thermoelectric conversion module

Abstract

Provided is a thin thermoelectric conversion module without a support substrate, comprising: a unified body that comprises P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips arranged in an alternating and separated manner, and includes insulating bodies configured so as to fill the resulting gaps; common first electrodes that are on one surface of the unified body, and by which one surface of the P-type thermoelectric conversion material chips and one surface of the N-type thermoelectric conversion material chips are joined; and common second electrodes that are on the other surface of the unified body and are facing the first electrodes, and by which the other surface of the N-type thermoelectric conversion material chips and the other surface of the P-type thermoelectric conversion material chips are joined, wherein the P-type thermoelectric conversion material chips and the N-type thermoelectric conversion material chips are electrically connected in series due to the first electrodes and the second electrodes, and the thermoelectric conversion module does not have a substrate on either surface thereof.

Description

[Technical Field]

[0001] The present invention relates to a thermoelectric conversion module. [Background technology]

[0002] 2. Description of the Related Art Conventionally, as one of the means for effectively utilizing energy, there has been a device that directly converts thermal energy into electrical energy and vice versa using a thermoelectric conversion module that has a thermoelectric effect such as the Seebeck effect or the Peltier effect.

[0003] The use of so-called π-type thermoelectric conversion elements as the thermoelectric conversion module is known. A π-type thermoelectric conversion element is a basic unit in which a pair of electrodes spaced apart from each other are provided on a substrate. For example, the lower surface of a P-type thermoelectric element is provided on one electrode, and the lower surface of an N-type thermoelectric element is provided on the other electrode, also spaced apart from each other. The upper surfaces of both types of thermoelectric elements are connected to electrodes on the opposing substrates. Typically, multiple such basic units are configured within both substrates, electrically connected in series and thermally connected in parallel. Also known is the use of so-called uni-leg thermoelectric conversion elements. A uni-leg thermoelectric conversion element, like the π-type thermoelectric conversion element described above, is configured to consist of only P-type or N-type thermoelectric elements, and the upper and lower surfaces of adjacent thermoelectric elements are electrically connected in series using a conductive member or the like. In recent years, in order to put into full-scale practical use products using thermoelectric conversion modules including such π-type thermoelectric conversion elements, there have been various demands for thinner thermoelectric conversion modules, reduced material use, improved productivity, improved reliability, etc. For example, Patent Documents 1 and 2 disclose thermoelectric conversion modules using the above-mentioned π-type thermoelectric conversion elements. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-102643 [Patent Document 2] International Publication No. 2017 / 074003 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the thermoelectric conversion module of Patent Document 1 is composed of a P-type element made of a P-type thermoelectric material, an N-type element made of an N-type thermoelectric material, and two substrates having metal electrodes capable of joining these dissimilar elements in pairs to form PN junction pairs, and since a substrate is used to support at least the metal electrodes and elements, no consideration is given to reducing the thickness of the thermoelectric conversion module, reducing the number of constituent materials, etc. Similarly, the thermoelectric conversion module of Patent Document 2 does not include a substrate that will serve as a support in the final configuration, but a contact thermal conduction layer is provided where the substrate would normally be placed, and this contact thermal conduction layer is made of the same type of aluminum nitride, silicon nitride, alumina, etc. as commonly used substrates and also functions as a support, so no consideration is given to reducing the thickness of the thermoelectric conversion module, reducing the number of constituent materials, etc.

[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thin thermoelectric conversion module that does not have a supporting substrate. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the inventors have discovered that by directly arranging electrodes on both sides of a free-standing integrated body including an insulator configured to fill the gaps between alternately spaced chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material, or between alternately spaced chips of P-type thermoelectric conversion material or chips of N-type thermoelectric conversion material and conductive chips, a free-standing thin thermoelectric conversion module can be obtained that does not require a support substrate with high thermal resistance as a conventional support, and have completed the present invention. That is, the present invention provides the following [1] to

[12] . [1] A thermoelectric conversion module comprising: an integrated body including an insulator configured to fill gaps between alternately spaced chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material; a common first electrode on one side of the integrated body, which joins one side of the chips of P-type thermoelectric conversion material and one side of the chips of N-type thermoelectric conversion material; and a common second electrode on the other side of the integrated body, which faces the first electrode and joins the other side of the chips of N-type thermoelectric conversion material and the other side of the chips of P-type thermoelectric conversion material, wherein the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material are electrically connected in series by the first electrode and the second electrode, and wherein neither side of the thermoelectric conversion module has a supporting substrate. [2] A thermoelectric conversion module comprising: an integrated body including an insulator configured to fill gaps formed by alternately spaced thermoelectric conversion material chips and conductive chips; a common first electrode on one side of the integrated body, which joins one side of the thermoelectric conversion material chip and one side of the conductive chip; and a common second electrode on the other side of the integrated body, which faces the first electrode and joins the other side of the thermoelectric conversion material chip and the other side of the conductive chip; the thermoelectric conversion material chips and the conductive chips are electrically connected in series by the first electrode and the second electrode; the thermoelectric conversion material chips are selected from chips of P-type thermoelectric conversion material or chips of N-type thermoelectric conversion material; and no supporting substrate is provided on either side of the thermoelectric conversion module. [3] The thermoelectric conversion module according to the above [1] or [2], wherein an adhesive layer is provided on at least one surface of the thermoelectric conversion module. [4] The thermoelectric conversion module according to any one of the above [1] to [3], wherein a release sheet is laminated on the adhesive layer. [5] The thermoelectric conversion module according to [1] or [2] above, wherein the first electrode and the second electrode are each independently formed of at least one film selected from the group consisting of a vapor-deposited film, a plated film, a conductive composition, and a metal foil. [6] The thermoelectric conversion module according to any one of the above [1] to [5], wherein the insulator is selected from an insulating resin and a ceramic. [7] The thermoelectric conversion module according to [6] above, wherein the insulating resin is selected from the group consisting of polyimide resins, silicone resins, rubber resins, acrylic resins, olefin resins, maleimide resins, and epoxy resins. [8] The thermoelectric conversion module according to any one of the above [1] to [7], wherein the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material are made of a thermoelectric semiconductor composition. [9] The thermoelectric conversion module according to [8] above, wherein the thermoelectric semiconductor composition contains a thermoelectric semiconductor material, a resin, and one or both of an ionic liquid and an inorganic ionic compound.

