JPH11243169A - Electronic cooling module and method of manufacturing the same - Google Patents

Abstract

(57) [Problem] To provide an electronic cooling module having high reliability and sufficient cooling performance capable of coping with various electronic devices. SOLUTION: A p-type thermoelectric semiconductor element 4p is formed in the through hole 3 of an electrically insulating substrate 2 having a large number of through holes 3 formed therein.
And the n-type thermoelectric semiconductor element 4n are individually provided, and the space between the p-type thermoelectric semiconductor element 4p and the n-type thermoelectric semiconductor element 4n extends from the surface of the base 2 to the inner wall of the through hole 3 of the base 2. An electrode 5 on the front side formed over a range that does not penetrate the base 2 and an electrode 6 on the back side formed over the range not penetrating the base 2 from the back side of the base 2 to the inner wall of the through hole 3 of the base 2. Electronic cooling modules 1 connected alternately.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electronic cooling module suitable for cooling a component by efficiently radiating heat generated by an electronic device or an electronic component, and a method of manufacturing the same.

[0002]

2. Description of the Related Art In electronic components such as semiconductor lasers, power transistors, relays, and microprocessors, which generate a large amount of heat, or electronic devices using these components, heat radiation and cooling of the electronic components are required for stable and normal operation. It is an indispensable technology in a high temperature environment.

Conventionally, cooling components such as a heat sink, a cooling fan, and a heat spreader have been used for the heat radiation and cooling. A method using an electronic cooling module using p-type and n-type thermoelectric semiconductor elements (Peltier elements) has also been adopted.

As shown in FIG. 12, the electronic cooling module includes a pn element unit 102 including a p-type thermoelectric semiconductor element 102P and an n-type thermoelectric semiconductor element 102n, which constitute the electronic cooling module 101, and a heat absorbing side substrate 103. A large number of them are alternately arranged between the heat radiation side substrate 104 and the substrate 1.
The electrodes are electrically connected in series via the electrodes 105 and 106 formed on the electrodes 03 and 104, and a power supply (not shown) is connected via the lead wires 107 and 108 connected to the electrodes 105 and 106, so that the heat is absorbed from the heat absorbing side to the heat radiating side. It is an electronic device that transfers heat.

The conventional electronic cooling module 101 comprises a p-type thermoelectric semiconductor element 102p and an n-type thermoelectric semiconductor element 102n.
Were manufactured as follows using the pn element unit 102 consisting of That is, a raw material powder obtained by pulverizing a semiconductor ingot melted to have a desired composition is formed into a wafer by hot pressing, Ni plating is performed, electrodes are formed, and then a solder plating is performed. A semiconductor element is manufactured. Then, a large number of thermoelectric semiconductor elements are assembled into a module together with the heat-absorbing side substrate 103 and the heat-dissipating side substrate 104 separately manufactured.
As shown in FIG. 3, the thermoelectric semiconductor elements 102p, 1
The electronic cooling module 101 was manufactured by disposing and soldering 02n (for example, JP-A-1-106478 (however, the structure is not described in the drawings)).

[0006]

The electronic cooling module manufactured in this way goes through many steps,
There are the following problems (1) in terms of manufacturing and yield.

(1) Since the pn element unit is arranged on the substrate only by soldering, the mechanical strength against impact or the like is not sufficient.

[0008] Further, since the wafer is cut to obtain the element in the production of the pn element unit, there are the following problems (2), (3) and (4).

(2) There is a limit to miniaturization of elements (chips), and it is difficult to cope with miniaturization and high density of electronic components as a module.

(3) There is no degree of freedom in the element (chip) shape, and it is difficult to design flexibly when applied to electronic parts.

(4) The steps of mounting and arranging elements (chips) on a substrate are complicated.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and relates to an electronic cooling module in which a large number of p-type thermoelectric semiconductor elements and n-type thermoelectric semiconductor elements are directly connected via electrodes. It is an object of the present invention to provide an electronic cooling module having high reliability and sufficient cooling performance capable of supporting various electronic devices and a simplified manufacturing method by adopting a novel configuration and manufacturing method.

[0013]

According to a first aspect of the present invention, there is provided an electronic cooling module having a plurality of through holes formed in a through hole of an electrically insulating substrate having a plurality of through holes formed therein. A thermoelectric semiconductor element and an n-type thermoelectric semiconductor element are separately provided, and the p-type thermoelectric semiconductor element and n-type
A surface-side electrode formed between the surface of the base and the inner wall of the through hole of the base so as not to penetrate the base from the surface of the base and the inner wall of the through hole of the base from the back of the base. It is characterized in that the electrodes are alternately connected by electrodes on the back surface formed over a range that does not penetrate the base.

In the embodiment of the electronic cooling module according to the present invention, the p-type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element are each composed of a p-type thermoelectric semiconductor element material. It is characterized by comprising a fired body of thermoelectric semiconductor element paste containing powder and thermoelectric semiconductor element paste containing n-type thermoelectric semiconductor element material powder.

Similarly, in the embodiment of the electronic cooling module according to the present invention, as described in claim 3, the cross-sectional shape of the inside of the through hole formed in the base is the cross section of the opening of the through hole. It is characterized by having a shape similar to the shape and having a cross-sectional area equal to or smaller than the cross-sectional area of the opening.

