WO2015141839A1 - 積層体及び、その製造方法 - Google Patents

積層体及び、その製造方法 Download PDF

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WO2015141839A1
WO2015141839A1 PCT/JP2015/058555 JP2015058555W WO2015141839A1 WO 2015141839 A1 WO2015141839 A1 WO 2015141839A1 JP 2015058555 W JP2015058555 W JP 2015058555W WO 2015141839 A1 WO2015141839 A1 WO 2015141839A1
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mass
copper alloy
nitride
concentration
alloy layer
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PCT/JP2015/058555
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English (en)
French (fr)
Japanese (ja)
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高村　博
矢作　政隆
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Jx日鉱日石金属株式会社
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/01—Alloys based on copper with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent

Definitions

  • the present invention relates to a laminate formed by laminating a metal layer containing copper and a ceramic substrate, and a method for producing the same, and in particular, to ensure a required bonding strength between the metal layer and the ceramic substrate. .
  • the power device fixes a laminated body in which a metal layer made of copper or the like that functions as a heat sink is bonded to at least one surface, usually both surfaces of a ceramic substrate, on a base plate (heat radiating plate).
  • the power semiconductor element and its control circuit are formed on the laminate.
  • alumina (Al 2 O 3 ) that can be directly bonded to the metal layer is generally used as the material of the ceramic substrate to be bonded to the metal layer made of copper or the like.
  • a nitride ceramic substrate such as aluminum nitride (AlN) having excellent thermal conductivity as described in Patent Documents 1 to 3 and the like.
  • a thin film bonding layer made of Ti or the like is formed in advance on the surface of a Cu conductor layer (metal layer) or an aluminum nitride substrate by vapor deposition, sputtering, plating, or the like. It is manufactured by bonding an aluminum nitride substrate or a copper layer via a bonding layer.
  • the above-mentioned bonding layer formed between the aluminum nitride substrate having poor wettability with the metal and the Cu conductor layer effectively bonds the aluminum nitride substrate and the Cu conductor layer.
  • the heat generated by the semiconductor element or the like can be effectively dissipated by the aluminum nitride substrate that has better thermal conductivity than alumina that has been used for a long time.
  • JP-A 64-84648 Japanese Patent Laid-Open No. 5-18477 JP-A-5-218229
  • An object of the present invention is to solve such a problem.
  • the object of the present invention is to bond a metal layer mainly made of copper and a nitride ceramic substrate sufficiently firmly, and It is providing the laminated body which can reduce a manufacturing man-hour, and its manufacturing method.
  • the inventor has found that it is difficult to directly bond a nitride ceramic substrate such as aluminum nitride and a Cu metal layer by comparison with alumina, and the Ti nitride between the aluminum nitride substrate and the Cu metal layer as described above.
  • a bonding layer such as a copper alloy layer
  • the Cu metal layer a copper alloy layer containing a predetermined element, such a copper alloy layer and nitride ceramics It has been found that the substrate can be effectively bonded without the intervention of the bonding layer.
  • the laminate of the present invention has a nitride ceramic substrate and a copper alloy layer laminated on at least one surface of the nitride ceramic substrate, and the copper alloy layer includes: Si, Mn, Ni, Ti, Al, Ce, Ga, In, P, As, Sb, Nb, Cr, Fe, Li, Be, Mg, Zn, Ge, Co, Mo, B, C, Sn, Y, It contains at least one element selected from Pr, Nd, Sm, Zr, Bi, V, W, Tl, Ca, Sr, Ba, and Hf.
  • the copper alloy layer is made of a copper alloy plate or a copper alloy foil.
  • it is preferably 0.0001% by mass or more, preferably 0.001% by mass or more, and 0.01% by mass or more.
  • it is 0.5% by mass or more, preferably 99.5% by mass or less, preferably 95% by mass or less, preferably 90% by mass or less, and 80% by mass or less.
  • 70 quality % Preferably less, and preferably preferably not more than 50 mass%, 40 mass% or less.
  • the copper alloy layer contains at least one element selected from Si, Mn, Ni, Ti, Zr, Ce, and Hf.
  • the Si concentration is 0.0001 to 3.0 mass%
  • Mn the Mn concentration is 0.0001 to 95 mass%
  • Ni the Ni concentration is 0.0001 to 95% by mass
  • Ti the Ti concentration is 0.0001 to 8.5% by mass
  • Zr the Zr concentration is 0. 0.0001 to 60% by mass in the case of containing Ce, and 0.0001 to 60% by mass of Hf in the case of containing Hf. preferable.
  • the copper alloy layer contains two or more elements selected from Si, Mn, Ni, Ti, Zr, Ce, and Hf, select from the Si, Mn, Ni, Ti, Zr, Ce, and Hf
  • the total concentration of the two or more kinds of elements is preferably 0.0001 to 99.5% by mass in order to make the bonding strength between the nitride ceramic substrate and the copper alloy layer more appropriate. It is preferably from ⁇ 95% by mass, preferably from 0.0005 to 70% by mass, and preferably from 0.0005 to 50% by mass.
