JP2001352107A - Method of manufacturing thermoelectric conversion module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable obtaining excellent bonding between thermoelectric conversion elements and electrodes without solder leakage, in the case that parts between a plurality of thermoelectric conversion element groups which are surrounded and retained by electric insulators are electrically bonded by using a plurality of electrode groups, and a thermoelectric conversion module is manufactured. SOLUTION: A thermoelectric conversion module chip 5B constituted of electric insulators 4 and thermoelectric conversion elements 2p, 2n groups is formed by forming previously Ni conductive covering films 10 different from the thermoelectric conversion elements 2p, 2n, on end surfaces of the thermoelectric conversion elements 2p, 2n to be bonded to electrodes 11. The chip 5B is soldered to the electrode pattern 11 on an electric insulating board 12. By selectively forming the Ni conductive covering films 10 only on the end surfaces of the thermoelectric conversion elements 2p, 2n, solder leakage is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoelectric conversion module, and more particularly, to a method for manufacturing a thermoelectric conversion module suitable for manufacturing a thermoelectric conversion module such as a thermoelectric conversion module or an electronic cooling module.

[0002]

2. Description of the Related Art In a thermoelectric conversion element pair having a junction in which p-type and n-type thermoelectric semiconductors are electrically joined, if the junction is heated to a high temperature and the other of the thermoelectric element semiconductors is cooled to a temperature difference, There is a phenomenon in which a thermoelectromotive force is generated, and this is called the Seebeck effect. Also, in the above thermoelectric conversion element pair, when a current flows from one thermoelectric semiconductor to the other thermoelectric semiconductor, there is a phenomenon that one junction absorbs heat and the other generates heat, which is called a Peltier effect. ing. Further, when one of the p-type or n-type thermoelectric semiconductor is heated to a high temperature and the other is cooled to flow a current along a temperature gradient, there is a phenomenon that heat is absorbed or generated inside the semiconductor depending on the direction of the current, This is called the Thomson effect.

A thermoelectric conversion device utilizing such an effect has no moving parts that generate vibration, noise, wear, etc.
The present invention can be a simplified energy direct conversion device having features such as simple structure, high reliability, long life and easy maintenance.

A module portion for performing thermoelectric conversion includes at least one thermoelectric element pair having a configuration in which p-type and n-type thermoelectric semiconductors are electrically joined, and each thermoelectric element pair is electrically connected in series.
In general, it is generally thermally connected in parallel. By applying a temperature difference between both ends of the module, a thermoelectric generator utilizing the Seebeck effect to extract an electromotive force depending on the temperature difference, or by applying a voltage to both ends of the module to generate a temperature difference ,
The present invention can be used for a thermoelectric cooling device utilizing the Peltier effect for cooling one end of a module.

[0005] As a method of manufacturing such a thermoelectric conversion module, for example, there is a method through a process as shown in FIG.

First, as shown in FIG. 10 (A), a p-type thermoelectric conversion material powder and an n-type thermoelectric conversion material powder are pressed and sintered by a hot press method or the like, so that a p-type disk-shaped powder is fired. The sintered body 22p and the n-type disk-shaped powder sintered body (22n) are obtained.

Next, as shown in FIG. 10B, the upper and lower surfaces of the disk-shaped powdery sintered bodies 22p and 22n are plated to form conductive coatings 23U and 23D.
To form

Next, as shown in FIG. 10C, the disc-shaped powdery sintered bodies 22p and 22n are cut and, as shown in FIG. ,
A p-type thermoelectric conversion element 24p and an n-type thermoelectric conversion element (24n) having predetermined dimensions on which the 23D is formed are manufactured.

Next, as shown in FIG. 10E, a predetermined pattern formed on the insulating substrate 25D is formed by using a large number of p-type thermoelectric conversion elements 24p having conductive films 23U and 23D on the upper and lower sides. It is mounted and arranged on the surface of the electrode 26D, and the electrode 26D and the thermoelectric conversion element 24p are electrically and mechanically joined to each other with a bonding agent such as solder.

