Method for manufacturing insulated circuit board, insulated circuit board, and thermoelectric conversion module

Abstract

The method for manufacturing an insulated circuit board of the present invention includes: a ceramic/aluminum-joining step of joining an aluminum material to a ceramic substrate and thereby, forming an aluminum layer; a titanium material-disposing step of disposing a titanium material on a surface of the aluminum layer or the aluminum material in a circuit pattern shape; a titanium layer-forming step of performing a heat treatment in a state where the titanium material is laminated on the surface of the aluminum layer or the aluminum material and thereby, forming the titanium layer; and an etching treatment step of etching the aluminum layer on which the titanium layer is formed, into the circuit pattern shape.

Claims

1. A method for manufacturing an insulated circuit board including a ceramic substrate and a circuit layer having a circuit pattern disposed on one surface of the ceramic substrate, wherein the circuit layer includes an aluminum layer disposed on the one surface of the ceramic substrate, and a titanium layer formed on a surface of the aluminum layer on a side opposite to the ceramic substrate, and the method comprises: a ceramic/aluminum-joining step of joining an aluminum material to the ceramic substrate and thereby, forming the aluminum layer; a titanium material-disposing step of disposing a titanium material, which is to become the titanium layer, on a surface of the aluminum layer or the aluminum material in the circuit pattern shape; a titanium layer-forming step of performing a heat treatment in a state where the titanium material is laminated on the surface of the aluminum layer or the aluminum material and thereby, forming the titanium layer; an etching treatment step of etching the aluminum layer on which the titanium layer is formed, into the circuit pattern shape; and the method further comprises a Si-enriched layer-forming step of forming a Si-enriched layer containing Si in an amount of 0.03 mass % or more and 1.0 mass % or less on the surface of the aluminum layer or the aluminum material on which the titanium layer is to be formed, before the titanium material-disposing step.

2. The method for manufacturing an insulated circuit board according to claim 1, wherein the circuit layer includes a metal member layer consisting of copper, a copper alloy, nickel, a nickel alloy, silver, or a silver alloy laminated on a surface of the titanium layer on a side opposite to the aluminum layer, and the method further comprises a metal member layer-forming step of forming the metal member layer on the surface of the titanium layer formed into the circuit pattern shape after the etching treatment step.

3. The method for manufacturing an insulated circuit board according to claim 2, wherein the titanium material-disposing step and the titanium layer-forming step are performed after the ceramic/aluminum-joining step.

4. The method for manufacturing an insulated circuit board according to claim 2, wherein the ceramic/aluminum-joining step is performed after the titanium layer-forming step.

5. The method for manufacturing an insulated circuit board according to claim 2, wherein the titanium layer-forming step and the ceramic/aluminum-joining step are simultaneously performed.

6. The method for manufacturing an insulated circuit board according to claim 2, further comprising: an aluminum-cleaning step of cleaning the surface of the aluminum layer or the aluminum material before the titanium material-disposing step.

7. The method for manufacturing an insulated circuit board according to claim 2, further comprising: a titanium layer-cleaning step of cleaning the surface of the titanium layer before the metal member layer-forming step.

8. The method for manufacturing an insulated circuit board according to claim 7 wherein the titanium material-disposing step and the titanium layer-forming step are performed after the ceramic/aluminum-joining step.

9. The method for manufacturing an insulated circuit board according to claim 7, wherein the ceramic/aluminum-joining step is performed after the titanium layer-forming step.

10. The method for manufacturing an insulated circuit board according to claim 7, wherein the titanium layer-forming step and the ceramic/aluminum-joining step are simultaneously performed.

11. The method for manufacturing an insulated circuit board according to claim 7, further comprising: an aluminum-cleaning step of cleaning the surface of the aluminum layer or the aluminum material before the titanium material-disposing step.

12. The method for manufacturing an insulated circuit board according to claim 1, wherein the titanium material-disposing step and the titanium layer-forming step are performed after the ceramic/aluminum-joining step.

13. The method for manufacturing an insulated circuit board according to claim 1, wherein the ceramic/aluminum-joining step is performed after the titanium layer-forming step.

14. The method for manufacturing an insulated circuit board according to claim 1, wherein the titanium layer-forming step and the ceramic/aluminum-joining step are simultaneously performed.

15. The method for manufacturing an insulated circuit board according to claim 1, further comprising: an aluminum-cleaning step of cleaning the surface of the aluminum layer or the aluminum material before the titanium material-disposing step.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic explanatory view of a power module including an insulated circuit board according to a first embodiment of the present invention.

(2) FIG. 2 is an explanatory view of the insulated circuit board according to the first embodiment of the present invention.

(3) FIG. 3 is an enlarged explanatory view of a joint interface between an aluminum layer and a titanium layer in the insulated circuit board according to the first embodiment of the present invention.

(4) FIG. 4 is a flowchart illustrating a method for manufacturing the insulated circuit board according to the first embodiment of the present invention.

(5) FIG. 5 is a schematic explanatory view of the method for manufacturing the insulated circuit board according to the first embodiment of the present invention.

(6) FIG. 6 is a schematic explanatory view of a power module including an insulated circuit board according to a second embodiment of the present invention.

(7) FIG. 7 is an explanatory view of the insulated circuit board according to the second embodiment of the present invention.

(8) FIG. 8 is a flowchart illustrating a method for manufacturing the insulated circuit board according to the second embodiment of the present invention.

(9) FIG. 9 is a schematic explanatory view of the method for manufacturing the insulated circuit board according to the second embodiment of the present invention.

(10) FIG. 10 is a schematic explanatory view of a thermoelectric conversion module including an insulated circuit board according to a third embodiment of the present invention.