[10] The thermoelectric conversion module according to [2] above, wherein the material of the conductive chip is selected from copper, gold, silver, platinum, nickel, copper alloy, aluminum, and constantan.

[11] The thermoelectric conversion module according to the above [3], wherein a hard member is further provided on the adhesive layer on at least one surface of the thermoelectric conversion module.

[12] The thermoelectric conversion module according to

[11] above, wherein the hard member is a heat dissipation member. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a thin thermoelectric conversion module that does not have a supporting substrate and is suitable for use in narrow spaces. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view showing the configuration of a thermoelectric conversion module according to a first embodiment of the present invention. [Figure 2] FIG. 3 is a cross-sectional view showing the configuration of a second embodiment of a thermoelectric conversion module according to the present invention. [Figure 3] FIG. 4 is a cross-sectional view showing the configuration of a thermoelectric conversion module according to a third embodiment of the present invention. [Figure 4] FIG. 10 is a cross-sectional view showing the configuration of a fourth embodiment of a thermoelectric conversion module according to the present invention. [Figure 5] FIG. 10 is a cross-sectional view showing the configuration of a thermoelectric conversion module according to a fifth embodiment of the present invention. [Figure 6]FIG. 10 is a cross-sectional view showing the configuration of a thermoelectric conversion module according to a sixth embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Thermoelectric conversion module] The thermoelectric conversion module of the present invention comprises an integrated body including an insulator configured to fill gaps formed by alternately spaced chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material; a common first electrode on one side of the integrated body, which joins one side of the chips of P-type thermoelectric conversion material and one side of the chips of N-type thermoelectric conversion material; and a common second electrode on the other side of the integrated body, which faces the first electrode and joins the other side of the chips of N-type thermoelectric conversion material and the other side of the chips of P-type thermoelectric conversion material, the first electrode and the second electrode electrically connecting the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material in series, and both sides of the thermoelectric conversion module are free of supporting substrates. In the thermoelectric conversion module of the present invention, predetermined electrodes are provided directly on both sides of a self-standing integrated body consisting of a chip of P-type thermoelectric conversion material, a chip of N-type thermoelectric conversion material, and an insulator that constitutes the thermoelectric conversion module, thereby eliminating the need for a support substrate and enabling the thermoelectric conversion module to be made thinner. In this specification, the term "support substrate" refers to a substrate material used as a support for a thermoelectric conversion material, an electrode, or the like, and is not particularly limited, but examples thereof include glass, silicon, ceramics, resins, and the like that are commonly used in the thermoelectric field.

[0011] Another thermoelectric conversion module of the present invention comprises an integrated body including an insulator configured to fill gaps formed by alternately spaced thermoelectric conversion material chips and conductive chips; a common first electrode on one side of the integrated body, which joins one side of the thermoelectric conversion material chip and one side of the conductive chip; and a common second electrode on the other side of the integrated body, which faces the first electrode and joins the other side of the thermoelectric conversion material chip and the other side of the conductive chip; the thermoelectric conversion material chips and the conductive chips are electrically connected in series by the first electrode and the second electrode; the thermoelectric conversion material chips are selected from chips of P-type thermoelectric conversion material or chips of N-type thermoelectric conversion material; and the thermoelectric conversion module does not have a supporting substrate on either side. In another thermoelectric conversion module of the present invention, by providing predetermined electrodes on both sides of a self-standing integrated body consisting of a chip of P-type thermoelectric conversion material or a chip of N-type thermoelectric conversion material, a conductive chip, and an insulator that constitutes the thermoelectric conversion module, it is possible to eliminate the need for a support substrate and achieve a thin thermoelectric conversion module.

[0012] 1 is a cross-sectional view showing a first embodiment (basic configuration) of a thermoelectric conversion module of the present invention. The thermoelectric conversion module 1 includes an integrated body 4 including an insulator 3 configured to fill the gaps between alternately spaced P-type thermoelectric conversion material chips 2p and N-type thermoelectric conversion material chips 2n. A common first electrode 5a is provided on one side of the integrated body 4, connecting one side of the P-type thermoelectric conversion material chips 2p and one side of the N-type thermoelectric conversion material chips 2n. A common second electrode 5b is provided on the other side of the integrated body 4, facing the first electrode 5a, connecting the other side of the N-type thermoelectric conversion material chips 2n and the other side of the P-type thermoelectric conversion material chips 2p. The P-type thermoelectric conversion material chips 2p and the N-type thermoelectric conversion material chips 2n are electrically connected in series by the first electrode 5a and the second electrode 5b. This embodiment does not include a supporting substrate or a solder material for joining the electrodes.

[0013] Fig. 2 is a cross-sectional view showing a second embodiment of a thermoelectric conversion module of the present invention, in which a thermoelectric conversion module 11 has a configuration in which a pressure-sensitive adhesive layer 6 is provided on both surfaces of the first electrode 5a and the second electrode 5b in the configuration of Fig. 1. This embodiment also does not have a supporting substrate or a solder material used to join the electrodes.

[0014] 3 is a cross-sectional view showing a third embodiment (basic configuration) of the thermoelectric conversion module of the present invention. The thermoelectric conversion module 21 includes an integrated body 24 including an insulator 23 configured to fill the gaps between the alternately spaced P-type thermoelectric conversion material chips 22p and the conductive chips 22d. A common first electrode 25a is provided on one side of the integrated body 24, connecting one side of the P-type thermoelectric conversion material chips 22p and one side of the conductive chips 22d. A common second electrode 25b is provided on the other side of the integrated body 24, facing the first electrode 25a, connecting the other side of the conductive chips 22d and the other side of the P-type thermoelectric conversion material chips 22p. The P-type thermoelectric conversion material chips 22p and the conductive chips 22d are electrically connected in series by the first electrode 25a and the second electrode 25b. This embodiment does not include a supporting substrate or a solder material for joining the electrodes.

[0015] Fig. 4 is a cross-sectional view showing a fourth embodiment of a thermoelectric conversion module of the present invention, in which a thermoelectric conversion module 31 has a configuration in which a pressure-sensitive adhesive layer 26 is provided on both surfaces of the first electrode 25a and the second electrode 25b in the configuration of Fig. 3. This embodiment also does not have a supporting substrate or a solder material used to join the electrodes.

