WO2018163958A1 - Thermoelectric conversion module and method for manufacturing same - Google Patents

Thermoelectric conversion module and method for manufacturing same Download PDF

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Publication number
WO2018163958A1
WO2018163958A1 PCT/JP2018/007801 JP2018007801W WO2018163958A1 WO 2018163958 A1 WO2018163958 A1 WO 2018163958A1 JP 2018007801 W JP2018007801 W JP 2018007801W WO 2018163958 A1 WO2018163958 A1 WO 2018163958A1
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WO
WIPO (PCT)
Prior art keywords
thermoelectric conversion
conversion element
type thermoelectric
wiring
layer
Prior art date
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PCT/JP2018/007801
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French (fr)
Japanese (ja)
Inventor
皓也 新井
雅人 駒崎
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三菱マテリアル株式会社
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Priority claimed from JP2017163484A external-priority patent/JP6933055B2/en
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to KR1020197028503A priority Critical patent/KR20190121832A/en
Priority to CN201880011824.5A priority patent/CN110301051A/en
Priority to US16/491,734 priority patent/US20200013941A1/en
Priority to EP18763806.9A priority patent/EP3595023A4/en
Publication of WO2018163958A1 publication Critical patent/WO2018163958A1/en

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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01Manufacture or treatment
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/13Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80Constructional details
    • H10N10/81Structural details of the junction
    • H10N10/817Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80Constructional details
    • H10N10/85Thermoelectric active materials
    • H10N10/851Thermoelectric active materials comprising inorganic compositions

Definitions

  • the present invention relates to a thermoelectric conversion module in which a P-type thermoelectric conversion element and an N-type thermoelectric conversion element are arranged in series, and a manufacturing method thereof.
  • thermoelectric conversion module generally has a pair of P-type thermoelectric conversion elements and N-type thermoelectric conversion elements alternately arranged in the order of P-type, N-type, P-type, and N-type between a pair of wiring boards (insulating boards). It is set as the structure electrically connected in series so that it may be arrange
  • the thermoelectric conversion module connects both ends of the wiring to a DC power source and moves heat in each thermoelectric conversion element by the Peltier effect (P type moves in the same direction as the current, N type moves in the opposite direction of the current), Alternatively, a temperature difference is applied between the two wiring boards to generate an electromotive force in each thermoelectric conversion element by the Seebeck effect, which can be used for cooling, heating, or power generation.
  • thermoelectric conversion modules are more efficient as they operate at higher temperatures, so many high-temperature thermoelectric conversion modules have been developed.
  • a thermoelectric conversion module used at a medium high temperature (300 ° C.) or higher a resin cannot be used as a material for an insulating substrate, and therefore ceramics are generally used for the insulating substrate.
  • thermoelectric conversion elements there is a material having both insulating properties and thermal conductivity, such as aluminum nitride.
  • a material having both insulating properties and thermal conductivity such as aluminum nitride.
  • the linear expansion difference between thermoelectric conversion elements is changed to thermal stress as a rigid body. That is, when materials having different linear expansion coefficients are used as the thermoelectric conversion materials for both the P-type thermoelectric conversion element and the N-type thermoelectric conversion element, the thermoelectric conversion module is installed in the heat source. Cannot follow each shape change by being restrained by the ceramic substrate. For this reason, a compressive stress is generated in a thermoelectric conversion element having a large linear expansion coefficient, and a tensile stress is generated in a thermoelectric conversion element having a small linear expansion coefficient.
  • thermoelectric conversion element When a thermal stress is generated due to a thermal expansion / contraction difference, the thermoelectric conversion element may be peeled off from the wiring portion of the wiring board, or the thermoelectric conversion element may be cracked. In this case, electricity may not flow, the electrical conductivity may decrease, and the thermoelectric conversion module may become inoperable, or the amount of power generation may be significantly reduced even if the thermoelectric conversion module does not become inoperable.
  • foam metal porous metal material, porous metal member
  • metal fiber is connected to a wiring (electrode) connecting a plurality of thermoelectric conversion elements (thermoelectric semiconductor material, thermoelectric conversion semiconductor). Attempts have been made to relieve thermal stress due to thermal expansion and contraction by giving flexibility to the wiring by using the aggregate.
  • JP 2007-103580 A International Publication No. 2010/010883 Japanese Patent No. 5703871
  • Patent Documents 1 to 3 an assembly of foam metal or metal fiber is used for the wiring, and a current flows through these members themselves. For this reason, the internal resistance (thermal resistance and electrical resistance) of the wiring is significantly increased, and the output of the thermoelectric conversion module may be significantly decreased.
  • thermoelectric conversion module that can prevent the thermoelectric conversion element from being damaged due to a difference in thermal expansion and contraction, and has excellent bonding reliability, thermal conductivity, and conductivity, and a method for manufacturing the same.
  • the purpose is to provide.
  • the thermoelectric conversion module of the present invention includes a plurality of thermoelectric conversion elements composed of P-type thermoelectric conversion elements and N-type thermoelectric conversion elements having different linear expansion coefficients, and a first wiring disposed on one end side of the plurality of thermoelectric conversion elements.
  • thermoelectric conversion element and the N-type thermoelectric conversion element adjacent to the first wiring layer constituting the first wiring board are bonded.
  • the first thermoelectric conversion element and the N-type thermoelectric conversion element are electrically connected by the first wiring layer.
  • each of the first ceramic layers bonded to the first wiring layer is separated between any P-type thermoelectric conversion element and N-type thermoelectric conversion element among the plurality of thermoelectric conversion elements provided. ing.
  • the rigid first ceramic layer is divided between any of the P-type thermoelectric conversion elements and the N-type thermoelectric conversion elements, a plurality of the first ceramic layers are provided. Deformation due to thermal expansion and contraction is not constrained between the thermoelectric conversion elements by the mating first ceramic layers. For this reason, generation
  • the first wiring board is provided with a first ceramic layer. For this reason, when a thermoelectric conversion module is installed in a heat source etc., it can prevent that a heat source etc. and a 1st wiring layer contact with a 1st ceramic layer. Therefore, electrical connection (leakage) between the heat source and the first wiring layer can be reliably avoided, and the insulation state can be maintained satisfactorily. Since each thermoelectric conversion element has a low voltage, if the first ceramic layer as an insulating substrate is separated between the adjacent P-type thermoelectric conversion element and N-type thermoelectric conversion element, the first wiring layer Even if the first ceramic layers are not bonded to the entire surface, no electrical leakage will occur unless the first wiring layer is in physical contact with a heat source or the like.
  • the first wiring layer may be formed so as to straddle between the first ceramic layers.
  • thermoelectric conversion element the difference in thermal expansion between the adjacent P-type thermoelectric conversion element and N-type thermoelectric conversion element can be deformed by the connecting portion of the first wiring layer connecting the two thermoelectric conversion elements to absorb the dimensional change. Therefore, generation
  • the first ceramic layer may be formed independently for each thermoelectric conversion element.
  • the plurality of first ceramic layers constituting the first wiring board are formed independently for each thermoelectric conversion element provided, and each rigid first ceramic layer is interposed between the thermoelectric conversion elements. It is separated. For this reason, the deformation
  • the first wiring layer may be silver, aluminum, copper or nickel.
  • Silver, aluminum, copper, or nickel includes an alloy mainly composed of these.
  • the first wiring layer is made of aluminum having a purity of 99.99% by mass or more, or copper having a purity of 99.9% by mass or more.
  • High purity aluminum (Al) and copper (Cu) are easily elastically and plastically deformed.
  • Aluminum and copper are excellent in thermal conductivity and conductivity.
  • a soft material such as high purity pure aluminum or pure copper for the first wiring layer, it is possible to easily deform and follow the first wiring layer with the thermal expansion and contraction of each thermoelectric conversion element. Therefore, the thermal stress relaxation effect due to the thermal expansion / contraction difference of each thermoelectric conversion element can be further enhanced.
  • a thermoelectric conversion module can be manufactured at low cost.
  • the thermal conductivity and conductivity between both thermoelectric conversion elements connected by the first wiring layer can be favorably maintained.
  • the first wiring layer By forming the first wiring layer from silver (Ag), for example, when the first wiring substrate having the first wiring layer is disposed on the high temperature side of the thermoelectric conversion module, the heat resistance and oxidation resistance are improved. Or maintain good thermal conductivity and conductivity.
  • Nickel is inferior in oxidation resistance compared to aluminum and silver, but has relatively good heat resistance. Nickel is cheaper than silver and has relatively good element bonding. For this reason, the thermoelectric conversion module excellent in the balance of performance and price can be comprised by forming a 1st wiring layer with nickel.
  • the first wiring board is bonded to a surface opposite to a bonding surface of the plurality of first wiring layers and the first wiring layer of the first ceramic layer.
  • a first heat transfer metal layer, and the first heat transfer metal layer is formed between the two adjacent first wiring layers and between the two adjacent first ceramic layers. It is good to be formed straddling.
  • the first ceramic layers are connected by the first heat transfer metal layer, so that the first wiring layers can be handled integrally.
  • the handling property of one wiring board can be improved.
  • each 1st ceramic layer is only connected by either the 1st wiring layer or the 1st heat transfer metal layer, the 1st wiring layer and the 1st heat transfer metal layer are each thermoelectrical. It easily deforms and follows with the thermal expansion and contraction of the conversion element.
  • thermoelectric conversion element peels from a 1st wiring board (1st wiring layer), or each thermoelectric conversion element It is possible to prevent cracks from occurring.
  • thermoelectric conversion module when the thermoelectric conversion module is installed on a heat source or the like, the first heat transfer metal layer increases the adhesion between the heat source or the like and the thermoelectric conversion module. Can improve thermal conductivity. Therefore, the thermoelectric conversion performance (power generation efficiency) of the thermoelectric conversion module can be improved.
  • the first heat transfer metal layer is made of aluminum or copper, preferably aluminum having a purity of 99.99% by mass or more, or copper having a purity of 99.9% by mass or more. It is good to be taken.
  • the first heat transfer metal layer is made of a soft material such as pure aluminum having a high purity and pure copper, so that the first heat transfer metal layer can be easily moved along with the thermal expansion and contraction of each thermoelectric conversion element. Can be deformed and followed. Therefore, the thermal stress relaxation effect due to the thermal expansion / contraction difference of each thermoelectric conversion element can be further enhanced.
  • the first heat transfer metal layer from aluminum or copper, the thermal conductivity between the thermoelectric conversion module and the heat source can be maintained well, and the thermoelectric conversion performance can also be maintained well.
  • thermoelectric conversion module includes a second wiring board disposed on the other end side of the thermoelectric conversion element, and the first wiring board and the second wiring board that are arranged to face each other.
  • the P-type thermoelectric conversion element and the N-type thermoelectric conversion element may be electrically connected in series.
  • first ceramic layer constituting the first wiring substrate is separated between any P-type thermoelectric conversion element and N-type thermoelectric conversion element. Yes.
  • transformation accompanying a thermal expansion / contraction is not restrained by the 1st ceramic layer joined to the other party mutually.
  • the difference in thermal expansion and contraction between the P-type thermoelectric conversion element and the N-type thermoelectric conversion element is caused by deformation of the connection portion of the first wiring layer and the first heat transfer metal layer that connect the two thermoelectric conversion elements. Can absorb changes.
  • thermoelectric conversion module For this reason, generation
  • the second wiring board includes a second wiring layer in which the adjacent P-type thermoelectric conversion element and the N-type thermoelectric conversion element are joined, and the second wiring layer.
  • a second ceramic layer bonded to a surface opposite to a bonding surface between the P-type thermoelectric conversion element and the N-type thermoelectric conversion element, and each of the second ceramic layers is any of the second ceramic layers.
  • the P-type thermoelectric conversion element and the N-type thermoelectric conversion element may be separated from each other.
  • the second wiring layer may be formed so as to straddle between the second ceramic layers.
  • the second ceramic layer may be formed independently for each thermoelectric conversion element.
  • the second wiring layer may be silver, aluminum, copper or nickel.
  • the second wiring board includes a plurality of the second wiring layers and a second heat transfer metal layer bonded to a surface opposite to a bonding surface of the second ceramic layer to the second wiring layer.
  • the second heat transfer metal layer may be formed between both adjacent second wiring layers and between both adjacent second ceramic layers.
  • the second heat transfer metal layer may be aluminum or copper.
  • the second wiring layer in which the adjacent P-type thermoelectric conversion elements and N-type thermoelectric conversion elements are joined is divided into a plurality of separated second ceramic layers.
  • the P-type thermoelectric conversion element bonded to the second wiring layer and the N-type are formed by separating each second ceramic layer between the P-type thermoelectric conversion element and the N-type thermoelectric conversion element. Between the thermoelectric conversion elements, deformation due to thermal expansion and contraction is not constrained by the other second ceramic layer.
  • thermoelectric conversion element since the thermal expansion / contraction difference between the adjacent P-type thermoelectric conversion element and N-type thermoelectric conversion element can absorb the dimensional change due to the deformation of the connecting portion of the second wiring layer connecting the two thermoelectric conversion elements, Generation
  • thermoelectric conversion module As described above, the dimensional change caused by the thermal expansion / contraction difference can be absorbed in each thermoelectric conversion element in both the first wiring board and the second wiring board which are arranged to face each other, so that the first wiring layer and the second wiring layer are connected.
  • the electrical connection between the two thermoelectric conversion elements can be maintained well, and the joining reliability, thermal conductivity and conductivity of the thermoelectric conversion module can be maintained well.
  • the method for manufacturing a thermoelectric conversion module of the present invention includes a scribe line forming step for forming a scribe line for dividing a plurality of first ceramic layers from a ceramic base material on the ceramic base material, and after the scribe line forming step, A metal layer forming step of forming, on one surface of the ceramic base material, a first wiring layer straddling both adjacent first ceramic layer forming regions among the plurality of first ceramic layer forming regions partitioned by the scribe line; After the metal layer forming step, the ceramic base material on which the first wiring layer is formed is divided along the scribe line, and the first wiring layer and the first ceramic layer are joined together.
  • the dividing step of forming the substrate and the bonding surface of each of the first wiring layers to the first ceramic layers after the dividing step are opposite to each other Joining a P-type thermoelectric conversion element and an N-type thermoelectric conversion element having different linear expansion coefficients to each other, and manufacturing a thermoelectric conversion module in which the P-type thermoelectric conversion element and the N-type thermoelectric conversion element are connected in series And having.
  • thermoelectric conversion module in which a large number of thermoelectric conversion elements are joined (mounted), it is very difficult to align and join the first ceramic layers to the first wiring layer.
  • the ceramic base material is divided along the scribe lines, so that the first wiring easily arranged in a desired pattern
  • the 1st wiring board which has a layer and the separated 1st ceramic layer can be formed, and a thermoelectric conversion module can be manufactured smoothly.
  • the first wiring board can be handled integrally, and the handleability can be improved.
  • the joining step is performed between the first wiring layer of the first wiring board and the P-type thermoelectric conversion element between a pair of pressure plates arranged to face each other.
  • the N-type thermoelectric conversion element are disposed in advance, and the first wiring layer and the P-type thermoelectric conversion element are heated by heating the sandwiched body while being pressed in the stacking direction.
  • thermoelectric conversion element and in the bonding process, at least one of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element has a small linear expansion coefficient
  • the A complementary member is disposed between the pressure plate and the first thermoelectric conversion element and the complementary member at the time of joining the first wiring board, the P-type thermoelectric conversion element, and the N-type thermoelectric conversion element.
  • the difference between the height of the other thermoelectric conversion element and the complementary member may want to be smaller than the difference between the height of the height and the other thermoelectric conversion element of the one thermoelectric conversion element.
  • the first wiring board has a plurality of separated first ceramic layers, when the sandwich body is heated in the joining step, the first ceramic layers do not restrain each other on the other side.
  • the thermal expansion of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element stacked at each part can be followed. Therefore, in the joining process, a complementary member is disposed between one of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element and at least one of the thermoelectric conversion elements having a small linear expansion coefficient and the pressure plate. In some cases, the height of the other thermoelectric conversion element having a large linear expansion coefficient can be made closer to the height of the one thermoelectric conversion element and the complementary member.
  • thermoelectric conversion element and the 1st wiring layer can be stuck, and it can press uniformly. Therefore, each thermoelectric conversion element and the first wiring board can be reliably bonded, and the bonding reliability of the thermoelectric conversion module can be improved.
  • the joining step is performed between the first wiring layer of the first wiring board and the P-type thermoelectric conversion element between a pair of pressure plates arranged to face each other.
  • the N-type thermoelectric conversion element are disposed in advance, and the first wiring layer and the P-type thermoelectric conversion element are heated by heating the sandwiched body while being pressed in the stacking direction.
  • the N-type thermoelectric conversion element, and in the bonding step an even number of the sandwiching bodies are arranged in the stacking direction, and the P-type thermoelectric conversion element and the N-type thermoelectric conversion element are arranged. And the same number in the stacking direction.
  • thermoelectric conversion elements and the N-type thermoelectric conversion elements can be arranged one by one (the same number) in the stacking direction.
  • one of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element has a small linear expansion coefficient and a large linear expansion coefficient.
  • the same number of the other thermoelectric conversion elements can always be arranged.
  • thermoelectric conversion module can be manufactured in a single joining step by stacking a plurality of sandwiching bodies in this way.
  • a graphite sheet may be disposed between the sandwiching bodies in the joining step.
  • thermoelectric conversion module By interposing a graphite sheet having cushioning properties between the sandwiching bodies, the inclination of each thermoelectric conversion element in the surface direction of the first wiring board can be corrected, and each thermoelectric conversion element and the first wiring can be corrected.
  • the substrate can be pressed more uniformly. Therefore, each thermoelectric conversion element and the first wiring board can be reliably bonded, and the bonding reliability of the thermoelectric conversion module can be further increased.
  • the metal layer forming step includes forming the plurality of first wiring layers on the one surface of the ceramic base material and the other of the ceramic base materials. Forming a first heat transfer metal layer on the surface of the first heat transfer metal layer, and forming the first heat transfer metal layer straddling between both adjacent first wiring layers in the metal layer forming step; It is formed straddling between the matching first ceramic layer forming regions.
  • the first wiring layers are connected by the first heat transfer metal layer. For this reason, each 1st wiring layer can be handled integrally, and the handleability of a 1st wiring board can be improved.
  • the ceramic base material is divided along the scribe line so that the first wiring layer can be easily arranged in a desired pattern. And the 1st wiring board which has the separated 1st ceramic layer can be formed, and a thermoelectric conversion module can be manufactured smoothly.
  • thermoelectric conversion module can be manufactured stably.
  • the scribe line is a non-joined portion excluding a planned joining region of the first wiring layer on one surface of the ceramic base material. It is good to form.
  • the scribe line may be formed in a non-joining portion excluding a planned joining region of the first heat transfer metal layer on the other surface of the ceramic base material.
  • a plurality of scribe lines are formed on both surfaces of the ceramic base material by forming the scribe lines on the non-bonded portion of the first wiring layer, the non-bonded portion of the first heat transfer metal layer, or both of these non-bonded portions.
  • the first ceramic layer forming region can be partitioned by the scribe line thus formed.
  • the ceramic base material can be easily divided along the scribe line by forming the scribe line on the surface (opposite surface) opposite to the bonding surface of the first wiring layer or the first heat transfer metal layer. Accordingly, the first wiring board having the first wiring layers arranged in a desired pattern and the separated first ceramic layers can be formed easily, and the thermoelectric conversion module can be manufactured smoothly.
  • the scribe line is formed not only at the non-joint portion of the first wiring layer and the non-joint portion of the first heat transfer metal layer, but also at the joint portion of the first wiring layer and the joint portion of the first heat transfer metal layer. It is good to keep. By forming scribe lines at the junction of the first wiring layer and the junction of the first heat transfer metal layer, the ceramic base material can be further easily divided.
  • the scribe line in the scribe line forming step, may be formed by a straight line penetrating opposite sides of the ceramic base material.
  • the ceramic base material can be smoothly divided along the scribe line. Therefore, the manufacturing process can be simplified.
  • thermoelectric conversion element can be prevented from being damaged due to the difference in thermal expansion and contraction, and a thermoelectric conversion module having excellent bonding reliability, thermal conductivity, and conductivity can be provided.
  • thermoelectric conversion module of 1st Embodiment It is a longitudinal cross-sectional view which shows the thermoelectric conversion module of 1st Embodiment. It is a flowchart of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. It is a longitudinal cross-sectional view explaining the scribe line formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. It is a longitudinal cross-sectional view explaining the metal layer formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment, and shows the first half part of a process. It is a longitudinal cross-sectional view explaining the metal layer formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment, and shows the second half part of a process.
  • thermoelectric conversion module of 1st Embodiment It is a longitudinal cross-sectional view explaining the division
  • thermoelectric conversion module of 1st Embodiment It is a longitudinal cross-sectional view explaining the division
  • FIG. 10 is a cross-sectional plan view taken along the line AA in FIG. 9.
  • FIG. 10 is a cross-sectional plan view taken along the line BB in FIG. FIG.
  • FIG. 10 is a cross-sectional plan view taken along the line CC of FIG.
  • FIG. 10 is a cross-sectional plan view in the direction of the arrows along the line DD in FIG. 9. It is the top view which orient
  • FIG. 16B is a plan view in which the other surface of the first wiring board shown in FIG. 16A faces the front side. It is the top view which orient
  • FIG. 17B is a plan view in which the other surface of the first wiring board shown in FIG. 17A faces the front side.
  • FIG. 19B is a plan view in which the other surface of the first wiring board shown in FIG. 19A faces the front side.
  • FIG. 1 shows a thermoelectric conversion module 101 according to the first embodiment.
  • the thermoelectric conversion module 101 is a combination of a plurality of thermoelectric conversion elements 3 and 4, and the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 of the thermoelectric conversion elements 3 and 4 are on one end side (FIG. 1).
  • the first wiring board 2A disposed on the lower side is electrically connected in series.
  • the P-type thermoelectric conversion element 3 is expressed as “P”
  • the N-type thermoelectric conversion element 4 is expressed as “N”.
  • the thermoelectric conversion module 101 has a configuration in which the external wiring 91 is directly drawn out from the other end of each thermoelectric conversion element 3, 4.
  • the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are composed of, for example, a sintered body such as a tellurium compound, skutterudite, filled skutterudite, Heusler, half-Heusler, clastrate, silicide, oxide, or silicon germanium. Is done. There are compounds that can take both P-type and N-type depending on the dopant, and compounds that have either P-type or N-type properties.
  • Bi 2 Te 3 , Sb 2 Te 3 , PbTe, TAGS Ag—Sb—Ge—Te
  • Zn 4 Sb 3 , CoSb 3 , CeFe 4 Sb 12 , Yb 14 MnSb 11, feVAl, MnSi 1.73, FeSi 2, such as Na x CoO 2, Ca 3 Co 4 O 7, Bi 2 Sr 2 Co 2 O 7, SiGe is used.
  • N-type thermoelectric conversion element 4 Bi 2 Te 3, PbTe , La 3 Te 4, CoSb 3, FeVAl, ZrNiSn, Ba 8 Al 16 Si 30, Mg 2 Si, FeSi 2, SrTiO 3, CaMnO 3, ZnO SiGe or the like is used.
  • thermoelectric conversion material of the intermediate temperature type about 300 ° C. to 500 ° C.
  • manganese silicide MnSi 1.73
  • magnesium silicide Mg 2 Si
  • the linear expansion coefficient of manganese silicide used in the P-type thermoelectric conversion element 3 is about 10.8 ⁇ 10 ⁇ 6 / K
  • the linear expansion coefficient of magnesium silicide used in the N-type thermoelectric conversion element 4 is 17.0 ⁇ 10. It is about -6 / K.
  • the linear expansion coefficient of the P-type thermoelectric conversion element 3 is larger than the linear expansion coefficient of the N-type thermoelectric conversion element 4. Get smaller.
  • thermoelectric conversion elements 3 and 4 are formed in, for example, a prismatic shape having a square cross section (for example, 1 mm to 8 mm on one side) or a circular column having a circular cross section (for example, a diameter of 1 mm to 8 mm).
  • the length (the length along the vertical direction in FIG. 1) is 1 mm to 10 mm.
  • the length of the P-type thermoelectric conversion element 3 and the length of the N-type thermoelectric conversion element 4 are set to be equal (substantially the same length) at room temperature (25 ° C.).
  • a metallized layer 41 made of nickel, silver, gold or the like is formed on both end faces of each thermoelectric conversion element 3, 4.
  • the thickness of the metallized layer 41 is 1 ⁇ m or more and 100 ⁇ m or less.
  • the first wiring board 2 ⁇ / b> A includes a first wiring layer 11 ⁇ / b> A to which the thermoelectric conversion elements 3 and 4 are bonded and a bonding surface of the first wiring layer 11 ⁇ / b> A to the thermoelectric conversion elements 3 and 4.
  • the first ceramic layer 21A is bonded to the opposite surface, and the first heat transfer metal layer 32A is bonded to the opposite surface of the first ceramic layer 21A to the wiring layer 11A.
  • the heat transfer metal layer 32A is not an essential component.
  • the first ceramic layer 21A is formed of a general ceramic material such as alumina (Al 2 O 3 ), aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), or the like having a high thermal conductivity and an insulating property. Is done.
  • the first ceramic layer 21 ⁇ / b> A is divided into a plurality (two in FIG. 1) and is formed independently for each of the thermoelectric conversion elements 3 and 4.
  • the first ceramic layer 21A is formed, for example, in a square shape in plan view. Further, the thickness of the first ceramic layer 21A is set to 0.1 mm or more and 2 mm or less.
  • the first wiring board 2A is provided with one first wiring layer 11A having a rectangular shape in plan view and two first heat transfer metal layers 32A having a square shape in plan view.
  • the first wiring layer 11A is formed by connecting the adjacent P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4, and straddles between the two first ceramic layers 21A and 21A. Is formed.
  • the first heat transfer metal layer 32A is formed independently for each first ceramic layer 21A.
  • the first wiring layer 11A is made of a material mainly composed of silver, aluminum, copper, or nickel, and is formed in a planar shape.
  • As the material of the first wiring layer 11A aluminum having a purity of 99.99% by mass or more (so-called 4N aluminum) or copper having a purity of 99.9% by mass or more is preferable.
  • the thickness of the first wiring layer 11A that connects the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 is preferably 0.1 mm or more and 2 mm or less.
  • the first wiring layer 11A is made of a soft material such as high purity pure aluminum or pure copper, and is formed with a relatively thin thickness so that the two adjacent thermoelectric conversion elements 3 and 4 are connected.
  • the planar first wiring layer 11 ⁇ / b> A provided can be easily deformed and followed by the thermal expansion and contraction of both thermoelectric conversion elements 3 and 4, and can be easily bent between these thermoelectric conversion elements 3 and 4. Since aluminum and copper are cheaper than silver, the thermoelectric conversion module 101 can be manufactured at low cost by forming the first wiring layer 11A with aluminum or copper. Further, by forming the first wiring layer 11A from aluminum or copper, the thermal conductivity and conductivity between the thermoelectric conversion elements 3 and 4 connected by the first wiring layer 11A can be favorably maintained.
  • the thermoelectric conductivity and the electrical conductivity can be maintained well, and the electric resistance can be lowered even when the thickness is relatively thin.
  • the first wiring board 2A including the first wiring layer 11A is disposed on the high temperature side of the thermoelectric conversion module 101, heat resistance and oxidation resistance can be improved.
  • the thickness of the first wiring layer 11A is preferably 10 ⁇ m or more and 200 ⁇ m or less.
  • the thermoelectric conversion module 101 having an excellent balance between performance and price can be configured.
  • the first wiring board 2A including the first wiring layer 11A is disposed on the high temperature side of the thermoelectric conversion module 101, heat resistance and oxidation resistance can be improved.
  • the thickness of the first wiring layer 11A is preferably 0.1 mm or more and 1 mm or less.
  • the first heat transfer metal layer 32A is made of a material mainly composed of aluminum or copper (aluminum, aluminum alloy, copper or copper alloy), and is formed in a planar shape.
  • a material for the first heat transfer metal layer 32A aluminum having a purity of 99.99% by mass or more (so-called 4N aluminum) or copper having a purity of 99.9% by mass or more is preferable.
  • 4N aluminum aluminum having a purity of 99.9% by mass or more
  • the followability is improved when the first heat transfer metal layer 32A contacts the heat source or the cooling source. And heat transferability is improved. Therefore, the thermoelectric exchange performance of the thermoelectric conversion module 101 is not deteriorated.
  • the size (planar size) of the first wiring layer 11A and the first heat transfer metal layer 32A depends on the size of the thermoelectric conversion elements 3 and 4 connected to the first wiring layer 11A. , 4 is set equal to or slightly larger than the area of the end face. Further, the first ceramic layer 21A has a space of 0.1 mm or more in width around the first wiring layer 11A, the first heat transfer metal layers 32A, 32A, and between the first heat transfer metal layers 32A, 32A. It is formed in a planar shape that can be secured.
  • thermoelectric conversion module 101 configured as described above.
  • the method for manufacturing the thermoelectric conversion module of the present embodiment includes a plurality of steps S11 to S14.
  • 3A to 3D and 4A to 4D show an example of each process of the method for manufacturing the thermoelectric conversion module of the present embodiment.
  • scribe line forming process First, as shown in FIGS. 3A and 4A, a scribe line (dividing groove) for dividing the plurality of first ceramic layers 21A, 21A into a large ceramic base material 201 constituting the first ceramic layers 21A, 21A. 202 is formed (scribe line forming step S11). Then, a plurality of (two) first ceramic layer forming regions 203 and 203 are defined in the ceramic base material 201 by forming the scribe line 202.
  • the scribe line 202 can be formed by laser processing, for example, as shown in FIG. 3A.
  • the scribe line 202 can be processed by irradiating a laser beam L such as a CO 2 laser, a YAG laser, a YVO 4 laser, and a YLF laser to one surface of the ceramic base material 201.
  • a laser beam L such as a CO 2 laser, a YAG laser, a YVO 4 laser, and a YLF laser.
  • the scribe line 202 is formed on at least one surface of the ceramic base material 201 as shown in FIG. 4A. Specifically, the scribe line 202 is formed not on the bonding surface of the first wiring layer 11A formed across the two first ceramic layers 21A and 21A but on the opposite surface (opposite surface). That is, when the first wiring layer 11A is bonded to one surface of the ceramic base material 201 as shown in FIG. 4C, the scribe line 202 is connected to the other side of the ceramic base material 201 as shown in FIG. 4A. It forms in the non-joining part except the joining plan area
  • the scribe line 202 is formed not only at the non-joining portion of the first wiring layer 11A and the non-joining portion of the first heat transfer metal layer 32A, but also at the joining portion of the first wiring layer 11A. It can also be formed on both sides of the base material 201.