(11) FIG. 11 is an explanatory view of the insulated circuit board according to the third embodiment of the present invention.

(12) FIG. 12 is a flowchart illustrating a method for manufacturing the insulated circuit board according to the third embodiment of the present invention.

(13) FIG. 13 is a schematic explanatory view of the method for manufacturing the insulated circuit board according to the third embodiment of the present invention.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

(14) Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the following description, a brazing filler material is not necessarily limited to a material containing lead.

First Embodiment

(15) FIG. 1 shows a power module 1 using an insulated circuit board 10 according to a first embodiment of the present invention.

(16) The power module 1 includes the insulated circuit board 10, a semiconductor element 3 joined to one surface (upper surface in FIG. 1) of the insulated circuit board 10 via a first solder layer 2, and a heat sink 41 joined to the lower side of the insulated circuit board 10 via a second solder layer 42.

(17) The semiconductor element 3 includes a semiconductor material such as Si and the like. The first solder layer 2 for joining the insulated circuit board 10 and the semiconductor element 3 together consists of, for example, a SnAg-based, SnCu-based, SnIn-based, or SnAgCu-based solder material (so-called lead-free solder material).

(18) The heat sink 41 is for dissipating heat on the insulated circuit board 10 side. The heat sink 41 consists of copper or a copper alloy, and in this embodiment, the heat sink 41 consists of oxygen-free copper. The second solder layer 42 for joining the insulated circuit board 10 and the heat sink 41 together consists of, for example, a SnAg-based, SnCu-based, SnIn-based, or SnAgCu-based solder material (so-called lead-free solder material).

(19) In addition, as shown in FIGS. 1 and 2, the insulated circuit board 10 according to this embodiment includes a ceramic substrate 11, a circuit layer 20 disposed on one surface (upper surface in FIGS. 1 and 2) of the ceramic substrate 11, and a metal layer 30 disposed on the other surface (lower surface in FIGS. 1 and 2) of the ceramic substrate 11.

(20) The ceramic substrate 11 consists of highly insulating AlN (aluminum nitride), Si.sub.3N.sub.4 (silicon nitride), Al.sub.2O.sub.3 (alumina), or the like. In this embodiment, the ceramic substrate 11 consists of Si.sub.3N.sub.4 (silicon nitride) having excellent strength. Furthermore, the thickness of the ceramic substrate 11 is set to be in a range of 0.2 to 1.5 mm, and the thickness of the ceramic substrate 11 is set to 0.32 mm in this embodiment.

(21) As shown in FIGS. 1 and 2, the circuit layer 20 includes an aluminum layer 21 disposed on the one surface of the ceramic substrate 11, and a copper layer 22 (metal member layer) laminated on one surface of the aluminum layer 21 via a titanium layer 25.

(22) The thickness of the aluminum layer 21 in the circuit layer 20 is set to be in a range of 0.1 mm or more and 1.0 mm or less, and the thickness of the aluminum layer 21 is set to 0.4 mm in this embodiment.

(23) The thickness of the copper layer 22 in the circuit layer 20 is set to be in a range of 0.1 mm or more and 6.0 mm or less, and the thickness of the copper layer 22 is set to 1.0 mm in this embodiment.

(24) In the circuit layer 20, a circuit pattern is formed as shown in FIG. 2.

(25) As shown in FIGS. 1 and 2, the metal layer 30 includes an aluminum layer 31 disposed on the other surface of the ceramic substrate 11, and a copper layer 32 (metal member layer) laminated on one surface of the aluminum layer 31 via a titanium layer 35.

(26) The thickness of the aluminum layer 31 in the metal layer 30 is set to be in a range of 0.1 mm or more and 3.0 mm or less, and the thickness of the aluminum layer 31 is set to 0.4 mm in this embodiment.

(27) Furthermore, the thickness of the copper layer 32 in the metal layer 30 is set to be in a range of 0.1 mm or more and 6.0 mm or less, and the thickness of the copper layer 32 is set to 1.0 mm in this embodiment.

(28) As shown in FIG. 5, the aluminum layers 21 and 31 are formed by joining aluminum sheets 51 and 61 to the one surface and the other surface of the ceramic substrate 11, respectively.

(29) In addition, the aluminum sheets 51 and 61 which are to become the aluminum layers 21 and 31 consist of aluminum (2N aluminum) having a purity of 99 mass % or more. The amount of Si therein is in a range of 0.03 mass % or more and 1.0 mass % or less.

(30) The copper layers 22 and 32 are formed by joining copper sheets (metal member) consisting of copper or a copper alloy to one surface and the other surface of the aluminum layers 21 and 31 via the titanium layers 25 and 35, respectively. In this embodiment, the copper sheets (metal members) forming the copper layers 22 and 32 are rolled sheets consisting of oxygen-free copper.

(31) As shown in FIG. 3, AlTiSi layers 26 and 36 are formed at the joint interfaces between the aluminum layers 21 and 31 and the titanium layers 25 and 35, respectively.

(32) Al.sub.3Ti is formed by mutual diffusion of Al atoms of the aluminum layers 21 and 31 and Ti atoms of the titanium layers 25 and 35, and the AlTiSi layers 26 and 36 are formed by solid-solubilizing Si of the aluminum layers 21 and 31 in Al.sub.3Ti, respectively.

(33) The thickness of the AlTiSi layers 26 and 36 is set to 0.5 m or more and 10 m or less, and the thickness of the AlTiSi layers 26 and 36 is 3 m in this embodiment.