[0016] Fig. 5 is a cross-sectional view showing a fifth embodiment of a thermoelectric conversion module of the present invention, in which a thermoelectric conversion module 41 has a configuration in which a hard member 7 is provided on the surface of the adhesive layer 6 on the surface of the second electrode 5b in the configuration of Fig. 2. This embodiment also does not have a supporting substrate or a solder material used to join the electrodes.

[0017] Fig. 6 is a cross-sectional view showing a sixth embodiment of a thermoelectric conversion module according to the present invention, in which a thermoelectric conversion module 51 has a configuration in which a hard member 7 is provided instead of the adhesive layer 6 on the surface of the second electrode 5b in the configuration shown in Fig. 2. This embodiment also does not have a supporting substrate or a solder material used to join the electrodes.

[0018] <Thermoelectric conversion material chip> The thermoelectric conversion material chip used in the present invention is not particularly limited, and may be made of a thermoelectric semiconductor material or a thin film made of a thermoelectric semiconductor composition. From the viewpoints of flexibility, thinness, and thermoelectric performance, it is preferable that the thin film be made of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material (hereinafter sometimes referred to as "thermoelectric semiconductor particles"), a resin, an ionic liquid, and / or an inorganic ionic compound. In this specification, the terms "thermoelectric conversion material" and "thermoelectric conversion material chip" are synonymous, and also "thermoelectric conversion material layer."

[0019] (Thermoelectric semiconductor materials) The thermoelectric semiconductor material used in the thermoelectric conversion material chips is preferably pulverized to a predetermined size using, for example, a fine grinding device and used as thermoelectric semiconductor particles (hereinafter, the thermoelectric semiconductor material may be referred to as "thermoelectric semiconductor particles"). The particle size of the thermoelectric semiconductor particles is preferably 10 nm to 100 μm, more preferably 20 nm to 50 μm, and even more preferably 30 nm to 30 μm. The average particle size of the thermoelectric semiconductor particles was obtained by measurement using a laser diffraction particle size analyzer (Malvern, Mastersizer 3000) and was taken as the median value of the particle size distribution.

[0020] In the chip of the thermoelectric conversion material used in the present invention, as the thermoelectric semiconductor materials constituting the chip of the P-type thermoelectric conversion material and the chip of the N-type conversion material, there is no particular limitation as long as it is a material capable of generating a thermoelectromotive force by applying a temperature difference. For example, bismuth-tellurium-based thermoelectric semiconductor materials such as P-type bismuth telluride and N-type bismuth telluride; telluride-based thermoelectric semiconductor materials such as GeTe and PbTe; antimony-tellurium-based thermoelectric semiconductor materials; zinc-antimony-based thermoelectric semiconductor materials such as ZnSb and Zn3Sb 2、 Zn4Sb3; silicon-germanium-based thermoelectric semiconductor materials such as SiGe; bismuth selenide-based thermoelectric semiconductor materials such as Bi2Se3; β-FeSi2, CrSi2, MnSi 1.73 , Mg2Si and other silicide-based thermoelectric semiconductor materials; oxide-based thermoelectric semiconductor materials; Heusler materials such as FeVAl, FeVAlSi, FeVTiAl, and sulfide-based thermoelectric semiconductor materials such as TiS2 are used.

[0021] Among these, the thermoelectric semiconductor material used in the present invention is preferably a bismuth-tellurium-based thermoelectric semiconductor material such as P-type bismuth telluride or N-type bismuth telluride. The P-type bismuth telluride has holes as carriers and a positive value for the Seebeck coefficient. For example, Bi X Te3Sb 2-X represented by is preferably used. In this case, X is preferably 0 < X ≦ 0.8, more preferably 0.4 ≦ X ≦ 0.6. When X is greater than 0 and less than or equal to 0.8, the Seebeck coefficient and electrical conductivity increase, and the characteristics as a P-type thermoelectric conversion material are maintained, which is preferable. Further, the N-type bismuth telluride has electrons as carriers and a negative value for the Seebeck coefficient. For example, Bi2Te 3-Y Se Y represented by is preferably used. In this case, Y is preferably 0 ≦ Y ≦ 3 (when Y = 0: Bi2Te3), more preferably 0.1 < Y ≦ 2.7. When Y is 0 or more and 3 or less, the Seebeck coefficient and electrical conductivity increase, and the characteristics as an N-type thermoelectric conversion material are maintained, which is preferable.

[0022] The content of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass, more preferably 50 to 96% by mass, and even more preferably 70 to 95% by mass. When the content of the thermoelectric semiconductor particles is within the above range, the Seebeck coefficient (absolute value of the Peltier coefficient) is large, and a decrease in electrical conductivity is suppressed, with only a decrease in thermal conductivity, so that a film exhibiting high thermoelectric performance and having sufficient film strength and flexibility is obtained, which is preferable.

[0023] Furthermore, the thermoelectric semiconductor particles are preferably subjected to an annealing treatment (hereinafter sometimes referred to as "annealing treatment A"). By performing annealing treatment A, the crystallinity of the thermoelectric semiconductor particles is improved, and furthermore, the surface oxide film of the thermoelectric semiconductor particles is removed, thereby increasing the Seebeck coefficient (absolute value of the Peltier coefficient) of the thermoelectric conversion material and further improving the thermoelectric figure of merit.

[0024] (resin) The resin used in the present invention has the effect of physically bonding the thermoelectric semiconductor material (thermoelectric semiconductor particles) together, which can increase the flexibility of the thermoelectric conversion module and also makes it easier to form a thin film by coating or the like. The resin is preferably a heat-resistant resin or a binder resin.

[0025] The heat-resistant resin maintains its various physical properties such as mechanical strength and thermal conductivity as a resin without being impaired when the thin film made of the thermoelectric semiconductor composition is annealed or otherwise treated to cause crystal growth of thermoelectric semiconductor particles. The heat-resistant resin is preferably a polyamide resin, a polyamide-imide resin, a polyimide resin, or an epoxy resin, because it has higher heat resistance and does not adversely affect the crystal growth of the thermoelectric semiconductor particles in the thin film, and more preferably a polyamide resin, a polyamide-imide resin, or a polyimide resin, because it has excellent flexibility.

