JPH08153899A - Thermomodule for thermoelectric conversion and production thereof - Google Patents

Abstract

PURPOSE: To facilitate the arrangement of N-type and P-type semiconductor compound elements and the connection of electrode thereof by bonding an insulating frame, the N-type and P-type semiconductor compound elements, and a plurality of electrodes integrally. CONSTITUTION: A plurality of through holes 11 are made through an insulating frame 12 while spaced apart from each other and then the through holes 11 are filled, alternately, with N-type and P-type semiconductor compound elements 13, 14. On the upper and lower surfaces of the insulating frame 12, a plurality of electrodes 16, 17 of the N-type and P-type semiconductor compound elements 13, 14 are connected electrically in series in the order of N, P, N, P. The insulating frame 12, the N-type and P-type semiconductor compound elements 13, 14 and the electrodes 16, 17 are bonded integrally. This method facilitates the arrangement of the N-type and P-type semiconductor compound elements 13, 14 and the connection with the electrodes 16, 17.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoelectric conversion thermomodule using a plurality of pairs of thermoelectric semiconductor compound elements having a Peltier effect and a method for manufacturing the thermomodule.

[0002]

2. Description of the Related Art As shown in FIG. 5, a thermoelectric conversion thermomodule 1 has a plurality of N-type semiconductor compound elements 2 and P-type semiconductor compound elements 3 electrically connected in series in the order of N, P, N, P. A plurality of metal electrodes 4a and 4b are soldered so as to be connected, and lead wires 5 and 6 are respectively connected to the N-type semiconductor compound element 2a at the end and a P-type semiconductor compound element (not shown). When a positive voltage V _M is applied to the N-type semiconductor compound element 2a which is the N-side terminal and a negative voltage VM is applied to the P-type semiconductor compound element (not shown) which is the P-side terminal, a current I changes from the N-type of each element to P The amount of heat that flows into the mold and is absorbed by each upper bonding electrode 4a is transported downward in parallel through each element. As a result, the total heat quantity Q _c is absorbed on the upper surface of the module 1, and this heat is added to the heat quantity corresponding to the total supplied power P _M on the lower electrode surface to become the total heat generation quantity Q _{h on} the lower surface of the module 1. Is released.

Conventionally, a thermoelectric conversion thermomodule is manufactured by the following method, for example. First, an ingot (crystal rod) for an N-type semiconductor compound element and an ingot for a P-type semiconductor compound element are prepared. After slicing the ingot for the N-type semiconductor compound device, it is pulverized into a fine powder of about 50 μm or less. This fine powder is compression-molded into a chip shape, sintered, and then Ni-plated to obtain an N-type semiconductor compound element. After the P-type semiconductor compound device is also manufactured in the same manner, a plurality of N-type and P-type semiconductor compound devices are arranged in the order of N, P, N, P as shown in FIG. Soldered to metal electrode.

[0004]

However, the above-mentioned conventional manufacturing method has many steps and is complicated, and the N-type semiconductor compound element and the P-type semiconductor compound element are arranged so as to have the Peltier effect. The work of connecting to the electrodes requires careful attention, and it was difficult to efficiently mass-produce the thermoelectric conversion thermomodule. Further, since the thermoelectric conversion thermomodule manufactured by the above method is a skeleton type, it has a problem that mechanical strength is not sufficient and dust and the like easily enter between the elements.

An object of the present invention is that the number of steps is relatively small and simple, the arrangement of the N-type semiconductor compound element and the P-type semiconductor compound element to have the Peltier effect and the connection with the electrodes are easy, and the thermoelectric conversion is performed. It is to provide a manufacturing method capable of efficiently mass-producing thermoelectric modules for use. Another object of the present invention is to provide a thermoelectric conversion thermomodule that has high mechanical strength and is free from dust and the like between elements.

