JP2003086850A - Thermoelectric element module and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoelectric element module that is excellent in thermal efficiency, can be improved in strength, and can be manufactured easily by reducing the size of the module and improving the mass-productivity of the module, and to provide a method of manufacturing the module. SOLUTION: This thermoelectric element module is constituted by arranging a plurality of n- and p-type thermoelectric semiconductor elements in a matrix- like state and joining the end faces of the elements to the surfaces of electrodes. At the time of arranging the elements in rows and columns, the elements are restricted in the matrix-like state by superimposing plate materials which regulate the elements in the direction of rows upon another in the direction of columns so that the elements are also regulated in the columnar direction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoelectric element module in which a large number of thermoelectric elements are arranged and a method for manufacturing the same, and more specifically, it utilizes the Seebeck effect, which is excellent in mechanical strength and thermal history and highly reliable. The present invention relates to a thermoelectric element module that can be used as a power generation module or as a cooling or heating module utilizing the Peltier effect, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a plurality of substrates are arranged so as to face each other, and conductive metal electrodes are respectively bonded to the facing surfaces of the plurality of substrates facing each other, and a plurality of substrates are provided through the metal electrodes. 2. Description of the Related Art A thermoelectric element module in which n-type and p-type thermoelectric semiconductor elements are arranged next to each other is widely known and is used in various fields. These thermoelectric element modules are, for example, Seebeck effect, that is, an n-type thermoelectric semiconductor element and a p-type thermoelectric semiconductor element are connected in series,
The connecting portion is held at a high temperature as a high temperature side end, and each leg of the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element on the opposite side of the high temperature side end is kept at a low temperature as a low temperature side end, It is used as a thermoelectric element module for power generation by utilizing the principle that an electromotive force is generated when there is a temperature difference between the high temperature side end portion and the low temperature side end portion, or it is used as a Peltier effect, that is, an n-type thermoelectric element. A semiconductor element and a p-type thermoelectric semiconductor element are connected in series, and a positive voltage is applied to the leg portion of the n-type thermoelectric semiconductor element on the side opposite to the connecting portion and a negative voltage is applied to the leg portion of the p-type thermoelectric semiconductor element. , When a current is passed from the n-type thermoelectric semiconductor element to the p-type thermoelectric semiconductor element, heat is absorbed at the junction between the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element, and the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element Heat is generated in each leg and, conversely, p-type thermoelectric When a current is passed from the conductor element to the n-type thermoelectric semiconductor element, heat is generated at the joint between the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element, and the heat is absorbed by each leg of the n-type semiconductor and the p-type semiconductor. It is used as a thermoelectric element module for cooling or heating by utilizing the principle.

These conventional thermoelectric element modules have 1
There is a multi-stage module or a multi-stage module, but the basic structure in the case of a single-stage module in which two substrates are arranged facing each other is the structure shown in the schematic cross-sectional view of FIG. That is, in the thermoelectric element module A, the metal electrodes 4 and 4'are respectively bonded to the facing surfaces 2 and 2'of the two cane substrates 1 and 1'which face each other.
A plurality of n-type thermoelectric semiconductor elements 5 and p-type thermoelectric semiconductor elements 6 are alternately connected via 4 '. Figure 3
Although illustration is omitted in FIG.
Are bonded to the substrates 1 and 1 ′ by a bonding means such as an adhesive, and the n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element 6 are connected to the metal electrodes 4 and 4 ′ such as a solder layer. It is joined by joining means. Similarly, although not shown in FIG. 3, parts or equipment such as heating means, cooling means, or an object to be cooled are generally joined to the outer surfaces 3, 3'of the substrates 1, 1 '. That is, when the thermoelectric element module is used as a thermoelectric element module for power generation utilizing the Seebeck effect, the facing surface 2 side of the substrate 1 has the leg portions of the n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element 6 respectively. If it is the low temperature side end side and the facing surface 2 ′ side of the substrate 1 ′ is the high temperature side end side of the junction between the n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element 6, the outer surface 3 of the substrate 1 is assumed. A cooling means, such as a radiation fin, for keeping the low temperature side end portion of each leg portion at a low temperature is joined to the one end of the substrate 1 '.
The heating means for keeping the high temperature side end portion of the connection portion such as a heat receiving fin at a high temperature is joined to the outer surface 3'of the. When the thermoelectric element module uses the Peltier effect, for example, as a thermoelectric element module for cooling, a current is passed from the p-type thermoelectric semiconductor element 6 to the n-type thermoelectric semiconductor element 5 to face the substrate 1. The surface 2 side is the heat absorbing side end of each leg of the n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element 6, and the facing surface 2'side of the substrate 1'is the n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element. Assuming that the end of the joint portion 6 on the heat generation side is the outer surface 3 of the substrate 1, an object to be cooled is joined by the end portion on the heat absorption side of each leg, while the outer surface 3 of the substrate 1 ′ is joined. A cooling means for radiating the heat of the heat generating side end of the connecting portion, such as a radiation fin, is joined to the ′.