Similarly, in the embodiment of the electronic cooling module according to the present invention, as described in claim 4, the opening of the through hole formed in the base is chamfered. It is characterized by.

Similarly, in an embodiment of the electronic cooling module according to the present invention, as described in claim 5, the substrate is an electrically insulating substrate selected from alumina, aluminum nitride, quartz and glass. It is characterized by having it.

Similarly, in the embodiment of the electronic cooling module according to the present invention, as described in claim 6, the electrode material on the front side and the back side is made of silver, copper, palladium, platinum, aluminum, nickel. And at least one selected from the group consisting of:

Similarly, in the embodiment of the electronic cooling module according to the present invention, the material of the p-type thermoelectric semiconductor element is Bi: 0.05 to
0.10, Te: 0.55 to 0.70, Sb: 0.25
In the atomic composition range of 0.35 to 0.35, and the material of the n-type thermoelectric semiconductor element is Bi: 0.35 to 0.45, Te: 0.55
0.65 and Se: 0.02 to 0.04.

Similarly, in the embodiment of the electronic cooling module according to the present invention, as described in claim 8, both the p-type thermoelectric semiconductor element material powder and the n-type thermoelectric semiconductor element material powder have a particle size. It is characterized in that it is not more than 10 μm.

According to a ninth aspect of the present invention, there is provided a method of manufacturing an electronic cooling module, wherein a p-type thermoelectric semiconductor element is provided in a through hole of an electrically insulating substrate having a large number of through holes. And an n-type thermoelectric semiconductor element are separately provided, and a region between the p-type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element does not penetrate from the surface of the base to the inner wall of the through hole of the base. In manufacturing an electronic cooling module in which the front-side electrodes formed over the substrate and the back surface of the base are alternately connected to the inner wall of the through hole of the base by the back-side electrodes formed over a range that does not penetrate the base. Forming an electrode on the front side from the surface of the substrate having the large number of through holes to the inner wall of the through hole of the substrate so as not to penetrate the substrate; After forming an electrode on the back surface on the inner wall of the through hole of the body over a range not penetrating the base, a thermoelectric semiconductor element paste containing a p-type thermoelectric semiconductor element material powder and an n-type thermoelectric semiconductor element material powder inside the through hole Are injected individually from the openings of the through-holes, and the p-type and n-type thermoelectric semiconductor element pastes are heated and heated in an inert atmosphere or a reducing atmosphere.
It is characterized by firing.

In a preferred embodiment of the method for manufacturing an electronic cooling module according to the present invention, a thermoelectric semiconductor element paste is formed in a through-hole by using a dispenser having a pressurizer. It is characterized by being injected from the portion into the inside of the through hole.

Similarly, in an embodiment of the method for manufacturing an electronic cooling module according to the present invention, as described in claim 11, a mask having an opening equivalent to a through hole formed in a substrate is used. It is characterized in that the thermoelectric semiconductor element paste is injected from the opening of the through hole into the inside of the through hole.

Similarly, in an embodiment of the method for manufacturing an electronic cooling module according to the present invention, the electrodes on the front side and the back side are made of silver,
It is characterized by being formed using an electrode paste containing at least one selected from copper, palladium, platinum, aluminum and nickel.

Similarly, in an embodiment of the method for manufacturing an electronic cooling module according to the present invention, as described in claim 13, the electrode paste is formed by printing using a mask having a desired pattern. It is characterized by having.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of an electronic cooling module and a method for manufacturing the same according to the present invention will be described.

The electronic cooling module according to the present invention is used in contact with an electronic component to be cooled.

(1) Arrangement Structure of Thermoelectric Semiconductor Element The arrangement of the thermoelectric semiconductor element can be set to a desired arrangement including the element shape and the number of elements depending on the base.

FIG. 1 shows a part of an electronic module according to an embodiment of the present invention.

In the electronic cooling module 1, a large number of through holes 3 are formed in a base 2 having a role as a structural base so as to penetrate the base 2, and inside the large number of through holes 3, , Every other, p-type thermoelectric semiconductor element 4p
And an n-type thermoelectric semiconductor element 4n. The p-type thermoelectric semiconductor element 4p and the n-type thermoelectric semiconductor element 4n are formed by a surface-side electrode 5 formed from the surface of the base 2 to the inner wall of the through hole 3 of the base 2 so as not to penetrate the base 2. The electrodes are alternately connected to each other by electrodes on the back side formed from the back surface of the base 2 to the inner wall of the through hole 3 of the base 2 so as not to penetrate the base 2.

Although not shown, the edges of the openings of the through holes 3 are chamfered.

The electronic cooling module 1 having the structure as shown in FIG. 1 can further increase the number of p-type thermoelectric semiconductor elements 4p and n-type thermoelectric semiconductor elements 4n as shown in FIG. It is assumed that the electrodes 5 on the side and the electrodes 6 on the back side are connected alternately.

