CN115064637A - Method for enhancing high temperature stability of thermoelectric semiconductor device - Google Patents
Method for enhancing high temperature stability of thermoelectric semiconductor device Download PDFInfo
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- CN115064637A CN115064637A CN202210517457.4A CN202210517457A CN115064637A CN 115064637 A CN115064637 A CN 115064637A CN 202210517457 A CN202210517457 A CN 202210517457A CN 115064637 A CN115064637 A CN 115064637A
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- thermoelectric
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- thermoelectric semiconductor
- copper substrate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N19/00—Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
- H10N19/101—Multiple thermocouples connected in a cascade arrangement
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- 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
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- 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
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- 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
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
Abstract
The invention relates to a method for enhancing the high temperature stability of a thermoelectric semiconductor device, which comprises the following steps: the thermoelectric arms are made of antimony telluride, and two ends of each thermoelectric arm are provided with nickel plates beneficial to welding; the Sn paste is printed on the copper substrate through the printing screen plate, the Sn paste amount between the copper substrate and the thermoelectric arm is controlled, the thermoelectric arm and the copper substrate are assembled to form a thermoelectric semiconductor assembly, the thermoelectric semiconductor assembly is heated in a vacuum state with small welding pressure, welding interconnection is realized, a Sn bridge cannot be generated between the thermoelectric arms of the manufactured thermoelectric semiconductor device, when the thermoelectric semiconductor device works in a high-temperature environment for a long time, element diffusion cannot be easily generated on a welding interface, Cu elements of the copper substrate cannot be diffused to the thermoelectric arms, and high-temperature stability is enhanced.
Description
Technical Field
The invention relates to the technical field of thermoelectric semiconductor devices, in particular to a method for enhancing the high-temperature stability of a thermoelectric semiconductor device.
Background
The semiconductor can obtain the thermoelectric electromotive force which is much larger than that of metal, the conversion of heat energy and electric energy has higher efficiency, and thermoelectric power generation usually adopts a thermoelectric semiconductor device for thermoelectric conversion; the thermoelectric semiconductor device comprises two copper substrates and a plurality of thermoelectric arms made of thermoelectric materials, wherein two ends of each thermoelectric arm are correspondingly welded and interconnected with the two copper substrates one by one; chinese patent application No.: the invention of CN202010419067.4 relates to a high reliability thermoelectric module system, comprising N single thermoelectric modules; the single thermoelectric module comprises a semiconductor thermoelectric arm, a copper conducting strip and an insulating layer. The single thermoelectric module is a thermoelectric semiconductor device, the copper conducting strip is a copper substrate, and the semiconductor thermoelectric arm is a thermoelectric arm. The thermoelectric arm and the copper conducting strip are welded by adopting a hot (carbon) plate welding heating mode and are interconnected through Sn welding; because the copper substrate bears larger welding pressure during welding, element diffusion is easy to generate on a welding interface, residual Sn can be extruded during welding, Sn bridges are easy to generate between thermoelectric arms, and when the copper substrate works in a high-temperature environment for a long time, Cu elements of the copper substrate can diffuse to the thermoelectric arms through the Sn bridges of diffusion channels, so that the components of the thermoelectric arms are changed, the resistance and the thermoelectric performance of a thermoelectric semiconductor device are influenced, the stability of the thermoelectric semiconductor device in the high-temperature environment is reduced, and the service life of the thermoelectric semiconductor device is influenced, therefore, the method for enhancing the high-temperature stability of the semiconductor device is designed, wherein the element diffusion is not easy to generate on the welding interface, Sn bridges are not generated between the thermoelectric arms, and the Cu elements of the copper substrate cannot diffuse to the thermoelectric arms when the copper substrate works in the high-temperature environment for a long time, the resistance and the thermoelectric performance of the thermoelectric semiconductor device are not influenced, and the stability of the thermoelectric semiconductor device in the high-temperature environment is enhanced, the problem to be solved is to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for enhancing the high-temperature stability of a thermoelectric semiconductor device, wherein element diffusion is not easy to generate on a welding interface, an Sn bridge is not easy to generate between thermoelectric arms, Cu element of a copper substrate is not diffused to the thermoelectric arms when the thermoelectric semiconductor device works in a high-temperature environment for a long time, the resistance and the thermoelectric performance of the thermoelectric semiconductor device are not influenced, and the stability of the thermoelectric semiconductor device in the high-temperature environment is enhanced.
