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WO1997013283A1 - Fabrication of thermoelectric modules and solder for such fabrication - Google Patents

Fabrication of thermoelectric modules and solder for such fabrication Download PDF

Info

Publication number
WO1997013283A1
WO1997013283A1 PCT/US1996/016077 US9616077W WO9713283A1 WO 1997013283 A1 WO1997013283 A1 WO 1997013283A1 US 9616077 W US9616077 W US 9616077W WO 9713283 A1 WO9713283 A1 WO 9713283A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight percent
thermoelectric
phosphorous
bismuth
antimony
Prior art date
Application number
PCT/US1996/016077
Other languages
French (fr)
Inventor
Michael Yahatz
James Harper
Original Assignee
Melcor Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BR9610829-0A priority Critical patent/BR9610829A/en
Priority to DK96936249T priority patent/DK0870337T3/en
Priority to AU73947/96A priority patent/AU702453B2/en
Priority to IL12377396A priority patent/IL123773A/en
Priority to JP51451897A priority patent/JP3862179B2/en
Priority to AT96936249T priority patent/ATE228270T1/en
Priority to KR1019980702474A priority patent/KR19990066931A/en
Priority to UA98041709A priority patent/UA51672C2/en
Application filed by Melcor Corporation filed Critical Melcor Corporation
Priority to EP96936249A priority patent/EP0870337B1/en
Priority to EA199800303A priority patent/EA000388B1/en
Priority to DE69624936T priority patent/DE69624936T2/en
Priority to CA002233979A priority patent/CA2233979C/en
Publication of WO1997013283A1 publication Critical patent/WO1997013283A1/en
Priority to NO981507A priority patent/NO981507L/en

Links

Classifications

    • 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
    • H10N10/82—Connection of interconnections
    • 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