[0006]

Means for Solving the Problems FIG. 1A and FIG.
As shown in (b), in the thermoelectric conversion thermomodule 10 of the present invention, an insulating form 12 having a plurality of through holes 11 provided at intervals, and these through holes 11 are alternately filled. N-type semiconductor compound device 13 and P-type semiconductor compound device 1
4, a pair of N-type semiconductor compound element 13 and P-type semiconductor compound element 14 on the upper surface and the lower surface of the mold 12,
A plurality of electrodes 16 electrically connected in series in the order of N and P,
Prepare with 17. The characteristic structure is that the mold 12 and the N-type and P-type semiconductor compound elements 13 and 14 and the electrodes 16 and 17 are integrally fixed.

As shown in FIGS. 1 and 2, the first method for manufacturing a thermoelectric conversion thermomodule according to the present invention has an insulating form 12 so that a plurality of through holes 11 are formed at intervals.
On the first mask 21 (FIG. 2 (a)), a step of covering the mold 12 with a first mask 21 that covers every other of these through holes 11 (FIG. 2 (b)). And the step of filling the plurality of through holes 11 not covered with the mask 21 with the N-type semiconductor compound element material 13a (FIG. 2C), the plurality of through holes not filled with the N-type semiconductor compound element material 13a. A step of covering the mold 12 with the second mask 22 that covers the mask 11 (FIG. 2D).
A step of filling a plurality of through holes 11 not covered with 2 with a P-type semiconductor compound element material 14a (FIG. 2 (e)), and a pair of N-type semiconductor compound element material 13a and P-type semiconductor compound element material 14a. The N-type and P-type semiconductor compound element materials 13a, 1 filled in the upper and lower surfaces of the mold 12 so as to be electrically connected in series in the order of N, P, N, P regularly
4a, a step of applying a conductive paste on each surface, and heat treatment of the mold 12 coated with the conductive paste to change the conductive paste into baking electrodes 16 and 17 and N-type and P-type semiconductor compound element materials 13a and 14a. To the sintered N-type and P-type semiconductor compound devices 13 and 14, respectively, and form 1
2 and N-type and P-type semiconductor compound devices 13 and 14 and electrode 1
6 and 17 are integrally fixed to each other (FIGS. 1A and 1B).

Further, as shown in FIGS. 3 and 4, in the second method of manufacturing the thermoelectric conversion thermomodule of the present invention, the electrodes 16 and 17 are made of the N-type and P-type semiconductor compound element material, and the electrodes of the mold 12 are made transparent. Before filling the holes 11, electrodes 16 and 17 are formed on the upper surface and the lower surface of the form 12 so as to connect the pair of adjacent through holes 11 and 11, and the through hole edges adjacent to the upper surface and the lower surface, Then, as shown in FIGS. 2A to 2E, N-type and P-type semiconductor compound element materials 13a,
14a is filled in the through holes 11 of the mold 12 and heat-treated.

[0009]

[Function] The mold 12 is formed by the first and second masks 21 and 22.
The N-type semiconductor compound element material 13a and the P-type semiconductor compound element material 14a can be filled into the plurality of through-holes 11 exactly one by one so as to have the Peltier effect. Electrodes 16,1
7 can be easily formed by applying a conductive paste by screen printing or the like. By heat treatment, the mold 12 and the N-type and P-type semiconductor compound elements 13 and 14 and the electrodes 16 and 17 are formed.
Since they are integrally fixed, the number of steps is relatively small. The thermoelectric conversion thermomodule 10 thus obtained has high mechanical strength due to the presence of the mold 12, and has high reliability because dust or the like does not enter between the elements.

[0010]

Embodiments of the present invention will now be described in detail with reference to the drawings. <Example 1> A thermoelectric conversion thermomodule obtained by the first manufacturing method will be described with reference to Figs. In this example, the thermoelectric semiconductor compound is Bi ₂ Te ₃
A system semiconductor compound was used. First, a B ₂ O ₃ —PbO low-melting glass powder, an acrylic resin, and water are uniformly kneaded, and the kneaded product is extruded to form a plurality of through holes 11 at equal intervals as shown in FIG. 2 (a). An insulative mold 12 having a grid pattern like a square was obtained. The mold 12 was covered with the first mask 21 that covers every other of these through holes 11 (FIG. 2B). That is, the mask 21 has a square window hole 2 of the same shape and size as the through hole 11.
1a are arranged in a zigzag pattern.