FIG. 3 shows the electronic cooling module 1 shown in FIG.
In the electronic cooling module 1 shown in FIG. 3, a large number of through holes 3 are formed in a base 2 having a role as a structural base so as to penetrate the base 2. The p-type thermoelectric semiconductor element 4p and the n-type thermoelectric semiconductor element 4n are alternately provided inside the plurality of through holes 3.
Are arranged. In the case of this modified example, it is assumed that the through-hole 3 has an opening provided with a conical portion 3A so that the cross-sectional area of the opening is wider than the internal cross-sectional area of the through-hole 3. It is formed. In addition, it goes without saying that the shapes of the through hole 3 and the opening thereof are not limited to the two types shown in FIGS. 1 and 3.

(2) Method of Manufacturing Electronic Cooling Module In the method of manufacturing the electronic cooling module according to the present invention, the substrate is penetrated from the surface of the electrically insulating substrate having a large number of through holes to the inner wall of the through hole of the substrate. The electrode on the front side is formed over the range not to be formed, and the electrode on the back side is formed from the back side of the base to the inner wall of the through hole of the base so as not to penetrate the base, and thereafter the p-type thermoelectric semiconductor element material powder and Thermoelectric semiconductor element pastes containing n-type thermoelectric semiconductor element material powders are individually injected into the through holes, and the p-type and n-type thermoelectric semiconductor element pastes are heated and fired to form the above-described electronic cooling module structure. As described above, this step will be described in more detail.

(A) Substrate FIG. 4 shows a substrate used for the electronic cooling module having the structure shown in FIG. 1, and FIG. 5 shows a substrate used for the electronic cooling module having the structure shown in FIG. As shown in FIGS. 4 and 5, through holes 3 are formed in each of the bases 2 so as to penetrate the bases 2. A thermoelectric semiconductor element paste containing the thermoelectric semiconductor element material powder and a thermoelectric semiconductor element paste containing the n-type thermoelectric semiconductor element material powder are injected from the opening of each through hole 3. Here, the cross-sectional area inside the through hole 3 is
So that the cross-sectional area is less than or equal to the cross-sectional area of the opening,
Equal as shown in FIG. 4 or FIG.
Is adjusted to be smaller as shown in FIG.
The edge of the opening of each through hole 3 is chamfered. In addition, it is essential that the substrate 2 has an electrical insulation property, and alumina (Al ₂ O ₃ )
Or aluminum nitride (AlN) can be preferably used, but a metal substrate having an electrically insulating layer formed on a conductive metal surface can also be used.

(B) Electrode type FIG. 6 shows the front side and the back side of the substrate 2 after the front side electrode 5 and the back side electrode 6 are formed. That is,
As shown in FIG. 6, the base 2 has a surface-side electrode 5 formed from the surface of the base 2 to the inner wall of the through hole 3 of the base 2 so as not to penetrate the base 2. An electrode 6 on the back surface side is formed on the inner wall of the through hole 3 of the base 2 from the back surface of the base 2 so as not to penetrate the base 2.

The electrodes 5 and 6 are made of silver, copper, palladium,
For example, a method using screen printing using an electrode paste containing at least one selected from platinum, aluminum, and nickel can be suitably used, but a method using a dispenser can also be used.

Then, the electrodes 2 and 5 having conductivity are obtained by firing the electrode paste on the substrate 2 on which the electrode paste has been printed.

(C) Formation of Thermoelectric Semiconductor Element A thermoelectric semiconductor element paste containing a p-type thermoelectric semiconductor element material powder is provided on the substrate 2 on which the electrodes shown in FIG.
The p-type and n-type thermoelectric semiconductor elements are formed by injecting the thermoelectric semiconductor element paste containing the n-type thermoelectric semiconductor element material powder every other through the opening of the through hole 3.
For injecting the thermoelectric semiconductor element paste into the through-holes 3, there are a method using a dispenser, a method using a mask for printing, and the like.

After the injection of the thermoelectric semiconductor element paste is completed, the substrate 2 is fired in an inert atmosphere such as an argon gas or a nitrogen gas to complete the manufacture of the electronic cooling module 1 according to the present invention. The firing in this case may be performed in a preliminary firing step for burning out the binder contained in the thermoelectric semiconductor paste described below and a main firing step for sintering the thermoelectric semiconductor element material powder. Good.

(3) Preparation of Thermoelectric Semiconductor Element Paste The p-type and n-type thermoelectric semiconductor element pastes are prepared by kneading a raw material powder and a binder, which will be described in detail below.

(A) Production of Raw Material Ingot The raw material ingot is composed of Bi,
It is made of Te, Sb, and Se, and is produced by adding a small amount of a dopant material as needed.

Here, a Bi-Te alloy, a Bi-Te-Sb alloy, or the like is used as an ingot for a p-type thermoelectric semiconductor device, and a Bi-Te alloy, Bi-Te alloy is used as an ingot for an n-type thermoelectric semiconductor device. -Se alloy or the like is used.

The preferred compositions thereof are as follows:
In the case of a p-type thermoelectric semiconductor element, Bi: 0.05 to 0.1
0, Te: 0.55 to 0.70, Sb: 0.25 to 0.
35, and in the case of an n-type thermoelectric semiconductor element, Bi: 0.35 to 0.45, Te: 0.55 to 0.5.
65, Se: an atomic composition range of 0.02 to 0.04. Further, as the dopant material preferably used, antimony iodide (SbI ₂ ), mercury bromide (HgBr ₂ )
And so on.