(34) As shown in FIG. 3, the AlTiSi layers 26 and 36 include first AlTiSi layers 26A and 36A formed on the titanium layers 25 and 35 side and second AlTiSi layers 26B and 36B formed on the aluminum layers 21 and 31 side, respectively. That is, the titanium layers 25 and 35, the first AlTiSi layers 26A and 36A, and the second AlTiSi layers 26B and 36B are formed at the joints between the aluminum layers 21 and 31 and the copper layers 22 and 32, respectively.

(35) As described above, the first AlTiSi layers 26A and 36A and the second AlTiSi layers 26B and 36B consist of AlTiSi phases in which Si is solid-solubilized in Al.sub.3Ti, and the Si concentration of the second AlTiSi layers 26B and 36B is lower than the Si concentration of the first AlTiSi layers 26A and 36A, respectively. In this embodiment, Si contained in the first AlTiSi layers 26A and 36A and the second AlTiSi layers 26B and 36B is Si which diffuses into the aluminum layers 21 and 31 and diffuses into the AlTiSi layers 26 and 36, respectively so as to be enriched as will be described later.

(36) The Si concentration of the first AlTiSi layers 26A and 36A is 10 at % or more and 30 at % or less, and the Si concentration of the first AlTiSi layers 26A and 36A is 20 at % in this embodiment. The Si concentration of the second AlTiSi layers 26B and 36B is 1 at % or more and 10 at % or less, and the Si concentration of the second AlTiSi layers 26B and 36B is 3 at % in this embodiment.

(37) Next, a method for manufacturing the insulated circuit board 10 according to this embodiment will be described with reference to FIGS. 4 and 5.

(38) (Titanium Material-Disposing Step S01)

(39) As shown in FIGS. 4 and 5, titanium materials 55 and 65 are disposed on the surfaces of the aluminum sheets 51 and 61, respectively. At this time, the titanium material 55 is disposed in a circuit pattern shape on the surface of the aluminum sheet 51 which is to become the circuit layer 20. When the titanium material 55 is disposed in the circuit pattern shape, a film formation method such as vapor deposition, ion plating, or the like may be applied. In this case, by forming a titanium film using a metal mask, the titanium material 55 can be disposed in the circuit pattern shape. Alternatively, the titanium foil may be disposed in the circuit pattern shape.

(40) In the case where the titanium material 65 is disposed on the surface of the aluminum sheet 61 which is to become the metal layer 30, it is preferable to dispose the titanium foil.

(41) It is preferable that the thickness of the titanium materials 55 and 65 be in a range of 7 m or more and 20 m or less.

(42) (Titanium Layer-Forming Step and Ceramic/Aluminum-Joining Step S02)

(43) Next, as shown in FIGS. 4 and 5, the aluminum sheet 51 and the titanium material 55 are disposed on the one surface of the ceramic substrate 11, and the aluminum sheet 61 and the titanium material 65 are disposed on the other surface of the ceramic substrate 11. At this time, an AlSi brazing filler material is interposed between the aluminum sheet 51 and the ceramic substrate 11, and between the aluminum sheet 61 and the ceramic substrate 11.

(44) In addition, the laminate is disposed in a vacuum heating furnace and heated in a state of being pressurized in the lamination direction (under a load of 3 to 20 kgf/cm.sup.2 (0.29 to 1.96 MPa)). It is preferable that the pressure in the vacuum heating furnace be set to be in a range of 10.sup.6 Pa or more and 10.sup.3 Pa or less, the heating temperature be set to be in a range of 600 C. or higher and 640 C. or lower, and the holding time be set to be in a range of 30 minutes or longer and 180 minutes or shorter.

(45) Accordingly, the aluminum sheet 51 and the ceramic substrate 11 are joined, and the ceramic substrate 11 and the aluminum sheet 61 are joined (ceramic/aluminum-joining step).

(46) In addition, the aluminum sheet 51 and the titanium material 55 are joined and the aluminum sheet 61 and the titanium material 65 are joined; and thereby, the titanium layers 25 and 35 are formed (titanium layer-forming step). At this time, Al.sub.3Ti is formed at the joint interface between the aluminum sheet 51 and the titanium material 55 and at the joint interface between the aluminum sheet 61 and the titanium material 65. Since the aluminum sheets 51 and 61 contain Si in an amount of 0.03 mass % or more and 1.0 mass % or less, Si is solid-solubilized in Al.sub.3Ti so that the AlTiSi layers 26 and 36 described above are formed.

(47) The titanium layer 25 is formed in the circuit pattern shape on the aluminum sheet 51 which is to become the circuit layer 20.

(48) (Etching Treatment Step S03)

(49) Next, as shown in FIGS. 4 and 5, the aluminum layer 21 on which the titanium layer 25 is formed in the circuit pattern shape is subjected to an etching treatment. At this time, ferric chloride is used as the etchant. For example, etching can be performed under conditions where a ferric chloride concentration in the etchant (etching solution) is 35 wt % to 60 wt %, an etching temperature is 40 C. to 60 C., and a time is 2 minutes to 20 minutes.

(50) Since the titanium layer 25 is hardly etched by ferric chloride, the titanium layer 25 acts as a resist material. That is, portions where the titanium layer 25 is formed are not etched, and only portions where the titanium layer 25 is not formed are etched. Accordingly, the aluminum layer 21 is also formed into the circuit pattern shape.

(51) (Titanium Layer-Cleaning Step S04)

(52) Next, as shown in FIG. 4, the surfaces of the titanium layers 25 and 35 on which the copper layers 22 and 32 are to be disposed are cleaned. A mixed solution of ammonia and hydrogen peroxide is used for cleaning the titanium layers 25 and 35. For example, an aqueous solution containing 10 wt % of ammonia, 3 wt % of hydrogen peroxide, and 12 wt % of ethylenediaminetetraacetic acid (EDTA) can be used. Cleaning may be performed at a temperature of 40 C. to 50 C. for 10 minutes to 30 minutes as a cleaning condition.