Definitions

  • thermoelectric devices relate to improved thermoelectric devices and to improved methods of fabricating such devices. More particularly, the invention relates to an improved joining solder, based on an alloy of bismuth and antimony, for use with thermoelectric modules; to thermoelectric elements soldered to a phosphorus-nickel surface on a conductor, such as copper, to form thermoelectric modules; and to the use of such thermoelectric modules.
  • thermoelectric generators TEG
  • thermoelectric coolers When the modules are used as heat pumps, the modules are called thermoelectric coolers (TEC) or thermoelectric heaters (TEH) and demonstrate the Peltier effect. With the Peltier effect a temperature change results when current passes through a junction of two different types of semiconductors. Generally such semiconductors are assembled into thermoelectric modules where heat is transferred from one side of the module to the other side when current is applied. These modules can act as cooling devices where the heat pumped from the cooling side dissipates into a heatsink on the other side. The sides of the modules are generally composed of a ceramic material.
  • CMOS complementary metal-oxide-semiconductor
  • the semiconductor elements are doped to create either an excess (n- type) or a deficiency (p-type) of electrons.
  • Typical modules of this type are described in U.S. Patent 4,855,810, Gelb et al. According to the prior art, these modules contain semiconductor elements soldered to conductors using a solder including bismuth and tin.
  • a solder is described in U.S. Patent 3,079,455, Haba. Haba describes a solder formed of tin, antimony, and bismuth.
  • the bismuth is described as being in an amount from 40 to 50 weight percent and the antimony is described as being in an amount of 1.5 to 3.5 weight percent.
  • thermoelectric modules built with bismuth telluride elements are used in applications where they are exposed to temperatures ranging from about -80 °C to about 250°C.
  • the performance of such thermoelectric modules made with a tin-containing solder suffers as a result of long term exposure to wide temperature ranges. In fact, the performance of the modules has been found to decrease about fifteen percent or more per year.
  • Thermoelectric modules made with tin-containing solder are not truly considered serviceable at temperatures substantially above 80°C.
  • the standard bismuth tin solder melts at 138°C. At temperatures above 80°C, the tin in the solder tends to diffuse rapidly into the semiconductor elements and into the crystal lattice of the semiconductor elements, where it acts as a dopant or reacts with material of the elements. Also, the tin forms a film over the surface of the material adjacent to the soldered ends, the tin acting as a resistor connected across the elements causing an IR drop and/or a short.
  • Gelb et al. sought to overcome the problems of tin diffusion and resistor formation by replacing the tin-based solder with a lead-antimony solder. However, at elevated temperatures, lead also diffuses and reacts with the thermoelectric semiconductor material to form a region of poor thermoelectric performance.
  • thermoelectric module having an improved life-time and low failure rate at elevated temperatures, including temperatures up to 275 °C.
  • a further object of the invention is to provide a thermoelectric module having a soldered structure where the solder does not form resistors across the thermoelectric elements.
  • thermoelectric module which eliminates the need for a costly diffusion barrier.
  • the invention comprises a solder for joining conductors (e.g. buss-bars), such as those made from copper, aluminum and other well-known conductive materials, to a conductive material deposited on an end of a thermoelectric element in a thermoelectric module, wherein said solder comprises about 50-99 weight percent bismuth and about 1 -50 weight percent antimony, where the combined weight percent of the bismuth and antimony is about 100 percent, particularly when the conductors are provided with a surface of phosphorous- nickel.
  • conductors e.g. buss-bars
  • thermoelectric modules comprising:
  • step 1 joining said conductive material to said phosphorous-nickel surface with a solder comprising about 50 to 99 weight percent bismuth and about 1 to 50 weight percent antimony wherein the combined weight percent of the bismuth and antimony is about 100.
  • the conductive material of step 1 is a material comprising about 50 to 100 weight percent bismuth, the remainder being, essentially, antimony.
  • thermoelectric module To generate electricity from a thermal gradient, the device is subjected to a temperature gradient across the thermoelectric elements and the conductive elements are connected to complete the electrical circuit. To generate a thermal gradient, as required for thermoelectric cooling or heating, the device is subjected to a flow of electric current. A temperature gradient is created along the direction of the current flow through the thermoelectric elements due to the Peltier effect and this functions to cool at the cold junction and heat at the hot junction.
  • the invention provides for a thermoelectric module that can be used in applications having wide operating temperatures up to and including about 275°C.
  • Figure 1 is an isometric view of a thermoelectric module with one of the two ceramic sides removed to more clearly show the module elements;
  • FIG. 2 is a cross-sectional view of a thermoelectric module taken along line 2-2 of Fig. 1 ;
  • Figure 3 is a phase diagram of a binary solder alloy system of bismuth and antimony suitable for use in the present invention.
  • thermoelectric module comprising an array of n-type and p-type thermoelectric elements formed of a semiconductive material, particularly a bismuth telluride material.
  • the elements have a first end and a second end and are arranged in rows and columns of alternately placed n-type and p-type elements, as known in the prior art.
  • the elements have a thin coating of a conductive material deposited on each end wherein said coating is substantially free of a diffusion barrier such as nickel.
  • Suitable materials for the coating are a bismuth-antimony alloy or pure bismuth.
  • the conductive material comprises from about 50 to 100 weight percent bismuth, the remainder being, essentially, antimony.
  • This coating which provides a solderable surface, has a thickness of up to 0.001 inch.
  • a conductor, formed on a non-conductive substrate, is used to connect the elements. This conductor is provided with a surface of phosphorus-nickel containing at least 3.5% phosphorus. One method of forming the surface is to provide a layer of phosphorus-nickel on top of the conductor.
  • the amount of phosphorous contained in the phosphorus-nickel surface is generally in the range of about 3.5 to 18%. Preferably, the amount of phosphorous is from 7 to 13%, and, most preferably, from 8 to 12%.
  • the thickness of the phosphorus-nickel layer is generally from about 20 to about 400 micro-inches.
  • the conductor is copper.
  • the phosphorous-nickel surface is soldered to the thin coating of conductive material on the thermoelectric elements using a solder comprising about 50 to 99 weight percent bismuth and about 50 to 1 weight percent antimony.
  • the solder is free of elements that act as dopants, such as tin, copper, silver, gold, lead, zinc, cadmium, indium, gallium, iodine, chlorine, sodium, and potassium.
  • the solder comprises about 75 to 96 weight percent bismuth and about 25 to 4 weight percent antimony.
  • the solder comprises about 80 to 95 weight percent bismuth and about 20 to 5 weight percent antimony.
  • thermoelectric module 10 (Figs. 1 and 2) is shown having an array of bismuth telluride thermoelectric elements (12, 14) of n-type (Bi 2 Te 3 - Bi 2 Se 3 ) and p-type (Bi 2 Te 3 - Sb 2 Te 3 ).
  • the n-type and p-type elements are shown having deposited on their ends thin coatings (16, 18) of pure bismuth or a bismuth-antimony alloy.
  • the coatings are shown soldered to layers of phosphorus-nickel (20, 22) formed on conductors (24, 26).
  • Connecting joints (28, 30) are formed from a solder of bismuth-antimony.
  • the conductors are formed on non-conductive or insulating ceramic substrates (32, 34), such as aluminum oxide or beryllium oxide.
  • the invention is an improvement over standard modules as it provides a module that is capable of withstanding high temperatures, such as up to 275 °C.
  • This improvement allows the module to be used, for example, at 200°C in autoclaves and other types of sterilization equipment. At temperatures above 200 °C the modules can be used in downhole oil well equipment and in automobile engines.
  • Example illustrates manufacture of a preferred embodiment in accordance with the present invention:
  • Example Thermoelectric modules were fabricated using aluminum oxide plates having copper metallizations with a phosphorous-nickel layer containing approximately 10% (8% to 12%) phosphorous.
  • the copper metallizations were connected to n-t ⁇ pe and p-type elements as described below.
  • Semiconductor elements made from Bi 2 Te 3 -Bi 2 Se 3 (n-type) and Bi 2 Te 3 - Sb 2 Te 3 (p-type) were provided.
  • the ends of the semiconductor elements were coated with a thin layer, approximately 0.001 inch in thickness, of a 95% bismuth: 5% antimony alloy.
  • the coated layer on the semiconductor element was connected to the phosphorous nickel layer using a bismuth-antimony joining solder.
  • a standard acid base flux and standard soldering techniques well known in the art were used.
  • the modules using the 95:5 joining solder were tested at 165°C to 200 °C for 7000 hours with acceptable performance and no drastic changes in thermoelectric properties.
  • the modules passed through 75,000 cycles in instant power reversal testing and 1000 temperature cycles without any failures. Improved results, compared to the prior art, are obtained with other bismuth, antimony ratios within the disclosed range for the joining solder along with the bismuth or bismuth-antimony coating on the semiconductor elements.
  • Results superior to prior art products are obtained with a phosphorus content between 7 and 13% and improved results, compared with the prior art, are obtained with a phosphorous content between about 3.5 and 18%.

