WO2017098863A1 - Module de conversion thermoélectrique et son procédé de fabrication - Google Patents

Module de conversion thermoélectrique et son procédé de fabrication Download PDF

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Publication number
WO2017098863A1
WO2017098863A1 PCT/JP2016/083693 JP2016083693W WO2017098863A1 WO 2017098863 A1 WO2017098863 A1 WO 2017098863A1 JP 2016083693 W JP2016083693 W JP 2016083693W WO 2017098863 A1 WO2017098863 A1 WO 2017098863A1
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Prior art keywords
layer
thermoelectric conversion
conversion module
bonding
electrode
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PCT/JP2016/083693
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English (en)
Japanese (ja)
Inventor
藤原　伸一
知丈 東平
山本　礼
石島　善三
孝広 地主
征央 根岸
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日立化成株式会社
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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/81—Structural details of the junction
    • H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/33—Structure, shape, material or disposition of the layer connectors after the connecting process of a plurality of layer connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/34—Strap connectors, e.g. copper straps for grounding power devices; Manufacturing methods related thereto
    • H01L2224/39—Structure, shape, material or disposition of the strap connectors after the connecting process
    • H01L2224/40—Structure, shape, material or disposition of the strap connectors after the connecting process of an individual strap connector
    • H01L2224/401—Disposition
    • H01L2224/40135—Connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip
    • H01L2224/40137—Connecting between different semiconductor or solid-state bodies, i.e. chip-to-chip the bodies being arranged next to each other, e.g. on a common substrate

Definitions

  • the present invention relates to a thermoelectric conversion module that converts heat into electricity and a method for manufacturing the same.
  • thermoelectric conversion modules used by being attached to piping of industrial furnaces such as blast furnaces and incinerators and exhaust pipes of automobiles are assumed to be used in a high temperature environment of 300 to 600 ° C.
  • stress is generated at the joint between the thermoelectric conversion element and the electrode due to the difference in thermal expansion between the thermoelectric conversion element and the electrode, and the joint and the thermoelectric conversion element are destroyed.
  • the thermoelectric conversion module is used in an environment of 300 ° C. or higher, (1) the junction between the thermoelectric conversion element and the electrode does not melt during operation of the module, and (2) heat such as voids caused by diffusion between members. It is necessary to form a stable bonding layer that does not cause mechanical deterioration.
  • Patent Document 1 Japanese Patent Laid-Open No. 2008-235898 as a background art of a high-temperature compatible bonding technique. This gazette states that “the solder disposed between the soldering base materials is pressed against each other with a predetermined pressure to melt the solder, and after a predetermined time has elapsed, the copper diffused from the liquid solder And tin form a connection layer comprising an intermetallic copper-tin phase ”(see abstract).
  • Patent Document 1 for the problem of (1) high heat resistance of the joint and (2) relaxation of thermomechanical stress, for (1), formation of a Cu 3 Sn compound layer having a melting point of 676 ° C. after bonding
  • (2) is described as a stress relaxation layer by forming a soft aluminum (Al) layer having a thickness of 200 to 700 nm on the surface of the semiconductor substrate.
  • Patent Document 1 Although the melting point of the joint can be increased, the stress relaxation layer is not considered to lack stress relaxation because the thickness of Al as the stress relaxation layer is very thin.
  • thermoelectric conversion module that is assumed to be used in a high temperature environment of 300 ° C. or more, the influence of thermal stress due to the difference in thermal expansion between the members becomes significant, but for use in such a high temperature environment. Is not considered.
  • An object of this invention is to provide the thermoelectric conversion module which has stress relaxation property and heat resistance.
  • the present invention adopts, for example, the configurations described in the claims.
  • the present invention includes a plurality of means for solving the above problems.
  • the bonding layer Has a first layer that is a central layer and a second layer that is disposed so as to sandwich the first layer, and the first layer is a layer mainly composed of any one of Al, Ni, and Ti.
  • the second layer is a layer containing a Ni component.
  • thermoelectric conversion module in which P-type or N-type thermoelectric elements are connected via a bonding layer, the electrodes, bonding layer forming members, P-type thermoelectric elements, or N-type thermoelectric elements are arranged in this order.
  • the forming member has a first layer that is a central layer and a second layer that is disposed so as to sandwich the first layer, and a third layer is disposed on both surfaces of the second layer, One layer has an Al component of 80% by mass or more, the second layer has an Ni component, and the third layer has Sn as a main component.
  • thermoelectric conversion module that can sufficiently relieve stress generated at the joint between the thermoelectric conversion element and the electrode and is excellent in heat resistance. That is, the reliability of the thermoelectric conversion module can be improved.
  • thermoelectric conversion module of Example 1 of this invention It is sectional drawing which extracted a part of thermoelectric conversion module of Example 1 of this invention. It is a figure which shows the manufacture flow of the thermoelectric conversion module of Example 1 of this invention. It is a figure which shows the manufacture flow of the thermoelectric conversion module of Example 1 of this invention. It is a figure which shows the manufacture flow of the thermoelectric conversion module of Example 1 of this invention. It is sectional drawing which extracted a part of thermoelectric conversion module in the case of no metallization in Example 1 of this invention. It is a perspective view which shows an example of the thermoelectric conversion module of Example 1 of this invention. It is sectional drawing which shows the 1st modification of Example 1 of this invention. It is sectional drawing which extracted a part of thermoelectric conversion module of Example 2 of this invention.