(53) (Copper Layer-Forming Step S05)

(54) Next, the copper layers 22 and 32 are formed by joining the copper sheets (metal members) on the surfaces of the titanium layers 25 and 35, respectively. At this time, when the titanium layers 25 and 35 and the copper sheets (metal members) are joined, a solid-phase diffusion bonding method may be applied or a brazing filler material may be used for the joining.

(55) For example, in the case of applying the solid-phase diffusion bonding method, the titanium layers 25 and 35 and the copper sheets (metal members) may be laminated, and joining may be conducted in a state of being pressurized in the lamination direction (under a load of 3 to 20 kgf/cm.sup.2) under conditions where a pressure in the vacuum heating furnace is in a range of 10.sup.6 Pa or more and 10.sup.3 Pa or less and a heating temperature is in a range of 600 C. or higher and 650 C. or lower, and more preferably 620 C. or higher and 643 C. or lower, and a holding time is in a range of 30 minutes or longer and 180 minutes or shorter, and more preferably 60 minutes or longer and 120 minutes or shorter.

(56) In the case of joining using the brazing filler material, a brazing filler material foil such as a CuPSn brazing filler material, CuPSnNi-based brazing filler material, CuPSnFe-based brazing filler material, CuPSnMn-based brazing filler material, or CuPSnCr-based brazing filler material may be disposed between the titanium layers 25 and 35 and the copper sheets (metal members), and joining may be conducted in a state of being pressured in the lamination direction (under a load of 3 to 20 kgf/cm.sup.2) under conditions where a pressure in the vacuum heating furnace is in a range of 10.sup.6 Pa or more and 10.sup.3 Pa or less and a heating temperature is in a range of 600 C. or higher and 650 C. or lower, and more preferably 620 C. or higher and 643 C. or lower, and a holding time is in a range of 15 minutes or longer and 120 minutes or shorter, and more preferably 30 minutes or longer and 90 minutes or shorter.

(57) At this time, on the circuit layer 20 side, the copper sheet (metal member) is disposed on and joined to the titanium layer 25 formed in the circuit pattern shape.

(58) Through the above-described steps, the circuit pattern is formed in the circuit layer 20 in which the aluminum layer 21, the titanium layer 25, and the copper layer 22 are laminated; and thereby, the insulated circuit board 10 according to this embodiment is manufactured.

(59) In the method for manufacturing the insulated circuit board 10 according to this embodiment having the above-described configuration, since the titanium material-disposing step S01 of disposing the titanium material 55 which is to become the titanium layer 25 on the surface of the aluminum sheet 51 in the circuit pattern shape is provided, the titanium layer 25 can be formed on the surface of the aluminum layer 21 in the circuit pattern shape by the subsequent titanium layer-forming step and ceramic/aluminum-joining step S02.

(60) Next, since the etching treatment step S03 of performing the etching treatment on the aluminum layer 21 on which the titanium layer 25 is formed is provided, the titanium layer 25 acts as the resist material and the aluminum layer 21 can be etched into the circuit pattern shape. That is, by using the titanium layer 25 as the resist material, an applying step, a curing step, and a peeling step of a resist material can be omitted, and the etching treatment step S03 can be efficiently performed.

(61) In addition, since the copper layer-forming step S05 of forming the copper layer 22 by joining the copper sheet (metal member) on the titanium layer 25 formed in the circuit pattern shape is provided, the copper layer 22 can be formed on the titanium layer 25 in the circuit pattern shape.

(62) Accordingly, the circuit pattern can be accurately and efficiently formed in the circuit layer 20 in which the aluminum layer 21, the titanium layer 25, and the copper layer 22 are laminated.

(63) Furthermore, in this embodiment, since the titanium layer-forming step and ceramic/aluminum-joining step S02 in which the titanium layer-forming step and the ceramic/aluminum-joining step are simultaneously performed is provided, the insulated circuit board 10 having the circuit pattern can be efficiently manufactured.

(64) In addition, in the method for manufacturing the insulated circuit board 10 according to this embodiment, since the titanium layer-cleaning step S04 of cleaning the surface of the titanium layer 25 is provided before the copper layer-forming step S05, the titanium layer 25 and the copper sheet (metal member) can be reliably joined; and thereby, the copper layer 22 can be reliably formed.

(65) Furthermore, in the method for manufacturing the insulated circuit board 10 according to this embodiment, since the aluminum sheets 51 and 61 contain Si in an amount of 0.03 mass % or more and 1.0 mass % or less, Si is solid-solubilized in Al.sub.3Ti at the joint interfaces between the titanium layers 25 and 35 and the aluminum layers 21 and 31; and thereby, the AlTiSi layers 26 and 36 described above are formed, respectively. Since the hardness of the AlTiSi layers 26 and 36 is relatively low, the occurrence of cracks in the circuit layer 20 and the metal layer 30 can be prevented when a heat cycle is applied.

(66) Furthermore, the Si concentration of the first AlTiSi layers 26A and 36A formed on the titanium layers 25 and 35 side is higher than the Si concentration of the second AlTiSi layers 26B and 36B formed on the aluminum layers 21 and 31 side, the diffusion of Ti atoms into the aluminum layers 21 and 31 side is prevented by the first AlTiSi layers 26A and 36A having a high Si concentration; and therefore, the thickness of the AlTiSi layers 26 and 36 can be reduced. In addition, by reducing the thickness of the AlTiSi layers 26 and 36 as described above, the occurrence of cracks at the joints between the aluminum layers 21 and 31 and the copper layers 22 and 32 can be prevented when a heat cycle is applied.