Landscapes

  • Measuring Temperature Or Quantity Of Heat (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Powder Metallurgy (AREA)
  • Chemically Coating (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Ceramic Products (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

A thermoelectric module (10) is formed with solder joints (28, 30), the solder containing about 50 to 99 weight percent bismuth and about 50 to 1 weight percent antimony, between the thermoelectric elements (12, 14) and the connecting conductors (24, 26). Also provided is a thermoelectric module (10) having bismuth telluride elements (12, 14) coated with a conductive material (16, 18) that does not require a nickel or other diffusion barrier. Further provided are modules (10) having conductors (24, 26) with a phosphorus-nickel surface (20, 22). Methods of manufacturing and using such thermoelectric modules (10) are further provided.

Description

FABRICATION OF THERMOELECTRIC MODULES
AND SOLDER FOR SUCH FABRICATION
This is a Continuation-in-Part of application Serial No. 08/535,449, filed October 3, 1995, for "Fabrication of Thermoelectric Modules and Solder for Such Fabricator". Field of the Invention
This invention relates to improved thermoelectric devices and to improved methods of fabricating such devices. More particularly, the invention relates to an improved joining solder, based on an alloy of bismuth and antimony, for use with thermoelectric modules; to thermoelectric elements soldered to a phosphorus-nickel surface on a conductor, such as copper, to form thermoelectric modules; and to the use of such thermoelectric modules.
Background of the Invention Thermoelectric modules are small solid-state devices that can operate as heat pumps or as electrical power generators. When used to generate electricity, the modules are called thermoelectric generators (TEG). TEG use the
Seebeck effect to generate a voltage when a temperature differential is applied.
When the modules are used as heat pumps, the modules are called thermoelectric coolers (TEC) or thermoelectric heaters (TEH) and demonstrate the Peltier effect. With the Peltier effect a temperature change results when current passes through a junction of two different types of semiconductors. Generally such semiconductors are assembled into thermoelectric modules where heat is transferred from one side of the module to the other side when current is applied. These modules can act as cooling devices where the heat pumped from the cooling side dissipates into a heatsink on the other side. The sides of the modules are generally composed of a ceramic material.
Located between the ceramic sides are semiconductor elements made from bismuth telluride, which is composed of bismuth, tellurium, selenium, and antimony. The semiconductor elements are doped to create either an excess (n- type) or a deficiency (p-type) of electrons. Typical modules of this type are described in U.S. Patent 4,855,810, Gelb et al. According to the prior art, these modules contain semiconductor elements soldered to conductors using a solder including bismuth and tin. One such solder is described in U.S. Patent 3,079,455, Haba. Haba describes a solder formed of tin, antimony, and bismuth. The bismuth is described as being in an amount from 40 to 50 weight percent and the antimony is described as being in an amount of 1.5 to 3.5 weight percent.
Thermoelectric modules built with bismuth telluride elements are used in applications where they are exposed to temperatures ranging from about -80 °C to about 250°C. The performance of such thermoelectric modules made with a tin-containing solder suffers as a result of long term exposure to wide temperature ranges. In fact, the performance of the modules has been found to decrease about fifteen percent or more per year. Thermoelectric modules made with tin-containing solder are not truly considered serviceable at temperatures substantially above 80°C.
One reason for the lack of serviceability is that the standard bismuth tin solder melts at 138°C. At temperatures above 80°C, the tin in the solder tends to diffuse rapidly into the semiconductor elements and into the crystal lattice of the semiconductor elements, where it acts as a dopant or reacts with material of the elements. Also, the tin forms a film over the surface of the material adjacent to the soldered ends, the tin acting as a resistor connected across the elements causing an IR drop and/or a short.
Gelb et al. sought to overcome the problems of tin diffusion and resistor formation by replacing the tin-based solder with a lead-antimony solder. However, at elevated temperatures, lead also diffuses and reacts with the thermoelectric semiconductor material to form a region of poor thermoelectric performance.
To prevent diffusion of lead or tin, the industry standard has been to employ a diffusion barrier between the elements and the solder, such as nickel layered on the elements. Such a system is shown, for example, in U. S. Patent 5,429,680, Fuschetti. However, this technology is very complicated, costly, and does not completely prevent diffusion of the lead or tin. Furthermore, elements made from material covered with nickel are structurally weak and do not hold up in applications involving long term power or temperature cycling. A solder formed from bismuth and antimony has been described to "tin" semiconductors. For example, Kolenko, Ye A., "Thermoelectric Cooling Devices," Foreign Science and Technology Center, U.S. Army Material Command, Department of the Army (AD 691 974), pp 131-138 (1967) describes, at Table 15, a solder having 90% bismuth and 10% antimony for the tinning of semiconductors and a BiSn joining solder. Also described at Table 15 is a solder having 80% bismuth and 20% antimony for the tinning of semiconductors. However, there is no suggestion of using this as a joining solder or in conjunction with a phosphorous -nickel surface for joining to conductors. It is an object of the invention to provide a solder which does not react with the thermoelectric material to provide a source of diffusants, dopants, and reagents.
Another object of the invention is to provide a thermoelectric module having an improved life-time and low failure rate at elevated temperatures, including temperatures up to 275 °C. A further object of the invention is to provide a thermoelectric module having a soldered structure where the solder does not form resistors across the thermoelectric elements.
Yet a further object is to provide a thermoelectric module which eliminates the need for a costly diffusion barrier.
Summarv of the Invention
The invention comprises a solder for joining conductors (e.g. buss-bars), such as those made from copper, aluminum and other well-known conductive materials, to a conductive material deposited on an end of a thermoelectric element in a thermoelectric module, wherein said solder comprises about 50-99 weight percent bismuth and about 1 -50 weight percent antimony, where the combined weight percent of the bismuth and antimony is about 100 percent, particularly when the conductors are provided with a surface of phosphorous- nickel.
The present invention also provides a method for manufacturing thermoelectric modules comprising:
1 ) depositing on each end of a bismuth telluride thermoelectric element a conductive material that does not require a diffusion barrier;
2) forming a surface of phosphorous-nickel on a conductor, such as copper or aluminum; and