[0026] The heat-resistant resin preferably has a decomposition temperature of 300° C. or higher. If the decomposition temperature is within the above range, the resin will not lose its function as a binder and will be able to maintain flexibility even when a thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.

[0027] Furthermore, the heat-resistant resin preferably has a mass loss rate of 10% or less, more preferably 5% or less, and even more preferably 1% or less at 300°C as measured by thermogravimetry (TG). If the mass loss rate is within the above range, as will be described later, even when a thin film made of the thermoelectric semiconductor composition is annealed, the resin does not lose its function as a binder and the flexibility of the thermoelectric conversion material chip can be maintained.

[0028] The content of the heat-resistant resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 15% by mass. When the content of the heat-resistant resin is within the above range, it functions as a binder for the thermoelectric semiconductor material, making it easier to form a thin film, and a film that achieves both high thermoelectric performance and film strength is obtained, and a resin portion is present on the outer surface of the chip of the thermoelectric conversion material.

[0029] The binder resin also facilitates the separation of the thermoelectric conversion material from the substrate, such as glass, alumina, or silicon, used in the production of chips after the firing (annealing) treatment (corresponding to "annealing treatment B" described below, and the same applies below).

[0030] The binder resin refers to a resin that decomposes at 90% by mass or more at a baking (annealing) temperature or higher, more preferably a resin that decomposes at 95% by mass or more, and particularly preferably a resin that decomposes at 99% by mass or more. Furthermore, a resin that maintains various physical properties such as mechanical strength and thermal conductivity without being impaired when a coating film (thin film) made of a thermoelectric semiconductor composition is subjected to a baking (annealing) treatment or the like to cause crystal growth of thermoelectric semiconductor particles is more preferred. When a resin that decomposes at 90% by mass or more at temperatures equal to or higher than the firing (annealing) temperature, i.e., a resin that decomposes at a temperature lower than the heat-resistant resin described above, is used as the binder resin, the binder resin is decomposed by firing, and therefore the content of the binder resin, which serves as an insulating component in the fired body, is reduced, and crystal growth of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is promoted, thereby reducing voids in the thermoelectric conversion material layer and improving the filling rate. Whether or not a resin decomposes to a predetermined extent (e.g., 90% by mass) at or above the baking (annealing) temperature is determined by measuring the mass loss rate (the value obtained by dividing the mass after decomposition by the mass before decomposition) at the baking (annealing) temperature using thermogravimetry (TG).

[0031] Thermoplastic resins and curable resins can be used as such binder resins. Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polymethylpentene; polycarbonate; thermoplastic polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyvinyl polymers such as polystyrene, acrylonitrile-styrene copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride, polyvinylpyridine, polyvinyl alcohol, and polyvinylpyrrolidone; polyurethane; and cellulose derivatives such as ethyl cellulose. Examples of curable resins include thermosetting resins and photocurable resins. Examples of thermosetting resins include epoxy resins and phenolic resins. Examples of photocurable resins include photocurable acrylic resins, photocurable urethane resins, and photocurable epoxy resins. These resins may be used alone or in combination. Among these, from the viewpoint of the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer, thermoplastic resins are preferred, polycarbonate and cellulose derivatives such as ethyl cellulose are more preferred, and polycarbonate is particularly preferred.

[0032] The binder resin is appropriately selected depending on the temperature of the annealing treatment of the thermoelectric semiconductor material in the annealing treatment step. From the viewpoint of the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer, it is preferable to perform the annealing treatment at a temperature equal to or higher than the final decomposition temperature of the binder resin. In this specification, the term "final decomposition temperature" refers to the temperature at which the mass reduction rate at the firing (annealing) temperature determined by thermogravimetry (TG) is 100% (the mass after decomposition is 0% of the mass before decomposition).

[0033] The final decomposition temperature of the binder resin is usually 150 to 600° C., preferably 200 to 560° C., more preferably 220 to 460° C., and particularly preferably 240 to 360° C. If a binder resin with a final decomposition temperature within this range is used, it functions as a binder for the thermoelectric semiconductor material, making it easier to form a thin film during printing.

[0034] The content of the binder resin in the thermoelectric semiconductor composition is 0.1 to 40 mass%, preferably 0.5 to 20 mass%, more preferably 0.5 to 10 mass%, and particularly preferably 0.5 to 5 mass%. When the content of the binder resin is within the above range, the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer can be reduced.

[0035] The content of the binder resin in the thermoelectric conversion material is preferably 0 to 10 mass %, more preferably 0 to 5 mass %, and particularly preferably 0 to 1 mass %. If the content of the binder resin in the thermoelectric conversion material is within the above range, the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer can be reduced.

[0036] (ionic liquid) The ionic liquid that can be contained in the thermoelectric semiconductor composition is a molten salt formed by combining a cation and an anion, and refers to a salt that can exist in liquid form at any temperature range from -50°C to less than 400°C. In other words, an ionic liquid is an ionic compound with a melting point in the range of -50°C to less than 400°C. The melting point of the ionic liquid is preferably -25°C to 200°C, more preferably 0°C to 150°C. Ionic liquids have characteristics such as extremely low vapor pressure and nonvolatility, excellent thermal and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, as a conductive additive, they can effectively suppress a decrease in electrical conductivity between thermoelectric semiconductor materials. Furthermore, ionic liquids exhibit high polarity due to their aprotic ionic structure and excellent compatibility with heat-resistant resins, thereby enabling the electrical conductivity of thermoelectric conversion materials to be uniform.

[0037] The ionic liquid may be a known or commercially available one. For example, a nitrogen-containing cyclic cationic compound such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, or imidazolium, or a derivative thereof; a tetraalkylammonium-based amine-based cation and a derivative thereof; a phosphine-based cation such as phosphonium, trialkylsulfonium, or tetraalkylphosphonium, or a derivative thereof; a lithium cation and a derivative thereof; or a mixture of a cation component and a Cl cation. - , Br - , I - , AlCl4 - , Al2Cl7 - , BF4 - , PF6 - , ClO4 - , NO3 - , CH3COO - , CF3COO - , CH3SO3 - , CF3SO3 - , (FSO2)2N - , (CF3SO2)2N - , (CF3SO2)3C - , AsF6 - , SbF6 - , NbF6 - , TaF6- , F(HF) n - , (CN)2N - , C4F9SO3 - , (C2F5SO2)2N - , C3F7COO - , (CF3SO2)(CF3CO)N - and an anion component such as the above.

