセラミックス板２５の間に介在される接合材に含まれる活性金属が、セラミックス板２５に含まれる窒素と反応することによって形成されるものである。
　活性金属窒化物層４１を構成する活性金属としては、例えば、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂから選択される１種又は２種以上を用いることができる。本実施形態では、活性金属はＴｉとされており、活性金属窒化物層４１はチタン窒化物（Ｔｉ－Ｎ）で構成されている。 The active metal nitride layer 41 is formed by reacting the active metal contained in the bonding material interposed between the carbon plate 21 and the ceramic plate 25 with nitrogen contained in the ceramic plate 25 at the time of bonding. is there.
As the active metal constituting the active metal nitride layer 41, for example, one kind or two or more kinds selected from Ti, Zr, Hf, and Nb can be used. In the present embodiment, the active metal is Ti, and the active metal nitride layer 41 is made of titanium nitride (Ti—N).
　ここで、活性金属窒化物層４１の厚さｔ１が０．０５μｍ未満であると、接合材とセラミックス板２５との反応が十分ではなく、セラミックス板２５の接合強度が不十分となるおそれがある。一方、活性金属窒化物層４１の厚さｔ１が２μｍを超えると、冷熱サイクル負荷時に活性金属窒化物層４１においてクラックが発生するおそれがある。
　よって、本実施形態では、活性金属窒化物層４１の厚さｔ１を、０．０５μｍ以上２μｍ以下の範囲内に設定している。
　なお、活性金属窒化物層４１の厚さｔ１の下限は０．１μｍ以上であることがさらに好ましく、０．２μｍ以上であることがより好ましい。一方、活性金属窒化物層４１の厚さｔ１の上限は１μｍ以下であることがさらに好ましく、０．７μｍ以下であることがより好ましい。 Here, if the thickness t1 of the active metal nitride layer 41 is less than 0.05 μm, the reaction between the bonding material and the ceramic plate 25 may not be sufficient, and the bonding strength of the ceramic plate 25 may be insufficient. .. On the other hand, if the thickness t1 of the active metal nitride layer 41 exceeds 2 μm, cracks may occur in the active metal nitride layer 41 during a cold cycle load.
Therefore, in the present embodiment, the thickness t1 of the active metal nitride layer 41 is set within the range of 0.05 μm or more and 2 μm or less.
The lower limit of the thickness t1 of the active metal nitride layer 41 is more preferably 0.1 μm or more, and more preferably 0.2 μm or more. On the other hand, the upper limit of the thickness t1 of the active metal nitride layer 41 is more preferably 1 μm or less, and more preferably 0.7 μm or less.
　活性金属化合物層４２は、接合時において炭素板２１とセラミックス板２５の間に介在される接合材に含まれる活性金属が、酸素及び炭素と反応することで形成されるものである。
　上述のように、本実施形態では、活性金属はＴｉとされており、活性金属化合物層４２は、チタン酸化物（Ｔｉ－Ｏ）及びチタン炭化物（Ｔｉ－Ｃ）の１種又は２種を含むものとされている。 The active metal compound layer 42 is formed by reacting the active metal contained in the bonding material interposed between the carbon plate 21 and the ceramic plate 25 at the time of bonding with oxygen and carbon.
As described above, in the present embodiment, the active metal is Ti, and the active metal compound layer 42 contains one or two types of titanium oxide (Ti—O) and titanium carbide (Ti—C). It is supposed to be.
　ここで、活性金属化合物層４２の厚さｔ２が０．０５μｍ以上であれば、接合材と炭素板２１との反応が促進されており、炭素板２１の接合強度が十分に確保される。一方、活性金属化合物層４２の厚さｔ２が３μｍ以下であれば、冷熱サイクル負荷時に活性金属化合物層４２におけるクラックの発生を抑制することができる。
　よって、本実施形態においては、活性金属化合物層４２の厚さｔ２は、０．０５μｍ以上３μｍ以下の範囲内とされていることが好ましい。
　なお、活性金属化合物層４２の厚さｔ２の下限は０．１μｍ以上であることがさらに好ましく、０．２μｍ以上であることがより好ましい。一方、活性金属化合物層４２の厚さｔ２の上限は２μｍ以下であることがさらに好ましく、１．８μｍ以下であることがより好ましい。 Here, when the thickness t2 of the active metal compound layer 42 is 0.05 μm or more, the reaction between the bonding material and the carbon plate 21 is promoted, and the bonding strength of the carbon plate 21 is sufficiently secured. On the other hand, when the thickness t2 of the active metal compound layer 42 is 3 μm or less, it is possible to suppress the occurrence of cracks in the active metal compound layer 42 when the active metal compound layer 42 is loaded.
Therefore, in the present embodiment, the thickness t2 of the active metal compound layer 42 is preferably in the range of 0.05 μm or more and 3 μm or less.
The lower limit of the thickness t2 of the active metal compound layer 42 is more preferably 0.1 μm or more, and more preferably 0.2 μm or more. On the other hand, the upper limit of the thickness t2 of the active metal compound layer 42 is more preferably 2 μm or less, and more preferably 1.8 μm or less.
　合金層４３は、接合時において炭素板２１とセラミックス板２５の間に介在される接合材に含まれるＡｇ、Ｃｕが反応することで形成されるものである。
　本実施形態においては、この合金層４３は、Ａｇを３０ｍａｓｓ％以上７０ｍａｓｓ％以下の範囲内、Ｃｕを１５ｍａｓｓ％以上４５ｍａｓｓ％以下の範囲内で含むものとされている。 The alloy layer 43 is formed by reacting Ag and Cu contained in the bonding material interposed between the carbon plate 21 and the ceramic plate 25 at the time of bonding.
In the present embodiment, the alloy layer 43 contains Ag in the range of 30 mass% or more and 70 mass% or less, and Cu in the range of 15 mass% or more and 45 mass% or less.
　ここで、合金層４３の厚さｔ３が１μｍ以上であれば、接合材の反応が十分に促進されており、炭素板２１とセラミックス板２５との接合強度が十分に確保される。一方、合金層４３の厚さｔ３が２０μｍ以下であれば、冷熱サイクル負荷時に合金層４３におけるクラックの発生を抑制することができる。
　よって、本実施形態においては、合金層４３の厚さｔ３は、１μｍ以上２０μｍ以下の範囲内とされていることが好ましい。
　なお、合金層４３の厚さｔ３の下限は２μｍ以上であることがさらに好ましく、３μｍ以上であることがより好ましい。一方、合金層４３の厚さｔ３の上限は１０μｍ以下であることがさらに好ましく、８μｍ以下であることがより好ましい。 Here, when the thickness t3 of the alloy layer 43 is 1 μm or more, the reaction of the bonding material is sufficiently promoted, and the bonding strength between the carbon plate 21 and the ceramic plate 25 is sufficiently secured. On the other hand, when the thickness t3 of the alloy layer 43 is 20 μm or less, it is possible to suppress the occurrence of cracks in the alloy layer 43 during a cold cycle load.
Therefore, in the present embodiment, the thickness t3 of the alloy layer 43 is preferably in the range of 1 μm or more and 20 μm or less.
The lower limit of the thickness t3 of the alloy layer 43 is more preferably 2 μm or more, and more preferably 3 μm or more. On the other hand, the upper limit of the thickness t3 of the alloy layer 43 is more preferably 10 μm or less, and more preferably 8 μm or less.
　次に、本実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板２０）の製造方法について、図５に示すフロー図を参照して説明する。 Next, the method for manufacturing the graphene-containing carbonaceous member / ceramics joint (insulating substrate 20) according to the present embodiment will be described with reference to the flow chart shown in FIG.
　（炭素板形成工程Ｓ０１）
　まず、上述した扁平形状の黒鉛粒子とグラフェン集合体とを所定の配合比となるように秤量し、これをボールミル等の既存の混合装置によって混合する。
　得られた混合物を、所定の形状の金型に充填して加圧することにより成形体を得る。なお、加圧時に加熱を実施してもよい。
　そして、得られた成形体に対して切り出し加工を行い、炭素板２１を得る。 (Carbon plate forming step S01)
First, the above-mentioned flat graphite particles and graphene aggregates are weighed so as to have a predetermined blending ratio, and these are mixed by an existing mixing device such as a ball mill.