3) joining said conductive material to said phosphorous-nickel surface with a solder comprising about 50 to 99 weight percent bismuth and about 1 to 50 weight percent antimony wherein the combined weight percent of the bismuth and antimony is about 100. The conductive material of step 1 is a material comprising about 50 to 100 weight percent bismuth, the remainder being, essentially, antimony.
To generate electricity from a thermal gradient, the device is subjected to a temperature gradient across the thermoelectric elements and the conductive elements are connected to complete the electrical circuit. To generate a thermal gradient, as required for thermoelectric cooling or heating, the device is subjected to a flow of electric current. A temperature gradient is created along the direction of the current flow through the thermoelectric elements due to the Peltier effect and this functions to cool at the cold junction and heat at the hot junction. The invention provides for a thermoelectric module that can be used in applications having wide operating temperatures up to and including about 275°C.
Brief Description Of the Drawings In the accompanying drawings:
Figure 1 is an isometric view of a thermoelectric module with one of the two ceramic sides removed to more clearly show the module elements;
Figure 2 is a cross-sectional view of a thermoelectric module taken along line 2-2 of Fig. 1 ; Figure 3 is a phase diagram of a binary solder alloy system of bismuth and antimony suitable for use in the present invention.
Detailed Description of the Invention
According to the present invention, a thermoelectric module is provided comprising an array of n-type and p-type thermoelectric elements formed of a semiconductive material, particularly a bismuth telluride material. The elements have a first end and a second end and are arranged in rows and columns of alternately placed n-type and p-type elements, as known in the prior art.
The elements have a thin coating of a conductive material deposited on each end wherein said coating is substantially free of a diffusion barrier such as nickel. Suitable materials for the coating are a bismuth-antimony alloy or pure bismuth. Thus, the conductive material comprises from about 50 to 100 weight percent bismuth, the remainder being, essentially, antimony. This coating, which provides a solderable surface, has a thickness of up to 0.001 inch. A conductor, formed on a non-conductive substrate, is used to connect the elements. This conductor is provided with a surface of phosphorus-nickel containing at least 3.5% phosphorus. One method of forming the surface is to provide a layer of phosphorus-nickel on top of the conductor. The amount of phosphorous contained in the phosphorus-nickel surface is generally in the range of about 3.5 to 18%. Preferably, the amount of phosphorous is from 7 to 13%, and, most preferably, from 8 to 12%. The thickness of the phosphorus-nickel layer is generally from about 20 to about 400 micro-inches. Preferably, the conductor is copper.
The phosphorous-nickel surface is soldered to the thin coating of conductive material on the thermoelectric elements using a solder comprising about 50 to 99 weight percent bismuth and about 50 to 1 weight percent antimony. Particularly for high temperature use, the solder is free of elements that act as dopants, such as tin, copper, silver, gold, lead, zinc, cadmium, indium, gallium, iodine, chlorine, sodium, and potassium. In a preferred embodiment of the present invention, the solder comprises about 75 to 96 weight percent bismuth and about 25 to 4 weight percent antimony. In a most preferred embodiment of the present invention the solder comprises about 80 to 95 weight percent bismuth and about 20 to 5 weight percent antimony.
Referring to the drawings, an improved thermoelectric module (10) (Figs. 1 and 2) is shown having an array of bismuth telluride thermoelectric elements (12, 14) of n-type (Bi2Te3 - Bi2Se3) and p-type (Bi2Te3 - Sb2Te3). The n-type and p-type elements are shown having deposited on their ends thin coatings (16, 18) of pure bismuth or a bismuth-antimony alloy. The coatings are shown soldered to layers of phosphorus-nickel (20, 22) formed on conductors (24, 26). Connecting joints (28, 30) are formed from a solder of bismuth-antimony. The conductors are formed on non-conductive or insulating ceramic substrates (32, 34), such as aluminum oxide or beryllium oxide.
The invention is an improvement over standard modules as it provides a module that is capable of withstanding high temperatures, such as up to 275 °C. This improvement allows the module to be used, for example, at 200°C in autoclaves and other types of sterilization equipment. At temperatures above 200 °C the modules can be used in downhole oil well equipment and in automobile engines. By orienting the device properly relative to the actual or desired thermal gradient and by providing electrical connections placing the device in series with a load or power source, energy conversion may be effected. When oriented so that the thermoelectric elements are all parallel to each other and to the direction of a thermal gradient, electricity will be supplied to a load or source in the circuit so long as the temperature gradient is maintained.
In a similar manner, if a current is applied to the device, it will generate a thermal gradient via the Peltier effect. Proper orientation of the device and current direction will result in either heating or cooling as desired. The following Example illustrates manufacture of a preferred embodiment in accordance with the present invention:
Example Thermoelectric modules were fabricated using aluminum oxide plates having copper metallizations with a phosphorous-nickel layer containing approximately 10% (8% to 12%) phosphorous. The copper metallizations were connected to n-tγpe and p-type elements as described below.
Semiconductor elements made from Bi2Te3-Bi2Se3 (n-type) and Bi2Te3- Sb2Te3 (p-type) were provided. The ends of the semiconductor elements were coated with a thin layer, approximately 0.001 inch in thickness, of a 95% bismuth: 5% antimony alloy. The coated layer on the semiconductor element was connected to the phosphorous nickel layer using a bismuth-antimony joining solder. A standard acid base flux and standard soldering techniques well known in the art were used.
Joining solder was used having the following Bismuth:Antimony weight percent content:
98.5:1.5
97.5:2.5 94.25:4.75
95:5
90:10
80:20. Further, in place of the bismuth-antimony coating on the semiconductor elements, a pure bismuth coating was formed on the semiconductor elements before applying the joining solder.
The modules using the 95:5 joining solder were tested at 165°C to 200 °C for 7000 hours with acceptable performance and no drastic changes in thermoelectric properties. The modules passed through 75,000 cycles in instant power reversal testing and 1000 temperature cycles without any failures. Improved results, compared to the prior art, are obtained with other bismuth, antimony ratios within the disclosed range for the joining solder along with the bismuth or bismuth-antimony coating on the semiconductor elements.
Results superior to prior art products are obtained with a phosphorus content between 7 and 13% and improved results, compared with the prior art, are obtained with a phosphorous content between about 3.5 and 18%.
In comparison, standard modules containing the nickel barrier and tin- containing solder did not pass even a limited number of power cycles.
The foregoing description is merely illustrative of the preferred embodiments and examples of the present invention and the scope of the invention is not to be limited thereto. Additional modifications of the invention will readily occur to one skilled in the art without departing from the scope of the invention.