  • the scribe line 202 is formed by a straight line penetrating opposite sides of the ceramic base material 201 as shown in FIG. 4A.
  • one scribe line 202 penetrating the long sides is formed in the ceramic base material 201, and the ceramic base material 201 is divided into two by this one scribe line 202, and the first ceramic layer 21A, Two first ceramic layer forming regions 203, 203 partitioned into the size of the outer shape of 21A are formed in alignment.
  • the ceramic base material 201 on which the scribe line 202 is formed is cleaned by immersing it in an etching solution.
  • the scribe line forming step S11 is not limited to laser processing, and can be performed by other processing methods such as a diamond scriber.
  • the first wiring layer 11A is formed on one surface of the ceramic base material 201, and the first heat transfer metal layer 32A is formed on the other surface (metal layer forming step S12).
  • a metal plate 301 to be the first wiring layer 11 ⁇ / b> A is bonded to one surface of the ceramic base material 201, that is, the surface where the scribe line 202 is not formed, and the scribe line 202 is used.
  • the metal plate 302 to be the first heat transfer metal layer 32A is joined to the other surface on which the is formed.
  • the metal plate 301 and the ceramic base material 201 and the ceramic base material 201 and the metal plate 302 are joined using a brazing material or the like.
  • the metal plates 301 and 302 are formed of a metal material mainly composed of aluminum
  • a metal plate is used by using a bonding material such as Al-Si, Al-Ge, Al-Cu, Al-Mg, or Al-Mn.
  • 301 and 302 and the ceramic base material 201 are joined.
  • the metal plates 301 and 302 are formed of a metal material mainly composed of copper
  • the metal plates 301 and 302 and the ceramic base material 201 are used by using a bonding material such as Ag-Cu-Ti or Ag-Ti.
  • the metal plates 301 and 302 and the ceramic base material 201 may be joined by a transient liquid phase joining method called TLP joining method (Transient Liquid Phase Bonding) in addition to brazing.
  • TLP joining method Transient Liquid Phase Bonding
  • the ceramic base material 201 to which the metal plates 301 and 302 are bonded is subjected to an etching process.
  • the first ceramic layer forming regions 203, The first wiring layer 11 ⁇ / b> A disposed across the 203 is patterned, and the first heat transfer metal layers 32 ⁇ / b> A and 32 ⁇ / b> A independent of the first ceramic layer formation regions 203 and 203 are formed on the other surface of the ceramic base material 201. Is patterned.
  • the scribe line 202 is formed in a non-joined portion excluding the planned joining region of the first heat transfer metal layers 32A and 32A.
  • the entire scribe line 202 can be exposed by removing the metal layer portion (metal plate) formed over the scribe line 202. Thereby, the laminated body 204 including the patterned first wiring layer 11A and the first heat transfer metal layers 32A and 32A and the ceramic base material 201 is formed.
  • the first wiring layer 11A can also be formed without performing an etching process by bonding a previously patterned metal plate to one surface of the ceramic base material 201.
  • the first heat transfer metal layers 32 ⁇ / b> A and 32 ⁇ / b> A can be formed without performing an etching process by joining a piece of metal plate patterned in advance to the other surface of the ceramic base material 201.
  • the first wiring layer 11A can be composed of a sintered body of silver (Ag).
  • a silver paste containing glass and silver containing glass is applied to one surface of the ceramic base material 201 and subjected to heat treatment, whereby a silver paste is obtained. Can be formed by firing. Therefore, the patterned first wiring layer 11A can be formed without performing an etching process.
  • the surface of the ceramic base material 201 that contacts at least the interface with the silver paste is composed of alumina (Al 2 O 3 ).
  • the entire ceramic base material 201 may be made of alumina, or a ceramic substrate in which aluminum nitride is oxidized and the surface is made of alumina may be used.
  • the ceramic base material 201 of the laminated body 204 is divided along the scribe line 202 by bending the ceramic base material 201 so as to protrude toward the surface on which the scribe line 202 is formed. 1 Ceramic layers 21A and 21A are separated. Then, as shown in FIGS. 3D and 4D, a first wiring board 2A is formed in which the first wiring layer 11A, the first ceramic layers 21A and 21A, and the first heat transfer metal layers 32A and 32A are joined. (Division process S13).
  • the ceramic base material 201 can be easily divided along the scribe line 202.
  • the scribe line 202 is formed by a simple straight line that penetrates the opposing sides of the ceramic base material 201, the ceramic base material 201 can be smoothly divided along the scribe line 202.
  • thermoelectric conversion element 3 and one end face of the N-type thermoelectric conversion element 4 are joined to the first wiring layer 11A of the first wiring board 2A (joining step S14).
  • first wiring layer 11A is bonded to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 by bonding using a paste or brazing material, solid phase diffusion bonding by applying a load, or the like. .
  • each of the pressure plates 401A and 401B is composed of a carbon plate.
  • thermoelectric conversion element 3 At the time of joining the first wiring layer 11A to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, at least one of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 has a small linear expansion coefficient.
  • a complementary member 411 is disposed between the thermoelectric conversion element and the pressure plates 401 ⁇ / b> A and 401 ⁇ / b> B to complement the thermal expansion / contraction difference caused by the linear expansion difference between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4.
  • thermoelectric conversion element 3 of manganese silicide (linear expansion coefficient of about 10.8 ⁇ 10 ⁇ 6 / K) and an N-type of magnesium silicide (linear expansion coefficient of about 17.0 ⁇ 10 ⁇ 6 / K).
  • the linear expansion coefficient of the P-type thermoelectric conversion element 3 is smaller than the linear expansion coefficient of the N-type thermoelectric conversion element 4.
  • the complementary member 411 is arrange
  • the complementary member 411 is easily handled by being fixed to the pressure plates 401A and 401B in advance and integrated.
  • a graphite sheet is disposed between the complementary member 411 and the metallized layer 41 of the P-type thermoelectric conversion element 3 and the first heat transfer metal layer 32A to prevent bonding.
  • the complementary member 411 when the complementary member 411 is disposed only on the P-type thermoelectric conversion element 3 side, the complementary member 411 needs to use a material having a higher linear expansion coefficient than the N-type thermoelectric conversion element 4.
  • a material having a higher linear expansion coefficient than the N-type thermoelectric conversion element 4. For example, aluminum (23 ⁇ 10 ⁇ 6 / K) is a material whose linear expansion coefficient is higher than that of the N-type thermoelectric conversion element 4 (about 17.0 ⁇ 10 ⁇ 6 / K). This material is used for the complementary member 411.
  • thermoelectric conversion elements 3 and 4 and the first wiring layer 11A can be brought into close contact with each other between the pair of pressurizing plates 401A and 401B, and can be uniformly pressed.
  • the complementary member 411 is disposed between the lower pressure plate 401 ⁇ / b> A and the sandwiching body 405, and the complementary member 411 is disposed between the upper pressure plate 401 ⁇ / b> B and the sandwiching body 405.
  • the complementary members 412 and 413 can also be arrange
  • a complementary member 412 made of a material having a large linear expansion coefficient is disposed on the P-type thermoelectric conversion element 3 side having a small linear expansion coefficient, and the N-type thermoelectric conversion element 4 side having a large linear expansion coefficient is lined more than the complementary member 412.
  • a complementary member 413 made of a material having a small expansion coefficient is arranged.
  • a graphite sheet is arrange
  • aluminum (23 ⁇ 10 ⁇ 6 / K) or copper (17 ⁇ 10 ⁇ 6 / K) can be used as the material of the complementary member 412 disposed on the P-type thermoelectric conversion element 3 side.
  • iron (12 ⁇ 10 ⁇ 6 / K) or nickel (13 ⁇ 10 ⁇ 6 / K) can be used as the material of the complementary member 413 disposed on the N-type thermoelectric conversion element 4 side.
  • the difference between the height of 413 can be made smaller than the difference between the height of the P-type thermoelectric conversion element 3 and the height of the N-type thermoelectric conversion element 4, and the height of the P-type thermoelectric conversion element 3 and the complementary member 412 and the N-type thermoelectric conversion can be reduced.
  • the height of the element 4 and the complementary member 413 can be made uniform. Therefore, the thermoelectric conversion elements 3 and 4 and the first wiring layer 11A can be brought into close contact with each other between the pair of pressurizing plates 401A and 401B, and can be uniformly pressed.
  • the complementary member 412 made of a material having a large linear expansion coefficient is disposed on the P-type thermoelectric conversion element 3 side having a small linear expansion coefficient, and the complementary member 412 is disposed on the N-type thermoelectric conversion element 4 side having a large linear expansion coefficient.
  • the complementary member 413 made of a material having a smaller linear expansion coefficient is arranged, the complementary member made of a material having a smaller linear expansion coefficient is arranged on the P-type thermoelectric conversion element 3 side, and the wire is arranged on the N-type thermoelectric conversion element 4 side.
  • a complementary member made of a material having a large expansion coefficient may be arranged.
  • the thickness of each complementary member may be adjusted.
  • the first wiring board 2A has a plurality of individual first ceramic layers 21A, 21A, when the sandwiching body 405 is heated in the joining step S14, each first ceramic layer 21A , 21A do not restrain each other. For this reason, it can move following the thermal expansion of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 stacked in each part of the first wiring board 2A. Thereby, the thermoelectric conversion module 101 by which the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 were connected in series via the 1st wiring board 2A can be manufactured.
  • thermoelectric conversion module 101 manufactured in this way has an external heat source (not shown), a cooling channel (not shown), and the like, for example, on the lower side of FIG. Thereby, an electromotive force corresponding to the upper and lower temperature difference is generated in each thermoelectric conversion element 3, 4, and the potential difference of the sum of the electromotive force generated in each thermoelectric conversion element 3, 4 is between the wires 91, 91 at both ends of the array. Can be obtained.
  • thermoelectric conversion module 101 Under such a use environment, a difference occurs in the thermal expansion between both thermoelectric conversion elements 3 and 4 of the thermoelectric conversion module 101.
  • the first ceramic layers 21A and 21A constituting the first wiring board 2A are separated between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4, and the thermoelectric conversion element 3 and 4 are formed independently, and the connection between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the rigid first ceramic layers 21A and 21A is divided. For this reason, the thermoelectric conversion elements 3 and 4 are not restrained from being deformed by the thermal expansion and contraction by the first ceramic layers 21A and 21A.
  • thermoelectric conversion elements 3 and 4 are peeled off from the first wiring board 2A (first wiring layer 11A) or cracks are generated in the thermoelectric conversion elements 3 and 4 due to the difference in thermal expansion and contraction between the thermoelectric conversion elements 3 and 4. Can be prevented. Therefore, the electrical connection between the thermoelectric conversion elements 3 and 4 connected by the first wiring layer 11A can be maintained satisfactorily, and the junction reliability, thermal conductivity, and conductivity of the thermoelectric conversion module 101 can be maintained satisfactorily.
  • the first wiring board 2A is provided with first ceramic layers 21A and 21A which are insulating boards. For this reason, when the thermoelectric conversion module 101 is installed in a heat source or the like, the first ceramic layers 21A and 21A can prevent the heat source and the first wiring layer 11A from contacting each other. Therefore, electrical leakage between the heat source and the first wiring layer 11A can be reliably avoided, and the insulation state can be maintained well.
  • thermoelectric conversion elements 3 and 4 themselves have a low voltage, if the first ceramic layers 21A and 21A, which are insulating substrates, are formed independently for each thermoelectric conversion element 3 and 4, the first wiring layer Even if the first ceramic layers 21A and 21A are not bonded to the entire surface of 11A, as long as the first wiring layer 11A is not in physical contact with a heat source or the like, electrical leakage does not occur.
  • thermoelectric conversion module 101 when the thermoelectric conversion module 101 is installed in a heat source or the like, the first heat transfer metal layers 32A and 32A are used as the heat source. Etc. and the thermoelectric conversion module 101 can be improved in adhesion, and heat transfer can be improved. Therefore, the thermoelectric exchange performance (power generation efficiency) of the thermoelectric conversion module 101 can be improved.
  • thermoelectric conversion element P-type thermoelectric conversion element 3 having a small linear expansion coefficient
  • the pressure plates 401A and 401B, complementary members 411 to 413 are arranged to compensate for the thermal expansion / contraction difference caused by the linear expansion difference between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4.
  • the thermoelectric conversion elements 3 and 4 and the first wiring layer 11A are brought into close contact with each other between the pair of pressure plates 401A and 401B, and the pressure is uniformly applied.
  • the bonding process is limited to this. It is not a thing.
  • thermoelectric conversion elements 3 and 4 and the first wiring layer 11A are brought into close contact with each other when the first wiring layer 11A is bonded to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4.
  • Each can be uniformly pressurized.
  • thermoelectric conversion elements 3 and 4 in the surface direction of the first wiring board 2 ⁇ / b> A can be arranged at each location.
  • the inclination can be corrected, and the thermoelectric conversion elements 3 and 4 and the first wiring board 2A can be more uniformly pressurized.
  • the first wiring boards 2A and 2A of the two sandwiching bodies 405 and 405 adjacent to each other in the stacking direction are arranged to face each other, so that the thermoelectric conversion elements 3 in the surface direction of the first wiring board 2A are arranged.
  • the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4 can be arranged one by one (the same number) in the stacking direction.
  • thermoelectric conversion elements 3 and 4 and the first wiring board 2A can be corrected. Can be more uniformly pressurized.
  • thermoelectric conversion elements 3 and 4 and the first wiring layer 11A can be brought into close contact with each other between the pair of pressure plates 401A and 401B, and the thermoelectric conversion elements 3 and 4 and the first wiring board can be pressed uniformly. 2A can be reliably joined. Moreover, a plurality of thermoelectric conversion modules 101 can be manufactured in a single joining step S14 by stacking a plurality of sandwiching bodies 405 in this way.
  • the first wiring board 2 ⁇ / b> A is provided on one end side of the thermoelectric conversion elements 3, 4, but the thermoelectric conversion module of the second embodiment shown in FIG. 8.
  • the 1st wiring board 2A is arrange
  • the 2nd wiring board 2B is arrange
  • the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 can be electrically connected in series via the first wiring board 2A and the second wiring board 2B that are arranged to face each other.
  • thermoelectric conversion module 102 of the second embodiment elements common to the thermoelectric conversion module 101 of the first embodiment are denoted by the same reference numerals and description thereof is omitted.
  • the first wiring board 2A disposed on one end side (the lower side in FIG. 8) of the thermoelectric conversion elements 3 and 4 is the same as that in the first embodiment, and a description thereof will be omitted.
  • the second wiring board 2B disposed on the other end side (upper side in FIG. 8) of the thermoelectric conversion elements 3 and 4 includes the second wiring layers 12B and 12B and the thermoelectric conversion elements 3 and 2 of the second wiring layers 12B and 12B.
  • the second ceramic layers 21B, 21B constituting the second wiring board 2B are separated into a plurality (two in FIG. 8), and are formed independently for each thermoelectric conversion element 3, 4 as in the first embodiment. ing.
  • Each of the second ceramic layers 21B and 21B is formed in a square shape in plan view.
  • the second wiring board 2B is provided with two second wiring layers 12B, 12B having a square shape in plan view, and one second heat transfer metal layer 31B having a rectangular shape in plan view.
  • the second wiring layers 12B, 12B are formed independently for each of the second ceramic layers 21B, 21B, and are individually connected to the thermoelectric conversion elements 3, 4.
  • the second heat transfer metal layer 31B is formed between both adjacent second wiring layers 12B and 12B, and is formed between both adjacent second ceramic layers 21B and 21B. .
  • the first wiring layer 11A of the first wiring board 2A and the second heat transfer metal layer 31B of the second wiring board 2B are made of the same metal material (the same thickness and the same thickness).
  • the first heat transfer metal layers 32A, 32A of the first wiring board 2A and the second wiring layers 12B, 12B of the second wiring board 2B are formed in the same shape with the same metal material. Yes.
  • the first wiring board 2A and the second wiring board 2B are bonded to two ceramic layers (the first ceramic layers 21A and 21A or the second ceramic layers 21B and 21B) and one surface of both ceramic layers.
  • first wiring layer 11A or second heat transfer metal layer 31B in plan view and the square shape in plan view formed independently of each ceramic layer bonded to the other surface of both ceramic layers.
  • Metal layers first heat transfer metal layers 32A and 32A or second wiring layers 12B and 12B). That is, both the wiring boards 2A and 2B are configured by one type of wiring board having the same configuration.
  • thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4 are alternately connected in series between the pair of wiring boards 2A and 2B configured as described above, so that the thermoelectric conversion module 102 is It is configured. Therefore, the description of the manufacturing method of the thermoelectric conversion module 102 is omitted.
  • thermoelectric conversion module 102 of the second embodiment manufactured in this way the ceramic layers 21A and 21B constituting the wiring boards 2A and 2B are formed independently for each thermoelectric conversion element 3 and 4.
  • the connection between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the rigid ceramic layers 21A and 21B is cut off. For this reason, the thermoelectric conversion elements 3 and 4 are not restrained from being deformed by the thermal expansion and contraction by the ceramic layers 21A and 21B.
  • the first ceramic layers 21A and 21A of the first wiring board 2A are connected by the first wiring layer 11A, and the second ceramic layers 21B and 21B of the second wiring board 2B are connected by the second heat transfer metal. They are only connected by the layer 31B.
  • the thermal expansion / contraction difference between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4 is the first wiring layer 11A or the second heat transfer metal layer 31B connecting the two thermoelectric conversion elements 3 and 4. Therefore, the connecting portion can be deformed to absorb the dimensional change. For this reason, generation
  • thermoelectric conversion elements 3 and 4 are peeled off from both the wiring boards 2A and 2B (the first wiring layer 11A or the second wiring layers 12B and 12B) due to the difference in thermal expansion and contraction between the thermoelectric conversion elements 3 and 4. It is possible to prevent cracks from occurring in the third and fourth. Therefore, the electrical connection between the thermoelectric conversion elements 3 and 4 connected by the first wiring layer 11A and the second wiring layers 12B and 12B can be satisfactorily maintained, and the joining reliability and thermal conductivity of the thermoelectric conversion module 102 can be maintained. In addition, the conductivity can be maintained well.
  • the ceramic layers 21A and 21B which are insulating substrates, are provided on the wiring boards 2A and 2B, respectively, when the thermoelectric conversion module 102 is installed on a heat source or the like, the ceramic layers 21A and 21B It is possible to prevent the first wiring layer 11A or the second wiring layers 12B and 12B from contacting each other. Therefore, electrical leakage between the heat source and the first wiring layer 11A or the second wiring layers 12B and 12B can be reliably avoided, and the insulation state can be maintained satisfactorily.
  • the wiring board 2A, 2B is provided with the first heat transfer metal layer 32A or the second heat transfer metal layer 31B.
  • thermoelectric conversion element 3 and 4 in one set of wiring boards 2A and 2B.
  • it is not limited to this. Only at least one wiring board has a ceramic layer formed independently for each thermoelectric conversion element 3, 4, so that the dimensional change due to the difference in thermal expansion and contraction between both thermoelectric conversion elements 3, 4 can be reduced. Further, it is possible to prevent the occurrence of cracks in the thermoelectric conversion elements 3 and 4 due to the thermal expansion / contraction difference, separation from the set of wiring boards, and the like. Therefore, at least one of the ceramic layers of the set of wiring boards 2A and 2B may be formed independently for each thermoelectric conversion element 3 and 4.
  • thermoelectric conversion module 103 shows a thermoelectric conversion module 103 according to a third embodiment of the present invention.
  • the thermoelectric conversion modules 101 and 102 are configured by combining the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 one by one.
  • a large thermoelectric conversion module can be configured by combining a plurality of P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4.
  • the thermoelectric conversion module 103 includes a plurality of P-type thermoelectric conversion elements 3 and N between a pair of wiring boards 5A and 5B of a first wiring board 5A and a second wiring board 5B that are arranged to face each other.
  • the type thermoelectric conversion elements 4 are combined and arranged in a planar shape (two-dimensional).
  • Each P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4 are electrically connected in series via the upper and lower wiring boards 5A and 5B.
  • thermoelectric conversion module 103 of 3rd Embodiment the same code
  • the first wiring board 5A is opposite to the joint surface between the plurality of first wiring layers 11A and 12A and the thermoelectric conversion elements 3 and 4 of the first wiring layers 11A and 12A.
  • the second wiring board 5 ⁇ / b> B is a surface opposite to the bonding surface between the second wiring layer 11 ⁇ / b> B and the thermoelectric conversion elements 3 and 4 of the second wiring layer 11 ⁇ / b> B.
  • the ceramic layers 21A and 21B constituting the wiring boards 5A and 5B are independently formed for each thermoelectric conversion element 3 and 4 as in the first embodiment.
  • the thermoelectric conversion module 103 is provided with seven P-type thermoelectric conversion elements 3 and seven N-type thermoelectric conversion elements 4, and a total of 14 thermoelectric conversion elements are provided.
  • Each of the wiring boards 5A and 5B is provided with 16 ceramic layers 21A and 21B that are larger than the number of thermoelectric conversion elements 3 and 4, respectively.
  • first ceramic layers 21A of the first wiring board 5A are connected by either the first wiring layer 11A or the first heat transfer metal layer 31A, and a plurality of parts constituting the first wiring board 5A.
  • the first ceramic layer 21A is integrally provided.
  • the second ceramic layers 21B of the second wiring board 5B are connected by either the second wiring layer 11B or the second heat transfer metal layer 31B, and a plurality of parts constituting the second wiring board 5B.
  • the second ceramic layer 21B is integrally provided.
  • the first wiring substrate 5A disposed on the lower side of FIG. 9 includes seven first wiring layers 11A having a rectangular shape in plan view and a first wiring layer 12A having a square shape in plan view.
  • first wiring layers 11A having a rectangular shape in plan view and a first wiring layer 12A having a square shape in plan view are provided, and as shown in FIG. 11, eight first heat transfer metal layers 31A having a rectangular shape in plan view are provided.
  • the second wiring board 5B disposed on the upper side of FIG. 9 is provided with eight second wiring layers 11B having a rectangular shape in plan view as shown in FIG. 12, and as shown in FIG. Seven second heat transfer metal layers 31B having a rectangular shape in plan view and two second heat transfer metal layers 32B having a square shape in plan view are provided.
  • the first wiring layer 11A of the first wiring board 5A is formed by connecting between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4, and the first of both thermoelectric conversion elements 3 and 4 is connected. It is formed between the ceramic layers 21A and 21A.
  • the first wiring layer 12A is independently formed only on the first ceramic layer 21A where the first wiring layer 11A is not formed.
  • the first heat transfer metal layer 31A is formed between both adjacent first wiring layers 11A, 11A, and is formed between both adjacent first ceramic layers 21A, 21A. .
  • the second wiring layer 11B of the second wiring board 5B is formed by connecting between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4, and the two thermoelectric conversion elements 3 and 4 It is formed straddling between the second ceramic layers 21B, 21B. Further, the second heat transfer metal layer 31B is formed between the adjacent second wiring layers 11B and 11B, and is formed between the adjacent second ceramic layers 21B and 21B. . On the other hand, the second heat transfer metal layer 32B is independently formed only on the second ceramic layer 21B where the second heat transfer metal layer 32B is not formed.
  • first wiring layer 11A of the first wiring board 5A and the second heat transfer metal layer 31B of the second wiring board 5B are formed in the same shape (same thickness, same plane size) from the same metal material.
  • first wiring layer 12A and the second heat transfer metal layer 32B of the first wiring board 5A are formed in the same shape from the same metal material.
  • first heat transfer metal layer 31A of the first wiring board 5A and the second wiring layer 11B of the second wiring board 5B are formed in the same shape from the same metal material.
  • the first wiring board 5A and the second wiring board 5B are configured by one type of wiring board having the same configuration.
  • the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4 are alternately connected in series between the pair of wiring boards 5A and 5B configured as described above, so that the thermoelectric conversion module 103 is It is configured.
  • thermoelectric conversion module 103 configured as described above.
  • the manufacturing method of the thermoelectric conversion module of 3rd Embodiment is comprised by the flow similar to the flow of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. Therefore, the manufacturing method of the thermoelectric conversion module of the third embodiment will also be described using the flowchart of FIG.
  • the description of the manufacturing process of the second wiring board 5B is omitted in steps S11 to S13. Only the manufacturing process of the first wiring board 5A will be described.
  • FIGS. 14A and 14B First, as shown in FIGS. 14A and 14B, scribe lines 202a and 202b for dividing the plurality of ceramic layers 21A are formed on a large ceramic base material 205 constituting the first ceramic layer 21A, and the ceramic base material is formed. A plurality (16) of first ceramic layer forming regions 203 are partitioned into 205 (scribe line forming step S11).
  • FIG. 14A is a plan view of the ceramic base material 205 in which one surface of the ceramic base material 205 on which the first wiring layers 11A and 12A are formed faces the front side, and FIG. 14B shows the first heat transfer metal layer.
  • positioned the other surface of the ceramic base material 205 in which 31A is formed facing the front side is represented.
  • one surface of the ceramic base material 205 is passed between the planned bonding regions of the first wiring layers 11A and 12A, and the bonding planned regions of the first wiring layers 11A and 12A are excluded.
  • a scribe line 202b is formed at the non-joining portion. Specifically, two scribe lines 202b formed by straight lines penetrating the laterally opposed sides of the ceramic base material 205 are formed.
  • the other surface of the ceramic base material 205 is passed between the region where the first heat transfer metal layer 31A is to be bonded, and the region where the first heat transfer metal layer 31A is to be bonded Scribe lines 202a and 202b are formed in the non-joining portions except for.
  • the three scribe lines 202 a formed by straight lines penetrating the sides facing the vertical direction of the ceramic base material 205 and the straight lines penetrating the sides facing the lateral direction of the ceramic base material 205.
  • One formed scribe line 202b is formed.
  • the ceramic base material 205 has 16 first ceramic layer formation regions 203 divided vertically and horizontally in the size of the outer shape of the first ceramic layer 21A. Aligned and formed.
  • the scribe lines 202a and 202b are not only formed in the non-joined portion of the first wiring layers 11A and 12A and the non-joined portion of the first heat transfer metal layer 31A, but also in the joint portion and the first of the first wiring layer 11A. It can also be formed on both surfaces of the ceramic base material 205 by forming it at the joint portion of the heat transfer metal layer 31A.
  • the first wiring layers 11A and 12A are formed on one surface of the ceramic base material 205 as shown in FIG. 15A, and the other surface of the ceramic base material 205 is shown in FIG. 15B.
  • the first heat transfer metal layer 31A is formed, and a laminate 206 is formed in which the first wiring layers 11A and 12A and the first heat transfer metal layer 31A are bonded to both surfaces of the ceramic base material 205 (metal layer forming step S12). ).
  • a metal plate to be the first wiring layers 11A and 12A is bonded to one surface of the ceramic base material 205, and the first heat transfer metal layer 31A and the other surface of the ceramic base material 205 are connected to each other. After joining the metal plates, the first wiring layers 11A and 12A are patterned on one surface of the ceramic base material 205 by performing an etching process, and the first heat transfer is performed on the other surface of the ceramic base material 205. The metal layer 31A is patterned.
  • the scribe lines 202a and 202b are formed in the non-joined portion except the planned joining region of the first wiring layers 11A and 11B and the non-joined portion except the planned joining region of the first heat transfer metal layer 31A.
  • the metal layer portion (metal plate) formed over the scribe lines 202a and 202b By removing the metal layer portion (metal plate) formed over the scribe lines 202a and 202b, the entire scribe lines 202a and 202b can be exposed.
  • the first wiring layers 11A and 12A and the first heat transfer metal layer 31A can be formed without performing an etching process by bonding a previously patterned metal plate to the ceramic base material 205.
  • the first wiring layers 11A and 12A can also be formed of a sintered body of silver (Ag).
  • the ceramic base material 205 is bent along the scribe lines 202a and 202b by bending the ceramic base material 205 so as to protrude toward the surface on which the scribe lines 202a and 202b are formed.
  • the first ceramic layer forming region 203 is divided into individual first ceramic layers 21A.
  • the first wiring substrate 5A in which the first wiring layers 11A and 12A, the first ceramic layer 21A, and the first heat transfer metal layer 31A are joined is formed (division step S13).
  • the ceramic base material 205 can be easily divided along the scribe lines 202a and 202b. . Further, since the scribe lines 202a and 202b are formed by simple straight lines that pass through the opposing sides of the ceramic base material 205, the ceramic base material 205 can be smoothly divided along the scribe lines 202a and 202b.
  • the second wiring board 5B is manufactured by the same process as the first wiring board 5A.
  • the first wiring board 5A formed in this way has a plurality of first wiring layers 11A and 12A, and the first wiring layers 11A and 11A or 11A and 12A are formed by the first heat transfer metal layer 31A. Are connected to each other. Moreover, since the separated first ceramic layer 21A is connected by the first wiring layer 11A or the first heat transfer metal layer 31A, in the first wiring board 5A, the first wiring layers 11A, 12A, One ceramic layer 21A and the first heat transfer metal layer 31A can be handled integrally.
  • the second wiring board 5B configured similarly to the first wiring board 5A can also handle the second wiring layer 11B, the second ceramic layer 21B, and the second heat transfer metal layers 31B and 32B integrally.
  • thermoelectric conversion module 103 in which P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4 are alternately connected in series between the wiring boards 5A and 5B is manufactured.
  • each of the wiring layers 11A and 11B and the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are bonded by bonding using a paste or brazing material, solid phase diffusion bonding by applying a load, or the like. To do.
  • the thermoelectric conversion elements 3 and 4 and the first wiring layers 11A and 11B are interposed between the pair of pressure plates 401A and 401B. And pressurizing uniformly.
  • thermoelectric conversion elements 3, 4 and the first wiring layers 11A, 11B are brought into close contact with each other. Can be pressurized uniformly.
  • a graphite sheet having a cushioning property is disposed between the sandwiching bodies, so that both wiring boards 5A and 5B can be arranged in the plane direction. The respective inclinations of the thermoelectric conversion elements 3 and 4 can be corrected, and the thermoelectric conversion elements 3 and 4 and the wiring boards 5A and 5B can be more uniformly pressurized.
  • the first wiring board 5A has a plurality of first wiring layers 11A and 12A, but the first wiring layers 11A and 12A are connected by the first heat transfer metal layer 31A. Therefore, the first wiring layers 11A and 12A can be handled integrally, and the first wiring board 5A can be easily handled.
  • the second wiring board 5B has a plurality of second wiring layers 11B. Since the second wiring layers 11B are connected by the second heat transfer metal layer 31B, each second wiring layer 11B is connected to each second wiring layer 11B. The wiring layer 11B can be handled integrally, and the second wiring board 5B can be easily handled.
  • the ceramic base material 205 is attached to the scribe line 202a, By dividing along 202b, the first wiring substrate 5A having the first wiring layers 11A, 12A and the separated first ceramic layers 21A arranged in a predetermined pattern can be easily formed.