(67) In addition, since the concentration of Si contained in the second AlTiSi layers 26B and 36B formed on the aluminum layers 21 and 31 side is 1 at % or more and 10 at % or less, the excessive diffusion of Al atoms toward the titanium layers 25 and 35 side is prevented; and therefore, the thickness of the second AlTiSi layers 26B and 36B can be reduced. The Si concentration of the second AlTiSi layers 26B and 36B is more preferably 1 at % or more and 10 at % or less, but is not limited thereto.

(68) In addition, since the concentration of Si contained in the first AlTiSi layers 26A and 36A formed on the titanium layers 25 and 35 side is 10 at % or more and 30 at % or less, the excessive diffusion of Ti atoms toward the aluminum layers 21 and 31 side is prevented; and therefore, the thickness of the first AlTiSi layers 26A and 36A can be reduced. The Si concentration of the first AlTiSi layers 26A and 36A is more preferably 10 at % or more and 30 at % or less, but is not limited thereto.

(69) Furthermore, in this embodiment, since the copper layers 22 and 32 having relatively high deformation resistance are formed on the surfaces of the circuit layer 20 and the metal layer 30, respectively, when a heat cycle is applied, the deformation of the surfaces of the circuit layer 20 and the metal layer 30 is suppressed, and the occurrence of cracks and the like in the first solder layer 2 for joining the semiconductor element 3 to the circuit layer 20 and the second solder layer 42 for joining the heat sink 41 to the metal layer 30 can be prevented; and thereby, the reliability of the joining can be improved.

(70) In addition, since the copper layers 22 and 32 having good thermal conductivity are formed on the surfaces of the circuit layer 20 and the metal layer 30, respectively, heat from the semiconductor element 3 can spread in a surface direction and heat can be efficiently transferred to the heat sink 41 side.

Second Embodiment

(71) Next, a second embodiment of the present invention will be described. Members having the same configurations as those of the first embodiment are denoted by the same reference numerals, and detailed descriptions thereof will be omitted.

(72) FIG. 6 shows a power module 101 provided with an insulated circuit board 110 according to the second embodiment of the present invention.

(73) The power module 101 includes the insulated circuit board 110, the semiconductor element 3 joined to one surface (upper surface in FIG. 6) of the insulated circuit board 110 via a solder layer 2, and a heat sink 141 joined to the lower side of the insulated circuit board 110.

(74) The heat sink 141 is for dissipating heat on the insulated circuit board 110 side. The heat sink 141 consists of aluminum or an aluminum alloy, and in this embodiment, the heat sink 141 consists of an A6063 alloy. The insulated circuit board 110 and the heat sink 141 are joined together using a brazing filler material.

(75) As shown in FIGS. 6 and 7, the insulated circuit board 110 includes the ceramic substrate 11, a circuit layer 120 disposed on the one surface of the ceramic substrate 11, and a metal layer 130 disposed on the other surface of the ceramic substrate 11.

(76) As shown in FIGS. 6 and 7, the circuit layer 120 includes an aluminum layer 121 disposed on the one surface of the ceramic substrate 11, and a copper layer 122 (metal member layer) laminated on one surface of the aluminum layer 121 via a titanium layer 125.

(77) The thickness of the aluminum layer 121 in the circuit layer 120 is set to be in a range of 0.1 mm or more and 1.0 mm or less, and the thickness of the aluminum layer 121 is set to 0.6 mm in this embodiment.

(78) The thickness of the copper layer 122 in the circuit layer 120 is set to be in a range of 0.1 mm or more and 6.0 mm or less, and the thickness of the copper layer 122 is set to 1.5 mm in this embodiment.

(79) In the circuit layer 120, a circuit pattern is formed as shown in FIG. 7.

(80) As shown in FIG. 9, the aluminum layer 121 is formed by joining an aluminum sheet 151 to the one surface of the ceramic substrate 11.

(81) In addition, the aluminum sheet 151 which is to become the aluminum layer 121 consists of aluminum (2N aluminum) having a purity of 99 mass % or more. The amount of Si therein is in a range of 0.03 mass % or more and 1.0 mass % or less.

(82) As shown in FIG. 9, the copper layer 122 is formed by joining a copper sheet (metal member) consisting of copper or a copper alloy to one surface of the aluminum layer 121 via the titanium layer 125. In this embodiment, the copper sheet (metal member) forming the copper layer 122 is a rolled sheet consisting of oxygen-free copper.

(83) At the joint interface between the aluminum layer 121 and the titanium layer 125, as is the case with the first embodiment, an AlTiSi layer in which Si is solid-solubilized in Al.sub.3Ti is formed. Al.sub.3Ti is formed by mutual diffusion of Al atoms of the aluminum layer 121 and Ti atoms of the titanium layer 125, and Si of the aluminum layer 121 is solid-solubilized in the Al.sub.3Ti; and thereby, the AlTiSi layer is formed.

(84) As shown in FIG. 9, the metal layer 130 is formed by joining an aluminum sheet 161 to the one surface of the ceramic substrate 11. In this embodiment, the metal layer 130 is formed by joining a rolled sheet of aluminum (4N aluminum) having a purity of 99.99 mass % or more. The thickness of the aluminum sheet 161 to be joined is set to be in a range of 0.1 mm or more and 1.0 mm or less, and the thickness of the aluminum sheet 161 is set to 0.6 mm in this embodiment.

(85) Next, a method for manufacturing the insulated circuit board 110 according to this embodiment will be described with reference to FIGS. 8 and 9.