Claims

What is Claimed is: 1. A thermoelectric module comprising: a. an array of n-type and p-type thermoelectric elements formed of semi-conductive material; b. a thin coat of a conductive material deposited on each end of the elements, said material comprising about 50 to 100 weight percent bismuth, the remainder being, essentially antimony; c. a buss bar having a phosphorous-nickel surface wherein the phosphorous content of the surface is at least 3.5%. d. a solder comprising 50 to 99 weight percent bismuth and 50 to 1 weight percent antimony joining said coated thermoelectric elements to said phosphorous-nickel on said buss bar.
2. The module of claim 1 , wherein the solder comprises about 75 to 96 weight percent bismuth and about 25 to 4 weight percent antimony.
3. The module of claim 2, wherein the solder comprises about 80 to 95 weight percent bismuth and about 20 to 5 weight percent antimony.
4. The module of claim 1 , wherein the phosphorous content is about 3.5 to 18%.
5. The module of claim 4, wherein the phosphorous content is about 7 to 13 weight percent.
6. The module of claim 5, wherein the phosphorus content is about 8 to 12 weight percent.
7. The module of claim 1 , wherein the buss bar is formed of copper.
8. The module of claim 1 , wherein the phosphorous nickel surface on the buss bar is a layer of phosphorus-nickel formed on the buss bar.
9. A method of manufacturing thermoelectric modules capable of withstanding high temperature use comprising: a. depositing on each end of a thermoelectric element a conductive material, said material comprising about 50 to 100 weight percent bismuth, the remainder being, essentially, antimony; b. forming a surface of phosphorous-nickel onto a buss bar; c. joining said conductive material to said phosphorous-nickel surface with a solder comprised of about 50 to 99 weight percent bismuth and about 50 to 1 weight percent antimony wherein the combined weight percent of the bismuth and antimony is about 100 percent.
10. The method of claim 9 wherein the solder comprises about 75 to 96 weight percent bismuth and about 25 to 4- weight percent antimony.
11. The method of claim 10 wherein the solder comprises about 80 to 95 weight percent bismuth and about 20 to 5 weight percent antimony.
12. The method of claim 9 wherein the phosphorous-nickel layer comprises at least 3.5 weight percent phosphorous.
13. The method of claim 12 wherein the phosphorous content is about 3.5 to 18%.
14. The method of claim 13 wherein the phosphorous content is about 7 to 13 weight percent.
15. The method of claim 14 wherein the phosphorous content is about 8 to 12 weight percent.
16. The method of claim 9 wherein the buss bar is formed of copper.
17. The method of claim 9 wherein the phosphorous nickel surface is a layer formed on said buss bar.
18. A method for generating electricity comprising subjecting the thermoelectric device of Claim 1 to a temperature gradient and connecting the respective conductive elements to complete an electrical circuit.
19. A method for generating electricity from a thermal gradient, comprising: (a) orienting the device of Claim 1 so that the direction of the thermal gradient is parallel to the desired direction of current flow through the thermoelectric elements; (b) maintaining said thermal gradient; (c) completing an electric circuit whereby an electrical current is generated.
20. A method of generating a thermal gradient comprising subjecting the thermoelectric device of Claim 1 to the flow of an electric current, thereby creating a temperature gradient due to the Peltier effect along the direction of current flow in the thermoelectric element.
21. A method of effecting refrigeration comprising thermally connecting the cold junction of the thermoelectric device of Claim 1 to an object to be refrigerated, thermally connecting the hot junction to a heat sink, and applying a direct current through the semiconductor elements of the device in a direction parallel to the temperature gradient in a direction so as to maintain the desired thermal gradient.
22. A method of effecting thermoelectric heating comprising connecting the hot junction of the thermoelectric device of Claim 1 to an object to be heated, connecting the cold junction to a heat sink and applying a direct current through the semiconductor elements of the device in a direction parallel to the temperature gradient in a direction so as to maintain the desired thermal gradient.
PCT/US1996/016077 1995-10-03 1996-09-30 Fabrication of thermoelectric modules and solder for such fabrication WO1997013283A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
KR1019980702474A KR19990066931A (en) 1995-10-03 1996-09-30 Fabrication of thermoelectric modules and solder used in them
AU73947/96A AU702453B2 (en) 1995-10-03 1996-09-30 Fabrication of thermoelectric modules and solder for such fabrication
IL12377396A IL123773A (en) 1995-10-03 1996-09-30 Thermoelectric modules method of their production and solder for use in said method
JP51451897A JP3862179B2 (en) 1995-10-03 1996-09-30 Manufacture and production of thermoelectric modules
AT96936249T ATE228270T1 (en) 1995-10-03 1996-09-30 MANUFACTURING THERMOELECTRIC MODULES AND SOLDER FOR THIS MANUFACTURING
BR9610829-0A BR9610829A (en) 1995-10-03 1996-09-30 Thermoelectric module, method to manufacture thermoelectric modules, method to generate electricity, method to generate a thermal gradient, method to perform cooling and method to perform thermoelectric heating, thermoelectric module, method to manufacture thermoelectric modules, method to generate electricity, method to generate a thermal gradient, method to perform cooling and method to perform thermoelectric heating.
UA98041709A UA51672C2 (en) 1995-10-03 1996-09-30 Thermo-electric module and a method of manufacture thereof; method for generating electric energy, method for creating temperature gradient, method for heating and cooling by the thermo-electric module
DK96936249T DK0870337T3 (en) 1995-10-03 1996-09-30 Preparation of thermoelectric modules and solder for such manufacture
EP96936249A EP0870337B1 (en) 1995-10-03 1996-09-30 Fabrication of thermoelectric modules and solder for such fabrication
EA199800303A EA000388B1 (en) 1995-10-03 1996-09-30 Method of fabrication of thermoelectric modules and solder for such fabrication
DE69624936T DE69624936T2 (en) 1995-10-03 1996-09-30 MANUFACTURE OF THERMOELECTRIC MODULES AND SOLDER FOR THIS MANUFACTURING
CA002233979A CA2233979C (en) 1995-10-03 1996-09-30 Fabrication of thermoelectric modules and solder for such fabrication
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0969525A1 (en) * 1998-06-29 2000-01-05 Tellurex Corporation thermoelectric module