In such a thermoelectric element module,
Generally, a ceramic plate is used as the substrate.
However, in the conventional thermoelectric element module using the ceramic plate as the substrate, the ceramic plate has a poor thermal conductivity, and thus has a problem of poor thermal efficiency and cooling efficiency. That is, when used as a thermoelectric element module for power generation utilizing the Seebeck effect, heating for maintaining the high temperature side end part at a high temperature and cooling for maintaining a low temperature side end part at a low temperature are performed through a ceramic substrate having poor thermal conductivity. As a result, thermal efficiency and cooling efficiency are inevitably lowered. Also,
Even when used as a thermoelectric element module for cooling or heating utilizing the Peltier effect, cooling of the object to be cooled by the end on the heat absorption side and heating of the object to be heated by the end on the heat generating side are performed through a ceramic substrate with poor thermal conductivity. In order to be
Inevitably, the thermal efficiency and cooling efficiency decrease. Further, since the upper and lower sides of the thermoelectric element are fixed by the ceramic plates, the thermoelectric element module has a rigid structure, and the thermoelectric element is easily broken. Further, in the conventional thermoelectric element module, since the p-type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element used as the thermoelectric element are brittle materials, when the impact or load is applied to the thermoelectric element module, or the thermoelectric element module is used. At times, when thermal stress is applied to the thermoelectric element, the thermoelectric element may be destroyed and cracks or chips may occur. Further, these thermoelectric elements have poor moisture resistance, and there is a possibility that the thermoelectric elements may be corroded and the element performance may be deteriorated during repeated condensation / melting or in an atmosphere of high humidity. For example, in the case of a lanthanoid sulfide-based thermoelectric element that was announced to have an excellent Seebeck coefficient, it is possible that corrosive substances such as sulfuric acid may be by-produced due to its sulfur component, and moisture resistance measures are also required. Met.

In order to solve the problems and the like of the conventional thermoelectric element module, various types have been proposed so far. For example, in Japanese Unexamined Patent Publication No. 5-275754, the bonding material between the ceramic substrate and the electrodes is heated. A curable resin that absorbs thermal stress to improve the durability of the thermomodule is disclosed in Japanese Patent Laid-Open No. 11-307825, in which a protective plate and a fixing member are arranged to cause destruction and deformation due to thermal stress. In Japanese Patent Laid-Open No. 2000-164942, the surface of the thermoelectric element other than the bonding surface with the electrode is coated with an insulating material composed of a polyimide vapor deposition polymer film to improve the strength and reliability of the thermoelectric module. In order to improve the above, Japanese Patent Laid-Open Nos. 10-178216 and 2000-5893 are known.
No. 0 gazette discloses a thermoelectric element having a skeleton structure as shown in FIG. 4, which has a thermoelectric element structure held by a partition plate to prevent a decrease in cooling efficiency and
A thermoelectric element having a long life is disclosed. However, in spite of these proposals, a thermoelectric element module that solves the problems of the conventional thermoelectric element module, has excellent thermal efficiency and cooling efficiency, and has improved reliability for mechanical strength, thermal history, etc. I wasn't satisfied enough.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the conventional thermoelectric element module in view of the circumstances surrounding the thermoelectric element module, and to provide excellent thermal efficiency.
It is an object of the present invention to provide a high-performance thermoelectric element module which can improve the strength of the thermoelectric element module, can be miniaturized and can be easily mass-produced, and can be easily manufactured, and a manufacturing method thereof.

[0007]

As a result of intensive studies on the above-mentioned problems, the present inventor has found that, in constructing a thermoelectric element module, n-type and p-type thermoelectric semiconductor elements used as thermoelectric elements are provided between the thermoelectric semiconductor elements. The resulting voids are filled with a plate material made of thermosetting resin or the like having electrical insulation and heat insulation properties, that is, the voids between thermoelectric semiconductor elements are filled with a plate material made of thermosetting resin or the like. When the thermoelectric semiconductor element is exhausted, the thermoelectric semiconductor element is restrained by the plate material, and as a result, the thermoelectric element is not destroyed even if a shock or load is applied to the thermoelectric element module, and reliability and durability are improved. It was found that the object of the present invention can be achieved. The present invention has been completed based on these findings.

That is, according to the first aspect of the present invention,
In arranging a plurality of thermoelectric semiconductor elements in rows and columns in a thermoelectric element module in which a plurality of n-type and p-type thermoelectric semiconductor elements are arranged in a matrix and joined to the end surface of the thermoelectric semiconductor element and the electrode surface A thermoelectric semiconductor element whose row-direction position is regulated by a plate material is also regulated in a column-direction position by overlapping the plate material in the column direction, and the thermoelectric semiconductor elements are arranged and restrained in a matrix. A thermoelectric device module is provided.

According to the second aspect of the present invention, the first aspect
In the invention, the thermoelectric element module is characterized in that a filling adhesive is applied or filled between the plate materials and between the plate material and the thermoelectric semiconductor elements, and the thermoelectric semiconductor elements are arranged and constrained in a matrix. Provided. Further, according to a third invention of the present invention, there is provided a thermoelectric element module according to the first or second invention, wherein the electrodes are formed in advance on a carbonaceous substrate.

On the other hand, according to the fourth aspect of the present invention, a thermoelectric element module in which a plurality of n-type and p-type thermoelectric semiconductor elements are arranged in a matrix and the end surface of the thermoelectric semiconductor element is joined to the electrode surface In the manufacturing method of (1), an element placement step (a) of placing a predetermined number of thermoelectric semiconductor elements on a plate material whose row-direction positions can be regulated, and a plate material where thermoelectric semiconductor elements are placed with their row-direction positions regulated A plurality of plate material polymerization steps (b) for overlapping and joining in the column direction, and these (a)
And (b) an element electrode joining step (c) of joining the respective end surfaces of the thermoelectric semiconductor elements, which are arranged and constrained between the plate materials in a matrix by the step, to the respective opposing surfaces of the electrodes formed on the substrate. A method of manufacturing a featured thermoelectric element module is provided. According to the fifth aspect of the present invention, the fourth aspect
In the invention of claim 1, the method for manufacturing a thermoelectric element module is characterized in that the element arranging step (a) is performed using a plate material in which streaks capable of dropping the thermoelectric semiconductor element are formed and a row direction position can be regulated. Will be provided. Further, according to a sixth invention of the present invention, in the fourth or fifth invention,
An element arranging step (a) of arranging a predetermined number of thermoelectric semiconductor elements on a plate material whose row-direction positions can be regulated, and a plurality of plate materials in which thermoelectric semiconductor elements are arranged with their row-direction positions regulated in the column direction. In the plate material polymerization step (b) of overlapping and joining, a filling adhesive is applied or filled between the plate materials and between the plate material and the thermoelectric semiconductor element, and the thermoelectric semiconductor elements are arranged and constrained in a matrix. A method of manufacturing a thermoelectric element module is provided.