Similarly, conductive films 23U, 23D
Are mounted and arranged on the surface of the electrode 26U having a predetermined pattern formed on the insulating substrate 25U using a large number of n-type thermoelectric conversion elements 24n having 24n is electrically and mechanically joined.

Subsequently, as shown in FIG. 10F, the p-type substrate 25D and the n-type substrate 25 manufactured in the above-described steps are formed.
U and the p-type thermoelectric conversion element 24p is connected to the n-type substrate 25.
The thermoelectric conversion module 21 is manufactured by arranging the n-type thermoelectric conversion element 24n on the U electrode 26U and the n-type thermoelectric conversion element 24n on the electrode 26D of the p-type substrate 25D and bonding them with a bonding agent such as solder in the same manner as described above. .

According to this method, the thermoelectric conversion elements 24p,
Although the bonding of the electrodes 24U and the electrodes 26U and 26D can be performed well, the electrode 2
There is a problem that high processing accuracy is required in order to accurately mount and arrange on the 6U and 26D, and that there is a large amount of material loss (chip) of the thermoelectric conversion material at the time of cutting.

In addition, there is a problem that time is required for mounting in order to accurately perform bonding with the electrodes 26U and 26D.

Therefore, in order to improve the problem of such a conventional method of manufacturing a thermoelectric conversion module, the thermoelectric conversion elements 24p and 24n are not manufactured and mounted from the beginning, but are shown in FIG. such preparatory steps _{S 1} followed by the long axis of the thermoelectric conversion element rod 34p, once the fabricated after the thermoelectric conversion element rod 24p (step _{S 2} in FIG. 11 (D)), and arranged 24n to 34n, (11 (D) Step S ₃ ), and set in a resin case 35 as shown in FIG. 11A, and electrically insulate the resin case 35 as shown in FIG. 11B. Element support 36
Foaming and curing (Fig. 11)
After performing step S ₄ ) of FIG. 11D, the resin case 35 on which the element rods are arranged is cut into a round slice (step S ₅ of FIG. 11D), and as shown in FIG. 11C. , A large number of thermoelectric conversion module pieces 37 are formed at a time (FIG. 10).
There is a method of forming a thermoelectric conversion module by performing step S _{6 in} (D) and further bonding electrodes (step S _{7 in} FIG. 11D).

According to this method, the required level of processing accuracy in processing the thermoelectric conversion element is reduced, and the steps of mounting the element can be greatly reduced.

[0016]

However, the latter conventional method has the following problems.

That is, the thermoelectric conversion elements 34p, 3 supported by the thermoelectric element support 36 made of resin having electrical insulation properties.
A conductive film is not formed on the end face to be joined to the 4n electrode, unlike the former conventional method described above.

In general, thermoelectric conversion elements have poor wettability with respect to Sn-Pb solder, Sn-Ag solder, Sn-Cu solder and the like, and have a disadvantage that it is difficult to obtain good bonding with electrodes. Although low melting point solder such as Sn-Bi solder may be used, it is not preferable for the heat resistance of the thermoelectric conversion module because of its low melting point. Further, the solder layer and the element come into direct contact with each other, so that the element material component moves to the solder and the solder component moves to the element.
There was a so-called migration problem.

[0019]

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and is intended to provide a resin thermoelectric conversion element support (electric insulator) for a thermoelectric conversion module element. By forming a conductive film only on the end face that is joined to the electrode of the supported thermoelectric conversion element, a good junction between the thermoelectric conversion element and the electrode is obtained without direct contact between the solder layer and the thermoelectric conversion element It is an object of the present invention to provide a method for manufacturing a thermoelectric conversion module that can be used.

[0020]

SUMMARY OF THE INVENTION The present invention has been made to achieve such an object, and has a plurality of objects supported by an electric insulator. In the manufacturing process of the thermoelectric conversion module manufactured by electrically joining the thermoelectric conversion element groups with a plurality of electrode groups, the end face of the thermoelectric conversion element joined to the electrode has a different conductivity from the thermoelectric conversion element. When the film is formed in advance, a module support member made of a material that is more electrically less than the thermoelectric element material made of the electric insulator and the thermoelectric conversion element group is brought into contact with the thermoelectric conversion element end face and supported, and the conductive coating is formed. It is characterized in that it is formed selectively only on the end face of the thermoelectric conversion element.

