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 PDFInfo
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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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- 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
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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
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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
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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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
- C22C9/02—Alloys based on copper with tin as the next major constituent
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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
- C22C9/04—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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Abstract
Description
ここで、パワーデバイスは、セラミックス基板の少なくとも一方の表面、通常は両面のそれぞれに、ヒートシンクとして機能する銅製等の金属層が接合されてなる積層体を、ベース板(放熱板)上に固定し、そして、積層体上に、パワー半導体素子及び、その制御回路が形成されて構成される。
これによれば、金属との濡れ性に乏しい窒化アルミニウム基板と、Cu導体層との間に形成した上記の接合層が、窒化アルミニウム基板とCu導体層とを有効に接合させることになる。その結果として、以前から使用されてきたアルミナに比して熱伝導性に優れる窒化アルミニウム基板により、半導体素子等が発する熱を有効に放散させることができる。
ここで好ましくは、前記銅合金層が銅合金板または銅合金箔からなるものとする。
ここで、前記窒化物セラミックス基板が窒化アルミニウムを主成分とするものである場合、その窒化物セラミックス基板がさらに、Ca、Y、Oからなる群から選択される一種以上の元素を含有し、Caを含む場合には、Ca濃度は0.0001~3質量%であり、Yを含む場合にはY濃度は0.0001~10質量%であり、Oを含む場合には、O濃度は0.0001~20質量%であるものとすることができる。
また前記窒化物セラミックス基板のO含有濃度は0.0001~20質量%であることが好ましい。
ここにおいて、この発明の積層体では、前記銅合金層と前記窒化物セラミックス基板との剥離強度は、15kN/m以上であることが好ましい。
また、銅合金層の表面には、たとえば有機物による防錆層等が形成されることがあるので、接合の強さに大きな悪影響を及ぼさない程度に、銅合金層の少なくとも窒化物セラミックス基板側の表面には、一般的に用いられる粗化処理層、耐熱層、防錆層、クロメート処理層、シランカップリング処理層の群から選択される一つ以上の層を施してもよい。この場合は、銅合金層と窒化物セラミックス層とが、粗化処理層、耐熱層、防錆層、クロメート処理層、シランカップリング処理層の群から選択される一つ以上の層だけを介して間接的に接合される。
この発明の一の実施形態に係る積層体は、窒化物セラミックス基板と、その窒化物セラミックス基板の少なくとも一方の表面に積層された銅合金箔等の銅合金層とを備え、この銅合金層が、Cuの他、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、Hfから選択される少なくとも一種類の元素を含有するものである。なお、銅合金層の導電率や熱伝導率をより良好なものとすることができるため、銅合金層において、Cuが主成分であることが好ましい。
また、銅合金層は窒化物や酸化物等の化合物や無機物、上述した元素以外の元素を含む金属、上述以外の元素等を含んでもよい。
また、前記窒化物はNと、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およびBaからなる群から選択される一種以上の元素とからなる化合物であることがより好ましい。