According to the seventh aspect of the present invention, the fourth aspect
In any one of the inventions 1 to 6, the method further comprises a substrate manufacturing step (X) of forming an electrode after forming an electrically insulating layer on the carbonaceous substrate, and the substrate obtained by the substrate manufacturing step (X). There is provided a method for manufacturing a thermoelectric element module, characterized by being subjected to the element electrode bonding step (c). Further, according to an eighth invention of the present invention, in any one of the fourth to seventh inventions, after the plate material polymerization step (b),
The plate further thinned by the slicing step (Y), which further includes a slicing step (Y) of cutting the thermoelectric semiconductor elements arranged in a matrix between the plate materials together with the plate material in a direction orthogonal to the thermoelectric semiconductor elements. Provided is a method for manufacturing a thermoelectric element module, which comprises subjecting thermoelectric semiconductor elements, which are arranged and constrained in a matrix between materials, to an element electrode bonding step (c).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. 1. Substrate As the substrate used in the thermoelectric element module of the present invention, a ceramic substrate or a carbonaceous substrate which has been conventionally used is used, and among them, a carbonaceous substrate is preferable. As the carbonaceous substrate, a plate-like material made of a carbonaceous material such as a carbon fiber-reinforced carbon composite material having carbon fiber as a reinforcing material and carbon as a matrix, or an isotropic high-density carbon material is generally used. The thickness of the carbonaceous substrate can be appropriately set as necessary, but generally, 0.3 to 5 mm is suitable in terms of strength and cost.

As the carbon fiber reinforced carbon composite material used for the carbonaceous substrate, various conventionally known carbon fiber reinforced carbon composite materials can be appropriately selected and used.
Carbon fiber reinforced carbon composite materials generally have various methods of arranging carbon fibers, and primary alignment materials in which carbon fibers are arranged in one direction and bundled, plain weave, twill weave,
There are woven fabrics such as satin weave and other secondary orientations, so-called three-dimensionally woven carbon fibers, and three-dimensional orientations, and also those in which carbon fibers are used as felts or short fibers.

In the present invention, various carbon fiber arranging methods can be appropriately selected and used. Further, the carbon fiber reinforced carbon composite material is generally obtained by adding a thermosetting synthetic resin such as a phenol resin or a matrix material such as a pitch such as petroleum pitch to the carbon fiber aggregate having various orientations described above. An impregnated prepreg is prepared, and a plurality of such prepregs are laminated, if necessary, heated under pressure to cure the matrix material, and further fired at a high temperature in an inert atmosphere to carbonize the matrix material. Manufactured. When the carbon fibers are short fibers, generally, short fibers of carbon fibers are mixed with a matrix material, the mixture is molded into a predetermined shape, and the molded material is heated under pressure to cure the matrix material, Further, the matrix material is carbonized by firing at a high temperature in an inert atmosphere to produce a carbon fiber reinforced carbon composite material. The carbon fiber reinforced carbon composite material used for the carbonaceous substrate may be one produced in a plate shape having a predetermined thickness as the carbonaceous substrate, or from a carbon fiber reinforced carbon composite material produced in a block shape,
It may be cut out by cutting it into a plate having a predetermined thickness as a carbonaceous substrate. Further, the carbon fibers and the carbon matrix forming the various carbon fiber reinforced carbon composite materials may be graphitized.

Among the various carbon fiber reinforced carbon composite materials described above, a carbon fiber reinforced carbon composite material block of primary orientation in which carbon fibers are arranged in one direction is arranged in the direction of arrangement of the carbon fibers. A plate-shaped product in which carbon fibers are arranged in the thickness direction in a carbon matrix, which is cut out in a plate shape having a predetermined thickness in the perpendicular direction, is particularly excellent in thermal conductivity in the thickness direction. Therefore, it is preferably used as a carbonaceous substrate. The plate-shaped material can be cut out from the block of the carbon fiber reinforced carbon composite material by a cutting means known per se such as a wire saw or a rotary diamond saw.

As the isotropic high density carbon material used for the carbonaceous substrate, various conventionally known high density isotropic carbon materials can be appropriately selected and used. The isotropic high-density carbon material is generally obtained by pressing fine particles of a graphite precursor having a sinterability such as raw coke and mesocarbon microbeads at a high temperature while pressure-molding, or by using graphite fine particles or carbon whisker powder. It is manufactured by mixing a body and the like with a binder made of a carbon precursor such as pitch or synthetic resin, and press-molding and firing. The isotropic high-density carbon material used for the carbonaceous substrate may be a plate-like one having a predetermined thickness as the carbonaceous substrate, or may be a block-shaped isotropic high-density carbon material. Alternatively, it may be cut out by cutting it into a plate shape having a predetermined thickness as a carbonaceous substrate. Further, the above various isotropic high-density carbon materials may be graphitized.

The above-mentioned carbon fiber reinforced carbon composite material or isotropic high-density carbon material is generally porous with fine pores derived from the manufacturing process thereof. Then, by impregnating the fine pores of these materials with an inorganic coating agent or a metal to make them non-porous, the thermal conductivity and mechanical strength of the materials are further improved. Therefore, in the present invention, each of the above carbonaceous materials can be used as a carbonaceous substrate by impregnating the fine pores with an inorganic coating agent or a metal, if necessary, and the thermal conductivity and mechanical strength of the substrate can be obtained. From the viewpoint of further improving the above, it is preferable to do so.