(B) Preparation of Raw Material Powder First, the alloy ingot was formed into flake-like pieces having a thickness of several tens to several hundreds of μm, and then a particle size of about 30 was obtained with a cutter mill.
It is pulverized to not more than 10 μm, more preferably not more than 10 μm. At the time of this pulverization, pulverization is performed in an inert atmosphere to prevent oxidation of the raw material powder. The pulverizing means is not limited to pulverization using a cutter mill. For example, a wet pulverization method using a ball mill may be used.

(C) Kneading with a binder The raw material powder and the binder are prepared and kneaded to obtain a thermoelectric semiconductor material paste. Here, as the binder, polyvinyl alcohol (PVA), polyvinyl butyral (PVB), an acrylic resin, or the like can be used.
Then, the binder and an appropriate solvent are added to the raw material powder and kneaded to obtain a p-type thermoelectric semiconductor element paste and an n-type thermoelectric semiconductor element paste. In addition, it is also possible to add a plasticizer, a surfactant and the like as needed.

[0047]

According to the electronic cooling module of the present invention,
As described in claim 1, a p-type thermoelectric semiconductor element and an n-type thermoelectric semiconductor element are individually provided inside the through holes of the electrically insulating substrate having a large number of through holes, The surface-side electrode formed between the p-type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element from the surface of the base to the inner wall of the through hole of the base so as not to penetrate the base, Since the inner wall of the through hole of the base is alternately connected to the back side electrode formed over a range that does not penetrate the base, the adhesion between the thermoelectric semiconductor element and the substrate is strong, and the reliability is improved. A remarkable improvement can be obtained, and a remarkable effect that it is possible to provide an electronic cooling module having sufficient cooling performance capable of supporting various electronic devices is provided.

And, as described in claim 2,
The p-type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element are respectively formed of a thermoelectric semiconductor element paste containing a p-type thermoelectric semiconductor element material powder and a fired body of a thermoelectric semiconductor element paste containing an n-type thermoelectric semiconductor element material powder. By doing so, the remarkable effect that the adhesion between the thermoelectric semiconductor element and the substrate is strong, and it is possible to provide a highly reliable electronic cooling module in which the thermoelectric semiconductor element is protected by the substrate. Brought.

According to a third aspect of the present invention, the cross-sectional shape inside the through-hole formed in the base has a shape similar to the cross-sectional shape of the opening of the through-hole, and the cross-sectional area is the same. By having a cross-sectional area equal to or smaller than the cross-sectional area of the opening, the formation of electrodes and thermoelectric semiconductor elements can be simplified, and the adhesion between the electrodes and thermoelectric semiconductor elements and the substrate can be further improved. There is a great effect that it is possible to make it.

Further, as described in claim 4,
The opening of the through-hole formed in the base body is chamfered, so that the edge of the opening of the through-hole is eliminated, and it is possible to prevent the electrode from being thinned when there is an edge. Is a great effect.

Further, as described in claim 5, the substrate is an electrically insulating substrate selected from alumina, aluminum nitride, quartz and glass, so that the structure A remarkable effect that an electronic cooling module excellent in strength can be provided is brought about.

Furthermore, as described in claim 6, the electrode material on the front side and the back side contains at least one selected from silver, copper, palladium, platinum, aluminum and nickel. Thereby, a remarkable effect that an electronic cooling module having good conductivity and excellent thermoelectric figure of merit can be provided can be provided.

Still further, as described in claim 7, the material of the p-type thermoelectric semiconductor element is Bi: 0.05 to
0.10, Te: 0.55 to 0.70, Sb: 0.25
In the atomic composition range of 0.35 to 0.35, and the material of the n-type thermoelectric semiconductor element is Bi: 0.35 to 0.45, Te: 0.55
By setting the atomic composition in the range of 0.65 to 0.65 and Se: 0.02 to 0.04, it is possible to provide an electronic cooling module having a high thermoelectric figure of merit and excellent cooling characteristics. A great effect is brought.

Further, as set forth in claim 8, the p-type thermoelectric semiconductor element material powder and the n-type thermoelectric semiconductor element material powder both have a particle size of 10 μm or less, so that sintering is achieved. A remarkable effect is provided that it is possible to provide an electronic cooling module including a thermoelectric semiconductor element having excellent thermoelectric performance index and excellent thermoelectric performance index.

In the method of manufacturing an electronic cooling module according to the present invention, as described in claim 9, a p-type thermoelectric semiconductor element is provided inside the through hole of the electrically insulating substrate having a large number of through holes. The n-type thermoelectric semiconductor elements are individually provided, and the space between the p-type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element extends from the surface of the base to the inner wall of the through hole of the base without penetrating the base. In manufacturing the electronic cooling module which is alternately connected with the formed back surface electrode and the back surface side electrode formed over a range that does not penetrate the base from the back surface of the base to the inner wall of the through hole of the base, An electrode on the front side is formed from the surface of the substrate having the large number of through holes to the inner wall of the through hole of the substrate so as not to penetrate the substrate. After forming an electrode on the back surface on the inner wall of the through hole of the body over a range not penetrating the base, a thermoelectric semiconductor element paste containing a p-type thermoelectric semiconductor element material powder and an n-type thermoelectric semiconductor element material powder inside the through hole The thermoelectric semiconductor element paste containing is separately injected from the openings of the through holes, and the p-type and n-type thermoelectric semiconductor element pastes are heated and fired. It is possible to manufacture an electronic cooling module with sufficient cooling performance, which has a strong power and can significantly improve the reliability, and has a sufficient cooling performance for various electronic devices. A semiconductor element can be manufactured by forming electrodes in advance on a substrate serving as a mold, then injecting a thermoelectric semiconductor element paste and firing the same. Can simplify the production of thermoelectric semiconductor elements and mounting on a substrate, which is a problem with the module, making the design and production of the module extremely easy. Therefore, a remarkable effect can be obtained such that the thermoelectric semiconductor element can be fired without being affected by the electrode forming conditions.