また、前記窒化物はNと、Si、Al、B、Ga、InおよびTiからなる群から選択される一種以上の元素とを含む化合物であることがより好ましい。
また、前記窒化物はNと、Si、Al、B、Ga、InおよびTiからなる群から選択される一種以上の元素とからなる化合物であることがより好ましい。
なかでも、窒化アルミニウム及び窒化珪素はいずれも熱伝導率に優れ、しかも、窒化アルミニウムは熱膨張率が低く、この種の積層体のセラミックス基板として用いることが好適である。また、窒化珪素は、強度が高く、製造時に破損しにくいため、生産性の観点から好ましい。
本願において、例えば、Aを「主成分とする」とは、Aを50質量%以上、より好ましくは60質量%以上、より好ましくは70質量%以上であることを意味する。また、窒化物の濃度は、窒素の濃度と、窒化物を構成する窒素以外の元素の濃度との合計の濃度とする。
このことに対し、発明者は以下の検討を行った。
アルミナ(Al2O3)製のセラミックス基板は、純Cu金属層と所要の強度で直接接合することが可能である。この理由を検討するため、1000℃の温度条件の下、酸素の量に応じて、アルミナと銅との界面で安定する各物質量の変化をシミュレーションした結果を、図1にグラフで示す。ここで、横軸は酸素の量を示し、縦軸は物質量を規格化した指標を示す。いずれも数値が大きいほど量が多いことを意味する。また、図1上に記載されている「Al2O3+Cu+<Alpha>*O2」は物質量を規格化した指標で表した場合に、Al2O3が1、Cuが1、O2がAlpha(図1の横軸)で存在する場合の、各物質量をシミュレーションした結果であることを意味する。
図1に示すところから、アルミナと銅との界面では、酸素の量の増減に伴い、Cu単体及びAl2O3が減少又は増加する一方で、CuとAl2O3とで形成される複合酸化物(CuAl2O3)の量が増加又は減少することが解かり、この複合化合物が、アルミナと銅との密着力を向上させ、それらの接合に寄与していると考えられる。
一方、窒化物セラミックスの代表例としての窒化アルミニウム(AlN)のセラミックス基板は、純Cu金属層と直接的に接合することが難しい。窒化アルミニウムと銅との同様のシミュレーション結果を図2にグラフに示す。
図2に示すところでは、酸素の量に関わらず、窒化アルミニウムと銅との間では化合物が形成されず、これにより、窒化アルミニウムと銅との接合が困難になると考えられる。
窒化アルミニウムのセラミックス基板と純Cu金属層との間に、その表面へのスパッタリング等によってチタン接合層を形成した場合は、そのチタン接合層を介して、窒化アルミニウムのセラミックス基板と純Cu金属層とが接合されることになる。この場合の窒化アルミニウムとチタンとの界面状態を同様に図3にグラフで示す。
図3によれば、窒化アルミニウムとチタンとの界面には、TiNが形成されており、酸素の量が増加するに従って、このTiNの量が増加する。また、酸素の量が増加するにつれて減少するが、窒化アルミニウムとチタンとの界面にはTiAl3も、形成されることになる。チタンを介在させることにより、これらの化合物が形成されて、窒化アルミニウムと銅とが接合されると考えられる。
このことを検証するため、Tiを3.1質量%で含有するチタン銅合金(Cu-Ti)と窒化アルミニウムとの界面状態につき、同様のシミュレーションを行ったところ、図4に示す結果を得た。
図4に示すシミュレーション結果から、チタン銅合金に含まれるTiと、窒化アルミニウムのNでTiNが形成され、これが、チタン銅合金と窒化アルミニウムとの接合に有効に働くと考えられる。
銅合金層がMnを含有する場合は、そのMn濃度の下限値は0.0001質量%、より好ましくは0.05質量%、より好ましくは0.1質量%、より好ましくは0.2質量%とする。Mn濃度の上限値は、好ましくは95質量%、より好ましくは80質量%、より好ましくは50質量%、より好ましくは40質量%、より好ましくは30質量%とする。
銅合金層がTiを含有する場合は、そのTi濃度の下限値は、好ましくは0.0001質量%、より好ましくは0.05質量%、より好ましくは0.1質量%、より好ましくは0.2質量%とする。Ti濃度の上限値は、好ましくは8.5質量%、より好ましくは8.0質量%、より好ましくは7.7質量%、より好ましくは7.5質量%とする。
銅合金層がZrを含有する場合は、そのZr濃度は0.0001~8.0質量%とすることができ、好ましくは0.01~7.0質量%、より好ましくは0.05~5.0質量%である。
銅合金層がCeを含有する場合は、そのCe濃度は、たとえば0.0001~60質量%とすることができ、好ましくは0.001~50質量%、より好ましくは0.01~40質量%、より好ましくは0.01~10質量%、より好ましくは0.01~5質量%とする。
銅合金層がHfを含有する場合は、そのHf濃度は、たとえば0.0001~20質量%とすることができ、好ましくは0.001~15質量%、より好ましくは0.01~10質量%、より好ましくは0.01~8質量%、より好ましくは0.01~5質量%とする。