  • thermoelectric conversion module of Example 2 of this invention It is a figure which shows the 1st manufacturing flow of the thermoelectric conversion module of Example 2 of this invention. It is a figure which shows the 1st manufacturing flow of the thermoelectric conversion module of Example 2 of this invention. It is a figure which shows the 1st manufacturing flow of the thermoelectric conversion module of Example 2 of this invention. It is a figure which shows the 2nd manufacturing flow of the thermoelectric conversion module of Example 2 of this invention. It is a figure which shows the 2nd manufacturing flow of the thermoelectric conversion module of Example 2 of this invention. It is a figure which shows the 2nd manufacturing flow of the thermoelectric conversion module of Example 2 of this invention. It is a figure which shows the 3rd manufacturing flow of the thermoelectric conversion module of Example 2 of this invention.
  • thermoelectric conversion module of Example 2 of this invention It is a figure which shows the 3rd manufacturing flow of the thermoelectric conversion module of Example 2 of this invention. It is a figure which shows the 3rd manufacturing flow of the thermoelectric conversion module of Example 2 of this invention. It is sectional drawing which extracted a part of thermoelectric conversion module of Example 3 of this invention. It is a figure which shows the reliability evaluation result of the thermoelectric conversion module of Example 3 of this invention. It is sectional drawing which extracted a part of thermoelectric conversion module of Example 4 of this invention. It is an example of sectional drawing which connected the thermoelectric element and electrode of this invention. It is an example of sectional drawing which connected the thermoelectric element and electrode of this invention. It is an example of sectional drawing which connected the thermoelectric element and electrode of this invention. It is an example of sectional drawing which connected the thermoelectric element and electrode of this invention.
  • thermoelectric element and electrode of this invention It is an example of sectional drawing which connected the thermoelectric element and electrode of this invention. It is an example of sectional drawing which connected the thermoelectric element and electrode of this invention. It is an example of sectional drawing which connected the thermoelectric element and electrode of this invention. It is an example of sectional drawing which connected the thermoelectric element and Example of Example 1 of this invention.
  • the constituent elements are not necessarily indispensable unless otherwise specified and clearly considered essential in principle. Needless to say.
  • FIG. 1 shows an example of a thermoelectric conversion module according to the first embodiment of the present invention.
  • the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 include a metallization 41 on the bonding surface, and are bonded to the electrode 21 via the bonding layer 31.
  • the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are silicon (Si) -germanium (Ge) -based, Mg-Si-based, Mn-Si-based, bismuth (Bi) -tellurium (Te) -based, lead (Pb
  • a thermoelectric conversion element made of any combination of a tellurium (Te), skutterudite, Heusler alloy, and half-Heusler alloy is desirable.
  • the P-type thermoelectric conversion element 11 will be described as an Mn—Si-based element
  • the N-type thermoelectric conversion element 12 will be described as an Mg—Si-based element.
  • the metallization 41 is made of Ni, Ti, molybdenum (Mo), tungsten (W), palladium (Pd), chromium (Cr), gold (Au), silver (Ag), Al metal, or any of those metals.
  • An alloy having a main component is desirable.
  • the metallization 41 may be any plating method, aerosol deposition method, thermal spraying method, sputtering method, vapor deposition method, ion plating method, simultaneous integral sintering method, etc.
  • the metallization 41 will be described as Ni.
  • the electrode 21 may be composed of Mo, copper (Cu), W, Ti, Ni, Cr, Al, iron (Fe) alone, an alloy containing them, or a multi-layer structure in which those simple or alloys are stacked. That's fine.
  • the electrode 21 will be described as Ni.
  • the structure in the bonding layer 31 is a second layer made of Ni or an alloy containing Ni and Al as main components with the first layer 311 as a central layer mainly containing 80% by mass or more of Al and the first layer 311 interposed therebetween.
  • the layer 312 and the third layer 313 made of an alloy or intermetallic compound containing Sn or Sn and Ni as main components with the first layer 311 and the second layer 312 interposed therebetween are desirable.
  • the main component refers to a component having the highest content rate in a member containing a plurality of elements. Further, in one layer structure, when the main component is 2 or more, it means the element having the largest content and the element having the second largest content.
  • the main component in the first embodiment is a concept including a case where the total value of the main component among the plurality of elements contained in the member is larger than other elements.
  • the metallization 41 is an alloy of Cu, Ni, and Al, if Cu is 34%, Ni is 33%, and Al is 33%, it can be said that Cu is the main component.
  • the main component is not limited to one of them, and includes cases where two or more components are pointed out. Note that the concept of the main component is the same even in the case of an alloy or a structure after bonding.
  • the third layer 313 is shown as a single layer in FIG. 1, a case where a plurality of layers having different main components is formed is also included in the third layer 313.
  • the third layer 313 includes the three layers.
  • the first layer 311 will be described as Al
  • the second layer 312 as Ni
  • the third layer 313 as Ni 3 Sn 4 which is an intermetallic compound of Sn and Ni.
  • thermoelectric conversion module is a module that generates an electromotive force according to a temperature difference by giving a temperature difference to both ends of the thermoelectric conversion element.
  • the case where the upper surface of FIG. 1 is made low temperature and the lower surface is made high temperature is shown below.
  • thermoelectric conversion module element assembly 1 Current is generated in the thermoelectric conversion module element assembly 1 due to the temperature difference applied to the upper and lower surfaces.
  • the current flows from the high temperature side to the low temperature side (in FIG. 1, from bottom to top) in the P-type thermoelectric conversion element 11, and from the low temperature side to the high temperature side (in FIG. 1, from top to bottom) in the N-type thermoelectric conversion element 12. These are joined in series to form an electrical circuit.