Families Citing this family (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3459328B2 (en) * 1996-07-26 2003-10-20 日本政策投資銀行 Thermoelectric semiconductor and method for manufacturing the same
JPH10178216A (en) * 1996-12-18 1998-06-30 Seru Appl Kk Thermoelectric element and thermoelectric cooling device
JP3144328B2 (en) * 1996-12-24 2001-03-12 松下電工株式会社 Thermoelectric conversion element and method of manufacturing the same
US6034318A (en) * 1997-02-21 2000-03-07 Volvo Aero Corporation Thermoelectric generator unit
JP3982080B2 (en) 1997-12-05 2007-09-26 松下電工株式会社 Thermoelectric module manufacturing method and thermoelectric module
IL123238A0 (en) * 1998-02-09 1998-09-24 Israel Thermo Electrical Ltd Thermo-electric generator and module for use therein
US6222113B1 (en) * 1999-12-09 2001-04-24 International Business Machines Corporation Electrically-isolated ultra-thin substrates for thermoelectric coolers
US20020119079A1 (en) * 1999-12-10 2002-08-29 Norbert Breuer Chemical microreactor and microreactor made by process
US6492585B1 (en) 2000-03-27 2002-12-10 Marlow Industries, Inc. Thermoelectric device assembly and method for fabrication of same
US6271459B1 (en) 2000-04-26 2001-08-07 Wafermasters, Inc. Heat management in wafer processing equipment using thermoelectric device
JP2002134796A (en) * 2000-10-19 2002-05-10 Nhk Spring Co Ltd Bi-Te SEMICONDUCTOR ELEMENT AND Bi-Te THERMO-ELECTRIC MODULE
US6555413B1 (en) * 2001-02-23 2003-04-29 Triquint Technology Holding Co. Method for interconnecting semiconductor elements to form a thermoelectric cooler and a thermoelectric cooler formed therefrom
US6484513B1 (en) * 2001-09-05 2002-11-26 Chin-Lung Chou Freezing sucker
US7166796B2 (en) * 2001-09-06 2007-01-23 Nicolaou Michael C Method for producing a device for direct thermoelectric energy conversion
US7038234B2 (en) * 2001-12-12 2006-05-02 Hi-Z Technology, Inc. Thermoelectric module with Si/SiGe and B4C/B9C super-lattice legs
JP2003198117A (en) * 2001-12-28 2003-07-11 Matsushita Electric Ind Co Ltd Soldering method and junction structure body
US6756536B2 (en) * 2002-03-28 2004-06-29 Bae Systems Information And Electronic Systems Integration Inc. Thermoelectric microactuator
US6679064B2 (en) * 2002-05-13 2004-01-20 Taiwan Semiconductor Manufacturing Co., Ltd Wafer transfer system with temperature control apparatus
JP3989486B2 (en) * 2002-06-06 2007-10-10 古河電気工業株式会社 Thermoelectric element module and manufacturing method thereof
JP4401754B2 (en) * 2003-11-28 2010-01-20 清仁 石田 Method for manufacturing thermoelectric conversion module
US8309838B2 (en) * 2004-01-16 2012-11-13 Massachusetts Institute Of Technology Potential amplified nonequilibrium thermal electric device (PANTEC)
CN100353534C (en) * 2004-06-16 2007-12-05 华孚科技股份有限公司 Method for making electric-heating radiator and electric-heating radiator thereby
CN100346490C (en) * 2004-06-21 2007-10-31 浙江大学 A preparation method for slice type thermoelectric converter
DE102004048220A1 (en) * 2004-09-30 2006-04-06 Basf Ag Contacting of thermoelectric materials by ultrasonic welding
US7527101B2 (en) * 2005-01-27 2009-05-05 Schlumberger Technology Corporation Cooling apparatus and method
US8039726B2 (en) * 2005-05-26 2011-10-18 General Electric Company Thermal transfer and power generation devices and methods of making the same
US20070101737A1 (en) 2005-11-09 2007-05-10 Masao Akei Refrigeration system including thermoelectric heat recovery and actuation
US7310953B2 (en) 2005-11-09 2007-12-25 Emerson Climate Technologies, Inc. Refrigeration system including thermoelectric module
US20070277866A1 (en) * 2006-05-31 2007-12-06 General Electric Company Thermoelectric nanotube arrays
CN101409324B (en) * 2008-07-24 2013-10-16 中国科学院上海硅酸盐研究所 Manufacturing method of bismuth-telluride-based thermoelectric electrification device
US20100024436A1 (en) * 2008-08-01 2010-02-04 Baker Hughes Incorporated Downhole tool with thin film thermoelectric cooling
WO2010125411A1 (en) * 2009-04-27 2010-11-04 Szenergia Kft. Procedure for producing a device containing metal and intermetallic semiconductor parts joined together with an electrically conductive and heat conducting connection, especially a rod suitable for use with thermoelectric modules