[0038] Among the above-mentioned ionic liquids, from the viewpoints of high-temperature stability, compatibility with thermoelectric semiconductor materials and resins, and suppression of a decrease in the electrical conductivity of the gaps between thermoelectric semiconductor materials, it is preferred that the cationic component of the ionic liquid contains at least one selected from pyridinium cations and derivatives thereof, and imidazolium cations and derivatives thereof.

[0039] As the ionic liquid in which the cationic component contains a pyridinium cation or a derivative thereof, 1-butyl-4-methylpyridinium bromide, 1-butylpyridinium bromide, and 1-butyl-4-methylpyridinium hexafluorophosphate are preferred.

[0040] Furthermore, as the ionic liquid in which the cationic component contains an imidazolium cation and a derivative thereof, [1-butyl-3-(2-hydroxyethyl)imidazolium bromide] and [1-butyl-3-(2-hydroxyethyl)imidazolium tetrafluoroborate] are preferred.

[0041] The ionic liquid preferably has a decomposition temperature of 300° C. or higher. If the decomposition temperature is within the above range, the ionic liquid can maintain its effect as a conductive additive even when a thin film made of the thermoelectric semiconductor composition is annealed, as described below.

[0042] The content of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50 mass%, more preferably 0.5 to 30 mass%, and even more preferably 1.0 to 20 mass%. If the content of the ionic liquid is within the above range, a decrease in electrical conductivity is effectively suppressed, and a film with high thermoelectric performance is obtained.

[0043] (inorganic ionic compounds) The inorganic ionic compound that can be contained in the thermoelectric semiconductor composition is a compound composed of at least a cation and an anion. The inorganic ionic compound exists in a solid state over a wide temperature range from 400 to 900°C and has characteristics such as high ionic conductivity, so that it can act as a conductive additive to suppress a decrease in electrical conductivity between thermoelectric semiconductor materials.

[0044] The content of the inorganic ionic compound in the thermoelectric semiconductor composition is preferably 0.01 to 50 mass%, more preferably 0.5 to 30 mass%, and even more preferably 1.0 to 10 mass%. If the content of the inorganic ionic compound is within the above range, a decrease in electrical conductivity can be effectively suppressed, and as a result, a film with improved thermoelectric performance can be obtained. When an inorganic ionic compound and an ionic liquid are used in combination, the total content of the inorganic ionic compound and the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50 mass%, more preferably 0.5 to 30 mass%, and even more preferably 1.0 to 10 mass%.

[0045] (Method for preparing thermoelectric semiconductor composition) The method for preparing the thermoelectric semiconductor composition is not particularly limited, and the thermoelectric semiconductor composition may be prepared by, for example, mixing and dispersing the thermoelectric semiconductor particles, the ionic liquid, the inorganic ionic compound (when used in combination with the ionic liquid), the heat-resistant resin, and, if necessary, the other additives and a solvent, using a known method such as an ultrasonic homogenizer, a spiral mixer, a planetary mixer, a disperser, or a hybrid mixer. Examples of the solvent include toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, ethyl cellosolve, etc. These solvents may be used alone or in combination of two or more. The solids concentration of the thermoelectric semiconductor composition is not particularly limited as long as the composition has a viscosity suitable for coating.

[0046] The thermoelectric conversion material chip made of the thermoelectric semiconductor composition is not particularly limited, but can be formed, for example, by applying the thermoelectric semiconductor composition to a substrate such as glass, alumina, silicon, or a resin film, or to a substrate on which a sacrificial layer (described later) is formed, to obtain a coating film, drying the film, and then separating the substrate as appropriate to obtain a thermoelectric conversion material chip. By forming the thermoelectric conversion material in this manner, a large number of thermoelectric conversion material chips can be obtained easily and at low cost. The resin film should preferably be heat-resistant, and a film made of a polyamide resin, a polyamideimide resin, a polyimide resin, or the like is preferred. Methods for applying the thermoelectric semiconductor composition to obtain chips of thermoelectric conversion material include, but are not limited to, known methods such as screen printing, flexographic printing, gravure printing, spin coating, dip coating, die coating, spray coating, bar coating, doctor blade, etc. When forming a coating film in a pattern, screen printing, slot die coating, etc., which allow for easy pattern formation using a screen plate having a desired pattern, are preferably used. The resulting coating film is then dried to form chips of the thermoelectric conversion material, and any conventionally known drying method can be used as the drying method, such as hot air drying, hot roll drying, infrared irradiation, etc. The heating temperature is typically 80 to 150°C, and the heating time, which varies depending on the heating method, is typically several seconds to several tens of minutes. When a solvent is used in preparing the thermoelectric semiconductor composition, the heating temperature is not particularly limited as long as it is within a temperature range that allows the solvent used to be dried.

[0047] The thickness of the thin film made of the thermoelectric semiconductor composition is not particularly limited, but from the viewpoint of thermoelectric performance and film strength, it is preferably 100 nm to 1000 μm, more preferably 300 nm to 600 μm, and even more preferably 5 to 400 μm.

[0048] The thermoelectric conversion material chip in the form of a thin film made of the thermoelectric semiconductor composition is preferably further annealed (hereinafter, sometimes referred to as "annealing treatment B"). Annealing treatment B stabilizes the thermoelectric performance and allows the thermoelectric semiconductor particles in the thin film to undergo crystal growth, further improving the thermoelectric performance. Annealing treatment B is not particularly limited, but is typically performed in an inert gas atmosphere such as nitrogen or argon, a reducing gas atmosphere, or a vacuum condition with a controlled gas flow rate. It is performed at 100 to 500°C for several minutes to several tens of hours, depending on the heat resistance temperature of the resin and ionic compound used. Furthermore, in annealing treatment B, the thermoelectric semiconductor composition may be pressed to increase the density of the thermoelectric semiconductor composition.