The mask 21 is brought into close contact with the mold 12 so that the mold 12
Was placed on a base plate (not shown), and then the entire through hole 11 was filled by the slip casting method in which the slip 13a in which the N-type semiconductor compound powder was mixed with the solvent was injected from the window frame 21a (FIG. 2C). After volatilizing the solvent from the slip 13a, the mold 12 was covered with the second mask 22 that covers the plurality of through holes 11 not filled with the slip 13a (FIG. 2D). That is, in the mask 22, square window holes 22a having the same shape and size as the through holes 11 are arranged in a zigzag pattern. After the mask 22 is brought into close contact with the mold 12, the slip casting method of injecting the slip 14a in which the P-type semiconductor compound powder is mixed with the solvent from the window frame 22a is filled into the entire through hole 11 to evaporate the solvent from the slip 14a. (Fig. 2 (e)).

In this example, the N-type semiconductor compound element powder has an atomic ratio of Bi40%, Te57%, Se3%, and P
Type semiconductor compound device powder has an atomic ratio of Bi 28%, Sb1
2% and Te 60%, both powders have an average particle size of about 50
μm. Terepineol was used as the solvent, and the slips 13a and 14a were each composed of the semiconductor compound element powder 5
It was prepared by mixing 0% by weight and 50% by weight of solvent. After the slips 13a and 14a are dried, the pair of N-type slips 13a and P-type slips 14a are regularly N, P,
The upper and lower surfaces of the mold 12 and the dried slips 13a and 14a so as to be electrically connected in series in the order of N and P.
A conductive paste was applied to each surface of the above by a screen printing method (FIGS. 1 (a) and 1 (b)). In this example, the conductive paste contains Al powder and glass frit.

After applying the conductive paste, the mold 12 was heat-treated at 460 ° C. for 10 hours in an Ar gas atmosphere. As shown in FIGS. 1 (a) and 1 (b), the conductive paste becomes the baking electrodes 16 and 17 by the heat treatment, and the N-type slip 13a and the P-type slip 14a are the N-type and P-type semiconductors of the sintered body. It was changed to compound devices 13 and 14, respectively.
At the same time, the mold 12 and the N-type and P-type semiconductor compound device 1
3, 14 and the electrodes 16, 17 were integrally fixed. Lead wires 18 and 19 were soldered to the N-type semiconductor compound element 13b and the P-type semiconductor compound element 14b at the ends, respectively.

When a positive voltage of the DC power source is applied to the N-type semiconductor compound element 13b which is the N-side terminal and a negative voltage is applied to the P-type semiconductor compound element 14b which is the P-side terminal via the leads 18 and 19, a current is generated. The amount of heat that flows from the N-type to the P-type of each element and is absorbed by each upper bonding electrode 16 is transported in parallel downward through each element. As a result, the total amount of heat Q _c is absorbed by the upper surface of the module 10, and this heat is added to the amount of heat corresponding to the total supplied power on the lower electrode surface, and becomes the total amount of heat generation Q _h , which is radiated on the lower surface of the module 10. It

<Embodiment 2> A thermoelectric conversion thermomodule obtained by the second manufacturing method will be described with reference to FIGS. 3 and 4. Among the plurality of through holes 11 of the mold 12 obtained by extrusion molding in Example 1, a pair of adjacent through holes 1
Electrodes 16 and 17 were formed on the upper and lower surfaces of the mold 12 and the through-hole edges adjacent to the upper and lower surfaces so as to connect 1 and 11. That is, after the Al paste is applied by a printing method to the upper and lower surfaces of the mold 12 that is the boundary between the pair of through holes 11 and 11 and the edge of the through holes adjacent to the upper and lower surfaces, the mold 12 is covered with Ar. In a gas atmosphere, it was heat-treated at 600 ° C. for 1 hour to be sintered, and at the same time, Ni paste was baked into electrodes 16 and 17.