A molded product is obtained by filling the obtained mixture in a mold having a predetermined shape and pressurizing the mixture. In addition, heating may be carried out at the time of pressurization.
Then, the obtained molded product is cut out to obtain a carbon plate 21.
　なお、成形時の圧力は、２０ＭＰａ以上１０００ＭＰａ以下の範囲内とすることが好ましく、１００ＭＰａ以上３００ＭＰａ以下の範囲内とすることがさらに好ましい。
　また、成形時の温度は、５０℃以上３００℃以下の範囲内とすることが好ましい。
　さらに、加圧時間は、０．５分以上１０分以下の範囲内とすることが好ましい。 The pressure at the time of molding is preferably in the range of 20 MPa or more and 1000 MPa or less, and more preferably in the range of 100 MPa or more and 300 MPa or less.
Further, the temperature at the time of molding is preferably in the range of 50 ° C. or higher and 300 ° C. or lower.
Further, the pressurizing time is preferably in the range of 0.5 minutes or more and 10 minutes or less.
　（積層工程Ｓ０２）
　次に、セラミックス板２５の両主面に、接合材を介して、上述の炭素板２１をそれぞれ積層する。
　ここで、接合材としては、ＡｇとＣｕと活性金属（本実施形態ではＴｉ）を含有するものを使用する。なお、接合材は、ペースト状であってもよいし、箔であってもよい。また、例えばＣｕ－Ａｇ合金と活性金属とを積層したものであってもよい。
　本実施形態では、接合材として、Ｃｕを１８ｍａｓｓ％以上３４ｍａｓｓ％以下の範囲、Ｔｉを０．３ｍａｓｓ％以上７ｍａｓｓ％以下の範囲で含み、残部がＡｇ及び不可避不純物とされた組成のものを用いている。 (Laminating step S02)
Next, the above-mentioned carbon plates 21 are laminated on both main surfaces of the ceramic plate 25 via a bonding material.
Here, as the bonding material, a material containing Ag, Cu, and an active metal (Ti in this embodiment) is used. The bonding material may be in the form of a paste or in the form of a foil. Further, for example, a Cu—Ag alloy and an active metal may be laminated.
In the present embodiment, as the bonding material, a material having a composition containing Cu in the range of 18 mass% or more and 34 mass% or less, Ti in the range of 0.3 mass% or more and 7 mass% or less, and the balance being Ag and unavoidable impurities is used. There is.
　（接合工程Ｓ０３）
　次に、接合材を介して積層したセラミックス板２５及び炭素板２１を、積層方向に加圧するとともに加熱した後、冷却することにより、セラミックス板２５と炭素板２１とを接合する。
　ここで、加熱温度は７９０℃以上９００℃以下の範囲内とすることが好ましい。また、加熱温度での保持時間は２０分以上１８０分以下の範囲内とすることが好ましい。さらに、加圧圧力は０．１ＭＰａ以上３．５ＭＰａ以下の範囲内とすることが好ましい。また、雰囲気は減圧雰囲気や窒素ガス雰囲気などの非酸化雰囲気とされていることが好ましい。 (Joining step S03)
Next, the ceramic plate 25 and the carbon plate 21 laminated via the bonding material are pressed in the laminating direction, heated, and then cooled to join the ceramic plate 25 and the carbon plate 21.
Here, the heating temperature is preferably in the range of 790 ° C. or higher and 900 ° C. or lower. Further, the holding time at the heating temperature is preferably in the range of 20 minutes or more and 180 minutes or less. Further, the pressurizing pressure is preferably in the range of 0.1 MPa or more and 3.5 MPa or less. Further, the atmosphere is preferably a non-oxidizing atmosphere such as a reduced pressure atmosphere or a nitrogen gas atmosphere.
　この接合工程Ｓ０３により、接合材に含まれる活性金属（本実施形態ではＴｉ）がセラミックス板２５に含まれる窒素と反応することで、セラミックス板２５の接合面に活性金属窒化物層４１が形成される。
　また、接合材に含まれる活性金属（本実施形態ではＴｉ）が酸素及び炭素と反応することで、炭素板２１の接合面に活性金属化合物層４２が形成される。
　さらに、接合材に含まれるＣｕとＡｇが反応することで、活性金属窒化物層４１と活性金属化合物層４２の間に合金層４３が形成される。 In this joining step S03, the active metal (Ti in the present embodiment) contained in the joining material reacts with nitrogen contained in the ceramic plate 25 to form the active metal nitride layer 41 on the joining surface of the ceramic plate 25. To.
Further, the active metal (Ti in this embodiment) contained in the bonding material reacts with oxygen and carbon to form the active metal compound layer 42 on the bonding surface of the carbon plate 21.
Further, the reaction between Cu and Ag contained in the bonding material forms an alloy layer 43 between the active metal nitride layer 41 and the active metal compound layer 42.
　以上の工程により、本実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板２０）が製造されることになる。 By the above steps, the graphene-containing carbonaceous member / ceramics joint (insulating substrate 20) of the present embodiment will be manufactured.
　以上のような構成とされた本実施形態のグラフェン含有炭素質部材／セラミックス接合体（絶縁基板２０）によれば、グラフェン含有炭素質部材からなる炭素板２１と窒素を含むセラミックスからなるセラミックス板２５の接合界面４０において、セラミックス板２５の接合面に活性金属窒化物層４１が形成されており、この活性金属窒化物層４１の厚さが０．０５μｍ以上とされているので、接合材に含まれる活性金属（本実施形態では、Ｔｉ）とセラミックス板２５とが十分に反応しており、炭素板２１とセラミックス板２５とを強固に接合することが可能となる。
　また、活性金属窒化物層４１の厚さが２μｍ以下に制限されているので、冷熱サイクル負荷時において活性金属窒化物層にクラックが生じることを抑制でき、冷熱サイクル信頼性を向上させることができる。 According to the graphene-containing carbonaceous member / ceramics joint (insulating substrate 20) of the present embodiment having the above-described configuration, the carbon plate 21 made of the graphene-containing carbonaceous member and the ceramic plate 25 made of nitrogen-containing ceramics In the bonding interface 40 of the above, an active metal nitride layer 41 is formed on the bonding surface of the ceramic plate 25, and the thickness of the active metal nitride layer 41 is 0.05 μm or more, and thus is included in the bonding material. The active metal (Ti in this embodiment) reacts sufficiently with the ceramic plate 25, and the carbon plate 21 and the ceramic plate 25 can be firmly bonded to each other.
Further, since the thickness of the active metal nitride layer 41 is limited to 2 μm or less, it is possible to suppress the occurrence of cracks in the active metal nitride layer under a cold cycle load, and it is possible to improve the cold cycle reliability. ..
　本実施形態において、炭素板２１とセラミックス板２５の接合界面４０における炭素板２１の接合面に、活性金属化合物層４２が形成されており、活性金属化合物層４２の厚さが０．０５μｍ以上とされている場合には、接合材に含まれる活性金属（本実施形態では、Ｔｉ）とグラフェン含有炭素質部材からなる炭素板２１の接合面が十分に反応しており、炭素板２１とセラミックス板２５との接合強度をさらに向上させることができる。一方、活性金属化合物層４２の厚さが３μｍ以下に制限されている場合には、冷熱サイクル負荷時に活性金属化合物層４２におけるクラックの発生を抑制することができる。 In the present embodiment, the active metal compound layer 42 is formed on the joint surface of the carbon plate 21 at the joint interface 40 between the carbon plate 21 and the ceramic plate 25, and the thickness of the active metal compound layer 42 is 0.05 μm or more. If so, the joint surface of the carbon plate 21 made of the active metal (Ti in this embodiment) and the graphene-containing carbonaceous member contained in the joint material is sufficiently reacted, and the carbon plate 21 and the ceramic plate are sufficiently reacted. The bonding strength with 25 can be further improved. On the other hand, when the thickness of the active metal compound layer 42 is limited to 3 μm or less, it is possible to suppress the occurrence of cracks in the active metal compound layer 42 when the active metal compound layer 42 is loaded.
