Method for manufacturing thermoelectric conversion modules

Abstract

Provided is a method for manufacturing a thermoelectric conversion module that does not require a support or a solder material and makes it possible to efficiently manufacture a plurality of thin thermoelectric conversion modules at once, the method including the following steps (A) to (D). (A) A step for arranging P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips separately on a support; (B) a step for filling an insulator between the P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips to obtain an integrated product composed of the P-type thermoelectric conversion material chips, N-type thermoelectric conversion material chips, and insulator; (C) a step for peeling the integrated product obtained in the step (B) from the support; and (D) a step for connecting the P-type thermoelectric conversion material chips and the N-type thermoelectric conversion material chips by electrodes in the integrated product after the step (C).

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing 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] Known examples of such thermoelectric conversion modules include so-called π-type thermoelectric conversion elements. A π-type thermoelectric conversion element has a pair of electrodes spaced apart on a substrate, with the bottom surface of a P-type thermoelectric element on one electrode and the bottom surface of an N-type thermoelectric element on the other electrode, also spaced apart, and the top surfaces of both thermoelectric elements connected to electrodes on the opposing substrates. Typically, multiple such basic units are connected electrically in series and thermally in parallel within each substrate. 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 Document 1 discloses a thermoelectric conversion module using the above-mentioned π-type thermoelectric conversion element. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-59823 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although the thermoelectric conversion module of Patent Document 1 discloses improvements in the reliability of the thermoelectric conversion module, such as by firmly joining the thermoelectric conversion element and the electrodes and preventing diffusion and thermal stress, it does not disclose any reduction in the thickness of the thermoelectric conversion module, reduction in material, improvement in productivity, etc.

[0006] The present invention has been made in consideration of the above-described circumstances, and an object of the present invention is to provide a method for manufacturing a thermoelectric conversion module that does not require a support or solder material and that can efficiently produce multiple thin thermoelectric conversion modules in a batch. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the inventors discovered a manufacturing method that allows multiple thin thermoelectric conversion modules to be obtained efficiently in one go, without using the conventional manufacturing method of mounting thermoelectric conversion material chips one by one on an electrode substrate using a solder material, by filling an insulator between chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material that are spaced apart on a support to form a self-supporting integrated body, and then providing electrodes directly on the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material on the top and bottom surfaces of the integrated body that has been peeled off from the support so that the π-type thermoelectric conversion elements operate, thereby completing the present invention. That is, the present invention provides the following [1] to

[11] . [1] A method for producing a thermoelectric conversion module, comprising the following steps (A) to (D): (A) A step of arranging a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material on a support at a distance from each other. (B) A step of filling an insulator between the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material to obtain an integrated product consisting of the chip of P-type thermoelectric conversion material, the chip of N-type thermoelectric conversion material, and the insulator. (C) A step of peeling off the integrated product obtained in the step (B) from the support. (D) a step of connecting the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material via electrodes in the integrated product after the step (C). [2] The method for producing a thermoelectric conversion module according to [1] above, further comprising the following step (B') after the step (B) and before the step (C): (B') a step of removing excess portions of the insulator that are in direct contact with at least the upper surface regions of the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material in the integrated product obtained in the step (B). [3] A method for producing a thermoelectric conversion module according to the above [1] or [2], comprising the following step (E) after the step (D): (E) A step of laminating an insulating layer on the electrode. [4] The method for producing a thermoelectric conversion module according to [3] above, further comprising the following step (F) after step (E): (F) a step of laminating a thermal diffusion layer on the insulating layer. [5] The method for producing a thermoelectric conversion module according to any one of the above [1] to [4], wherein the insulator is selected from insulating resins and ceramics. [6] The method for producing a thermoelectric conversion module according to [5] 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. [7] The method for manufacturing a thermoelectric conversion module according to any one of [1] to [6] above, further comprising a fixing layer between the support and the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material. [8] The method for producing a thermoelectric conversion module according to [7] above, wherein the fixing layer is an adhesive layer. [9] The method for producing a thermoelectric conversion module according to any one of the above [1] to [8], wherein the support is selected from glass, plastic, and silicon.

[10] The method for producing a thermoelectric conversion module according to any one of the above [1] to [9], wherein the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material are made of a thermoelectric semiconductor composition.