In the method of manufacturing a thermoelectric conversion module according to the present invention, the conductive film may be formed by electroless plating.

Further, in the method for manufacturing a thermoelectric conversion module according to the present invention, as set forth in claim 3, the module supporting member in contact with the end face of the thermoelectric conversion element includes:
The contact can be made with a smaller contact area than the thermoelectric conversion element end face, so that the plating solution can penetrate the module support member and the thermoelectric conversion element end face in the electroless plating.

Further, in the method for manufacturing a thermoelectric conversion module according to the present invention, the thermoelectric conversion element may be made of Bi, Te or Bi, Te, S.
b or a thermoelectric conversion element material selected from Bi, Te, Sb, and Se.

Further, in the method for manufacturing a thermoelectric conversion module according to the present invention, as described in claim 5, the electric insulator is made of a phenol resin, a urethane resin, a polyimide resin, a polycarbonate resin, an ABS resin. Can be configured.

Further, in the method for manufacturing a thermoelectric conversion module according to the present invention, as described in claim 6, the conductive film has a film thickness of 2 μm to 10 μm and an electric conductivity σ> σ. It may be 5 × 10 ⁵ (S / m).

Further, in the method for manufacturing a thermoelectric conversion module according to the present invention, the electroless plating may be Ni-P or Ni-B plating. .

Further, in the method of manufacturing a thermoelectric conversion module according to the present invention, the module supporting member may be made of stainless steel, alloy steel, or the like.
It is selected from carbon steel and an iron-based alloy, and may be a fibrous or mesh-like structure having a wire diameter of 100 μm or less.

Further, in the method for manufacturing a thermoelectric conversion module according to the present invention, as described in claim 9, the module support member is selected from stainless steel, low alloy steel, carbon steel and iron-based alloy. And
It is a structure made of a sword-like needle having a plurality of needles that can contact the end faces of the thermoelectric conversion elements, and the tip of the needle can be 100 μm or less.

Furthermore, in the method of manufacturing a thermoelectric conversion module according to the present invention, as described in claim 10, the module support member has a surface on which a material film that is more base than the thermoelectric conversion element material is formed. Alumina balls (including the case of equivalent ceramic balls), and the particle diameter of the balls can be smaller than the interval between a plurality of thermoelectric conversion elements in the thermoelectric conversion module.

[0030]

According to the method of manufacturing a thermoelectric conversion module according to the present invention, a plurality of thermoelectric conversion element groups supported by being surrounded by an electric insulator are separated by a plurality of electrode groups. In a manufacturing process of a thermoelectric conversion module manufactured by electrical bonding, when a conductive film different from the thermoelectric conversion element is previously formed on an end face of the thermoelectric conversion element bonded to the electrode, the electric insulator and A thermoelectric conversion module element composed of a thermoelectric conversion element group is supported by contacting a module support member made of a material that is more electrically less than the thermoelectric conversion element material with a thermoelectric conversion element end face, and a conductive film is formed on the thermoelectric conversion element end face. The conductive film is formed only on the end face of the thermoelectric conversion element supported by the electrical insulator, which is joined to the electrode. As a result, the solder layer and the thermoelectric conversion element do not come into direct contact with each other, and it is possible to obtain a good junction between the thermoelectric conversion element and the electrode without causing so-called micromotion. Effect is brought about.

And, as described in claim 2,
When the conductive film is formed of electroless nickel, a remarkably excellent effect is obtained in that the conductive film can be formed on the thermoelectric conversion module element piece easily and easily. .

Further, the module supporting member is in contact with the contact surface of the thermoelectric conversion element with a smaller contact area, and the plating solution can penetrate into the module supporting member and the thermoelectric conversion element end surface in electroless plating. By doing so, a remarkably excellent effect that a conductive film can be selectively formed only on the end face of the thermoelectric conversion element is brought about.

