Copper-ceramic bonded body and power module substrate

Abstract

There is a provided a copper-ceramic bonded body in which a copper member formed of copper or a copper alloy and a ceramic member formed of nitride ceramic are bonded to each other, in which an active element oxide layer containing an active element and oxygen is formed at bonding interfaces between the copper member and the ceramic member, and a thickness t of the active element oxide layer is in a range of 5 nm to 220 nm.

Claims

1. A copper-ceramic bonded body comprising: a copper member formed of copper or a copper alloy; and a ceramic member formed of nitride ceramic, wherein the copper member and the ceramic member are bonded to each other, wherein an active element oxide layer containing an active element and oxygen is formed at bonding interfaces between the copper member and the ceramic member, wherein a thickness of the active element oxide layer is in a range of 5 nm to 200 nm wherein the active element is selected from the group consisting of Ti, Zr, Hf, and Nb, wherein the active element oxide layer contains P, and wherein an amount of P of the active element oxide layer is in a range of 1.5 mass % to 10 mass %.

2. The copper-ceramic bonded body according to claim 1, wherein a CuAl eutectic layer is formed between the active element oxide layer and the copper member.

3. A power module substrate configured with the copper-ceramic bonded body according to claim 1, wherein in the copper-ceramic bonded body, a copper plate formed of copper or a copper alloy is bonded to a surface of a ceramic substrate formed of nitride ceramic.

4. The copper-ceramic bonded body according to claim 1, wherein a concentration of the active element of the active element oxide layer is in a range of 35% to 70%.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic explanatory diagram of a power module using a power module substrate of a first embodiment of the present invention.

(2) FIG. 2 is a schematic view of bonding interfaces between a circuit layer (copper member) and a ceramic substrate (ceramic member) of the power module substrate of the first embodiment of the present invention.

(3) FIG. 3 is a flowchart showing a manufacturing method of the power module substrate of the first embodiment of the present invention.

(4) FIG. 4 is an explanatory diagram showing the manufacturing method of the power module substrate of the first embodiment of the present invention.

(5) FIG. 5 is a schematic view of bonding interfaces between a circuit layer (copper member) and a ceramic substrate (ceramic member) of the power module substrate of a second embodiment of the present invention.

(6) FIG. 6 is an observation image of bonding interfaces of a copper-ceramic bonded body (power module substrate) of Example A1 of the present invention.

(7) FIG. 7 is an observation image of bonding interfaces of a copper-ceramic bonded body (power module substrate) of Example A13 of the present invention.

(8) FIG. 8 is a schematic explanatory diagram of a power module using a power module substrate of a third embodiment of the present invention.

(9) FIG. 9 is a schematic view of bonding interfaces between a circuit layer (copper member) and a ceramic substrate (ceramic member) of the power module substrate of the third embodiment of the present invention.

(10) FIG. 10 is an explanatory diagram showing the manufacturing method of the power module substrate of the third embodiment of the present invention.

(11) FIG. 11 is an observation image of bonding interfaces of a copper-ceramic bonded body (power module substrate) of Example B2 of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

First Aspect

First Embodiment

(12) Hereinafter, the first embodiment according to the first aspect of the present invention will be described with reference to the accompanied drawings.

(13) A copper-ceramic bonded body according to the first embodiment of the present invention is set as a power module substrate 10 configured by bonding a ceramic substrate 11 as a ceramic member formed of a nitride ceramic and a copper plate 22 (circuit layer 12) as a copper member formed of copper or a copper alloy to each other.

(14) FIG. 1 shows the power module substrate 10 of the first embodiment of the present invention and a power module 1 using this power module substrate 10.

(15) The power module 1 includes the power module substrate 10, a semiconductor element 3 bonded to a surface of one side (upper side in FIG. 1) of the power module substrate 10 through a solder layer 2, and a heat sink 51 disposed on the other side (lower side in FIG. 1) of the power module substrate 10.

(16) Here, the solder layer 2 is, for example, a SnAg-based, a SnIn-based or SnAgCu-based soldering material.

(17) The power module substrate 10 includes the ceramic substrate 11, the circuit layer 12 installed on one surface (upper surface in FIG. 1) of the ceramic substrate 11, and a metal layer 13 installed on the other surface (lower surface in FIG. 1) of the ceramic substrate 11.

(18) The ceramic substrate 11 prevents electric connection between the circuit layer 12 and the metal layer 13 and the ceramic substrate 11 of the first embodiment is configured with AlN (aluminum nitride) which is one kind of nitride ceramic. Herein, a thickness of the ceramic substrate 11 is preferably set in a range of 0.2 mm to 1.5 mm and is set to 0.635 mm in the first embodiment.

(19) As shown in FIG. 4, the circuit layer 12 is formed by bonding the copper plate 22 formed of copper or a copper alloy to one surface of the ceramic substrate 11. In the first embodiment, a rolled plate of oxygen-free copper is used as the copper plate 22 configuring the circuit layer 12. A circuit pattern is formed in this circuit layer 12 and the one surface (upper surface in FIG. 1) is set as a mounted surface where the semiconductor element 3 is mounted. Herein, a thickness of the circuit layer 12 is preferably set in a range of 0.1 mm to 1.0 mm and is set to 0.6 mm in the first embodiment.

(20) As shown in FIG. 4, the metal layer 13 is formed by bonding an aluminum plate 23 to the other surface of the ceramic substrate 11. In the first embodiment, the metal layer 13 is formed by bonding the aluminum plate 23 formed of a rolled plate of aluminum having purity equal to or greater than 99.99 mass % (so-called 4N aluminum) to the ceramic substrate 11.

(21) A 0.2% bearing force of the aluminum plate 23 is preferably equal to or smaller than 30 N/mm.sup.2. Here, a thickness of the metal layer 13 (aluminum plate 23) is preferably set in a range of 0.5 mm to 6 mm and is set to 2.0 mm in the first embodiment.

(22) The heat sink 51 is for cooling the power module substrate 10 described above and includes a top plate part 52 bonded to the power module substrate 10 and flow paths 53 for causing a cooling medium (for example, cooling water) to flow. The heat sink 51 (plate part 52) is desirably configured with a material having excellent thermal conductivity and is configured with A6063 (aluminum alloy) in the first embodiment.

(23) In the first embodiment, the heat sink 51 (plate part 52) is directly bonded to the metal layer 13 of the power module substrate 10 by brazing.

(24) Here, as shown in FIG. 2, an active element oxide layer 30 containing an active element and oxygen is formed at the bonding interfaces between the ceramic substrate 11 and the circuit layer 12 (copper plate 22). In the first embodiment, a thickness t of the active element oxide layer 30 is set to be in a range of 5 nm to 220 nm. The thickness t of the active element oxide layer 30 is preferably from 10 nm to 220 nm and is more preferably from 10 nm to 50 nm. The concentration of the active element of the active element oxide layer 30 is in a range of 35 at % to 70 at %. The concentration of the active element herein is concentration when the total content of the active element, P, and O is 100.

(25) In the first embodiment, Ti is used as the active element, and the active element oxide layer 30 is set as a TiO layer containing Ti and oxygen.