The specific technical scheme of the invention is as follows:
a method of enhancing high temperature stability of a thermoelectric semiconductor device, said thermoelectric semiconductor device comprising: the thermoelectric arms are made of antimony telluride, and two ends of each thermoelectric arm are provided with nickel plates beneficial to welding; the Sn paste is printed on the copper substrate through the printing screen plate, the Sn paste amount between the copper substrate and the thermoelectric arm is controlled, the thermoelectric arm and the copper substrate are assembled to form a thermoelectric semiconductor assembly, the thermoelectric semiconductor assembly is heated in a vacuum state with small welding pressure, welding interconnection is realized, a Sn bridge cannot be generated between the thermoelectric arms of the manufactured thermoelectric semiconductor device, when the thermoelectric semiconductor device works in a high-temperature environment for a long time, element diffusion cannot be easily generated on a welding interface, Cu elements of the copper substrate cannot be diffused to the thermoelectric arms, and high-temperature stability is enhanced.
Preferably, the method for enhancing the high temperature stability of the thermoelectric semiconductor device comprises the following steps: preparing a thermoelectric arm, a copper substrate and Sn paste; designing and manufacturing a printing screen; step three, printing the Sn paste on the copper substrate through a printing screen; fourthly, assembling the thermoelectric arm and the copper substrate to form a thermoelectric semiconductor component; and fifthly, putting the thermoelectric semiconductor assembly into a vacuum welding furnace for welding interconnection, and cooling after high-temperature heat preservation to obtain the thermoelectric semiconductor device.
Preferably, in the second step, the mesh of the printing screen plate penetrates through two ends of the printing screen plate, the cross-sectional shape of the mesh is designed according to the shape and the size of the welding surface of the thermoelectric arm, the cross-sectional shape of the mesh is a similar shape corresponding to the welding surface of the thermoelectric arm, and the size of the mesh is 0.8 to 1.2 times of the size of the welding surface of the thermoelectric arm; adjacent meshes cannot be interconnected; the shape of the mesh is square or rectangular or round.
Preferably, the cross section of the mesh is square, which is the same as the welding surface of the thermoelectric arm; the size of the soldering surface of the thermoelectric legs is 1.32mm x 1.32mm, and the height of the thermoelectric legs is 1.5 mm.
Preferably, in the third step, the Sn paste is printed on the copper substrate, and one end of the Sn paste far away from the copper substrate is flush with one end of the mesh far away from the copper substrate.
Preferably, in the fifth step, when the thermoelectric semiconductor assembly is placed into a vacuum welding furnace for welding interconnection, the preheating heating rate is less than or equal to 4 ℃/s, the welding temperature is 250 ℃ to 310 ℃, the welding time is 10 to 40s, the vacuum degree is kept less than or equal to 10Pa during welding, the heat preservation temperature is 190 ℃ to 210 ℃, the time is 90 to 120s, and the cooling rate is less than or equal to 4 ℃/s.
Preferably, the vacuum soldering furnace is a vacuum reflow furnace.
Compared with the prior art, the invention has the beneficial effects that: according to the method for enhancing the high-temperature stability of the thermoelectric semiconductor device, the corresponding printing screen plate is designed according to the shape and the size of the welding surface of the thermoelectric arm, Sn paste is printed on the copper substrate through the printing screen plate, the amount of the Sn paste between the copper substrate and the thermoelectric arm is controlled, the heating is carried out in a vacuum state with smaller welding pressure, the welding interconnection is realized, an Sn bridge cannot be generated between the thermoelectric arms, the diffusion channel of Cu of the copper substrate to the thermoelectric arm is reduced, the diffusion of Cu is inhibited, when the thermoelectric semiconductor device works in a high-temperature environment for a long time, Cu elements of the copper substrate cannot be diffused to the thermoelectric arm, the resistance and the thermoelectric performance of the thermoelectric semiconductor device cannot be influenced, and the stability of the thermoelectric semiconductor device in the high-temperature environment is enhanced. The vacuum welding furnace is adopted for heating welding, so that the pressure in the welding process is conveniently controlled, and the phenomenon that a great amount of Sn paste is extruded to generate Sn bridges due to higher welding pressure in the welding process is avoided; the vacuum welding furnace is a vacuum reflow welding furnace, the vacuum reflow welding adopts the infrared radiation heating principle, and the vacuum reflow welding furnace has the characteristics of uniform and consistent temperature, ultralow-temperature safe welding, no temperature difference, no overheating, reliable and stable process parameters, no need of complex process tests, low environmental protection cost operation and the like. When the thermoelectric semiconductor component is placed into a vacuum welding furnace for welding interconnection, the preheating temperature rise rate is less than or equal to 4 ℃/s, the welding temperature is 250-310 ℃, the welding time is 10-40 s, the vacuum degree is kept less than or equal to 10Pa during welding, the heat preservation temperature is 190-210 ℃, the time is 90-120 s, and the cooling rate is less than or equal to 4 ℃/s, so that the welding interconnection quality of the thermoelectric semiconductor device is favorably ensured.