DE102010035151A1 (en) * 2010-08-23 2012-02-23 Emitec Gesellschaft Für Emissionstechnologie Mbh Semiconductor element for a thermoelectric module and method for its production
WO2013119284A2 (en) * 2011-11-08 2013-08-15 Ut-Battelle, Llc Manufacture of thermoelectric generator structures by fiber drawing
JP5831554B2 (en) * 2011-11-08 2015-12-09 富士通株式会社 Thermoelectric conversion element and manufacturing method thereof
US8641917B2 (en) * 2011-12-01 2014-02-04 Toyota Motor Engineering & Manufacturing North America, Inc. Ternary thermoelectric material containing nanoparticles and process for producing the same
US20130139866A1 (en) * 2011-12-01 2013-06-06 Marlow Industries, Inc. Ceramic Plate
MD542Z (en) * 2012-01-13 2013-03-31 ИНСТИТУТ ЭЛЕКТРОННОЙ ИНЖЕНЕРИИ И НАНОТЕХНОЛОГИЙ "D. Ghitu" АНМ Thermoelectric anisotropic material on base of bismuth
JP6038187B2 (en) * 2013-01-28 2016-12-07 ニホンハンダ株式会社 Solder alloy for die bonding
US10290794B2 (en) 2016-12-05 2019-05-14 Sridhar Kasichainula Pin coupling based thermoelectric device
US11024789B2 (en) 2013-12-06 2021-06-01 Sridhar Kasichainula Flexible encapsulation of a flexible thin-film based thermoelectric device with sputter deposited layer of N-type and P-type thermoelectric legs
US10367131B2 (en) 2013-12-06 2019-07-30 Sridhar Kasichainula Extended area of sputter deposited n-type and p-type thermoelectric legs in a flexible thin-film based thermoelectric device
US20180090660A1 (en) 2013-12-06 2018-03-29 Sridhar Kasichainula Flexible thin-film based thermoelectric device with sputter deposited layer of n-type and p-type thermoelectric legs
US10566515B2 (en) 2013-12-06 2020-02-18 Sridhar Kasichainula Extended area of sputter deposited N-type and P-type thermoelectric legs in a flexible thin-film based thermoelectric device
US10141492B2 (en) 2015-05-14 2018-11-27 Nimbus Materials Inc. Energy harvesting for wearable technology through a thin flexible thermoelectric device
CA2868197C (en) 2014-01-31 2020-03-10 Berken Energy Llc Methods for thick film thermoelectric device fabrication
US20150240793A1 (en) * 2014-02-21 2015-08-27 The Boeing Company Temperature control system for shape-memory alloy
TWI575786B (en) * 2014-04-08 2017-03-21 財團法人紡織產業綜合研究所 Thermoelectric transfer element
KR20160028697A (en) 2014-09-04 2016-03-14 한국전기연구원 Bulk type small area thermoelectric module and method of manufacturing thereof
US11283000B2 (en) 2015-05-14 2022-03-22 Nimbus Materials Inc. Method of producing a flexible thermoelectric device to harvest energy for wearable applications
US11276810B2 (en) 2015-05-14 2022-03-15 Nimbus Materials Inc. Method of producing a flexible thermoelectric device to harvest energy for wearable applications
US9995288B2 (en) 2016-01-28 2018-06-12 The Boeing Company Solid-state motor and associated systems and methods
US11616181B2 (en) * 2016-06-14 2023-03-28 Ariel Scientific Innovations Ltd. Thermoelectric generator
US10288048B2 (en) 2016-12-16 2019-05-14 The Boeing Company Deforming shape memory alloy using self-regulating thermal elements
CN109873096A (en) * 2017-12-01 2019-06-11 中国电力科学研究院有限公司 A kind of vehicle mounted dynamic battery group of temperature adjustable
CN108461617A (en) * 2018-02-08 2018-08-28 南方科技大学 Temperature regulation device and preparation method
CN108281541A (en) * 2018-02-08 2018-07-13 南方科技大学 Pre-formable thermoelectric device and preparation method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3110100A (en) * 1962-01-11 1963-11-12 Gen Instrument Corp Method of bonding bismuth-containing bodies
US3449173A (en) * 1964-09-18 1969-06-10 Siemens Ag Thermoelectric couple with soft solder electrically connecting semi-conductors and method of making same
US3859143A (en) * 1970-07-23 1975-01-07 Rca Corp Stable bonded barrier layer-telluride thermoelectric device
US4489742A (en) * 1983-07-21 1984-12-25 Energy Conversion Devices, Inc. Thermoelectric device and method of making and using same
US4503131A (en) * 1982-01-18 1985-03-05 Richardson Chemical Company Electrical contact materials
US5429680A (en) * 1993-11-19 1995-07-04 Fuschetti; Dean F. Thermoelectric heat pump