(26) In the first embodiment, as will be described later, since the ceramic substrate 11 and the circuit layer 12 (copper plate 22) are bonded to each other using a CuP-based brazing material 24 containing P, the active element oxide layer 30 contains P. In the first embodiment, the content of P of the active element oxide layer 30 is preferably in a range of 1.5 mass % to 10 mass % and more preferably in a range of 3 mass % to 8 mass %. The content of P herein is content when the total content of Ti, P, and O is 100.

(27) Since the content of P is equal to or greater than 1.5 mass %, it is possible to reliably form the active element oxide layer 30 and to reliably bond the ceramic substrate 11 and the circuit layer 12 to each other. In addition, since the content of P is equal to or smaller than 10 mass %, the active element oxide layer 30 does not become excessively hard, and it is possible to decrease the load applied to the ceramic substrate due to thermal stress during cold-hot cycling loading, for example, and to prevent a decrease in reliability of the bonding interfaces.

(28) In a case of bonding the ceramic substrate 11 and the circuit layer 12 (copper plate 22) to each other without using the CuP-based brazing material 24 containing P, a CuAl brazing material which will be described later can be used as the brazing material 24.

(29) The thickness t of the active element oxide layer 30 is measured by observing the bonding interfaces with magnification of 200000 using a transmission electron microscope and assuming a portion having concentration of the active element in a range of 35 at % to 70 at % as the active element oxide layer 30. The concentration (at %) of the active element is measured by an energy dispersive X-ray spectrometer (EDS) attached to the transmission electron microscope and is set as concentration of the active element when the total of P concentration, active element concentration, and O concentration is 100. An average value of 5 viewing fields is set as the thickness of the active element oxide layer.

(30) For the content (mass %) of P of the active element oxide layer 30, the P concentration (mass %), the Ti concentration (mass %), and O concentration (mass %) in the active element oxide layer 30 are measured by the EDS attached to the transmission electron microscope and the P concentration (mass %) is calculated, when the total of the P concentration, the Ti concentration, and the O concentration is 100. The measurement points are set as 5 points and an average value thereof is set as the content (mass %) of P.

(31) Next, a manufacturing method of the power module substrate 10 of the first embodiment described above will be described with reference to FIG. 3 and FIG. 4.

(32) First, as shown in FIG. 4, the CuP-based brazing material 24, a Ti material 25 (active element material), and the copper plate 22 to be the circuit layer 12 are laminated on one surface (upper surface in FIG. 4) of the ceramic substrate 11 in order (first laminating Step S01), and the Al plate 23 to be the metal layer 13 is laminated on the other surface (lower surface in FIG. 4) of the ceramic substrate 11 in order with a bonding material 27 interposed therebetween (second laminating Step S02).

(33) Herein, in the first embodiment, it is preferable that a CuPSnNi brazing material containing 3 mass % to 10 mass % of P, 7 mass % to 50 mass % of Sn which is a low-melting-point element, and 2 mass % to 15 mass % of Ni is used as the CuP-based brazing material 24. A thickness of the CuP-based brazing material 24 is preferably in a range of 5 m to 50 m.

(34) In addition, a CuPZn brazing material or the like can be used as the CuP-based brazing material 24.

(35) In the first embodiment, a thickness of the Ti material 25 is preferably in range of 0.1 m to 25 m and a Ti foil having a thickness of 12 m is used in the first embodiment. In a case where the thickness is 0.1 m to 0.5, the Ti material 25 is preferably formed as a film by vapor deposition or sputtering, and in a case where the thickness is equal to or greater than 0.5 m, a foil material is preferably used.

(36) In the first embodiment, a AlSi-based brazing material (for example, Al-7.5 mass % Si brazing material) containing Si as a melting-point decreasing element is preferably used as the bonding material 27 which bonds the aluminum plate 23 to the ceramic substrate 11.

(37) In addition, an AlCu brazing material or Cu can be used as the bonding material 27. In a case where Cu (for example, fixed amount is from 0.08 mg/cm.sup.2 to 2.7 mg/cm.sup.2) is used as the bonding material 27, bonding can be performed by transient liquid phase diffusion bonding (TLP).

(38) Next, the ceramic substrate 11, the CuP-based brazing material 24, the Ti foil 25, the copper plate 22, the bonding material 27, and the Al plate 23 are charged and heated in a vacuum heating furnace, in a state of being pressurized (pressure of 1 kgf/cm.sup.2 to 35 kgf/cm.sup.2) in a laminating direction (heating treatment Step S03). In the first embodiment, the pressure in the vacuum heating furnace is set in a range of 10.sup.6 Pa to 10.sup.3 Pa, the heating temperature is set in a range of 600 C. to 650 C., and the holding time is set in a range of 30 minutes to 360 minutes.

(39) The power module substrate 10 of the first embodiment is manufactured in Steps S01 to S03 described above.

(40) Next, the heat sink 51 is bonded to the other surface side of the metal layer 13 of the power module substrate 10 (heat sink bonding Step S04).

(41) The power module substrate 10 and the heat sink 51 are laminated with a brazing material 28 interposed therebetween, pressurized in a laminating direction, and charged in a vacuum furnace to perform brazing. Accordingly, the metal layer 13 of the power module substrate 10 and the top plate part 52 of the heat sink 51 are bonded to each other. At this time, an AlSi-based brazing material foil (for example, Al-10 mass % Si brazing material foil) having a thickness of 20 m to 110 m can be used as the brazing material 28, for example, and the brazing temperature is set to a temperature lower than the temperature condition in the heating treatment Step S03.

(42) Next, the semiconductor element 3 is bonded to one surface of the circuit layer 12 of the power module substrate 10 by soldering (semiconductor element mounting Step S05).

(43) The power module 1 shown in FIG. 1 is manufactured in Steps S01 to S05 described above.

(44) Herein, in the heating treatment Step S03, Ti of the Ti foil 25, P of the CuP-based brazing material 24, oxygen existing in the ceramic substrate 11 or the CuP-based brazing material 24 react with each other in the bonding interfaces between the ceramic substrate 11 and the copper plate 22, and the active element oxide layer 30 (TiO layer) containing P is formed. An oxide existing in the surface of the ceramic substrate 11 or an oxide contained in the Ti foil 25 or the CuP-based brazing material 24 is used, for example, as oxygen existing in the ceramic substrate 11 or the CuP-based brazing material 24.

(45) According to the copper-ceramic bonded body (power module substrate 10) of the first embodiment having the configuration described above, since the copper plate 22 (circuit layer 12) formed of oxygen-free copper and the ceramic substrate 11 formed of AlN are bonded to each other with the CuP-based brazing material 24 and the Ti foil 25 interposed therebetween, and the active element oxide layer 30 (TiO layer) is formed at the bonding interfaces between the ceramic substrate 11 and the copper plate 22 (circuit layer 12), the ceramic substrate 11 and the circuit layer 12 are strongly bonded to each other.

(46) In the first embodiment, since the thickness t of the active element oxide layer 30 (TiO layer) is set to be equal to or greater than 5 nm, the ceramic substrate 11 and the copper plate 22 (circuit layer 12) are reliably bonded to each other and it is possible to ensure bonding strength thereof. In addition, since the thickness t of the active element oxide layer 30 (TiO layer) is set to be equal to or smaller than 220 nm, it is possible to prevent generation of cracks on the ceramic substrate 11 due to thermal stress during hot-cold cycling loading.