  • the thermoelectric conversion module 1 is configured by joining a plurality of thermoelectric conversion elements connected in series as described above in a planar shape or on a line.
  • the manganese-silicon element as the P-type thermoelectric conversion element 11 and the Mg-Si element as the N-type thermoelectric conversion element 12 are elements that can perform the most efficient power generation in the temperature range of 300 to 600 ° C. is there.
  • thermoelectric conversion module when using Mn—Si and Mg—Si elements, the operating temperature of the thermoelectric conversion module is 300 to 600 ° C., and the junction between the thermoelectric conversion element and the electrode must withstand a temperature of 300 to 600 ° C. There is.
  • the first layer 311 is Al (melting point: 660 ° C.)
  • the second layer 312 is Ni (melting point: 1455 ° C.)
  • the third layer 313 is Ni 3 Sn 4 (melting point: 794). Therefore, it is possible to maintain good bonding without re-melting the bonded portion during operation of the thermoelectric conversion module.
  • thermoelectric conversion element due to the thermal expansion difference between the thermoelectric conversion element, the electrode, and the joint may be excessively applied to the element and the joint, and cracks may occur in the thermoelectric conversion element and the joint.
  • cracks occur, in addition to the decrease in mechanical strength, the electrical resistance increases, so that the bonding reliability and the thermoelectric conversion efficiency decrease.
  • a metal foil having Ni plating on both surfaces of the Al foil and further Sn plating on the surface is used as the bonding layer forming member 51.
  • Ni plating on Al may be performed by a generally known method such as zincate treatment or double zincate treatment. Electrolysis and electrolysis are not particularly limited for Sn plating.
  • metal foil produced by plating, but is produced using clad foil rolled with metal foil of Al, Ni, Sn, thermal spraying, vapor deposition, sputtering, ion plating method, aerosol deposition method, etc.
  • a metal foil may be used.
  • the Ni layer and the Sn layer formed on the Al surface also have a role of preventing the formation of an Al oxide film that deteriorates the bondability because Al easily forms a strong oxide film on the surface.
  • the bonding layer forming member 51 When the bonding layer forming member 51 is heated to a melting point of tin of 232 ° C. or higher, tin which is the outermost surface is melted. Diffusion occurs between the melted tin and the Ni of the metallization 41 formed on the element side and the Ni of the electrode 21, and Ni 3 Sn 4 can be formed at the junction.
  • Ni 3 Sn 4 can be formed at the junction without increasing the junction temperature up to the melting point of 794 ° C. of Ni 3 Sn 4 , thereby preventing the occurrence of cracks in the thermoelectric conversion element and the junction that are a concern during cooling of the junction. Is possible.
  • the linear expansion coefficient of the Mn—Si-based element that is the P-type thermoelectric conversion element 11 is 8 ppm / ° C.
  • the linear expansion coefficient of the Mg-Si-based element that is the N-type thermoelectric conversion element 12 is 14.5 ppm / ° C. Therefore, the amount of expansion / contraction when heating / cooling in the joining process or when a temperature change in the actual use environment is applied differs between the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12.
  • thermoelectric conversion element In the case where each thermoelectric conversion element is bonded to the electrode, stress and strain are generated in the vicinity of the joint due to the difference in expansion coefficient between the electrode material and each thermoelectric conversion element, and the joint is broken or the P-type thermoelectric conversion element 11. Or cracks in the N-type thermoelectric conversion element 12 may occur.
  • Al that creep-deforms from about 200 ° C. or higher is provided as the first layer 311.
  • high purity Al has a soft property and a linear expansion coefficient of 23.1 ppm / ° C., which is larger than Mg—Si based elements, Mn—Si based elements and nickel. Therefore, it is also possible to adjust the amount of thermal expansion and contraction with the member to be joined by adding a low thermal expansion material such as Si or an inorganic filler into Al.
  • the rigidity is increased and the original Al flexibility is also impaired. Therefore, it is desirable to leave the Al component at 80 mass% or more.
  • the thickness of the Al of the first layer 311 only needs to have a thickness that can sufficiently relieve the thermal stress that occurs during cooling of the joint and during operation of the module. It is possible to demonstrate.
  • the rigidity of Al becomes high, so that the deformation of Al may be hindered and the stress relaxation effect may be reduced.
  • a thickness of 25 to 500 ⁇ m is desirable.
  • the third layer 313 when the third layer 313 is very thin, it is difficult to adjust the height variation of the thermoelectric element and the electrode at the time of assembling the module at the joining portion, so that the joining property may be lowered. On the other hand, if the third layer 313 is too thick, the Al deformation of the first layer 311 is hindered, and the stress relaxation effect is unlikely to occur. Therefore, it is desirable that the third layer 313 has a thickness of 1 to 100 ⁇ m.
  • FIGS. 2A to 2C are flowcharts showing the flow of the method for manufacturing the thermoelectric conversion module according to the first embodiment of the present invention.
  • 2A-2C in addition to FIG. 1, a bonding layer forming member 51, a supporting jig 61, and a pressing jig 62 are added.
  • the P-type thermoelectric conversion element 11, the N-type thermoelectric conversion element 12, the electrode 21, and the bonding layer 31 have the same configuration as in FIG.
  • the supporting jig 61 and the pressing jig 62 may be any material that does not melt in the joining process, such as ceramics, carbon, metal, etc., and suppresses reaction by forming a layer that does not react with the electrode 21 or does not react with the surface. Is desirable.
  • thermoelectric conversion module 1 of FIG. 1 the flow of the assembly method of the thermoelectric conversion module 1 of FIG. 1 will be described with reference to the assembly method of the thermoelectric conversion module using FIGS. 2A to 2C.