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685608A (en) * 1951-11-02 1954-08-03 Siemens Ag Thermoelement, particularly for the electrothermic production of cold
US3079455A (en) * 1956-09-14 1963-02-26 Rca Corp Method and materials for obtaining low resistance bonds to bismuth telluride
US3037064A (en) * 1960-12-12 1962-05-29 Rca Corp Method and materials for obtaining low resistance bonds to thermoelectric bodies
GB1142200A (en) * 1965-11-17 1969-02-05 Ass Elect Ind Improvements relating to vacuum switch contacts
CN85108316B (en) * 1985-11-07 1987-09-09 西北大学 Solder for semiconductor refrigerator
US4764212A (en) * 1986-02-21 1988-08-16 Kabushiki Kaisha Komatsu Seisakusho Thermoelectric material for low temperature use and method of manufacturing the same
US4855810A (en) * 1987-06-02 1989-08-08 Gelb Allan S Thermoelectric heat pump
US4806309A (en) * 1988-01-05 1989-02-21 Willard Industries, Inc. Tin base lead-free solder composition containing bismuth, silver and antimony

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3110100A (en) * 1962-01-11 1963-11-12 Gen Instrument Corp Method of bonding bismuth-containing bodies
US3449173A (en) * 1964-09-18 1969-06-10 Siemens Ag Thermoelectric couple with soft solder electrically connecting semi-conductors and method of making same
US3859143A (en) * 1970-07-23 1975-01-07 Rca Corp Stable bonded barrier layer-telluride thermoelectric device
US4503131A (en) * 1982-01-18 1985-03-05 Richardson Chemical Company Electrical contact materials
US4489742A (en) * 1983-07-21 1984-12-25 Energy Conversion Devices, Inc. Thermoelectric device and method of making and using same
US5429680A (en) * 1993-11-19 1995-07-04 Fuschetti; Dean F. Thermoelectric heat pump

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TERMOELEKTRICHESKIYE CKHLAZHDAYUSHCHIYE PRIBORY, 1967, YE A. KOLENKO, "Thermoelectric Cooling Devices", pages 131-138. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0969525A1 (en) * 1998-06-29 2000-01-05 Tellurex Corporation thermoelectric module

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