[0049] The sacrificial layer can be made of a resin such as polymethyl methacrylate or polystyrene, or a release agent such as a fluorine-based release agent or a silicone-based release agent. By using the sacrificial layer, the chip of the thermoelectric conversion material formed on the substrate such as glass can be easily peeled off from the glass or the like after the annealing treatment B. The method for forming the sacrificial layer is not particularly limited, and can be performed by a known method such as flexographic printing or spin coating.

[0050] <Conductive tip> The conductive chip used in the present invention is used to electrically connect a chip of a P-type thermoelectric conversion material or a chip of an N-type thermoelectric conversion material via a first electrode and a second electrode. The conductive tip may be made of a conductive material as described below, or may be a thin film made of a composition containing such a material.

[0051] Examples of conductive materials constituting the conductive tip include metal materials such as copper, silver, gold, platinum, nickel, aluminum, constantan, chromium, indium, iron, or copper alloys, indium tin oxide (ITO), zinc oxide (ZnO), etc. Preferred are copper, gold, silver, platinum, nickel, copper alloys, aluminum, and constantan, and more preferred are copper, gold, silver, platinum, and nickel. Among these, from the viewpoint of thermoelectric performance, it is preferable to use a material that has a low electrical resistance of the conductive tip and a low contact electrical resistance between the conductive tips, and that is easy to increase thermal resistance. However, in actual use, these materials tend to have high electrical conductivity and low electrical resistance, but also low thermal resistance, which can lead to high heat leakage. For this reason, it is necessary to optimize the structure, including the shape of the conductive tip, and adjust the balance appropriately.

[0052] The thickness of the conductive tip is the same as the thickness of the thermoelectric conversion material tip, and is preferably 100 nm to 1000 μm, more preferably 300 nm to 600 μm, and even more preferably 5 to 400 μm.

[0053] <Insulator> The insulator used in the present invention is not particularly limited as long as it can provide insulation between chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material, between chips of P-type thermoelectric conversion material or between chips of N-type thermoelectric conversion material, and can maintain mechanical strength when they are integrated together, but examples of the insulator include insulating resins and ceramics.

[0054] Examples of insulating resins include polyimide resins, silicone resins, rubber resins, acrylic resins, olefin resins, maleimide resins, and epoxy resins. From the viewpoint of heat resistance and mechanical strength, the insulating resin is preferably selected from polyimide resins, silicone resins, acrylic resins, maleimide resins, and epoxy resins. The insulating resin is preferably a curable resin or a foamable resin. The insulating resin may further contain a filler. A hollow filler is preferred as the filler. The hollow filler is not particularly limited, and known hollow fillers can be used. Examples of hollow fillers include inorganic hollow fillers such as glass balloons, silica balloons, shirasu balloons, fly ash balloons, and metal silicates, as well as organic resin hollow fillers such as acrylonitrile, vinylidene chloride, phenolic resins, epoxy resins, and urea resins. The use of hollow fillers reduces the thermal conductivity of the insulating resin, further improving thermoelectric performance. Examples of ceramics include materials containing aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicon carbide, etc. as their main components (50% by mass or more of the ceramics). In addition to the main components, rare earth compounds, for example, can also be added.

[0055] The insulator filling method can be performed by a known method. For example, a liquid resin is used to spread and fill the surface of a support on which chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material are alternately arranged using a coating member such as a squeegee. Alternatively, the resin is dripped from approximately the center of the support to the outside and then filled by spin coating. Furthermore, the support is immersed in a liquid resin storage tank or the like and then lifted up to fill. Furthermore, a sheet-shaped insulating resin is used to attach the sheet-shaped insulating resin to the surface of a support on which chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material are alternately arranged, and the sheet-shaped insulating resin is melted and filled by heating and / or pressure. After filling, thermal curing or the like is performed.

[0056] The support is not particularly limited and may be glass, silicon, ceramics, metal, plastic, or the like. Preferably, it is selected from glass, plastic, and silicon. When annealing or the like is performed at high temperatures, glass, silicon, ceramics, or metal is preferred. From the viewpoints of process and dimensional stability, the thickness of the support is preferably from 100 to 1200 μm, more preferably from 200 to 800 μm, and even more preferably from 400 to 700 μm. The support is peeled off after the integrated product is obtained.

[0057] <Adhesive layer> It is preferable that a pressure-sensitive adhesive layer be provided on at least one surface of the thermoelectric conversion module. That is, by providing a pressure-sensitive adhesive layer on both or either of the first and second electrodes, including the gaps between adjacent first electrodes and the gaps between adjacent second electrodes, the thermoelectric conversion module can be easily installed, for example, by adhering it to an adherend such as a heat source or an object to be cooled. Furthermore, by including the gaps between the first electrodes and the gaps between the second electrodes, weather resistance can be improved.

[0058] The pressure-sensitive adhesive layer is not particularly limited as long as it can be easily adhered to an adherend such as a desired heat source or an object to be cooled, and may contain an adhesive resin, and may optionally contain additives for pressure-sensitive adhesives such as a crosslinking agent, a tackifier, a polymerizable compound, a polymerization initiator, a silane coupling agent, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a softener, a filler, a refractive index adjuster, a colorant, etc. In this specification, the term "tacky adhesive resin" is a concept that includes both a resin having tackiness and a resin having adhesive properties, and includes, for example, not only resins that themselves have tacky adhesive properties, but also resins that exhibit tackiness when used in combination with other components such as additives, and resins that exhibit adhesive properties in the presence of a trigger such as heat or water.

[0059] Examples of adhesive resins include rubber-based resins such as acrylic resins, urethane resins, and polyisobutylene resins, polyester resins, olefin resins, silicone resins, and polyvinyl ether resins. The thickness of the adhesive layer is not particularly limited, but is preferably 1 to 50 μm, and more preferably 2 to 30 μm.

[0060] The adhesive layer may be formed directly on the electrode on the integrated product from an adhesive composition containing an adhesive resin by a known method, such as spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, or gravure coating.