  • the nitride ceramic substrate is mainly composed of aluminum nitride, silicon nitride, titanium nitride, boron nitride, indium nitride or gallium nitride, or a composite material of titanium carbide and titanium nitride, or It is preferable that the main component is a composite material of boron nitride and silicon carbide.
  • the nitride ceramic substrate when the nitride ceramic substrate is mainly composed of aluminum nitride, the nitride ceramic substrate further contains one or more elements selected from the group consisting of Ca, Y, and O, and Ca
  • the Ca concentration is 0.0001 to 3% by mass.
  • the Y concentration is 0.0001 to 10% by mass. It may be 0001 to 20% by mass.
  • the O-containing concentration of the nitride ceramic substrate is preferably 0.0001 to 20% by mass.
  • the thickness of the copper alloy layer can be 1 ⁇ m to 7000 ⁇ m
  • the thickness of the nitride ceramic substrate can be 1 ⁇ m to 7000 ⁇ m.
  • the peel strength between the copper alloy layer and the nitride ceramic substrate is preferably 15 kN / m or more.
  • the heat dissipating body of the present invention has any one of the above laminated bodies.
  • the power device of the present invention has any one of the above laminates.
  • the element of the present invention has any one of the above laminates.
  • the electronic component of the present invention has any one of the above laminates.
  • the electronic device of the present invention has any one of the above-described laminates.
  • the vehicle of this invention has said power device or said element, or said electronic component.
  • the copper alloy layer is made of Si, Mn, Ni, Ti, Al, Ce, Ga, In, P, As, Sb, Nb, Cr, Fe, Li, Be, Mg, Zn, Ge, Co, Mo, B, C, Sn, Y, Pr, Nd, Sm, Zr, Bi, V, W, It contains at least one element selected from Tl, Ca, Sr, Ba, and Hf, and the copper alloy layer is laminated on at least one surface of the nitride ceramic substrate by thermocompression bonding.
  • it is preferably 0.0001% by mass or more, preferably 0.001% by mass or more, and 0.01% by mass or more.
  • it is 0.5% by mass or more, preferably 99.5% by mass or less, preferably 95% by mass or less, preferably 90% by mass or less, and 80% by mass or less.
  • 70 quality % Preferably less, and preferably preferably not more than 50 mass%, 40 mass% or less.
  • the copper alloy layer preferably contains at least one element selected from Si, Mn, Ni, Ti, Zr, Ce, and Hf, and in this case, the copper alloy layer
  • Si is contained
  • Mn is contained
  • Mn is 0.0001 to 95% by mass
  • Ni is contained
  • the Ni concentration is 0.0001 to 95% by mass
  • Ti is contained
  • Zr is contained
  • the Zr concentration is 0.0001 to 8.0% by mass.
  • Ce concentration is preferably 0.0001 to 60% by mass
  • Hf concentration is preferably 0.0001 to 20% by mass.
  • the copper alloy layer contains two or more elements selected from Si, Mn, Ni, Ti, Zr, Ce, and Hf, select from the Si, Mn, Ni, Ti, Zr, Ce, and Hf
  • the total concentration of the two or more kinds of elements is preferably 0.0001 to 99.5% by mass in order to make the bonding strength between the nitride ceramic substrate and the copper alloy layer more appropriate. It is preferably from ⁇ 95% by mass, preferably from 0.0005 to 70% by mass, and preferably from 0.0005 to 50% by mass.
  • the manufacturing method of the present invention when the copper alloy layer and the nitride ceramic substrate are bonded, 0.6 N / mm 2 to 1 at a temperature of 800 to 1000 ° C. in a nitrogen or argon atmosphere or in a vacuum. It is preferable to join the copper alloy layer and the nitride ceramic substrate by applying a pressure of 5 N / mm 2 .
  • the laminated nitride ceramic substrate and the copper alloy layer laminated on the surface of the nitride ceramic substrate are directly joined, or a roughened layer, a heat-resistant layer, and a rust-proof layer.
  • bonding is indirectly performed through only one or more layers selected from the group consisting of a chromate treatment layer and a silane coupling treatment layer. Therefore, a bonding layer such as Ti does not have to exist between the copper alloy layer and the nitride ceramic substrate.
  • direct bonding means that the composition of the copper alloy layer itself or the surface of the copper alloy layer made of an oxide thereof, and the composition of the nitride ceramic substrate itself or the substrate surface made of an oxide thereof are different from each other. It means that they are fixed to each other in contact with each other without intervening layers composed of the composition. In other words, this means that there may be an oxide film between the copper alloy layers and the nitride ceramic substrate that are laminated to each other, but there is no other layer having a composition other than those.
  • a rust preventive layer made of an organic material or the like may be formed on the surface of the copper alloy layer, for example, at least on the nitride ceramic substrate side of the copper alloy layer so as not to have a large adverse effect on the bonding strength.