それにより、銅合金層と窒化物セラミックス基板との間に他の接合層等を形成するための工程が不要となって、製造工数を減らすことができる。また、接合層等を形成するためのスパッタリング等を行う設備、材料等も不要となって製造コストを小さく抑えることができる。
この観点からは、銅合金層が、Ce、Ti、Zr、Hfから選択される少なくとも一種類の元素を含有することが好ましい。
また、前記窒化物セラミックス基板の厚みは、1μm~15000μm、1μm~7000μmとすることができ、好ましくは5μm以上2000μm以下、より好ましくは10μm以上1500μm以下、より好ましくは20μm以上1200μm以下、より好ましくは50μm以上1100μm以下、より好ましくは100μm以上1050μm以下、より好ましくは200μm以上1000μm以下とすることができる。
銅合金層の上記表面粗さは、たとえば、圧延ロールの表面粗さ及び/又は圧延時の油膜当量を制御して冷間圧延をすることによって調整することが可能である。
この窒化物セラミックス基板の表面粗さは、ショットブラスト等によって調整可能である。
そして、この発明の実施形態の車両は、上記のパワーデバイスまたは素子または電子部品を有するものである。
はじめに、Cuを含有し、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、Hfから選択される少なくとも一種類の元素を含有する銅合金層、及び、窒化アルミニウムもしくは窒化珪素その他の窒化物セラミックス基板をそれぞれ用意する。なお、銅合金層の導電率や熱伝導率をより良好なものとすることができるため、銅合金層に含まれるCuは主成分であることが好ましい。
この場合、銅合金層は、上記の元素のなかでも、先述したように、銅合金として安定し、かつ窒化物セラミックスとの強固な直接接合を実現できるSi、Mn、Ni、Ti、Zr、Ce、Hfから選択される少なくとも一種類の元素を含有することが好ましい。
ここでは、温度条件を、好ましくは800~1000℃、より好ましくは850~950℃とし、互いに重ね合せた窒化物セラミックス基板と銅合金層を挟んで両側から、好ましくは0.6N/mm2~1.5N/mm2の圧力を作用させて、それらの窒化物セラミックス基板と銅合金層とを相互に、固相接合等によって接合する。上記の圧力は、たとえば、0.083時間~5時間、好ましくは0.167時間~4時間、より好ましくは0.5~3時間にわたって作用させることができる。
その結果として、蒸着、スパッタリング、めっきその他の処理を施すことなしに、銅合金層と窒化物セラミックス基板を接合できるので、そのような処理を施す工程を経ることに起因する工数の増大を有効に防止することができ、積層体を安価にして容易に製造することができる。なお、蒸着、スパッタリング、めっきその他の処理を銅合金層または窒化物セラミックス基板に行ってもよい。
なお、本発明に係る銅合金層は、銅合金板や銅合金箔であることが好ましい。また本発明に係る銅合金層は、圧延加工により製造された圧延銅合金板、圧延銅合金箔や、電解めっきや無電解めっき等の湿式めっきにより形成された、電解銅合金板、電解銅合金箔であることが好ましい。銅合金板や銅合金箔を用いることで、窒化物セラミックス基板へスパッタリング等の方法により、銅合金層を形成するよりも、生産性が高く、製造コストを低減することができる。
表1、表2に示す組成及び形態、厚みの銅合金層を、同表に示す組成の窒化物セラミックス基板に重ね合わせ、0.98N/mm2の圧力を作用させて窒素中(圧力:760Torr)またはアルゴン中(圧力:760Torr)または真空中(圧力:3.0×10-4Torr)で830℃の温度で10分間にわたって加熱して積層させた。
実施例14、16、40は窒素中にて上記加熱・積層を行い、実施例15はアルゴン中にて上記加熱・積層を行い、実施例14~16及び40以外は真空中にて上記加熱・積層を行った。
なお、圧延箔は表1、表2に記載の組成となるように成分を調整した後に、溶解・鋳造を行ってインゴットを製造した後に、表1、表2の板厚となるまで焼鈍と圧延を繰り返し行うことで製造した。
また、電解箔は電解槽とチタン製の陰極回転ドラムとドラムの周囲に5mm程度の極間距離を置いて電極(アノード)を配置した電解箔製造装置を用いて、以下の条件で表1、表2の記載の厚みとなるまで電気めっきによる析出を行って製造した。
<めっき液組成>
NaCN:10~30g/L
NaOH:40~100g/L
CuCN:60~120g/L
Zn(CN)2:5~40g/L
<めっき条件>
めっき液温度:60~80℃
電流密度:1~10A/dm2
pH:10~13
<めっき液組成>
銅濃度:60~120g/L
ニッケル濃度:1~10g/L
<めっき条件>
めっき液温度:45~80℃
電流密度:1~10A/dm2
pH:1~4
<めっき液組成>
銅濃度:80~100g/L
硫酸濃度:70~90g/L
<めっき条件>
めっき液温度:45~65℃
電流密度:50~70A/dm2