  • a large thermoelectric conversion module 103 to which a large number of thermoelectric conversion elements 3 and 4 are joined (mounted) can be easily manufactured.
  • each first ceramic layer 21A constituting the first wiring board 5A is formed independently for each thermoelectric conversion element 3, 4.
  • the connection between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the rigid first ceramic layer 21A is disconnected.
  • each second ceramic layer 21B is formed independently for each of the thermoelectric conversion elements 3 and 4, and P in the rigid second ceramic layer 21B is formed.
  • the connection between the type thermoelectric conversion element 3 and the N type thermoelectric conversion element 4 is disconnected. For this reason, the thermoelectric conversion elements 3 and 4 are not restrained from being deformed by the thermal expansion and contraction by the ceramic layers 21A and 21B.
  • first ceramic layers 21A are only connected by either the first wiring layer 11A or the first heat transfer metal layer 31A
  • second wiring layers 11B are connected between the second ceramic layers 21B.
  • they are only connected by any one of the second heat transfer metal layers 31B.
  • the thermal expansion / contraction difference between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4 is the first wiring layer 11A or the first heat transfer metal layer 31A connecting the two thermoelectric conversion elements 3 and 4.
  • the connection portion of the second wiring layer 11B or the second heat transfer metal layer 31B is deformed to absorb the dimensional change. For this reason, generation
  • thermoelectric conversion elements 3 and 4 are peeled off from the wiring boards 5A and 5B (the first wiring layers 11A and 12A and the second wiring layer 11B) due to the difference in thermal expansion and contraction between the thermoelectric conversion elements 3 and 4. , 4 can be prevented from cracking. Therefore, the electrical connection between the thermoelectric conversion elements 3 and 4 connected by the first wiring layers 11A and 12A and the second wiring layer 11B can be satisfactorily maintained, and the junction reliability and thermal conductivity of the thermoelectric conversion module 103 can be maintained. In addition, the conductivity can be maintained well.
  • each of the wiring boards 5A and 5B is provided with the ceramic layer 21A or 21B which is an insulating substrate, when the thermoelectric conversion module 103 is installed in a heat source or the like, the ceramic layer 21A or 21B can be connected to the heat source or the like. Contact with the layer 11A, 12A or 11B can be prevented. Therefore, electrical leakage between the heat source and the wiring layer 11A, 12A, or 11B can be reliably avoided, and the insulation state can be maintained satisfactorily.
  • thermoelectric conversion module 103 since the heat transfer metal layers 31A or 31B, 32B are provided on the wiring boards 5A, 5B, when the thermoelectric conversion module 103 is installed in a heat source or the like, the heat transfer metal layers 31A, 31B, 32B Etc. and the thermoelectric conversion module 103 can be improved in adhesion, and heat transfer can be improved. Therefore, the thermoelectric exchange performance (power generation efficiency) of the thermoelectric conversion module 103 can be improved.
  • the first wiring boards 2A and 5A and the second wiring boards 2B and 5B are formed by a plurality of first thermoelectric conversion elements 3 and 4 formed independently of each other.
  • the first ceramic layer 21A or the second ceramic layer 21B is provided, it is separated into a plurality of thermoelectric conversion elements 3 and 4 as in the first wiring boards 6A to 6C shown in FIGS. 16A to 18B.
  • the first ceramic layers 22A to 22C separated between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 may be used.
  • the first wiring board 6A shown in FIGS. 16A and 16B includes the first wiring layers 11A and 12A and the first heat transfer metal layer 31A similar to the first wiring board 5A of the thermoelectric conversion module 103 of the second embodiment. It has the pattern which consists of.
  • the first ceramic layer 22A is separated for each pair of adjacent (two) thermoelectric conversion elements 3 and 4, and is constituted by a total of eight first ceramic layers 22A.
  • the first ceramic layers 22A and 22A are connected by the first wiring layer 11A, and a plurality of first ceramic layers 22A constituting the first wiring board 6A are integrally formed. Is provided.
  • the first wiring layer 11A of the first wiring board 6A is formed by connecting between a pair of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, and both the thermoelectric conversion elements 3 and 4 are connected. Formed between the first ceramic layers 22A and 22A.
  • the rigid first ceramic layer 22A is divided between any of the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4. A plurality of them are provided. For this reason, between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are formed by the first ceramic layer 22A bonded to each other. The deformation accompanying the thermal expansion and contraction is not restricted. Further, the difference in thermal expansion and contraction between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the separation portion of each first ceramic layer 22A is that of the first wiring layer 11A connecting the two thermoelectric conversion elements 3 and 4. The connecting portion can be deformed to absorb the dimensional change. Therefore, it is possible to suppress the generation of thermal stress generated in each thermoelectric conversion element 3, 4 due to the thermal expansion / contraction difference of each thermoelectric conversion element 3, 4.
  • first ceramic layers can be further reduced as compared with the first wiring board 6A shown in FIGS. 16A and 16B.
  • the first ceramic layer 22B of the first wiring board 6B shown in FIGS. 17A and 17B is separated into four thermoelectric conversion elements 3 and 4, and is constituted by a total of four first ceramic layers 22B.
  • the first ceramic layer 22C of the first wiring board 6C shown in FIGS. 18A and 18B is separated into eight thermoelectric conversion elements 3 and 4, and is constituted by a total of two first ceramic layers 22C.
  • the first ceramic layers 22B and 22C that are provided in a divided manner between any of the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4, these P-type thermoelectric conversion elements are provided. 3 and the N-type thermoelectric conversion element 4, the first ceramic layers 22 ⁇ / b> B and 22 ⁇ / b> C bonded to each other cause deformation due to thermal expansion and contraction between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4. There is no restraint. Further, the difference in thermal expansion and contraction between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the separated portions of the first ceramic layers 22B and 22C is the first wiring layer that connects the thermoelectric conversion elements 3 and 4 together. The connecting portion of 11A can be deformed to absorb the dimensional change. Therefore, it is possible to suppress the generation of thermal stress generated in each thermoelectric conversion element 3, 4 due to the thermal expansion / contraction difference of each thermoelectric conversion element 3, 4.
  • thermoelectric conversion elements 3 and 3 are caused by the thermal expansion / contraction difference of the thermoelectric conversion elements 3 and 4.
  • the generation of thermal stress generated in 4 can be suppressed. Therefore, it is possible to prevent the thermoelectric conversion elements 3 and 4 from being peeled off from the first wiring boards 6A to 6C (first wiring layer 11A) and the thermoelectric conversion elements 3 and 4 from being cracked. Therefore, the electrical connection between the thermoelectric conversion elements 3 and 4 connected by the first wiring layer 11A can be maintained satisfactorily, and the junction reliability, thermal conductivity, and conductivity of the thermoelectric conversion module can be maintained satisfactorily.
  • the first wiring boards 2A, 5A, 6A to 6C of the above embodiment have the first heat transfer metal layers 31A and 32A separated into a plurality of patterns, respectively, but in FIGS. 19A and 19B, As shown in the first wiring board 7A, the first heat transfer metal layer 31C can be configured to have a large size connecting three or more first ceramic layers 22A. In this case, since each first ceramic layer 22A can be connected by the first heat transfer metal layer 31C, the first wiring board 7A is integrated and configured without connecting each first ceramic layer 22A by the first wiring layer 11A. it can.
  • thermoelectric conversion module using the first wiring board 7A shown in FIG. 19A and FIG. 19B a plurality of first ceramic layers 22A are provided between any one of the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4.
  • first ceramic layers 22A are provided between any one of the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4.
  • thermoelectric conversion element 3 the difference in thermal expansion and contraction between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the separated portion of each first ceramic layer 22A is the first heat transfer metal layer that connects the two thermoelectric conversion elements 3 and 4 together.
  • the connecting portion of 31C can be deformed to absorb the dimensional change. Therefore, it is possible to suppress the generation of thermal stress generated in each thermoelectric conversion element 3, 4 due to the thermal expansion / contraction difference of each thermoelectric conversion element 3, 4.
  • the second wiring layer, the second ceramic layer, and the second heat transfer metal layer have the same configuration as the first wiring layer, the first ceramic layer, and the second heat transfer metal layer, respectively. Can do.
  • thermoelectric conversion module that can prevent the thermoelectric conversion element from being damaged due to a difference in thermal expansion and contraction and is excellent in bonding reliability, thermal conductivity, and conductivity.
  • thermoelectric conversion element thermoelectric conversion element
  • N-type thermoelectric conversion element thermoelectric conversion element 11A, 12A First wiring layer 11B, 12B Second wiring layer 21A, 22A, 22B, 22C First ceramic layer 21B Second ceramic layer 31A, 32A, 31C First heat transfer metal layer 31B, 32B Second heat transfer metal layer 41

Abstract

A thermoelectric conversion module has: a plurality of thermoelectric conversion elements comprising a P-type thermoelectric conversion element and an N-type thermoelectric conversion element having differing linear expansion coefficients; and a first wiring substrate arranged at one end side of the plurality of thermoelectric conversion elements, the first wiring substrate having a first wiring layer in which the adjacent P-type thermoelectric conversion element and N-type thermoelectric conversion element are joined, and first ceramic layers in which the P-type thermoelectric conversion elements and the N-type thermoelectric conversion elements of the first wiring layer are joined to the opposite surface and multiply separated, each first ceramic layer being separated from the P-type thermoelectric conversion element or the N-type thermoelectric conversion element.

Description

熱電変換モジュール及びその製造方法Thermoelectric conversion module and manufacturing method thereof
 本発明は、P型熱電変換素子とN型熱電変換素子とを直列に配列した熱電変換モジュール及びその製造方法に関する。 The present invention relates to a thermoelectric conversion module in which a P-type thermoelectric conversion element and an N-type thermoelectric conversion element are arranged in series, and a manufacturing method thereof.
 本願は、2017年3月8日に出願された特願2017‐43487及び2017年8月28日に出願された特願2017‐163484に基づき優先権を主張し、その内容をここに援用する。 This application claims priority based on Japanese Patent Application No. 2017-43487 filed on March 8, 2017 and Japanese Patent Application No. 2017-163484 filed on August 28, 2017, the contents of which are incorporated herein by reference.
 熱電変換モジュールは、一般に、一組の配線基板(絶縁基板)の間に、一対のP型熱電変換素子とN型熱電変換素子とを、P型、N型、P型、N型の順に交互に配置されるように、電気的に直列に接続した構成とされる。熱電変換モジュールは、配線の両端を直流電源に接続して、ペルチェ効果により各熱電変換素子中で熱を移動させる(P型では電流と同方向、N型では電流と逆方向に移動させる)、あるいは、両配線基板間に温度差を付与して各熱電変換素子にゼーベック効果により起電力を生じさせるものであり、冷却、加熱、あるいは発電としての利用が可能である。 A thermoelectric conversion module generally has a pair of P-type thermoelectric conversion elements and N-type thermoelectric conversion elements alternately arranged in the order of P-type, N-type, P-type, and N-type between a pair of wiring boards (insulating boards). It is set as the structure electrically connected in series so that it may be arrange | positioned. The thermoelectric conversion module connects both ends of the wiring to a DC power source and moves heat in each thermoelectric conversion element by the Peltier effect (P type moves in the same direction as the current, N type moves in the opposite direction of the current), Alternatively, a temperature difference is applied between the two wiring boards to generate an electromotive force in each thermoelectric conversion element by the Seebeck effect, which can be used for cooling, heating, or power generation.
 熱電変換モジュールにおいては、高温作動になるほど高効率であることから、高温型の熱電変換モジュールが多く開発されている。中高温(300℃)以上で使用される熱電変換モジュールでは、絶縁基板の材料に樹脂は使用できないため、絶縁基板にセラミックスを用いることが一般的に行われている。 Thermoelectric conversion modules are more efficient as they operate at higher temperatures, so many high-temperature thermoelectric conversion modules have been developed. In a thermoelectric conversion module used at a medium high temperature (300 ° C.) or higher, a resin cannot be used as a material for an insulating substrate, and therefore ceramics are generally used for the insulating substrate.
 セラミックスの中には、例えば窒化アルミニウムのように、絶縁性と熱伝導性とが両立した材料が存在する。しかし、セラミックスはいずれも硬くて剛性の高い材料であるため、剛体として熱電変換素子間の線膨張差を熱応力に変えてしまう。つまり、P型熱電変換素子とN型熱電変換素子との両熱電変換素子の熱電変換材料に、線膨張係数の異なる材料を用いた場合は、熱電変換モジュールを熱源に設置すると、両熱電変換素子はセラミックス基板によって拘束されることで各々の形状変化に追従できない。このため、線膨張係数の大きな熱電変換素子には圧縮応力が生じ、線膨張係数の小さな熱電変換素子には引張応力が生じる。 Among ceramics, there is a material having both insulating properties and thermal conductivity, such as aluminum nitride. However, since all ceramics are hard and highly rigid materials, the linear expansion difference between thermoelectric conversion elements is changed to thermal stress as a rigid body. That is, when materials having different linear expansion coefficients are used as the thermoelectric conversion materials for both the P-type thermoelectric conversion element and the N-type thermoelectric conversion element, the thermoelectric conversion module is installed in the heat source. Cannot follow each shape change by being restrained by the ceramic substrate. For this reason, a compressive stress is generated in a thermoelectric conversion element having a large linear expansion coefficient, and a tensile stress is generated in a thermoelectric conversion element having a small linear expansion coefficient.
 熱伸縮差により熱応力が生じた場合には、熱電変換素子が配線基板の配線部から剥がれたり、熱電変換素子にクラックが生じたりすることがある。この場合には、電気が流れなくなったり、電気伝導度が低下したりして熱電変換モジュールが動作不能になったり、動作不能に至らなくても発電量が大幅に低下したりするおそれがある。 When a thermal stress is generated due to a thermal expansion / contraction difference, the thermoelectric conversion element may be peeled off from the wiring portion of the wiring board, or the thermoelectric conversion element may be cracked. In this case, electricity may not flow, the electrical conductivity may decrease, and the thermoelectric conversion module may become inoperable, or the amount of power generation may be significantly reduced even if the thermoelectric conversion module does not become inoperable.
 そこで、例えば特許文献1~3では、複数の熱電変換素子(熱電半導体材料、熱電変換半導体)を接続する配線(電極)にいわゆる発泡金属(多孔性金属材料、多孔質金属部材)や金属繊維の集合体を用いることにより、配線に柔軟性を与えて、熱伸縮差による熱応力を緩和する試みがなされている。 Therefore, for example, in Patent Documents 1 to 3, so-called foam metal (porous metal material, porous metal member) or metal fiber is connected to a wiring (electrode) connecting a plurality of thermoelectric conversion elements (thermoelectric semiconductor material, thermoelectric conversion semiconductor). Attempts have been made to relieve thermal stress due to thermal expansion and contraction by giving flexibility to the wiring by using the aggregate.
特開2007‐103580号公報JP 2007-103580 A 国際公開第2010/010783号International Publication No. 2010/010883 特許第5703871号公報Japanese Patent No. 5703871
 特許文献1~3では、配線に発泡金属や金属繊維の集合体を用いており、これらの部材自体に電流が流れる構成とされている。このため、配線の内部抵抗(熱抵抗及び電気抵抗)が大幅に上昇し、熱電変換モジュールの出力を大幅に低下させるおそれがある。 In Patent Documents 1 to 3, an assembly of foam metal or metal fiber is used for the wiring, and a current flows through these members themselves. For this reason, the internal resistance (thermal resistance and electrical resistance) of the wiring is significantly increased, and the output of the thermoelectric conversion module may be significantly decreased.
 本発明は、このような事情に鑑みてなされたもので、熱電変換素子の熱伸縮差による破壊を防止でき、接合信頼性、熱伝導性及び導電性に優れた熱電変換モジュール及びその製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, a thermoelectric conversion module that can prevent the thermoelectric conversion element from being damaged due to a difference in thermal expansion and contraction, and has excellent bonding reliability, thermal conductivity, and conductivity, and a method for manufacturing the same. The purpose is to provide.
 本発明の熱電変換モジュールは、線膨張係数の異なるP型熱電変換素子とN型熱電変換素子からなる複数の熱電変換素子と、複数の前記熱電変換素子の一端側に配設された第1配線基板と、を有し、前記第1配線基板は、隣り合う前記P型熱電変換素子と前記N型熱電変換素子とが接合された第1配線層と、該第1配線層の前記P型熱電変換素子と前記N型熱電変換素子との接合面とは反対面に接合され複数に分離された第1セラミックス層と、を有しており、各第1セラミックス層がいずれかの前記P型熱電変換素子と前記N型熱電変換素子との間で分離されている。 The thermoelectric conversion module of the present invention includes a plurality of thermoelectric conversion elements composed of P-type thermoelectric conversion elements and N-type thermoelectric conversion elements having different linear expansion coefficients, and a first wiring disposed on one end side of the plurality of thermoelectric conversion elements. A first wiring layer in which the adjacent P-type thermoelectric conversion element and the N-type thermoelectric conversion element are joined, and the P-type thermoelectric of the first wiring layer. A first ceramic layer bonded to a surface opposite to a bonding surface between the conversion element and the N-type thermoelectric conversion element and separated into a plurality of the first ceramic layers, and each of the first ceramic layers is one of the P-type thermoelectric elements. It isolate | separates between the conversion element and the said N type thermoelectric conversion element.
 複数の熱電変換素子の一端側が接合される第1配線基板において、この第1配線基板を構成する第1配線層に隣り合うP型熱電変換素子とN型熱電変換素子とが接合され、これらP型熱電変換素子とN型熱電変換素子との間が第1配線層により電気的に接続される。一方、第1配線層に接合された各第1セラミックス層は、複数設けられる熱電変換素子のうち、いずれかのP型熱電変換素子とN型熱電変換素子との間で分離され、複数設けられている。 In the first wiring board to which one end sides of the plurality of thermoelectric conversion elements are bonded, the P-type thermoelectric conversion element and the N-type thermoelectric conversion element adjacent to the first wiring layer constituting the first wiring board are bonded. The first thermoelectric conversion element and the N-type thermoelectric conversion element are electrically connected by the first wiring layer. On the other hand, each of the first ceramic layers bonded to the first wiring layer is separated between any P-type thermoelectric conversion element and N-type thermoelectric conversion element among the plurality of thermoelectric conversion elements provided. ing.
 このように、剛体の第1セラミックス層は、いずれかのP型熱電変換素子とN型熱電変換素子との間で分断され、複数設けられているので、これらのP型熱電変換素子とN型熱電変換素子との間で、互いに相手側の第1セラミックス層によって熱伸縮に伴う変形が拘束されることがない。このため、各熱電変換素子の熱伸縮差により各熱電変換素子内に生じる熱応力の発生を抑制でき、各熱電変換素子が第1配線基板(第1配線層)から剥がれたり、各熱電変換素子にクラックが生じたりすることを防止できる。したがって、第1配線層により接続される両熱電変換素子間の電気的な接続を良好に維持でき、熱電変換モジュールの接合信頼性、熱伝導性及び導電性を良好に維持できる。 Thus, since the rigid first ceramic layer is divided between any of the P-type thermoelectric conversion elements and the N-type thermoelectric conversion elements, a plurality of the first ceramic layers are provided. Deformation due to thermal expansion and contraction is not constrained between the thermoelectric conversion elements by the mating first ceramic layers. For this reason, generation | occurrence | production of the thermal stress which arises in each thermoelectric conversion element by the thermal expansion-contraction difference of each thermoelectric conversion element can be suppressed, and each thermoelectric conversion element peels from a 1st wiring board (1st wiring layer), or each thermoelectric conversion element It is possible to prevent cracks from occurring. Therefore, the electrical connection between the two thermoelectric conversion elements connected by the first wiring layer can be maintained satisfactorily, and the joining reliability, thermal conductivity, and conductivity of the thermoelectric conversion module can be maintained satisfactorily.
 また、第1配線基板には第1セラミックス層が設けられている。このため、熱電変換モジュールを熱源等に設置したときに、第1セラミックス層により熱源等と第1配線層とが接触することを防止できる。したがって、熱源等と第1配線層との電気的な接続(リーク)を確実に回避でき、絶縁状態を良好に維持できる。なお、各熱電変換素子は電圧が低いことから、絶縁基板である第1セラミックス層が隣り合うP型熱電変換素子とN型熱電変換素子との間で分離されていれば、第1配線層の全面に各第1セラミックス層が接合されていなくても、第1配線層が熱源等と物理的に接触しない限り、電気的なリークを生じることはない。 The first wiring board is provided with a first ceramic layer. For this reason, when a thermoelectric conversion module is installed in a heat source etc., it can prevent that a heat source etc. and a 1st wiring layer contact with a 1st ceramic layer. Therefore, electrical connection (leakage) between the heat source and the first wiring layer can be reliably avoided, and the insulation state can be maintained satisfactorily. Since each thermoelectric conversion element has a low voltage, if the first ceramic layer as an insulating substrate is separated between the adjacent P-type thermoelectric conversion element and N-type thermoelectric conversion element, the first wiring layer Even if the first ceramic layers are not bonded to the entire surface, no electrical leakage will occur unless the first wiring layer is in physical contact with a heat source or the like.
 本発明の熱電変換モジュールの好ましい実施態様として、前記第1配線層が、前記第1セラミックス層どうしの間に跨って形成されているとよい。 As a preferred embodiment of the thermoelectric conversion module of the present invention, the first wiring layer may be formed so as to straddle between the first ceramic layers.
 この場合、隣り合うP型熱電変換素子とN型熱電変換素子との熱伸縮差を、両熱電変換素子の間を接続する第1配線層の接続部分が変形して寸法変化を吸収できる。したがって、各熱電変換素子の熱伸縮差により各熱電変換素子内に生じる熱応力の発生を抑制できる。 In this case, the difference in thermal expansion between the adjacent P-type thermoelectric conversion element and N-type thermoelectric conversion element can be deformed by the connecting portion of the first wiring layer connecting the two thermoelectric conversion elements to absorb the dimensional change. Therefore, generation | occurrence | production of the thermal stress which arises in each thermoelectric conversion element by the thermal expansion-contraction difference of each thermoelectric conversion element can be suppressed.
 本発明の熱電変換モジュールの好ましい実施態様として、前記第1セラミックス層が、前記熱電変換素子毎に独立して形成されているとよい。 As a preferred embodiment of the thermoelectric conversion module of the present invention, the first ceramic layer may be formed independently for each thermoelectric conversion element.
 この場合、第1配線基板を構成する複数の第1セラミックス層が複数配設される熱電変換素子毎に独立して形成されており、剛体の各第1セラミックス層が各熱電変換素子の間で分離されている。このため、各熱電変換素子は各第1セラミックス層によって熱伸縮に伴う変形が拘束されることがない。また、隣り合うP型熱電変換素子とN型熱電変換素子との熱伸縮差は、両熱電変換素子の間を接続する第1配線層の接続部分が変形して寸法変化を吸収することができる。したがって、熱伸縮差により各熱電変換素子内に生じる熱応力の発生を抑制できる。 In this case, the plurality of first ceramic layers constituting the first wiring board are formed independently for each thermoelectric conversion element provided, and each rigid first ceramic layer is interposed between the thermoelectric conversion elements. It is separated. For this reason, the deformation | transformation accompanying thermal expansion-contraction is not restrained by each 1st ceramic layer in each thermoelectric conversion element. Further, the difference in thermal expansion / contraction between the adjacent P-type thermoelectric conversion element and N-type thermoelectric conversion element can absorb the dimensional change due to the deformation of the connecting portion of the first wiring layer connecting the two thermoelectric conversion elements. . Therefore, generation | occurrence | production of the thermal stress which arises in each thermoelectric conversion element by a thermal expansion-contraction difference can be suppressed.
 本発明の熱電変換モジュールの好ましい実施態様として、前記第1配線層が、銀、アルミニウム、銅又はニッケルであるとよい。銀、アルミニウム、銅又はニッケルには、これらを主成分とする合金を含む。好ましくは、前記第1配線層は、純度99.99質量%以上のアルミニウム、あるいは純度99.9質量%以上の銅であるとよい。 As a preferred embodiment of the thermoelectric conversion module of the present invention, the first wiring layer may be silver, aluminum, copper or nickel. Silver, aluminum, copper, or nickel includes an alloy mainly composed of these. Preferably, the first wiring layer is made of aluminum having a purity of 99.99% by mass or more, or copper having a purity of 99.9% by mass or more.
 高純度のアルミニウム(Al)や銅(Cu)は、弾性変形、塑性変形しやすい。また、アルミニウムや銅は熱伝導性や導電性に優れる。このため、第1配線層に純度の高い純アルミニウムや純銅等の軟らかい材料を用いることで、第1配線層を各熱電変換素子の熱伸縮に伴って容易に変形し追従させることができる。したがって、各熱電変換素子の熱伸縮差による熱応力の緩和効果をより高めることができる。また、アルミニウムや銅は、銀とと比較して安価であるから、熱電変換モジュールを安価に製造できる。また、第1配線層をアルミニウム又は銅により形成することで、第1配線層により接続される両熱電変換素子間の熱伝導性や導電性を良好に維持できる。 High purity aluminum (Al) and copper (Cu) are easily elastically and plastically deformed. Aluminum and copper are excellent in thermal conductivity and conductivity. For this reason, by using a soft material such as high purity pure aluminum or pure copper for the first wiring layer, it is possible to easily deform and follow the first wiring layer with the thermal expansion and contraction of each thermoelectric conversion element. Therefore, the thermal stress relaxation effect due to the thermal expansion / contraction difference of each thermoelectric conversion element can be further enhanced. Moreover, since aluminum and copper are cheaper than silver, a thermoelectric conversion module can be manufactured at low cost. In addition, by forming the first wiring layer from aluminum or copper, the thermal conductivity and conductivity between both thermoelectric conversion elements connected by the first wiring layer can be favorably maintained.
 第1配線層を銀(Ag)で形成することで、例えば、第1配線層を有する第1配線基板を熱電変換モジュールの高温側に配置した場合において、耐熱性や耐酸化性を向上させることができたり、熱伝導性や導電性を良好に維持できたりする。 By forming the first wiring layer from silver (Ag), for example, when the first wiring substrate having the first wiring layer is disposed on the high temperature side of the thermoelectric conversion module, the heat resistance and oxidation resistance are improved. Or maintain good thermal conductivity and conductivity.
 ニッケル(Ni)は、アルミニウムや銀と比較すると耐酸化性に劣るが、比較的良好な耐熱性を有する。また、ニッケルは銀と比較して安価であるとともに、比較的素子接合性が良い。このため、第1配線層をニッケルで形成することで、性能と価格のバランスに優れた熱電変換モジュールを構成できる。 Nickel (Ni) is inferior in oxidation resistance compared to aluminum and silver, but has relatively good heat resistance. Nickel is cheaper than silver and has relatively good element bonding. For this reason, the thermoelectric conversion module excellent in the balance of performance and price can be comprised by forming a 1st wiring layer with nickel.
 本発明の熱電変換モジュールの好ましい実施態様として、前記第1配線基板は、複数の前記第1配線層と、前記第1セラミックス層の前記第1配線層との接合面とは反対面に接合された第1熱伝達金属層と、を有しており、前記第1熱伝達金属層が、隣り合う両第1配線層の間に跨って形成され、かつ、隣り合う両第1セラミックス層の間に跨って形成されているとよい。 As a preferred embodiment of the thermoelectric conversion module of the present invention, the first wiring board is bonded to a surface opposite to a bonding surface of the plurality of first wiring layers and the first wiring layer of the first ceramic layer. A first heat transfer metal layer, and the first heat transfer metal layer is formed between the two adjacent first wiring layers and between the two adjacent first ceramic layers. It is good to be formed straddling.
 複数の第1配線層を有する第1配線基板においても、第1熱伝達金属層により各第1セラミックス層の間が接続されているので、各第1配線層を一体に取り扱うことができ、第1配線基板の取り扱い性を向上できる。また、各第1セラミックス層の間は、第1配線層又は第1熱伝達金属層のいずれかにより連結されているのみであるので、第1配線層と第1熱伝達金属層とは各熱電変換素子の熱伸縮に伴って容易に変形し追従する。このため、各熱電変換素子の熱伸縮差により各熱電変換素子内に生じる熱応力の発生を抑制でき、各熱電変換素子が第1配線基板(第1配線層)から剥がれたり、各熱電変換素子にクラックが生じたりすることを防止できる。 Also in the first wiring board having a plurality of first wiring layers, the first ceramic layers are connected by the first heat transfer metal layer, so that the first wiring layers can be handled integrally. The handling property of one wiring board can be improved. Moreover, since each 1st ceramic layer is only connected by either the 1st wiring layer or the 1st heat transfer metal layer, the 1st wiring layer and the 1st heat transfer metal layer are each thermoelectrical. It easily deforms and follows with the thermal expansion and contraction of the conversion element. For this reason, generation | occurrence | production of the thermal stress which arises in each thermoelectric conversion element by the thermal expansion-contraction difference of each thermoelectric conversion element can be suppressed, and each thermoelectric conversion element peels from a 1st wiring board (1st wiring layer), or each thermoelectric conversion element It is possible to prevent cracks from occurring.
 また、第1配線基板に第1熱伝達金属層を設けることで、熱電変換モジュールを熱源等に設置したときに、第1熱伝達金属層により熱源等と熱電変換モジュールとの密着性を高めることができ、熱伝導性を向上できる。したがって、熱電変換モジュールの熱電変換性能(発電効率)を向上させることができる。 Further, by providing the first heat transfer metal layer on the first wiring board, when the thermoelectric conversion module is installed on a heat source or the like, the first heat transfer metal layer increases the adhesion between the heat source or the like and the thermoelectric conversion module. Can improve thermal conductivity. Therefore, the thermoelectric conversion performance (power generation efficiency) of the thermoelectric conversion module can be improved.
 本発明の熱電変換モジュールの好ましい実施態様として、前記第1熱伝達金属層は、アルミニウム又は銅とされ、好ましくは、純度99.99質量%以上のアルミニウム、あるいは純度99.9質量%以上の銅とされるとよい。 As a preferred embodiment of the thermoelectric conversion module of the present invention, the first heat transfer metal layer is made of aluminum or copper, preferably aluminum having a purity of 99.99% by mass or more, or copper having a purity of 99.9% by mass or more. It is good to be taken.
 第1熱伝達金属層にも、第1配線層と同様に純度の高い純アルミニウムや純銅等の軟らかい材料を用いることで、第1熱伝達金属層を各熱電変換素子の熱伸縮に伴って容易に変形し追従させることができる。したがって、各熱電変換素子の熱伸縮差による熱応力の緩和効果をより高めることができる。また、第1熱伝達金属層をアルミニウム又は銅により形成することで、熱電変換モジュールと熱源等との間の熱伝導性を良好に維持でき、熱電変換性能も良好に維持できる。 As with the first wiring layer, the first heat transfer metal layer is made of a soft material such as pure aluminum having a high purity and pure copper, so that the first heat transfer metal layer can be easily moved along with the thermal expansion and contraction of each thermoelectric conversion element. Can be deformed and followed. Therefore, the thermal stress relaxation effect due to the thermal expansion / contraction difference of each thermoelectric conversion element can be further enhanced. In addition, by forming the first heat transfer metal layer from aluminum or copper, the thermal conductivity between the thermoelectric conversion module and the heat source can be maintained well, and the thermoelectric conversion performance can also be maintained well.