(86) (Ceramic/Aluminum-Joining Step S101)

(87) First, as shown in FIGS. 8 and 9, the aluminum sheet 151 is laminated on the one surface of the ceramic substrate 11 via an AlSi-based brazing filler material foil (not shown). In addition, the aluminum sheet 161 is laminated on the other surface of the ceramic substrate 11 via a brazing filler material foil (not shown).

(88) Next, the aluminum sheet 151, the ceramic substrate 11, and the aluminum sheet 161 which are laminated are disposed in the vacuum heating furnace and heated in a state of being pressurized in the lamination direction (under a load of 3 to 20 kgf/cm.sup.2). Accordingly, the aluminum sheet 151 and the ceramic substrate 11 are joined and the ceramic substrate 11 and the aluminum sheet 161 are joined; and thereby, the aluminum layer 121 and the metal layer 130 are formed.

(89) (Aluminum-Cleaning Step S102)

(90) Next, as shown in FIG. 8, the surface of the aluminum layer 121 on the side where a titanium material 155 is to be disposed is cleaned. Cleaning of the aluminum layer 121 can be performed using, for example, an aqueous solution of 5 wt % to 10 wt % of sulfuric acid or an aqueous solution of 5 wt % to 10 wt % of nitric acid at a temperature of 20 C. to 30 C. for 30 seconds to 60 seconds.

(91) (Titanium Material-Disposing Step S103)

(92) Next, as shown in FIGS. 8 and 9, the titanium material 155 is disposed in a circuit pattern shape on the surface of the aluminum layer 121. When the titanium material 155 is disposed in the circuit pattern shape, a film formation method such as vapor deposition, ion plating, or the like may be applied. In this case, by forming a titanium film using a metal mask, the titanium material 155 can be disposed in the circuit pattern shape. Alternatively, the titanium foil may be disposed in the circuit pattern shape.

(93) It is preferable that the thickness of the titanium material 155 be in a range of 7 m or more and 20 m or less.

(94) (Titanium Layer-Forming Step S104)

(95) Next, as shown in FIGS. 8 and 9, in a state where the titanium material 155 is disposed on the surface of the aluminum layer 121, the laminate is disposed in the vacuum heating furnace and heated in a state of being pressurized in the lamination direction (under a load of 3 to 20 kgf/cm.sup.2). It is preferable that the pressure in the vacuum heating furnace be set to be in a range of 10.sup.6 Pa or more and 10.sup.3 Pa or less, the heating temperature be set to be in a range of 600 C. or higher and 640 C. or lower, and the holding time be set to be in a range of 30 minutes or longer and 180 minutes or shorter.

(96) Accordingly, the aluminum layer 121 and the titanium material 155 are joined together, and the titanium layer 125 is formed in the circuit pattern shape. The AlTiSi layer described above is formed at the joint interface between the aluminum layer 121 and the titanium layer 125.

(97) (Etching Treatment Step S105)

(98) Next, as shown in FIGS. 8 and 9, an etching treatment is performed on the aluminum layer 121 on which the titanium layer 125 is formed in the circuit pattern shape. Ferric chloride is used as the etchant. At this time, by allowing the titanium layer 125 to act as a resist film, the aluminum layer 121 is etched into the circuit pattern shape.

(99) (Titanium Layer-Cleaning Step S106)

(100) Next, as shown in FIG. 8, the surface of the titanium layer 125 on which the copper layer 122 is to be disposed is cleaned. The cleaning of the titanium layer 125 can be performed in the same manner as in the first embodiment.

(101) (Copper Layer-Forming Step S107)

(102) Next, the copper layer 122 is formed by joining the copper sheet (metal member) on the surface of the titanium layer 125 formed in the circuit pattern shape. At this time, when the titanium layer 125 and the copper sheet (metal member) are joined, in the same manner as in the first embodiment, a solid-phase diffusion bonding method may be applied or a brazing filler material may be used for the joining.

(103) Through the above-described steps, the circuit pattern is formed in the circuit layer 120 in which the aluminum layer 121, the titanium layer 125, and the copper layer 122 are laminated; and thereby, the insulated circuit board 110 according to this embodiment is manufactured.

(104) In the method for manufacturing the insulated circuit board 110 according to this embodiment having the above-described configuration, as is the case with the first embodiment, since the titanium material-disposing step S103, the titanium layer-forming step S104, the etching treatment step S105, and the copper layer-forming step S107 are provided, the circuit pattern can be accurately and efficiently formed in the circuit layer 120 in which the aluminum layer 121, the titanium layer 125, and the copper layer 122 are laminated. In addition, in the etching treatment step S105, since the titanium layer 125 is used as the resist material, an applying step and a peeling step of a resist material can be omitted, and the etching treatment step S105 can be efficiently performed.

Third Embodiment

(105) Next, a third embodiment of the present invention will be described. Members having the same configurations as those of the first and second embodiments are denoted by the same reference numerals, and detailed descriptions thereof will be omitted.

(106) FIG. 10 shows a thermoelectric conversion module 201 provided with insulated circuit boards 210 according to the third embodiment of the present invention.

(107) The thermoelectric conversion module 201 includes thermoelectric elements 203 and the insulated circuit boards 210 respectively disposed on one end side and the other end side of the thermoelectric elements 203.

(108) The thermoelectric element 203 is joined to a circuit layer 220 of the insulated circuit board 210 via a joining layer 202. The joining layer 202 is a sintered body of silver paste containing silver particles.

(109) As shown in FIGS. 10 and 11, the insulated circuit board 210 includes the ceramic substrate 11, and the circuit layer 220 disposed on the one surface of the ceramic substrate 11.