なお、実施例46については、銅合金層の窒化物セラミックス基板に積層される側の表面に以下の条件で防錆処理を行い、防錆層を形成した銅合金層を用いた。形成された防錆皮膜の厚みは50~500Åである。
<防錆処理液>
ベンゾトリアゾール0.1質量%
ベンゾトリアゾール・モノエタノールアミン塩0.2質量%
イソプロピルアルコール10質量%
残部水
<防錆処理条件>
防錆処理液温度:30℃
処理(浸漬)時間:60秒
<防錆層>
・めっき液
Zn:5~50g/L
Ni:5~50g/L
・めっき条件
pH:2.5~4
温度:30~60℃
電流密度:0.5~5A/dm2
めっき時間:6~60秒
・付着量
Zn:300~1500μg/dm2
Ni:300~1500μg/dm2
<クロメート処理層>
・クロメート処理液
K2Cr2O7:2~10g/L
NaOH:10~50g/L
ZnSO4 ・7H2O:0.05~10g/L
・クロメート処理条件
pH:7~13
浴温:20~80℃
電流密度:0.05~5 A/dm2
時間:5~50秒
・付着量
Cr付着量:15~100μg/dm2
Zn付着量:30~200μg/dm2
実施例1~20、44~55及び、比較例1~8のそれぞれで銅合金層に積層させた窒化物セラミックスとしてのAlNは、一般に市販されているものを用いた。
平均粒径1.4μmのAlN粉末に、Yを含む実施例においては、Y源として平均粒径0.8μmのY2O3粉末を用い、Caを含む実施例においてはCa源として平均粒径1.8μmのCaO粉末を用い、表2に記載のY濃度、Ca濃度となるように、Y2O3粉末とCaO粉末を添加し、また実施例43においては表2のO濃度となるように平均粒径1.5μmのA2O3粉末を添加し、ボールミルを用いて粉砕、混合して原料調整した。
次ぎにこの原料にパラフィンワックス6重量%を添加して造粒した後、1000kg/cm2の圧力でプレス成形し、45mm×45mm×3mmの圧粉体とした。この圧粉体を窒素ガス雰囲気中で、まず300℃まで加熱して脱脂した。
その後、前記脱脂済み圧粉体をカーボン型中に収納し、窒素ガス雰囲気中、1800℃で0.5時間常圧焼結することでAlNを主体とした窒化物セラミックス基板を製造した。
TiNについては、純チタンの板(Ti濃度99質量%以上)を、1vol%の水素を含んだ窒素中で1000℃で加熱することで作製した。
(1)サファイア基板を有機洗浄し、基板の昇温性を改善するために裏面に高融点金属モリブデンを蒸着したサファイア基板を、真空に保たれているMBE成長室内の基板ヒーターに設置する。そして、基板を800℃程度まで昇温して、そのまま30分間保持し、サファイア基板表面の高温クリーニングを行う。その後、同温度で基板にRFプラズマで窒素ガスを分解して得た窒素ラジカルを照射してサファイア基板表面を30分間窒化し、表面に薄い窒化アルミニウムを形成する。
(2)RFプラズマセルのシャッターを閉じて基板表面への窒素ラジカルの照射を中断し、基板温度を350℃まで降温する。
(3)その後、GaセルとRFプラズマセルのシャッターを同時に開けて、GaNバッファ層を膜厚20nmとなるまで成長させる。
(4)Gaセルのシャッターを閉じると同時にInセルのシャッターを開き、基板温度350℃のままで、InNバッファ層を膜厚10nmとなるまで成長させる。
(5)InNバッファ層の成長終了後、Inセルのシャッターを閉じ、RFプラズマセルのシャッターを開け、窒素ラジカルだけを試料表面に照射しつづけながら基板を470℃に昇温する。
(6)基板温度が470℃に達したらInセルのシャッターを開き、基板温度470℃でInN層を膜厚2000nmとなるまで成長させる。
なお、以上に述べた実施例及び比較例において、銅合金層および窒化物セラミックス基板中の各元素の濃度は、銅合金層または窒化物セラミックス基板を切断または粉砕した後、一般的に銅合金層または窒化物セラミックス基板を溶かすために用いられる液(例えば硝酸、フッ酸、塩酸またはこれらを混合した酸等)を用いて溶解を行った後に、原子吸光法により定量することができる。また、銅合金層および窒化物セラミックス基板中の酸素濃度、窒素濃度については、銅合金層または窒化物セラミックス基板を切断または粉砕し、LECO社製のO/N同時分析計(TC-300、TC-400、TC-436、TC-500等)にて定量することができる。酸素濃度、窒素濃度が高い場合には、測定する試料の量を少なく(例えば0.01~0.1g等)して、酸素濃度、窒素濃度を測定すると良い。
このようにして作製した積層体で銅合金層と窒化物セラミックス基板の接合強度を評価するためにピ-ル強度試験を行った。ピ-ル強度試験は、銅板の一端部が基板の外部に5mm程度突出するように、また、接合面積を10mm×10mmとして接合し、これを50mm/minの速度で90度上方に引張り上げるのに要する単位幅当りの力(剥離強度)を算出し、評価した。この結果を表1に示す。