[0061] The pressure-sensitive adhesive layer may be covered with a release film. The release film is not particularly limited, but from the viewpoint of ease of handling, it is preferable that the release film comprises a release substrate and a release agent layer formed by applying a release agent to the release substrate. The release film may comprise a release agent layer on only one side of the release substrate, or on both sides of the release substrate. Examples of release substrates include paper substrates, laminated paper obtained by laminating a thermoplastic resin such as polyethylene to the paper substrate, and plastic films. Examples of paper substrates include glassine paper, coated paper, and cast-coated paper. Examples of plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, as well as polyolefin films such as polypropylene and polyethylene. Examples of release agents include olefin-based resins, rubber-based elastomers (e.g., butadiene-based resins, isoprene-based resins, etc.), long-chain alkyl resins, alkyd-based resins, fluorine-based resins, and silicone-based resins.

[0062] The thickness of the release film is not particularly limited, but is usually 20 to 200 μm, and preferably 25 to 150 μm. The thickness of the release agent layer is not particularly limited, but when the release agent layer is formed by applying a solution containing a release agent, the thickness of the release agent layer is preferably 0.01 to 2.0 μm, and more preferably 0.03 to 1.0 μm. When a plastic film is used as the release substrate, the thickness of the plastic film is preferably 3 to 50 μm, and more preferably 5 to 40 μm.

[0063] The adhesive layer having a release film is produced, for example, through the following steps. First, a pressure-sensitive adhesive composition is applied onto a release film to form a coating film. Next, the coating film is dried to form a pressure-sensitive adhesive layer. Next, the pressure-sensitive adhesive layer on the release film and the electrode on the integrated product are bonded together to produce the electrode.

[0064] <Hard materials> It is preferable that a hard member be further provided on the adhesive layer on at least one surface of the thermoelectric conversion module. It is also preferable that the adhesive layer is provided on one surface of the thermoelectric conversion module, and a hard member is provided on the other surface. The hard member is preferably a heat dissipation member. By using a heat dissipation member, for example, a temperature difference can be efficiently created in the thickness direction of the chip of P-type thermoelectric conversion material and the chip of N-type conversion material of the thermoelectric conversion module. When a heat dissipation member is used as the hard member, the electrodes and chips of thermoelectric conversion material can be stacked directly on the heat dissipation member, thereby making the support substrate unnecessary.

[0065] The heat dissipation member may be made of a metal material, a ceramic material, or a mixture of these materials with a resin, and is preferably made of at least one material selected from the group consisting of a metal material and a ceramic material. Examples of metal materials include single metals such as gold, silver, copper, nickel, tin, iron, chromium, platinum, palladium, rhodium, iridium, ruthenium, osmium, indium, zinc, molybdenum, manganese, titanium, and aluminum, and alloys containing two or more metals such as stainless steel and brass. Examples of ceramic materials include barium titanate, aluminum nitride, boron nitride, aluminum oxide, silicon carbide, and silicon nitride. Among these, metal materials are preferred from the viewpoints of high thermal conductivity, workability, and flexibility. Among metal materials, copper (including oxygen-free copper) and stainless steel are preferred, and copper is more preferred because of its high thermal conductivity and easier workability. The resin to be used as a mixture with a metal material or a ceramic material is not particularly limited, but examples thereof include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, nylon, acrylic resin, cycloolefin polymer, and aromatic polymer.

[0066] Representative metal materials having high thermal conductivity that can be used in the present invention are listed below. <Oxygen-free copper> Oxygen-free copper (OFC) generally refers to high-purity copper with a purity of 99.95% (3N) or higher, which is free of oxides. The Japanese Industrial Standards specify oxygen-free copper (JIS H 3100, C1020) and oxygen-free copper for electronic devices (JIS H 3510, C1011). Stainless steel (JIS) SUS304: 18Cr-8Ni (containing 18% Cr and 8% Ni) SUS316: 18Cr-12Ni (stainless steel containing 18% Cr, 12% Ni, and molybdenum (Mo))

[0067] The method for forming the hard member used in the present invention is not particularly limited, but examples include a method of processing a sheet-like hard member to a predetermined size, or a method of processing the sheet-like hard member into a predetermined pattern shape by previously performing a known physical or chemical treatment mainly based on photolithography, or a combination of these.

[0068] The thermal conductivity of the heat dissipation member is preferably 15 to 500 W / (m·K), more preferably 100 to 450 W / (m·K), and even more preferably 250 to 420 W / (m·K). When the thermal conductivity of the heat dissipation member is within the above range, a temperature difference can be created efficiently.

[0069] The thickness of the heat dissipation member is preferably 15 to 550 μm, more preferably 30 to 530 μm, and even more preferably 70 to 510 μm. If the thickness of the heat dissipation member is within this range, a temperature difference can be efficiently created in the thickness direction between the chip of P-type thermoelectric conversion material and the chip of N-type conversion material.

[0070] <First electrode and second electrode> The first electrode and second electrode (hereinafter sometimes simply referred to as "electrodes") used in the present invention are preferably formed of at least one film selected from the group consisting of a vapor-deposited film, a plated film, a conductive composition, and a metal foil. The metal material used for the electrodes is not particularly limited, but examples thereof include copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, solder, and alloys containing any of these metals.

[0071] Examples of methods for forming an electrode include a method in which an electrode without a pattern is provided on the above-mentioned integrated product, and then processed into a predetermined pattern shape by known physical or chemical treatments, mainly photolithography, or a combination of these, or a method in which an electrode pattern is directly formed by screen printing, inkjet printing, or the like using a conductive paste made of a conductive composition containing the above-mentioned metal material, etc. Examples of methods for forming electrodes without patterns include dry processes such as PVD (physical vapor deposition) methods such as vacuum deposition, sputtering, and ion plating, or CVD (chemical vapor deposition) methods such as thermal CVD and atomic layer deposition (ALD), or wet processes such as various coating methods and electrodeposition methods such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade methods, silver halide plating, electroplating, electroless plating, and metal foil lamination, which are appropriately selected depending on the electrode material. The metal foil lamination may be joined to a thermoelectric material or the like using solder. The electrodes used in the present invention are required to have high electrical conductivity and high thermal conductivity in order to maintain thermoelectric performance, so it is more preferable to use electrodes formed by plating or vacuum film formation. Vacuum film formation methods such as vacuum deposition and sputtering, as well as electroplating and electroless plating, are preferred because they can easily achieve high electrical conductivity and high thermal conductivity. Depending on the dimensions and dimensional accuracy required for the formed pattern, a hard mask such as a metal mask can also be used to easily form a pattern.