  • the electrode 21 is installed on the support jig 61. Thereafter, the bonding layer forming member 51, the P-type thermoelectric conversion element 11, and the N-type thermoelectric conversion element 12 are aligned and installed on the electrode 21 in this order. The bonding layer forming member 51 is again installed on each thermoelectric conversion element, and finally the electrode 21 is disposed.
  • a jig (not shown) may be installed in a lump or may be installed individually, and any method may be used.
  • the electrode 21, the P-type thermoelectric conversion element 11, and the N-type thermoelectric conversion element 12 are bonded to each other by the pressurizing jig 62 and heated from above. It joins through.
  • the pressure applied to the thermoelectric conversion element is 0.12 kPa or more for bonding.
  • the layer mainly composed of tin formed on the outermost surface of the bonding layer forming member 51 is formed on the surface of the electrode 21, the P-type thermoelectric conversion element 11, and the N-type thermoelectric conversion element 12 during bonding.
  • a third layer 313 is formed by a diffusion reaction with theization 41.
  • thermoelectric conversion module 1 can be formed by removing the pressurizing jig 61 and the supporting jig 62.
  • thermoelectric conversion module assembly 1 may be formed by bonding the electrode 21 on the support jig 61 side and then bonding the upper surface of the thermoelectric conversion element and the electrode 21 via the bonding layer forming member 51.
  • the reason why the applied pressure at the time of bonding is 0.12 kPa or more is to prevent the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 from being tilted at the time of bonding.
  • the upper limit of the applied pressure is not particularly limited, but is set to be less than the crushing strength of the element because it is necessary that the element is not destroyed.
  • the bonding atmosphere may be a non-oxidizing atmosphere. Specifically, a vacuum atmosphere, a nitrogen atmosphere, a nitrogen-hydrogen mixed atmosphere, or the like can be used.
  • Mn—Si elements and Mg—Si elements which are thermoelectric elements for high temperature, were used, but in this bonding method, bonding was performed at a melting point of 232 ° C. or higher of Sn formed on the outermost surface of the bonding layer forming member 51. Therefore, it can be applied to Bi-Te-based elements, which are low-temperature elements.
  • a thermoelectric conversion module using both a high-temperature thermoelectric element and a low-temperature thermoelectric element can also be produced by the same process. .
  • the bonding layer 31 is formed even when a thermoelectric element in which the metallization 41 is not formed is used as shown in FIG. Is possible.
  • third layer 313 is Ni 3 Sn 4, the third layer 313 is Ni 3 Sn 4, Ni 3 Sn , at least one or more may be formed of Ni 3 Sn 2. If the melting point of Sn is 232 ° C. or higher, the above-mentioned intermetallic compound can be produced. However, when bonding is performed at a high temperature, thermal stress is excessively applied during bonding cooling, so the bonding temperature is 232 to 500 ° C. Is desirable.
  • the layer mainly composed of Sn and Ni has a composition in which at least one of Ni 3 Sn 4 , Ni 3 Sn, and Ni 3 Sn 2 or a composition in which Ni is added to the Sn phase. Therefore, even after re-heating to a temperature equal to or higher than the melting point of Sn, no Sn liquid phase is generated and a good bonding state can be maintained.
  • Ni 3 Sn the melting point of Ni 3 Sn 2 is higher than Ni 3 Sn 4, it is possible to obtain a joint which is excellent in heat resistance than Ni 3 Sn 4.
  • an intermetallic compound of Ni and Sn may remain in the intermetallic compound layer.
  • the metallization 41 and the second layer 312 are Ni
  • an intermetallic compound of Ni and Sn is formed at each interface between the metallization 41 and the second layer 312 when heated to the bonding temperature.
  • this intermetallic compound is configured as a layer structure between the metallization 41 and the second layer 312. That is, the metallization 41 and the second layer 312 have a structure connected via an intermetallic compound.
  • an intermetallic compound is disposed so as to cover the metallization 41, and the second layer 312 is disposed via the intermetallic compound.
  • the metallization 41 and the second layer 312 are not in direct physical contact but are connected via an intermetallic compound layer.
  • the intermetallic compound of Ni and Sn formed at the interface between the metallization 41 and the second layer 312 grows in a needle shape or a scallop shape from each interface. Therefore, even if Sn remains in the third layer 313, the acicular and scalloped intermetallic compounds formed at the interfaces of the metallization 41 and the second layer 312 are connected in part or at a plurality of locations.
  • the module operating temperature exceeds 232 ° C., which is the melting point of Sn, the remaining tin becomes a liquid phase, but the intermetallic compound of Ni and Sn is connected between the metallization 41 and the second layer 312. Since it is possible to ensure the junction thickness, it is possible to prevent the molten tin from flowing out.
  • the Ni amount before bonding is 35% by mass or more of the Sn amount.
  • FIG. 4 is a perspective view of an example of the thermoelectric conversion module according to the first embodiment of the present invention, in which 46 thermoelectric conversion elements are aligned and joined in a grid pattern.
  • the process shown in FIG. 2 is applied to produce the thermoelectric conversion module 1 shown in FIG.
  • This thermoelectric conversion module may be used by being enclosed in a case, or may be used as it is.
  • the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are represented as quadrangular columns, but the shape of the thermoelectric conversion element may be a columnar shape such as a quadrangular column, a triangular column, a polygonal column, a cylinder, or an elliptical column.
  • thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are bonded to the electrode 21 through the bonding layer 31 as shown in the first embodiment, high heat resistance of the bonding portion can be realized.