According to a tenth aspect of the present invention, the thermoelectric semiconductor element paste is injected into the through hole from the opening of the through hole by using a dispenser having a pressurizer. This makes it possible to extremely easily form every other p-type and n-type thermoelectric semiconductor elements inside the through hole.

Further, as described in claim 11,
By injecting the thermoelectric semiconductor element paste from the opening of the through hole into the inside of the through hole using a mask having an opening equivalent to the through hole formed in the substrate, every other part of the inside of the through hole of the substrate is also used. A remarkable effect that p-type and n-type thermoelectric semiconductor elements can be formed extremely easily can be obtained.

Further, as described in claim 12, an electrode paste containing at least one selected from silver, copper, palladium, platinum, aluminum, nickel is used for the front and rear electrodes. With such a configuration, a remarkable effect that an electrode having good conductivity can be formed extremely easily can be obtained.

Further, by forming the electrode paste by printing using a mask having a desired pattern, it is possible to form a large number of electrodes in a very short time. A great effect is achieved in that it can also be performed with high precision.

[0060]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the electronic cooling module and the method of manufacturing the same according to the present invention will be described in detail together with comparative examples, but it goes without saying that the present invention is not limited to only such embodiments.

(Embodiment 1) In this embodiment, a case where an electronic cooling module 1 having the structure shown in FIG. 2 is manufactured will be described.

(1) Preparation of Thermoelectric Semiconductor Element Paste (I) Preparation of Ingot As a raw material ingot for a p-type thermoelectric semiconductor element, Bi:
An ingot having an atomic ratio composition of 0.055, Te: 0.61, Sb: 0.33 was prepared, and Bi: 0.37, Te: 0.6 was used as a raw material ingot for an n-type thermoelectric semiconductor element.
An ingot having an atomic ratio composition of 0, Se: 0.03 was produced.

(II) Preparation of Raw Material Powder These ingots are tens to hundreds of μm thick in nitrogen gas.
And then pulverized into a raw material powder having an average particle size of 3 μm with a cutter mill.

(III) Preparation of Paste A solvent was added at a ratio of 10 parts by weight of polyvinyl alcohol (PVA) to 100 parts by weight of the raw material powder to prepare p-type and n-type thermoelectric semiconductor element pastes.

(2) Preparation of Substrate FIG. 7 shows a substrate 2 prepared in this example. This base 2
Is made of alumina having a thickness of 3 mm, and a large number of formed through holes 3 have a cross-sectional shape of 2 mm square. The edge of the opening of the through hole 3 is chamfered at C = 0.4.

(3) Formation of Electrode The surface mesh mask 8A shown in FIG. 8A corresponds to the large number of through holes 3 formed in the base 2 shown in FIG.
And the back surface mesh mask 8B shown in FIG. 8B are disposed on the front surface side and the back surface side of the substrate 2, respectively. Nickel paste is used as an electrode material, and the inner wall of the through hole 3 of the substrate 2 from the surface side of the substrate 2. On the front side, unfired electrodes are formed by screen printing over a range not penetrating the base 2, and the through holes 3 of the base 2 are formed from the back side of the base 2.
An unfired electrode on the back side is formed on the inner wall of the substrate by screen printing over a range that does not penetrate the base 2. And
After printing, the unfired electrode made of a nickel paste is fired at 950 ° C. in a nitrogen atmosphere to obtain a substrate 2 having a front-side electrode 5 and a back-side electrode 6 as shown in FIG.

(4) Injection of thermoelectric semiconductor element paste As shown in FIG. 9, the p-type thermoelectric semiconductor element paste 4p (P) and the n-type thermoelectric semiconductor element paste 4n (P) described in (1) are used. Then, every other nickel was injected into the through hole 3 of the base 2 on which the nickel electrodes 5 and 6 had been formed by a dispenser.

(5) Firing P-type and n-type thermoelectric semiconductor element pastes 4p (P), 4
The substrate 2 into which n (P) was injected was fired at 500 ° C. in a nitrogen atmosphere to obtain the electronic cooling module 1 shown in FIG.

(6) Performance Regarding the performance of the obtained electronic cooling module, the thermoelectric performance index was 2.5 × 10 ⁻³ (1 / K), indicating good cooling performance. When the electronic cooling module was dropped naturally from a height of 70 cm on a concrete floor covered with a vinyl sheet, and the impact resistance was examined, the cooling module was found not to be damaged and had excellent mechanical strength. Met.