  • One or more layers selected from the group of a generally used roughening treatment layer, heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may be applied to the surface.
  • the copper alloy layer and the nitride ceramic layer pass through only one or more layers selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. And indirectly joined.
  • the metal layer to be laminated on the nitride ceramic substrate is a copper alloy layer containing the above-described elements, so that the copper alloy layer and the nitride ceramic can be joined with a required strength, Since a process for forming a bonding layer as in the technique is not required, the number of manufacturing steps can be reduced.
  • a laminate according to an embodiment of the present invention includes a nitride ceramic substrate and a copper alloy layer such as a copper alloy foil laminated on at least one surface of the nitride ceramic substrate.
  • a copper alloy layer such as a copper alloy foil laminated on at least one surface of the nitride ceramic substrate.
  • Cu, Si, Mn, Ni, Ti, Al, Ce, Ga, In, P, As, Sb, Nb, Cr, Fe, Li, Be, Mg, Zn, Ge, Co, Mo, B, C , Sn, Y, Pr, Nd, Sm, Zr, Bi, V, W, Tl, Ca, Sr, Ba, and Hf are contained.
  • Cu is a main component in a copper alloy layer.
  • it is preferably 0.0001% by mass or more, preferably 0.001% by mass or more, and 0.01% by mass or more.
  • the copper alloy layer may contain a compound such as nitride or oxide, an inorganic substance, a metal containing an element other than the elements described above, an element other than those described above, and the like.
  • the nitride ceramic substrate means a ceramic substrate containing nitride.
  • the nitride concentration of the nitride ceramic substrate is preferably 50% by mass or more, preferably 60% by mass or more, preferably 70% by mass or more, preferably 80% by mass or more, preferably 90% by mass or more, preferably 95% by mass. That's it.
  • the ceramic substrate may be a sintered body and / or a substrate including a polycrystalline body and / or a single crystal body, and may be a sintered body and / or a polycrystalline body and / or Alternatively, it may be a substrate made of a single crystal, and is a concept including a metal or compound or semiconductor or conductor substrate obtained by vapor phase growth or epitaxial growth.
  • the nitride is N, Si, Mn, Ni, Ti, Al, Ce, Ga, In, P, As, Sb, Nb, Cr, Fe, Li, Be, Mg, Zn, Ge, Co, B , C, Sn, Y, Pr, Nd, Sm, Zr, Bi, V, W, Tl, Ca, B, Sr, Hf and a compound containing one or more elements selected from the group consisting of Ba and Ba Is preferred.
  • the nitride is N, Si, Mn, Ni, Ti, Al, Ce, Ga, In, P, As, Sb, Nb, Cr, Fe, Li, Be, Mg, Zn, Ge, Co, B , C, Sn, Y, Pr, Nd, Sm, Zr, Bi, V, W, Tl, Ca, B, Sr, Hf and a compound composed of one or more elements selected from the group consisting of Ba and Ba Is more preferable.
  • the nitride is more preferably a compound containing N and one or more elements selected from the group consisting of Si, Al, B, Ga, In, and Ti.
  • the nitride is more preferably a compound composed of N and one or more elements selected from the group consisting of Si, Al, B, Ga, In, and Ti.
  • the nitride ceramic substrate is made of aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), titanium nitride (TiN), nitride nitride from the viewpoint of effectively dissipating the semiconductor element and the like by increasing thermal conductivity.
  • Main component is boron (BN), indium nitride (InN) or gallium nitride (GaN), or a composite material of titanium carbide and titanium nitride (TiC-TiN), or a composite material of boron nitride and silicon carbide ( It is preferably made of a material mainly composed of (BN—SiC).
  • the nitride ceramic substrate is made of aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), titanium nitride (TiN), boron nitride (BN), indium nitride (InN), and gallium nitride (GaN). It is preferable to include one or more selected nitrides. Among these, aluminum nitride and silicon nitride are both excellent in thermal conductivity, and aluminum nitride has a low coefficient of thermal expansion, and is preferably used as a ceramic substrate for this type of laminate. Silicon nitride is preferable from the viewpoint of productivity because it has high strength and is difficult to break during manufacturing.
  • the nitride ceramic substrate is mainly composed of aluminum nitride or silicon nitride
  • its concentration in the case of aluminum nitride, the total concentration of nitrogen and aluminum is taken as the concentration of aluminum nitride.
  • the lower limit of the concentration of nitrogen and silicon is the concentration of silicon nitride.
  • the upper limit of the aluminum nitride or silicon nitride concentration is not particularly required, but can be, for example, 100% by mass or less, 99.999% by mass or less, 99.99% by mass or less, or 99.9% by mass or less. .
  • the nitride ceramic substrate mainly made of aluminum nitride may contain one or more elements selected from the group consisting of Ca, Y, and O.
  • the Ca concentration can be 0.0001 to 3% by mass
  • the Y concentration can be 0.0001 to 10% by mass.