Drawings
FIG. 1 is a schematic view of a thermoelectric semiconductor device according to the present invention;
FIG. 2 is a schematic diagram of a prior art thermoelectric semiconductor device having Sn bridges;
fig. 3 is a graph comparing the rate of change of resistance of thermoelectric semiconductor devices without Sn bridges and with Sn bridges.
In the figure: the thermoelectric module comprises a copper substrate 1, a thermoelectric arm 2, Sn paste 3, Sn bridges 4, a resistance change rate curve A without Sn bridges and a resistance change rate curve B with Sn bridges.
Detailed Description
The invention will be further described with reference to the drawings.
As shown in the attached figures 1 and 2: a method of enhancing high temperature stability of a thermoelectric semiconductor device, said thermoelectric semiconductor device comprising: two copper substrates 1, a plurality of thermoelectric arms 2 with two ends corresponding to the two copper substrates 1 in a one-to-one manner and connected with each other in a welding manner; the method comprises the steps of printing Sn paste 3 on a copper substrate 1 through a printing screen, controlling the amount of the Sn paste 3 between the copper substrate 1 and a thermoelectric arm 2, assembling the thermoelectric arm 2 and the copper substrate 1 to form a thermoelectric semiconductor assembly, heating the thermoelectric semiconductor assembly in a vacuum state with small welding pressure, realizing welding interconnection, avoiding Sn bridges 4 between the thermoelectric arms 2 of the manufactured thermoelectric semiconductor device, ensuring that a welding interface is not easy to generate element diffusion when the thermoelectric semiconductor device works in a high-temperature environment for a long time, avoiding the Cu element of the copper substrate 1 from diffusing to the thermoelectric arms 2, and enhancing high-temperature stability.
The method for enhancing the high-temperature stability of the thermoelectric semiconductor device comprises the following steps: preparing a thermoelectric arm 2, a copper substrate 1 and Sn paste 3; designing and manufacturing a printing screen; step three, printing the Sn paste 3 on the copper substrate 1 through a printing screen; step four, assembling the thermoelectric arm 2 and the copper substrate 1 to form a thermoelectric semiconductor component; and fifthly, placing the thermoelectric semiconductor assembly into a vacuum welding furnace for welding interconnection, and cooling after high-temperature heat preservation to obtain the thermoelectric semiconductor device.
In the second step, the meshes of the printing screen penetrate through two ends of the printing screen, the cross-sectional shapes of the meshes are designed according to the shape and the size of the welding surface of the thermoelectric arm 2, the cross-sectional shapes of the meshes are similar to the shape corresponding to the welding surface of the thermoelectric arm 2, and the size of the meshes is 0.8 to 1.2 times of the size of the welding surface of the thermoelectric arm 2; adjacent meshes cannot be interconnected; the shape of the mesh is square or rectangular or round.
In the embodiment, the cross section of the mesh is square, which is the same as the welding surface of the thermoelectric arm 2; the size of the welding surface of the thermoelectric arm 2 is 1.32mm x 1.32mm, and the height size of the thermoelectric arm 2 is 1.5 mm; mesh size was 1.32 mm.
In the third step, the Sn paste 3 is printed on the copper substrate 1, and one end of the Sn paste 3, which is far away from the copper substrate 1, is flush with one end of the mesh, which is far away from the copper substrate 1; the Sn paste 3 is an SnSb based Sn paste 3.
In the fifth step, when the thermoelectric semiconductor assembly is placed into a vacuum welding furnace for welding interconnection, the preheating heating rate is less than or equal to 4 ℃/s, the welding temperature is 250 ℃ to 310 ℃, the welding time is 10 to 40s, the vacuum degree is kept less than or equal to 10Pa during welding, the heat preservation temperature is 190 ℃ to 210 ℃, the time is 90 to 120s, and the cooling rate is less than or equal to 4 ℃/s. In the embodiment, the welding temperature is 290 ℃, the welding time is 30s, and the vacuum degree is kept at 5Pa during welding; keeping the temperature at 175 ℃ for 100 s; the temperature is reduced for 32h, the resistance change rate is 23.36 percent, the temperature is lower than that of the thermoelectric semiconductor device with the Sn bridge for the same time 32h, and the resistance change rate is 42.86 percent.