(Embodiment 2) In this embodiment, a case will be described in which an electronic cooling module 1 having the structure shown in FIG. 3 (although having a structure similar to that shown in FIG. 2 as a whole) is manufactured. I do.

The production of the ingot, the production of the thermoelectric semiconductor element paste, the formation of the electrodes, the injection of the thermoelectric semiconductor element paste, and the sintering described in the first embodiment are the same as in the second embodiment, so that the description thereof is omitted.

(1) Production of Substrate FIG. 10 shows the structure of the alumina substrate 2 used in this example. That is, the substrate 2 is made of alumina having a thickness of 3 mm, and the inside of a large number of through holes 3 has a diameter of 2 mm.
And a conical portion 3A having an opening diameter of 2.5 mm is formed at the opening end on the front side and the back side of each through hole 3. Then, the substrate 2 shown in FIG.
Was used to manufacture the electronic cooling module 1 in the same steps as in Example 1.

(2) Performance Regarding the performance of the obtained electronic cooling module, the thermoelectric performance index was 2.7 × 10 ⁻³ (1 / K), indicating good cooling performance. When the electronic cooling module was dropped naturally from a height of 70 cm on a concrete floor covered with a vinyl sheet, and the impact resistance was examined, the cooling module was found not to be damaged and had excellent mechanical strength. Met.

(Embodiment 3) A description will be given of a case where an acrylic resin is used as a binder for a thermoelectric semiconductor element paste in manufacturing the electronic cooling module 1 having the structure shown in FIG.

The formation of the electrodes, the injection of the thermoelectric semiconductor element paste, and the sintering described in the first embodiment are the same as in the third embodiment, and therefore will not be described.

(1) Preparation of paste Preparation of ingot and preparation of raw material powder were performed in the same manner as in Example 1. Then, p-type and n-type thermoelectric semiconductor element pastes were prepared by adding 150 parts by weight of ethanol and 10 parts by weight of acrylic resin to 100 parts by weight of the raw material powder obtained here. Then, using this thermoelectric semiconductor element paste, an electronic cooling module was manufactured in the same process as in Example 1.

(2) Performance Regarding the performance of the obtained electronic cooling module, a thermoelectric figure of merit was 2.6 × 10 ⁻³ (1 / K), indicating good cooling performance. When the electronic cooling module was dropped naturally from a height of 70 cm on a concrete floor covered with a vinyl sheet, and the impact resistance was examined, the cooling module was found not to be damaged and had excellent mechanical strength. Met.

(Comparative Example 1) Here, the conventional electronic cooling module 101 shown in FIG.
The performance was evaluated in the same manner as described above.

The thermoelectric performance index of this electronic cooling module was 2.8 × 10 ⁻³ (1 / K), indicating good cooling performance.
When it was dropped naturally from a height on a concrete floor covered with a vinyl sheet and the impact resistance was examined, an element part was broken between the thermoelectric semiconductor element and the electrode, resulting in poor mechanical reliability. Was.

(Embodiment 4) In manufacturing the electronic cooling module 1 having the structure shown in FIG.
The case where the back electrode 6 is made of an aluminum electrode will be described.

The preparation of the thermoelectric semiconductor element paste, the injection of the thermoelectric semiconductor element paste, and the sintering described in the first embodiment are the same as in the fourth embodiment, and therefore will not be described.

(1) Formation of electrodes The mesh masks 8 shown in FIGS. 8A and 8B correspond to the large number of through holes 3 formed in the base 2 shown in FIG.
A and 8B are arranged on the front side and the back side of the base 2 respectively, and aluminum paste is used as an electrode material.
Is formed by screen printing over a range that does not penetrate the base 2, and a back-side unfired electrode is formed over the range that does not penetrate the base 2 from the back side of the base 2 to the inner wall of the through hole 3 of the base 2. It is formed by screen printing. Then, by firing the unfired electrode made of aluminum paste at 550 ° C. after printing, the substrate 2 having the front-side electrode 5 and the back-side electrode 6 as shown in FIG. 6 is obtained.

(2) Performance Regarding the performance of the obtained electronic cooling module, the thermoelectric performance index was 2.6 × 10 ⁻³ (1 / K), indicating good cooling performance. When the electronic cooling module was dropped naturally from a height of 70 cm on a concrete floor covered with a vinyl sheet, and the impact resistance was examined, the cooling module was found not to be damaged and had excellent mechanical strength. Met.

(Comparative Example 2) A case where the edge portion of the opening of the through hole 3 of the base 2 is not chamfered when the electronic cooling module 1 having the structure shown in FIG. 2 is manufactured will be described.

The preparation of the thermoelectric semiconductor element paste, the formation of the electrodes, the injection of the thermoelectric semiconductor element paste, and the firing of the thermoelectric semiconductor element paste described in the first embodiment are the same as in the comparative example 2, so that the description thereof is omitted.

(1) Fabrication of Substrate FIG. 7 shows a substrate 2 fabricated in this example. This base 2
Is made of alumina having a thickness of 3 mm.
Has a cross-sectional shape of 2 mm square.
The edge of the opening is not chamfered.