The inorganic coating agent to be impregnated into each of the above carbonaceous materials is liquid and can be impregnated into the fine pores of the carbonaceous material, and is cured after impregnation to make the carbonaceous material non-porous. Various inorganic coating agents that form a cured product can be appropriately selected and used. As an example, an inorganic silicon-containing polymer, which undergoes a crosslinking reaction at room temperature or under heating to form a ceramic-like cured product,
Examples thereof include cement such as alumina cement and an inorganic binder containing water glass and the like. These inorganic coating agents can be diluted with an organic solvent to enhance their impregnating properties. In addition, more specific examples of the above inorganic coating agent include HEATLESS GLASS GA forming a silicon-containing polymer.
Series (trade name: Homer Technology Co., Ltd.), polysilazanes Tonen Polysilazane (trade name: Tonen Co.), inorganic binder Red Proof MR-1
Examples include the 00 series (trade name: manufactured by Netsuken Co.).

As the method of impregnating the fine pores of the carbonaceous material with the inorganic coating agent, a method of applying the inorganic coating agent to the carbonaceous material with a brush or the like, a method of immersing the carbonaceous material in the inorganic coating agent, and a high pressure And a method of injecting the inorganic coating agent into the carbonaceous material, and a method of inhaling the inorganic coating agent into the carbonaceous material under high vacuum. The inorganic coating agent impregnated in the carbonaceous material is
Hardened. At this time, the curing conditions of the inorganic coating agent can be appropriately set according to the type of the inorganic coating agent used.
In the case of ATLESS GLASS, generally about 13
Suitably heating at 0 ° C. for 60 minutes.

In general, aluminum, copper, or both are preferable as the metal with which the above-mentioned carbonaceous materials are impregnated. As a method of impregnating the fine pores of the carbonaceous material with a metal, a method of impregnating a molten metal such as aluminum or copper under high temperature and high pressure can be used. As a carbonaceous material impregnated with aluminum, CC-M
A (trade name: C / C composite base manufactured by Advanced Materials Co., which is a primary array of carbon fibers), C-MA (trade name: isotropic high-density carbon material base manufactured by Advanced Materials), and the like, As a carbonaceous material impregnated with copper, MB-
18 (Brand name: Mobius A with a primary array of carbon fibers
-T / C composite base) and the like. The above-mentioned carbonaceous material is obtained as a hard plate, but the carbonaceous substrate in the present invention is relatively unlikely to be a hard plate, and in that respect, a flexible sheet called a graphite sheet or a graphite film is used. Various carbonaceous materials can also be used.

2. Thermoelectric semiconductor element In the first invention of the present invention, as the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element used in the thermoelectric element module, various conventionally known n-type thermoelectric semiconductor elements and p-type thermoelectric semiconductor elements are used. Can be appropriately selected and used,
Examples of these include p-type or n-type thermoelectric semiconductor elements such as Bi-Te series, Si-Ge series, and lanthanoid sulfide series.

3. Metal Electrode In the thermoelectric element module of the present invention, copper, nickel or the like is preferably used as the metal of the conductive metal electrode that connects the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element used. The metal electrode is conventionally generally used by being bonded or vapor-deposited on the above-mentioned substrate, but in the present invention, in addition to this, it can be directly formed on the thermoelectric semiconductor element side. As a method of bonding or vapor depositing on a substrate or a method of directly forming on the thermoelectric semiconductor element side, various conventionally known methods can be appropriately adopted. Note that the vapor deposition method includes a plating method, and includes a wet method such as electroless plating, and a dry method such as vacuum deposition, low temperature sputtering, and ion plating. Among them, electroless plating and vacuum deposition are preferably used. Of course, when the carbonaceous material is used for the substrate, it is necessary to form the metal electrode after laminating the electrically insulating layer on the carbonaceous material.

Further, in the thermoelectric element module of the present invention,
A heat conductive electrically insulating thin film may be bonded to one surface of the metal electrode, that is, the lower surface in the case of the lower electrode, and the upper surface in the case of the upper electrode. The heat conductive electrically insulating thin film has a thickness of tens to hundreds of μ.
m, preferably about 15 to 100 μm, and the material is, for example, an epoxy resin to which a heat conductive filler is added, a fluororesin coat, a silicon heat conductive adhesive, etc. Alternatively, a film-shaped one can be used.

4. Plate Material In the thermoelectric element module of the present invention, when a plurality of thermoelectric semiconductor elements are arranged in rows and columns, the thermoelectric semiconductor elements whose position in the row direction is regulated by the plate material are stacked in the column direction. Thus, the position in the column direction is also regulated, and the thermoelectric semiconductor elements are arranged and restrained in a matrix. Then, a filling adhesive is applied or filled between the plate materials and between the plate material and the thermoelectric semiconductor elements to constrain the thermoelectric semiconductor elements in a matrix. That is, between thermoelectric semiconductor elements, or between the thermoelectric semiconductor elements and in the voids formed between the substrate and the metal electrode, a thermosetting resin or an inorganic material having electrical insulation and heat insulation properties, which is substantially constant. It is characterized in that it is filled with a plurality of plate materials arranged at intervals and a filling adhesive that bonds the plate materials and the plate material and each thermoelectric semiconductor element.