(47) In order to exhibit the operation effects described above, the thickness t of the active element oxide layer 30 (TiO layer) is preferably from 10 nm to 220 nm.

(48) The concentration of the active element (Ti in the first embodiment) of the active element oxide layer 30 is set in a range of 35 at % to 70 at %. The concentration of the active element herein is concentration when the total content of the active element (Ti in the first embodiment), P, and O is 100.

(49) In the first embodiment, since the bonding is performed using the CuP-based brazing material 24, P of the CuP-based brazing material 24 and Ti of the Ti foil 25 react with each other and further react with oxygen, and accordingly, it is possible to reliably form the active element oxide layer 30 (TiO layer) containing P. Accordingly, it is possible to reliably bond the ceramic substrate 11 and the copper plate 22 (circuit layer 12) to each other. That is, P which is an element easily reacting with Ti used as an active element and which is the element easily reacting with oxygen is interposed in the interface, and accordingly, the formation of the active element oxide layer 30 (TiO layer) described above is promoted and the ceramic substrate 11 and the copper plate 22 are reliably bonded to each other under the conditions of a low temperature.

(50) In a case where the ceramic substrate 11 formed of AlN and the copper plate 22 are held at a high temperature with Ti interposed therebetween (for example, 790 C. to 850 C.), nitrogen in the ceramic substrate 11 and Ti react with each other and TiN is formed. However, in the first embodiment, since the condition of a low temperature (range of 600 C. to 650 C.) is set in the heating treatment Step S03, the active element oxide layer 30 (TiO layer) is formed without forming TiN.

(51) In the first embodiment, as described above, the ceramic substrate 11 and the copper plate 22 can be bonded to each other under the conditions of a low temperature, and accordingly, the ceramic substrate 11 and the copper plate 22 are bonded to each other and the ceramic substrate 11 and the aluminum plate 23 are bonded to each other at the same time in the heating treatment Step S03, in the first embodiment. Therefore, it is possible to significantly improve manufacturing efficiency of the power module substrate 10 and to reduce the manufacturing cost. Since the copper plate 22 and the aluminum plate 23 are bonded to both surfaces of the ceramic substrate 11 at the same time, it is possible to prevent generation of a warp of the ceramic substrate 11 at the time of bonding.

Second Embodiment

(52) Next, a second embodiment according to the first aspect of the present invention will be described with reference to the accompanied drawings.

(53) A copper-ceramic bonded body according to the second embodiment of the present invention is a power module substrate configured by bonding the ceramic substrate 11 as a ceramic member formed of a nitride ceramic and the copper plate 22 (circuit layer 12) as a copper member formed of copper or a copper alloy to each other, in the same manner as in the first embodiment, and a structure of the bonding interfaces between the ceramic substrate 11 and the copper plate 22 (circuit layer 12) is different from the power module substrate shown in FIG. 1.

(54) FIG. 5 shows a structure of the bonding interfaces between the ceramic substrate 11 and the copper plate 22 (circuit layer 12) of the second embodiment of the present invention.

(55) In the second embodiment, as shown in FIG. 5, an active element oxide layer 130 containing an active element and oxygen and a CuAl eutectic layer 131 are laminated and disposed at the bonding interfaces between the ceramic substrate 11 and the circuit layer 12 (copper plate 22). That is, the CuAl eutectic layer 131 is formed between the active element oxide layer 130 and the copper plate 22 (circuit layer 12).

(56) Herein, in the second embodiment, a thickness t of the active element oxide layer 130 is in a range of 5 nm to 220 nm, is preferably in a range of 10 nm to 220 nm, and more preferably in a range of 10 nm to 50 nm. In the second embodiment, Ti is included as the active element, and the active element oxide layer 130 is a TiO layer containing Ti and oxygen.

(57) In the second embodiment, a thickness to of the CuAl eutectic layer 131 is preferably in a range of 10 m to 60 m and more preferably in a range of 10 m to 30 m. The CuAl eutectic layer 131 may include an active element thickened layer 131a obtained by thickening the active element (Ti in the second embodiment) on the active element oxide layer 130 side.

(58) The concentration of the active element of the active element oxide layer 130 is in a range of 35 at % to 70 at %.

(59) A CuAl eutectic layer is a portion having a composition in which the Cu concentration is 60 at % to 90 at % when the total of the Cu concentration and the Al concentration is 100 at %.

(60) The concentration of the active element of the active element thickened layer 131a is preferably in a range of 40 at % to 60 at % and more preferably in a range of 50 at % to 60 at %. The thickness of the active element thickened layer 131a is preferably in a range of 10 nm to 200 nm and more preferably in a range of 10 nm to 50 nm.

(61) The concentration and the thickness of the active element of the active element oxide layer 130 are measured by the same method as the concentration and the thickness of the active element of the active element oxide layer 30 of the first embodiment.

(62) For the thickness of the CuAl eutectic layer, the thicknesses of five portions having a composition in which the Cu concentration is 60 at % to 90 at % when the total of the Cu concentration and the Al concentration is 100 at % are measured using the EDS attached to the transmission electron microscope and an average value thereof is acquired.

(63) The composition of the active element thickened layer 131a is measured using the EDS attached to the transmission electron microscope.

(64) The manufacturing method of the power module substrate of the second embodiment is different from the manufacturing method of the power module substrate of the first embodiment in that the CuAl-based brazing material is used instead of the CuP-based brazing material 24.

(65) In the second embodiment, a CuAl-based brazing material containing Al in a range of 45 mass % to 95 mass % is used as the CuAl-based brazing material. In addition, the thickness of the CuAl-based brazing material is preferably in a range of 5 m to 50 m.

(66) The heating temperature at the time of bonding is desirably from 580 C. to 650 C.

(67) In the second embodiment, the ceramic substrate 11 and the circuit layer 12 (copper plate 22) are bonded to each other using the CuAl-based brazing material containing Al and Al in this CuAl-based brazing material is subjected to a eutectic reaction with Cu, and thus, the generation of liquid phases is caused under the conditions of a low temperature and the CuAl eutectic layer 131 described above is formed.

(68) According to the copper-ceramic bonded body (power module substrate) of the second embodiment having the configuration described above, since the active element oxide layer 130 (TiO layer) is formed at the bonding interfaces between the ceramic substrate 11 and the copper plate 22 (circuit layer 12), the ceramic substrate 11 and the circuit layer 12 are strongly bonded to each other.

(69) Furthermore, since the CuAl eutectic layer 131 is formed between the active element oxide layer 130 and the copper plate 22 (circuit layer 12), the generation of liquid phases is caused by a eutectic reaction under the conditions of a low temperature, and it is possible to reliably bond the ceramic substrate 11 and the circuit layer 12.

(70) Herein, since the thickness to of the CuAl eutectic layer 131 is equal to or greater than 10 m, the liquid phases are sufficiently formed as described above, and it is possible to reliably bond the ceramic substrate 11 and the circuit layer 12. Since the thickness to of the CuAl eutectic layer 131 is equal to or smaller than 60 m, it is possible to prevent a portion around the bonding interfaces from being brittle and to ensure high hot-cold cycle reliability.