The vacuum welding furnace is a vacuum reflow furnace.
In addition to the above embodiments, the technical features or technical data of the present invention may be reselected and combined to form new embodiments within the scope of the claims and the specification of the present invention, which are all realized by those skilled in the art without creative efforts, and thus, the embodiments of the present invention not described in detail should be regarded as specific embodiments of the present invention and are within the protection scope of the present invention.
Claims (7)
1. A method of enhancing high temperature stability of a thermoelectric semiconductor device, said thermoelectric semiconductor device comprising: the thermoelectric arms are welded and interconnected with the two copper substrates one by one, and the two ends of each thermoelectric arm correspond to the copper of the two copper substrates one by one; the method is characterized in that Sn paste is printed on a copper substrate through a printing screen plate, the amount of the Sn paste between the copper substrate and a thermoelectric arm is controlled, the thermoelectric arm and the copper substrate are assembled to form a thermoelectric semiconductor assembly, the thermoelectric semiconductor assembly is heated in a vacuum state, welding interconnection is realized, an Sn bridge cannot be generated between the thermoelectric arms of the manufactured thermoelectric semiconductor device, when the thermoelectric semiconductor device works in a high-temperature environment for a long time, element diffusion cannot be easily generated on a welding interface, Cu elements of the copper substrate cannot be diffused to the thermoelectric arms, and high-temperature stability is enhanced.
2. The method of enhancing high temperature stability of a thermoelectric semiconductor device as recited in claim 1, comprising the steps of: preparing a thermoelectric arm, a copper substrate and Sn paste; designing and manufacturing a printing screen; step three, printing the Sn paste on the copper substrate through a printing screen; fourthly, assembling the thermoelectric arm and the copper substrate to form a thermoelectric semiconductor component; and fifthly, placing the thermoelectric semiconductor assembly into a vacuum welding furnace for welding interconnection, and cooling after high-temperature heat preservation to obtain the thermoelectric semiconductor device.
3. The method of claim 2, wherein in the second step, the mesh holes of the printing screen penetrate through the two ends of the printing screen, the cross-sectional shape of the mesh holes is designed according to the shape and size of the welding surface of the thermoelectric arms, the cross-sectional shape of the mesh holes is similar to the shape corresponding to the welding surface of the thermoelectric arms, and the size of the mesh holes is 0.8 to 1.2 times of the size of the welding surface of the thermoelectric arms; adjacent meshes cannot be interconnected.
4. A method for enhancing high temperature stability of a thermoelectric semiconductor device as recited in claim 3, wherein said mesh has a cross-sectional shape of a square same as a bonding surface of said thermoelectric legs.
5. The method of claim 3, wherein in step three, the Sn paste is printed on the copper substrate, and the end of the Sn paste away from the copper substrate is flush with the end of the mesh away from the copper substrate.
6. The method for enhancing high temperature stability of a thermoelectric semiconductor device as claimed in claim 2, 3, 4 or 5, wherein in the fifth step, when the thermoelectric semiconductor assembly is placed into a vacuum welding furnace for welding interconnection, the preheating temperature rise rate is less than or equal to 4 ℃/s, the welding temperature is 250 ℃ to 310 ℃, the welding time is 10 to 40s, the vacuum degree is maintained to be less than or equal to 10Pa during welding, the holding temperature is 190 to 210 ℃, the time is 90 to 120s, and the cooling temperature fall rate is less than or equal to 4 ℃/s.
7. The method of enhancing high temperature stability of a thermoelectric semiconductor device as recited in claim 6, wherein said vacuum soldering furnace is a vacuum reflow furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210517457.4A CN115064637A (en) | 2022-05-12 | 2022-05-12 | Method for enhancing high temperature stability of thermoelectric semiconductor device |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210517457.4A CN115064637A (en) | 2022-05-12 | 2022-05-12 | Method for enhancing high temperature stability of thermoelectric semiconductor device |
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| CN115064637A true CN115064637A (en) | 2022-09-16 |
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| CN202210517457.4A Pending CN115064637A (en) | 2022-05-12 | 2022-05-12 | Method for enhancing high temperature stability of thermoelectric semiconductor device |
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