Still further, as described in claim 4, the thermoelectric conversion element is made of a thermoelectric conversion element material selected from Bi, Ti or Bi, Te, Sb or Bi, Te, Sb, Se. By doing so, a remarkably excellent effect that a p-type thermoelectric conversion element and an n-type thermoelectric conversion element can be easily obtained is provided.

Further, as described in claim 5, the electric insulator is made of a resin selected from phenol resin, urethane resin, polyimide resin, polycarbonate resin and ABS resin. In addition, a remarkably excellent effect that the plurality of thermoelectric conversion element groups can be easily surrounded and supported by the electric insulator is provided.

Further, as described in claim 6, the conductive film has a thickness of 2 μm or more and 10 μm or less and an electric conductivity σ of σ> 5 × 10 ⁵ (S / m). Thereby, a remarkably excellent effect that a good conduction state between the electrode and the thermoelectric conversion element can be obtained, and a thermoelectric conversion module with small output loss can be obtained is provided.

Further, by forming the electroless plating by Ni-P or Ni-B plating, it is possible to further improve the formation of the conductive film. A remarkably excellent effect is achieved.

Still further, as described in claim 8, the module supporting member is selected from stainless steel, alloy steel, carbon steel and iron-based alloy, and has a wire diameter of 100 μm.
By using the following fibrous or mesh-like structure, a remarkably excellent effect that a conductive film can be selectively and satisfactorily formed only on the thermoelectric conversion element end face is provided. .

Still further, as described in claim 9, the module supporting member is selected from stainless steel, alloy steel, carbon steel and iron-based alloy, and a needle capable of contacting a plurality of thermoelectric conversion element end faces is provided. It is possible to selectively and satisfactorily form the conductive film only on the end face of the thermoelectric conversion element by making the structure of the needle-shaped needle body having a needle tip of 100 μm or less. This is a remarkably excellent effect.

Still further, as described in claim 10, the module supporting member is an alumina ball formed on the surface with a material film which is more base than the thermoelectric conversion element material, and the particle size of the ball is thermoelectric. By making the gap smaller than the interval between the plurality of thermoelectric conversion elements in the conversion module, a remarkably excellent effect that the conductive film can be selectively and satisfactorily formed only on the end faces of the thermoelectric conversion elements. Is brought.

[0040]

EXAMPLES Examples of the present invention will be described below in detail together with comparative examples, but it goes without saying that the present invention is not limited to only such examples.

(Example 1) As a thermoelectric conversion element material, n
The type is made of BiTeSe, and the p type is made of BiTeSb, and 32 p-type and n-type thermoelectric conversion elements (rods) (1.4 mm square × L50 mm) 2p and 2n are prepared as shown in FIG. 1, respectively. This is placed in a polycarbonate resin box (1.2 mm thick, 55 mm deep) 3 in a predetermined arrangement as shown in FIG. 1, and urethane is placed in the polycarbonate resin box 3 as shown in FIG. The resin 4 is injected and foamed and cured in the resin box 3.

Next, this is cut with a diamond blade in a direction perpendicular to the longitudinal direction of the thermoelectric conversion elements (rods) 2p, 2n.
Cut to a thickness of 2.5 mm, thermoelectric conversion module element 5
Get 16 A's.

As shown in FIG. 2, the thermoelectric conversion module element 5A thus obtained has an outer frame 3F having a thickness of 1.
There is a 2mm polycarbonate resin box 3 and an outer frame 3F
And a urethane resin (electric insulator) 4 closely adhered to the thermoelectric conversion elements 2p and 2n.

Next, a conductive film is formed on the end surfaces of the thermoelectric conversion elements 2p and 2n of the thermoelectric conversion module element (before forming the conductive film) 5A in the following procedure.

(1) The upper and lower surfaces of the thermoelectric conversion module element 5A are polished as necessary to remove burrs and dirt on the element end faces.

(2) The end face of the thermoelectric conversion element is cleaned by performing an alkali degreasing treatment. At this time, for example, an alkaline degreasing solution (K330) manufactured by Nippon Kanigen Co., Ltd. having a concentration of 50 g was used.
/ 100 ml, adjusted to an aqueous solution at a temperature of 60 ° C., and degreased therein for about 5 minutes.