(71) Hereinabove, the first and second embodiments according to the first aspect of the present invention have been described, but the present invention is not limited thereto and can be suitably modified within a range not departing technical ideas of the present invention.

(72) For example, the power module substrate in which the copper plate (circuit layer) as the copper member and the ceramic substrate as the ceramic member are bonded to each other has been described as an example, but there is no limitation and a copper-ceramic bonded body in which the copper member formed of copper or a copper alloy and the ceramic member formed of nitride ceramic are bonded to each other, may be used.

(73) An example of forming the circuit layer by bonding the copper plate has been described, but there is no limitation and the metal layer may be formed by bonding the copper plate.

(74) The copper plate has been described as the rolled plate of oxygen-free copper or tough pitch copper, but there is no limitation and the copper plate may be configured with other copper or copper alloy.

(75) The aluminum plate configuring the metal layer has been described as the rolled plate of pure aluminum having purity of 99.99 mass %, but there is no limitation and the aluminum plate may be configured with other aluminum or aluminum alloys such as aluminum having purity of 99 mass % (2N aluminum).

(76) The metal layer is not limited to a layer configured with an aluminum plate and may be configured with other metal.

(77) AlN has been described as the nitride ceramic, but there is no limitation and other nitride ceramic such as Si.sub.3N.sub.4 may be used.

(78) Ti has been described as the active element, but there is no limitation and other active elements such as Zr, Hf, or Nb may be used.

(79) In the first and second embodiments of the present invention, an example in which P is contained in the active element oxide layer formed at the bonding interfaces has been described, but there is no limitation.

(80) In the first and second embodiments of the present invention, an example in which the ceramic substrate and the copper plate are bonded to each other using the CuPSnNi-based brazing material and the CuAl-based brazing material has been described, but there is no limitation and other brazing materials may be used.

(81) In the first and second embodiments of the present invention, an example in which the CuPSnNi-based brazing material, the CuAl-based brazing material, and the Ti foil are interposed between the ceramic substrate and the copper plate has been described, but there is no limitation and CuPSnNi paste, CuAl paste, and Ti paste may be interposed.

(82) In the first and second embodiments, an example in which the Ti foil is interposed has been described, but there is no limitation and hydrogenated Ti can be used. In this case, a method of directly interposing powder of hydrogenated Ti or a method of applying hydrogenated Ti paste can be used. Not only the hydrogenated Ti, a hydride of other active elements such as Zr, Hf, or Nb can be used.

(83) The heat sink is not limited to the example in the first and second embodiments of the present invention and there is no particular limitation to the structure of the heat sink.

(84) A buffer layer formed of aluminum, an aluminum alloy, or a composite material (for example, AlSiC or the like) containing aluminum may be provided between the top plate part or a radiator plate of the heat sink and the metal layer.

Second Aspect

Third Embodiment

(85) Hereinafter, the third embodiment according to the second aspect of the present invention will be described with reference to the accompanied drawings.

(86) The members having the same configuration as those in the first embodiment have the same reference numerals and detailed description will be omitted.

(87) A copper-ceramic bonded body according to the third embodiment is a power module substrate 210 configured by bonding a ceramic substrate 211 as a ceramic member formed of alumina and the copper plate 22 (circuit layer 12) as a copper member formed of copper or a copper alloy to each other.

(88) FIG. 8 shows the power module substrate 210 of the third embodiment of the present invention and a power module 201 using this power module substrate 210.

(89) The power module 201 includes the power module substrate 210, the semiconductor element 3 bonded to a surface of one side (upper side in FIG. 8) of the power module substrate 210 through the solder layer 2, and the heat sink 51 disposed on the other side (lower side in FIG. 8) of the power module substrate 210.

(90) In the solder layer 2, the same soldering material as that in the first embodiment can be used.

(91) The power module substrate 210 includes the ceramic substrate 211, the circuit layer 12 installed on one surface (upper surface in FIG. 8) of the ceramic substrate 211, and the metal layer 13 installed on the other surface (lower surface in FIG. 8) of the ceramic substrate 211.

(92) The ceramic substrate 211 prevents electric connection between the circuit layer 12 and the metal layer 13 and the ceramic substrate 211 of the third embodiment is configured with 98% alumina (Al.sub.2O.sub.3 purity equal to or greater than 98 mass %) which is one kind of alumina. Herein, a thickness of the ceramic substrate 211 is preferably set in a range of 0.2 mm to 1.5 mm and is set to 0.38 mm in the third embodiment.

(93) As shown in FIG. 10, the circuit layer 12 is formed by bonding the copper plate 22 formed of copper or a copper alloy to one surface of the ceramic substrate 211. In the third embodiment, the circuit layer 12 has the same configurations (the material, the usage, the thickness, and the like) as those of the circuit layer 12 of the first embodiment.

(94) As shown in FIG. 10, the metal layer 13 is formed by bonding the aluminum plate 23 to the other surface of the ceramic substrate 211. In the third embodiment, the metal layer 13 is formed by bonding the aluminum plate 23 formed of a rolled plate of aluminum having purity equal to or greater than 99.99 mass % (so-called 4N aluminum) to the ceramic substrate 211.

(95) The aluminum plate 23 of the third embodiment has the same configurations (the bearing force, the thickness, and the like) as those of the aluminum plate 23 of the first embodiment.

(96) The heat sink 51 is for cooling the power module substrate 210 described above and has the same configurations (the structure, the material, the bonding method to the metal layer 13 of the power module substrate) as those of the heat sink 51 of the first embodiment, except the power module substrate 10 is the power module substrate 210.

(97) Here, as shown in FIG. 9, an active element oxide layer 230 containing an active element, oxygen, phosphorous is formed at the bonding interfaces between the ceramic substrate 211 and the circuit layer 12 (copper plate 22). In the third embodiment, a thickness t of the active element oxide layer 230 is set to be in a range of 5 nm to 220 nm. The thickness t of the active element oxide layer 230 is preferably from 10 nm to 220 nm and is more preferably from 10 nm to 50 nm.

(98) In the third embodiment, Ti is included as the active element, and the active element oxide layer 230 described above is set as a TiPO layer containing Ti, oxygen (O), and phosphorous (P).

(99) In a case where Zr is used as the active element, the active element oxide layer 230 is a ZrPO layer, and in a case where Nb is used, the active element oxide layer 230 is a NbPO layer, and in a case where Hf is used, the active element oxide layer 230 is a HfPO layer.

(100) The concentration of the active element of the active element oxide layer 230 is set to be in a range of 35 at % to 70 at %. The concentration of the active element herein is concentration when the total content of the active element, P, and O is 100.

(101) In the third embodiment, the content of P of the active element oxide layer 230 is preferably in a range of 1.5 mass % to 10 mass % and more preferably in a range of 3 mass % to 8 mass %. The content of P herein is content when the total content of the active metal, P, and O is 100.

(102) Since the content of P is equal to or greater than 1.5 mass %, it is possible to reliably form the active element oxide layer 230 and to reliably bond the ceramic substrate 211 and the circuit layer 12 to each other. In addition, since the content of P is equal to or smaller than 10 mass %, the active element oxide layer 230 does not become excessively hard, and it is possible to decrease the load applied to the ceramic substrate due to thermal stress during cold-hot cycling loading, for example, and to prevent a decrease in reliability of the bonding interfaces.