　また、本実施形態において、炭素板２１とセラミックス板２５の接合界面４０に、ＡｇとＣｕを含む合金層４３が形成されており、この合金層４３の厚さが１μｍ以上とされている場合には、接合材に含まれるＡｇとＣｕが十分に反応しており、炭素板２１とセラミックス板２５との接合強度をさらに向上させることができる。一方、合金層４３の厚さが２０μｍ以下に制限されている場合には、冷熱サイクル負荷時に合金層４３におけるクラックの発生を抑制することができる。 Further, in the present embodiment, when an alloy layer 43 containing Ag and Cu is formed at the bonding interface 40 between the carbon plate 21 and the ceramic plate 25, and the thickness of the alloy layer 43 is 1 μm or more. Ag and Cu contained in the bonding material are sufficiently reacted with each other, and the bonding strength between the carbon plate 21 and the ceramic plate 25 can be further improved. On the other hand, when the thickness of the alloy layer 43 is limited to 20 μm or less, it is possible to suppress the occurrence of cracks in the alloy layer 43 during a cold cycle load.
　さらに、本実施形態において、炭素板２１を構成するグラフェン含有炭素質部材が、単層又は多層のグラフェンが堆積してなるグラフェン集合体と扁平形状の黒鉛粒子とを含み、扁平形状の前記黒鉛粒子が、そのベーサル面が折り重なるように前記グラフェン集合体をバインダーとして積層され、扁平形状の前記黒鉛粒子のベーサル面が一方向に向けて配向した構造とされている場合には、炭素板２１（グラフェン含有炭素質部材）における熱伝導特性をさらに向上させることが可能となる。 Further, in the present embodiment, the graphene-containing carbonaceous member constituting the carbon plate 21 contains graphene aggregates formed by depositing single-layer or multi-layer graphene and flat-shaped graphite particles, and the flat-shaped graphite particles. However, when the graphene aggregates are laminated as a binder so that the basal surfaces are folded so that the basal surfaces of the flat graphite particles are oriented in one direction, the carbon plate 21 (graphene) is used. It is possible to further improve the heat conduction characteristics of the graphite-containing member).
　（第２の実施形態）
　次に、図６及び図７を参照して本発明の第２の実施形態である銅／グラフェン含有炭素質部材／セラミックス接合体について説明する。
　本実施形態における銅／グラフェン含有炭素質部材／セラミックス接合体は、銅又は銅合金からなる銅部材と、グラフェン集合体を含有するグラフェン含有炭素質部材と、窒素を含むセラミックスと、を接合した構造の絶縁回路基板１１０とされている。 (Second Embodiment)
Next, the copper / graphene-containing carbonaceous member / ceramics joint according to the second embodiment of the present invention will be described with reference to FIGS. 6 and 7.
The copper / graphene-containing carbonaceous member / ceramics joint in the present embodiment has a structure in which a copper member made of copper or a copper alloy, a graphene-containing carbonaceous member containing a graphene aggregate, and nitrogen-containing ceramics are joined. Insulated circuit board 110.
　まず、本実施形態である銅／グラフェン含有炭素質部材／セラミックス接合体（絶縁回路基板１１０）を用いたパワーモジュールについて説明する。
図６に示すパワーモジュール１０１は、絶縁回路基板１１０と、この絶縁回路基板１１０の一方の面側（図６において上側）にはんだ層２を介して接合された半導体素子３と、絶縁回路基板１１０の他方の面側（図６において下側）に配設されたヒートシンク３１とを備えている。 First, a power module using a copper / graphene-containing carbonaceous member / ceramics joint (insulated circuit board 110) according to the present embodiment will be described.
The power module 101 shown in FIG. 6 includes an insulating circuit board 110, a semiconductor element 3 bonded to one surface side (upper side in FIG. 6) of the insulating circuit board 110 via a solder layer 2, and an insulating circuit board 110. It is provided with a heat sink 31 arranged on the other surface side (lower side in FIG. 6).
　ヒートシンク３１は、前述の絶縁回路基板１０を冷却するためのものであり、冷却媒体（例えば冷却水）を流通するための流路３２が複数設けられた構造をなしている。
　このヒートシンク３１は、熱伝導性が良好な材質、例えばアルミニウム又はアルミニウム合金、銅又は銅合金で構成されていることが好ましく、本実施形態においては、純度が９９ｍａｓｓ％以上の２Ｎアルミニウムで構成されている。
なお、本実施形態では、絶縁回路基板１０の金属層１３とヒートシンク３１は、固相拡散接合法によって接合されている。 The heat sink 31 is for cooling the above-mentioned insulating circuit board 10, and has a structure in which a plurality of flow paths 32 for flowing a cooling medium (for example, cooling water) are provided.
The heat sink 31 is preferably made of a material having good thermal conductivity, for example, aluminum or aluminum alloy, copper or copper alloy, and in this embodiment, it is made of 2N aluminum having a purity of 99 mass% or more. There is.
In this embodiment, the metal layer 13 of the insulating circuit board 10 and the heat sink 31 are joined by a solid phase diffusion joining method.
　半導体素子３は、例えばＳｉやＳｉＣ等の半導体材料で構成されている。この半導体素子３は、例えばＳｎ－Ａｇ系、Ｓｎ－Ｉｎ系、若しくはＳｎ－Ａｇ－Ｃｕ系のはんだ材からなるはんだ層２を介して回路層１２上に搭載されている。 The semiconductor element 3 is made of a semiconductor material such as Si or SiC. The semiconductor element 3 is mounted on the circuit layer 12 via, for example, a solder layer 2 made of a Sn—Ag-based, Sn—In-based, or Sn—Ag—Cu-based solder material.
　本実施形態である銅／グラフェン含有炭素質部材／セラミックス接合体（絶縁回路基板１１０）は、第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体からなる絶縁基板２０と、この絶縁基板２０の一方の面（図６において上面）に配設された回路層１１２と、絶縁基板２０の他方の面（図６において下面）に配設された金属層１１３とを備えている。 The copper / graphene-containing carbonaceous member / ceramics joint (insulating circuit substrate 110) of the present embodiment is the insulating substrate 20 made of the graphene-containing carbonaceous member / ceramics joint of the first embodiment and the insulating substrate. It includes a circuit layer 112 disposed on one surface (upper surface in FIG. 6) of 20 and a metal layer 113 arranged on the other surface (lower surface in FIG. 6) of the insulating substrate 20.
　回路層１１２は、絶縁基板２０の一方の面に、導電性に優れた銅板が接合されることによって形成されている。本実施形態では、回路層１１２を構成する銅板として、無酸素銅の圧延板が用いられている。
　ここで、回路層１１２となる銅板（銅板）の厚さは０．１ｍｍ以上１．０ｍｍ以下の範囲内に設定されており、本実施形態では、０．６ｍｍに設定されている。
　なお、本実施形態では、図６に示すように、回路層１１２の大きさは、炭素板２１と同等以上とされている。 The circuit layer 112 is formed by joining a copper plate having excellent conductivity to one surface of the insulating substrate 20. In the present embodiment, an oxygen-free copper rolled plate is used as the copper plate constituting the circuit layer 112.
Here, the thickness of the copper plate (copper plate) to be the circuit layer 112 is set within the range of 0.1 mm or more and 1.0 mm or less, and in this embodiment, it is set to 0.6 mm.
In this embodiment, as shown in FIG. 6, the size of the circuit layer 112 is equal to or larger than that of the carbon plate 21.