  • the O concentration can be, for example, 0.0001 to 20% by mass, preferably 0.005 to 15% by mass, and more preferably 0.01 to 10% by mass.
  • “having A as a main component” means that A is 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more.
  • the concentration of nitride is the sum of the concentration of nitrogen and the concentration of elements other than nitrogen constituting the nitride.
  • the inventor made the copper metal layer into a copper alloy layer by making the copper metal layer a copper alloy layer containing an element that brings about bonding between aluminum nitride and copper, such as titanium described above. It was thought that the element contained included could form a compound with the nitride ceramic substrate and realize the bonding between the copper alloy layer and the nitride ceramic substrate.
  • the same simulation was performed for the interface state between titanium copper alloy (Cu—Ti) containing 3.1% by mass of Ti and aluminum nitride, and the result shown in FIG. 4 was obtained. . From the simulation results shown in FIG. 4, it is considered that TiN is formed by Ti contained in the titanium-copper alloy and N of aluminum nitride, and this effectively works for joining the titanium-copper alloy and aluminum nitride.
  • the inventor examined elements that form a compound (nitride) in combination with nitrogen and can be contained in a copper alloy, and are elements that form a nitride and are dissolved in Cu.
  • elements to be performed Si, Mn, Ni, Ti, Al, Ce, Ga, In, P, As, Sb, Nb, Fe, Li, Be, Mg, Zn, Ge, Cr, Co, B, C, Sn, Mo, Hf, and elements that form nitrides and do not dissolve or hardly dissolve in Cu, but have an elemental phase diagram with Cu (that is, a compound with Cu exists)
  • Elements include Y, Pr, Nd, Sm, Zr, Bi, V, W, Tl, Ca, Sr, and Ba. Therefore, not only Ti but also copper alloys containing these elements are nitride ceramics. Used for copper alloy layers to be bonded to substrates I thought that it is possible.
  • the copper alloy layer bonded to at least one surface of the nitride ceramic substrate is Si, Mn, Ni, Ti, Al, Ce, Ga, In, P, As, Sb, Nb, Cr. , Fe, Li, Be, Mg, Zn, Ge, Co, B, C, Sn, Mo, Y, Pr, Nd, Sm, Zr, Bi, V, W, Tl, Ca, Sr, Ba, Hf It may contain at least one kind of element.
  • it is preferably 0.0001% by mass or more, preferably 0.001% by mass or more, and 0.01% by mass or more.
  • it is 0.5% by mass or more, preferably 99.5% by mass or less, preferably 95% by mass or less, preferably 90% by mass or less, and 80% by mass or less.
  • 70 quality % Preferably less, and preferably preferably not more than 50 mass%, 40 mass% or less.
  • the copper alloy layer is made of Si, Mn, Ni, Ti, Zr, Ce, and Hf.
  • the lower limit value of the Si concentration is preferably 0.0001% by mass, more preferably 0.05% by mass, more preferably 0.1% by mass, more preferably Is 0.2% by mass.
  • the upper limit value of the Si concentration is preferably 3.0% by mass, particularly preferably 2.7% by mass, more preferably 2.4% by mass, and even more preferably 2.0% by mass.
  • the lower limit of the Mn concentration is 0.0001% by mass, more preferably 0.05% by mass, more preferably 0.1% by mass, more preferably 0.2% by mass.
  • the upper limit of the Mn concentration is preferably 95% by mass, more preferably 80% by mass, more preferably 50% by mass, more preferably 40% by mass, and more preferably 30% by mass.
  • the lower limit of the Ni concentration is 0.0001% by mass, more preferably 0.05% by mass, more preferably 0.1% by mass, more preferably 0.2% by mass.
  • the upper limit of the Ni concentration is preferably 95% by mass, more preferably 80% by mass, more preferably 50% by mass, more preferably 40% by mass, and more preferably 30% by mass.
  • the lower limit of the Ti concentration is preferably 0.0001% by mass, more preferably 0.05% by mass, more preferably 0.1% by mass, and more preferably 0.00%. 2% by mass.
  • the upper limit of the Ti concentration is preferably 8.5% by mass, more preferably 8.0% by mass, more preferably 7.7% by mass, and more preferably 7.5% by mass.
  • the Zr concentration can be 0.0001 to 8.0% by mass, preferably 0.01 to 7.0% by mass, more preferably 0.05 to 5%. 0.0% by mass.
  • the Ce concentration can be, for example, 0.0001 to 60% by mass, preferably 0.001 to 50% by mass, more preferably 0.01 to 40% by mass. More preferably, the content is 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass.
  • the Hf concentration can be, for example, 0.0001 to 20% by mass, preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass. More preferably, the content is 0.01 to 8% by mass, and more preferably 0.01 to 5% by mass.