In the conventional thermoelectric element module, as described above, since the elements are firmly sandwiched by the substrates,
That is, although the module as a whole has a rigid body structure, the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element are fragile materials, and there is a space between them to leave deformation space. It is difficult to withstand the strain caused by the shock, the external impact and the load, which causes the failure of the thermoelectric element module, and the durability and the reliability are poor. Therefore, the space around the thermoelectric semiconductor element is filled with a plate material that serves as a support, that is, the space is filled with a plate material made of thermosetting resin or the like, and the thermoelectric semiconductor element is reinforced with the plate material. By improving the mechanical strength against stress due to thermal strain and external impact,
The durability and reliability of the thermoelectric element module can be improved. In order to improve the performance as described above, it is desirable that the plate material that fills the gaps between the thermoelectric elements be a material that is less likely to expand in volume due to heat, a material that has a thermal expansion coefficient close to that of the substrate or the thermoelectric elements, and the like. Further, by using a material having a low thermal conductivity, that is, a material having a heat insulating property, it is expected that the efficiency of heat conversion is improved. Also, impurities in the material, such as solvents,
If water, alcohol, etc. are mixed, foaming will occur at the time of heating, causing damage to the thermoelectric element block. Therefore, it is necessary to avoid mixing of foaming impurities.

The plate material used in the present invention is required to have electrical insulation and heat insulation properties, and it is desirable to use a material that does not easily expand in volume or a material having a low thermal conductivity, but the operating temperature of the thermoelectric element module of the present invention. Depending on the range, for low temperatures up to 150 ° C., an organic resin, for example, a cured product of a heat resistant resin or a thermosetting resin (that is, a thermosetting resin) is desirable. Examples of the thermosetting resin include epoxy resin, urethane resin, amino resin (urea resin, melamine resin), phenol resin, unsaturated polyester resin, and condensation type silicone resin (rubber). Various additives and fillers (materials) may be appropriately added to these resins. The epoxy resin may be a resin obtained by appropriately mixing the epoxy resin (A) with a polyalkylene glycol polymer (B) having a glycidyl group at the terminal and an amine compound (C) (for example, a weight ratio A / B / C = 100 / 100/31) or a mixed resin thereof, in which an appropriate amount of silica balloons made of borosilicate silica and phenol balloons made of a phenol resin are mixed in order to further impart heat insulating property. Further, the condensation type silicone resin (rubber), a room temperature curable condensation type polysiloxane polymer, a silica balloon made of borosilicate silica and a phenol balloon made of a phenol resin are mixed in an appropriate amount in order to impart heat insulating property, Further, a mixture of antimony oxide and a phosphoric acid ester compound can be used. On the other hand, for high temperatures of 150 ° C. or higher, inorganic materials are used. Examples of such materials include a glass epoxy plate having a thickness of about 0.2 to 0.5 mm, an aluminum plate subjected to alumite processing, or Examples include a plate obtained by mixing heatless glass and the like with an inorganic filler such as shirasu balloon and firing.

5. Preparation of Thermoelectric Element Unit In the method for producing a thermoelectric element module of the present invention, a plurality of n-type and p-type thermoelectric semiconductor elements are arranged in a matrix and the end surface of the thermoelectric semiconductor element and the electrode surface are joined together. It is preferable to manufacture a thermoelectric element unit. Regarding the method for producing the thermoelectric element unit, a plate having a desired shape, for example, a cubic mold, in which a predetermined number of thermoelectric semiconductor elements are formed, and a line groove in which the position in the row direction can be regulated, for example, the thermoelectric semiconductor elements can be depressed is formed. On the material, that is, on the plate material having the recess for arranging the thermoelectric semiconductor element, the element arranging step (a) and a plurality of plate materials in which the thermoelectric semiconductor elements are arranged with their row-direction positions regulated, It is desirable to adopt a plate material polymerization step (b) of overlapping and joining in the column direction. Then, in both steps (a) and (b), a filling adhesive is applied or filled between the plate materials and between the plate material and the thermoelectric semiconductor elements to constrain the thermoelectric semiconductor elements in a matrix. It is a thing.

As the above-mentioned filling adhesive, in order to bond the plate materials or to bond the plate material and the thermoelectric semiconductor element, various kinds such as epoxy type are appropriately used depending on the material of the plate materials. . In this way, it is possible to obtain the thermoelectric element unit in which the gap between the thermoelectric elements is applied or filled with the plate material and the filling adhesive.

6. Manufacture of Thermoelectric Module The manufacture of the thermoelectric module of the present invention includes, for example,
In the case of a tiered module, it is generally done as follows.
That is, first, the ceramic substrate,
A metal electrode is bonded and formed on a carbonaceous substrate made of a carbonaceous material, after impregnating the fine pores thereof with the above-mentioned inorganic coating agent or metal, if necessary.

For example, as one method for joining and forming a metal electrode on a carbonaceous substrate, first, on the carbonaceous substrate,
A metal foil equivalent to the metal electrode is joined by a joining means that has electrical insulation and can join the metal foil to the carbonaceous substrate,
A metal-clad laminate is prepared. This metal-bonded laminated plate may be a metal-bonded laminated plate in which a metal foil is laminated only on one side of a carbonaceous substrate, or a metal-bonded laminated plate in which metal foils are laminated on both sides, if necessary. You can also Then
On the metal foil side of the obtained metal-clad laminate, on the metal foil side of one side in the case of a metal-clad laminate with metal foil laminated on both sides, the photolithography established as a printed wiring board manufacturing technology Applying the E technology, that is, drawing a desired pattern of the metal foil portion necessary for electrode formation using photoresist, and performing etching etc. in accordance with the pattern to remove the metal foil portion unnecessary for electrode formation By carrying out, etc., the metal electrode can be joined and formed on this carbonaceous substrate.