 本発明の熱電変換モジュールの好ましい実施態様として、前記熱電変換素子の他端側に配設された第2配線基板を有し、対向配置される前記第1配線基板と前記第2配線基板とを介して前記P型熱電変換素子と前記N型熱電変換素子とが電気的に直列に接続されているとよい。 As a preferred embodiment of the thermoelectric conversion module of the present invention, the thermoelectric conversion module includes a second wiring board disposed on the other end side of the thermoelectric conversion element, and the first wiring board and the second wiring board that are arranged to face each other. The P-type thermoelectric conversion element and the N-type thermoelectric conversion element may be electrically connected in series.
 対向配置される第1配線基板と第2配線基板のうち、少なくとも第1配線基板を構成する第1セラミックス層がいずれかのP型熱電変換素子とN型熱電変換素子との間で分離されている。このため、これらP型熱電変換素子とN型熱電変換素子との間では、互いに相手側に接合された第1セラミクス層によって熱伸縮に伴う変形が拘束されることがない。また、これらのP型熱電変換素子とN型熱電変換素子との熱伸縮差は、両熱電変換素子の間を接続する第1配線層や第1熱伝達金属層の接続部分が変形して寸法変化を吸収できる。このため、各熱電変換素子の熱伸縮差により各熱電変換素子内に生じる熱応力の発生を抑制できる。したがって、第1配線層により接続される両熱電変換素子間の電気的な接続を良好に維持でき、熱電変換モジュールの接合信頼性、熱伝導性及び導電性を良好に維持できる。 Of the first wiring substrate and the second wiring substrate arranged to face each other, at least a first ceramic layer constituting the first wiring substrate is separated between any P-type thermoelectric conversion element and N-type thermoelectric conversion element. Yes. For this reason, between these P-type thermoelectric conversion elements and N-type thermoelectric conversion elements, the deformation | transformation accompanying a thermal expansion / contraction is not restrained by the 1st ceramic layer joined to the other party mutually. Further, the difference in thermal expansion and contraction between the P-type thermoelectric conversion element and the N-type thermoelectric conversion element is caused by deformation of the connection portion of the first wiring layer and the first heat transfer metal layer that connect the two thermoelectric conversion elements. Can absorb changes. For this reason, generation | occurrence | production of the thermal stress which arises in each thermoelectric conversion element by the thermal expansion-contraction difference of each thermoelectric conversion element can be suppressed. Therefore, the electrical connection between the two thermoelectric conversion elements connected by the first wiring layer can be maintained satisfactorily, and the joining reliability, thermal conductivity, and conductivity of the thermoelectric conversion module can be maintained satisfactorily.
 本発明の熱電変換モジュールの好ましい実施態様として、前記第2配線基板は、隣り合う前記P型熱電変換素子と前記N型熱電変換素子とが接合された第2配線層と、該第2配線層の前記P型熱電変換素子と前記N型熱電変換素子との接合面とは反対面に接合され複数に分離された第2セラミックス層と、を有しており、各第2セラミックス層がいずれかの前記P型熱電変換素子と前記N型熱電変換素子との間で分離されているとよい。 As a preferred embodiment of the thermoelectric conversion module of the present invention, the second wiring board includes a second wiring layer in which the adjacent P-type thermoelectric conversion element and the N-type thermoelectric conversion element are joined, and the second wiring layer. A second ceramic layer bonded to a surface opposite to a bonding surface between the P-type thermoelectric conversion element and the N-type thermoelectric conversion element, and each of the second ceramic layers is any of the second ceramic layers. The P-type thermoelectric conversion element and the N-type thermoelectric conversion element may be separated from each other.
 前記第2配線層が、前記第2セラミックス層どうしの間に跨って形成されているとよい。前記第2セラミックス層が、前記熱電変換素子毎に独立して形成されているとよい。前記第2配線層が、銀、アルミニウム、銅又はニッケルであるとよい。 The second wiring layer may be formed so as to straddle between the second ceramic layers. The second ceramic layer may be formed independently for each thermoelectric conversion element. The second wiring layer may be silver, aluminum, copper or nickel.
 前記第2配線基板は、複数の前記第2配線層と、前記第2セラミックス層の前記第2配線層との接合面とは反対面に接合された第2熱伝達金属層と、を有しており、前記第2熱伝達金属層が、隣り合う両第2配線層の間に跨って形成され、かつ、隣り合う両第2セラミックス層の間に跨って形成されているとよい。前記第2熱伝達金属層が、アルミニウム又は銅であるとよい。 The second wiring board includes a plurality of the second wiring layers and a second heat transfer metal layer bonded to a surface opposite to a bonding surface of the second ceramic layer to the second wiring layer. The second heat transfer metal layer may be formed between both adjacent second wiring layers and between both adjacent second ceramic layers. The second heat transfer metal layer may be aluminum or copper.
 第1配線基板と対向配置される第2配線基板においても、隣り合うP型熱電変換素子とN型熱電変換素子とが接合された第2配線層を複数に分離された第2セラミックス層どうしの間に跨って形成し、各第2セラミックス層をP型熱電変換素子とN型熱電変換素子との間で分離させておくことで、第2配線層に接合されたP型熱電変換素子とN型熱電変換素子との間では、互いに相手側の第2セラミックス層によって熱伸縮に伴う変形が拘束されることがない。また、隣り合うP型熱電変換素子とN型熱電変換素子との熱伸縮差は、両熱電変換素子の間を接続する第2配線層の接続部分が変形して寸法変化を吸収できるので、各熱電変換素子の熱伸縮差により各熱電変換素子内に生じる熱応力の発生を抑制できる。 Also in the second wiring board disposed opposite to the first wiring board, the second wiring layer in which the adjacent P-type thermoelectric conversion elements and N-type thermoelectric conversion elements are joined is divided into a plurality of separated second ceramic layers. The P-type thermoelectric conversion element bonded to the second wiring layer and the N-type are formed by separating each second ceramic layer between the P-type thermoelectric conversion element and the N-type thermoelectric conversion element. Between the thermoelectric conversion elements, deformation due to thermal expansion and contraction is not constrained by the other second ceramic layer. In addition, since the thermal expansion / contraction difference between the adjacent P-type thermoelectric conversion element and N-type thermoelectric conversion element can absorb the dimensional change due to the deformation of the connecting portion of the second wiring layer connecting the two thermoelectric conversion elements, Generation | occurrence | production of the thermal stress which arises in each thermoelectric conversion element by the thermal expansion-contraction difference of a thermoelectric conversion element can be suppressed.
 このように、対向配置される第1配線基板と第2配線基板との双方において、各熱電変換素子に熱伸縮差により生じる寸法変化を吸収できるので、第1配線層及び第2配線層により接続される両熱電変換素子間の電気的な接続を良好に維持でき、熱電変換モジュールの接合信頼性、熱伝導性及び導電性を良好に維持できる。 As described above, the dimensional change caused by the thermal expansion / contraction difference can be absorbed in each thermoelectric conversion element in both the first wiring board and the second wiring board which are arranged to face each other, so that the first wiring layer and the second wiring layer are connected. Thus, the electrical connection between the two thermoelectric conversion elements can be maintained well, and the joining reliability, thermal conductivity and conductivity of the thermoelectric conversion module can be maintained well.
 本発明の熱電変換モジュールの製造方法は、セラミックス母材から複数の第1セラミックス層を分割するためのスクライブラインを該セラミックス母材に形成するスクライブライン形成工程と、前記スクライブライン形成工程後に、前記セラミックス母材の一方の面に、前記スクライブラインにより区画された複数の第1セラミックス層形成領域のうちの隣接する両第1セラミックス層形成領域に跨る第1配線層を形成する金属層形成工程と、前記金属層形成工程後に、前記第1配線層が形成された前記セラミックス母材を前記スクライブラインに沿って分割し、前記第1配線層と前記第1セラミックス層とが接合された第1配線基板を形成する分割工程と、前記分割工程後に、前記第1配線層の各第1セラミックス層との接合面とは反対面に線膨張係数の異なるP型熱電変換素子とN型熱電変換素子とを接合し、前記P型熱電変換素子と前記N型熱電変換素子とが直列に接続された熱電変換モジュールを製造する接合工程と、を有する。 The method for manufacturing a thermoelectric conversion module of the present invention includes a scribe line forming step for forming a scribe line for dividing a plurality of first ceramic layers from a ceramic base material on the ceramic base material, and after the scribe line forming step, A metal layer forming step of forming, on one surface of the ceramic base material, a first wiring layer straddling both adjacent first ceramic layer forming regions among the plurality of first ceramic layer forming regions partitioned by the scribe line; After the metal layer forming step, the ceramic base material on which the first wiring layer is formed is divided along the scribe line, and the first wiring layer and the first ceramic layer are joined together. The dividing step of forming the substrate and the bonding surface of each of the first wiring layers to the first ceramic layers after the dividing step are opposite to each other Joining a P-type thermoelectric conversion element and an N-type thermoelectric conversion element having different linear expansion coefficients to each other, and manufacturing a thermoelectric conversion module in which the P-type thermoelectric conversion element and the N-type thermoelectric conversion element are connected in series And having.
 熱電変換素子が多数接合(搭載)される熱電変換モジュールにおいて、各々の第1セラミックス層を整列させて第1配線層に接合することは非常に困難である。しかし、本発明の製造方法のように、第1配線層をセラミックス母材に接合した後に、セラミックス母材をスクライブラインに沿って分割することで、容易に所望のパターンに配列された第1配線層と、個片化された第1セラミックス層とを有する第1配線基板を形成でき、熱電変換モジュールを円滑に製造できる。また、個片化された複数のセラミックス層の間は、第1配線層により接続されているので、第1配線基板を一体に取り扱うことができ、取り扱い性を向上できる。 In a thermoelectric conversion module in which a large number of thermoelectric conversion elements are joined (mounted), it is very difficult to align and join the first ceramic layers to the first wiring layer. However, as in the manufacturing method of the present invention, after the first wiring layer is joined to the ceramic base material, the ceramic base material is divided along the scribe lines, so that the first wiring easily arranged in a desired pattern The 1st wiring board which has a layer and the separated 1st ceramic layer can be formed, and a thermoelectric conversion module can be manufactured smoothly. In addition, since the plurality of separated ceramic layers are connected by the first wiring layer, the first wiring board can be handled integrally, and the handleability can be improved.
 本発明の熱電変換モジュールの製造方法の好ましい実施態様として、前記接合工程は、対向配置される一組の加圧板の間に、前記第1配線基板の前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子とをそれぞれ重ねた挟持体を配置しておき、該挟持体をその積層方向に加圧した状態で加熱することにより、前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子とをそれぞれ接合する工程とされ、前記接合工程において、前記P型熱電変換素子と前記N型熱電変換素子とのうち少なくとも線膨張係数が小さい一方の熱電変換素子と前記加圧板との間に補完部材を配置しておき、前記第1配線基板と前記P型熱電変換素子及び前記N型熱電変換素子との接合時における前記一方の熱電変換素子及び前記補完部材の高さと前記他方の熱電変換素子及び前記補完部材の高さとの差を、前記一方の熱電変換素子の高さと前記他方の熱電変換素子の高さとの差よりも小さくしておくとよい。 As a preferred embodiment of the method for producing a thermoelectric conversion module of the present invention, the joining step is performed between the first wiring layer of the first wiring board and the P-type thermoelectric conversion element between a pair of pressure plates arranged to face each other. And the N-type thermoelectric conversion element are disposed in advance, and the first wiring layer and the P-type thermoelectric conversion element are heated by heating the sandwiched body while being pressed in the stacking direction. And the N-type thermoelectric conversion element, and in the bonding process, at least one of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element has a small linear expansion coefficient, and the A complementary member is disposed between the pressure plate and the first thermoelectric conversion element and the complementary member at the time of joining the first wiring board, the P-type thermoelectric conversion element, and the N-type thermoelectric conversion element. And the difference between the height of the other thermoelectric conversion element and the complementary member, may want to be smaller than the difference between the height of the height and the other thermoelectric conversion element of the one thermoelectric conversion element.
 第1配線基板は、個片化された複数の第1セラミックス層を有しているので、接合工程において挟持体が加熱された際、各第1セラミックス層が互いを相手側を拘束することなく、各部位に積層されたP型熱電変換素子とN型熱電変換素子の熱膨張に追従できる。そこで、接合工程において、P型熱電変換素子とN型熱電変換素子とのうち、少なくとも線膨張係数が小さい一方の熱電変換素子と加圧板との間に補完部材を配置しておくことで、接合時において、線膨張係数が大きい他方の熱電変換素子の高さと、一方の熱電変換素子及び補完部材の高さとを近づけることができる。このため、一組の加圧板の間で、各熱電変換素子と第1配線層とを密着させて均一に加圧できる。したがって、各熱電変換素子と第1配線基板とを確実に接合でき、熱電変換モジュールの接合信頼性を高めることができる。 Since the first wiring board has a plurality of separated first ceramic layers, when the sandwich body is heated in the joining step, the first ceramic layers do not restrain each other on the other side. The thermal expansion of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element stacked at each part can be followed. Therefore, in the joining process, a complementary member is disposed between one of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element and at least one of the thermoelectric conversion elements having a small linear expansion coefficient and the pressure plate. In some cases, the height of the other thermoelectric conversion element having a large linear expansion coefficient can be made closer to the height of the one thermoelectric conversion element and the complementary member. For this reason, between each set of pressurization plates, each thermoelectric conversion element and the 1st wiring layer can be stuck, and it can press uniformly. Therefore, each thermoelectric conversion element and the first wiring board can be reliably bonded, and the bonding reliability of the thermoelectric conversion module can be improved.
 本発明の熱電変換モジュールの製造方法の好ましい実施態様として、前記接合工程は、対向配置される一組の加圧板の間に、前記第1配線基板の前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子とをそれぞれ重ねた挟持体を配置しておき、該挟持体をその積層方向に加圧した状態で加熱することにより、前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子とをそれぞれ接合する工程とされ、前記接合工程において、前記挟持体を前記積層方向に偶数個重ねて配置するとともに、前記P型熱電変換素子と前記N型熱電変換素子とを前記積層方向に同数配置しておくとよい。 As a preferred embodiment of the method for producing a thermoelectric conversion module of the present invention, the joining step is performed between the first wiring layer of the first wiring board and the P-type thermoelectric conversion element between a pair of pressure plates arranged to face each other. And the N-type thermoelectric conversion element are disposed in advance, and the first wiring layer and the P-type thermoelectric conversion element are heated by heating the sandwiched body while being pressed in the stacking direction. And the N-type thermoelectric conversion element, and in the bonding step, an even number of the sandwiching bodies are arranged in the stacking direction, and the P-type thermoelectric conversion element and the N-type thermoelectric conversion element are arranged. And the same number in the stacking direction.
 例えば、各挟持体のうち、積層方向に隣接する2個の挟持体の各第1配線基板どうしを対向させて配置することで、第1配線基板の面方向の各熱電変換素子の配置箇所において、それぞれP型熱電変換素子とN型熱電変換素子とを積層方向に1個ずつ(同数)配置できる。このようにして挟持体を積層方向に偶数個重ねて配置することで、P型熱電変換素子とN型熱電変換素子のうち、線膨張係数が小さい一方の熱電変換素子と、線膨張係数が大きい他方の熱電変換素子とを常に同数重ねて配置できる。これにより、接合(加熱)時において、複数個を重ねた挟持体の高さを、面方向において均一にできる。このため、一組の加圧板の間で、各熱電変換素子と第1配線層とを密着させて均一に加圧できる。したがって、各熱電変換素子と第1配線基板とを確実に接合でき、熱電変換モジュールの接合信頼性を高めることができる。また、このように挟持体を複数重ねることで、一度の接合工程において、熱電変換モジュールを複数製造できる。 For example, among the sandwiching bodies, by arranging the first wiring boards of the two sandwiching bodies adjacent to each other in the stacking direction so as to face each other, at the location where each thermoelectric conversion element is arranged in the surface direction of the first wiring board The P-type thermoelectric conversion elements and the N-type thermoelectric conversion elements can be arranged one by one (the same number) in the stacking direction. By arranging an even number of sandwiched bodies in the stacking direction in this way, one of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element has a small linear expansion coefficient and a large linear expansion coefficient. The same number of the other thermoelectric conversion elements can always be arranged. Thereby, at the time of joining (heating), the height of the plurality of sandwiched bodies can be made uniform in the surface direction. For this reason, between each set of pressurization plates, each thermoelectric conversion element and the 1st wiring layer can be stuck, and it can press uniformly. Therefore, each thermoelectric conversion element and the first wiring board can be reliably bonded, and the bonding reliability of the thermoelectric conversion module can be improved. Moreover, a plurality of thermoelectric conversion modules can be manufactured in a single joining step by stacking a plurality of sandwiching bodies in this way.
 本発明の熱電変換モジュールの製造方法の好ましい実施形態として、前記接合工程において、各挟持体の間にグラファイトシートを配設しておくとよい。 As a preferred embodiment of the method for manufacturing a thermoelectric conversion module of the present invention, a graphite sheet may be disposed between the sandwiching bodies in the joining step.
 各挟持体の間にクッション性を有するグラファイトシートを介在させることで、第1配線基板の面方向の各熱電変換素子の配置箇所において、それぞれの傾きを補正でき、各熱電変換素子と第1配線基板とをより均一に加圧できる。したがって、各熱電変換素子と第1配線基板とを確実に接合でき、熱電変換モジュールの接合信頼性をより高めることができる。 By interposing a graphite sheet having cushioning properties between the sandwiching bodies, the inclination of each thermoelectric conversion element in the surface direction of the first wiring board can be corrected, and each thermoelectric conversion element and the first wiring can be corrected. The substrate can be pressed more uniformly. Therefore, each thermoelectric conversion element and the first wiring board can be reliably bonded, and the bonding reliability of the thermoelectric conversion module can be further increased.
 本発明の熱電変換モジュールの製造方法の好ましい実施態様として、前記金属層形成工程は、前記セラミックス母材の前記一方の面に複数の前記第1配線層を形成するとともに、前記セラミックス母材の他方の面に第1熱伝達金属層を形成する工程とされ、前記金属層形成工程において、前記第1熱伝達金属層を、隣り合う両第1配線層の間に跨って形成し、かつ、隣り合う両第1セラミックス層形成領域の間に跨って形成する。 As a preferred embodiment of the method for manufacturing a thermoelectric conversion module of the present invention, the metal layer forming step includes forming the plurality of first wiring layers on the one surface of the ceramic base material and the other of the ceramic base materials. Forming a first heat transfer metal layer on the surface of the first heat transfer metal layer, and forming the first heat transfer metal layer straddling between both adjacent first wiring layers in the metal layer forming step; It is formed straddling between the matching first ceramic layer forming regions.
 複数の第1配線層を有する第1配線基板においても、第1熱伝達金属層により各第1配線層の間が連結されている。このため、各第1配線層を一体に取り扱うことができ、第1配線基板の取り扱い性を向上できる。また、第1配線層と第1熱伝達金属層とをセラミックス母材に接合した後に、セラミックス母材をスクライブラインに沿って分割することで、容易に所望のパターンに配列された第1配線層と、個片化された第1セラミックス層とを有する第1配線基板を形成できるので、熱電変換モジュールを円滑に製造できる。 Also in the first wiring board having a plurality of first wiring layers, the first wiring layers are connected by the first heat transfer metal layer. For this reason, each 1st wiring layer can be handled integrally, and the handleability of a 1st wiring board can be improved. In addition, after the first wiring layer and the first heat transfer metal layer are joined to the ceramic base material, the ceramic base material is divided along the scribe line so that the first wiring layer can be easily arranged in a desired pattern. And the 1st wiring board which has the separated 1st ceramic layer can be formed, and a thermoelectric conversion module can be manufactured smoothly.
 また、接合工程において、各挟持体の間にグラファイトシートを介在させることで、各熱電変換モジュールどうしが接合されることを防止でき、各熱電変換モジュールの間を容易に解体できる。したがって、熱電変換モジュールを安定して製造できる。 Also, in the joining step, by interposing the graphite sheet between the sandwiched bodies, it is possible to prevent the thermoelectric conversion modules from being joined to each other, and the thermoelectric conversion modules can be easily disassembled. Therefore, the thermoelectric conversion module can be manufactured stably.
 本発明の熱電変換モジュールの製造方法の好ましい実施態様として、前記スクライブライン形成工程において、前記スクライブラインは、前記セラミックス母材の一方の面における前記第1配線層の接合予定領域を除く非接合部に形成するとよい。また、スクライブラインは、前記セラミックス母材の他方の面における前記第1熱伝達金属層の接合予定領域を除く非接合部に形成するとよい。 As a preferred embodiment of the method for manufacturing a thermoelectric conversion module of the present invention, in the scribe line forming step, the scribe line is a non-joined portion excluding a planned joining region of the first wiring layer on one surface of the ceramic base material. It is good to form. In addition, the scribe line may be formed in a non-joining portion excluding a planned joining region of the first heat transfer metal layer on the other surface of the ceramic base material.
 スクライブラインは、第1配線層の非接合部又は第1熱伝達金属層の非接合部、若しくはこれらの非接合部の双方に形成しておくことで、これらのセラミックス母材の両面に複数形成されたスクライブラインにより、第1セラミックス層形成領域を区画できる。スクライブライン上に第1配線層又は第1熱伝達金属層を重ねて接合した場合には、セラミックス母材をスクライブラインに沿って分割することが難しい。しかし、スクライブラインを第1配線層又は第1熱伝達金属層の接合面とは反対側の面(反対面)に形成することで、セラミックス母材をスクライブラインに沿って容易に分割できる。したがって、容易に所望のパターンに配列された第1配線層と、個片化された第1セラミックス層とを有する第1配線基板を形成でき、熱電変換モジュールを円滑に製造できる。 A plurality of scribe lines are formed on both surfaces of the ceramic base material by forming the scribe lines on the non-bonded portion of the first wiring layer, the non-bonded portion of the first heat transfer metal layer, or both of these non-bonded portions. The first ceramic layer forming region can be partitioned by the scribe line thus formed. When the first wiring layer or the first heat transfer metal layer is overlapped and joined on the scribe line, it is difficult to divide the ceramic base material along the scribe line. However, the ceramic base material can be easily divided along the scribe line by forming the scribe line on the surface (opposite surface) opposite to the bonding surface of the first wiring layer or the first heat transfer metal layer. Accordingly, the first wiring board having the first wiring layers arranged in a desired pattern and the separated first ceramic layers can be formed easily, and the thermoelectric conversion module can be manufactured smoothly.
 スクライブラインは、第1配線層の非接合部及び第1熱伝達金属層の非接合部に形成するだけでなく、第1配線層の接合部及び第1熱伝達金属層の接合部にも形成しておくとよい。第1配線層の接合部及び第1熱伝達金属層の接合部にもスクライブラインを形成しておくことにより、さらにセラミックス母材を容易に分割できる。 The scribe line is formed not only at the non-joint portion of the first wiring layer and the non-joint portion of the first heat transfer metal layer, but also at the joint portion of the first wiring layer and the joint portion of the first heat transfer metal layer. It is good to keep. By forming scribe lines at the junction of the first wiring layer and the junction of the first heat transfer metal layer, the ceramic base material can be further easily divided.
 本発明の熱電変換モジュールの製造方法の好ましい実施態様として、前記スクライブライン形成工程において、前記スクライブラインは、前記セラミックス母材の対向する辺同士を貫通する直線で形成するとよい。 As a preferred embodiment of the method for producing a thermoelectric conversion module of the present invention, in the scribe line forming step, the scribe line may be formed by a straight line penetrating opposite sides of the ceramic base material.
 セラミックス母材の対向する辺同士を貫通する単純なスクライブラインとすることで、セラミックス母材をスクライブラインに沿って円滑に分割できる。したがって、製造工程を簡略化できる。 By using a simple scribe line that penetrates the opposing sides of the ceramic base material, the ceramic base material can be smoothly divided along the scribe line. Therefore, the manufacturing process can be simplified.
 本発明によれば、熱電変換素子の熱伸縮差による破壊を防止でき、接合信頼性、熱伝導性及び導電性に優れた熱電変換モジュールを提供できる。 According to the present invention, the thermoelectric conversion element can be prevented from being damaged due to the difference in thermal expansion and contraction, and a thermoelectric conversion module having excellent bonding reliability, thermal conductivity, and conductivity can be provided.
第1実施形態の熱電変換モジュールを示す縦断面図である。It is a longitudinal cross-sectional view which shows the thermoelectric conversion module of 1st Embodiment. 第1実施形態の熱電変換モジュールの製造方法のフロー図である。It is a flowchart of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. 第1実施形態の熱電変換モジュールの製造方法のスクライブライン形成工程を説明する縦断面図である。It is a longitudinal cross-sectional view explaining the scribe line formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. 第1実施形態の熱電変換モジュールの製造方法の金属層形成工程を説明する縦断面図であり、工程の前半部分を示す。It is a longitudinal cross-sectional view explaining the metal layer formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment, and shows the first half part of a process. 第1実施形態の熱電変換モジュールの製造方法の金属層形成工程を説明する縦断面図であり、工程の後半部分を示す。It is a longitudinal cross-sectional view explaining the metal layer formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment, and shows the second half part of a process. 第1実施形態の熱電変換モジュールの製造方法の分割工程を説明する縦断面図である。It is a longitudinal cross-sectional view explaining the division | segmentation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. 第1実施形態の熱電変換モジュールの製造方法のスクライブライン形成工程を説明する斜視図である。It is a perspective view explaining the scribe line formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. 第1実施形態の熱電変換モジュールの製造方法の金属層形成工程を説明する縦断面図であり、工程の前半部分を示す。It is a longitudinal cross-sectional view explaining the metal layer formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment, and shows the first half part of a process. 第1実施形態の熱電変換モジュールの製造方法の金属層形成工程を説明する縦断面図であり、工程の後半部分を示す。It is a longitudinal cross-sectional view explaining the metal layer formation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment, and shows the second half part of a process. 第1実施形態の熱電変換モジュールの製造方法の分割工程を説明する縦断面図である。It is a longitudinal cross-sectional view explaining the division | segmentation process of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. 第1実施形態の熱電変換モジュールの接合工程を説明する縦断面図である。It is a longitudinal cross-sectional view explaining the joining process of the thermoelectric conversion module of 1st Embodiment. 他の実施態様の接合工程を説明する縦断面図である。It is a longitudinal cross-sectional view explaining the joining process of another embodiment. 他の実施態様の接合工程を説明する縦断面図である。It is a longitudinal cross-sectional view explaining the joining process of another embodiment. 第2実施形態の熱電変換モジュールを示す正面図である。It is a front view which shows the thermoelectric conversion module of 2nd Embodiment. 第3実施形態の熱電変換モジュールを示す正面図である。It is a front view which shows the thermoelectric conversion module of 3rd Embodiment. 図9のA‐A線の矢視方向の平断面図である。FIG. 10 is a cross-sectional plan view taken along the line AA in FIG. 9. 図9のB‐B線の矢視方向の平断面図である。FIG. 10 is a cross-sectional plan view taken along the line BB in FIG. 図9のC‐C線の矢視方向の平断面図である。FIG. 10 is a cross-sectional plan view taken along the line CC of FIG. 図9のD‐D線の矢視方向の平断面図である。FIG. 10 is a cross-sectional plan view in the direction of the arrows along the line DD in FIG. 9. スクライブライン形成工程において形成されるセラミックス母材の一方の面を表側に向けた平面図である。It is the top view which orient | assigned one surface of the ceramic base material formed in a scribe line formation process to the front side. スクライブライン形成工程において形成されるセラミックス母材の他方の面を表側に向けた平面図である。It is the top view which orient | assigned the other surface of the ceramic base material formed in a scribe line formation process to the front side. 金属層形成工程において配線層及び熱伝達金属層のパターンが形成されたセラミックス母材の一方の面を表側に向けた平面図である。It is the top view which turned one side of the ceramic base material in which the pattern of the wiring layer and the heat transfer metal layer was formed in the metal layer formation process toward the front side. 金属層形成工程において配線層及び熱伝達金属層のパターンが形成されたセラミックス母材の他方の面を表側に向けた平面図である。It is the top view which turned the other surface of the ceramic base material in which the pattern of the wiring layer and the heat transfer metal layer was formed in the metal layer formation process toward the front side. 第4実施形態の熱電変換モジュールの第1配線基板の一方の面を表側に向けた平面図である。It is the top view which orient | assigned one surface of the 1st wiring board of the thermoelectric conversion module of 4th Embodiment to the front side. 図16Aに示す第1配線基板の他方の面を表側に向けた平面図である。FIG. 16B is a plan view in which the other surface of the first wiring board shown in FIG. 16A faces the front side. 第5実施形態の熱電変換モジュールの第1配線基板の一方の面を表側に向けた平面図である。It is the top view which orient | assigned one surface of the 1st wiring board of the thermoelectric conversion module of 5th Embodiment to the front side. 図17Aに示す第1配線基板の他方の面を表側に向けた平面図である。FIG. 17B is a plan view in which the other surface of the first wiring board shown in FIG. 17A faces the front side. 第6実施形態の熱電変換モジュールの第1配線基板の一方の面を表側に向けた平面図である。It is the top view which orient | assigned one surface of the 1st wiring board of the thermoelectric conversion module of 6th Embodiment to the front side. 図18Aに示す第1配線基板の他方の面を表側に向けた平面図である。It is a top view which turned the other surface of the 1st wiring board shown to FIG. 18A to the front side. 第7実施形態の熱電変換モジュールの第1配線基板の一方の面を表側に向けた平面図である。It is the top view which turned one surface of the 1st wiring board of the thermoelectric conversion module of 7th Embodiment to the front side. 図19Aに示す第1配線基板の他方の面を表側に向けた平面図である。FIG. 19B is a plan view in which the other surface of the first wiring board shown in FIG. 19A faces the front side.