(103) The concentration and the thickness of the active element and the P content of the active element oxide layer 230 are measured by the same method as the concentration and the thickness of the active element and the P content of the active element oxide layer 30 of the first embodiment.

(104) Next, a manufacturing method of the power module substrate 210 of the third embodiment described above will be described with reference to FIG. 3 and FIG. 10.

(105) First, as shown in FIG. 10, a CuP-based brazing material 224, a Ti foil 225, and the copper plate 22 to be the circuit layer 12 are laminated on one surface (upper surface in FIG. 10) of the ceramic substrate 211 in order (first laminating Step S01), and the Al plate 23 to be the metal layer 13 is laminated on the other surface (lower surface in FIG. 10) of the ceramic substrate 211 in order with the bonding material 27 interposed therebetween (second laminating Step S02).

(106) Herein, in the third embodiment, it is preferable that a CuPSnNi brazing material containing 3 mass % to 10 mass % of P, 7 mass % to 50 mass % of Sn which is a low-melting-point element, and 2 mass % to 15 mass % of Ni is used as the CuP-based brazing material 224. A thickness of the CuP-based brazing material 224 is preferably in a range of 5 m to 50 m.

(107) In addition, a CuPZn brazing material or the like can be used as the CuP-based brazing material 224.

(108) In the third embodiment, a thickness of the Ti foil 225 is preferably in range of 0.5 m to 25 m and a Ti foil having a thickness of 12 m is used in the third embodiment.

(109) In the third embodiment, a AlSi-based brazing material (for example, Al-7.5 mass % Si brazing material) containing Si as a melting-point decreasing element is preferably used as the bonding material 27 which bonds the aluminum plate 23 to the ceramic substrate 211. In addition, the same material as the brazing material used in the first embodiment can be used as the bonding material 27.

(110) Next, the ceramic substrate 211, the CuP-based brazing material 224, the Ti foil 225, the copper plate 22, the bonding material 27, and the Al plate 23 are charged and heated in a vacuum heating furnace, in a state of being pressurized (pressure of 1 kgf/cm.sup.2 to 35 kgf/cm.sup.2) in a laminating direction (heating treatment Step S03). In the third embodiment, the pressure in the vacuum heating furnace is set in a range of 10.sup.6 Pa to 10.sup.3 Pa, the heating temperature is set in a range of 600 C. to 650 C., and the holding time is set in a range of 30 minutes to 360 minutes.

(111) The power module substrate 210 of the third embodiment is manufactured in Steps S01 to S03 described above.

(112) Next, the heat sink 51 is bonded to the other surface side of the metal layer 13 of the power module substrate 210 (heat sink bonding Step S04).

(113) The power module substrate 210 and the heat sink 51 are laminated with the brazing material 28 interposed therebetween, pressurized in a laminating direction, and charged in a vacuum furnace to perform brazing. Accordingly, the metal layer 13 of the power module substrate 210 and the top plate part 52 of the heat sink 51 are bonded to each other. At this time, an AlSi-based brazing material foil (for example, Al-10 mass % Si brazing material foil) having a thickness of 20 m to 110 m can be used as the brazing material 28, for example, and the brazing temperature is set to a temperature lower than the temperature condition in the heating treatment Step S03.

(114) Next, the semiconductor element 3 is bonded to one surface of the circuit layer 12 of the power module substrate 210 by soldering (semiconductor element mounting Step S05).

(115) The power module 201 shown in FIG. 8 is manufactured in Steps S01 to S05 described above.

(116) Herein, in the heating treatment Step S03, Ti of the Ti foil 225, P of the CuP-based brazing material 224, oxygen existing in the ceramic substrate 211 or the CuP-based brazing material 224 react with each other in the bonding interfaces between the ceramic substrate 211 and the copper plate 22, and the active element oxide layer 30 (TiPO layer) containing P is formed. An oxide in the surface of the ceramic substrate 211 or an oxide contained in the Ti foil 225 or the CuP-based brazing material 224 is used, for example, as oxygen existing in the ceramic substrate 211 or the CuP-based brazing material 224. In the third embodiment, since the heating treatment Step S03 is executed under the conditions of a low temperature, decomposition of alumina configuring the ceramic substrate 211 is prevented, the supply of oxygen from alumina is prevented, and it is possible to form the thin active element oxide layer 230.

(117) According to the copper-ceramic bonded body (power module substrate 210) of the third embodiment having the configuration described above, since the copper plate 22 (circuit layer 12) formed of oxygen-free copper and the ceramic substrate 211 formed of alumina are bonded to each other with the CuP-based brazing material 224 and the Ti foil 225 interposed therebetween, and the active element oxide layer 230 (TiPO layer) is formed at the bonding interfaces between the ceramic substrate 211 and the copper plate 22 (circuit layer 12), the ceramic substrate 211 and the circuit layer 12 are strongly bonded to each other.

(118) In the third embodiment, since the thickness t of the active element oxide layer 230 (TiPO layer) is set to be equal to or greater than 5 nm, the ceramic substrate 211 and the copper plate 22 (circuit layer 12) are reliably bonded to each other and it is possible to ensure bonding strength thereof. Meanwhile, since the thickness t of the active element oxide layer 230 (TiPO layer) is set to be equal to or smaller than 220 nm, it is possible to prevent generation of cracks on the ceramic substrate 211 due to thermal stress during hot-cold cycling loading.

(119) In order to exhibit the operation effects described above, the thickness t of the active element oxide layer 230 (TiPO layer) is preferably from 10 nm to 220 nm.

(120) In the third embodiment, since the bonding is performed using the CuP-based brazing material 224, P of the CuP-based brazing material 224 and Ti of the Ti foil 225 react with each other and further react with oxygen, and accordingly, it is possible to reliably form the active element oxide layer 230 (TiPO layer) containing P.

(121) Accordingly, it is possible to reliably bond the ceramic substrate 211 and the copper plate 22 (circuit layer 12) to each other. That is, P which is an element easily reacting with Ti used as an active element and which is the element easily reacting with oxygen is interposed in the interface, and accordingly, the formation of the active element oxide layer 230 (TiPO layer) described above is promoted and the ceramic substrate 211 and the copper plate 22 are reliably bonded to each other under the conditions of a low temperature.

(122) In a case where the ceramic substrate 211 formed of alumina and the copper plate 22 are held at a high temperature with Ti interposed therebetween (for example, 790 C. to 850 C.), oxygen in the ceramic substrate 211 and Ti react with each other and a thick Ti oxide layer is formed. However, in the third embodiment, since the condition of a low temperature (range of 600 C. to 650 C.) is set in the heating treatment Step S03, the active element oxide layer 230 (TiPO layer) described above is formed to be comparatively thin.

(123) In the third embodiment, as described above, the ceramic substrate 211 and the copper plate 22 can be bonded to each other under the conditions of a low temperature, and accordingly, the ceramic substrate 211 and the copper plate 22 are bonded to each other and the ceramic substrate 211 and the aluminum plate 23 are bonded to each other at the same time in the heating treatment Step S03, in the third embodiment. Therefore, it is possible to significantly improve manufacturing efficiency of the power module substrate 210 and to reduce the manufacturing cost. Since the copper plate 22 and the aluminum plate 23 are bonded to both surfaces of the ceramic substrate 211 at the same time, it is possible to prevent generation of a warp of the ceramic substrate 211 at the time of bonding.