As another method of joining and forming the metal electrode on the carbonaceous substrate, a so-called lead frame produced by punching a metal plate into a desired pattern of the metal electrode is formed on the carbonaceous substrate. It is also possible to directly carry out the above without the need for etching or the like by joining the lead frame with a joining means capable of joining the lead frame to the carbonaceous substrate. Generally, the method of applying the photolithography technique is relatively complicated in the process of joining and forming the metal electrodes, but is suitable for microfabrication, while the method of using the lead frame is not suitable for microfabrication. Although not suitable, the process of joining and forming metal electrodes is relatively simple,
By using a lead frame having a corresponding thickness and bonding and forming the metal electrode having a corresponding thickness, a metal electrode capable of handling a large current and having reduced resistance loss can be bonded and formed. Especially suitable.

Next, the metal electrodes obtained as described above are joined together, the two carbonaceous substrates formed are opposed to each other, and the n-type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element are formed through the metal electrodes formed by joining them. When alternately connecting the p-type thermoelectric semiconductor elements, the thermoelectric element unit of the present invention is manufactured using the thermoelectric element unit in which the thermoelectric semiconductor elements are filled with a plate material such as a thermosetting resin. At this time, the metal electrode and the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element can be joined by a conventionally known joining means such as soldering. Further, the thermoelectric element module of the present invention, except that the gaps between adjacent thermoelectric semiconductor elements are applied or filled with a plate material and a filling adhesive, and as the substrate, for example, preferably a carbonaceous substrate is used. For example, the basic structure is the same as that of the conventional 1 whose cross section is schematically shown in FIG.
It is similar to the basic structure of the thermoelectric element module in stages. Also, the basic structure of the multi-stage thermoelectric element module of the present invention is the same as the basic structure of the conventional multi-stage thermoelectric element module except for the above points. In addition to the case where a carbonaceous substrate made of a carbonaceous material is used for all of the plurality of substrates (for example, two substrates in a one-stage thermoelectric element module) as described above, The present invention also includes the case where a carbonaceous substrate is used as a part of the inside. Therefore, for example, the carbonaceous substrate may be used only for the heat receiving side substrate and the heat radiating side substrate may be a conventional ceramic substrate.

Further, in the thermoelectric element module of the present invention, for example, when it is a one-stage module, for example, on the outer surface of the ceramic substrate or the carbonaceous substrate, as in the conventional one-stage thermoelectric element module, heating means, It is possible to join parts or equipment such as cooling means or objects to be cooled. When joining these components or equipment to the outer surface of this ceramic substrate or carbonaceous substrate, the joining means does not need to be electrically insulating, and these components or equipment can be firmly bonded to the ceramic substrate or carbonaceous substrate. Any means can be used as long as it can be bonded to the above. Further, in the thermoelectric element module of the present invention, for example, when it is a one-stage module, heat receiving or radiating fins can be integrally formed on the outer surface of the ceramic substrate or the carbonaceous substrate. As a specific example, there is a case where a slit is formed on a ceramic substrate or a carbonaceous substrate with a disc cutter, a saw blade, or the like to process the ceramic substrate or the carbonaceous substrate itself into a fin shape. Of course, in the thermoelectric element module of the present invention, the circuit electrode is directly formed on the thermoelectric semiconductor element side, that is, the circuit electrode is directly formed so as to straddle the end surfaces of the thermoelectric semiconductor element exposed on the front and back sides of the thermoelectric element unit. It is also possible to electrically bond them to each other and further to attach a film having electric insulation and heat resistance to the thermoelectric element module.
In that case, the film may be a resin film, but a flexible carbonaceous material called a graphite sheet or a graphite film may be attached through an electrically insulating layer.

[0034]

EXAMPLES The present invention will now be described in more detail with reference to the examples using the drawings, but the present invention is not limited to these examples.

[Example 1] [Preparation of thermoelectric semiconductor element unit in which voids between thermoelectric semiconductor elements were coated or filled with a plate material and a filling adhesive (Fig. 1)] In preparing a thermoelectric semiconductor element module,
A thermoelectric semiconductor element unit is manufactured in which the voids between the thermoelectric semiconductor elements are coated or filled with a plate material and a filling adhesive. The manufacturing process consists of the following 2 (,) processes or 3 (~) processes as desired, and is shown in FIG.

Element arranging step (a): a step of arranging a predetermined number of thermoelectric semiconductor elements on the plate material so that the position in the row direction is regulated, and in the embodiment shown in FIG. N-type and p-type thermoelectric semiconductor elements are alternately placed in the recesses on a plate material in which a predetermined number of recesses are formed at predetermined intervals so that the row direction position of the thermoelectric semiconductor elements can be regulated. ing. The lengths of the plate material and the thermoelectric semiconductor elements (the lengths in the direction orthogonal to the paper surface in the drawing) at this time are almost the same, and unless a subsequent slicing step is planned, one thermoelectric element module The thickness is about the same, and if the subsequent slicing process is scheduled, the thickness is a multiple of the thickness, but they are probably related to how long a uniform thermoelectric semiconductor element can be manufactured. Also,
The thermoelectric semiconductor element may have a circular cross section as in the illustrated embodiment or a rectangular cross section, but it is desirable to determine the concave shape of the plate material in consideration of the sectional shape.

Since the original purpose in the element arranging step (a) is to arrange a predetermined number of thermoelectric semiconductor elements on the plate material such that the position in the row direction is regulated, the thermoelectric semiconductor elements remain in the recesses. If there is no problem, there is no need to apply or fill the filling adhesive in this step, but if you are concerned that the position of the thermoelectric semiconductor element in the row direction will move during the subsequent work, in this step, filling adhesive It is preferable to apply or fill a filling adhesive to the contact position between the thermoelectric semiconductor element and the concave portion on the plate material or the like so as not to solidify in a state where the agent is excessively overflowed to perform temporary adhesion or primary adhesion. In addition, as a matter of course, the end surface positions of at least one of the plate material and the thermoelectric semiconductor element are aligned on the same surface. In addition, this element placement step (a)
May be repeated to obtain a large number of plate materials on which the thermoelectric semiconductor elements are arranged, or the plate material polymerization step (b) of the next step may be performed until one thermoelectric element unit is obtained. It may be repeated alternately.
Further, when arranging the thermoelectric semiconductor element so as to drop it into the concave portion of the plate material, this may be done manually, but by applying ultrasonic vibration or the like to move the thermoelectric semiconductor element in a self-sustaining manner. However, depending on the electrode pattern, it may not always be n.
Type and p-type thermoelectric semiconductor elements do not need to be arranged alternately, and only the n-type thermoelectric semiconductor elements, p type
You may make it arrange | position the thermoelectric semiconductor element only of a type | mold.