Then, as in the first embodiment, the first mask 21 is used.
Was cast on the mold 12 and N-type semiconductor compound device powder was injected through the window 21a, and then pressed at a pressure of 30 kg / mm ² . Subsequently, as in the second embodiment, the second mask 22 is attached to the mold 1
2 and the P-type semiconductor compound device powder was similarly injected through the window 22a and then pressed. These N-type semiconductor compound device powders and P-type semiconductor compound device powders are used in Example 1.
The same powder as that contained in the slips 13a and 14a of Example 1 was used. The mold 12 was heat-treated at 460 ° C. for 10 hours in an Ar gas atmosphere. Although not shown, the heat treatment converts the N-type semiconductor compound element powder and the P-type semiconductor compound element powder into a sintered N-type semiconductor compound element and a P-type semiconductor compound element, respectively, and simultaneously forms the mold and the N-type and P-type semiconductors. The compound element and the electrode were integrally fixed. A thermoelectric conversion thermomodule was obtained by connecting a pair of lead wires to the N-type and P-type semiconductor compound elements at the ends.

In the first embodiment, the slips 13a and 13a
Although 4a was injected into the unsintered mold, it may be injected into the sintered mold as in Example 2. Although B ₂ O ₃ —PbO-based low-melting glass was used as the material for the mold, other ceramic materials may be used as long as they have the same shrinkage amount during sintering as the N-type and P-type semiconductor compound elements. Good. Further, the second mask 22 may be replaced by the first mask 21. In this case, after forming the mask larger than the mold 12 and increasing the number of window holes, the positions of the window holes may be shifted by one row before use.

[0018]

As described above, according to the manufacturing method of the present invention, the N-type semiconductor compound element material and the P-type semiconductor compound element material are formed in a plurality of through holes of the mold by a predetermined mask.
Can be filled every other time, and can be heat treated to form and N type and P
Type semiconductor compound element and electrode are integrally fixed,
In addition to the relatively small number of steps, the arrangement of the N-type semiconductor compound element and the P-type semiconductor compound element and the connection with the electrodes for having the Peltier effect can be easily performed. As a result, thermoelectric conversion thermomodules can be mass-produced efficiently and connection errors between elements can be eliminated.
The thermoelectric conversion thermomodule thus obtained has high mechanical strength due to the presence of the mold, and has high reliability because dust or the like does not enter between the elements.

[Brief description of drawings]

FIG. 1A is an upper perspective view of a thermoelectric conversion thermomodule of the present invention. (B) The lower perspective view of the thermoelectric conversion thermomodule of the present invention.

FIG. 2 is a perspective view showing the first method for manufacturing a thermoelectric conversion thermomodule of the present invention in the order of steps.

FIG. 3A is an upper perspective view of a mold for manufacturing the second thermoelectric conversion thermomodule of the present invention. (B) The lower perspective view of the form for manufacturing the 2nd thermoelectric conversion thermomodule of the present invention.

FIG. 4 is a cross-sectional view taken along line AA of FIGS. 3 (a) and 3 (b).

FIG. 5 is a perspective view of a conventional thermoelectric conversion thermomodule.

[Explanation of symbols]

 10 Thermoelectric Conversion Thermo Module 11 Through Hole 12 Insulating Form 13a N-type Semiconductor Compound Device Material 13 N-type Semiconductor Compound Device 14a P-type Semiconductor Compound Device Material 14 P-type Semiconductor Compound Device 16, 17 Electrode 21 First Mask 22th 2 masks

Claims (6)