  • the copper alloy layer contains two or more elements selected from Si, Mn, Ni, Ti, Zr, Ce, and Hf, select from the Si, Mn, Ni, Ti, Zr, Ce, and Hf
  • the total concentration of the two or more kinds of elements is preferably 0.0001 to 99.5% by mass in order to make the bonding strength between the nitride ceramic substrate and the copper alloy layer more appropriate. It is preferably from ⁇ 95% by mass, preferably from 0.0005 to 70% by mass, and preferably from 0.0005 to 50% by mass.
  • the composition and oxides of the copper alloy layer and the nitride ceramic substrate, as well as the heat-resistant layer and the rust-proof layer are provided.
  • a Ti-only layer or the like which is different from the chromate treatment layer and the silane coupling treatment layer, may not exist.
  • a process for forming another bonding layer or the like between the copper alloy layer and the nitride ceramic substrate becomes unnecessary, and the number of manufacturing steps can be reduced.
  • equipment, materials, and the like for performing sputtering and the like for forming the bonding layer and the like are unnecessary, and the manufacturing cost can be reduced.
  • the copper alloy layer and the nitride ceramic substrate are not affected between the copper alloy layer and the nitride ceramic substrate so long as the degree of bonding between the copper alloy layer and the nitride ceramic substrate is not greatly affected.
  • Elements from the substrate and / or oxides thereof, as well as a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, a silane coupling-treated layer and the like may be present.
  • one or more layers selected from the group of roughening treatment layer, heat-resistant layer, rust prevention layer, chromate treatment layer, silane coupling treatment layer are present between the copper alloy layer and the nitride ceramic substrate.
  • the thickness of one or more layers selected from the group of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer is 0.7 ⁇ m or less in total, preferably 0.5 ⁇ m or less. can do.
  • one or more layers selected from the group of a roughening treatment layer, a heat resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer exist between the copper alloy layer and the nitride ceramic substrate.
  • the total adhesion amount of one or more layers selected from the group of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer, and the silane coupling treatment layer is 70000 ⁇ g / dm 2 or less, preferably 40000 ⁇ g. / dm 2 or less, preferably 20000 ⁇ g / dm 2 or less, preferably 10000 / dm 2 or less, preferably to 5000 [mu] g / dm 2 or less. If such a layer has such a thickness or adhesion amount, it does not adversely affect the bonding between the copper alloy layer and the nitride ceramic layer.
  • a strong bonding with a nitride ceramic substrate can be realized by including an element capable of forming nitride by removing nitrogen from aluminum nitride in the copper alloy layer.
  • an element capable of forming nitride by removing nitrogen from aluminum nitride in the copper alloy layer Using, for example, aluminum nitride as a reference, Ce, Ti, Zr, and Hf, which have a low Gibbs energy and are stable as a nitride, are considered effective. From this viewpoint, it is preferable that the copper alloy layer contains at least one element selected from Ce, Ti, Zr, and Hf.
  • Such a laminate in which the nitride ceramic substrate and the copper alloy layer are laminated with each other can have a peel strength between the copper alloy layer and the nitride ceramic substrate of 15 kN / m or more. It can be used effectively for devices and the like.
  • the peel strength is preferably 20 kN / m or more, and more preferably 30 kN / m or more.
  • the thickness of the copper alloy layer can be 0.01 ⁇ m to 7000 ⁇ m, or can be 0.1 ⁇ m to 7000 ⁇ m, or can be 1 ⁇ m to 7000 ⁇ m. Can do.
  • the thickness of the copper alloy layer is preferably 5 ⁇ m to 2000 ⁇ m, more preferably 10 ⁇ m to 1500 ⁇ m, more preferably 20 ⁇ m to 1200 ⁇ m, more preferably 50 ⁇ m to 1100 ⁇ m, more preferably 100 ⁇ m to 1050 ⁇ m, preferably Is 200 ⁇ m or more and 1000 ⁇ m or less.
  • the nitride ceramic substrate may have a thickness of 1 ⁇ m to 15000 ⁇ m, 1 ⁇ m to 7000 ⁇ m, preferably 5 ⁇ m to 2000 ⁇ m, more preferably 10 ⁇ m to 1500 ⁇ m, more preferably 20 ⁇ m to 1200 ⁇ m, more preferably The thickness can be 50 ⁇ m or more and 1100 ⁇ m or less, more preferably 100 ⁇ m or more and 1050 ⁇ m or less, and more preferably 200 ⁇ m or more and 1000 ⁇ m or less.
  • the surface roughness Ra of the copper alloy layer at least the bonding surface with the nitride ceramic substrate (that is, the surface of the copper alloy layer laminated on the nitride ceramic substrate).
  • the lower limit of the surface roughness Ra is not particularly preferred, but can be, for example, 0.001 ⁇ m or more, 0.005 ⁇ m or more, 0.007 ⁇ m or more.
  • the surface roughness of the copper alloy layer can be adjusted, for example, by cold rolling while controlling the surface roughness of the rolling roll and / or the oil film equivalent during rolling.
  • the surface roughness Ra of the nitride ceramic substrate at least the bonding surface with the copper alloy layer can be 3.0 ⁇ m or less, preferably Is 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less, more preferably 1.7 ⁇ m or less, and more preferably 1.5 ⁇ m or less.