ここで剥離強度は、10kN/m未満の場合は不良品であり、10kN/m以上15kN/m未満の場合は一般的な大きさの強度であると評価する。また、剥離強度が15kN/m以上20kN/m未満の場合は、積層体として用いるに適しており、20kN/m以上30kN/m未満の場合はより良く、さらに、30kN/m以上の場合はさらに良いと考えられる。
従って、実施例1~55のような銅合金層は、窒化物セラミックス基板と積層させて、パワーデバイス等の積層体に用いることができることが解った。
Claims (17)
- 窒化物セラミックス基板と、該窒化物セラミックス基板の少なくとも一方の表面に積層された銅合金層とを有し、前記銅合金層が、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、Hfから選択される少なくとも一種類の元素を含有する、積層体。
- 前記銅合金層が銅合金板または銅合金箔からなる、請求項1に記載の積層体。
- 前記銅合金層が、Si、Mn、Ni、Ti、Zr、Ce、Hfから選択される少なくとも一種類の元素を含有し、該銅合金層が、Siを含有する場合はSi濃度が0.0001~3.0質量%であり、Mnを含有する場合はMn濃度が0.0001~95質量%あり、Niを含有する場合はNi濃度が0.0001~95質量%であり、Tiを含有する場合はTi濃度が0.0001~8.5質量%であり、Zrを含有する場合はZr濃度が0.0001~8.0 質量%であり、Ceを含有する場合はCe濃度が0.0001~60質量%であり、Hfを含有する場合はHf濃度が0.0001~20質量%である、請求項1又は2に記載の積層体。
- 前記窒化物セラミックス基板が、窒化アルミニウム、窒化珪素、窒化チタン、窒化ホウ素、窒化インジウム又は窒化ガリウムを主成分とし、あるいは、炭化チタンと窒化チタンとの複合材料、又は、窒化ホウ素と炭化ケイ素との複合材料を主成分としてなる、請求項1~3のいずれか一項に記載の積層体。
- 窒化アルミニウムを主成分とする前記窒化物セラミックス基板が、Ca、Y、Oからなる群から選択される一種以上の元素を含有し、Caを含む場合には、Ca濃度は0.0001~3質量%であり、Yを含む場合にはY濃度は0.0001~10質量%であり、Oを含む場合には、O濃度は0.0001~20質量%である、請求項4に記載の積層体。
- 前記窒化物セラミックス基板のO含有濃度が0.0001~20質量%である、請求項1~4のいずれか一項に記載の積層体。
- 前記銅合金層の厚みを、1μm~7000μmとし、前記窒化物セラミックス基板の厚みを、1μm~7000μmとしてなる、請求項1~6のいずれか一項に記載の積層体。
- 前記銅合金層と前記窒化物セラミックス基板との剥離強度が15kN/m以上である、請求項1~7のいずれか一項に記載の積層体。
- 請求項1~8のいずれか一項に記載の積層体を有する放熱体。
- 請求項1~8のいずれか一項に記載の積層体を有するパワーデバイス。
- 請求項1~8のいずれか一項に記載の積層体を有する素子。
- 請求項1~8のいずれか一項に記載の積層体を有する電子部品。
- 請求項1~8のいずれか一項に記載の積層体を有する電子機器。
- 請求項10に記載のパワーデバイスまたは請求項11に記載の素子または請求項12に記載の電子部品を有する車両。
- 銅合金層と窒化物セラミックス基板との積層体を製造するに当り、前記銅合金層が、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、Hfから選択される少なくとも一種類の元素を含有するものとし、窒化物セラミックス基板の少なくとも一方の表面に、前記銅合金層を、熱圧着により積層させる、積層体の製造方法。
- 前記銅合金層が、Si、Mn、Ni、Ti、Zr、Ce、Hfから選択される少なくとも一種類の元素を含有し、該銅合金層が、Siを含有する場合はSi濃度が0.0001~3.0質量%であり、Mnを含有する場合はMn濃度が0.0001~95質量%あり、Niを含有する場合はNi濃度が0.0001~95質量%であり、Tiを含有する場合はTi濃度が0.0001~8.5質量%であり、Zrを含有する場合はZr濃度が0.0001~8.0質量%であり、Ceを含有する場合はCe濃度が0.0001~60質量%であり、Hfを含有する場合はHf濃度が0.0001~20質量%である、請求項15に記載の積層体の製造方法。
- 前記銅合金層と前記窒化物セラミックス基板とを接合するに際し、窒素もしくはアルゴン雰囲気中または真空中で、800~1000℃の温度の下、0.6N/mm2~1.5N/mm2の圧力を作用させることにより、前記銅合金層と前記窒化物セラミックス基板とを接合する、請求項15又は16に記載の積層体の製造方法。
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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 |
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 |
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