[0072] The thickness of the electrode layer is preferably 10 nm to 200 μm, more preferably 30 nm to 150 μm, and even more preferably 50 nm to 120 μm. When the thickness of the electrode layer is within the above range, the electrical conductivity is high and the resistance is low, and sufficient strength as an electrode can be obtained.

[0073] The thermoelectric conversion module of the present invention does not require a substrate as a support, which has been used conventionally, and the thermoelectric conversion module can be made thin. [Industrial Applicability]

[0074] The thermoelectric conversion module of the present invention is expected to enable a thinner, lighter, and more highly integrated thermoelectric conversion module than conventional thermoelectric conversion modules. [Explanation of symbols]

[0075] 1, 11, 21, 31, 41, 51: Thermoelectric conversion module 2p, 22p: P-type thermoelectric conversion material chip 2n, 22n:N-type thermoelectric conversion material chips 2d: Conductive tip 3,23: Insulator 4,24:Integrated 5a, 25a: 1st electrode 5b, 25b: 2nd electrode 6,26:Adhesive layer 7: Hard material

Claims

1. an integrated body including an insulator configured to fill a gap between the alternating spaced apart chips of P-type thermoelectric material and chips of N-type thermoelectric material; a common first electrode on one surface of the integrated body, which joins one surface of the chip of the P-type thermoelectric conversion material and one surface of the chip of the N-type thermoelectric conversion material; a common second electrode, which is provided on the other surface of the integrated body and faces the first electrode and joins the other surface of the chip of the N-type thermoelectric conversion material and the other surface of the chip of the P-type thermoelectric conversion material, the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material are electrically connected in series by the first electrode and the second electrode; A π-type thermoelectric conversion module, The π-type thermoelectric conversion module has no supporting substrate on either side thereof, a pressure-sensitive adhesive layer configured to fill all of the voids between the first electrodes or the second electrodes and the insulator is provided on at least one surface of the π-type thermoelectric conversion module, a release sheet is laminated on the pressure-sensitive adhesive layer, and the thickness of the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material is 100 nm to 400 μm.

2. 2. The π-type thermoelectric conversion module according to claim 1, wherein the first electrode and the second electrode are each independently formed of at least one film selected from the group consisting of a vapor-deposited film, a plated film, a conductive composition, and a metal foil.

3. 3. The π-type thermoelectric conversion module according to claim 1, wherein the insulator is selected from the group consisting of insulating resins and ceramics.

4. 4. The π-type thermoelectric conversion module according to claim 3, wherein the insulating resin is selected from the group consisting of polyimide resins, silicone resins, rubber resins, acrylic resins, olefin resins, maleimide resins, and epoxy resins.

5. The π-type thermoelectric conversion module according to any one of claims 1 to 4, wherein the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material are made of a thermoelectric semiconductor composition.

6. 6. The π-type thermoelectric conversion module according to claim 5, wherein the thermoelectric semiconductor composition comprises a thermoelectric semiconductor material, a resin, and one or both of an ionic liquid and an inorganic ionic compound.

7. 7. The π-type thermoelectric conversion module according to claim 1, wherein a surface of the insulator on one side of the integrated body, which is located between adjacent first electrodes, is flush with a surface of the first electrode that is joined to the one side of the integrated body, and a surface of the insulator on the other side of the integrated body, which is located between adjacent second electrodes, is flush with a surface of the second electrode that is joined to the other side of the integrated body.

8. an integrated body including an insulator configured to fill a gap between the alternating spaced apart tips of thermoelectric material and conductive tips; a common first electrode on one surface of the integrated body, where one surface of the thermoelectric conversion material chip and one surface of the conductive chip are joined; a common second electrode, which is provided on the other surface of the integrated body and faces the first electrode and joins the other surface of the thermoelectric conversion material chip and the other surface of the conductive chip; the first electrode and the second electrode electrically connect the thermoelectric conversion material chip and the conductive chip in series; A uni-leg thermoelectric conversion module, wherein the chips of thermoelectric conversion material are selected from chips of P-type thermoelectric conversion material or chips of N-type thermoelectric conversion material, The uni-leg thermoelectric conversion module has no supporting substrate on either side thereof, a pressure-sensitive adhesive layer configured to fill all of the voids between the first electrodes or the second electrodes and the insulator is provided on at least one surface of the unileg thermoelectric conversion module, a release sheet is laminated on the pressure-sensitive adhesive layer, and a thickness of the P-type thermoelectric conversion material chip or the N-type thermoelectric conversion material chip is 100 nm to 400 μm.

9. A uni-leg thermoelectric conversion module as described in Claim 8, wherein the first electrode and the second electrode are each independently formed of at least one type of film selected from the group consisting of a vapor deposition film, a plated film, a conductive composition, and a metal foil.

10. A uni-leg thermoelectric conversion module as described in claim 8 or 9, wherein the insulator is selected from insulating resins and ceramics.

11. A uni-leg thermoelectric conversion module as described in Claim 10, wherein the insulating resin is selected from polyimide-based resins, silicone-based resins, rubber-based resins, acrylic-based resins, olefin-based resins, maleimide-based resins and epoxy-based resins.

12. A uni-leg thermoelectric conversion module described in any one of claims 8 to 11, wherein the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material are made of a thermoelectric semiconductor composition.

13. A uni-leg thermoelectric conversion module as described in Claim 12, wherein the thermoelectric semiconductor composition comprises a thermoelectric semiconductor material, a resin, and one or both of an ionic liquid and an inorganic ionic compound.

14. A uni-leg thermoelectric conversion module as described in Claim 8, wherein the material of the conductive chip is selected from copper, gold, silver, platinum, nickel, copper alloy, aluminum, and constantan.

15. A unileg thermoelectric conversion module described in any one of claims 8 to 14, wherein the surface of the insulator on one side of the integrated body located between adjacent first electrodes is flush with the surface of the first electrode that is joined to the one side of the integrated body, and the surface of the insulator on the other side of the integrated body located between adjacent second electrodes is flush with the surface of the second electrode that is joined to the other side of the integrated body.

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