Plate material superposition step (b): A plurality of plate materials in which thermoelectric semiconductor elements are arranged with their positions in the row direction regulated are stacked in the column direction (stacked in the upward direction in the drawing) and filled with adhesives. In the step of joining the plate material and the thermoelectric semiconductor element to each other, in the embodiment shown in FIG. 1 (B), one surface of each plate material is formed into a regulation frame shape in which three surfaces of the cubic box body are removed by removal. The two sides are brought into contact with each other, and they are sequentially overlapped. As described above, for example, even if the plate material polymerization step (b) and the element arranging step (a) are alternately repeated on this regulation frame mold until one thermoelectric element unit is obtained,
Alternatively, a large number of plate materials obtained in advance by repeating the element arranging step (a) may be superposed at once. In any case, it is desirable to apply or fill the adhesive filler so that the plate material and the thermoelectric semiconductor element can be well adhered to each other, or to fill them without any gap. For that purpose, for example, by using a slightly smaller regulation frame mold so as to face each other, the inside of the regulation frame mold is closed, and then a filling adhesive is further injected under pressure, or both regulation frame molds are It is preferable to press and press so as to clamp the mold.

As shown in (a) and (b) of FIG. 1 (B), the shape of the recess on the plate material (7) is intermediate with the shape of the plate material of the rows located at both ends constituting the thermoelectric element unit. The shape of the plate material in the row positioned at may be different or may be the same. That is, in the case of (a), the plate material in the middle row has recesses formed on both sides thereof with a depth of about half the diameter of the thermoelectric semiconductor element. In any case, each plate member has a recess having the same depth as the diameter of the thermoelectric semiconductor element formed on one surface thereof. It is desirable that these be determined in consideration of various efficiencies in the entire manufacturing process. It should be noted that, in the drawing, the plate materials are separated somewhat widely so that the existence of the filling adhesive is easily understood, and the filling adhesive is drawn as if it exists as a layer between them. Considering the thermal conductivity and the general adhesive strength of the adhesive, it is recommended to bond the plate materials with a thin film filling adhesive assuming that the depth of the recess of the plate material is almost the same as the diameter of the thermoelectric semiconductor element. preferable. After clamping the regulation frame molds together, press and press at least between the plate materials, and preferably leave them at a high temperature for an appropriate time to accelerate the curing of the filling adhesive, and then measure the curing degree of the filling adhesive. Then, the pressure and pressure are released to obtain an integrally solidified block (cubic shape in the figure). If the thickness of this block is the thickness of one thermoelectric element module, the thermoelectric element unit can be obtained with it. If the thickness is multiple times, the thermoelectric element unit is passed through the subsequent slicing step. One by one is obtained.

Slicing step (Y): Depending on the length of the thermoelectric semiconductor element exclusively used for the element arranging step (a), the plate material is superposed after the plate material superimposing step (b) in a matrix form. The constrained thermoelectric semiconductor element for each plate material,
That is, as shown in FIG. 1C, it is a step of cutting the thermoelectric unit in the form of a block in a direction perpendicular to the thermoelectric semiconductor element with an appropriate thickness. For cutting, a conventionally known appropriate cutting means may be used, but a disc cutter for cutting a semiconductor element or the like is preferably used. The thermoelectric element unit obtained in the plate material polymerization step (b) of the previous step or the thermoelectric element unit obtained by slicing to a desired thickness in this slicing step (Y) is a thermoelectric semiconductor in which the thermoelectric semiconductors are arranged and constrained in a matrix. The thermoelectric element module has a flat plate shape with the end faces of the element exposed on the front and back sides, and if necessary, the front and back surfaces are polished to remove excess filling adhesive and the like. That is, as the thermoelectric element module, if a plurality of n-type and p-type thermoelectric semiconductor elements are arranged in a matrix and the end faces of the thermoelectric semiconductor elements are electrically joined, the Peltier effect or the Seebeck effect, which originally functions, is obtained. Therefore, a metal electrode may be directly formed on the thermoelectric element unit in a circuit manner, and the end surfaces of the thermoelectric semiconductor elements exposed on the front and back may be electrically joined to each other to form the thermoelectric element module. However, in this case, since the metal electrode remains exposed, when the thermoelectric element module is incorporated into the device and the Peltier effect or the Seebeck effect is to be utilized, the thermoelectric element module is placed in the target part of the device. Since it is disadvantageous in terms of electrical insulation when mounting, a film with electrical insulation and heat resistance is pasted on the electrodes and the entire front and back surfaces of the thermoelectric element unit to make it a versatile thermoelectric element module. be able to. Of course, it is desirable that this film also has excellent thermal conductivity. In addition, as in the conventional case, the electrodes formed on the substrate made of ceramics or C / C material should be used for the opposing thermoelectric semiconductor element of the thermoelectric element unit. Of course, it is also possible to join the end faces with solder or the like to form a thermoelectric element module.