  • the surface roughness of the nitride ceramic substrate can be adjusted by shot blasting or the like.
  • the heat dissipating body, power device, element, electronic component, and electronic apparatus have the laminate as described above.
  • the radiator is an object having a heat dissipation function, and includes a heat sink, a heat sink, a semiconductor element having a heat dissipation function, an element having a heat dissipation function, and the like.
  • the heat radiator may have any shape.
  • a radiator is a band, plate, foil, strip, wire, rod, rectangular parallelepiped, cube, cone, cylinder, curve, circuit, wiring, polygon, square, circle, plane or curved surface, or a shape composed of a plane and a curved surface, etc. You may have the shape of.
  • the vehicle of embodiment of this invention has said power device or an element, or an electronic component.
  • An example of a method by which the laminate described above can be manufactured is as follows. First, containing Cu, Si, Mn, Ni, Ti, Al, Ce, Ga, In, P, As, Sb, Nb, Cr, Fe, Li, Be, Mg, Zn, Ge, Co, Mo, B Copper alloy layer containing at least one element selected from C, Sn, Y, Pr, Nd, Sm, Zr, Bi, V, W, Tl, Ca, Sr, Ba, and Hf, and aluminum nitride Alternatively, silicon nitride and other nitride ceramic substrates are prepared.
  • the electrical conductivity and thermal conductivity of a copper alloy layer can be made more favorable, it is preferable that Cu contained in a copper alloy layer is a main component.
  • the copper alloy layer is Si, Mn, Ni, Ti, Zr, Ce, which is stable as a copper alloy and can realize strong direct bonding with nitride ceramics, as described above. It is preferable to contain at least one element selected from Hf.
  • the copper alloy layer is bonded to at least one surface, generally both surfaces, of the nitride ceramic substrate by thermocompression bonding without any other composition layer except for the oxide or the anticorrosive layer.
  • the temperature condition is preferably 800 to 1000 ° C., more preferably 850 to 950 ° C., and preferably from 0.6 N / mm 2 to both sides of the nitride ceramic substrate and the copper alloy layer stacked on each other.
  • the nitride ceramic substrate and the copper alloy layer are bonded to each other by solid phase bonding or the like by applying a pressure of 1.5 N / mm 2 .
  • the above pressure can be applied, for example, for 0.083 hours to 5 hours, preferably 0.167 hours to 4 hours, more preferably 0.5 to 3 hours.
  • the bonding here is preferably performed in a nitrogen or argon atmosphere or in a vacuum.
  • a vacuum means that the ambient pressure is 5.0 ⁇ 10 ⁇ 3 Torr or less, preferably 7.0 ⁇ 10 ⁇ 4 Torr or less, more preferably 3.0 ⁇ 10 ⁇ 4 Torr or less, more preferably This refers to the condition where the pressure is 5.0 ⁇ 10 ⁇ 5 Torr or less.
  • the above-mentioned element contained in the copper alloy layer forms a compound with the element of the nitride ceramic substrate at the interface between the copper alloy layer and the nitride ceramic substrate.
  • the layer and the nitride ceramic substrate are bonded sufficiently firmly with a required strength.
  • the copper alloy layer and the nitride ceramic substrate can be joined without performing vapor deposition, sputtering, plating, or other treatment, effectively increasing the number of man-hours resulting from the process of performing such treatment. Therefore, the laminate can be easily manufactured at a low cost.
  • vapor deposition, sputtering, plating, and other treatments may be performed on the copper alloy layer or the nitride ceramic substrate.
  • thermocompression bonding if the temperature at the time of thermocompression bonding is too low, there is a risk of poor bonding. On the other hand, if the temperature is too high, the copper alloy layer may melt and be damaged. Further, if the pressure applied to the laminated nitride ceramic substrate and the copper alloy layer is too low, bonding will be poor, and if the pressure is too high, the nitride ceramic substrate or the copper alloy layer may be damaged.
  • the copper alloy layer may have any shape.
  • a copper alloy layer is a band, plate, foil, strip, wire, rod, rectangular parallelepiped, cube, cone, cylinder, curve, circuit, wiring, polygon, square, circle, plane or curved surface, or a plane and curved surface Or the like.
  • the copper alloy layer according to the present invention is preferably a copper alloy plate or a copper alloy foil.
  • the copper alloy layer according to the present invention includes a rolled copper alloy plate, a rolled copper alloy foil produced by rolling, and an electrolytic copper alloy plate and an electrolytic copper alloy formed by wet plating such as electrolytic plating and electroless plating.
  • a foil is preferred.
  • the electrolytic foil was prepared by using an electrolytic foil manufacturing apparatus in which an electrode (anode) was disposed around an electrolytic cell, a titanium cathode rotating drum, and a distance of about 5 mm around the drum under the following conditions. It was manufactured by performing deposition by electroplating until the thickness described in Table 2 was reached.