 以下、本発明の実施形態について、図面を参照しながら説明する。図1に、第1実施形態の熱電変換モジュール101を示す。この熱電変換モジュール101は、複数の熱電変換素子3,4が組み合わされて配列され、熱電変換素子3,4のP型熱電変換素子3とN型熱電変換素子4とがその一端側(図1において下側)に配設された第1配線基板2Aを介して電気的に直列に接続された構成とされる。図中、P型熱電変換素子3には「P」、N型熱電変換素子4には「N」と表記する。なお、熱電変換モジュール101では、外部への配線91を、各熱電変換素子3,4の他端部から直接引き出す構成としている。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. FIG. 1 shows a thermoelectric conversion module 101 according to the first embodiment. The thermoelectric conversion module 101 is a combination of a plurality of thermoelectric conversion elements 3 and 4, and the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 of the thermoelectric conversion elements 3 and 4 are on one end side (FIG. 1). The first wiring board 2A disposed on the lower side is electrically connected in series. In the figure, the P-type thermoelectric conversion element 3 is expressed as “P”, and the N-type thermoelectric conversion element 4 is expressed as “N”. The thermoelectric conversion module 101 has a configuration in which the external wiring 91 is directly drawn out from the other end of each thermoelectric conversion element 3, 4.
 P型熱電変換素子3及びN型熱電変換素子4は、例えばテルル化合物、スクッテルダイト、充填スクッテルダイト、ホイスラー、ハーフホイスラー、クラストレート、シリサイド、酸化物、シリコンゲルマニウム等の焼結体により構成される。なお、ドーパントによりP型とN型の両方をとれる化合物と、P型かN型のどちらか一方のみの性質をもつ化合物がある。 The P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are composed of, for example, a sintered body such as a tellurium compound, skutterudite, filled skutterudite, Heusler, half-Heusler, clastrate, silicide, oxide, or silicon germanium. Is done. There are compounds that can take both P-type and N-type depending on the dopant, and compounds that have either P-type or N-type properties.
 P型熱電変換素子3の材料として、BiTe、SbTe、PbTe、TAGS(=Ag‐Sb‐Ge‐Te)、ZnSb、CoSb、CeFeSb12、Yb14MnSb11、FeVAl、MnSi1.73、FeSi、NaCoO、CaCo、BiSrCo、SiGeなどが用いられる。 As materials for the P-type thermoelectric conversion element 3, Bi 2 Te 3 , Sb 2 Te 3 , PbTe, TAGS (= Ag—Sb—Ge—Te), Zn 4 Sb 3 , CoSb 3 , CeFe 4 Sb 12 , Yb 14 MnSb 11, feVAl, MnSi 1.73, FeSi 2, such as Na x CoO 2, Ca 3 Co 4 O 7, Bi 2 Sr 2 Co 2 O 7, SiGe is used.
 N型熱電変換素子4の材料として、BiTe、PbTe、LaTe、CoSb、FeVAl、ZrNiSn、BaAl16Si30、MgSi、FeSi、SrTiO、CaMnO、ZnO、SiGeなどが用いられる。 As the material of N-type thermoelectric conversion element 4, Bi 2 Te 3, PbTe , La 3 Te 4, CoSb 3, FeVAl, ZrNiSn, Ba 8 Al 16 Si 30, Mg 2 Si, FeSi 2, SrTiO 3, CaMnO 3, ZnO SiGe or the like is used.
 これらの材料のうち、環境への影響が少なく、資源埋蔵量も豊富なシリサイド系材料が注目されている。中温型(300℃~500℃程度)の熱電変換モジュールの熱電変換材料としては、P型熱電変換素子3にマンガンシリサイド(MnSi1.73)、N型熱電変換素子4にマグネシウムシリサイド(MgSi)が用いられる。P型熱電変換素子3に用いられるマンガンシリサイドの線膨張係数は10.8×10-6/K程度であり、N型熱電変換素子4に用いられるマグネシウムシリサイドの線膨張係数は17.0×10-6/K程度である。このため、マンガンシリサイドのP型熱電変換素子3とマグネシウムシリサイドのN型熱電変換素子4との組み合わせでは、P型熱電変換素子3の線膨張係数はN型熱電変換素子4の線膨張係数よりも小さくなる。 Among these materials, silicide-based materials that have little impact on the environment and have abundant resource reserves are attracting attention. As the thermoelectric conversion material of the intermediate temperature type (about 300 ° C. to 500 ° C.) thermoelectric conversion module, manganese silicide (MnSi 1.73 ) is used for the P-type thermoelectric conversion element 3, and magnesium silicide (Mg 2 Si) is used for the N-type thermoelectric conversion element 4. ) Is used. The linear expansion coefficient of manganese silicide used in the P-type thermoelectric conversion element 3 is about 10.8 × 10 −6 / K, and the linear expansion coefficient of magnesium silicide used in the N-type thermoelectric conversion element 4 is 17.0 × 10. It is about -6 / K. For this reason, in the combination of the P-type thermoelectric conversion element 3 of manganese silicide and the N-type thermoelectric conversion element 4 of magnesium silicide, the linear expansion coefficient of the P-type thermoelectric conversion element 3 is larger than the linear expansion coefficient of the N-type thermoelectric conversion element 4. Get smaller.
 これらの熱電変換素子3,4は、例えば横断面が正方形(例えば、一辺が1mm~8mm)の角柱状や、横断面が円形(例えば、直径が1mm~8mm)の円柱状に形成され、長さ(図1の上下方向に沿う長さ)は1mm~10mmとされる。P型熱電変換素子3の長さとN型熱電変換素子4の長さは、常温(25℃)において、同等(ほぼ同じ長さ)に設定される。なお、各熱電変換素子3,4の両端面にはニッケル、銀、金等からなるメタライズ層41が形成される。メタライズ層41の厚さは1μm以上100μm以下とされる。 These thermoelectric conversion elements 3 and 4 are formed in, for example, a prismatic shape having a square cross section (for example, 1 mm to 8 mm on one side) or a circular column having a circular cross section (for example, a diameter of 1 mm to 8 mm). The length (the length along the vertical direction in FIG. 1) is 1 mm to 10 mm. The length of the P-type thermoelectric conversion element 3 and the length of the N-type thermoelectric conversion element 4 are set to be equal (substantially the same length) at room temperature (25 ° C.). A metallized layer 41 made of nickel, silver, gold or the like is formed on both end faces of each thermoelectric conversion element 3, 4. The thickness of the metallized layer 41 is 1 μm or more and 100 μm or less.
 第1配線基板2Aは、図1に示されるように、熱電変換素子3,4が接合される第1配線層11Aと、第1配線層11Aの熱電変換素子3,4との接合面とは反対面に接合された第1セラミックス層21Aと、第1セラミックス層21Aの配線層11Aとの接合面とは反対面に接合された第1熱伝達金属層32Aと、を有する構成とされる。なお、熱伝達金属層32Aは、必須の構成要素ではない。 As shown in FIG. 1, the first wiring board 2 </ b> A includes a first wiring layer 11 </ b> A to which the thermoelectric conversion elements 3 and 4 are bonded and a bonding surface of the first wiring layer 11 </ b> A to the thermoelectric conversion elements 3 and 4. The first ceramic layer 21A is bonded to the opposite surface, and the first heat transfer metal layer 32A is bonded to the opposite surface of the first ceramic layer 21A to the wiring layer 11A. The heat transfer metal layer 32A is not an essential component.
 第1セラミックス層21Aは、一般的なセラミックス、例えばアルミナ(Al)、窒化アルミニウム(AlN)、窒化ケイ素(Si)等の熱伝導性が高く、絶縁性を有する部材により形成される。また、第1セラミックス層21Aは複数(図1では2個)に分離され、熱電変換素子3,4毎に独立して形成される。第1セラミックス層21Aは、例えば平面視正方形状に形成される。また、第1セラミックス層21Aの厚さは、0.1mm以上2mm以下とされる。 The first ceramic layer 21A is formed of a general ceramic material such as alumina (Al 2 O 3 ), aluminum nitride (AlN), silicon nitride (Si 3 N 4 ), or the like having a high thermal conductivity and an insulating property. Is done. The first ceramic layer 21 </ b> A is divided into a plurality (two in FIG. 1) and is formed independently for each of the thermoelectric conversion elements 3 and 4. The first ceramic layer 21A is formed, for example, in a square shape in plan view. Further, the thickness of the first ceramic layer 21A is set to 0.1 mm or more and 2 mm or less.
 第1配線基板2Aには、平面視長方形状の第1配線層11Aが1個設けられるとともに、平面視正方形状の第1熱伝達金属層32Aが2個設けられている。第1配線層11Aは、隣り合うP型熱電変換素子3とN型熱電変換素子4との間を接続して形成され、かつ、2個の第1セラミックス層21A,21Aどうしの間に跨って形成されている。一方、第1熱伝達金属層32Aは、個々の第1セラミックス層21A毎に独立して形成されている。 The first wiring board 2A is provided with one first wiring layer 11A having a rectangular shape in plan view and two first heat transfer metal layers 32A having a square shape in plan view. The first wiring layer 11A is formed by connecting the adjacent P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4, and straddles between the two first ceramic layers 21A and 21A. Is formed. On the other hand, the first heat transfer metal layer 32A is formed independently for each first ceramic layer 21A.
 第1配線層11Aは、銀、アルミニウム、銅又はニッケルを主成分とする材料からなり、平面状に形成されている。第1配線層11Aの材料としては、純度99.99質量%以上のアルミニウム(いわゆる4Nアルミニウム)や純度99.9質量%以上の銅が好ましい。また、P型熱電変換素子3とN型熱電変換素子4とを接続する第1配線層11Aの厚さとしては、0.1mm以上2mm以下とすることが好ましい。 The first wiring layer 11A is made of a material mainly composed of silver, aluminum, copper, or nickel, and is formed in a planar shape. As the material of the first wiring layer 11A, aluminum having a purity of 99.99% by mass or more (so-called 4N aluminum) or copper having a purity of 99.9% by mass or more is preferable. The thickness of the first wiring layer 11A that connects the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 is preferably 0.1 mm or more and 2 mm or less.
 第1配線層11Aに、純度の高い純アルミニウムや純銅等の軟らかい材料を用いて、厚さを比較的薄く形成しておくことで、隣り合う両熱電変換素子3,4の間を連結して設けられる平面状の第1配線層11Aを両熱電変換素子3,4の熱伸縮に伴って容易に変形、追従させることができ、これら熱電変換素子3,4の間で容易に屈曲できる。なお、アルミニウム及び銅は銀と比較して安価であるから、第1配線層11Aをアルミニウム又は銅により成形することで、熱電変換モジュール101を安価に製造できる。また、第1配線層11Aをアルミニウム又は銅により形成することで、第1配線層11Aにより接続される両熱電変換素子3,4間の熱伝導性や導電性を良好に維持できる。 The first wiring layer 11A is made of a soft material such as high purity pure aluminum or pure copper, and is formed with a relatively thin thickness so that the two adjacent thermoelectric conversion elements 3 and 4 are connected. The planar first wiring layer 11 </ b> A provided can be easily deformed and followed by the thermal expansion and contraction of both thermoelectric conversion elements 3 and 4, and can be easily bent between these thermoelectric conversion elements 3 and 4. Since aluminum and copper are cheaper than silver, the thermoelectric conversion module 101 can be manufactured at low cost by forming the first wiring layer 11A with aluminum or copper. Further, by forming the first wiring layer 11A from aluminum or copper, the thermal conductivity and conductivity between the thermoelectric conversion elements 3 and 4 connected by the first wiring layer 11A can be favorably maintained.
 また、第1配線層11Aに銀を用いることで、熱電伝導性や導電性を良好に維持でき、厚さを比較的薄く形成した場合でも電気抵抗を低くできる。また、第1配線層11Aを含む第1配線基板2Aが熱電変換モジュール101の高温側に配置される場合等において、耐熱性や耐酸化性を向上させることができる。なお、第1配線層11Aを銀で形成する場合、第1配線層11Aの厚さは10μm以上200μm以下とすることが好ましい。 Further, by using silver for the first wiring layer 11A, the thermoelectric conductivity and the electrical conductivity can be maintained well, and the electric resistance can be lowered even when the thickness is relatively thin. In addition, when the first wiring board 2A including the first wiring layer 11A is disposed on the high temperature side of the thermoelectric conversion module 101, heat resistance and oxidation resistance can be improved. When the first wiring layer 11A is formed of silver, the thickness of the first wiring layer 11A is preferably 10 μm or more and 200 μm or less.
 また、ニッケルは、アルミニウムや銀と比較すると耐酸化性に劣るが、比較的良好な耐熱性を有する。また、ニッケルは銀と比較して安価であるとともに、比較的素子接合性が良い。このため、第1配線層11Aにニッケルを用いた場合、性能と価格のバランスに優れた熱電変換モジュール101を構成できる。また、第1配線層11Aを含む第1配線基板2Aが熱電変換モジュール101の高温側に配置される場合等において、耐熱性や耐酸化性を向上させることができる。なお、第1配線層11Aをニッケルで形成する場合、第1配線層11Aの厚さは0.1mm以上1mm以下とすることが好ましい。 Moreover, nickel is inferior in oxidation resistance as compared with aluminum and silver, but has relatively good heat resistance. Nickel is cheaper than silver and has relatively good element bonding. For this reason, when nickel is used for the first wiring layer 11A, the thermoelectric conversion module 101 having an excellent balance between performance and price can be configured. In addition, when the first wiring board 2A including the first wiring layer 11A is disposed on the high temperature side of the thermoelectric conversion module 101, heat resistance and oxidation resistance can be improved. When the first wiring layer 11A is made of nickel, the thickness of the first wiring layer 11A is preferably 0.1 mm or more and 1 mm or less.
 また、第1熱伝達金属層32Aは、アルミニウム又銅を主成分とする材料(アルミニウム、アルミニウム合金、銅又は銅合金)からなり、平面状に形成されている。この第1熱伝達金属層32Aの材料としては、純度99.99質量%以上のアルミニウム(いわゆる4Nアルミニウム)や純度99.9質量%以上の銅が好ましい。このように、第1熱伝達金属層32Aに、純度の高い純アルミニウムや純銅等の軟らかい材料を用いることで、第1熱伝達金属層32Aが熱源又は冷却源に接触する際に追従性が向上し、熱伝達性が向上する。したがって、熱電変換モジュール101の熱電交換性能を低下させることがない。 The first heat transfer metal layer 32A is made of a material mainly composed of aluminum or copper (aluminum, aluminum alloy, copper or copper alloy), and is formed in a planar shape. As a material for the first heat transfer metal layer 32A, aluminum having a purity of 99.99% by mass or more (so-called 4N aluminum) or copper having a purity of 99.9% by mass or more is preferable. Thus, by using a soft material such as high purity pure aluminum or pure copper for the first heat transfer metal layer 32A, the followability is improved when the first heat transfer metal layer 32A contacts the heat source or the cooling source. And heat transferability is improved. Therefore, the thermoelectric exchange performance of the thermoelectric conversion module 101 is not deteriorated.
 なお、第1配線層11Aや第1熱伝達金属層32Aの大きさ(平面サイズ)は、第1配線層11Aに接続される熱電変換素子3,4の大きさに応じて、熱電変換素子3,4の端面の面積よりも同等あるいは若干大きく設定されている。また、第1セラミックス層21Aは、第1配線層11A,各第1熱伝達金属層32A,32Aの周囲、及び各第1熱伝達金属層32A,32Aの間に幅0.1mm以上のスペースを確保できる程度の平面形状に形成されている。 Note that the size (planar size) of the first wiring layer 11A and the first heat transfer metal layer 32A depends on the size of the thermoelectric conversion elements 3 and 4 connected to the first wiring layer 11A. , 4 is set equal to or slightly larger than the area of the end face. Further, the first ceramic layer 21A has a space of 0.1 mm or more in width around the first wiring layer 11A, the first heat transfer metal layers 32A, 32A, and between the first heat transfer metal layers 32A, 32A. It is formed in a planar shape that can be secured.
 次に、このように構成された熱電変換モジュール101の製造方法について説明する。本実施形態の熱電変換モジュールの製造方法は、図2のフロー図に示されるように、複数の工程S11~S14により構成される。また、図3A~D及び図4A~Dには、本実施形態の熱電変換モジュールの製造方法の各工程の一例を図示している。 Next, a method for manufacturing the thermoelectric conversion module 101 configured as described above will be described. As shown in the flowchart of FIG. 2, the method for manufacturing the thermoelectric conversion module of the present embodiment includes a plurality of steps S11 to S14. 3A to 3D and 4A to 4D show an example of each process of the method for manufacturing the thermoelectric conversion module of the present embodiment.
(スクライブライン形成工程)
 まず、図3A及び図4Aに示すように、第1セラミックス層21A,21Aを構成する大型のセラミックス母材201に、複数の第1セラミックス層21A,21Aを分割するためのスクライブライン(分割溝)202を形成する(スクライブライン形成工程S11)。そして、スクライブライン202を形成することにより、セラミックス母材201に複数(2個)の第1セラミックス層形成領域203,203を区画する。
(Scribe line forming process)
First, as shown in FIGS. 3A and 4A, a scribe line (dividing groove) for dividing the plurality of first ceramic layers 21A, 21A into a large ceramic base material 201 constituting the first ceramic layers 21A, 21A. 202 is formed (scribe line forming step S11). Then, a plurality of (two) first ceramic layer forming regions 203 and 203 are defined in the ceramic base material 201 by forming the scribe line 202.
 スクライブライン202は、例えば図3Aに示すように、レーザ加工により形成できる。具体的には、セラミックス母材201の片面に、COレーザ、YAGレーザ、YVOレーザ、YLFレーザ等のレーザ光Lを照射することにより、スクライブライン202の加工を行うことができる。レーザ加工によるスクライブライン202の加工では、セラミックス母材201の表面においてレーザ光Lが照射された部分が切削加工され、スクライブライン202が形成される。 The scribe line 202 can be formed by laser processing, for example, as shown in FIG. 3A. Specifically, the scribe line 202 can be processed by irradiating a laser beam L such as a CO 2 laser, a YAG laser, a YVO 4 laser, and a YLF laser to one surface of the ceramic base material 201. In the processing of the scribe line 202 by laser processing, the portion irradiated with the laser beam L on the surface of the ceramic base material 201 is cut to form the scribe line 202.
 スクライブライン202は、図4Aに示すように、少なくともセラミックス母材201の片面に形成する。具体的には、2個の第1セラミックス層21A,21Aに跨って形成される第1配線層11Aの接合面ではなく、その反対側の面(反対面)にスクライブライン202を形成する。つまり、図4Cに示されるようにセラミックス母材201の一方の面に第1配線層11Aが接合される場合には、スクライブライン202は、図4Aに示されるようにセラミックス母材201の他方の面における第1熱伝達金属層32Aの接合予定領域を除く非接合部に形成しておく。なお、スクライブライン202は、第1配線層11Aの非接合部及び第1熱伝達金属層32Aの非接合部に形成するだけでなく、第1配線層11Aの接合部にも形成して、セラミックス母材201の両面に形成することもできる。 The scribe line 202 is formed on at least one surface of the ceramic base material 201 as shown in FIG. 4A. Specifically, the scribe line 202 is formed not on the bonding surface of the first wiring layer 11A formed across the two first ceramic layers 21A and 21A but on the opposite surface (opposite surface). That is, when the first wiring layer 11A is bonded to one surface of the ceramic base material 201 as shown in FIG. 4C, the scribe line 202 is connected to the other side of the ceramic base material 201 as shown in FIG. 4A. It forms in the non-joining part except the joining plan area | region of 32 A of 1st heat-transfer metal layers in the surface. The scribe line 202 is formed not only at the non-joining portion of the first wiring layer 11A and the non-joining portion of the first heat transfer metal layer 32A, but also at the joining portion of the first wiring layer 11A. It can also be formed on both sides of the base material 201.
 また、スクライブライン202は、図4Aに示すように、セラミックス母材201の対向する辺同士を貫通する直線で形成する。この場合、セラミックス母材201に、長辺同士を貫通する1本のスクライブライン202を形成しており、この1本のスクライブライン202によりセラミックス母材201が二分割され、第1セラミックス層21A,21Aの外形形状の大きさに区画された2個の第1セラミックス層形成領域203,203が整列して形成される。 Further, the scribe line 202 is formed by a straight line penetrating opposite sides of the ceramic base material 201 as shown in FIG. 4A. In this case, one scribe line 202 penetrating the long sides is formed in the ceramic base material 201, and the ceramic base material 201 is divided into two by this one scribe line 202, and the first ceramic layer 21A, Two first ceramic layer forming regions 203, 203 partitioned into the size of the outer shape of 21A are formed in alignment.
 なお、図示は省略するが、レーザ加工後に、スクライブライン202が形成されたセラミックス母材201を、エッチング液に浸漬させることにより洗浄する。 Although not shown in the figure, after the laser processing, the ceramic base material 201 on which the scribe line 202 is formed is cleaned by immersing it in an etching solution.
 また、スクライブライン形成工程S11は、レーザ加工に限定されるものではなく、ダイヤモンドスクライバー等の他の加工方法により実施することもできる。 Further, the scribe line forming step S11 is not limited to laser processing, and can be performed by other processing methods such as a diamond scriber.
(金属層形成工程)
 スクライブライン形成工程S11後に、セラミックス母材201の一方の面に第1配線層11A形成し、他方の面に第1熱伝達金属層32Aを形成する(金属層形成工程S12)。例えば、図3B及び図4Bに示すように、セラミックス母材201の一方の面、すなわちスクライブライン202が形成されていない面に第1配線層11Aとなる金属板301を接合するとともに、スクライブライン202が形成された他方の面に第1熱伝達金属層32Aとなる金属板302を接合する。これら金属板301とセラミックス母材201、セラミックス母材201と金属板302との接合は、ろう材等を用いて行われる。
(Metal layer forming process)
After the scribe line forming step S11, the first wiring layer 11A is formed on one surface of the ceramic base material 201, and the first heat transfer metal layer 32A is formed on the other surface (metal layer forming step S12). For example, as shown in FIGS. 3B and 4B, a metal plate 301 to be the first wiring layer 11 </ b> A is bonded to one surface of the ceramic base material 201, that is, the surface where the scribe line 202 is not formed, and the scribe line 202 is used. The metal plate 302 to be the first heat transfer metal layer 32A is joined to the other surface on which the is formed. The metal plate 301 and the ceramic base material 201 and the ceramic base material 201 and the metal plate 302 are joined using a brazing material or the like.
 金属板301,302がアルミニウムを主成分とする金属材料により形成される場合は、Al‐Si、Al‐Ge、Al‐Cu、Al‐Mg又はAl‐Mn等の接合材を用いて、金属板301,302とセラミックス母材201とを接合する。また、金属板301,302が銅を主成分とする金属材料により形成される場合は、Ag‐Cu‐TiやAg‐Ti等の接合材を用いて、金属板301,302とセラミックス母材201とを活性金属ろう付けにより接合する。また、金属板301,302とセラミックス母材201との接合は、ろう付け以外にもTLP接合法(Transient Liquid Phase Bonding)と称される過渡液相接合法によって接合してもよい。 When the metal plates 301 and 302 are formed of a metal material mainly composed of aluminum, a metal plate is used by using a bonding material such as Al-Si, Al-Ge, Al-Cu, Al-Mg, or Al-Mn. 301 and 302 and the ceramic base material 201 are joined. Further, when the metal plates 301 and 302 are formed of a metal material mainly composed of copper, the metal plates 301 and 302 and the ceramic base material 201 are used by using a bonding material such as Ag-Cu-Ti or Ag-Ti. Are joined by active metal brazing. Further, the metal plates 301 and 302 and the ceramic base material 201 may be joined by a transient liquid phase joining method called TLP joining method (Transient Liquid Phase Bonding) in addition to brazing.
 次に、金属板301,302を接合したセラミックス母材201にエッチング処理を施し、図3C及び図4Cに示すように、セラミックス母材201の一方の面に、各第1セラミックス層形成領域203,203に跨って配設される第1配線層11Aをパターニングするとともに、セラミックス母材201の他方の面に、各第1セラミックス層形成領域203,203に独立した第1熱伝達金属層32A,32Aをパターニングする。スクライブライン202は、第1熱伝達金属層32A,32Aの接合予定領域を除く非接合部に形成している。このため、スクライブライン202上に重なって形成された金属層部分(金属板)が除去されることで、スクライブライン202の全体を露出させることができる。これにより、パターニングされた第1配線層11A及び第1熱伝達金属層32A,32Aとセラミックス母材201とを有する積層体204が形成される。 Next, the ceramic base material 201 to which the metal plates 301 and 302 are bonded is subjected to an etching process. As shown in FIGS. 3C and 4C, the first ceramic layer forming regions 203, The first wiring layer 11 </ b> A disposed across the 203 is patterned, and the first heat transfer metal layers 32 </ b> A and 32 </ b> A independent of the first ceramic layer formation regions 203 and 203 are formed on the other surface of the ceramic base material 201. Is patterned. The scribe line 202 is formed in a non-joined portion excluding the planned joining region of the first heat transfer metal layers 32A and 32A. For this reason, the entire scribe line 202 can be exposed by removing the metal layer portion (metal plate) formed over the scribe line 202. Thereby, the laminated body 204 including the patterned first wiring layer 11A and the first heat transfer metal layers 32A and 32A and the ceramic base material 201 is formed.
 なお、第1配線層11Aは、予めパターニングされた金属板をセラミックス母材201の一方の面に接合することにより、エッチング処理を施すことなく形成することもできる。同様に、第1熱伝達金属層32A,32Aも、予めパターニングされた個片の金属板をセラミックス母材201の他方の面に接合することにより、エッチング処理を施すことなく形成することができる。 The first wiring layer 11A can also be formed without performing an etching process by bonding a previously patterned metal plate to one surface of the ceramic base material 201. Similarly, the first heat transfer metal layers 32 </ b> A and 32 </ b> A can be formed without performing an etching process by joining a piece of metal plate patterned in advance to the other surface of the ceramic base material 201.
 また、第1配線層11Aは、銀(Ag)の焼結体により構成することもできる。第1配線層11Aを銀の焼結体で構成する場合には、セラミックス母材201の一方の面に、銀及びガラスを含むガラス入り銀ペーストを塗布して加熱処理を行うことにより、銀ペーストを焼成して形成できる。したがって、エッチング処理を施すことなくパターニングされた第1配線層11Aを形成できる。なお、第1配線層11Aを銀の焼結体で構成する場合には、セラミックス母材201の少なくとも銀ペーストとの界面と接する面をアルミナ(Al)で構成することが好ましい。この場合、例えば、セラミックス母材201の全体をアルミナで構成しても良いし、窒化アルミニウムを酸化させて表面がアルミナとなっているセラミックス基板を用いても良い。 Also, the first wiring layer 11A can be composed of a sintered body of silver (Ag). When the first wiring layer 11A is composed of a silver sintered body, a silver paste containing glass and silver containing glass is applied to one surface of the ceramic base material 201 and subjected to heat treatment, whereby a silver paste is obtained. Can be formed by firing. Therefore, the patterned first wiring layer 11A can be formed without performing an etching process. When the first wiring layer 11A is composed of a silver sintered body, it is preferable that the surface of the ceramic base material 201 that contacts at least the interface with the silver paste is composed of alumina (Al 2 O 3 ). In this case, for example, the entire ceramic base material 201 may be made of alumina, or a ceramic substrate in which aluminum nitride is oxidized and the surface is made of alumina may be used.
(分割工程)
 金属層形成工程S12後に、スクライブライン202が形成された面側に凸となるようにセラミックス母材201を曲げることで、積層体204のセラミックス母材201をスクライブライン202に沿って分割し、第1セラミックス層21A,21Aを個片化する。そして、図3D及び図4Dに示すように、第1配線層11Aと、第1セラミックス層21A,21Aと、第1熱伝達金属層32A,32Aとが接合された第1配線基板2Aを形成する(分割工程S13)。
(Division process)
After the metal layer forming step S12, the ceramic base material 201 of the laminated body 204 is divided along the scribe line 202 by bending the ceramic base material 201 so as to protrude toward the surface on which the scribe line 202 is formed. 1 Ceramic layers 21A and 21A are separated. Then, as shown in FIGS. 3D and 4D, a first wiring board 2A is formed in which the first wiring layer 11A, the first ceramic layers 21A and 21A, and the first heat transfer metal layers 32A and 32A are joined. (Division process S13).
 スクライブライン202は、第1配線層11Aの接合面の反対側(反対面)に形成されているので、セラミックス母材201をスクライブライン202に沿って容易に分割できる。また、スクライブライン202は、セラミックス母材201の対向する辺同士を貫通する単純な直線で形成されていることから、セラミックス母材201をスクライブライン202に沿って円滑に分割できる。 Since the scribe line 202 is formed on the opposite side (opposite surface) of the bonding surface of the first wiring layer 11A, the ceramic base material 201 can be easily divided along the scribe line 202. In addition, since the scribe line 202 is formed by a simple straight line that penetrates the opposing sides of the ceramic base material 201, the ceramic base material 201 can be smoothly divided along the scribe line 202.
(接合工程)
 第1配線基板2Aの第1配線層11Aに、P型熱電変換素子3の一方の端面とN型熱電変換素子4の一方の端面とを接合する(接合工程S14)。具体的には、第1配線層11Aと、P型熱電変換素子3及びN型熱電変換素子4との接合は、ペーストやろう材を用いた接合、荷重印加による固相拡散接合等により接合する。
(Joining process)
One end face of the P-type thermoelectric conversion element 3 and one end face of the N-type thermoelectric conversion element 4 are joined to the first wiring layer 11A of the first wiring board 2A (joining step S14). Specifically, the first wiring layer 11A is bonded to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 by bonding using a paste or brazing material, solid phase diffusion bonding by applying a load, or the like. .
 接合工程S14では、第1配線層11Aと、P型熱電変換素子3及びN型熱電変換素子4との接合時において適切な荷重を負荷するため、図5に示すように、対向配置される一組の加圧板401A,401Bの間に、第1配線基板2Aの第1配線層11AとP型熱電変換素子3及びN型熱電変換素子4とをそれぞれ重ねた挟持体405を配置しておき、挟持体405をその積層方向に加圧した状態で加熱する。これにより、第1配線層11AとP型熱電変換素子3及びN型熱電変換素子4とをそれぞれ接合する。この場合、各加圧板401A,401Bは、カーボン板により構成される。 In the bonding step S14, in order to load an appropriate load when the first wiring layer 11A is bonded to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, as shown in FIG. Between the pair of pressure plates 401A and 401B, a sandwiching body 405 in which the first wiring layer 11A of the first wiring board 2A and the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are overlapped is disposed. The holding body 405 is heated in a state of being pressurized in the stacking direction. Thereby, 11 A of 1st wiring layers, the P-type thermoelectric conversion element 3, and the N-type thermoelectric conversion element 4 are each joined. In this case, each of the pressure plates 401A and 401B is composed of a carbon plate.