[Example 2] [Outline of thermoelectric semiconductor element module and manufacturing method thereof (Fig. 2)] Fig. 2 is a thermoelectric element of Example 2 using the thermoelectric element unit prepared in advance in Example 1. It is sectional drawing which shows a module. In this Example 2, a plate-like carbon fiber reinforced carbon composite material (hereinafter referred to as “C / C composite”) having a thickness of 1 mm in which carbon fibers are arranged in a carbon matrix in a thickness direction and copper is impregnated under high pressure. ) As a base, an electric insulating layer of polyimide resin is laminated and formed on the entire surface of the C / C composite, and a predetermined electrode is further formed on the electric insulating layer.
1 ') is used. Then, the end face of the thermoelectric semiconductor element on the thermoelectric element unit prepared in advance in Example 1 and the electrodes on this substrate (1, 1 ′) are joined to each other by soldering or the like to form a thermoelectric element module. . C /
The thermoelectric element module using the C composite substrate has the strength of the thermoelectric semiconductor element reinforced, and even if a shock or a load is applied to the thermoelectric element module, the thermoelectric semiconductor element is not destroyed and reliability and durability are improved. In addition to being able to be improved, the thermal conductivity is also excellent as compared with the one using the conventional ceramic substrate, so that the efficiency as a thermoelectric element module is also improved.

[0042]

According to the present invention, there is provided a high-performance thermoelectric element module which is excellent in thermal efficiency and which is not broken even when a shock or load is applied to the thermoelectric element module and which is highly reliable. It INDUSTRIAL APPLICABILITY The thermoelectric element module of the present invention has high thermal efficiency and high reliability, and can function as power generation utilizing the Seebeck effect, or as cooling or heating utilizing the Peltier effect, and can be used in various fields. Is useful in.

[Brief description of drawings]

FIG. 1 is a diagram showing a manufacturing process of a thermoelectric element unit according to the present invention and an outline thereof.

FIG. 2 is a cross-sectional view showing a cross section of a thermoelectric element module (Example 2) of the present invention.

FIG. 3 is a sectional view showing an example of a conventional thermoelectric element module.

FIG. 4 is a cross-sectional view showing an example of a thermoelectric element module having a skeleton structure.

[Explanation of symbols]

1: Substrate 1 ': substrate 2: Opposite surface of substrate 2 ': Opposing surface of substrate 3: Outer surface of substrate 4: Metal electrode 5: n-type thermoelectric semiconductor element 6: p-type thermoelectric semiconductor element 7: Plate material 8: Partition board 9: Thermally conductive electrically insulating flexible sheet thin film 9 ': Thermally conductive electrically insulating flexible sheet-like thin film 10: Filling adhesive

Claims (8)

[Claims] 1. A thermoelectric element module in which a plurality of n-type and p-type thermoelectric semiconductor elements are arranged in a matrix, and an end surface of a thermoelectric semiconductor element and an electrode surface are joined to each other, the thermoelectric semiconductor elements are arranged in rows and columns, respectively. When arranging multiple,
The thermoelectric semiconductor elements whose row-direction positions are regulated by the plate material are also regulated in the column-direction position by overlapping the plate materials in the column direction, and the thermoelectric semiconductor elements are arranged and restrained in a matrix. Characteristic thermoelectric element module. 2. The thermoelectric semiconductor elements are arranged and restrained in a matrix by applying or filling a filling adhesive between the plate materials and between the plate materials and the thermoelectric semiconductor elements. The thermoelectric element module described. 3. The thermoelectric element module according to claim 1, wherein the electrodes are formed in advance on the carbonaceous substrate. 4. A row direction position can be regulated in a method of manufacturing a thermoelectric element module in which a plurality of n-type and p-type thermoelectric semiconductor elements are arranged in a matrix and the end surface of the thermoelectric semiconductor element and an electrode surface are joined. An element disposing step (a) of disposing a predetermined number of thermoelectric semiconductor elements on a plate material, and a plurality of plate materials in which the thermoelectric semiconductor elements are arranged in a row direction.
The plate material polymerization step (b) of overlapping and joining in the column direction, and the end surfaces of the thermoelectric semiconductor elements constrained to be arranged in a matrix between the plate materials by these step (a) and (b),
A method of manufacturing a thermoelectric element module, comprising: an element electrode joining step (c) of electrically joining each other with electrodes. 5. The element arranging step (a) is performed by using a plate material in which streak grooves that allow the thermoelectric semiconductor element to be depressed are formed and the position in the row direction can be regulated. Method for manufacturing thermoelectric module. 6. An element arranging step (a) of arranging a predetermined number of thermoelectric semiconductor elements on a plate material whose position in the row direction can be regulated.
And in the plate material superimposing step (b) in which a plurality of plate materials in which the thermoelectric semiconductor elements are arranged with their positions in the row direction being regulated are stacked and joined in the column direction, the plate materials are separated from each other and between the plate materials and the thermoelectric semiconductor elements. The method for producing a thermoelectric element module according to claim 4 or 5, wherein a filling adhesive is applied or filled between the thermoelectric semiconductor elements to constrain them in a matrix. 7. The method further comprises a substrate manufacturing step (X) of forming an electrode after forming an electrically insulating layer on the carbonaceous substrate,
The substrate obtained by the substrate manufacturing step (X) is subjected to a device electrode bonding step (c).
The method for manufacturing a thermoelectric element module according to any one of 1. 8. A slicing step (Y) for cutting the thermoelectric semiconductor elements arranged and constrained in a matrix between the plate materials together with the plate materials in a direction orthogonal to the thermoelectric semiconductor elements after the plate material superposing step (b). 8. A thermoelectric semiconductor device, which is further included and is thinned by the slicing process (Y) and constrained to be arranged in a matrix between the plate materials, is subjected to the device electrode bonding process (c). The method for manufacturing a thermoelectric element module according to any one of claims.