  • Electrolytic foils of Examples 6 and 32 were manufactured under the following conditions.
  • Electrolytic foils of Examples 9 and 35 were manufactured under the following conditions. ⁇ Plating solution composition> Copper concentration: 60-120 g / L Nickel concentration: 1-10g / L ⁇ Plating conditions> Plating solution temperature: 45-80 ° C Current density: 1-10 A / dm 2 pH: 1 to 4
  • the electrolytic foil of Comparative Example 2 was produced under the following conditions. ⁇ Plating solution composition> Copper concentration: 80-100g / L Sulfuric acid concentration: 70-90g / L ⁇ Plating conditions> Plating solution temperature: 45 to 65 ° C Current density: 50 to 70 A / dm 2
  • Example 46 (Method of forming rust prevention layer and chromate treatment layer)
  • the thickness of the formed anticorrosive film is 50 to 500 mm.
  • Anti-rust treatment liquid > Benzotriazole 0.1% by mass Benzotriazole monoethanolamine salt 0.2% by mass Isopropyl alcohol 10% by mass Remaining water
  • Example 47 after forming a rust prevention layer on the surface of the side laminated
  • Niride ceramic substrate As the nitride ceramics laminated on the copper alloy layer in each of Examples 1 to 20, 44 to 55 and Comparative Examples 1 to 8, AlN as a commercially available product was used.
  • a 2 O 3 powder having an average particle size of 1.5 ⁇ m was added to the mixture, and pulverized and mixed using a ball mill to prepare raw materials.
  • 6% by weight of paraffin wax was added to the raw material and granulated, followed by press molding at a pressure of 1000 kg / cm 2 to obtain a green compact of 45 mm ⁇ 45 mm ⁇ 3 mm.
  • This green compact was first degreased by heating to 300 ° C. in a nitrogen gas atmosphere. Thereafter, the degreased green compact was housed in a carbon mold and sintered at 1800 ° C. for 0.5 hours in a nitrogen gas atmosphere to produce a nitride ceramic substrate mainly composed of AlN.
  • TiC ⁇ TiN (cermet), TiN, Si 3 N 4 , BN, BN ⁇ SiC, InN, and GaN as nitride ceramics laminated on the copper alloy layer in each of Examples 24 to 30 and 34 to 40, respectively. The following were used. The thickness was adjusted by polishing or the like as necessary.
  • TiC ⁇ TiN (cermet), Si 3 N 4 , BN, BN ⁇ SiC, and GaN, commercially available products were used.
  • TiN was prepared by heating a pure titanium plate (Ti concentration 99% by mass or more) at 1000 ° C. in nitrogen containing 1 vol% hydrogen.
  • InN was produced according to the procedures described in the following (1) to (6) to obtain indium nitride.
  • the sapphire substrate is organically cleaned, and a sapphire substrate having a refractory metal molybdenum deposited on the back surface is placed on a substrate heater in an MBE growth chamber maintained in a vacuum in order to improve the temperature rise property of the substrate. Then, the temperature of the substrate is raised to about 800 ° C. and held as it is for 30 minutes, and the surface of the sapphire substrate is cleaned at a high temperature.
  • the substrate is irradiated with nitrogen radicals obtained by decomposing nitrogen gas with RF plasma at the same temperature to nitride the surface of the sapphire substrate for 30 minutes, thereby forming thin aluminum nitride on the surface.
  • nitrogen radicals obtained by decomposing nitrogen gas with RF plasma at the same temperature to nitride the surface of the sapphire substrate for 30 minutes, thereby forming thin aluminum nitride on the surface.
  • the shutter of the In cell is opened, and the InN buffer layer is grown to a film thickness of 10 nm with the substrate temperature kept at 350 ° C.
  • the shutter of the In cell is closed, the shutter of the RF plasma cell is opened, and the substrate is heated to 470 ° C. while continuing to irradiate only the nitrogen radicals on the sample surface.
  • the substrate temperature reaches 470 ° C.
  • the shutter of the In cell is opened, and the InN layer is grown until the film thickness reaches 2000 nm at the substrate temperature of 470 ° C.
  • the concentration of each element in the copper alloy layer and the nitride ceramic substrate is generally determined after the copper alloy layer or the nitride ceramic substrate is cut or pulverized. Alternatively, it can be quantified by an atomic absorption method after dissolution using a solution (for example, nitric acid, hydrofluoric acid, hydrochloric acid, or a mixed acid thereof) used for dissolving the nitride ceramic substrate.
  • a solution for example, nitric acid, hydrofluoric acid, hydrochloric acid, or a mixed acid thereof
  • the copper alloy layer or nitride ceramic substrate was cut or pulverized, and a LECO O / N simultaneous analyzer (TC-300, TC -400, TC-436, TC-500, etc.).
  • a LECO O / N simultaneous analyzer TC-300, TC -400, TC-436, TC-500, etc.
  • peel strength test was conducted to evaluate the bonding strength between the copper alloy layer and the nitride ceramic substrate of the laminate thus produced.