(124) Hereinabove, the third embodiment of the present invention has been described, but the present invention is not limited thereto and can be suitably modified within a range not departing technical ideas of the present invention.

(125) For example, the power module substrate in which the copper plate (circuit layer) as the copper member and the ceramic substrate as the ceramic member are bonded to each other has been described as an example, but there is no limitation and a copper-ceramic bonded body in which the copper member formed of copper or a copper alloy and the ceramic member formed of alumina are bonded to each other, may be used.

(126) An example of forming the circuit layer by bonding the copper plate has been described, but there is no limitation and the metal layer may be formed by bonding the copper plate.

(127) The copper plate has been described as the rolled plate of oxygen-free copper or tough pitch copper, but there is no limitation and the copper plate may be configured with other copper or copper alloy.

(128) The aluminum plate configuring the metal layer has been described as the rolled plate of pure aluminum having purity equal to or greater than 99.99 mass %, but there is no limitation and the aluminum plate may be configured with other aluminum or aluminum alloys such as aluminum having purity equal to or greater than 99 mass % (2N aluminum).

(129) The metal layer is not limited to a layer configured with an aluminum plate and may be configured with other metal.

(130) 98% alumina (Al.sub.2O.sub.3 purity equal to or greater than 98 mass %) has been described as the nitride ceramic, but there is no limitation and other alumina such as 92% alumina (Al.sub.2O.sub.3 purity equal to or greater than 92 mass %), 96% alumina (Al.sub.2O.sub.3 purity equal to or greater than 96 mass %), or zirconia-toughened alumina may be used. Ti has been described as the active element, but there is no limitation and other active elements such as Zr or Hf may be used.

(131) In the third embodiment, an example in which the ceramic substrate and the copper plate are bonded to each other using the CuPSnNi-based brazing material has been described, but there is no limitation and other brazing materials may be used.

(132) In the third embodiment, an example in which the CuPSnNi-based brazing material and the Ti foil are interposed between the ceramic substrate and the copper plate has been described, but there is no limitation and CuPSnNi paste and Ti paste may be interposed.

(133) The heat sink is not limited to the example in the third embodiment and there is no particular limitation to the structure of the heat sink.

(134) A buffer layer formed of aluminum, an aluminum alloy, or a composite material (for example, AlSiC or the like) containing aluminum may be provided between the top plate part or a radiator plate of the heat sink and the metal layer.

EXAMPLES

(135) Confirmation experiments performed for confirming effectiveness of the first embodiment and the second embodiment of the invention will be described.

Example 1

(136) A copper-ceramic bonded body (power module substrate) was formed using a ceramic substrate, a brazing material, an active element, and a copper plate shown in Table 1.

(137) More specifically, a copper plate (rolled plate of oxygen-free copper) having a size of 38 mm38 mm and a thickness of 0.3 mm was laminated on one and the other surfaces of a ceramic substrate having a size of 40 mm40 mm and a thickness of 0.635 mm with a brazing material and an active element shown in Table 1 interposed therebetween, and these components were charged and heated in a vacuum heating furnace (degree of vacuum of 510.sup.4 Pa) in a state of being pressurized at pressure of 6 kgf/cm.sup.2 in a laminating direction to manufacture a power module substrate. The conditions of the heating treatment step are shown in Table 2.

(138) In Example A4 of the invention, Cu-7 mass % P-15 mass % Sn-10 mass % Ni powder and paste formed of Ti powder were used as the brazing material and the active element. A coating thickness of the paste was set as 85 km.

(139) Regarding the power module substrate obtained as described above, the bonding interfaces between the circuit layer (copper plate) and the ceramic substrate were observed and an initial bonding rate and a bonding rate after the hot-cold cycle were evaluated.

(140) (Bonding Interface Observation)

(141) The bonding interfaces between the copper plate and the ceramic substrate were observed using a transmission electron microscope (JEM-2010F manufactured by JEOL Ltd.)

(142) The interface observation results of Example A1 of the invention and element mapping are shown in FIG. 6.

(143) The thickness of the active element oxide layer was measured by observing the bonding interfaces with magnification of 200000 and assuming a portion having concentration of the active element in a range of 35 at % to 70 at % as the active element oxide layer. The P concentration (at %), the active element concentration (at %), and the O concentration (at %) were measured by the EDS attached to the transmission electron microscope and the concentration (at %) of the active element was set as concentration of the active element when the total of P concentration, active element concentration, and O concentration is 100. An average value of 5 viewing fields was set as the thickness of the active element oxide layer.

(144) The P concentration (mass %), the Ti concentration (mass %), and O concentration (mass %) in the active element oxide layer were measured by the EDS attached to the transmission electron microscope, the P concentration when the total of the P concentration, the Ti concentration, and the O concentration was 100, was calculated, and the P concentration in the active element oxide layer was set as the P concentration (mass %). Five measurement points were used and an average value thereof was used as the P concentration.

(145) The results are shown in Table 2.

(146) (Hot-Cold Cycle Test)

(147) In the hot-cold cycle test, 2000 cycles of 40 C.5 min.fwdarw.150 C.5 min are executed with respect to the power module substrate with the liquid phase (Fluorinert) using a hot-cold shock testing device TSB-51 manufactured by ESPEC Corporation.

(148) (Bonding Rate)

(149) The bonding rate of the copper substrate and the ceramic substrate was acquired using the following equation using an ultrasonic test device. Herein, the initial bonding area was an area to be bonded before the bonding, that is, the area of the copper plate. Since the peeling is shown as a white portion in the bonded portion in an ultrasonic flaw detection image, the area of the white portion was used as the peeling area.
(bonding rate)={(initial bonding area)(peeling area)}/(initial bonding area)

(150) TABLE-US-00001 TABLE 1 Brazing material Active element Ceramic Thickness Thickness substrate Composition [m] Shape [m] Example A1 of the invention AIN Cu-7mass % P-10mass % Sn-6.5mass % Ni 20 Ti foil 25 Example A2 of the invention AIN Cu-7mass % P-15mass % Sn-10mass % Ni 20 Ti foil 0.6 Example A3 of the invention AIN Cu-7mass % P-15mass % Sn-10mass % Ni 20 Ti foil 6 Example A4 of the invention AIN Brazing material pasteTi paste Example A5 of the invention Si.sub.3N.sub.4 Cu-7mass % P-15mass % Sn-10mass % Ni 50 Ti foil 10 Example A6 of the invention Si.sub.3N.sub.4 Cu-7mass % P-15mass % Sn-10mass % Ni 50 Ti foil 10 Example A7 of the invention AIN Cu-7mass % P-10mass % Sn-6.5mass % Ni 20 Ti vapor 0.1 deposited film Example A8 of the invention Si.sub.3N.sub.4 Cu-7mass % P-10mass % Sn-6.5mass % Ni 20 Ti vapor 0.1 deposited film Example A9 of the invention AIN Cu-50mass % Sn 50 Ti foil 4 Example A10 of the invention AIN Cu-7mass % P-15mass % Sn-10mass % Ni 25 Zr foil 1 Example A11 of the invention AIN Cu-7mass % P-15mass % Sn-10mass % Ni 50 Hf foil 1 Example A12 of the invention AIN Cu-7mass % P-15mass % Sn-10mass % Ni 50 Nb foil 1 Example A13 of the invention AIN Cu-7mass % P-15mass % Sn-10mass % Ni 20 Ti foil 6 Comparative Example A1 AIN Cu-7mass % P-15mass % Sn-10mass % Ni 20 Ti foil 10 Comparative Example A2 AIN Cu-7mass % P-15mass % Sn-10mass % Ni 20 Ti foil 10 Related Art Example A1 AIN Ag-28mass % Cu-3mass % Ti 20

