Method for manufacturing thermoelectric conversion module, thermoelectric conversion module, and binder for thermoelectric conversion module
A method for manufacturing a thermoelectric conversion module of the present invention is a method for manufacturing a thermoelectric conversion module including a thermoelectric semiconductor part in which a plurality of p-type semiconductors and a plurality of n-type semiconductors are alternately arranged, and a high temperature side electrode bound to a binding surface of the p-type semiconductor and the n-type semiconductor on a high temperature heat source side and a low temperature side electrode bound to a binding surface of the p-type semiconductor and the n-type semiconductor on a low temperature heat source side, which electrically connect the p-type semiconductor and the n-type semiconductor adjacent to each other in series, and includes a binding step of binding at least one of the high temperature side electrode and the low temperature side electrode, and the p-type semiconductor and the n-type semiconductor together, by sintering a binding layer containing metal particles, which is provided between the electrode and the semiconductor.
1. A method for manufacturing a thermoelectric conversion module including a thermoelectric semiconductor part in which a plurality of p-type semiconductors and a plurality of n-type semiconductors are alternately arranged, and a high temperature side electrode bound to a binding surface of the plurality of p-type semiconductors and the plurality of n-type semiconductors on a high temperature heat source side and a low temperature side electrode bound to a binding surface of the plurality of p-type semiconductors and the plurality of n-type semiconductors on a low temperature heat source side, which electrically connect the plurality of p-type semiconductors and the plurality of n-type semiconductors adjacent to each other in series, the method comprising:
a binding step of binding at least one of the high temperature side electrode and the low temperature side electrode, and the plurality of p-type semiconductors and the plurality of n-type semiconductors together, by sintering a binding layer containing metal particles, which is provided between the electrode and the plurality of p-type semiconductors and the plurality of n-type semiconductors,
wherein the binding layer is formed of a binder containing metal particles comprising copper particles, the copper particles comprising submicrocopper particles having a volume average particle diameter of greater than or equal to 0.12 μm and less than or equal to 0.8 μm by greater than or equal to 30 mass % and less than or equal to 90 mass % on the basis of a total mass of the metal particles.
2. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein in the binding step, the binding layer is sintered under a load of 0 MPa to 100 MPa.
3. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein the binding layer is formed of a coating film of the binder having a thickness of 10 μm to 1000 μm.
4. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein a variation in a length of the plurality of p-type semiconductors and the plurality n-type semiconductors in a current direction before binding is 10 μm to 200 μm.
5. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein a part or all of at least one surface of the binding surface of the plurality of p-type semiconductors and the plurality of n-type semiconductors with respect to the high temperature side electrode and the low temperature side electrode, and a binding surface of the high temperature side electrode and the low temperature side electrode with respect to the plurality of p-type semiconductors and the plurality of n-type semiconductors includes a metal diffusion prevention layer.
6. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein the binder further contains a dispersion medium.
7. The method for manufacturing the thermoelectric conversion module according to claim 6 ,
wherein the binder contains a solvent having a boiling point of higher than or equal to 300° C. by greater than or equal to 2 mass % on the basis of a total mass of the binder or greater than or equal to 15 volume % on the basis of a total volume of the binder, as the dispersion medium.
8. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein the copper particles further comprise flaky microcopper particles having a volume average particle diameter of greater than or equal to 2 μm and less than or equal to 50 μm and an aspect ratio of greater than or equal to 3.0 by greater than or equal to 10 mass % and less than or equal to 50 mass % on the basis of the total mass of the metal particles.
9. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein the binder contains other particles in addition to the copper particles, as the metal particles, and the other particles contain at least one type of metal selected from the group consisting of zinc, nickel, silver, gold, palladium, and platinum.
10. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein a sintered body having a volume resistivity, a heat conductivity, and a binding strength of less than or equal to 1×10 −5 Ω·cm, greater than or equal to 50 W·m − ·K −1 , and greater than or equal to 20 MPa, respectively, is formed by heating the binding layer at lower than or equal to 350° C. in hydrogen having a concentration of greater than or equal to 1%.
11. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein the binder contains 0.2 mass % to 0.9 mass % of a monovalent carboxylic acid having 1 to 9 carbon atoms, on the basis of the total mass of the dispersion medium.
12. The method for manufacturing the thermoelectric conversion module according to claim 1 ,
wherein the binding layer is sintered under a pressure of less than or equal to 0.01 MPa.
13. A method for manufacturing a thermoelectric conversion module including a thermoelectric semiconductor part in which a plurality of p-type semiconductors and a plurality of n-type semiconductors are alternately arranged, and a high temperature side electrode bound to a binding surface of the plurality of p-type semiconductors and the plurality of n-type semiconductors on a high temperature heat source side and a low temperature side electrode bound to a binding surface of the plurality of p-type semiconductors and the plurality of n-type semiconductors on a low temperature heat source side, which electrically connect the plurality of p-type semiconductors and the plurality of n-type semiconductors adjacent to each other in series, the method comprising:
a binding step of binding at least one of the high temperature side electrode and the low temperature side electrode, and the plurality of p-type semiconductors and the plurality of n-type semiconductors together, by sintering a binding layer containing metal particles, which is provided between the electrode and the plurality of p-type semiconductors and the plurality of n-type semiconductors,
wherein the binding layer is formed of a binder containing metal particles comprising copper particles, the copper particles comprising flaky microcopper particles having a volume average particle diameter of greater than or equal to 2 μm and less than or equal to 50 μm and an aspect ratio of greater than or equal to 3.0 by greater than or equal to 10 mass % and less than or equal to 50 mass % on the basis of the total mass of the metal particles.