 この第1配線層11AとP型熱電変換素子3及びN型熱電変換素子4との接合時において、P型熱電変換素子3とN型熱電変換素子4とのうち少なくとも線膨張係数が小さい一方の熱電変換素子と、加圧板401A,401Bとの間に補完部材411を配置し、P型熱電変換素子3とN型熱電変換素子4との線膨張差に起因する熱伸縮差を補完する。具体的には、マンガンシリサイド(線膨張係数10.8×10-6/K程度)のP型熱電変換素子3とマグネシウムシリサイド(線膨張係数17.0×10-6/K程度)のN型熱電変換素子4との組み合わせでは、P型熱電変換素子3の線膨張係数はN型熱電変換素子4の線膨張係数よりも小さくなる。このため、少なくとも線膨張係数が小さいP型熱電変換素子3と加圧板401A,401Bとの間に補完部材411を配置する。 At the time of joining the first wiring layer 11A to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, at least one of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 has a small linear expansion coefficient. A complementary member 411 is disposed between the thermoelectric conversion element and the pressure plates 401 </ b> A and 401 </ b> B to complement the thermal expansion / contraction difference caused by the linear expansion difference between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4. Specifically, a P-type thermoelectric conversion element 3 of manganese silicide (linear expansion coefficient of about 10.8 × 10 −6 / K) and an N-type of magnesium silicide (linear expansion coefficient of about 17.0 × 10 −6 / K). In combination with the thermoelectric conversion element 4, the linear expansion coefficient of the P-type thermoelectric conversion element 3 is smaller than the linear expansion coefficient of the N-type thermoelectric conversion element 4. For this reason, the complementary member 411 is arrange | positioned between the P-type thermoelectric conversion element 3 with small linear expansion coefficient, and the pressurization plates 401A and 401B.
 なお、補完部材411は、予め加圧板401A,401Bに固定し一体化しておくことで、取り扱いが容易になる。また、図示は省略するが、補完部材411とP型熱電変換素子3のメタライズ層41や第1熱伝達金属層32Aと間には、接合防止のためにグラファイトシートが配置される。 Note that the complementary member 411 is easily handled by being fixed to the pressure plates 401A and 401B in advance and integrated. Although not shown, a graphite sheet is disposed between the complementary member 411 and the metallized layer 41 of the P-type thermoelectric conversion element 3 and the first heat transfer metal layer 32A to prevent bonding.
 図5に示すように、例えば、補完部材411をP型熱電変換素子3側にのみ配置する場合、補完部材411は、N型熱電変換素子4よりも線膨張係数が高い材料を用いる必要がある。線膨張係数がN型熱電変換素子4の線膨張係数(17.0×10-6/K程度)よりも高い材料には、例えばアルミニウム(23×10-6/K)がある。この材料を補完部材411に用いる。 As shown in FIG. 5, for example, when the complementary member 411 is disposed only on the P-type thermoelectric conversion element 3 side, the complementary member 411 needs to use a material having a higher linear expansion coefficient than the N-type thermoelectric conversion element 4. . For example, aluminum (23 × 10 −6 / K) is a material whose linear expansion coefficient is higher than that of the N-type thermoelectric conversion element 4 (about 17.0 × 10 −6 / K). This material is used for the complementary member 411.
 そして、第1配線基板2AとP型熱電変換素子3及びN型熱電変換素子4との接合時におけるP型熱電変換素子3及び補完部材411の高さとN型熱電変換素子4の高さとの差を、P型熱電変換素子3の高さとN型熱電変換素子4の高さとの差よりも小さくする。これにより、線膨張係数が大きいN型熱電変換素子4の高さと、線膨張係数が小さいP型熱電変換素子3及び補完部材411の高さとを近づけることができる。したがって、一組の加圧板401A,401Bの間で、各熱電変換素子3,4と第1配線層11Aとを密着させてそれぞれ均一に加圧できる。 Then, the difference between the height of the P-type thermoelectric conversion element 3 and the complementary member 411 and the height of the N-type thermoelectric conversion element 4 at the time of joining the first wiring board 2 </ b> A to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4. Is made smaller than the difference between the height of the P-type thermoelectric conversion element 3 and the height of the N-type thermoelectric conversion element 4. Thereby, the height of the N-type thermoelectric conversion element 4 having a large linear expansion coefficient can be brought close to the heights of the P-type thermoelectric conversion element 3 and the complementary member 411 having a small linear expansion coefficient. Therefore, the thermoelectric conversion elements 3 and 4 and the first wiring layer 11A can be brought into close contact with each other between the pair of pressurizing plates 401A and 401B, and can be uniformly pressed.
 なお、図5に示した例では、下側の加圧板401Aと挟持体405との間に補完部材411を配置するとともに、上側の加圧板401Bと挟持体405との間に補完部材411を配置したが、いずれか一方の間に補完部材411を配置してもよい。 In the example shown in FIG. 5, the complementary member 411 is disposed between the lower pressure plate 401 </ b> A and the sandwiching body 405, and the complementary member 411 is disposed between the upper pressure plate 401 </ b> B and the sandwiching body 405. However, you may arrange | position the complementary member 411 between either one.
 なお、接合工程S14では、図6に示すように、補完部材412,413を、P型熱電変換素子3側とN型熱電変換素子4側との双方に配置して行うこともできる。例えば線膨張係数の小さいP型熱電変換素子3側には線膨張係数の大きい材料からなる補完部材412を配置し、線膨張係数の大きいN型熱電変換素子4側には補完部材412よりも線膨張係数の小さい材料からなる補完部材413を配置する。なお、図示は省略するが、各補完部材412,413と両熱電変換素子3,4のメタライズ層41との間には、接合防止のためにグラファイトシートが配置される。 In addition, in joining process S14, as shown in FIG. 6, the complementary members 412 and 413 can also be arrange | positioned and arranged on both the P-type thermoelectric conversion element 3 side and the N-type thermoelectric conversion element 4 side. For example, a complementary member 412 made of a material having a large linear expansion coefficient is disposed on the P-type thermoelectric conversion element 3 side having a small linear expansion coefficient, and the N-type thermoelectric conversion element 4 side having a large linear expansion coefficient is lined more than the complementary member 412. A complementary member 413 made of a material having a small expansion coefficient is arranged. In addition, although illustration is abbreviate | omitted, a graphite sheet is arrange | positioned between each complementary member 412 and 413 and the metallization layer 41 of both the thermoelectric conversion elements 3 and 4 for joining prevention.
 例えば、P型熱電変換素子3側に配置する補完部材412の材料としてアルミニウム(23×10-6/K)や銅(17×10-6/K)を用いることができる。また、N型熱電変換素子4側に配置する補完部材413の材料として鉄(12×10-6/K)やニッケル(13×10-6/K)を用いることができる。 For example, aluminum (23 × 10 −6 / K) or copper (17 × 10 −6 / K) can be used as the material of the complementary member 412 disposed on the P-type thermoelectric conversion element 3 side. Further, iron (12 × 10 −6 / K) or nickel (13 × 10 −6 / K) can be used as the material of the complementary member 413 disposed on the N-type thermoelectric conversion element 4 side.
 これにより、第1配線基板2AとP型熱電変換素子3及びN型熱電変換素子4との接合時において、P型熱電変換素子3及び補完部材412の高さとN型熱電変換素子4及び補完部材413の高さとの差を、P型熱電変換素子3の高さとN型熱電変換素子4の高さとの差よりも小さくでき、P型熱電変換素子3及び補完部材412の高さとN型熱電変換素子4及び補完部材413の高さとを揃えることができる。したがって、一組の加圧板401A,401Bの間で、各熱電変換素子3,4と第1配線層11Aとを密着させてそれぞれ均一に加圧できる。 Thereby, the height of the P-type thermoelectric conversion element 3 and the complementary member 412 and the N-type thermoelectric conversion element 4 and the complementary member at the time of joining the first wiring board 2 </ b> A to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4. The difference between the height of 413 can be made smaller than the difference between the height of the P-type thermoelectric conversion element 3 and the height of the N-type thermoelectric conversion element 4, and the height of the P-type thermoelectric conversion element 3 and the complementary member 412 and the N-type thermoelectric conversion can be reduced. The height of the element 4 and the complementary member 413 can be made uniform. Therefore, the thermoelectric conversion elements 3 and 4 and the first wiring layer 11A can be brought into close contact with each other between the pair of pressurizing plates 401A and 401B, and can be uniformly pressed.
 なお、上記においては、線膨張係数の小さいP型熱電変換素子3側に線膨張係数の大きい材料からなる補完部材412を配置し、線膨張係数の大きいN型熱電変換素子4側に補完部材412よりも線膨張係数の小さい材料からなる補完部材413を配置したが、P型熱電変換素子3側に線膨張係数の小さい材料からなる補完部材を配置して、N型熱電変換素子4側に線膨張係数の大きい材料からなる補完部材を配置してもよい。この場合、第1配線基板2AとP型熱電変換素子3及びN型熱電変換素子4との接合(加熱)時における、P型熱電変換素子3側の高さとN型熱電変換素子4側の高さとを揃えるため、各補完部材の厚みを調整すればよい。 In the above description, the complementary member 412 made of a material having a large linear expansion coefficient is disposed on the P-type thermoelectric conversion element 3 side having a small linear expansion coefficient, and the complementary member 412 is disposed on the N-type thermoelectric conversion element 4 side having a large linear expansion coefficient. Although the complementary member 413 made of a material having a smaller linear expansion coefficient is arranged, the complementary member made of a material having a smaller linear expansion coefficient is arranged on the P-type thermoelectric conversion element 3 side, and the wire is arranged on the N-type thermoelectric conversion element 4 side. A complementary member made of a material having a large expansion coefficient may be arranged. In this case, the height of the P-type thermoelectric conversion element 3 side and the height of the N-type thermoelectric conversion element 4 side at the time of joining (heating) the first wiring board 2A, the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 Therefore, the thickness of each complementary member may be adjusted.
 なお、第1配線基板2Aは、個片化された複数の第1セラミックス層21A,21Aを有しているので、接合工程S14において挟持体405が加熱された際に、各第1セラミックス層21A,21Aは互いに相手側を拘束することがない。このため、第1配線基板2Aの各部位に積層されたP型熱電変換素子3とN型熱電変換素子4の熱膨張に追従して移動できる。これにより、第1配線基板2Aを介してP型熱電変換素子3とN型熱電変換素子4とが直列に接続された熱電変換モジュール101を製造できる。 Since the first wiring board 2A has a plurality of individual first ceramic layers 21A, 21A, when the sandwiching body 405 is heated in the joining step S14, each first ceramic layer 21A , 21A do not restrain each other. For this reason, it can move following the thermal expansion of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 stacked in each part of the first wiring board 2A. Thereby, the thermoelectric conversion module 101 by which the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 were connected in series via the 1st wiring board 2A can be manufactured.
 このようにして製造された熱電変換モジュール101は、例えば図1の下側に外部の熱源(図示略)や冷却流路(図示略)等が配置される。これにより、各熱電変換素子3,4に上下の温度差に応じた起電力が発生し、配列の両端の配線91,91間に、各熱電変換素子3,4に生じる起電力の総和の電位差を得ることができる。 The thermoelectric conversion module 101 manufactured in this way has an external heat source (not shown), a cooling channel (not shown), and the like, for example, on the lower side of FIG. Thereby, an electromotive force corresponding to the upper and lower temperature difference is generated in each thermoelectric conversion element 3, 4, and the potential difference of the sum of the electromotive force generated in each thermoelectric conversion element 3, 4 is between the wires 91, 91 at both ends of the array. Can be obtained.
 また、このような使用環境下において、熱電変換モジュール101の両熱電変換素子3,4の熱膨張に差が生じる。しかし、熱電変換モジュール101では、第1配線基板2Aを構成する各第1セラミックス層21A,21Aが隣り合うP型熱電変換素子3とN型熱電変換素子4との間で分離され、熱電変換素子3,4毎に独立して形成されており、剛体の第1セラミックス層21A,21AにおけるP型熱電変換素子3とN型熱電変換素子4との間の接続が分断されている。このため、各熱電変換素子3,4は、各第1セラミックス層21A,21Aによって熱伸縮に伴う変形が拘束されることがない。 Further, under such a use environment, a difference occurs in the thermal expansion between both thermoelectric conversion elements 3 and 4 of the thermoelectric conversion module 101. However, in the thermoelectric conversion module 101, the first ceramic layers 21A and 21A constituting the first wiring board 2A are separated between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4, and the thermoelectric conversion element 3 and 4 are formed independently, and the connection between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the rigid first ceramic layers 21A and 21A is divided. For this reason, the thermoelectric conversion elements 3 and 4 are not restrained from being deformed by the thermal expansion and contraction by the first ceramic layers 21A and 21A.
 また、隣り合うP型熱電変換素子3とN型熱電変換素子4との熱伸縮差は、両熱電変換素子3,4の間を接続する第1配線層11Aの接続部分が変形して寸法変化を吸収することができる。このため、熱伸縮差により熱電変換素子3,4内に生じる熱応力の発生を抑制できる。そして、各熱電変換素子3,4の熱伸縮差により、熱電変換素子3,4が第1配線基板2A(第1配線層11A)から剥がれたり、熱電変換素子3,4にクラックが生じたりすることを防止できる。したがって、第1配線層11Aにより接続される熱電変換素子3,4間の電気的な接続を良好に維持でき、熱電変換モジュール101の接合信頼性、熱伝導性及び導電性を良好に維持できる。 Further, the thermal expansion / contraction difference between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4 is caused by deformation of the connecting portion of the first wiring layer 11A that connects the two thermoelectric conversion elements 3 and 4 to each other. Can be absorbed. For this reason, generation | occurrence | production of the thermal stress which arises in the thermoelectric conversion elements 3 and 4 by a thermal expansion-contraction difference can be suppressed. The thermoelectric conversion elements 3 and 4 are peeled off from the first wiring board 2A (first wiring layer 11A) or cracks are generated in the thermoelectric conversion elements 3 and 4 due to the difference in thermal expansion and contraction between the thermoelectric conversion elements 3 and 4. Can be prevented. Therefore, the electrical connection between the thermoelectric conversion elements 3 and 4 connected by the first wiring layer 11A can be maintained satisfactorily, and the junction reliability, thermal conductivity, and conductivity of the thermoelectric conversion module 101 can be maintained satisfactorily.
 また、第1配線基板2Aには、絶縁基板である第1セラミックス層21A,21Aが設けられている。このため、熱電変換モジュール101を熱源等に設置したときに、第1セラミックス層21A,21Aにより熱源等と第1配線層11Aとが接触することを防止できる。したがって、熱源等と第1配線層11Aとの電気的なリークを確実に回避でき、絶縁状態を良好に維持できる。 The first wiring board 2A is provided with first ceramic layers 21A and 21A which are insulating boards. For this reason, when the thermoelectric conversion module 101 is installed in a heat source or the like, the first ceramic layers 21A and 21A can prevent the heat source and the first wiring layer 11A from contacting each other. Therefore, electrical leakage between the heat source and the first wiring layer 11A can be reliably avoided, and the insulation state can be maintained well.
 なお、熱電変換素子3,4自体は電圧が低いことから、絶縁基板である第1セラミックス層21A,21Aが各熱電変換素子3,4毎に独立して形成されていれば、第1配線層11Aの全面に第1セラミックス層21A,21Aが接合されていなくても、第1配線層11Aが熱源等と物理的に接触しない限り、電気的なリークを生じることはない。 Since the thermoelectric conversion elements 3 and 4 themselves have a low voltage, if the first ceramic layers 21A and 21A, which are insulating substrates, are formed independently for each thermoelectric conversion element 3 and 4, the first wiring layer Even if the first ceramic layers 21A and 21A are not bonded to the entire surface of 11A, as long as the first wiring layer 11A is not in physical contact with a heat source or the like, electrical leakage does not occur.
 また、第1配線基板2Aには、第1熱伝達金属層32A,32Aが設けられているので、熱電変換モジュール101を熱源等に設置したときに、第1熱伝達金属層32A,32Aにより熱源等と熱電変換モジュール101との密着性を高めることができ、熱伝達性を向上できる。したがって、熱電変換モジュール101の熱電交換性能(発電効率)を向上させることができる。 Further, since the first wiring board 2A is provided with the first heat transfer metal layers 32A and 32A, when the thermoelectric conversion module 101 is installed in a heat source or the like, the first heat transfer metal layers 32A and 32A are used as the heat source. Etc. and the thermoelectric conversion module 101 can be improved in adhesion, and heat transfer can be improved. Therefore, the thermoelectric exchange performance (power generation efficiency) of the thermoelectric conversion module 101 can be improved.
 なお、第1実施形態の接合工程S14では、図5及び図6に示すように、補完部材411~413を用いることにより、少なくとも線膨張係数が小さい一方の熱電変換素子(P型熱電変換素子3)と、加圧板401A,401Bとの間に補完部材411~413を配置し、P型熱電変換素子3とN型熱電変換素子4との線膨張差に起因する熱伸縮差を補完した。そして、一組の加圧板401A,401Bの間で、各熱電変換素子3,4と第1配線層11Aとを密着させて均一に加圧することにしたが、接合工程は、これに限定されるものではない。 In the joining step S14 of the first embodiment, as shown in FIGS. 5 and 6, by using complementary members 411 to 413, at least one thermoelectric conversion element (P-type thermoelectric conversion element 3) having a small linear expansion coefficient is used. ) And the pressure plates 401A and 401B, complementary members 411 to 413 are arranged to compensate for the thermal expansion / contraction difference caused by the linear expansion difference between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4. Then, the thermoelectric conversion elements 3 and 4 and the first wiring layer 11A are brought into close contact with each other between the pair of pressure plates 401A and 401B, and the pressure is uniformly applied. However, the bonding process is limited to this. It is not a thing.
 例えば、図7に示すように、挟持体405を積層方向に偶数個(図7においては2個)重ねて配置するとともに、P型熱電変換素子3とN型熱電変換素子4とを積層方向に同数配置しておくことにより、第1配線層11Aと、P型熱電変換素子3及びN型熱電変換素子4との接合時において、各熱電変換素子3,4と第1配線層11Aとを密着させてそれぞれ均一に加圧できる。また、各挟持体405,405の間にクッション性を有するグラファイトシート420を配設しておくことで、第1配線基板2Aの面方向の各熱電変換素子3,4の配置箇所において、それぞれの傾きを補正でき、各熱電変換素子3,4と第1配線基板2Aとをより均一に加圧できる。 For example, as shown in FIG. 7, an even number of sandwiching bodies 405 (two in FIG. 7) are stacked in the stacking direction, and the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are stacked in the stacking direction. By arranging the same number, the thermoelectric conversion elements 3 and 4 and the first wiring layer 11A are brought into close contact with each other when the first wiring layer 11A is bonded to the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4. Each can be uniformly pressurized. In addition, by placing a graphite sheet 420 having cushioning properties between the sandwiching bodies 405 and 405, each of the thermoelectric conversion elements 3 and 4 in the surface direction of the first wiring board 2 </ b> A can be arranged at each location. The inclination can be corrected, and the thermoelectric conversion elements 3 and 4 and the first wiring board 2A can be more uniformly pressurized.
 この場合、積層方向に隣接する2個の挟持体405,405の各第1配線基板2A,2Aどうしを対向させて配置することで、第1配線基板2Aの面方向の各熱電変換素子3,4の配置箇所において、それぞれP型熱電変換素子3とN型熱電変換素子4とを積層方向に1個ずつ(同数)配置できる。このようにして挟持体405,405を積層方向に偶数個重ねて配置することで、P型熱電変換素子3とN型熱電変換素子4のうち、線膨張係数が小さい一方の熱電変換素子と、線膨張係数が大きい他方の熱電変換素子とを常に同数重ねて配置でき、接合(加熱)時において、複数個を重ねた挟持体405,405の高さを面方向において均一にできる。また、前述したように、各挟持体405,405の間にクッション性を有するグラファイトシート420を介在させることで、それぞれの傾きを補正でき、各熱電変換素子3,4と第1配線基板2Aとをより均一に加圧できる。 In this case, the first wiring boards 2A and 2A of the two sandwiching bodies 405 and 405 adjacent to each other in the stacking direction are arranged to face each other, so that the thermoelectric conversion elements 3 in the surface direction of the first wiring board 2A are arranged. 4, the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4 can be arranged one by one (the same number) in the stacking direction. In this way, by arranging even numbers of the sandwiching bodies 405 and 405 in the stacking direction, one of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 with a small linear expansion coefficient, The same number of the other thermoelectric conversion elements having a large linear expansion coefficient can always be arranged in an overlapping manner, and the height of the plurality of sandwiched bodies 405 and 405 can be made uniform in the surface direction during bonding (heating). Further, as described above, by interposing the graphite sheet 420 having cushioning properties between the sandwiching bodies 405 and 405, respective inclinations can be corrected, and the thermoelectric conversion elements 3 and 4 and the first wiring board 2A can be corrected. Can be more uniformly pressurized.
 したがって、一組の加圧板401A、401Bの間で、各熱電変換素子3,4と第1配線層11Aとを密着させて均一に加圧でき、各熱電変換素子3,4と第1配線基板2Aとを確実に接合できる。また、このように挟持体405を複数重ねることで、一度の接合工程S14において、熱電変換モジュール101を複数製造できる。 Therefore, the thermoelectric conversion elements 3 and 4 and the first wiring layer 11A can be brought into close contact with each other between the pair of pressure plates 401A and 401B, and the thermoelectric conversion elements 3 and 4 and the first wiring board can be pressed uniformly. 2A can be reliably joined. Moreover, a plurality of thermoelectric conversion modules 101 can be manufactured in a single joining step S14 by stacking a plurality of sandwiching bodies 405 in this way.
 また、図1に示す第1実施形態では、熱電変換素子3,4の一端側に配設された第1配線基板2Aを有する構成としたが、図8に示す第2実施形態の熱電変換モジュール102のように、熱電変換素子3,4の一端側(図8において下側)に第1配線基板2Aを配設し、他端側(図8において上側)に第2配線基板2Bを配設することもできる。この場合、対向配置される第1配線基板2Aと第2配線基板2Bとを介してP型熱電変換素子3とN型熱電変換素子4とを電気的に直列に接続できる。 In the first embodiment shown in FIG. 1, the first wiring board 2 </ b> A is provided on one end side of the thermoelectric conversion elements 3, 4, but the thermoelectric conversion module of the second embodiment shown in FIG. 8. Like 102, the 1st wiring board 2A is arrange | positioned in the one end side (lower side in FIG. 8) of the thermoelectric conversion elements 3 and 4, and the 2nd wiring board 2B is arrange | positioned in the other end side (upper side in FIG. 8). You can also In this case, the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 can be electrically connected in series via the first wiring board 2A and the second wiring board 2B that are arranged to face each other.
 以下、第2実施形態の熱電変換モジュール102において、第1実施形態の熱電変換モジュール101と共通する要素には、同一符号を付して説明を省略する。熱電変換素子3,4の一端側(図8において下側)に配設される第1配線基板2Aは、第1実施形態と同じであり、説明を省略する。 Hereinafter, in the thermoelectric conversion module 102 of the second embodiment, elements common to the thermoelectric conversion module 101 of the first embodiment are denoted by the same reference numerals and description thereof is omitted. The first wiring board 2A disposed on one end side (the lower side in FIG. 8) of the thermoelectric conversion elements 3 and 4 is the same as that in the first embodiment, and a description thereof will be omitted.
 熱電変換素子3,4の他端側(図8において上側)に配設される第2配線基板2Bは、第2配線層12B,12Bと、第2配線層12B,12Bの熱電変換素子3,4との接合面とは反対面に接合された第2セラミックス層21B,21Bと、第2セラミックス層21B,21Bの第2配線層12B,12Bとの接合面とは反対面に接合された第2熱伝達金属層31Bとを有する構成とされる。 The second wiring board 2B disposed on the other end side (upper side in FIG. 8) of the thermoelectric conversion elements 3 and 4 includes the second wiring layers 12B and 12B and the thermoelectric conversion elements 3 and 2 of the second wiring layers 12B and 12B. The second ceramic layers 21B and 21B bonded to the surface opposite to the bonding surface with the fourth ceramic layer 21 and the second ceramic layers 21B and 21B bonded to the surface opposite to the bonding surface with the second wiring layers 12B and 12B. 2 heat transfer metal layer 31B.
 第2配線基板2Bを構成する第2セラミックス層21B,21Bは複数(図8では2個)に分離され、第1実施形態と同様に、各熱電変換素子3,4毎に独立して形成されている。また、各第2セラミックス層21B,21Bは、それぞれ平面視正方形状に形成される。第2配線基板2Bには、平面視正方形状の第2配線層12B,12Bが2個設けられるとともに、平面視長方形状の第2熱伝達金属層31Bが1個設けられている。第2配線層12B,12Bは、第2セラミックス層21B,21B毎に独立して形成されており、各熱電変換素子3,4に個別に接続されている。一方、第2熱伝達金属層31Bは、隣り合う両第2配線層12B,12Bの間に跨って形成され、かつ、隣り合う両第2セラミックス層21B,21Bの間に跨って形成されている。 The second ceramic layers 21B, 21B constituting the second wiring board 2B are separated into a plurality (two in FIG. 8), and are formed independently for each thermoelectric conversion element 3, 4 as in the first embodiment. ing. Each of the second ceramic layers 21B and 21B is formed in a square shape in plan view. The second wiring board 2B is provided with two second wiring layers 12B, 12B having a square shape in plan view, and one second heat transfer metal layer 31B having a rectangular shape in plan view. The second wiring layers 12B, 12B are formed independently for each of the second ceramic layers 21B, 21B, and are individually connected to the thermoelectric conversion elements 3, 4. On the other hand, the second heat transfer metal layer 31B is formed between both adjacent second wiring layers 12B and 12B, and is formed between both adjacent second ceramic layers 21B and 21B. .
 第2実施形態の熱電変換モジュール102では、第1配線基板2Aの第1配線層11Aと第2配線基板2Bの第2熱伝達金属層31Bとを同一の金属材料により同形状(同じ厚み、同じ平面サイズ)に形成するとともに、第1配線基板2Aの第1熱伝達金属層32A,32Aと第2配線基板2Bの第2配線層12B,12Bとを同一の金属材料により同形状に形成している。そして、第1配線基板2Aと第2配線基板2Bとが、2個のセラミックス層(第1セラミックス層21A,21A又は第2セラミックス層21B,21B)と、両セラミックス層の一方の面に接合された平面視長方形状の金属層(第1配線層11A又は第2熱伝達金属層31B)と、両セラミックス層の他方の面に接合され、各セラミックス層に独立して形成された平面視正方形状の金属層(第1熱伝達金属層32A,32A又は第2配線層12B,12B)と、を有する構成とされる。つまり、両配線基板2A,2Bは、同じ構成の1種類の配線基板により構成されている。 In the thermoelectric conversion module 102 of the second embodiment, the first wiring layer 11A of the first wiring board 2A and the second heat transfer metal layer 31B of the second wiring board 2B are made of the same metal material (the same thickness and the same thickness). The first heat transfer metal layers 32A, 32A of the first wiring board 2A and the second wiring layers 12B, 12B of the second wiring board 2B are formed in the same shape with the same metal material. Yes. Then, the first wiring board 2A and the second wiring board 2B are bonded to two ceramic layers (the first ceramic layers 21A and 21A or the second ceramic layers 21B and 21B) and one surface of both ceramic layers. The rectangular metal layer (first wiring layer 11A or second heat transfer metal layer 31B) in plan view and the square shape in plan view formed independently of each ceramic layer bonded to the other surface of both ceramic layers. Metal layers (first heat transfer metal layers 32A and 32A or second wiring layers 12B and 12B). That is, both the wiring boards 2A and 2B are configured by one type of wiring board having the same configuration.
 そして、このように構成される一組の配線基板2A,2Bの間に、P型熱電変換素子3とN型熱電変換素子4とが交互に直列に接続されることにより、熱電変換モジュール102が構成されている。したがって、熱電変換モジュール102の製造方法については、説明を省略する。 The P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4 are alternately connected in series between the pair of wiring boards 2A and 2B configured as described above, so that the thermoelectric conversion module 102 is It is configured. Therefore, the description of the manufacturing method of the thermoelectric conversion module 102 is omitted.
 このようにして製造される第2実施形態の熱電変換モジュール102においても、各配線基板2A,2Bを構成する各セラミックス層21A,21Bが熱電変換素子3,4毎に独立して形成されており、剛体のセラミックス層21A,21BにおけるP型熱電変換素子3とN型熱電変換素子4との間の接続が分断されている。このため、各熱電変換素子3,4は、各セラミックス層21A,21Bによって熱伸縮に伴う変形が拘束されることがない。 Also in the thermoelectric conversion module 102 of the second embodiment manufactured in this way, the ceramic layers 21A and 21B constituting the wiring boards 2A and 2B are formed independently for each thermoelectric conversion element 3 and 4. The connection between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the rigid ceramic layers 21A and 21B is cut off. For this reason, the thermoelectric conversion elements 3 and 4 are not restrained from being deformed by the thermal expansion and contraction by the ceramic layers 21A and 21B.
 また、第1配線基板2Aの各第1セラミックス層21A,21Aの間は第1配線層11Aにより連結され、第2配線基板2Bの各第2セラミックス層21B,21Bの間は第2熱伝達金属層31Bにより連結されているのみである。これにより、隣り合うP型熱電変換素子3とN型熱電変換素子4との熱伸縮差は、両熱電変換素子3,4の間を接続する第1配線層11A又は第2熱伝達金属層31Bの接続部分が変形して寸法変化を吸収することができる。このため、熱伸縮差により熱電変換素子3,4内に生じる熱応力の発生を抑制できる。そして、各熱電変換素子3,4の熱伸縮差により、熱電変換素子3,4が両配線基板2A,2B(第1配線層11A又は第2配線層12B,12B)から剥がれたり、熱電変換素子3,4にクラックが生じたりすることを防止できる。したがって、第1配線層11Aと第2配線層12B,12Bとにより接続される熱電変換素子3,4間の電気的な接続を良好に維持でき、熱電変換モジュール102の接合信頼性、熱伝導性及び導電性を良好に維持できる。 The first ceramic layers 21A and 21A of the first wiring board 2A are connected by the first wiring layer 11A, and the second ceramic layers 21B and 21B of the second wiring board 2B are connected by the second heat transfer metal. They are only connected by the layer 31B. Thereby, the thermal expansion / contraction difference between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4 is the first wiring layer 11A or the second heat transfer metal layer 31B connecting the two thermoelectric conversion elements 3 and 4. Therefore, the connecting portion can be deformed to absorb the dimensional change. For this reason, generation | occurrence | production of the thermal stress which arises in the thermoelectric conversion elements 3 and 4 by a thermal expansion-contraction difference can be suppressed. The thermoelectric conversion elements 3 and 4 are peeled off from both the wiring boards 2A and 2B (the first wiring layer 11A or the second wiring layers 12B and 12B) due to the difference in thermal expansion and contraction between the thermoelectric conversion elements 3 and 4. It is possible to prevent cracks from occurring in the third and fourth. Therefore, the electrical connection between the thermoelectric conversion elements 3 and 4 connected by the first wiring layer 11A and the second wiring layers 12B and 12B can be satisfactorily maintained, and the joining reliability and thermal conductivity of the thermoelectric conversion module 102 can be maintained. In addition, the conductivity can be maintained well.