[Claims] 1. An insulating mold (12) having a plurality of through holes (11) provided at intervals, and an N-type semiconductor compound element (13) alternately filled in the plurality of through holes (11). ) And a P-type semiconductor compound element (14), and a pair of N-type semiconductor compound element (13) and P-type semiconductor compound element (14) on the upper surface and the lower surface of the mold (12).
A thermoelectric conversion thermomodule (10) comprising a plurality of electrodes (16, 17) electrically connected in series in the order of P, comprising the mold (12) and the N-type and P-type semiconductor compound device. (13,
A thermomodule for thermoelectric conversion, characterized in that 14) and the electrodes (16, 17) are integrally fixed. 2. The thermoelectric conversion thermomodule according to claim 1, wherein the insulating mold (12) is a low melting point glass of B ₂ O ₃ —PbO type. 3. A step of forming an insulative mold (12) so as to have a plurality of through holes (11) at intervals, and a first mask covering every other of the plurality of through holes (11). Covering the mold (12) with (21), and forming a plurality of through holes (11) not covered with the mask (21) from above the first mask (21) with the N-type semiconductor compound element material (13a). )
And a step of covering the mold (12) with a second mask (22) covering the plurality of through holes (11) not filled with the N-type semiconductor compound element material (13a), 2 P-type semiconductor compound device material (14a) from above the mask (22) to a plurality of through holes (11) not covered by this mask (22)
And a step of electrically connecting the pair of N-type semiconductor compound device material (13a) and P-type semiconductor compound device material (14a) in order of N, P, N, P electrically in series. A step of applying a conductive paste to the upper and lower surfaces of the mold (12) and the surfaces of the filled N-type and P-type semiconductor compound element materials (13a, 14a), and a mold to which the conductive paste is applied. The frame (12) is heat-treated to change the conductive paste into the baking electrodes (16, 17), and the N-type and P-type semiconductor compound element materials (13a, 14a) are sintered into N.
Type and P type semiconductor compound elements (13, 14) respectively, and the mold (12) and the N type and P type semiconductor compound elements (1
3, 14) and a step of integrally fixing the electrodes (16, 17) to each other, a method of manufacturing a thermoelectric conversion thermomodule. 4. A step of forming an insulating form (12) so as to have a plurality of through holes (11) at intervals, and a pair of adjacent through holes among the plurality of through holes (11). A step of forming electrodes (16, 17) on the upper surface and the lower surface of the mold (12) and the edge portions of the through holes adjacent to the upper surface and the lower surface so as to connect, and the plurality of through holes (11) Covering the mold with a first mask covering every other step; filling a plurality of through holes not covered by the mask with N-type semiconductor compound element material from above the first mask; Covering the mold with a second mask that covers a plurality of through holes that are not filled with device material; and applying a P-type semiconductor compound device material to the plurality of through holes that are not covered with the mask from above the second mask. And a step of heat-treating the mold filled with the N-type and P-type semiconductor compound device materials, A step of changing the N-type and P-type semiconductor compound element materials to N-type and P-type semiconductor compound elements of a sintered body, respectively, and integrally fixing the form, the N-type and P-type semiconductor compound elements, and the electrodes. The electrodes (16, 17) in the electrode forming step include
-Type semiconductor compound device material and P-type semiconductor compound device material are formed on the upper surface and the lower surface of the mold (12) so as to be electrically connected in series in the order of N, P, N, P regularly. And a method for manufacturing a thermoelectric conversion thermomodule. 5. The insulating mold (12) is a molded body of B ₂ O ₃ —PbO-based low melting point glass powder, wherein the N-type and P-type semiconductor compound element materials (13a, 14a) are N-type, respectively. And a P-type semiconductor compound powder mixed in a solvent, which is a slip (1) of the N-type and P-type semiconductor compound element materials (13a, 14a).
5. The method for manufacturing a thermoelectric conversion thermomodule according to claim 3, wherein the filling of the through hole (11) of 2) is performed by a slip casting method. 6. The insulating mold (12) is a sintered body of B ₂ O ₃ —PbO-based low melting point glass, wherein the N-type and P-type semiconductor compound element materials (13a, 14a) are N-type, respectively. And P-type semiconductor compound powders, which are N-type and P-type semiconductor compound device materials
The method for producing a thermoelectric conversion thermomodule according to claim 3 or 4, wherein filling of the through holes (11) of the mold (12) with (13a, 14a) is performed by pressing the powder.