  • thermoelectric conversion module that can ensure high reliability even in an environment in which thermal stress occurs and in an environment in which vibration or impact is applied.
  • the bonding layer of the present invention is used for bonding to both the high temperature side electrode and the low temperature side electrode, but it can also be used only on the high temperature side where the influence of heat is large. Moreover, it can also be used for the thermoelectric conversion module for low temperature.
  • FIG. 15 shows a cross-sectional view of a sample joined in this example.
  • the bonding temperature is 300 ° C.
  • the pressure is 0.12 kPa.
  • Ni (312) and Ni 3 Sn 4 (313) are formed at the joint using Al as the core layer (311).
  • Reference numerals in parentheses are the same as those in FIG.
  • the Al component of the first layer was around 99% by weight. As described above, the Al component can be carried out if it is 80% by weight or more. Therefore, it was confirmed that the process can be carried out if at least the Al component is 80 wt% or more and 99 wt% or less. Bonding is possible even if the amount is less than 80% by weight, but 80% by weight or more is desirable in consideration of stress relaxation performance.
  • the electrode 22 mainly composed of Al with the metallization 41 formed on the surface thereof is used, and a bonding layer made of Sn or an alloy mainly composed of Sn and Ni or an intermetallic compound. 32 differs in that the thermoelectric conversion elements are joined.
  • the metallization 41 can be formed on the Al surface in the same manner as in the first embodiment.
  • the manufacturing method of the thermoelectric conversion module in the present embodiment is basically the same as the manufacturing method of Embodiment 1 described in FIG. In the first modification, the same effect as in Example 1 can be obtained by using Al which is excellent in deformability for at least one of the high temperature side electrode and the low temperature side electrode.
  • FIG. 6 is a cross-sectional view of a part of the thermoelectric conversion module according to the second embodiment.
  • the P-type thermoelectric element 11 uses a Mn—Si-based element
  • the N-type thermoelectric element 12 uses a Mg—Si-based element.
  • the metallization 41 described in the first embodiment is not formed in this embodiment, and the P-type thermoelectric element 11 and the N-type thermoelectric element 12 are connected via the bonding layer 32.
  • the bonding layer 32 includes a first layer 321 that is a central layer mainly composed of Ni and a second layer 322 containing at least Ni and an Al component.
  • the first layer 321 is connected to the P-type thermoelectric element 11 via the second layer 322 on one side and is connected to the electrode via the second layer 322 on the other side.
  • 23 is connected.
  • the electrode 23 may be composed of Mo, Cu, W, Ti, Ni, Cr, Al, Fe alone, an alloy containing them, or a multi-layered structure in which these simple substances or alloys are stacked.
  • the electrode 23 is made of Cu (thickness: 0.5 mm) having a high thermal conductivity because the higher the thermal conductivity, the easier the heat transfer to the thermoelectric element.
  • Ni plating was applied to the bonding surface of the electrode 23 to ensure bonding properties (not shown). Ni plating is disposed on the surface of the electrode 23, and Cu is connected through the Ni plating. This Cu is connected to the second layer 322.
  • the bonding layer 32 includes a first layer 321 having Ni as a central layer and a second layer 322 made of a compound layer containing Ni and Al so as to sandwich the first layer 321 on both sides.
  • the second layer 322 is shown as a single layer, but a case where a plurality of layers having different main components are formed may be included in the second layer 322.
  • the second layer 322 includes the three layers.
  • an Al 3 Ni layer, an Al 3 Ni 2 layer, and an AlNi layer are formed between the P-type thermoelectric element and the first layer 321. That is, the bonding layer 32 has a seven-layer structure.
  • the Ni layer of the first layer 321 may be formed thicker than the second layer 322. Specifically, it is desirably 25 ⁇ m or more and 500 ⁇ m or less.
  • the linear expansion coefficient of Cu of the electrode 23 is 17 ppm / ° C., which is larger than the linear expansion coefficient (14.5 ppm / ° C.) of the Mn—Si based element (8 ppm / ° C.) and the Mg—Si based element. Therefore, Ni (13.4 ppm / ° C.) of the first layer 321 is included in the bonding layer 32, so that it is possible to relieve the thermal stress caused by the difference in the linear expansion coefficient between the thermoelectric element and the electrode.
  • the thickness of Ni is small, it is difficult to obtain a stress relaxation effect, and there is a possibility that cracks may occur in the second bonding layer 322 in accordance with cracks in the Mn—Si-based element and the Mg—Si-based element.
  • the first layer 321 is too thick, the distance between the electrode 21 and the Mn—Si-based element and the Mg—Si-based element is increased, which may cause thermal and electrical loss and may decrease the power generation performance. is there.
  • the compound containing Ni and Al in the second layer 322 is only required to be formed thinner than the first layer 321, and a thickness of 1 to 25 ⁇ m is desirable. If the second layer 322 is too thick, thermal and electrical losses may occur and power generation performance may be reduced. On the other hand, if it is too thin, the second layer 322 may crack due to an increase in thermal stress applied to the second layer 322.
  • the first layer 321 which is the layer forming the bonding layer 32 and is the central layer is Ni (melting point: 1455 ° C.), the second layer is Al 3 Ni (melting point: 854 ° C.), and Al 3 Ni 2 (melting point: 1133 ° C.). ) And AlNi (melting point: 1638 ° C.), it is possible to maintain the joint having higher heat resistance than that of Example 1 without melting the joint during operation of the thermoelectric conversion module.
  • an intermetallic compound layer of Ni and Al is formed as the second layer 322, Al may remain.
  • the intermetallic compound layers are connected at a part or at a plurality of locations, so that the bonding can be maintained even when the remaining Al is melted.