  • one end of the copper plate protrudes to the outside of the substrate by about 5 mm, and the bonding area is 10 mm ⁇ 10 mm, and this is pulled up 90 degrees at a speed of 50 mm / min.
  • the force per unit width (peeling strength) required for the calculation was calculated and evaluated.
  • Table 1 Here, when the peel strength is less than 10 kN / m, it is a defective product, and when the peel strength is 10 kN / m or more and less than 15 kN / m, it is evaluated as a general strength.
  • the peel strength is 15 kN / m or more and less than 20 kN / m, it is suitable for use as a laminate.
  • the peel strength is 20 kN / m or more and less than 30 kN / m, it is better. It is considered good.
  • the said peel strength was measured.
  • the comparative example and Example whose thickness of a copper alloy layer is smaller than 0.15 mm after carrying out copper plating and making thickness thick to 0.15 mm, the said peel strength was measured.
  • the comparative example and Example whose thickness of a copper alloy layer is larger than 0.15 mm after making the thickness of a copper alloy layer into 0.15 mm by etching, the said peel strength was measured.

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CN105624454A (zh) * 2016-02-02 2016-06-01 王增琪 一种高强度高过滤通量合金构件的制备方法
WO2018159590A1 (ja) * 2017-02-28 2018-09-07 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、絶縁回路基板の製造方法
JP2018140929A (ja) * 2017-02-28 2018-09-13 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、絶縁回路基板の製造方法
JP2020001390A (ja) * 2018-06-27 2020-01-09 ベイパー テクノロジーズ、インコーポレイテッド 銅系の抗菌性ｐｖｄコーティング
WO2020045403A1 (ja) * 2018-08-28 2020-03-05 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、及び、絶縁回路基板の製造方法

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CN107868656A (zh) * 2016-09-26 2018-04-03 罗宇晴 导热铝料的组成物及其制造方法
JP6526888B1 (ja) * 2018-08-01 2019-06-05 Ｊｘ金属株式会社 セラミックス層と銅粉ペースト焼結体の積層体
EP4071128B1 (en) * 2019-12-02 2024-03-27 Mitsubishi Materials Corporation Copper/ceramic bonded body, insulating circuit board, method for producing copper/ceramic bonded body, and method for producing insulating circuit board
CN112359247B (zh) * 2020-11-16 2021-11-09 福州大学 一种Cu-Hf-Si-Ni-Ce铜合金材料及其制备方法
CN115124362B (zh) * 2022-06-20 2023-07-18 昆明冶金研究院有限公司北京分公司 陶瓷覆铜板及其制备方法

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CN105624454A (zh) * 2016-02-02 2016-06-01 王增琪 一种高强度高过滤通量合金构件的制备方法
KR102459745B1 (ko) 2017-02-28 2022-10-26 미쓰비시 마테리알 가부시키가이샤 구리/세라믹스 접합체, 절연 회로 기판, 및, 구리/세라믹스 접합체의 제조 방법, 절연 회로 기판의 제조 방법
WO2018159590A1 (ja) * 2017-02-28 2018-09-07 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、絶縁回路基板の製造方法
JP2018140929A (ja) * 2017-02-28 2018-09-13 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、絶縁回路基板の製造方法
KR20190123727A (ko) * 2017-02-28 2019-11-01 미쓰비시 마테리알 가부시키가이샤 구리/세라믹스 접합체, 절연 회로 기판, 및, 구리/세라믹스 접합체의 제조 방법, 절연 회로 기판의 제조 방법
US10818585B2 (en) 2017-02-28 2020-10-27 Mitsubishi Materials Corporation Copper/ceramic joined body, insulated circuit board, method for producing copper/ceramic joined body, and method for producing insulated circuit board
JP2020001390A (ja) * 2018-06-27 2020-01-09 ベイパー テクノロジーズ、インコーポレイテッド 銅系の抗菌性ｐｖｄコーティング
JP7409791B2 (ja) 2018-06-27 2024-01-09 ベイパー テクノロジーズ、インコーポレイテッド 銅系の抗菌性ｐｖｄコーティング
WO2020044594A1 (ja) * 2018-08-28 2020-03-05 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、及び、絶縁回路基板の製造方法
JPWO2020045403A1 (ja) * 2018-08-28 2021-08-12 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、及び、絶縁回路基板の製造方法
JP7008188B2 (ja) 2018-08-28 2022-01-25 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、及び、絶縁回路基板の製造方法
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CN112654593B (zh) * 2018-08-28 2022-11-11 三菱综合材料株式会社 铜-陶瓷接合体、绝缘电路基板、铜-陶瓷接合体的制造方法及绝缘电路基板的制造方法
WO2020045403A1 (ja) * 2018-08-28 2020-03-05 三菱マテリアル株式会社 銅／セラミックス接合体、絶縁回路基板、及び、銅／セラミックス接合体の製造方法、及び、絶縁回路基板の製造方法

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