(3) After the thermoelectric conversion module element 5A is washed with water, as shown in FIG. 4, the electrical insulating substrate 7 to which the module supporting member 6 made of steel wool having a wire diameter of about 80 μm is fixed is subjected to a degreasing treatment. Module support member 6 made of steel wool on upper and lower surfaces of completed module element 5A
And the end face of the thermoelectric conversion element are sandwiched between them so as to support the module element 5A.

(4) The module piece 5A sandwiched between the module supporting members 6 made of steel wool is put into a Ni plating solution 9 in a plating tank 8 as shown in FIG. A Ni plating film is formed on the thermoelectric conversion element end face as the film 10. At this time, for example, Ni-B plating solution (SB-55) (manufactured by Nippon Kanigen Co., Ltd.) (SB concentration: 5.5%) (200 ml) is adjusted to a temperature of 70 ° C., and plating is performed for about 20 minutes. be able to.

(5) After the plating is completed, the conductive (Ni) film 10 is formed only on the end face of the thermoelectric conversion element as shown in FIG. 6 by washing and drying.

(6) The conductive (Ni) film 10 thus formed has a film thickness of about 5 μm, an electric conductivity of 8 × 10 ⁵ S / m, and a good electric conductivity. Had.

(7) In addition, since the conductive (Ni) film 10 is formed on the end face of the thermoelectric conversion element, the leakage of Sn-Pb solder and Sn-Ag solder is improved, and the end face of the element and the solder layer are formed. No voids, blisters, etc., were present at the interface of.

By performing such treatment, a thermoelectric conversion module element piece 5B having the conductive film 10 formed on the end face of the thermoelectric conversion element as shown in FIG. 6 is obtained.

(8) Next, as shown in FIG. 7, an electrically insulative substrate 12 having a predetermined pattern of electrodes 11 is joined and placed on the thermoelectric conversion module element 5B with the above-mentioned solder material to form a thermoelectric conversion module 1 To produce

(Embodiment 2) The steps up to the manufacture of the thermoelectric conversion module element piece (before the formation of the conductive film) 5A are the same as those in Embodiment 1 and will not be described. Hereinafter, a method for forming the conductive film will be described.

(1) The upper and lower surfaces of the thermoelectric conversion module element 5A are polished as necessary to remove burrs and dirt on the element end faces.

(2) An alkali degreasing treatment is performed to clean the end faces of the thermoelectric conversion element. At this time, for example, an alkaline degreasing solution (K330) manufactured by Nippon Kanigen Co., Ltd. having a concentration of 50 g was used.
/ 100 ml, adjusted to an aqueous solution at a temperature of 60 ° C., and degreased therein for about 5 minutes.

(3) After washing the thermoelectric conversion module element 5A with water, as shown in FIG. 8, the module support member 14 made of a sword-like needle having a tip diameter of about 100 μm is attached to the thermoelectric conversion element in the module element 5A. As shown in FIG. 8, the upper and lower surfaces of the module piece 5A are sandwiched and supported by the electrically insulating substrates 15 arranged in accordance with the arrangement pitch so that the needle tips are in contact with the thermoelectric element end faces.

(4) The module piece 5A sandwiched between the module supporting members 14 made of a sword-like needle is put in a Ni plating solution 9 and a Ni plating film is formed as a conductive film 10 as shown in FIG. It is formed on the end face of the conversion element. At this time, for example, 200 ml of Ni-B plating solution (SB-55) (B concentration 5.5%) manufactured by Nippon Kanigen Co., Ltd., temperature 7
The temperature can be adjusted to 0 ° C., and plating can be performed for about 20 minutes.

(5) After the plating is completed, washing and drying are performed, so that only the end faces of the thermoelectric conversion element are exposed as shown in FIG.
A conductive (Ni) film 10 is formed.

(6) The conductive (Ni) film 10 thus formed has a thickness of about 4 μm, an electric conductivity of 8 × 10 ⁵ S / m, and a good electric conductivity. Had.