(110) As shown in FIGS. 10 and 11, the circuit layer 220 includes an aluminum layer 221 disposed on the one surface of the ceramic substrate 11, and a titanium layer 225 formed on one surface of the aluminum layer 221.

(111) The thickness of the aluminum layer 221 in the circuit layer 220 is set to be in a range of 0.1 mm or more and 1.0 mm or less, and the thickness of the aluminum layer 221 is set to 0.6 mm in this embodiment.

(112) In the circuit layer 220, a circuit pattern is formed as shown in FIG. 11.

(113) As shown in FIG. 13, the aluminum layer 221 is formed by joining an aluminum sheet 251 to the one surface of the ceramic substrate 11.

(114) The aluminum sheet 251 which is to become the aluminum layer 221 consists of aluminum (4N aluminum) having a purity of 99.99 mass % or more. At the interface of the aluminum layer 221 on the titanium layer 225 side, a Si-enriched layer in which the amount of Si is in a range of 0.03 mass % or more and 1.0 mass % or less is formed.

(115) At the joint interface between the aluminum layer 221 and the titanium layer 225, as is the case with the first and second embodiments, an AlTiSi layer in which Si is solid-solubilized in Al.sub.3Ti is formed. Al.sub.3Ti is formed by mutual diffusion of Al atoms of the aluminum layer 221 and Ti atoms of the titanium layer 225, and Si of the Si-enriched layer is solid-solubilized in the Al.sub.3Ti; and thereby, the AlTiSi layer is formed.

(116) Next, a method for manufacturing the insulated circuit board 210 according to this embodiment will be described with reference to FIGS. 12 and 13.

(117) (Si-Enriched Layer-Forming Step S201)

(118) First, the Si-enriched layer containing Si in an amount of 0.03 mass % or more and 1.0 mass % or less is formed on one surface of the aluminum sheet 251 consisting of aluminum (4N aluminum) having a purity of 99.99 mass % or more.

(119) Specifically, a Si material 252 (for example, an AlSi brazing filler material) containing Si is disposed on the one surface of the aluminum sheet 251, and a heating treatment is performed thereon to cause Si of the Si material to diffuse toward the aluminum sheet 251 side; and thereby, the Si-enriched layer mentioned above is formed.

(120) Regarding the Si concentration, five points on the surface on which the titanium layer is to be formed are measured by quantitative analysis using an electron probe microanalyzer (EPMA), and the average value thereof is used. The Si concentration is the concentration when the total amount of Al and Si is taken as 100.

(121) (Titanium Material-Disposing Step S202)

(122) Next, as shown in FIGS. 12 and 13, a titanium material 255 is disposed in a circuit pattern shape on one surface of the aluminum sheet 251 (the surface on which the Si-enriched layer is formed). When the titanium material 255 is disposed in the circuit pattern shape, a film formation method such as vapor deposition, ion plating, or the like may be applied. In this case, by forming a titanium film using a metal mask, the titanium material 255 can be disposed in the circuit pattern shape. Alternatively, the titanium foil may be disposed in the circuit pattern shape.

(123) It is preferable that the thickness of the titanium material 255 be in a range of 7 m or more and 20 m or less.

(124) (Titanium Layer-Forming Step S203)

(125) Next, as shown in FIGS. 12 and 13, the titanium material 255 is disposed on the surface of the aluminum sheet 251, and the laminate is disposed in the vacuum heating furnace and heated in a state of being pressurized in the lamination direction (under a load of 3 to 20 kgf/cm.sup.2). It is preferable that the pressure in the vacuum heating furnace be set to be in a range of 10.sup.6 Pa or more and 10.sup.3 Pa or less, the heating temperature be set to be in a range of 600 C. or higher and 640 C. or lower, and the holding time be set to be in a range of 30 minutes or longer and 180 minutes or shorter.

(126) Accordingly, the aluminum sheet 251 and the titanium material 255 are joined together, and the titanium layer 225 is formed in the circuit pattern shape. The AlTiSi layer described above is formed at the joint interface between the aluminum sheet 251 and the titanium layer 225.

(127) (Ceramic/Aluminum-Joining Step S204)

(128) Next, as shown in FIGS. 12 and 13, the aluminum sheet 251 on which the titanium layer 225 is formed is laminated on the one surface of the ceramic substrate 11 via an AlSi-based brazing filler material foil (not shown).

(129) Next, the aluminum sheet 251 and the ceramic substrate 11 which are laminated are disposed in the vacuum heating furnace and heated in a state of being pressurized in the lamination direction (under a load of 3 to 20 kgf/cm.sup.2).

(130) Accordingly, the aluminum sheet 251 and the ceramic substrate 11 are joined, and the aluminum layer 221 is formed.

(131) (Etching Treatment Step S205)

(132) Next, as shown in FIGS. 12 and 13, an etching treatment is performed on the aluminum layer 221 on which the titanium layer 225 is formed in the circuit pattern shape. Ferric chloride is used as the etchant. At this time, by allowing the titanium layer 225 to act as a resist film, the aluminum layer 221 is etched into the circuit pattern shape.

(133) Through the above-described steps, the circuit pattern is formed in the circuit layer 220 in which the aluminum layer 221 and the titanium layer 225 are laminated; and thereby, the insulated circuit board 210 according to this embodiment is manufactured.

(134) Then, the insulated circuit boards 210 are laminated on the one end side and the other end side of the thermoelectric element 203 via the silver paste so that the circuit layers 220 face the thermoelectric element 203 side, and the laminate is heated to join the insulated circuit boards 210 respectively to the one end side and the other end side of the thermoelectric element 203. Accordingly, the thermoelectric conversion module 201 shown in FIG. 10 is manufactured.