　金属層１１３は、絶縁基板２０の他方の面に、熱伝導性に優れた銅板が接合されることにより形成されている。本実施形態においては、金属層１１３を構成する銅板として、無酸素銅の圧延板が用いられている。
　ここで、金属層１１３となる銅板（銅板）の厚さは０．１ｍｍ以上１．０ｍｍ以下の範囲内に設定されており、本実施形態では、０．６ｍｍに設定されている。
　なお、本実施形態では、図６に示すように、金属層１１３の大きさは、炭素板２１と同等以上とされている。 The metal layer 113 is formed by joining a copper plate having excellent thermal conductivity to the other surface of the insulating substrate 20. In the present embodiment, an oxygen-free copper rolled plate is used as the copper plate constituting the metal layer 113.
Here, the thickness of the copper plate (copper plate) to be the metal layer 113 is set within the range of 0.1 mm or more and 1.0 mm or less, and in the present embodiment, it is set to 0.6 mm.
In this embodiment, as shown in FIG. 6, the size of the metal layer 113 is equal to or larger than that of the carbon plate 21.
　ここで、図７に、グラフェン含有炭素質部材からなる炭素板２１と回路層１１２（金属層１１３）との接合界面の模式図を示す。
　図７に示すように、グラフェン含有炭素質部材からなる炭素板２１と回路層１１２（金属層１１３）との接合界面１４０においては、炭素板２１の接合面に、活性金属酸化物及び活性金属炭化物の１種又は２種を含む活性金属化合物層１４２が形成されている。
　さらに、図４に示すように、回路層１１２（金属層１１３）と活性金属化合物層１４２の間には、ＡｇとＣｕを含有する合金層１４３が形成されている。
　すなわち、本実施形態においては、接合界面１４０は、回路層１１２（金属層１１３）側から順に、合金層１４３、活性金属化合物層１４２が積層された構造とされている。 Here, FIG. 7 shows a schematic view of the bonding interface between the carbon plate 21 made of a graphene-containing carbonaceous member and the circuit layer 112 (metal layer 113).
As shown in FIG. 7, at the bonding interface 140 between the carbon plate 21 made of a graphene-containing carbonaceous member and the circuit layer 112 (metal layer 113), the active metal oxide and the active metal carbide are formed on the bonding surface of the carbon plate 21. An active metal compound layer 142 containing one or two of the above is formed.
Further, as shown in FIG. 4, an alloy layer 143 containing Ag and Cu is formed between the circuit layer 112 (metal layer 113) and the active metal compound layer 142.
That is, in the present embodiment, the bonding interface 140 has a structure in which the alloy layer 143 and the active metal compound layer 142 are laminated in this order from the circuit layer 112 (metal layer 113) side.
　活性金属化合物層１４２は、接合時において炭素板２１と銅板の間に介在される接合材に含まれる活性金属が酸素及び炭素と反応することで形成されるものである。
　ここで、本実施形態では、活性金属はＴｉとされており、活性金属化合物層１４２は、チタン酸化物（Ｔｉ－Ｏ）及びチタン炭化物（Ｔｉ－Ｃ）の１種又は２種を含むものとされている。 The active metal compound layer 142 is formed by reacting the active metal contained in the bonding material interposed between the carbon plate 21 and the copper plate with oxygen and carbon at the time of bonding.
Here, in the present embodiment, the active metal is Ti, and the active metal compound layer 142 contains one or two types of titanium oxide (Ti—O) and titanium carbide (Ti—C). Has been done.
　ここで、活性金属化合物層１４２の厚さｔ１２が０．０５μｍ以上であれば、接合材と炭素板２１との反応が促進されており、炭素板２１の接合強度が十分に確保される。一方、活性金属化合物層１４２の厚さｔ１２が３μｍ以下であれば、冷熱サイクル負荷時に活性金属化合物層１４２におけるクラックの発生を抑制することができる。
　よって、本実施形態においては、活性金属化合物層１４２の厚さｔ２は、０．０５μｍ以上３μｍ以下の範囲内とされていることが好ましい。
　なお、活性金属化合物層１４２の厚さｔ１２の下限は０．１μｍ以上であることがさらに好ましく、０．２μｍ以上であることがより好ましい。一方、活性金属化合物層１４２の厚さｔ１２の上限は２μｍ以下であることがさらに好ましく、１．８μｍ以下であることがより好ましい。 Here, when the thickness t12 of the active metal compound layer 142 is 0.05 μm or more, the reaction between the bonding material and the carbon plate 21 is promoted, and the bonding strength of the carbon plate 21 is sufficiently secured. On the other hand, when the thickness t12 of the active metal compound layer 142 is 3 μm or less, it is possible to suppress the occurrence of cracks in the active metal compound layer 142 during a cold cycle load.
Therefore, in the present embodiment, the thickness t2 of the active metal compound layer 142 is preferably in the range of 0.05 μm or more and 3 μm or less.
The lower limit of the thickness t12 of the active metal compound layer 142 is more preferably 0.1 μm or more, and more preferably 0.2 μm or more. On the other hand, the upper limit of the thickness t12 of the active metal compound layer 142 is more preferably 2 μm or less, and more preferably 1.8 μm or less.
　合金層１４３は、接合時において炭素板２１と銅板の間に介在される接合材に含まれるＡｇ、Ｃｕが反応することで形成されるものである。
　本実施形態においては、この合金層１４３は、Ａｇを３０ｍａｓｓ％以上７０ｍａｓｓ％以下の範囲内、Ｃｕを１５ｍａｓｓ％以上４５ｍａｓｓ％以下の範囲内で含むものとされている。 The alloy layer 143 is formed by reacting Ag and Cu contained in the bonding material interposed between the carbon plate 21 and the copper plate at the time of bonding.
In the present embodiment, the alloy layer 143 contains Ag in the range of 30 mass% or more and 70 mass% or less, and Cu in the range of 15 mass% or more and 45 mass% or less.
　ここで、合金層１４３の厚さｔ１３が１μｍ以上であれば、接合材の反応が十分に促進されており、炭素板２１と回路層１１２および金属層１１３との接合強度が十分に確保される。一方、合金層１４３の厚さｔ１３が２０μｍ以下であれば、冷熱サイクル負荷時に合金層１４３におけるクラックの発生を抑制することができる。
　よって、本実施形態においては、合金層１４３の厚さｔ１３は、１μｍ以上２０μｍ以下の範囲内とされていることが好ましい。
　なお、合金層１４３の厚さｔ１３の下限は２μｍ以上であることがさらに好ましく、３μｍ以上であることがより好ましい。一方、合金層１４３の厚さｔ１３の上限は１０μｍ以下であることがさらに好ましく、８μｍ以下であることがより好ましい。 Here, when the thickness t13 of the alloy layer 143 is 1 μm or more, the reaction of the bonding material is sufficiently promoted, and the bonding strength between the carbon plate 21, the circuit layer 112, and the metal layer 113 is sufficiently secured. .. On the other hand, when the thickness t13 of the alloy layer 143 is 20 μm or less, it is possible to suppress the occurrence of cracks in the alloy layer 143 during a cold cycle load.
Therefore, in the present embodiment, the thickness t13 of the alloy layer 143 is preferably in the range of 1 μm or more and 20 μm or less.
The lower limit of the thickness t13 of the alloy layer 143 is more preferably 2 μm or more, and more preferably 3 μm or more. On the other hand, the upper limit of the thickness t13 of the alloy layer 143 is more preferably 10 μm or less, and more preferably 8 μm or less.
　ここで、本実施形態である銅／グラフェン含有炭素質部材／セラミックス接合体（絶縁回路基板１１０）は、例えば、第１の実施形態で説明したグラフェン含有炭素質部材／セラミックス接合体（絶縁基板２０）の炭素板２１の表面に、銅板を接合することによって製造することができる。
　あるいは、セラミックス板２５と炭素板２１とを接合してグラフェン含有炭素質部材／セラミックス接合体（絶縁基板２０）を製造する際に、炭素板２１と銅板とを同時に接合してもよい。
　いずれの場合でも、炭素板２１の表面に、接合材を介して銅板を積層し、積層方向に加圧しながら加熱することによって炭素板２１と銅板を接合することになる。 Here, the copper / graphene-containing carbonaceous member / ceramics joint (insulated circuit board 110) of the present embodiment is, for example, the graphene-containing carbonic member / ceramics joint (insulated substrate 20) described in the first embodiment. ), It can be manufactured by joining a copper plate to the surface of the carbon plate 21.