(7) Since the conductive (Ni) film 10 is formed on the end face of the thermoelectric conversion element, the wettability of Sn—Pb solder, Sn—Ag solder, and Sn—Cu solder is improved, and the end face of the element is improved. Bond at the interface between the part and the solder layer,
There were no blisters.

Hereinafter, the thermoelectric conversion module 1 as shown in FIG. 7 is manufactured in the same manner as in the first embodiment.

(Embodiment 3) The process up to the production of the thermoelectric conversion module element piece (before the formation of the conductive film) 5A is the same as that of the embodiment 1 and will not be described. Hereinafter, a method for forming the conductive film will be described.

(1) The upper and lower surfaces of the thermoelectric conversion module element 5A are polished as necessary to remove burrs and dirt on the element end surfaces.

(2) An alkali degreasing treatment is performed to clean the end faces of the thermoelectric conversion element. At this time, for example, an alkaline degreasing solution (K330) manufactured by Nippon Kanigen Co., Ltd. having a concentration of 50 g was used.
/ 100 ml, adjusted to an aqueous solution at a temperature of 60 ° C., and degreased therein for about 5 minutes.

(3) After the thermoelectric conversion module element 5A is washed with water, as shown in FIG. 9, the module is supported by a module supporting member 16 made of Ni-plated alumina balls on the surface having a particle size of about 0.5 m. The element 5A is supported by an alumina ball supporting member 16 with the element 5A interposed therebetween.

(4) The module element 5A sandwiched between the module support member 16 made of alumina balls and the electrically insulating substrate 17 is put into the Ni plating solution 9 to form the conductive film 10 as shown in FIG. A Ni plating film is formed on a thermoelectric conversion element end face. At this time, for example, Ni-B plating solution (SB-55) (manufactured by Nippon Kanigen Co., Ltd.) (SB concentration: 5.5%) (200 ml) is adjusted to a temperature of 70 ° C., and plating is performed for about 20 minutes. be able to.

(5) After the plating is completed, by washing with water and drying, as shown in FIG.
A conductive (Ni) film 10 is formed.

(6) The conductive (Ni) film 10 thus formed has a thickness of about 4 μm, an electric conductivity of 8 × 10 ⁵ S / m, and a good electric conductivity. Had.

(7) Since the conductive (Ni) film 10 is formed on the end face of the thermoelectric conversion element, the wettability of Sn—Pb solder, Sn—Ag solder, and Sn—Cu solder is improved, and the end face of the element is improved. Bond at the interface between the part and the solder layer,
There were no blisters.

Hereinafter, the thermoelectric conversion module 1 is manufactured as shown in FIG.

(Comparative Example) Steel wool 6, sword-shaped support needle 14 and alumina ball 16 described in Examples 1 to 3
The case in which is not used will be described.

At this time, the production of the thermoelectric conversion module element 5A and the adjustment of the module element such as deburring and deoiling are the same as those in the first embodiment, so that the description is omitted.

(1) The adjusted module piece 5A was placed in a Ni plating solution 9 in the same manner as in Example 1 and plated for about 20 minutes.

However, the Ni film was not formed on the end face of the thermoelectric conversion element of the module element after the plating process.

(2) Here, plating was further performed for 20 minutes, and when a total of 40 minutes were performed, a Ni film was formed on a part of the thermoelectric conversion element end face. The Ni film was not formed.

[Brief description of the drawings]

FIG. 1 is an explanatory cross-sectional view showing how a thermoelectric conversion element (rod) is installed in a polycarbonate resin box in an embodiment of the present invention.

FIG. 2 is an explanatory horizontal sectional view of a thermoelectric conversion module element obtained by injecting a urethane resin into a polycarbonate resin box, foaming and curing the same, and then cutting the same horizontally in an embodiment of the present invention.

FIG. 3 is an explanatory cross-sectional view of a thermoelectric conversion module element before a conductive film is formed.

FIG. 4 is an explanatory sectional view of a module piece sandwiched between steel wools.

FIG. 5 is an explanatory sectional view showing a state where a module element is immersed in a plating bath.

FIG. 6 is an explanatory cross-sectional view of a thermoelectric conversion module element after a conductive film is formed.