 また、各配線基板2A,2Bには、それぞれ絶縁基板であるセラミックス層21A,21Bが設けられているので、熱電変換モジュール102を熱源等に設置したときに、セラミックス層21A,21Bにより熱源等と第1配線層11A又は第2配線層12B,12Bとが接触することを防止できる。したがって、熱源等と第1配線層11A又は第2配線層12B,12Bとの電気的なリークを確実に回避でき、絶縁状態を良好に維持できる。 Moreover, since the ceramic layers 21A and 21B, which are insulating substrates, are provided on the wiring boards 2A and 2B, respectively, when the thermoelectric conversion module 102 is installed on a heat source or the like, the ceramic layers 21A and 21B It is possible to prevent the first wiring layer 11A or the second wiring layers 12B and 12B from contacting each other. Therefore, electrical leakage between the heat source and the first wiring layer 11A or the second wiring layers 12B and 12B can be reliably avoided, and the insulation state can be maintained satisfactorily.
 また、配線基板2A,2Bには、第1熱伝達金属層32A又は第2熱伝達金属層31Bが設けられている。このため、熱電変換モジュール102を熱源等に設置したときに、各熱伝達金属層32A,31Bにより熱源等と熱電変換モジュール102との密着性を高めることができ、熱伝達性を向上できる。したがって、熱電変換モジュール102の熱電交換性能(発電効率)を向上させることができる。 Further, the wiring board 2A, 2B is provided with the first heat transfer metal layer 32A or the second heat transfer metal layer 31B. For this reason, when the thermoelectric conversion module 102 is installed in a heat source or the like, the adhesion between the heat source or the like and the thermoelectric conversion module 102 can be increased by the heat transfer metal layers 32A and 31B, and the heat transfer performance can be improved. Therefore, the thermoelectric exchange performance (power generation efficiency) of the thermoelectric conversion module 102 can be improved.
 なお、図8に示す第2実施形態では、一組の配線基板2A,2Bの双方を、熱電変換素子3,4毎に独立して形成されたセラミックス層21A,21A又は21B,21Bを有する構成としたが、これに限定されない。少なくとも一方の配線基板のみを、熱電変換素子3,4毎に独立して形成されたセラミックス層を有する構成とすることにより、両熱電変換素子3,4の熱伸縮差に伴う寸法変化を緩和でき、熱伸縮差による熱電変換素子3,4のクラックや一組の配線基板との剥離等の発生を防止できる。したがって、一組の配線基板2A,2Bのうち、少なくともいずれか一方のセラミックス層を、熱電変換素子3,4毎に独立して形成すればよい。 In addition, in 2nd Embodiment shown in FIG. 8, it is the structure which has ceramic layer 21A, 21A or 21B, 21B formed independently for every thermoelectric conversion element 3 and 4 in one set of wiring boards 2A and 2B. However, it is not limited to this. Only at least one wiring board has a ceramic layer formed independently for each thermoelectric conversion element 3, 4, so that the dimensional change due to the difference in thermal expansion and contraction between both thermoelectric conversion elements 3, 4 can be reduced. Further, it is possible to prevent the occurrence of cracks in the thermoelectric conversion elements 3 and 4 due to the thermal expansion / contraction difference, separation from the set of wiring boards, and the like. Therefore, at least one of the ceramic layers of the set of wiring boards 2A and 2B may be formed independently for each thermoelectric conversion element 3 and 4.
 図9~図13は、本発明の第3実施形態の熱電変換モジュール103を示している。第1実施形態及び第2実施形態では、P型熱電変換素子3とN型熱電変換素子4とを1個ずつ組み合わせることにより熱電変換モジュール101,102を構成していたが、第3実施形態の熱電変換モジュール103のように、P型熱電変換素子3とN型熱電変換素子4とをぞれそれ複数組み合わせて、大型の熱電変換モジュールを構成することもできる。 9 to 13 show a thermoelectric conversion module 103 according to a third embodiment of the present invention. In the first embodiment and the second embodiment, the thermoelectric conversion modules 101 and 102 are configured by combining the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 one by one. Like the thermoelectric conversion module 103, a large thermoelectric conversion module can be configured by combining a plurality of P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4.
 第3実施形態の熱電変換モジュール103は、対向配置される第1配線基板5Aと第2配線基板5Bとの一組の配線基板5A,5Bの間に、複数のP型熱電変換素子3とN型熱電変換素子4とが組み合わされて面状(二次元)に配列されている。そして、各々のP型熱電変換素子3とN型熱電変換素子4とが、上下の配線基板5A,5Bを介して電気的に直列に接続された構成とされる。以下、第3実施形態の熱電変換モジュール103において、第1実施形態の熱電変換モジュール101及び第2実施形態の熱電変換モジュール102と共通する要素には、同一符号を付して説明を省略する。 The thermoelectric conversion module 103 according to the third embodiment includes a plurality of P-type thermoelectric conversion elements 3 and N between a pair of wiring boards 5A and 5B of a first wiring board 5A and a second wiring board 5B that are arranged to face each other. The type thermoelectric conversion elements 4 are combined and arranged in a planar shape (two-dimensional). Each P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4 are electrically connected in series via the upper and lower wiring boards 5A and 5B. Hereinafter, in the thermoelectric conversion module 103 of 3rd Embodiment, the same code | symbol is attached | subjected to the element which is common in the thermoelectric conversion module 101 of 1st Embodiment, and the thermoelectric conversion module 102 of 2nd Embodiment, and description is abbreviate | omitted.
 第1配線基板5Aは、図9~図13に示されるように、複数の第1配線層11A,12Aと、第1配線層11A,12Aの熱電変換素子3,4との接合面とは反対面に接合された複数の第1セラミックス層21Aと、第1セラミックス層21Aの第1配線層11A,12Aとの接合面とは反対面に接合された第1熱伝達金属層31Aとを有する構成とされる。 As shown in FIGS. 9 to 13, the first wiring board 5A is opposite to the joint surface between the plurality of first wiring layers 11A and 12A and the thermoelectric conversion elements 3 and 4 of the first wiring layers 11A and 12A. A structure having a plurality of first ceramic layers 21A bonded to a surface and a first heat transfer metal layer 31A bonded to a surface opposite to the bonding surface of the first ceramic layers 21A to the first wiring layers 11A and 12A. It is said.
 また、第2配線基板5Bは、図9、図12及び図13に示されるように、第2配線層11Bと、第2配線層11Bの熱電変換素子3,4との接合面とは反対面に接合された複数の第2セラミックス層21Bと、第2セラミックス層21Bの第2配線層11Bとの接合面とは反対面に接合された第2熱伝達金属層31B,32Bとを有する構成とされる。 Further, as shown in FIGS. 9, 12 and 13, the second wiring board 5 </ b> B is a surface opposite to the bonding surface between the second wiring layer 11 </ b> B and the thermoelectric conversion elements 3 and 4 of the second wiring layer 11 </ b> B. A plurality of second ceramic layers 21B bonded to each other, and second heat transfer metal layers 31B and 32B bonded to a surface opposite to the bonding surface of the second ceramic layer 21B to the second wiring layer 11B; Is done.
 各配線基板5A,5Bを構成するセラミックス層21A,21Bは、第1実施形態と同様に、各熱電変換素子3,4毎に独立して形成されている。なお、熱電変換モジュール103には、P型熱電変換素子3とN型熱電変換素子4とがそれぞれ7個ずつ設けられており、合計14個の熱電変換素子が設けられている。そして、各配線基板5A,5Bには、熱電変換素子3,4の個数よりも多い、16個ずつのセラミックス層21A,21Bがそれぞれ設けられている。 The ceramic layers 21A and 21B constituting the wiring boards 5A and 5B are independently formed for each thermoelectric conversion element 3 and 4 as in the first embodiment. The thermoelectric conversion module 103 is provided with seven P-type thermoelectric conversion elements 3 and seven N-type thermoelectric conversion elements 4, and a total of 14 thermoelectric conversion elements are provided. Each of the wiring boards 5A and 5B is provided with 16 ceramic layers 21A and 21B that are larger than the number of thermoelectric conversion elements 3 and 4, respectively.
 また、第1配線基板5Aの各第1セラミックス層21Aの間は、第1配線層11A又は第1熱伝達金属層31Aのいずれかにより連結されており、第1配線基板5Aを構成する複数の第1セラミックス層21Aが一体に設けられている。一方、第2配線基板5Bの各第2セラミックス層21Bの間は、第2配線層11B又は第2熱伝達金属層31Bのいずれかにより連結されており、第2配線基板5Bを構成する複数の第2セラミックス層21Bが一体に設けられている。 Further, the first ceramic layers 21A of the first wiring board 5A are connected by either the first wiring layer 11A or the first heat transfer metal layer 31A, and a plurality of parts constituting the first wiring board 5A. The first ceramic layer 21A is integrally provided. On the other hand, the second ceramic layers 21B of the second wiring board 5B are connected by either the second wiring layer 11B or the second heat transfer metal layer 31B, and a plurality of parts constituting the second wiring board 5B. The second ceramic layer 21B is integrally provided.
 図9の下側に配設される第1配線基板5Aには、図10に示されるように平面視長方形状の第1配線層11Aが7個と、平面視正方形状の第1配線層12Aが2個設けられるとともに、図11に示されるように平面視長方形状の第1熱伝達金属層31Aが8個設けられている。また、図9の上側に配設される第2配線基板5Bには、図12に示されるように平面視長方形状の第2配線層11Bが8個設けられるとともに、図13に示されるように平面視長方形状の第2熱伝達金属層31Bが7個と、平面視正方形状の第2熱伝達金属層32Bが2個設けられている。 As shown in FIG. 10, the first wiring substrate 5A disposed on the lower side of FIG. 9 includes seven first wiring layers 11A having a rectangular shape in plan view and a first wiring layer 12A having a square shape in plan view. Are provided, and as shown in FIG. 11, eight first heat transfer metal layers 31A having a rectangular shape in plan view are provided. Further, the second wiring board 5B disposed on the upper side of FIG. 9 is provided with eight second wiring layers 11B having a rectangular shape in plan view as shown in FIG. 12, and as shown in FIG. Seven second heat transfer metal layers 31B having a rectangular shape in plan view and two second heat transfer metal layers 32B having a square shape in plan view are provided.
 第1配線基板5Aの第1配線層11Aは、隣り合うP型熱電変換素子3とN型熱電変換素子4との間を接続して形成され、かつ、両熱電変換素子3,4の第1セラミックス層21A,21Aどうしの間に跨って形成されている。一方、第1配線層12Aは、第1配線層11Aが形成されていない第1セラミックス層21Aのみに、独立して形成されている。また、第1熱伝達金属層31Aは、隣り合う両第1配線層11A,11Aの間に跨って形成され、かつ、隣り合う両第1セラミックス層21A,21Aの間に跨って形成されている。 The first wiring layer 11A of the first wiring board 5A is formed by connecting between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4, and the first of both thermoelectric conversion elements 3 and 4 is connected. It is formed between the ceramic layers 21A and 21A. On the other hand, the first wiring layer 12A is independently formed only on the first ceramic layer 21A where the first wiring layer 11A is not formed. Further, the first heat transfer metal layer 31A is formed between both adjacent first wiring layers 11A, 11A, and is formed between both adjacent first ceramic layers 21A, 21A. .
 また、第2配線基板5Bの第2配線層11Bは、隣り合うP型熱電変換素子3とN型熱電変換素子4との間を接続して形成され、かつ、両熱電変換素子3,4の第2セラミックス層21B,21Bどうしの間に跨って形成されている。また、第2熱伝達金属層31Bは、隣り合う両第2配線層11B,11Bの間に跨って形成され、かつ、隣り合う両第2セラミックス層21B,21Bの間に跨って形成されている。一方、第2熱伝達金属層32Bは、第2熱伝達金属層32Bが形成されていない第2セラミックス層21Bのみに、独立して形成されている。 The second wiring layer 11B of the second wiring board 5B is formed by connecting between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4, and the two thermoelectric conversion elements 3 and 4 It is formed straddling between the second ceramic layers 21B, 21B. Further, the second heat transfer metal layer 31B is formed between the adjacent second wiring layers 11B and 11B, and is formed between the adjacent second ceramic layers 21B and 21B. . On the other hand, the second heat transfer metal layer 32B is independently formed only on the second ceramic layer 21B where the second heat transfer metal layer 32B is not formed.
 また、第1配線基板5Aの第1配線層11Aと第2配線基板5Bの第2熱伝達金属層31Bとは、同一の金属材料により同形状(同じ厚み、同じ平面サイズ)に形成されている。また、第1配線基板5Aの第1配線層12Aと第2熱伝達金属層32Bとは、同一の金属材料により同形状に形成されている。また、第1配線基板5Aの第1熱伝達金属層31Aと第2配線基板5Bの第2配線層11Bとは、同一の金属材料により同形状に形成されている。このように、第1配線基板5Aと第2配線基板5Bとは、同じ構成の1種類の配線基板により構成されている。そして、このように構成される一組の配線基板5A,5Bの間に、P型熱電変換素子3とN型熱電変換素子4とが交互に直列に接続されることにより、熱電変換モジュール103が構成されている。 Also, the first wiring layer 11A of the first wiring board 5A and the second heat transfer metal layer 31B of the second wiring board 5B are formed in the same shape (same thickness, same plane size) from the same metal material. . In addition, the first wiring layer 12A and the second heat transfer metal layer 32B of the first wiring board 5A are formed in the same shape from the same metal material. Further, the first heat transfer metal layer 31A of the first wiring board 5A and the second wiring layer 11B of the second wiring board 5B are formed in the same shape from the same metal material. Thus, the first wiring board 5A and the second wiring board 5B are configured by one type of wiring board having the same configuration. The P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4 are alternately connected in series between the pair of wiring boards 5A and 5B configured as described above, so that the thermoelectric conversion module 103 is It is configured.
 次に、このように構成された熱電変換モジュール103の製造方法について説明する。第3実施形態の熱電変換モジュールの製造方法は、第1実施形態の熱電変換モジュールの製造方法のフローと同様のフローにより構成される。したがって、第3実施形態の熱電変換モジュールの製造方法についても、図2のフロー図を用いて説明を行う。また、第1配線基板5Aと第2配線基板5Bとは、同じ構成の1種類の配線基板により構成されることから、工程S11~S13では、第2配線基板5Bの製造工程の説明を省略し、第1配線基板5Aの製造工程についてのみ説明する。 Next, a method for manufacturing the thermoelectric conversion module 103 configured as described above will be described. The manufacturing method of the thermoelectric conversion module of 3rd Embodiment is comprised by the flow similar to the flow of the manufacturing method of the thermoelectric conversion module of 1st Embodiment. Therefore, the manufacturing method of the thermoelectric conversion module of the third embodiment will also be described using the flowchart of FIG. In addition, since the first wiring board 5A and the second wiring board 5B are configured by one type of wiring board having the same configuration, the description of the manufacturing process of the second wiring board 5B is omitted in steps S11 to S13. Only the manufacturing process of the first wiring board 5A will be described.
(スクライブライン形成工程)
 まず、図14A及び図14Bに示すように、第1セラミックス層21Aを構成する大型のセラミックス母材205に、複数のセラミックス層21Aを分割するためのスクライブライン202a,202bを形成し、セラミックス母材205に複数(16個)の第1セラミックス層形成領域203を区画する(スクライブライン形成工程S11)。図14Aは、第1配線層11A,12Aが形成されるセラミックス母材205の一方の面を表側に向けて配置したセラミックス母材205の平面図であり、図14Bは、第1熱伝達金属層31Aが形成されるセラミックス母材205の他方の面を表側に向けて配置したセラミックス母材205の平面図を表す。
(Scribe line forming process)
First, as shown in FIGS. 14A and 14B, scribe lines 202a and 202b for dividing the plurality of ceramic layers 21A are formed on a large ceramic base material 205 constituting the first ceramic layer 21A, and the ceramic base material is formed. A plurality (16) of first ceramic layer forming regions 203 are partitioned into 205 (scribe line forming step S11). FIG. 14A is a plan view of the ceramic base material 205 in which one surface of the ceramic base material 205 on which the first wiring layers 11A and 12A are formed faces the front side, and FIG. 14B shows the first heat transfer metal layer. The top view of the ceramic base material 205 which has arrange | positioned the other surface of the ceramic base material 205 in which 31A is formed facing the front side is represented.
 セラミックス母材205の一方の面には、図14Aに示すように、第1配線層11A,12Aの接合予定領域の間を通すようにして、第1配線層11A,12Aの接合予定領域を除く非接合部にスクライブライン202bを形成する。具体的には、セラミックス母材205の横方向に対向する辺同士を貫通する直線で形成された2本のスクライブライン202bを形成する。 As shown in FIG. 14A, one surface of the ceramic base material 205 is passed between the planned bonding regions of the first wiring layers 11A and 12A, and the bonding planned regions of the first wiring layers 11A and 12A are excluded. A scribe line 202b is formed at the non-joining portion. Specifically, two scribe lines 202b formed by straight lines penetrating the laterally opposed sides of the ceramic base material 205 are formed.
 一方、セラミックス母材205の他方の面には、図14Bに示すように、第1熱伝達金属層31Aの接合予定領域の間を通すようにして、第1熱伝達金属層31Aの接合予定領域を除く非接合部にスクライブライン202a,202bを形成する。具体的には、セラミックス母材205の縦方向に対向する辺同士を貫通する直線で形成された3本のスクライブライン202aと、セラミックス母材205の横方向に対向する辺同士を貫通する直線で形成された1本のスクライブライン202bを形成する。 On the other hand, as shown in FIG. 14B, the other surface of the ceramic base material 205 is passed between the region where the first heat transfer metal layer 31A is to be bonded, and the region where the first heat transfer metal layer 31A is to be bonded Scribe lines 202a and 202b are formed in the non-joining portions except for. Specifically, the three scribe lines 202 a formed by straight lines penetrating the sides facing the vertical direction of the ceramic base material 205 and the straight lines penetrating the sides facing the lateral direction of the ceramic base material 205. One formed scribe line 202b is formed.
 このように、セラミックス母材205の一方の面と他方の面とにスクライブライン202a,202bを形成することにより、セラミックス母材205の縦方向に等間隔で3本のスクライブライン202aを形成するとともに、横方向に等間隔で3本のスクライブライン202bを形成でき、スクライブライン202a,202bが縦横に3本ずつ格子状に形成される。これらの6本のスクライブライン202a,202bにより、セラミックス母材205には、第1セラミックス層21Aの外形形状の大きさに区画された16個の第1セラミックス層形成領域203が縦横に4個ずつ整列して形成される。 Thus, by forming the scribe lines 202a and 202b on one surface and the other surface of the ceramic base material 205, three scribe lines 202a are formed at equal intervals in the vertical direction of the ceramic base material 205. The three scribe lines 202b can be formed at equal intervals in the horizontal direction, and the scribe lines 202a and 202b are formed in a lattice shape by three vertically and horizontally. By these six scribe lines 202a and 202b, the ceramic base material 205 has 16 first ceramic layer formation regions 203 divided vertically and horizontally in the size of the outer shape of the first ceramic layer 21A. Aligned and formed.
 なお、スクライブライン202a,202bは、第1配線層11A,12Aの非接合部及び第1熱伝達金属層31Aの非接合部に形成するだけでなく、第1配線層11Aの接合部及び第1熱伝達金属層31Aの接合部にも形成して、セラミックス母材205の両面に形成することもできる。 Note that the scribe lines 202a and 202b are not only formed in the non-joined portion of the first wiring layers 11A and 12A and the non-joined portion of the first heat transfer metal layer 31A, but also in the joint portion and the first of the first wiring layer 11A. It can also be formed on both surfaces of the ceramic base material 205 by forming it at the joint portion of the heat transfer metal layer 31A.
(金属層形成工程)
 スクライブライン形成工程S11後に、図15Aに示すように、セラミックス母材205の一方の面に第1配線層11A,12Aを形成し、図15Bに示すように、セラミックス母材205の他方の面に第1熱伝達金属層31Aを形成し、セラミックス母材205の両面に第1配線層11A,12Aと第1熱伝達金属層31Aとが接合された積層体206を形成する(金属層形成工程S12)。
(Metal layer forming process)
After the scribe line forming step S11, the first wiring layers 11A and 12A are formed on one surface of the ceramic base material 205 as shown in FIG. 15A, and the other surface of the ceramic base material 205 is shown in FIG. 15B. The first heat transfer metal layer 31A is formed, and a laminate 206 is formed in which the first wiring layers 11A and 12A and the first heat transfer metal layer 31A are bonded to both surfaces of the ceramic base material 205 (metal layer forming step S12). ).
 詳細な説明は省略するが、セラミックス母材205の一方の面に第1配線層11A,12Aとなる金属板を接合するとともに、セラミックス母材205の他方の面に第1熱伝達金属層31Aとなる金属板を接合した後、エッチング処理を施すことにより、セラミックス母材205の一方の面に第1配線層11A,12Aをパターンニングするとともに、セラミックス母材205の他方の面に第1熱伝達金属層31Aをパターンニングする。この際、スクライブライン202a,202bは、第1配線層11A,11Bの接合予定領域を除く非接合部と第1熱伝達金属層31Aの接合予定領域を除く非接合部に形成しているので、スクライブライン202a,202b上に重なって形成された金属層部分(金属板)が除去されることで、スクライブライン202a,202bの全体を露出させることができる。 Although a detailed description is omitted, a metal plate to be the first wiring layers 11A and 12A is bonded to one surface of the ceramic base material 205, and the first heat transfer metal layer 31A and the other surface of the ceramic base material 205 are connected to each other. After joining the metal plates, the first wiring layers 11A and 12A are patterned on one surface of the ceramic base material 205 by performing an etching process, and the first heat transfer is performed on the other surface of the ceramic base material 205. The metal layer 31A is patterned. At this time, since the scribe lines 202a and 202b are formed in the non-joined portion except the planned joining region of the first wiring layers 11A and 11B and the non-joined portion except the planned joining region of the first heat transfer metal layer 31A, By removing the metal layer portion (metal plate) formed over the scribe lines 202a and 202b, the entire scribe lines 202a and 202b can be exposed.
 なお、第1配線層11A,12A及び第1熱伝達金属層31Aは、予めパターニングされた金属板をセラミックス母材205に接合することにより、エッチング処理を施すことなく形成することもできる。また、第1配線層11A,12Aは、銀(Ag)の焼結体により構成することもできる。 The first wiring layers 11A and 12A and the first heat transfer metal layer 31A can be formed without performing an etching process by bonding a previously patterned metal plate to the ceramic base material 205. The first wiring layers 11A and 12A can also be formed of a sintered body of silver (Ag).
(分割工程)
 金属層形成工程S12後に、スクライブライン202a,202bが形成された面側に凸となるようにセラミックス母材205を曲げることで、積層体206のセラミックス母材205をスクライブライン202a,202bに沿って分割し、第1セラミックス層形成領域203を個々の第1セラミックス層21Aに個片化する。これにより、第1配線層11A,12Aと、第1セラミックス層21Aと、第1熱伝達金属層31Aとが接合された第1配線基板5Aを形成する(分割工程S13)。
(Division process)
After the metal layer forming step S12, the ceramic base material 205 is bent along the scribe lines 202a and 202b by bending the ceramic base material 205 so as to protrude toward the surface on which the scribe lines 202a and 202b are formed. The first ceramic layer forming region 203 is divided into individual first ceramic layers 21A. Thus, the first wiring substrate 5A in which the first wiring layers 11A and 12A, the first ceramic layer 21A, and the first heat transfer metal layer 31A are joined is formed (division step S13).
 スクライブライン202a,202bは、第1配線層11A又は第1熱伝達金属層31Aの接合面の反対側に形成されているので、セラミックス母材205をスクライブライン202a,202bに沿って容易に分割できる。また、スクライブライン202a,202bは、セラミックス母材205の対向する辺同士を貫通する単純な直線で形成されていることから、セラミックス母材205をスクライブライン202a,202bに沿って円滑に分割できる。なお、第2配線基板5Bは、第1配線基板5Aと同様の工程により製造される。 Since the scribe lines 202a and 202b are formed on the opposite side of the bonding surface of the first wiring layer 11A or the first heat transfer metal layer 31A, the ceramic base material 205 can be easily divided along the scribe lines 202a and 202b. . Further, since the scribe lines 202a and 202b are formed by simple straight lines that pass through the opposing sides of the ceramic base material 205, the ceramic base material 205 can be smoothly divided along the scribe lines 202a and 202b. The second wiring board 5B is manufactured by the same process as the first wiring board 5A.
 このようにして形成される第1配線基板5Aは、複数の第1配線層11A,12Aを有しているが、第1熱伝達金属層31Aにより各第1配線層11A,11A又は11A,12Aの間が連結された状態となる。また、個片化された第1セラミックス層21Aが、第1配線層11A又は第1熱伝達金属層31Aにより連結されているので、第1配線基板5Aでは、第1配線層11A,12A、第1セラミックス層21A、第1熱伝達金属層31Aを一体に取り扱うことができる。また、第1配線基板5Aと同様に構成される第2配線基板5Bも、第2配線層11B、第2セラミックス層21B,第2熱伝達金属層31B,32Bを一体に取り扱うことができる。 The first wiring board 5A formed in this way has a plurality of first wiring layers 11A and 12A, and the first wiring layers 11A and 11A or 11A and 12A are formed by the first heat transfer metal layer 31A. Are connected to each other. Moreover, since the separated first ceramic layer 21A is connected by the first wiring layer 11A or the first heat transfer metal layer 31A, in the first wiring board 5A, the first wiring layers 11A, 12A, One ceramic layer 21A and the first heat transfer metal layer 31A can be handled integrally. The second wiring board 5B configured similarly to the first wiring board 5A can also handle the second wiring layer 11B, the second ceramic layer 21B, and the second heat transfer metal layers 31B and 32B integrally.
(接合工程)
 次に、一方の第1配線基板5Aの第1配線層11Aに、P型熱電変換素子3の一方の端面とN型熱電変換素子4の一方の端面とを接合するとともに、他方の第2配線基板5Bの第2配線層11BにP型熱電変換素子3の他方の端面とN型熱電変換素子4の他方の端面とを接合する(接合工程S14)。これにより、図9に示すように、両配線基板5A,5Bの間に、P型熱電変換素子3とN型熱電変換素子4とが交互に直列に接続された熱電変換モジュール103を製造する。
(Joining process)
Next, one end face of the P-type thermoelectric conversion element 3 and one end face of the N-type thermoelectric conversion element 4 are joined to the first wiring layer 11A of one first wiring board 5A, and the other second wiring is connected. The other end face of the P-type thermoelectric conversion element 3 and the other end face of the N-type thermoelectric conversion element 4 are joined to the second wiring layer 11B of the substrate 5B (joining step S14). As a result, as shown in FIG. 9, a thermoelectric conversion module 103 in which P-type thermoelectric conversion elements 3 and N-type thermoelectric conversion elements 4 are alternately connected in series between the wiring boards 5A and 5B is manufactured.
 具体的には、各配線層11A,11Bと、P型熱電変換素子3及びN型熱電変換素子4との接合は、ペーストやろう材を用いた接合、荷重印加による固相拡散接合等により接合する。そして、図5~図7に示した第1実施形態の熱電変換モジュール101と同様に、一組の加圧板401A,401Bの間で、各熱電変換素子3,4と第1配線層11A,11Bとを密着させて均一に加圧して行う。 Specifically, each of the wiring layers 11A and 11B and the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are bonded by bonding using a paste or brazing material, solid phase diffusion bonding by applying a load, or the like. To do. Similarly to the thermoelectric conversion module 101 of the first embodiment shown in FIGS. 5 to 7, the thermoelectric conversion elements 3 and 4 and the first wiring layers 11A and 11B are interposed between the pair of pressure plates 401A and 401B. And pressurizing uniformly.
 図示は省略するが、この接合工程S14では、第1実施形態と同様に補完部材を用いたり、偶数個の挟持体を積層方向に重ねて配置して行うことができる。これにより、第1配線層11A,11Bと、P型熱電変換素子3及びN型熱電変換素子4との接合時において、各熱電変換素子3,4と第1配線層11A,11Bとを密着させてそれぞれ均一に加圧できる。また、偶数個の挟持体を積層方向に重ねて配置する場合には、各挟持体の間にクッション性を有するグラファイトシートを配設しておくことで、両配線基板5A,5Bの面方向の各熱電変換素子3,4の配置箇所において、それぞれの傾きを補正でき、各熱電変換素子3,4と両配線基板5A,5Bとをより均一に加圧できる。 Although illustration is omitted, in this joining step S14, a complementary member can be used as in the first embodiment, or an even number of sandwiched bodies can be stacked in the stacking direction. Thereby, at the time of joining the first wiring layers 11A, 11B and the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, the thermoelectric conversion elements 3, 4 and the first wiring layers 11A, 11B are brought into close contact with each other. Can be pressurized uniformly. Further, when an even number of sandwiching bodies are arranged in the stacking direction, a graphite sheet having a cushioning property is disposed between the sandwiching bodies, so that both wiring boards 5A and 5B can be arranged in the plane direction. The respective inclinations of the thermoelectric conversion elements 3 and 4 can be corrected, and the thermoelectric conversion elements 3 and 4 and the wiring boards 5A and 5B can be more uniformly pressurized.
 なお、前述したように、第1配線基板5Aは、複数の第1配線層11A,12Aを有しているが、各第1配線層11A,12Aの間が第1熱伝達金属層31Aにより連結されているので、各第1配線層11A,12Aを一体に取り扱うことができ、第1配線基板5Aを容易に取り扱うことができる。同様に、第2配線基板5Bは、複数の第2配線層11Bを有しているが、各第2配線層11Bの間が第2熱伝達金属層31Bにより連結されているので、各第2配線層11Bを一体に取り扱うことができ、第2配線基板5Bを容易に取り扱うことができる。 As described above, the first wiring board 5A has a plurality of first wiring layers 11A and 12A, but the first wiring layers 11A and 12A are connected by the first heat transfer metal layer 31A. Therefore, the first wiring layers 11A and 12A can be handled integrally, and the first wiring board 5A can be easily handled. Similarly, the second wiring board 5B has a plurality of second wiring layers 11B. Since the second wiring layers 11B are connected by the second heat transfer metal layer 31B, each second wiring layer 11B is connected to each second wiring layer 11B. The wiring layer 11B can be handled integrally, and the second wiring board 5B can be easily handled.