Alternatively, when the ceramic plate 25 and the carbon plate 21 are joined to produce a graphene-containing carbonaceous member / ceramics joint (insulating substrate 20), the carbon plate 21 and the copper plate may be joined at the same time.
In either case, the carbon plate 21 and the copper plate are joined by laminating the copper plate on the surface of the carbon plate 21 via a bonding material and heating while pressurizing in the stacking direction.
　このとき、接合材としては、ＡｇとＣｕと活性金属（本実施形態ではＴｉ）を含有するものを使用する。なお、接合材は、ペースト状であってもよいし、箔であってもよい。また、例えばＣｕ－Ａｇ合金と活性金属とを積層したものであってもよい。
　また、加熱温度は７９０℃以上９００℃以下の範囲内とすることが好ましい。加熱温度での保持時間は２０分以上１８０分以下の範囲内とすることが好ましい。加圧圧力は０．１ＭＰａ以上３．５ＭＰａ以下の範囲内とすることが好ましい。また、雰囲気は減圧雰囲気や窒素ガス雰囲気などの非酸化雰囲気とされていることが好ましい。 At this time, as the bonding material, a material containing Ag, Cu, and an active metal (Ti in this embodiment) is used. The bonding material may be in the form of a paste or in the form of a foil. Further, for example, a Cu—Ag alloy and an active metal may be laminated.
The heating temperature is preferably in the range of 790 ° C. or higher and 900 ° C. or lower. The holding time at the heating temperature is preferably in the range of 20 minutes or more and 180 minutes or less. The pressurizing pressure is preferably in the range of 0.1 MPa or more and 3.5 MPa or less. Further, the atmosphere is preferably a non-oxidizing atmosphere such as a reduced pressure atmosphere or a nitrogen gas atmosphere.
　そして、上述のように、炭素板２１に銅板を接合する際に、接合材に含まれる活性金属（本実施形態ではＴｉ）が酸素及び炭素と反応することで、炭素板２１の接合面に活性金属化合物層１４２が形成される。
　さらに、接合材に含まれるＣｕとＡｇが反応することで、銅板と活性金属化合物層１４２の間に合金層１４３が形成される。 Then, as described above, when the copper plate is bonded to the carbon plate 21, the active metal (Ti in this embodiment) reacts with oxygen and carbon to act on the bonding surface of the carbon plate 21. The metal compound layer 142 is formed.
Further, the reaction between Cu and Ag contained in the bonding material forms an alloy layer 143 between the copper plate and the active metal compound layer 142.
　以上のような構成とされた本実施形態の銅／グラフェン含有炭素質部材／セラミックス接合体（絶縁回路基板１１０）によれば、第１の実施形態であるグラフェン含有炭素質部材／セラミックス接合体（絶縁基板２０）の炭素板２１と回路層１１２および金属層１１３とが接合されているので、冷熱サイクル信頼性に優れることになる。また、回路層１１２および金属層１１３によって炭素板２１が保護され、炭素板２１におけるひび割れの発生を抑制することができる。特に、本実施形態では、回路層１１２および金属層１１３の大きさが炭素板２１と同等以上とされているので、炭素板２１におけるひび割れの発生をさらに抑制することができる。 According to the copper / graphene-containing carbonaceous member / ceramics joint (insulated circuit board 110) of the present embodiment having the above-described configuration, the graphene-containing carbonaceous member / ceramics joint (insulated circuit board 110) of the first embodiment ( Since the carbon plate 21 of the insulating substrate 20), the circuit layer 112, and the metal layer 113 are bonded to each other, the reliability of the thermal cycle is excellent. Further, the carbon plate 21 is protected by the circuit layer 112 and the metal layer 113, and the occurrence of cracks in the carbon plate 21 can be suppressed. In particular, in the present embodiment, since the size of the circuit layer 112 and the metal layer 113 is equal to or larger than that of the carbon plate 21, the occurrence of cracks in the carbon plate 21 can be further suppressed.
　また、本実施形態において、炭素板２１と回路層１１２および金属層１１３との接合界面において、炭素板２１の接合面に、活性金属化合物層１４２が形成され、活性金属化合物層１４２の厚さｔ１２が０．０５μｍ以上とされているので、活性金属によって炭素板２１の接合面が十分に反応しており、炭素板２１と回路層１１２および金属層１１３とをさらに強固に接合することが可能となる。また、活性金属化合物層１４２の厚さｔ１２が３μｍ以下に制限されているので、冷熱サイクル負荷時に活性金属化合物層１４２にクラックが生じることを抑制でき、冷熱サイクル信頼性を向上させることができる。 Further, in the present embodiment, at the bonding interface between the carbon plate 21, the circuit layer 112, and the metal layer 113, the active metal compound layer 142 is formed on the bonding surface of the carbon plate 21, and the thickness t12 of the active metal compound layer 142. Since the value is 0.05 μm or more, the bonding surface of the carbon plate 21 is sufficiently reacted by the active metal, and the carbon plate 21, the circuit layer 112, and the metal layer 113 can be bonded more firmly. Become. Further, since the thickness t12 of the active metal compound layer 142 is limited to 3 μm or less, it is possible to suppress the occurrence of cracks in the active metal compound layer 142 when loaded with a cold cycle, and it is possible to improve the reliability of the cold cycle.
　さらに、本実施形態において、炭素板２１と回路層１１２および金属層１１３との接合界面において、回路層１１２および金属層１１３と活性金属化合物層１４２の間に、ＡｇとＣｕを含む合金層１４３が形成されており、合金層１４３の厚さが１μｍ以上である場合には、炭素板２１と回路層１１２および金属層１１３との接合強度をさらに向上させることができる。また、合金層１４３の厚さが２０μｍ以下に制限されている場合には、冷熱サイクル負荷時に合金層１４３にクラックが生じることを抑制でき、冷熱サイクル信頼性を向上させることができる。 Further, in the present embodiment, at the bonding interface between the carbon plate 21, the circuit layer 112, and the metal layer 113, an alloy layer 143 containing Ag and Cu is formed between the circuit layer 112, the metal layer 113, and the active metal compound layer 142. When the alloy layer 143 is formed and the thickness of the alloy layer 143 is 1 μm or more, the bonding strength between the carbon plate 21, the circuit layer 112, and the metal layer 113 can be further improved. Further, when the thickness of the alloy layer 143 is limited to 20 μm or less, it is possible to suppress the occurrence of cracks in the alloy layer 143 when a cold cycle load is applied, and it is possible to improve the cold cycle reliability.
　以上、本発明の実施形態について説明したが、本発明はこれに限定されることはなく、その発明の技術的思想を逸脱しない範囲で適宜変更可能である。
　例えば、本実施形態では、絶縁回路基板の回路層に半導体素子（パワー半導体素子）を搭載してパワーモジュールを構成するものとして説明したが、これに限定されることはない。例えば、絶縁回路基板にＬＥＤ素子を搭載してＬＥＤモジュールを構成してもよいし、絶縁回路基板の回路層に熱電素子を搭載して熱電モジュールを構成してもよい。 Although the embodiments of the present invention have been described above, the present invention is not limited to this, and can be appropriately changed without departing from the technical idea of the invention.
For example, in the present embodiment, a semiconductor element (power semiconductor element) is mounted on the circuit layer of the insulated circuit board to form a power module, but the present embodiment is not limited to this. For example, an LED element may be mounted on an insulated circuit board to form an LED module, or a thermoelectric element may be mounted on a circuit layer of an insulated circuit board to form a thermoelectric module.