FIG. 7 is an explanatory cross-sectional view of the thermoelectric conversion module assembled using the thermoelectric conversion module pieces after the formation of the conductive film.

FIG. 8 is an explanatory cross-sectional view of a module element sandwiched between sword-shaped support needles in another embodiment of the present invention.

FIG. 9 is an explanatory sectional view of a module element sandwiched between alumina balls in still another embodiment of the present invention.

FIG. 10 is an explanatory diagram showing a method of manufacturing a thermoelectric conversion module according to a conventional example, divided into (A) to (F).

FIG. 11 is an explanatory view showing a method of manufacturing a thermoelectric conversion module according to another conventional example, divided into (A) to (D).

[Explanation of symbols]

 Reference Signs List 1 thermoelectric conversion module 2p p-type thermoelectric conversion element (rod) 2n n-type thermoelectric conversion element (rod) 3 Polycarbonate resin box 3F Polycarbonate resin box outer frame 4 Urethane resin (electric insulator) 5A Conductive film formation Previous thermoelectric conversion module element 5B Thermoelectric conversion module element after conductive film formation 6 Module support member made of steel wool 9 Plating bath 10 Conductive film 11 Electrode 12 Electrically insulating substrate 14 Module support made of sword-like needle Member 16 Module support member made of alumina balls

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01L 35/32 H01L 35/32 A

Claims (10)

[Claims] In a manufacturing process of a thermoelectric conversion module manufactured by electrically bonding a plurality of thermoelectric conversion element groups supported by an electric insulator with a plurality of electrode groups, the thermoelectric conversion module is bonded to the electrodes. When a conductive film different from the thermoelectric conversion element is previously formed on the end face of the thermoelectric conversion element to be formed, the thermoelectric conversion module element composed of the electrical insulator and the thermoelectric conversion element group is electrically less electrically conductive than the thermoelectric conversion element material. A method for producing a thermoelectric conversion module, comprising: supporting a module supporting member made of a suitable material in contact with an end face of a thermoelectric conversion element; and selectively forming a conductive film only on the end face of the thermoelectric conversion element. 2. The method for manufacturing a thermoelectric conversion module according to claim 1, wherein the conductive film is formed by electroless plating. 3. The module support member is in contact with a contact area smaller than an end face of the thermoelectric conversion element, so that a plating solution can penetrate into the module support member and the end face of the thermoelectric conversion element in electroless plating. A method for manufacturing the thermoelectric conversion module according to claim 2. 4. The thermoelectric conversion element is Bi, Te or B
4. The method for manufacturing a thermoelectric conversion module according to claim 1, wherein the thermoelectric conversion module is made of a thermoelectric conversion element material selected from i, Te, Sb or Bi, Te, Sb, Se. 5. The electric insulator is made of phenol resin, urethane resin, polyimide resin, polycarbonate resin, AB
The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 4, wherein the thermoelectric conversion module is made of a resin selected from S resins. 6. The conductive film has a thickness of 2 μm or more and 10 μm or more.
The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 5, wherein the electric conductivity σ is σ> 5 x 10 ⁵ (S / m), when m or less. 7. Electroless plating is performed using Ni-P or Ni-
The method for manufacturing a thermoelectric conversion module according to claim 2, wherein the plating is B plating. 8. The module supporting member is selected from stainless steel, alloy steel, carbon steel, and iron-based alloy, and is a fibrous or mesh-like structure having a wire diameter of 100 μm or less. Item 4. A method for manufacturing a thermoelectric conversion module according to Item 3. 9. The module supporting member is selected from stainless steel, alloy steel, carbon steel, and iron-based alloy, and is a structure made of a sword-like needle having needles capable of contacting a plurality of thermoelectric conversion element end faces. And the needle tip is 100μm
The method for manufacturing a thermoelectric conversion module according to claim 3, wherein: 10. The module supporting member is an alumina ball formed on the surface thereof with a material film which is more electrically less than the thermoelectric conversion element material, wherein the diameter of the ball is smaller than a plurality of thermoelectric conversion element intervals in the thermoelectric conversion module. The method for manufacturing a thermoelectric conversion module according to claim 3, wherein