(2) Performance Regarding the performance of the obtained electronic cooling module, the thermoelectric performance index was 2.2 × 10 ⁻³ (1 / K), and the cooling performance was inferior to that of Example 1. . This is because the edge portion of the opening of the through hole 3 is sharp, and the nickel electrode layer is thin. Further, when the electronic cooling module was naturally dropped from a height of 70 cm on a concrete floor covered with a vinyl sheet, and the impact resistance was examined, the cooling module was not damaged and had excellent mechanical strength. .

Embodiment 5 A description will be given of a case where the thermoelectric semiconductor element is fired in a reducing atmosphere in manufacturing the electronic cooling module 1 having the structure shown in FIG.

The fabrication of the thermoelectric semiconductor element, the fabrication of the base, the formation of the electrodes, and the injection of the thermoelectric semiconductor element paste described in the first embodiment are the same as in the fifth embodiment, and therefore will not be described.

(1) Firing of Thermoelectric Semiconductor Device After the thermoelectric semiconductor device paste is injected into the through hole 3 of the base 2 on which the electrodes 5 and 6 are formed, the base 2 is replaced with nitrogen 9.
It was calcined at 500 ° C. in a reducing gas mixture of 7% and 3% hydrogen.

(2) Performance Regarding the performance of the obtained electronic cooling module, the thermoelectric performance index was 2.7 × 10 ⁻³ (1 / K), indicating good cooling performance. When the electronic cooling module was dropped naturally from a height of 70 cm on a concrete floor covered with a vinyl sheet, and the impact resistance was examined, the cooling module was found not to be damaged and had excellent mechanical strength. Met.

(Comparative Example 3) A description will be given of a case where the thermoelectric semiconductor element material powder in the thermoelectric semiconductor element paste has an average particle diameter of 20 μm when manufacturing the electronic cooling module 1 having the structure shown in FIG. I do.

The fabrication of the base, the formation of the electrodes, and the injection of the thermoelectric semiconductor element paste described in the first embodiment are the same as in the third comparative example, and therefore will not be described.

(1) Performance Regarding the performance of the obtained electronic cooling module, the thermoelectric performance index was 1.9 × 10 ⁻³ (1 / K), and the cooling performance was inferior to that of Example 1. . This is because the raw material powder had a large particle size, and a good sintered thermoelectric semiconductor element could not be obtained. When the electronic cooling module was naturally dropped from a height of 70 cm onto a concrete floor covered with a vinyl sheet, and the impact resistance was examined, the cooling module was not damaged and had excellent mechanical strength. .

Embodiment 6 In manufacturing the electronic cooling module 1 having the structure shown in FIG. 2, when the thermoelectric semiconductor element paste is injected into the through hole 3 of the base 2,
A description will be given of a case where the process is performed using a thermoelectric semiconductor element mask having an opening at a position corresponding to the position of the through hole 3 of the base 2.

The preparation of the thermoelectric semiconductor element paste, the preparation of the base, the formation of the electrodes, and the sintering described in the first embodiment are the same as in the sixth embodiment and will not be described.

(1) Thermoelectric Semiconductor Element Mask FIG. 11 shows the structure of a thermoelectric semiconductor element paste injection mask 9 used in this embodiment.

The mask 9 for injecting the thermoelectric semiconductor element paste is made of stainless steel having a thickness of 0.3 mm and is equivalent to the opening of the through hole 3 for the p-type or n-type thermoelectric semiconductor element formed in the base 2. An opening 9A is formed at the position.
Then, the thermoelectric semiconductor element paste injection mask 9 is placed in close contact with the base 2 corresponding to the through hole 3. After that, first, a p-type thermoelectric semiconductor element paste is injected into the through holes 3 via the mask 9. At this time, a normal screen printing machine can be used.

Next, once the mask 9 is removed from the base 2 and the mask 9 is rotated by 90 ° and placed in close contact with the base 2, the opening 9A of the mask 9 is formed in the base 2 through the through hole for the n-type thermoelectric semiconductor element. 3, the n-type thermoelectric semiconductor element paste is injected into the through holes 3 via the mask 9.

(2) Performance Regarding the performance of the electronic cooling module thus obtained, the thermoelectric performance index was 2.5 × 10 ⁻³ (1 / K), indicating good cooling performance. When the electronic cooling module was dropped naturally from a height of 70 cm on a concrete floor covered with a vinyl sheet, and the impact resistance was examined, the cooling module was found not to be damaged and had excellent mechanical strength. Met.

[Brief description of the drawings]

FIG. 1 is a sectional explanatory view (FIG. 1A) and a plan explanatory view (FIG. 1) showing a part of an electronic cooling module according to the present invention.
(B)).

FIGS. 2A and 2B are a front view (FIG. 2A) and a rear view (FIG. 2B) of an example of an electronic cooling module according to the present invention.

FIG. 3 is an explanatory sectional view showing a part of another example of the electronic cooling module according to the present invention.

FIG. 4 is an explanatory sectional view showing an example of a base structure of the electronic cooling module according to the present invention.

FIG. 5 is an explanatory sectional view showing another example of the base structure of the electronic cooling module according to the present invention.

FIG. 6 is an explanatory view of the front side of the base (FIG. 6A) and an explanatory view of the back side of the base (FIG. B)).

FIG. 7 is an explanatory plan view showing the structure of a base used in the embodiment of the electronic cooling module according to the present invention.