 また、第3実施形態の製造方法のように、大型のセラミックス母材205に第1配線層11A,12Aと第1熱伝達金属層31Aとを形成した後に、セラミックス母材205をスクライブライン202a,202bに沿って分割することで、容易に所定のパターンに配列された第1配線層11A,12Aと個片化された第1セラミックス層21Aとを有する第1配線基板5Aを形成できる。そして、この第1配線基板5Aを用いることにより、熱電変換素子3,4が多数接合(搭載)される大型の熱電変換モジュール103を容易に製造できる。 Further, as in the manufacturing method of the third embodiment, after forming the first wiring layers 11A and 12A and the first heat transfer metal layer 31A on the large ceramic base material 205, the ceramic base material 205 is attached to the scribe line 202a, By dividing along 202b, the first wiring substrate 5A having the first wiring layers 11A, 12A and the separated first ceramic layers 21A arranged in a predetermined pattern can be easily formed. By using this first wiring board 5A, a large thermoelectric conversion module 103 to which a large number of thermoelectric conversion elements 3 and 4 are joined (mounted) can be easily manufactured.
 また、このようにして製造される第3実施形態の熱電変換モジュール103においても、第1配線基板5Aを構成する各第1セラミックス層21Aが熱電変換素子3,4毎に独立して形成されており、剛体の第1セラミックス層21AにおけるP型熱電変換素子3とN型熱電変換素子4との間の接続が分断されている。第1配線基板5Aと対向配置される第2配線基板5Bについても、各第2セラミックス層21Bが熱電変換素子3,4毎に独立して形成されており、剛体の第2セラミックス層21BにおけるP型熱電変換素子3とN型熱電変換素子4との間の接続が分断されている。このため、各熱電変換素子3,4は、各セラミックス層21A,21Bによって熱伸縮に伴う変形が拘束されることがない。 Also in the thermoelectric conversion module 103 of the third embodiment manufactured in this way, each first ceramic layer 21A constituting the first wiring board 5A is formed independently for each thermoelectric conversion element 3, 4. Thus, the connection between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the rigid first ceramic layer 21A is disconnected. Also for the second wiring board 5B disposed opposite to the first wiring board 5A, each second ceramic layer 21B is formed independently for each of the thermoelectric conversion elements 3 and 4, and P in the rigid second ceramic layer 21B is formed. The connection between the type thermoelectric conversion element 3 and the N type thermoelectric conversion element 4 is disconnected. For this reason, the thermoelectric conversion elements 3 and 4 are not restrained from being deformed by the thermal expansion and contraction by the ceramic layers 21A and 21B.
 また、各第1セラミックス層21Aの間は第1配線層11A又は第1熱伝達金属層31Aのいずれかにより連結されているのみであり、各第2セラミックス層21Bの間は第2配線層11B又は第2熱伝達金属層31Bのいずれかにより連結されているのみである。これにより、隣り合うP型熱電変換素子3とN型熱電変換素子4との熱伸縮差は、両熱電変換素子3,4の間を接続する第1配線層11A又は第1熱伝達金属層31Aの接続部分、第2配線層11B又は第2熱伝達金属層31Bの接続部分が変形して寸法変化を吸収することができる。このため、熱伸縮差により熱電変換素子3,4内に生じる熱応力の発生を抑制できる。そして、各熱電変換素子3,4の熱伸縮差により、熱電変換素子3,4が配線基板5A,5B(第1配線層11A,12A、第2配線層11B)から剥がれたり、熱電変換素子3,4にクラックが生じたりすることを防止できる。したがって、第1配線層11A,12Aと第2配線層11Bとにより接続される熱電変換素子3,4間の電気的な接続を良好に維持でき、熱電変換モジュール103の接合信頼性、熱伝導性及び導電性を良好に維持できる。 Further, the first ceramic layers 21A are only connected by either the first wiring layer 11A or the first heat transfer metal layer 31A, and the second wiring layers 11B are connected between the second ceramic layers 21B. Alternatively, they are only connected by any one of the second heat transfer metal layers 31B. Thereby, the thermal expansion / contraction difference between the adjacent P-type thermoelectric conversion element 3 and N-type thermoelectric conversion element 4 is the first wiring layer 11A or the first heat transfer metal layer 31A connecting the two thermoelectric conversion elements 3 and 4. The connection portion of the second wiring layer 11B or the second heat transfer metal layer 31B is deformed to absorb the dimensional change. For this reason, generation | occurrence | production of the thermal stress which arises in the thermoelectric conversion elements 3 and 4 by a thermal expansion-contraction difference can be suppressed. The thermoelectric conversion elements 3 and 4 are peeled off from the wiring boards 5A and 5B (the first wiring layers 11A and 12A and the second wiring layer 11B) due to the difference in thermal expansion and contraction between the thermoelectric conversion elements 3 and 4. , 4 can be prevented from cracking. Therefore, the electrical connection between the thermoelectric conversion elements 3 and 4 connected by the first wiring layers 11A and 12A and the second wiring layer 11B can be satisfactorily maintained, and the junction reliability and thermal conductivity of the thermoelectric conversion module 103 can be maintained. In addition, the conductivity can be maintained well.
 また、各配線基板5A,5Bには、絶縁基板であるセラミックス層21A又は21Bが設けられているので、熱電変換モジュール103を熱源等に設置したときに、セラミックス層21A又は21Bにより熱源等と配線層11A,12A又は11Bとが接触することを防止できる。したがって、熱源等と配線層11A,12A又は11Bとの電気的なリークを確実に回避でき、絶縁状態を良好に維持できる。 In addition, since each of the wiring boards 5A and 5B is provided with the ceramic layer 21A or 21B which is an insulating substrate, when the thermoelectric conversion module 103 is installed in a heat source or the like, the ceramic layer 21A or 21B can be connected to the heat source or the like. Contact with the layer 11A, 12A or 11B can be prevented. Therefore, electrical leakage between the heat source and the wiring layer 11A, 12A, or 11B can be reliably avoided, and the insulation state can be maintained satisfactorily.
 また、配線基板5A,5Bには、熱伝達金属層31A又は31B,32Bが設けられているので、熱電変換モジュール103を熱源等に設置したときに、熱伝達金属層31A,31B,32Bにより熱源等と熱電変換モジュール103との密着性を高めることができ、熱伝達性を向上できる。したがって、熱電変換モジュール103の熱電交換性能(発電効率)を向上させることができる。 Further, since the heat transfer metal layers 31A or 31B, 32B are provided on the wiring boards 5A, 5B, when the thermoelectric conversion module 103 is installed in a heat source or the like, the heat transfer metal layers 31A, 31B, 32B Etc. and the thermoelectric conversion module 103 can be improved in adhesion, and heat transfer can be improved. Therefore, the thermoelectric exchange performance (power generation efficiency) of the thermoelectric conversion module 103 can be improved.
 上記実施形態の熱電変換モジュール101,102,103では、第1配線基板2A,5Aと第2配線基板2B,5Bを、個々の熱電変換素子3,4毎に独立して形成された複数の第1セラミックス層21A又は第2セラミックス層21Bを有する構成としたが、図16A~図18Bに示す第1配線基板6A~6Cのように、複数個の熱電変換素子3,4毎に分離され、いずれかのP型熱電変換素子3とN型熱電変換素子4との間で分離された第1セラミックス層22A~22Cを有する構成としてもよい。 In the thermoelectric conversion modules 101, 102, and 103 of the above embodiment, the first wiring boards 2A and 5A and the second wiring boards 2B and 5B are formed by a plurality of first thermoelectric conversion elements 3 and 4 formed independently of each other. Although the first ceramic layer 21A or the second ceramic layer 21B is provided, it is separated into a plurality of thermoelectric conversion elements 3 and 4 as in the first wiring boards 6A to 6C shown in FIGS. 16A to 18B. The first ceramic layers 22A to 22C separated between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 may be used.
 例えば、図16A及び図16Bに示す第1配線基板6Aは、第2実施形態の熱電変換モジュール103の第1配線基板5Aと同様の第1配線層11A,12Aと第1熱伝達金属層31Aとからなるパターンを有している。しかし、第1セラミックス層22Aは隣り合う一組(2個)の熱電変換素子3,4毎に分離され、合計8個の第1セラミックス層22Aにより構成される。そして、図16Aに示すように、各第1セラミックス層22A,22Aの間は、第1配線層11Aにより連結されており、第1配線基板6Aを構成する複数の第1セラミックス層22Aが一体に設けられている。また、第1配線基板6Aの第1配線層11Aは、一組のP型熱電変換素子3とN型熱電変換素子4との間を接続して形成され、かつ、両熱電変換素子3,4の第1セラミックス層22A,22Aどうしの間に跨って形成されている。 For example, the first wiring board 6A shown in FIGS. 16A and 16B includes the first wiring layers 11A and 12A and the first heat transfer metal layer 31A similar to the first wiring board 5A of the thermoelectric conversion module 103 of the second embodiment. It has the pattern which consists of. However, the first ceramic layer 22A is separated for each pair of adjacent (two) thermoelectric conversion elements 3 and 4, and is constituted by a total of eight first ceramic layers 22A. As shown in FIG. 16A, the first ceramic layers 22A and 22A are connected by the first wiring layer 11A, and a plurality of first ceramic layers 22A constituting the first wiring board 6A are integrally formed. Is provided. The first wiring layer 11A of the first wiring board 6A is formed by connecting between a pair of the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, and both the thermoelectric conversion elements 3 and 4 are connected. Formed between the first ceramic layers 22A and 22A.
 このように構成される第1配線基板6Aを用いた熱電変換モジュールにおいても、剛体の第1セラミックス層22Aは、いずれかのP型熱電変換素子3とN型熱電変換素子4との間で分断され、複数設けられている。このため、これらのP型熱電変換素子3とN型熱電変換素子4との間では、互いに相手側に接合された第1セラミックス層22Aにより、P型熱電変換素子3とN型熱電変換素子4との熱伸縮に伴う変形が拘束されることがない。また、各第1セラミックス層22Aの分離部分におけるP型熱電変換素子3とN型熱電変換素子4との熱伸縮差は、両熱電変換素子3,4の間を接続する第1配線層11Aの接続部分が変形して寸法変化を吸収できる。したがって、各熱電変換素子3,4の熱伸縮差により各熱電変換素子3,4内に生じる熱応力の発生を抑制できる。 Also in the thermoelectric conversion module using the first wiring board 6A configured as described above, the rigid first ceramic layer 22A is divided between any of the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4. A plurality of them are provided. For this reason, between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4, the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 are formed by the first ceramic layer 22A bonded to each other. The deformation accompanying the thermal expansion and contraction is not restricted. Further, the difference in thermal expansion and contraction between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the separation portion of each first ceramic layer 22A is that of the first wiring layer 11A connecting the two thermoelectric conversion elements 3 and 4. The connecting portion can be deformed to absorb the dimensional change. Therefore, it is possible to suppress the generation of thermal stress generated in each thermoelectric conversion element 3, 4 due to the thermal expansion / contraction difference of each thermoelectric conversion element 3, 4.
 なお、第1セラミックス層の個数は、図16A及び図16Bに示す第1配線基板6Aよりも、さらに少なくすることができる。例えば、図17A及び図17Bに示す第1配線基板6Bの第1セラミックス層22Bは、4個の熱電変換素子3,4毎に分離され、合計4個の第1セラミックス層22Bにより構成される。また、図18A及び図18Bに示す第1配線基板6Cの第1セラミックス層22Cは、8個の熱電変換素子3,4毎に分離され、合計2個の第1セラミックス層22Cにより構成される。 Note that the number of first ceramic layers can be further reduced as compared with the first wiring board 6A shown in FIGS. 16A and 16B. For example, the first ceramic layer 22B of the first wiring board 6B shown in FIGS. 17A and 17B is separated into four thermoelectric conversion elements 3 and 4, and is constituted by a total of four first ceramic layers 22B. Further, the first ceramic layer 22C of the first wiring board 6C shown in FIGS. 18A and 18B is separated into eight thermoelectric conversion elements 3 and 4, and is constituted by a total of two first ceramic layers 22C.
 このように、複数設けられる第1セラミックス層22B,22Cを、いずれかのP型熱電変換素子3とN型熱電変換素子4との間で分断して設けることで、これらのP型熱電変換素子3とN型熱電変換素子4との間では、互いに相手側に接合された第1セラミックス層22B,22Cにより、P型熱電変換素子3とN型熱電変換素子4との熱伸縮に伴う変形が拘束されることがない。また、各第1セラミックス層22B,22Cの分離部分におけるP型熱電変換素子3とN型熱電変換素子4との熱伸縮差は、両熱電変換素子3,4の間を接続する第1配線層11Aの接続部分が変形して寸法変化を吸収できる。したがって、各熱電変換素子3,4の熱伸縮差により各熱電変換素子3,4内に生じる熱応力の発生を抑制できる。 Thus, by providing the first ceramic layers 22B and 22C that are provided in a divided manner between any of the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4, these P-type thermoelectric conversion elements are provided. 3 and the N-type thermoelectric conversion element 4, the first ceramic layers 22 </ b> B and 22 </ b> C bonded to each other cause deformation due to thermal expansion and contraction between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4. There is no restraint. Further, the difference in thermal expansion and contraction between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the separated portions of the first ceramic layers 22B and 22C is the first wiring layer that connects the thermoelectric conversion elements 3 and 4 together. The connecting portion of 11A can be deformed to absorb the dimensional change. Therefore, it is possible to suppress the generation of thermal stress generated in each thermoelectric conversion element 3, 4 due to the thermal expansion / contraction difference of each thermoelectric conversion element 3, 4.
 そして、このように複数の第1配線層11Aを有する大型の第1配線基板6A~6Cを用いた熱電変換モジュールにおいても、各熱電変換素子3,4の熱伸縮差により各熱電変換素子3,4内に生じる熱応力の発生を抑制できる。このため、各熱電変換素子3,4が第1配線基板6A~6C(第1配線層11A)から剥がれたり、各熱電変換素子3,4にクラックが生じたりすることを防止できる。したがって、第1配線層11Aにより接続される両熱電変換素子3,4間の電気的な接続を良好に維持でき、熱電変換モジュールの接合信頼性、熱伝導性及び導電性を良好に維持できる。 In the thermoelectric conversion module using the large first wiring boards 6A to 6C having the plurality of first wiring layers 11A as described above, the thermoelectric conversion elements 3 and 3 are caused by the thermal expansion / contraction difference of the thermoelectric conversion elements 3 and 4. The generation of thermal stress generated in 4 can be suppressed. Therefore, it is possible to prevent the thermoelectric conversion elements 3 and 4 from being peeled off from the first wiring boards 6A to 6C (first wiring layer 11A) and the thermoelectric conversion elements 3 and 4 from being cracked. Therefore, the electrical connection between the thermoelectric conversion elements 3 and 4 connected by the first wiring layer 11A can be maintained satisfactorily, and the junction reliability, thermal conductivity, and conductivity of the thermoelectric conversion module can be maintained satisfactorily.
 なお、上記実施形態の第1配線基板2A,5A,6A~6Cにおいては、それぞれ複数のパターンに分離された第1熱伝達金属層31A,32Aを有する構成としていたが、図19A及び図19Bに示す第1配線基板7Aのように、第1熱伝達金属層31Cを、3個以上の第1セラミックス層22Aを連結する大型に構成することもできる。この場合、各第1セラミックス層22Aを第1熱伝達金属層31Cにより連結できるので、第1配線層11Aにより各第1セラミックス層22Aを連結することなく、第1配線基板7Aを一体化して構成できる。 Note that the first wiring boards 2A, 5A, 6A to 6C of the above embodiment have the first heat transfer metal layers 31A and 32A separated into a plurality of patterns, respectively, but in FIGS. 19A and 19B, As shown in the first wiring board 7A, the first heat transfer metal layer 31C can be configured to have a large size connecting three or more first ceramic layers 22A. In this case, since each first ceramic layer 22A can be connected by the first heat transfer metal layer 31C, the first wiring board 7A is integrated and configured without connecting each first ceramic layer 22A by the first wiring layer 11A. it can.
 図19A及び図19Bに示す第1配線基板7Aを用いた熱電変換モジュールにおいても、複数設けられる第1セラミックス層22Aを、いずれかのP型熱電変換素子3とN型熱電変換素子4との間で分断して設けることで、これらのP型熱電変換素子3とN型熱電変換素子4との間では、互いに相手側に接合された第1セラミックス層22Aより、P型熱電変換素子3とN型熱電変換素子4との熱伸縮に伴う変形が拘束されることがない。また、各第1セラミックス層22Aの分離部分におけるP型熱電変換素子3とN型熱電変換素子4との熱伸縮差は、両熱電変換素子3,4の間を接続する第1熱伝達金属層31Cの接続部分が変形して寸法変化を吸収できる。したがって、各熱電変換素子3,4の熱伸縮差により各熱電変換素子3,4内に生じる熱応力の発生を抑制できる。 Also in the thermoelectric conversion module using the first wiring board 7A shown in FIG. 19A and FIG. 19B, a plurality of first ceramic layers 22A are provided between any one of the P-type thermoelectric conversion elements 3 and the N-type thermoelectric conversion elements 4. By separating the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 from the first ceramic layer 22A bonded to each other, the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 3 are separated from each other. The deformation accompanying thermal expansion and contraction with the mold thermoelectric conversion element 4 is not restricted. Further, the difference in thermal expansion and contraction between the P-type thermoelectric conversion element 3 and the N-type thermoelectric conversion element 4 in the separated portion of each first ceramic layer 22A is the first heat transfer metal layer that connects the two thermoelectric conversion elements 3 and 4 together. The connecting portion of 31C can be deformed to absorb the dimensional change. Therefore, it is possible to suppress the generation of thermal stress generated in each thermoelectric conversion element 3, 4 due to the thermal expansion / contraction difference of each thermoelectric conversion element 3, 4.
 なお、上述した実施形態において、第2配線層、第2セラミックス層及び第2熱伝達金属層は、それぞれ第1配線層、第1セラミックス層及び第2熱伝達金属層と同様の構成とすることができる。 In the above-described embodiment, the second wiring layer, the second ceramic layer, and the second heat transfer metal layer have the same configuration as the first wiring layer, the first ceramic layer, and the second heat transfer metal layer, respectively. Can do.
 なお、本発明は上記実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。 Note that the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.
 熱電変換素子の熱伸縮差による破壊を防止でき、接合信頼性、熱伝導性及び導電性に優れた熱電変換モジュールを提供できる。 It is possible to provide a thermoelectric conversion module that can prevent the thermoelectric conversion element from being damaged due to a difference in thermal expansion and contraction and is excellent in bonding reliability, thermal conductivity, and conductivity.
2A,5A,6A,6B,6C,7A 第1配線基板
2B,5B 第2配線基板
3 P型熱電変換素子(熱電変換素子)
4 N型熱電変換素子(熱電変換素子)
11A,12A 第1配線層
11B,12B 第2配線層
21A,22A,22B,22C 第1セラミックス層
21B 第2セラミックス層
31A,32A,31C 第1熱伝達金属層
31B,32B 第2熱伝達金属層
41 メタライズ層
91 配線
201,205 セラミックス母材
202,202a,202b スクライブライン
203 第1セラミックス層形成領域
204,206 積層体
301,302 金属板
401A,401B 加圧板
405 挟持体
411,412,413 補完部材
420 グラファイトシート
101,102,103 熱電変換モジュール
2A, 5A, 6A, 6B, 6C, 7A First wiring board 2B, 5B Second wiring board 3 P-type thermoelectric conversion element (thermoelectric conversion element)
4 N-type thermoelectric conversion element (thermoelectric conversion element)
11A, 12A First wiring layer 11B, 12B Second wiring layer 21A, 22A, 22B, 22C First ceramic layer 21B Second ceramic layer 31A, 32A, 31C First heat transfer metal layer 31B, 32B Second heat transfer metal layer 41 Metallized layer 91 Wiring 201, 205 Ceramic base material 202, 202a, 202b Scribe line 203 First ceramic layer forming region 204, 206 Laminated body 301, 302 Metal plate 401A, 401B Pressure plate 405 Holding body 411, 412, 413 Complementary member 420 Graphite Sheet 101, 102, 103 Thermoelectric Conversion Module

Claims (13)

  1.  線膨張係数の異なるP型熱電変換素子とN型熱電変換素子からなる複数の熱電変換素子と、
     複数の前記熱電変換素子の一端側に配設された第1配線基板と、を有し、
     前記第1配線基板は、隣り合う前記P型熱電変換素子と前記N型熱電変換素子とが接合された第1配線層と、該第1配線層の前記P型熱電変換素子と前記N型熱電変換素子との接合面とは反対面に接合され複数に分離された第1セラミックス層と、を有しており、
     各第1セラミックス層がいずれかの前記P型熱電変換素子と前記N型熱電変換素子との間で分離されていることを特徴とする熱電変換モジュール。
    A plurality of thermoelectric conversion elements composed of P-type thermoelectric conversion elements and N-type thermoelectric conversion elements having different linear expansion coefficients;
    A first wiring board disposed on one end side of the plurality of thermoelectric conversion elements,
    The first wiring board includes a first wiring layer in which the adjacent P-type thermoelectric conversion element and the N-type thermoelectric conversion element are joined, and the P-type thermoelectric conversion element and the N-type thermoelectric element of the first wiring layer. A first ceramic layer bonded to a surface opposite to the bonding surface with the conversion element and separated into a plurality of layers,
    Each first ceramic layer is separated between any one of the P-type thermoelectric conversion elements and the N-type thermoelectric conversion elements.
  2.  前記第1配線層が、前記第1セラミックス層どうしの間に跨って形成されていることを特徴とする請求項1に記載の熱電変換モジュール。 The thermoelectric conversion module according to claim 1, wherein the first wiring layer is formed between the first ceramic layers.
  3.  前記第1セラミックス層が、前記熱電変換素子毎に独立して形成されていることを特徴とする請求項1に記載の熱電変換モジュール。 The thermoelectric conversion module according to claim 1, wherein the first ceramic layer is formed independently for each thermoelectric conversion element.
  4.  前記第1配線基板は、複数の前記第1配線層と、前記第1セラミックス層の前記第1配線層との接合面とは反対面に接合された第1熱伝達金属層と、を有しており、
     前記第1熱伝達金属層が、隣り合う両第1配線層の間に跨って形成され、かつ、隣り合う両第1セラミックス層の間に跨って形成されていることを特徴とする請求項1に記載の熱電変換モジュール。
    The first wiring board includes a plurality of first wiring layers and a first heat transfer metal layer bonded to a surface opposite to a bonding surface of the first ceramic layer to the first wiring layer. And
    2. The first heat transfer metal layer is formed between two adjacent first wiring layers, and is formed between both adjacent first ceramic layers. The thermoelectric conversion module described in 1.
  5.  前記熱電変換素子の他端側に配設された第2配線基板を有し、
     対向配置される前記第1配線基板と前記第2配線基板とを介して前記P型熱電変換素子と前記N型熱電変換素子とが電気的に直列に接続されていることを特徴とする請求項1に記載の熱電変換モジュール。
    A second wiring board disposed on the other end side of the thermoelectric conversion element;
    The P-type thermoelectric conversion element and the N-type thermoelectric conversion element are electrically connected in series via the first wiring board and the second wiring board that are arranged to face each other. The thermoelectric conversion module according to 1.
  6.  前記第2配線基板は、隣り合う前記P型熱電変換素子と前記N型熱電変換素子とが接合された第2配線層と、該第2配線層の前記P型熱電変換素子と前記N型熱電変換素子との接合面とは反対面に接合され複数に分離された第2セラミックス層と、を有しており、
     各第2セラミックス層がいずれかの前記P型熱電変換素子と前記N型熱電変換素子との間で分離されていることを特徴とする請求項5に記載の熱電変換モジュール。
    The second wiring board includes a second wiring layer in which the adjacent P-type thermoelectric conversion element and the N-type thermoelectric conversion element are joined, and the P-type thermoelectric conversion element and the N-type thermoelectric element of the second wiring layer. A second ceramic layer bonded to the surface opposite to the bonding surface with the conversion element and separated into a plurality of layers,
    6. The thermoelectric conversion module according to claim 5, wherein each second ceramic layer is separated between any one of the P-type thermoelectric conversion elements and the N-type thermoelectric conversion elements.
  7.  セラミックス母材から複数の第1セラミックス層を分割するためのスクライブラインを該セラミックス母材に形成するスクライブライン形成工程と、
     前記スクライブライン形成工程後に、前記セラミックス母材の一方の面に、前記スクライブラインにより区画された複数の第1セラミックス層形成領域のうちの隣接する両第1セラミックス層形成領域に跨る第1配線層を形成する金属層形成工程と、
     前記金属層形成工程後に、前記第1配線層が形成された前記セラミックス母材を前記スクライブラインに沿って分割し、前記第1配線層と前記第1セラミックス層とが接合された第1配線基板を形成する分割工程と、
     前記分割工程後に、前記第1配線層の各第1セラミックス層との接合面とは反対面に線膨張係数の異なるP型熱電変換素子とN型熱電変換素子とを接合し、前記P型熱電変換素子と前記N型熱電変換素子とが直列に接続された熱電変換モジュールを製造する接合工程と、
     を有することを特徴とする熱電変換モジュールの製造方法。
    A scribe line forming step of forming, on the ceramic base material, a scribe line for dividing the plurality of first ceramic layers from the ceramic base material;
    After the scribe line forming step, a first wiring layer straddling both adjacent first ceramic layer forming regions among the plurality of first ceramic layer forming regions partitioned by the scribe line on one surface of the ceramic base material. Forming a metal layer,
    After the metal layer forming step, the ceramic base material on which the first wiring layer is formed is divided along the scribe line, and the first wiring layer and the first ceramic layer are joined together. Dividing step to form,
    After the dividing step, a P-type thermoelectric conversion element and an N-type thermoelectric conversion element having different linear expansion coefficients are bonded to the surface of the first wiring layer opposite to the bonding surface with each first ceramic layer, and the P-type thermoelectric A joining step for manufacturing a thermoelectric conversion module in which a conversion element and the N-type thermoelectric conversion element are connected in series;
    The manufacturing method of the thermoelectric conversion module characterized by having.
  8.  前記接合工程は、対向配置される一組の加圧板の間に、前記第1配線基板の前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子とをそれぞれ重ねた挟持体を配置しておき、該挟持体をその積層方向に加圧した状態で加熱することにより、前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子とをそれぞれ接合する工程とされ、
     前記接合工程において、
     前記P型熱電変換素子と前記N型熱電変換素子とのうち少なくとも線膨張係数が小さい一方の熱電変換素子と前記加圧板との間に補完部材を配置しておき、
     前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子との接合時における前記一方の熱電変換素子及び前記補完部材の高さと前記他方の熱電変換素子及び前記補完部材の高さとの差を、前記一方の熱電変換素子の高さと前記他方の熱電変換素子の高さとの差よりも小さくしておくことを特徴とする請求項7に記載の熱電変換モジュールの製造方法。
    In the joining step, a sandwich body in which the first wiring layer of the first wiring board, the P-type thermoelectric conversion element, and the N-type thermoelectric conversion element are overlapped between a pair of pressure plates arranged to face each other. The first wiring layer is bonded to the P-type thermoelectric conversion element and the N-type thermoelectric conversion element by arranging and heating the sandwiched body while being pressed in the stacking direction. ,
    In the joining step,
    A complementary member is disposed between one of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element having at least one linear expansion coefficient and the pressure plate,
    The height of the one thermoelectric conversion element and the complementary member and the height of the other thermoelectric conversion element and the complementary member at the time of joining the first wiring layer to the P-type thermoelectric conversion element and the N-type thermoelectric conversion element The method of manufacturing a thermoelectric conversion module according to claim 7, wherein the difference is made smaller than the difference between the height of the one thermoelectric conversion element and the height of the other thermoelectric conversion element.
  9.  前記接合工程は、対向配置される一組の加圧板の間に、前記第1配線基板の前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子とをそれぞれ重ねた挟持体を配置しておき、該挟持体をその積層方向に加圧した状態で加熱することにより、前記第1配線層と前記P型熱電変換素子及び前記N型熱電変換素子とをそれぞれ接合する工程とされ、
     前記接合工程において、
     前記挟持体を前記積層方向に偶数個重ねて配置するとともに、前記P型熱電変換素子と前記N型熱電変換素子とを前記積層方向に同数配置しておくことを特徴とする請求項7に記載の熱電変換モジュールの製造方法。
    In the joining step, a sandwich body in which the first wiring layer of the first wiring board, the P-type thermoelectric conversion element, and the N-type thermoelectric conversion element are overlapped between a pair of pressure plates arranged to face each other. The first wiring layer is bonded to the P-type thermoelectric conversion element and the N-type thermoelectric conversion element by arranging and heating the sandwiched body while being pressed in the stacking direction. ,
    In the joining step,
    The even number of the sandwiching bodies are arranged in the stacking direction, and the same number of the P-type thermoelectric conversion elements and the N-type thermoelectric conversion elements are arranged in the stacking direction. Manufacturing method of thermoelectric conversion module.
  10.  前記金属層形成工程は、
     前記セラミックス母材の前記一方の面に複数の前記第1配線層を形成するとともに、
     前記セラミックス母材の他方の面に第1熱伝達金属層を形成する工程とされ、
     前記金属層形成工程において、
     前記第1熱伝達金属層を、隣り合う両第1配線層の間に跨って形成し、かつ、隣り合う両第1セラミックス層形成領域の間に跨って形成することを特徴とする請求項7に記載の熱電変換モジュールの製造方法。
    The metal layer forming step includes
    Forming a plurality of the first wiring layers on the one surface of the ceramic base material;
    A step of forming a first heat transfer metal layer on the other surface of the ceramic base material;
    In the metal layer forming step,
    8. The first heat transfer metal layer is formed between both adjacent first wiring layers and formed between both adjacent first ceramic layer forming regions. The manufacturing method of the thermoelectric conversion module of description.
  11.  前記スクライブライン形成工程において、
     前記スクライブラインは、前記セラミックス母材の一方の面における前記第1配線層の接合予定領域を除く非接合部に形成することを特徴とする請求項7に記載の熱電変換モジュールの製造方法。
    In the scribe line forming step,
    The method of manufacturing a thermoelectric conversion module according to claim 7, wherein the scribe line is formed in a non-joined portion excluding a planned joining region of the first wiring layer on one surface of the ceramic base material.
  12.  前記スクライブライン形成工程において、
     前記スクライブラインは、前記セラミックス母材の他方の面における前記第1熱伝達金属層の接合予定領域を除く非接合部に形成することを特徴とする請求項10に記載の熱電変換モジュールの製造方法。
    In the scribe line forming step,
    11. The method of manufacturing a thermoelectric conversion module according to claim 10, wherein the scribe line is formed in a non-joining portion of the other surface of the ceramic base material excluding a planned joining region of the first heat transfer metal layer. .
  13.  前記スクライブライン形成工程において、
     前記スクライブラインは、前記セラミックス母材の対向する辺同士を貫通する直線で形成することを特徴とする請求項7に記載の熱電変換モジュールの製造方法。
    In the scribe line forming step,
    The method of manufacturing a thermoelectric conversion module according to claim 7, wherein the scribe line is formed by a straight line penetrating opposite sides of the ceramic base material.
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