　また、第１の実施形態では、図１に示すように、絶縁回路基板１０の絶縁層として、本実施形態である絶縁基板２０を適用したものとして説明したが、これに限定されることはなく、本発明のグラフェン含有炭素質部材／セラミックス接合体の使用方法に特に制限はない。
　さらに、第１の実施形態では、絶縁基板２０に接合する金属板として銅板を例に挙げて説明したが、これに限定されることはなく、アルミニウム板等の他の金属板であってもよい。 Further, in the first embodiment, as shown in FIG. 1, it has been described that the insulating substrate 20 of the present embodiment is applied as the insulating layer of the insulating circuit board 10, but the present invention is not limited to this. The method of using the graphene-containing carbonaceous member / ceramic joint of the present invention is not particularly limited.
Further, in the first embodiment, the copper plate has been described as an example of the metal plate to be bonded to the insulating substrate 20, but the present invention is not limited to this, and other metal plates such as an aluminum plate may be used. ..
　本発明の有効性を確認するために行った確認実験について説明する。 The confirmation experiment conducted to confirm the effectiveness of the present invention will be described.
　（実施例１）
　本実施形態で開示したように、扁平形状の黒鉛粒子とグラフェン集合体を所定の配合比で配合して混合し、加圧加熱して成形することにより、扁平形状の黒鉛粒子が、そのベーサル面が折り重なるようにグラフェン集合体をバインダーとして積層された構造の成形体を得た。得られた成形体を切り出して、グラフェン含有炭素質部材となる炭素板（４０ｍｍ×４０ｍｍ×厚さ１．５ｍｍ）を得た。 (Example 1)
As disclosed in the present embodiment, the flat graphite particles and the graphene aggregate are mixed at a predetermined blending ratio, mixed, and heated by pressurization to form the flat graphite particles on the basal surface thereof. A molded body having a structure in which graphene aggregates were laminated as a binder was obtained so as to be folded over. The obtained molded product was cut out to obtain a carbon plate (40 mm × 40 mm × thickness 1.5 mm) as a graphene-containing carbonaceous member.
　表１に示すセラミックス板（４０ｍｍ×４０ｍｍ×厚さ０．３２ｍｍ）の両面に、Ａｇ－２８ｍａｓｓ％Ｃｕ－３ｍａｓｓ％Ｔｉからなる組成の接合材（厚さ２０μｍ）を介して、上述の炭素板を積層し、表１に示す条件で、炭素板とセラミックス板とを接合した。
　そして、炭素板とセラミックス板との接合界面を観察し、活性金属窒化物層の厚さ、あるいは活性金属化合物層の厚さを確認した。 The above-mentioned carbon plate is placed on both sides of the ceramic plate (40 mm × 40 mm × thickness 0.32 mm) shown in Table 1 via a bonding material (thickness 20 μm) having a composition of Ag-28 mass% Cu-3 mass% Ti. After laminating, the carbon plate and the ceramic plate were joined under the conditions shown in Table 1.
Then, the bonding interface between the carbon plate and the ceramic plate was observed, and the thickness of the active metal nitride layer or the thickness of the active metal compound layer was confirmed.
　具体的には、グラフェン含有炭素質部材／セラミックス接合体の中央部から観察試料を採取し、接合界面を走査型透過電子顕微鏡（ＦＥＩ社製ＴｉｔａｎＣｈｅｍｉＳＴＥＭ（ＥＤＳ検出器付き））を用いて、倍率４００００倍、加速電圧２００ｋＶの条件で観察を行い、エネルギー分散型Ｘ線分析法（サーモサイエンティフィック社製ＮＳＳ７）を用いてマッピングを行い、活性金属窒化物層の場合は活性金属とＮが重なる領域の面積、活性金属化合物層の場合は、活性金属が存在する領域の面積を測定し、測定視野（縦：（２．３μｍ×横：３μｍ）の幅の寸法で除した値を求め、５視野の平均値を活性金属窒化物層あるいは活性金属化合物層の厚さとした。 Specifically, an observation sample is taken from the central part of the graphene-containing carbonaceous member / ceramics junction, and the junction interface is measured using a scanning transmission electron microscope (FEI TitanChemiSTEM (with EDS detector)) at a magnification of 40,000. Observation is performed under the condition of double acceleration voltage of 200 kV, mapping is performed using energy dispersive X-ray analysis method (NSS7 manufactured by Thermo Scientific Co., Ltd.), and in the case of an active metal nitride layer, the region where the active metal and N overlap. In the case of the active metal compound layer, the area of the region where the active metal exists is measured, and the value divided by the width of the measurement field (length: (2.3 μm × width: 3 μm)) is obtained. Was taken as the thickness of the active metal nitride layer or the active metal compound layer.
　また、合金層の厚さについては、グラフェン含有炭素質部材／セラミックス接合体の接合界面付近の断面観察試料を採取し、ＥＰＭＡ（日本電子株式会社製ＪＸＡ－８５３０Ｆ、加速電圧：１５ｋＶ、スポット径：１μｍ以下）を用いてＥＰＭＡマッピングを得て、Ａｇを３０ｍａｓｓ％以上７０ｍａｓｓ％以下の範囲内、Ｃｕを１５ｍａｓｓ％以上４５ｍａｓｓ％以下の領域を合金層と見なしてその面積を測定し、測定視野（縦：９０μｍ×横：１２０μｍ）の幅の寸法で除した値を求め、５視野の平均値を合金層の厚さとした。測定箇所としては絶縁回路基板の中心点の領域と、その点を中心とする２０ｍｍ×２０ｍｍの四角形の４つの頂点の領域の合計５点を観察した。 Regarding the thickness of the alloy layer, a cross-sectional observation sample near the junction interface of the graphene-containing carbonaceous member / ceramics junction was collected, and EPMA (JXA-8530F manufactured by JEOL Ltd., acceleration voltage: 15 kV, spot diameter: EPMA mapping was obtained using (1 μm or less), and the area of Ag within the range of 30 mass% or more and 70 mass% or less and Cu within the range of 15 mass% or more and 45 mass% or less was regarded as an alloy layer, and the area was measured. The value obtained by dividing by the width dimension of (: 90 μm × width: 120 μm) was obtained, and the average value of the five visual fields was taken as the thickness of the alloy layer. As measurement points, a total of 5 points were observed, which are the region of the center point of the insulated circuit board and the region of four vertices of a 20 mm × 20 mm quadrangle centered on that point.
　また、得られた接合体に対して、－４０℃×５分←→１５０℃×５分の冷熱サイクルを２０００サイクル負荷した。その後、炭素板と銅板との界面の接合率について超音波探傷装置（株式会社日立パワーソリューションズ製ＦｉｎｅＳＡＴ２００）を用いて評価し、以下の式から算出した。ここで、初期接合面積とは、接合前における接合すべき面積とした。超音波探傷像を二値化処理した画像において剥離は接合部内の白色部で示されることから、この白色部の面積を剥離面積とした。
　（接合率）＝｛（初期接合面積）－（非接合部面積）｝／（初期接合面積）×１００ Further, the obtained conjugate was subjected to 2000 cycles of cooling and heating at −40 ° C. × 5 minutes ← → 150 ° C. × 5 minutes. Then, the bonding ratio at the interface between the carbon plate and the copper plate was evaluated using an ultrasonic flaw detector (FineSAT200 manufactured by Hitachi Power Solutions, Ltd.) and calculated from the following formula. Here, the initial joining area is the area to be joined before joining. In the image obtained by binarizing the ultrasonic flaw detection image, the peeling is shown by the white part in the joint, and the area of this white part is defined as the peeling area.
(Joining ratio) = {(Initial joining area)-(Non-joining area)} / (Initial joining area) x 100
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　活性金属窒化物層の厚さが２．２０μｍ、活性金属化合物層の厚さが３．３０μｍである比較例１においては、冷熱サイクル試験後の接合率が７５％と低くなった。
　活性金属窒化物層の厚さが０．０３μｍ、活性金属化合物層の厚さが０．０３μｍである比較例２においては、冷熱サイクル試験後の接合率が７２％と低くなった。 In Comparative Example 1 in which the thickness of the active metal nitride layer was 2.20 μm and the thickness of the active metal compound layer was 3.30 μm, the bonding ratio after the thermal cycle test was as low as 75%.