8 is an explanatory plan view (FIG. 8A) of a front surface mesh mask used for forming an electrode in a through-hole portion of a base in the embodiment of the electronic cooling module according to the present invention, and a plan view of a rear surface mesh mask; It is explanatory drawing ((B) of FIG. 8).

FIG. 9 is a cross-sectional explanatory view showing a procedure for injecting a thermoelectric semiconductor element paste into a through hole formed in a substrate in an embodiment of an electronic cooling module according to the present invention.

FIG. 10 is an explanatory plan view showing the structure of a base used in another embodiment of the electronic cooling module according to the present invention.

FIG. 11 is an explanatory plan view of a thermoelectric element semiconductor element paste injection mask used in the embodiment of the electronic cooling module according to the present invention.

FIG. 12 is an explanatory side view illustrating a structure of a conventional electronic cooling module.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 electronic cooling module 2 base 3 through hole 3A conical portion of through hole 4n n-type thermoelectric semiconductor element 4p p-type thermoelectric semiconductor element 5 electrode on front side 6 electrode on rear side

Claims (13)

[Claims] A p-type thermoelectric semiconductor element and an n-type thermoelectric semiconductor element are individually provided inside said through-holes of an electrically insulating substrate having a large number of through-holes formed therein.
The surface-side electrode formed between the surface of the base and the inner wall of the through hole of the base so as not to penetrate the base between the type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element, and the base of the base from the back of the base An electronic cooling module, wherein the electronic cooling module is alternately connected to an inner wall of a through hole by electrodes on a back surface formed over a range not penetrating the base. 2. A fired body of a thermoelectric semiconductor element paste containing a p-type thermoelectric semiconductor element material powder and a thermoelectric semiconductor element paste containing an n-type thermoelectric semiconductor element material powder, respectively. The electronic cooling module according to claim 1, wherein the electronic cooling module comprises: 3. A cross-sectional shape inside a through-hole formed in a base has a shape similar to a cross-sectional shape of an opening of the through-hole, and a cross-sectional area thereof is equal to or less than a cross-sectional area of the opening. The electronic cooling module according to claim 1, wherein the electronic cooling module has a cross-sectional area of: 4. An opening of a through-hole formed in a base body is chamfered.
Electronic cooling module according to any one of the above. 5. A substrate comprising alumina, aluminum nitride,
The electronic cooling module according to any one of claims 1 to 4, wherein the electronic cooling module is an electrically insulating substrate selected from quartz and glass. 6. The electrode material on the front side and the back side is silver,
The electronic cooling module according to any one of claims 1 to 5, comprising at least one selected from copper, palladium, platinum, aluminum, and nickel. 7. The material of the p-type thermoelectric semiconductor element is Bi:
0.05-0.10, Te: 0.55-0.70, S
b: in the atomic composition range of 0.25 to 0.35, the material of the n-type thermoelectric semiconductor element is Bi: 0.35 to 0.45, T
7. The atomic composition range of e: 0.55 to 0.65 and Se: 0.02 to 0.04.
Electronic cooling module according to any one of the above. 8. The electronic cooling module according to claim 1, wherein each of the p-type thermoelectric semiconductor element material powder and the n-type thermoelectric semiconductor element material powder has a particle size of 10 μm or less. 9. A p-type thermoelectric semiconductor element and an n-type thermoelectric semiconductor element are individually provided inside said through-holes of an electrically insulating substrate having a large number of through-holes formed therein.
A surface-side electrode formed between the surface of the base and the inner wall of the through hole of the base so as not to penetrate the base, and the rear surface of the base is formed between the n-type thermoelectric semiconductor and the n-type thermoelectric semiconductor. When manufacturing an electronic cooling module that is alternately connected to the inner wall of the through hole by electrodes on the back side formed over a range that does not penetrate the base, the penetration of the base from the surface of the base having the large number of through holes is performed. After forming an electrode on the front surface over a range that does not penetrate the base on the inner wall of the hole, and forming an electrode on the back side over a range that does not penetrate the base on the inner wall of the through hole of the base from the back of the base, A thermoelectric semiconductor element paste containing a p-type thermoelectric semiconductor element material powder and a thermoelectric semiconductor element paste containing an n-type thermoelectric semiconductor element material powder inside the through hole are filled with the opening of the through hole. Et each injected separately, the manufacturing method of the electronic cooling module, characterized by heating and firing the p-type and n-type thermoelectric semiconductor elements paste. 10. The method according to claim 9, wherein the thermoelectric semiconductor element paste is injected into the through hole from the opening of the through hole using a dispenser having a pressurizer. 11. The thermoelectric semiconductor element paste is injected from the opening of the through hole into the inside of the through hole using a mask having an opening equivalent to the through hole formed in the substrate. A method for manufacturing an electronic cooling module according to claim 10. 12. The electrode on the front side and the back side is made of silver,
The method of manufacturing an electronic cooling module according to any one of claims 9 to 11, wherein the method is formed using an electrode paste containing at least one selected from copper, palladium, platinum, aluminum, and nickel. . 13. The method for manufacturing an electronic cooling module according to claim 9, wherein the electrode paste is formed by printing using a mask having a desired pattern.