(135) In the method for manufacturing the insulated circuit board 210 according to this embodiment having the above-described configuration, since the titanium material-disposing step S202, the titanium layer-forming step S203, and the etching treatment step S205 are provided, the circuit pattern can be accurately and efficiently formed in the circuit layer 220 in which the aluminum layer 221 and the titanium layer 225 are laminated. In addition, in the etching treatment step S205, since the titanium layer 225 is used as the resist material, an applying step and a peeling step of a resist material can be omitted, and the etching treatment step S205 can be efficiently performed.

(136) Furthermore, in this embodiment, the Si-enriched layer-forming step S201 is provided, and in the Si-enriched layer-forming step S201, the Si-enriched layer containing Si in an amount of 0.03 mass % or more and 1.0 mass % or less is formed on the surface of the aluminum sheet 251 on the side on which the titanium layer 225 is to be formed, and the aluminum sheet 251 consists of aluminum (4N aluminum) having a purity of 99.99 mass % or more. Therefore, even in the case where the aluminum layer 221 of the circuit layer 220 consists of aluminum (4N aluminum) having a purity of 99.99 mass % or more, it is possible to form the AlTiSi layer between the aluminum layer 221 and the titanium layer 225 as is the case with the first and second embodiments.

(137) In addition, in the insulated circuit board 210 and the thermoelectric conversion module 201 according to this embodiment, since the titanium layer 225 is formed on the surface of the aluminum layer 221 on the side opposite to the ceramic substrate 11, the titanium layer 225 can function as a diffusion prevention layer. Therefore, it is possible to prevent the diffusion of aluminum of the aluminum layer 221 to the thermoelectric element 203 mounted on the circuit layer 220. Accordingly, the deterioration of the characteristics of the thermoelectric element 203 can be prevented.

(138) While the embodiments of the present invention have been described above, the present invention is not limited thereto, and can be appropriately changed without departing from the technical features of the invention.

(139) For example, in the embodiments, the case where the aluminum layer and the copper layer consisting of copper as the metal member layer are joined together has been described. However, instead of the copper layer, a nickel layer consisting of nickel or a nickel alloy or a silver layer consisting of silver or a silver alloy may be joined.

(140) In the case where the nickel layer is formed instead of the copper layer, the solderability is improved, and the reliability of joining the semiconductor element or the heat sink can be improved. Furthermore, in the case of forming the nickel layer by solid-phase diffusion bonding, it is unnecessary to perform a masking treatment which is performed when a Ni plating film is formed by electroless plating or the like; and thereby, the manufacturing cost can be reduced. In this case, it is desirable that the thickness of the nickel layer be 1 m or more and 30 m or less. In the case where the thickness of the nickel layer is less than 1 m, there is a concern that the effect of improving the reliability of joining the semiconductor element or the heat sink may be lost, and in the case where the thickness of the nickel layer is more than 30 m, the nickel layer acts as a thermal resistor, and there is a concern that heat may not be efficiently transferred. In addition, in the case of forming the nickel layer by solid-phase diffusion bonding, the nickel layer can be formed by the solid-phase diffusion bonding under the same conditions as those in the case of forming the copper layer.

(141) In the case where the silver layer is formed instead of the copper layer, for example, when the semiconductor element or the heat sink is joined using a silver oxide paste containing silver oxide particles and a reducing agent consisting of an organic material, silver to which the silver oxide is reduced and the silver layer are connected, that is, metals of the same kind are joined together. Therefore, the joining reliability can be improved. In addition, since the silver layer having good thermal conductivity is formed, heat can spread in the surface direction and heat can be efficiently transferred. In this case, it is desirable that the thickness of the silver layer be 1 m or more and 20 m or less. In the case where the thickness of the silver layer is less than 1 m, there is a concern that the effect of improving the reliability of joining to the semiconductor element or the heat sink may be lost, and in the case where the thickness of the silver layer is more than 20 m, the effect of improving the joining reliability cannot be seen, and the cost increases. In addition, in the case of forming the silver layer by solid-phase diffusion bonding, the silver layer can be formed by the solid-phase diffusion bonding under the same conditions as those in the case of forming the copper layer.

(142) In the first and second embodiments, as the aluminum sheet which is to become the aluminum layer, an aluminum sheet which is 2N aluminum having a purity of 99 mass % or more and containing Si in an amount of 0.03 mass % or more and 1.0 mass % or less is exemplified. However, the aluminum sheet is not limited thereto, and another aluminum material may be used.

(143) In the case of using an aluminum material that does not contain Si, such as 4N aluminum having a purity of 99.99 mass % or more, as described in the third embodiment, the Si concentration of the surface of the aluminum material on which the titanium layer is to be formed may be adjusted to 0.03 mass % to 1.0 mass % in advance. Regarding the Si concentration, five points on the surface on which the titanium layer is to be formed are measured by quantitative analysis using the EPMA, and the average value thereof is used. The Si concentration is the concentration when the total amount of Al and Si is taken as 100.

INDUSTRIAL APPLICABILITY

(144) In the method for manufacturing the insulated circuit board according to the present invention, a circuit pattern can be accurately and efficiently formed in a circuit layer. In addition, the insulated circuit board of the present invention is suitable for a semiconductor device such as an LED, a power module, or the like, and a thermoelectric conversion module.

EXPLANATION OF REFERENCE SIGNS

(145) 10, 110, 210: insulated circuit board 11: ceramic substrate 20, 120, 220: circuit layer 30, 130: metal layer 21, 121, 221: aluminum layer 22, 122: copper layer (metal member layer) 51, 151, 251: aluminum sheet (aluminum material) 25, 125, 225: titanium layer 55, 155, 255: titanium material 201: thermoelectric conversion module 203: thermoelectric element