(151) TABLE-US-00002 TABLE 2 Heating Interface Bonding treatment step observation results rate [%] Temperature Time Thickness After hot-cold [ C.] [min] Bonding interface [nm] P concentration Initial cycle Example A1 of the invention 630 30 Active element oxide layer 6 1.5 98.4 93.9 Example A2 of the invention 610 240 Active element oxide layer 10 3.1 98.8 94.1 Example A3 of the invention 650 180 Active element oxide layer 200 9.7 99.3 96.8 Example A4 of the invention 630 150 Active element oxide layer 100 5.7 99.1 95.6 Example A5 of the invention 630 180 Active element oxide layer 100 6.4 98.7 96.2 Example A6 of the invention 650 60 Active element oxide layer 100 6.2 99.1 94.6 Example A7 of the invention 650 120 Active element oxide layer 160 7.4 99.2 95.8 Example A8 of the invention 650 120 Active element oxide layer 140 7.1 98.1 94.9 Example A9 of the invention 650 60 Active element oxide layer 120 0 98.9 87.5 Example A10 of the invention 650 60 Active element oxide layer 150 8.3 98.4 96.9 Example A11 of the invention 650 60 Active element oxide layer 20 3.2 98.6 93.7 Example A12 of the invention 650 60 Active element oxide layer 40 4.3 98.2 94.2 Example A13 of the invention 650 210 Active element oxide layer 220 9.6 98.9 92.9 Comparative Example A1 650 15 Active element oxide layer 2 1.1 80.1 58.4 Comparative Example A2 650 400 Active element oxide layer 300 9.8 99.7 Cracks in 1500 to 2000 Related Art Example A1 650 30

(152) The copper plate and the ceramic substrate were not bonded to each other in Related Art Example A1 in which the copper plate and the ceramic substrate were bonded using a AgCuTi brazing material at a low temperature.

(153) In Comparative Example A1 in which the thickness of the active element oxide layer is smaller than 5 nm, initial bonding rate was low and the bonding was insufficient.

(154) In Comparative Example A2 in which the thickness of the active element oxide layer exceeds 220 nm, cracks were generated on the ceramic substrate after the hot-cold cycle. It is assumed that the thermal stress applied to the ceramic substrate is increased due to the formation of the thick active element oxide layer at the bonding interfaces.

(155) With respect to this, in Example A1 to Example A13 of the invention in which the thickness of the active element oxide layer is from 5 nm to 220 nm, the initial bonding rate was high even under the conditions of a comparatively low temperature and the ceramic substrate and the copper plate were reliably bonded to each other. In addition, the bonding rate after the hot-cold cycle was high and the bond reliability was improved.

Example 2

(156) A copper-ceramic bonded body (power module substrate) was formed using a ceramic substrate, a brazing material, an active element, and a copper plate shown in Table 3.

(157) More specifically, a copper plate (rolled plate of oxygen-free copper) having a size of 38 mm38 mm and a thickness of 0.3 mm was laminated on one and the other surfaces of a ceramic substrate having a size of 40 mm40 mm and a thickness of 0.635 mm with a brazing material and an active element shown in Table 3 interposed therebetween, and these components were charged and heated in a vacuum heating furnace (degree of vacuum of 510.sup.4 Pa) in a state of being pressurized at pressure of 6 kgf/cm.sup.2 in a laminating direction to manufacture a power module substrate. The conditions of the heating treatment step are shown in Table 4.

(158) Regarding the power module substrate obtained as described above, the bonding interfaces between the circuit layer (copper plate) and the ceramic substrate were observed and an initial bonding rate and a bonding rate after the hot-cold cycle were evaluated. The evaluation method was the same as that in Example 1.

(159) In the bonding interface observation, the thickness of the element oxide layer, and the thickness and the composition analysis of the CuAl eutectic layer were measured using the EDS attached to the transmission electron microscope.

(160) A portion having a composition in which the Cu concentration is 60 at % to 90 at % when the total of the Cu concentration and the Al concentration is 100 at % was assumed as the CuAl eutectic layer and a thickness of the CuAl eutectic layer was measured.

(161) In the composition of the CuAl eutectic layer, five measurement points were used and an average value thereof was set. The observation results are shown in FIG. 7. The evaluation results are shown in Table 4.

(162) TABLE-US-00003 TABLE 3 Brazing material Active element Ceramic Thickness Thickness substrate composition [m] Shape [m] Example A14 of the invention AIN Cu-50mass % Al 5 Ti foil 25 Example A15 of the invention AIN Cu-50mass % Al 10 Ti foil 0.6 Example A16 of the invention AIN Cu-68mass % Al 30 Ti foil 6 Example A17 of the invention AIN Cu-68mass % Al 50 Ti foil 6 Example A18 of the invention AIN Cu-68mass % Al 70 Ti foil 6 Example A19 of the invention Si.sub.3N.sub.4 Cu-80mass % Al 20 Ti foil 10 Example A20 of the invention Si.sub.3N.sub.4 Cu-80mass % Al 20 Ti foil 10 Example A21 of the invention AIN Cu-68mass % Al 20 Ti vapor 0.1 deposited film Example A22 of the invention Si.sub.3N.sub.4 Cu-68mass % Al 20 Ti vapor 0.1 deposited film

(163) TABLE-US-00004 TABLE 4 Heating Interface observation results treatment Thickness of Cu concentration Thickness of Bonding step active element of CuAl CuAl rate [%] Temperature Time oxide layer eutectic layer eutectic layer After hot-cold [ C.] [min] Bonding interfaces [nm] [at %] [m] Initial cycle Example A14 of 600 30 Active element oxide 7 82.6 5 98.0 90.4 the invention layer Example A15 of 620 30 Active element oxide 15 76.9 10 98.7 95.2 the invention layer Example A16 of 580 120 Active element oxide 15 79.2 40 97.8 94.7 the invention layer Example A17 of 650 60 Active element oxide 100 69.5 60 98.7 95.8 the invention layer Example A18 of 650 120 Active element oxide 150 83.4 90 98.6 89.7 the invention layer Example A19 of 650 60 Active element oxide 90 76.6 50 97.7 95.5 the invention layer Example A20 of 650 90 Active element oxide 120 71.0 60 98.6 94.5 the invention layer Example A21 of 650 60 Active element oxide 100 81.6 40 97.5 95.0 the invention layer Example A22 of 650 60 Active element oxide 100 69.7 40 97.5 94.3 the invention layer

(164) In Example A14 to Example A22 of the invention in which the thickness of the active element oxide layer is set to be from 5 nm to 220 nm using the CuAl-based brazing material, the initial bonding rate was high even under the conditions of a comparatively low temperature and the ceramic substrate and the copper plate were reliably bonded to each other. Particularly, in Example A15 to Example A17 and Example A19 to Example A22 of the invention in which the thickness of the CuAl eutectic layer is from 10 m to 60 m, the bonding rate after the hot-cold cycle was high and a power module substrate having high bond reliability was obtained.