  • a metal foil in which Al is formed on both surfaces of Ni is used as the bonding layer forming member 52.
  • a method for producing the metal foil may be a method such as a clad method.
  • Al is melted by heating near the melting point 660 ° C. of Al of the bonding layer forming member 52.
  • By lowering the bonding temperature it is possible to prevent the occurrence of cracks in the bonded thermoelectric element and the bonded portion due to thermal stress.
  • the metal foil before joining is in a state where Al and Ni are in intimate contact, and eutectic melting of Al and Ni occurs at 640 ° C. Furthermore, the Al component of the metal foil on the side in contact with the Mg—Si element or Mn—Si element has a temperature lower than 640 ° C. due to the diffusion of Si, Mg, and Mn as the element components during heating. Melt. Thus, bonding is possible without raising the melting point of Al to 660 ° C.
  • a high melting point layer such as Al 3 Ni or Al 3 Ni 2 can be formed as the second layer 322.
  • Molten Al contains Si, Mg, and Mn, which are components of the element, but exists in the compound layer in a form that substitutes for Al or Ni. Also, it is not always necessary to form a binary compound of Al 3 Ni or Al 3 Ni 2, and a compound of a ternary system or higher such as an Al—Ni—Si system or Al—Ni—Si—Mn system is formed. Can exhibit the same effect.
  • thermoelectric conversion module 11 is flowcharts showing the flow of the manufacturing method of the thermoelectric conversion module according to the second embodiment of the present invention.
  • the P-type thermoelectric conversion element 11, the N-type thermoelectric conversion element 12, the support jig 61, and the pressure jig 62 have the same configuration as that in FIG.
  • thermoelectric conversion module 1 of FIG. 6 the flow of the assembly method of the thermoelectric conversion module 1 of FIG. 6 will be described with reference to the assembly method of the thermoelectric conversion module using FIGS. 7A-7C.
  • the electrode 23 is installed on the support jig 61. Thereafter, the bonding layer forming member 52, the P-type thermoelectric conversion element 11, and the N-type thermoelectric conversion element 12 are aligned and placed on the electrode 23 in this order.
  • the bonding layer forming member 52 is installed again on each thermoelectric conversion element, and finally the electrode 23 is arranged.
  • a jig (not shown) may be installed in a lump or may be installed individually, and any method may be used.
  • the electrode 23, the P-type thermoelectric conversion element 11, and the N-type thermoelectric conversion element 12 are bonded to each other by the pressurizing jig 62 and heated from above. It joins through.
  • the pressure applied to the thermoelectric conversion element is 10 MPa or more for bonding.
  • the Al formed on the outermost surface of the bonding layer forming member 52 undergoes a diffusion reaction with the first layer 321, the electrode 23, the P-type thermoelectric conversion element 11, and the N-type thermoelectric conversion element 12 during bonding.
  • a bilayer 322 is created.
  • thermoelectric conversion module 1 can be formed by removing the pressing jig 61 and the supporting jig 62.
  • thermoelectric conversion module assembly 1 may be formed by bonding the electrode 23 on the support jig 61 side and then bonding the upper surface of the thermoelectric conversion element and the electrode 23 via the bonding layer forming member 52.
  • the reason why the applied pressure is set to 10 MPa or more is to bring the new surface of the thermoelectric element into close contact with the new surface of Al formed on the surface of the bonding layer forming member 52. If the applied pressure is low, the new surfaces do not come into close contact with each other due to the influence of the oxide film, and the bondability may deteriorate due to the influence of the oxide film.
  • the upper limit of the thermoelectric element pressing force is not particularly limited, but it must be less than the crushing strength of the element because it is necessary to prevent the element from being destroyed. Specifically, it may be about 100 MPa or less, but in this embodiment, a sufficient effect can be obtained at a pressure of about 10 to 50 MPa.
  • the bonding atmosphere may be a non-oxidizing atmosphere. Specifically, a vacuum atmosphere, a nitrogen atmosphere, a nitrogen-hydrogen mixed atmosphere, or the like can be used.
  • the bonding temperature is preferably 600 to 700 ° C. As described above, in this embodiment, it is possible to form a joint having excellent heat resistance even when the melting point of Al is 660 ° C. or lower. Bonding is possible even at 600 ° C. or lower, but since the bonding temperature is low, eutectic melting does not occur and bonding may not be achieved.
  • Table 1 shows the results of Example 2.
  • the Ni thickness in the bonding layer forming member 52 is 100 ⁇ m and the Al thickness is 12 ⁇ m.
  • Sample Nos. 7 to 15 confirmed the melting of Al formed on the surface of the bonding layer forming member 52 and confirmed good bonding.
  • Sample No. 16 cracks were found in the Mg—Si element after bonding, and bonding failure occurred.
  • the manufacturing method is not limited to the manufacturing method shown in FIGS. 7A-7C, and for example, it can be manufactured by other manufacturing methods shown in FIGS. 8A-8C and FIGS. 9A-9C.
  • 8A-8C show a state in which the bonding layer forming member 52 is in close contact with the surface of the electrode 23 in advance.
  • Adhesion is possible by the clad method, ultrasonic bonding, pressure welding or the like. Since the electrode 23 and the bonding layer forming member 52 are in close contact with each other, the installation process of the bonding layer forming member 52 can be simplified.
  • the bonding layer forming member 52 may be formed in advance on the element side as shown in FIGS. 9A-9C.
  • thermoelectric conversion module 1 As that manufactured in FIGS. 7A-7C can be manufactured. Moreover, it is not limited only to the result implemented by Table 1, depending on the combination of joining conditions, favorable joining can be ensured even in combinations other than those shown in Table 1.