In Comparative Example 2 in which the thickness of the active metal nitride layer was 0.03 μm and the thickness of the active metal compound layer was 0.03 μm, the bonding ratio after the thermal cycle test was as low as 72%.
　これに対して、活性金属窒化物層の厚さが０．０５μｍ以上２μｍ以下の範囲内とされた本発明例１－１０においては、冷熱サイクル試験後の接合率が８０％以上であり、冷熱サイクル信頼性に優れていた。 On the other hand, in Example 1-10 of the present invention in which the thickness of the active metal nitride layer was in the range of 0.05 μm or more and 2 μm or less, the bonding ratio after the thermal cycle test was 80% or more, and the cold heat was obtained. It had excellent cycle reliability.
　（実施例２）
　上述した本発明例３、４、６、１０のグラフェン含有炭素質部材／セラミックス接合体を準備し、炭素板の表面に、Ａｇ－２８ｍａｓｓ％Ｃｕ－３ｍａｓｓ％Ｔｉからなる組成の接合材（厚さ２０μｍ）を介して、無酸素銅の圧延板からなる銅板（４０ｍｍ×４０ｍｍ×厚さ０．８ｍｍ）を積層し、表２に示す条件で、炭素板と銅板とを接合し、銅／グラフェン含有炭素質部材／セラミックス接合体を得た。
　そして、実施例１と同様に、炭素板と銅板との接合界面を観察し、活性金属化合物層の厚さを確認した。 (Example 2)
The graphene-containing carbonaceous member / ceramics joints of Examples 3, 4, 6 and 10 of the present invention described above were prepared, and a bonding material having a composition of Ag-28 mass% Cu-3 mass% Ti was prepared on the surface of the carbon plate (thickness). A copper plate (40 mm × 40 mm × thickness 0.8 mm) made of an oxygen-free copper rolled plate is laminated via 20 μm), and the carbon plate and the copper plate are joined under the conditions shown in Table 2 to contain copper / graphene. A carbonaceous member / ceramics joint was obtained.
Then, in the same manner as in Example 1, the bonding interface between the carbon plate and the copper plate was observed, and the thickness of the active metal compound layer was confirmed.
　また、炭素板（グラフェン含有炭素質部材）におけるひび割れをマイクロスコープ（キーエンス社製デジタルマイクロスコープVHX－７０００）による観察によって評価した。銅／グラフェン含有炭素質部材／セラミックス接合体の側面から、セラミックス板の両面にそれぞれ接合された炭素板が視野に入る倍率で観察し、長さが炭素板の厚さの２／３以上となるひび割れが１５本以内の場合を「〇」、１５本超えの場合を「×」と評価した。なお、ひび割れの長さは、ひび割れに沿った長さとし、途中で分岐した場合には最長の長さをひび割れとした。 In addition, cracks in the carbon plate (graphene-containing carbonaceous member) were evaluated by observing with a microscope (Digital Microscope VHX-7000 manufactured by KEYENCE CORPORATION). From the side surface of the copper / graphene-containing carbonaceous member / ceramics joint, observe the carbon plates bonded to both sides of the ceramic plate at a magnification that allows them to be seen, and the length is 2/3 or more of the thickness of the carbon plate. The case where the number of cracks was 15 or less was evaluated as "○", and the case where the number of cracks exceeded 15 was evaluated as "x". The length of the crack was defined as the length along the crack, and the longest length was defined as the crack when branched in the middle.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明例３、４、６、１０のグラフェン含有炭素質部材／セラミックス接合体に銅板を接合して形成した本発明例１３、１４、１６、２０の銅／グラフェン含有炭素質部材／セラミックス接合体においては、いずれも炭素板（グラフェン含有炭素質部材）におけるひび割れの発生を抑制することができた。 Copper / graphene-containing carbonaceous member / ceramic joint of Invention Examples 13, 14, 16 and 20 formed by joining a copper plate to the graphene-containing carbonaceous member / ceramic joint of Invention Examples 3, 4, 6 and 10. In each case, the occurrence of cracks in the carbon plate (graphene-containing carbonaceous member) could be suppressed.
　（実施例３）
　実施例１と同様の手順により、グラフェン含有炭素質部材となる炭素板（４０ｍｍ×４０ｍｍ×厚さ１．５ｍｍ）を得た。
　表３に示すセラミックス板（４０ｍｍ×４０ｍｍ×厚さ０．３２ｍｍ）の両面に、Ａｇ－２８ｍａｓｓ％Ｃｕ－３ｍａｓｓ％Ｔｉからなる組成の接合材（厚さ２０μｍ）を介して、上述の炭素板を積層した。また、炭素板の表面に、Ａｇ－２８ｍａｓｓ％Ｃｕ－３ｍａｓｓ％Ｔｉからなる組成の接合材（厚さ２０μｍ）を介して、無酸素銅の圧延板からなる銅板（４０ｍｍ×４０ｍｍ×厚さ０．８ｍｍ）を積層した。そして、表３に示す条件で、セラミックス板と炭素板と銅板とを同時接合し、銅／グラフェン含有炭素質部材／セラミックス接合体を得た。 (Example 3)
A carbon plate (40 mm × 40 mm × thickness 1.5 mm) to be a graphene-containing carbonaceous member was obtained by the same procedure as in Example 1.
The above-mentioned carbon plate is placed on both sides of the ceramic plate (40 mm × 40 mm × thickness 0.32 mm) shown in Table 3 via a bonding material (thickness 20 μm) having a composition of Ag-28 mass% Cu-3 mass% Ti. Laminated. Further, a copper plate (40 mm × 40 mm × thickness 0.) Made of rolled oxygen-free copper is interposed on the surface of the carbon plate via a bonding material (thickness 20 μm) having a composition of Ag-28 mass% Cu-3 mass% Ti. 8 mm) was laminated. Then, under the conditions shown in Table 3, the ceramic plate, the carbon plate, and the copper plate were simultaneously bonded to obtain a copper / graphene-containing carbonaceous member / ceramic bonded body.
　そして、実施例１と同様に、炭素板とセラミックス板との接合界面を観察し、活性金属窒化物層の厚さ、あるいは活性金属化合物層の厚さを確認した。また、炭素板と銅板との接合界面を観察し、活性金属化合物層の厚さを確認した。
　さらに、実施例２と同様に、炭素板（グラフェン含有炭素質部材）におけるひび割れをマイクロスコープによる観察によって評価した。 Then, in the same manner as in Example 1, the bonding interface between the carbon plate and the ceramic plate was observed, and the thickness of the active metal nitride layer or the thickness of the active metal compound layer was confirmed. In addition, the bonding interface between the carbon plate and the copper plate was observed to confirm the thickness of the active metal compound layer.
Further, as in Example 2, cracks in the carbon plate (graphene-containing carbonaceous member) were evaluated by observation with a microscope.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　セラミックス板と炭素板と銅板とを同時接合した本発明例２１－２４の銅／グラフェン含有炭素質部材／セラミックス接合体においても、いずれも炭素板（グラフェン含有炭素質部材）におけるひび割れの発生を抑制することができた。 In the copper / graphene-containing carbonaceous member / ceramics joint of Example 21-24 of the present invention in which the ceramic plate, the carbon plate, and the copper plate are simultaneously bonded, the occurrence of cracks in the carbon plate (graphene-containing carbonaceous member) is suppressed. We were able to.
　以上の実験結果から、本発明例によれば、セラミックス部材とグラフェン集合体を含有するグラフェン含有炭素質部材とが強固に接合されており、冷熱サイクル負荷時においても剥離が生じることがなく、冷熱サイクル信頼性に優れたグラフェン含有炭素質部材／セラミックス接合体、および、銅／グラフェン含有炭素質部材／セラミックス接合体を提供可能であることが確認された。 From the above experimental results, according to the example of the present invention, the ceramic member and the graphene-containing carbonaceous member containing the graphene aggregate are firmly bonded to each other, and peeling does not occur even under a cold cycle load. It was confirmed that it is possible to provide a graphene-containing carbonaceous member / ceramics joint having excellent cycle reliability and a copper / graphene-containing carbonaceous member / ceramics joint.