(165) From the above results, it was confirmed that, according to the invention, it is possible to provide a copper-ceramic bonded body (power module substrate) in which the copper member formed of copper or a copper alloy and the ceramic member formed of nitride ceramic are reliably bonded to each other under the conditions of a low temperature.

Example 3

(166) Confirmation experiments performed for confirming effectiveness of the third embodiment of the invention will be described.

(167) A copper-ceramic bonded body (power module substrate) was formed using a ceramic substrate (MARUWA Co., Ltd.), a brazing material, an active element, and a copper plate shown in Table 5.

(168) More specifically, a copper plate (rolled plate of oxygen-free copper) having a size of 38 mm38 mm and a thickness of 0.3 mm was laminated on one and the other surfaces of a ceramic substrate having a size of 40 mm40 mm and a thickness of 0.38 mm with a brazing material and an active element shown in Table 5 interposed therebetween, and these components were charged and heated in a vacuum heating furnace (degree of vacuum of 510.sup.4 Pa) in a state of being pressurized at pressure of 7 kgf/cm.sup.2 in a laminating direction to manufacture a power module substrate. The conditions of the heating treatment step are shown in Table 6.

(169) In Example B4 of the invention, Cu-7 mass % P-15 mass % Sn-10 mass % Ni powder and paste formed of Ti powder were used as the brazing material and the active element. A coating thickness of the paste was set as 80 m.

(170) Regarding the power module substrate obtained as described above, the bonding interfaces between the circuit layer (copper plate) and the ceramic substrate were observed and an initial bonding rate and a bonding rate after the hot-cold cycle were evaluated. Each layer shown in the bonding interfaces of Table 6 is the active element oxide layer. Evaluation method was the same as that in Example 1.

(171) The evaluation results are shown in Table 6. The interface observation results of Example B2 of the invention are shown in FIG. 11.

(172) TABLE-US-00005 TABLE 5 Brazing material Active element Ceramic Thickness Thickness substrate Composition [m] Shape [m] Example B1 of the invention 98% alumina Cu-7mass % P-10mass % Sn-6.5mass % Ni 20 Ti foil 0.5 Example B2 of the invention 98% alumina Cu-7mass % P-15mass % Sn-10mass % Ni 20 Ti foil 3 Example B3 of the invention 98% alumina Cu-7mass % P-15mass % Sn-10mass % Ni 20 Ti foil 10 Example B4 of the invention 98% alumina Brazing material pasteTi paste Example B5 of the invention Reinforced Cu-7mass % P-15mass % Sn-10mass % Ni 50 Ti foil 20 alumina Example B6 of the invention Reinforced Cu-7mass % P-15mass % Sn-10mass % Ni 50 Ti foil 25 alumina Example B7 of the invention 98% alumina Cu-4mass % P-20mass % Sn-7mass % Ni 50 Ti foil 10 Example B8 of the invention 98% alumina Cu-10mass % P-20mass % Sn-7mass % Ni 50 Ti foil 10 Example B9 of the invention 98% alumina Cu-7mass % P-15mass % Sn-10mass % Ni 50 Zr foil 5 Example B10 of the invention 98% alumina Cu-7mass % P-15mass % Sn-10mass % Ni 50 Nb foil 5 Example B11 of the invention 98% alumina Cu-7mass % P-15mass % Sn-10mass % Ni 50 Hf foil 5 Comparative Example B1 98% alumina Cu-7mass % P-15mass % Sn-10mass % Ni 50 Ti foil 20 Comparative Example B2 98% alumina Cu-7mass % P-15mass % Sn-10mass % Ni 50 Ti foil 20 Related Art Example B1 98% alumina Ag-28mass % Cu-3mass % Ti 20

(173) TABLE-US-00006 TABLE 6 Heating Interface Bonding treatment step observation results rate [%] Temperature Bonding Thickness After hot-cold [ C.] Time [min] interfaces [nm] P concentration Initial cycle Example B1 of the invention 610 200 TiPO layer 6 1.6 98.6 93.7 Example B2 of the invention 630 30 TiPO layer 10 2.1 98.9 94.8 Example B3 of the invention 630 180 TiPO layer 100 6.4 99.3 96.8 Example B4 of the invention 650 60 TiPO layer 100 4.9 99.2 96.6 Example B5 of the invention 650 30 TiPO layer 50 3.7 99.5 95.0 Example B6 of the invention 650 180 TiPO layer 200 9.4 99.7 97.1 Example B7 of the invention 610 200 TiPO layer 6 1.1 99.1 83.4 Example B8 of the invention 650 180 TiPO layer 200 14.2 98.8 84.2 Example B9 of the invention 650 180 ZrPO layer 220 9.6 99.6 97.2 Example B10 of the invention 650 240 NbPO layer 150 8.9 98.1 94.4 Example B11 of the invention 650 240 HfPO layer 150 9.1 98.2 93.8 Comparative Example B1 650 15 TiPO layer 3 1.0 83.4 60.1 Comparative Example B2 650 400 TiPO layer 300 9.7 99.6 Cracks in 1500 to 2000 Related Art Example B1 650 30

(174) The copper plate and the ceramic substrate were not bonded to each other in Related Art Example B1 in which the copper plate and the ceramic substrate were bonded using a AgCuTi brazing material under the conditions of a low temperature.

(175) In Comparative Example B1 in which the thickness of the active element oxide layer is smaller than 5 nm, initial bonding rate was low and the bonding was insufficient.

(176) In Comparative Example B2 in which the thickness of the active element oxide layer exceeds 220 nm, cracks were generated on the ceramic substrate after the hot-cold cycle. It is assumed that the thermal stress applied to the ceramic substrate is increased due to the formation of the thick active element oxide layer at the bonding interfaces.

(177) With respect to this, in Example B1 to Example B1 of the invention in which the thickness of the active element oxide layer is from 5 nm to 220 nm, the initial bonding rate was high even under the conditions of a comparatively low temperature and the ceramic substrate and the copper plate were reliably bonded to each other. In Examples B1 to B6 and B9 to B11 of the invention in which the phosphorous concentration of the active element oxide layer is in a range of 1.5 mass % to 10 mass %, the bonding rate after the hot-cold cycle was equal to or greater than 90% which was high, and bond reliability was improved.

(178) From the above results, it was confirmed that, according to the invention, it is possible to provide a copper-ceramic bonded body (power module substrate) in which the copper member formed of copper or a copper alloy and the ceramic member formed of alumina are reliably bonded to each other under the conditions of a low temperature.

REFERENCE SIGNS LIST

(179) 10, 210: POWER MODULE SUBSTRATE 11, 211: CERAMIC SUBSTRATE 12: CIRCUIT LAYER 13: METAL LAYER 22: COPPER PLATE 24, 224: CuP-BASED BRAZING MATERIAL 25, 225: Ti FOIL 30, 130, 230: ACTIVE ELEMENT OXIDE LAYER 131: CuAl EUTECTIC LAYER