  • the bonding temperature is 600 to 700 ° C.
  • the bonding pressure is 10 to 100 MPa
  • the Ni thickness of the first layer 321 is 25 to 500 ⁇ m
  • the thickness of the second layer 322 containing Al and Ni is 1 to 1 ⁇ m. Bonding is possible by setting the thickness to 25 ⁇ m.
  • thermoelectric conversion module according to the third embodiment will be described with reference to FIG.
  • FIG. 10 is a cross-sectional view of a part of the thermoelectric conversion module of Example 3.
  • the structure shown in FIG. 10 is an example in which an Mn—Si based element is used as the P-type thermoelectric element 11 and an Mg—Si based element is used as the N-type thermoelectric element 12 in the same manner as in the first and second embodiments. Since the bonding layer 32 is the same as that of the second embodiment, the description thereof is omitted.
  • a different point in this example was that a ceramic wiring substrate having a Cu layer (Cu wiring) 241 (0.2 mm thickness) formed on both surfaces of the ceramic 242 (0.32 mm thickness) was used as the electrode 24. Note that the thicknesses of the ceramic 242 and the Cu layer 241 can be changed as appropriate.
  • the ceramics 242 may be made of any material such as Al 2 O 3 , AlN, Si 3 N 4, etc., but the one having a linear expansion coefficient closer to that of the Mn—Si based element or Mg—Si based element is due to thermal stress. Since element cracking and joint cracking can be suppressed, Al 2 O 3 (7.0 ppm / ° C.) was selected in this example.
  • the surface of the Cu layer 241 is plated with 7 ⁇ m of Ni to ensure bonding (not shown).
  • the manufacturing method it implemented by the method similar to Example 2.
  • the bonding temperature was 660 ° C.
  • the bonding pressure was 30 MPa
  • whether or not bonding was possible was confirmed under the conditions shown in Sample Nos. 1 to 7 shown in Table 2 below in a nitrogen atmosphere.
  • thermoelectric elements used for the bonding two Mn-Si-based elements and Mg-Si-based elements were subjected to bonding experiments.
  • the Ni thickness in Table 2 indicates the thickness of the first layer 321 in the bonding layer 32.
  • Sample No. 1 is the result when the bonding layer 321 is not formed and the bonding layer 322 single layer is formed of only Al. From Table 2, in sample numbers 1, 2, and 3, cracks occurred in the Mg—Si element after bonding, resulting in poor bonding.
  • the Mn—Si based element is a harder material than the Mg—Si based element, and the Vickers hardness is more than twice that of the Mg—Si based element. Since the linear expansion coefficient of the Mn—Si-based element is 8.0 ppm / ° C., if the Ni thickness of the first layer 321 is increased, the influence of thermal stress generated in the element after bonding becomes large. No cracking occurs.
  • thermoelectric conversion module using both a Mn-Si element and a Mg-Si element can be manufactured under conditions that do not cause cracks in the Mg-Si element, thereby providing a highly reliable thermoelectric conversion module. It is.
  • the bonding temperature is 600 ° C. to 700 ° C.
  • the bonding pressure is 10 MPa to 100 MPa
  • the Ni thickness of the first layer 321 is 25 ⁇ m to 500 ⁇ m
  • the thickness of the second layer 322 containing Al and Ni can be joined by setting the thickness to 1 ⁇ m to 25 ⁇ m.
  • the Ni layer is desirably 500 ⁇ m or less.
  • the thickness of the second layer 322 and the component of the layer are the same as in the second embodiment.
  • FIG. 13A is an example of a cross-sectional view of the sample 5 when the Mg—Si thermoelectric element and the Cu electrode are connected.
  • the Mg—Si thermoelectric element is shown connected to the Cu electrode via the Ni core portion.
  • FIG. 13B is an enlarged view of the position surrounded by a square regarding the joint (connection) part.
  • the Cu electrode is connected to the Al 2 O 3 insulating substrate.
  • the bonding layer 32 is connected to the Mg—Si thermoelectric element.
  • the connection part 32 includes a first layer 321 and a second layer 322.
  • the second layer 322 includes an Al 3 Ni layer and an Al 3 Ni 2 layer, and these are collectively referred to as a second layer 322.
  • the Mg—Si thermoelectric element is connected to the Al 3 Ni layer.
  • the Al 3 Ni layer is connected to the Al 3 Ni 2 layer. Furthermore, the Al 3 Ni 2 layer is connected to the Ni core part.
  • FIG. 13C shows the results of measuring the components of the Al 3 Ni layer and the Al 3 Ni 2 layer.
  • the component of each layer can be specified by measuring a cut surface.
  • the first layer 321 is a layer mainly composed of Ni.
  • the second layer 322 is a layer containing Al as a main component and containing a Ni component. From the measurement results, since the Ni component is the second largest after the Al component, it can be said that the second layer 322 is a layer mainly composed of Al and Ni.
  • FIG. 14A is an example of a cross-sectional view of the sample 5 when a Mn—Si thermoelectric element and a Cu electrode are connected. It is shown that the Mn—Si thermoelectric element is connected to the Cu electrode via the Ni core portion.
  • FIG. 14B is an enlarged view of the position surrounded by a square regarding the joint (connection) part.
  • the Cu electrode is connected to the Al 2 O 3 insulating substrate.
  • the bonding layer 32 is connected to the Mn—Si thermoelectric element.
  • the connection part 32 includes a first layer 321 and a second layer 322.