産業の利用可能性Industrial availability
　セラミックス部材とグラフェン集合体を含有するグラフェン含有炭素質部材とが強固に接合されており、冷熱サイクル負荷時においても剥離が生じることがなく、冷熱サイクル信頼性に優れたグラフェン含有炭素質部材／セラミックス接合体、および、このグラフェン含有炭素質部材／セラミックス接合体に銅又は銅合金からなる銅部材が接合された銅／グラフェン含有炭素質部材／セラミックス接合体を提供することが可能となる。 The ceramics member and the graphene-containing carbonaceous member containing the graphene aggregate are firmly bonded to each other, and peeling does not occur even under a cold cycle load, and the graphene-containing carbonaceous member / ceramics having excellent thermal cycle reliability. It is possible to provide a joint body and a copper / graphene-containing carbonaceous member / ceramics joint body in which a copper member made of copper or a copper alloy is bonded to the graphene-containing carbonaceous member / ceramics joint body.
　　２０　絶縁基板（グラフェン含有炭素質部材／セラミックス接合体）
　　２１　炭素板（グラフェン含有炭素質部材）
　　２５　セラミックス板（セラミックス部材）
　　４０　接合界面
　　４１　活性金属窒化物層
　　４２　活性金属化合物層
　　４３　合金層
　　１１０　絶縁回路基板
　　１１２　回路層（銅部材）
　　１１３　金属層（銅部材）
　　１４０　接合界面
　　１４２　活性金属化合物層
　　１４３　合金層 20 Insulated substrate (graphene-containing carbonaceous member / ceramic joint)
21 Carbon plate (graphene-containing carbonaceous material)
25 Ceramic plate (ceramic member)
40 Bonding interface 41 Active metal nitride layer 42 Active metal compound layer 43 Alloy layer 110 Insulated circuit board 112 Circuit layer (copper member)
113 Metal layer (copper member)
140 Bonding interface 142 Active metal compound layer 143 Alloy layer

Claims (7)

  1. 　グラフェン集合体を含有するグラフェン含有炭素質部材と、窒素を含むセラミックスからなるセラミックス部材とが接合された構造のグラフェン含有炭素質部材／セラミックス接合体であって、
    　前記グラフェン含有炭素質部材と前記セラミックス部材との接合界面において、前記セラミックス部材の接合面に活性金属窒化物層が形成されており、この活性金属窒化物層の厚さが０．０５μｍ以上２μｍ以下の範囲内とされていることを特徴とするグラフェン含有炭素質部材／セラミックス接合体。     A graphene-containing carbonaceous member / ceramics joint having a structure in which a graphene-containing carbonaceous member containing a graphene aggregate and a ceramics member made of nitrogen-containing ceramics are joined.
    At the bonding interface between the graphene-containing carbonaceous member and the ceramic member, an active metal nitride layer is formed on the bonding surface of the ceramic member, and the thickness of the active metal nitride layer is 0.05 μm or more and 2 μm or less. A graphene-containing carbonaceous member / ceramics joint characterized by being within the range of.
  2. 　前記グラフェン含有炭素質部材と前記セラミックス部材との接合界面において、前記グラフェン含有炭素質部材の接合面に、活性金属化合物層が形成されており、前記活性金属化合物層の厚さが０．０５μｍ以上３μｍ以下の範囲内とされていることを特徴とする請求項１に記載のグラフェン含有炭素質部材／セラミックス接合体。 At the bonding interface between the graphene-containing carbonaceous member and the ceramic member, an active metal compound layer is formed on the bonding surface of the graphene-containing carbonaceous member, and the thickness of the active metal compound layer is 0.05 μm or more. The graphene-containing carbonaceous member / ceramic joint according to claim 1, wherein the graphene is within a range of 3 μm or less.
  3. 　前記グラフェン含有炭素質部材と前記セラミックス部材との接合界面において、前記活性金属窒化物層と前記活性金属化合物層の間に、ＡｇとＣｕを含む合金層が形成されており、前記合金層の厚さが１μｍ以上２０μｍ以下の範囲内とされていることを特徴とする請求項２に記載のグラフェン含有炭素質部材／セラミックス接合体。 At the junction interface between the graphene-containing carbonaceous member and the ceramic member, an alloy layer containing Ag and Cu is formed between the active metal nitride layer and the active metal compound layer, and the thickness of the alloy layer The graphene-containing carbonaceous member / ceramics joint according to claim 2, wherein the thickness is within the range of 1 μm or more and 20 μm or less.
  4. 　前記グラフェン含有炭素質部材は、単層又は多層のグラフェンが堆積してなるグラフェン集合体と扁平形状の黒鉛粒子とを含み、扁平形状の前記黒鉛粒子が、そのベーサル面が折り重なるように前記グラフェン集合体をバインダーとして積層され、扁平形状の前記黒鉛粒子のベーサル面が一方向に向けて配向した構造とされていることを特徴とする請求項１から請求項３のいずれか一項に記載のグラフェン含有炭素質部材／セラミックス接合体。 The graphene-containing carbonaceous member includes a graphene aggregate formed by depositing single-layer or multi-layer graphene and flat graphite particles, and the graphene aggregates such that the flat graphite particles fold their basal surfaces. The graphene according to any one of claims 1 to 3, wherein the graphene is laminated with the body as a binder, and the basal surface of the flat graphite particles is oriented in one direction. Containing carbonaceous member / ceramics joint.
  5. 　銅又は銅合金からなる銅部材と、グラフェン集合体を含有するグラフェン含有炭素質部材と、窒素を含むセラミックスからなるセラミックス部材とが接合された構造の銅／グラフェン含有炭素質部材／セラミックス接合体であって、
    　請求項１から請求項４のいずれか一項に記載のグラフェン含有炭素質部材／セラミックス接合体の前記グラフェン含有炭素質部材と前記銅部材とが接合されていることを特徴とする銅／グラフェン含有炭素質部材／セラミックス接合体。     A copper / graphene-containing carbonaceous member / ceramics joint having a structure in which a copper member made of copper or a copper alloy, a graphene-containing carbonaceous member containing a graphene aggregate, and a ceramics member made of nitrogen-containing ceramics are joined. There,
    A copper / graphene-containing member of the graphene-containing carbonaceous member / ceramics joint according to any one of claims 1 to 4, wherein the graphene-containing carbonaceous member and the copper member are bonded to each other. Carbonaceous member / ceramic joint.
  6. 　前記グラフェン含有炭素質部材と前記銅部材との接合界面において、前記グラフェン含有炭素質部材の接合面に、活性金属化合物層が形成されており、前記活性金属化合物層の厚さが０．０５μｍ以上３μｍ以下の範囲内とされていることを特徴とする請求項５に記載の銅／グラフェン含有炭素質部材／セラミックス接合体。 At the joint interface between the graphene-containing carbonaceous member and the copper member, an active metal compound layer is formed on the joint surface of the graphene-containing carbonaceous member, and the thickness of the active metal compound layer is 0.05 μm or more. The copper / graphene-containing carbonaceous member / ceramics joint according to claim 5, wherein the range is 3 μm or less.
  7. 　前記グラフェン含有炭素質部材と前記銅部材との接合界面において、前記銅部材と前記活性金属化合物層の間に、ＡｇとＣｕを含む合金層が形成されており、前記合金層の厚さが１μｍ以上２０μｍ以下の範囲内とされていることを特徴とする請求項６に記載の銅／グラフェン含有炭素質部材／セラミックス接合体。 At the bonding interface between the graphene-containing carbonaceous member and the copper member, an alloy layer containing Ag and Cu is formed between the copper member and the active metal compound layer, and the thickness of the alloy layer is 1 μm. The copper / graphene-containing carbonaceous member / ceramics joint according to claim 6, wherein the range is 20 μm or less.
PCT/JP2020/040652 2019-11-05 2020-10-29 Graphene-containing carbonaceous member/ceramic assembly and copper/graphene-containing carbonaceous member/ceramic assembly WO2021090759A1 (en)

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