  • the second layer 322 includes an Al—Mn—Si—Ni layer, an Al—Ni—Si—Mn layer, and an Al 3 Ni 2 layer, which are collectively referred to as a second layer 322.
  • the Mn—Si thermoelectric element is connected to the Al—Mn—Si—Ni layer.
  • the Al—Mn—Si—Ni layer is connected to the Al—Ni—Si—Ni layer. Furthermore, the Al—Ni—Si—Ni layer and the Al 3 Ni 2 layer are connected. Further, the Al 3 Ni 2 layer and the Ni core part are connected.
  • FIG. 14C shows the results of measuring the components of the Al—Mn—Si—Ni layer, the Al—Ni—Si—Mn layer, and the Al 3 Ni 2 layer.
  • the component of each layer can be specified by measuring a cut surface.
  • the first layer 321 is a layer mainly composed of Ni
  • the second layer 322 is a layer mainly composed of Al and containing a Ni component.
  • the Ni component is the second largest after the Al component, a layer mainly composed of Al and Ni is formed.
  • FIG. 11 shows the reliability evaluation results of sample number 2 and sample number 5 in Table 2.
  • FIG. 11 shows an initial output (power generation amount) remaining rate when a temperature difference is given to the thermoelectric conversion module at a low temperature side of 40 ° C. and a high temperature side of 500 ° C., and 10 heat cycles are loaded.
  • thermoelectric conversion module was excellent in reliability and power generation performance.
  • thermoelectric conversion module having high heat resistance can be provided by optimizing the bonding conditions.
  • the layer configuration of the bonding layer 32 can be obtained, and it is possible to provide a thermoelectric conversion module having excellent bonding reliability and power generation performance.
  • thermoelectric conversion module according to the fourth embodiment will be described with reference to FIG.
  • FIG. 12 is a cross-sectional view of a part of the thermoelectric conversion module of Example 4.
  • thermoelectric element 12 is an example in which an Mn—Si based element is used as the P-type thermoelectric element 11 and an Mg—Si based element is used as the N-type thermoelectric element 12 as in the second embodiment.
  • the bonding layer 32 of the electrode 23 and the N-type thermoelectric element 12 is the same as that in the second embodiment.
  • the bonding layer 33 of the P-type thermoelectric element 11 is different from that of the second embodiment.
  • the first layer 331 that is the central layer of the bonding layer 33 is Ti, and the second layer 332 is disposed so as to sandwich the first layer 331.
  • Example 2 is that the second layer 332 is made of a layer made of Ni, and a layer containing Al and Ni is formed in the third layer 333 so as to sandwich the first layer 331 and the second layer 332. And different.
  • the P-type element 11 is connected to the third layer 333 that is a layer containing Al and Ni.
  • the third layer 333 is connected to the second layer 332 that is a layer containing Ni.
  • the second layer 332 is connected to one surface of the first layer 331 of the layer containing Ti.
  • the second layer 332, the third layer 333, and the electrode 23 are connected in this order to another surface different from the one surface of the first layer 331.
  • the N-type thermoelectric element 12 is also connected to the electrode 23 with the same layer configuration.
  • Ti of the first layer 331 in the bonding layer 33 exerts a stress relaxation effect on the Mn—Si element.
  • the first layer 321 in the bonding layer 32 exhibits a stress relaxation effect.
  • the second layer 332 in the bonding layer 33 is made of Ni, so that the third layer 333 is a high heat-resistant bonding containing Al and Ni, like the second layer 322 in the bonding layer 32 on the N-type thermoelectric element 12 side. Layers can be formed.
  • the thickness of Ti is preferably 25 to 500 ⁇ m.
  • thermoelectric conversion module with excellent reliability can be provided by the same manufacturing method as in the second and third embodiments.
  • Example 4 the electrode 23 is made of Cu (with Ni plating) as in Example 2.
  • the ceramic wiring board of Example 3 may be used. Even when a ceramic wiring board is used, the same effect as in the third embodiment can be exhibited.
  • the P-type element is an Mn-Si element and the N-type element is an Mg-Si element, but the same effect can be obtained even when other thermoelectric elements are used.
  • the coefficient of linear expansion of a Co—Sb element that is a skutterudite element is equivalent to that of a Mn—Si element, so that even when a different element is used, a thermoelectric conversion module having excellent reliability similar to that of the present embodiment can be obtained. It is possible to provide.
  • thermoelectric conversion module of the present invention can be used for power generation in a high-temperature environment by being attached to, for example, piping of an industrial furnace such as a blast furnace or an incinerator or an exhaust pipe of an automobile.

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)

Abstract

L'invention concerne un module de conversion thermoélectrique qui présente d'excellentes propriétés de relaxation de contrainte, tout en garantissant une résistance à la chaleur. Le module de conversion thermoélectrique comprend : des électrodes disposées sur le côté haute température et le côté basse température, ainsi qu'un élément thermoélectrique de type P et un élément thermoélectrique de type N reliés mécaniquement et électriquement l'un à l'autre, une couche de liaison étant intercalée entre eux ; au moins une première couche qui sert de couche centrale dans la couche de liaison côté haute température et qui est conçue à partir d'Al, de Ni ou de Ti ; et des secondes couches qui prennent en sandwich la première couche et contiennent au moins du Ni.
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CN113272977A (zh) * 2018-12-26 2021-08-17 三菱综合材料株式会社 热电转换材料、热电转换元件及热电转换模块
EP4050669A4 (fr) * 2019-10-25 2023-10-25 Mitsuba Corporation Élément de conversion thermoélectrique et son procédé de production, et dispositif de conversion thermoélectrique

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