[11] The method for producing a thermoelectric conversion module according to

[10] above, wherein the thermoelectric semiconductor composition contains a thermoelectric semiconductor material, a heat-resistant resin, and one or both of an ionic liquid and an inorganic ionic compound. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a method for manufacturing a thermoelectric conversion module that does not require a support or a solder material and that can efficiently manufacture a plurality of thin thermoelectric conversion modules in a batch. [Brief explanation of the drawings]

[0009] [Figure 1] 1A to 1C are explanatory views showing an example of steps according to a method for manufacturing a thermoelectric conversion module of the present invention in the order of steps. [Figure 2] 1 is a cross-sectional view showing an embodiment of a thermoelectric conversion module of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Method of manufacturing thermoelectric conversion modules] The method for producing a thermoelectric conversion module of the present invention is characterized by including the following steps (A) to (D). (A) A step of arranging a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material on a support at a distance from each other. (B) A step of filling an insulator between the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material to obtain an integrated product consisting of the chip of P-type thermoelectric conversion material, the chip of N-type thermoelectric conversion material, and the insulator. (C) A step of peeling off the integrated product obtained in the step (B) from the support. (D) a step of connecting the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material via electrodes in the integrated product after the step (C). In the method for producing a thermoelectric conversion module of the present invention, for example, chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material are arranged alternately and spaced apart on a support, and an insulator is filled between the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material to form a self-standing integrated body consisting of chips of P-type thermoelectric conversion material, chips of N-type thermoelectric conversion material, and the insulator. After the support is peeled off, electrodes are formed directly on the integrated body, making it possible to efficiently produce multiple thin thermoelectric conversion modules in a single batch, eliminating the need for the solder material and support that were previously used.

[0011] In the following explanation, the steps (A), (B), (C), and (D) may be referred to, in this order, as "(A) a step of arranging chips of thermoelectric conversion material, or step (A)," "(B) a step of filling insulator, or step (B)," "(C) a step of peeling off the support, or step (C)," and "(D) a step of forming an electrode, or step (D)." The steps (B'), (E), and (F) may be referred to, in this order, as "(B') a step of removing excess insulator, or step (B')," "(E) a step of forming an insulating layer, or step (E)," and "(F) a step of forming a thermal diffusion layer." Furthermore, "chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material" may be simply referred to as "chips of thermoelectric conversion material." In addition, in this specification, "excess insulator" or "excess insulator" refers to a layer of insulator that extends to the region of the top surface of the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material when an insulator is filled between the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material in step (B).

[0012] FIG. 1 is an explanatory diagram showing an example of steps according to the method for manufacturing a thermoelectric conversion module of the present invention in the order of steps, in which (a) is a cross-sectional view showing the state after chips 2p of P-type thermoelectric conversion material and chips 2n of N-type thermoelectric conversion material have been arranged at a distance from each other on a support 1, (b) is a cross-sectional view showing the state after insulator 3 has been filled between the chips 2p of P-type thermoelectric conversion material and the chips 2n of N-type thermoelectric conversion material to form an integrated product 4a consisting of the chips 2p of P-type thermoelectric conversion material, the chips 2n of N-type thermoelectric conversion material, and the insulator 3, (c) is a cross-sectional view showing the state after excess insulator portions 3′ overcoated on and between the chips 2p of P-type thermoelectric conversion material and the chips 2n of N-type thermoelectric conversion material in (b) have been removed to form an integrated product 4b, and (d) is a cross-sectional view showing the state after the obtained integrated product 4b has been peeled off from the support 1. Also, (e) is a cross-sectional view showing the state after electrodes 5 have been formed on the upper and lower surfaces of chip 2p of P-type thermoelectric conversion material and chip 2n of N-type thermoelectric conversion material in the integrated body 4b so as to form a π-type thermoelectric conversion element, and this configuration is the basic configuration (first embodiment) of the thermoelectric conversion module of the present invention.

[0013] 2A and 2B are cross-sectional structural diagrams showing an embodiment of the thermoelectric conversion module of the present invention, in which (a) is a cross-sectional diagram showing the state after forming insulating layers 6 on the upper and lower surfaces of the electrode 5 in the basic structure obtained in (e) of FIG. 1 (second embodiment), and (b) is a cross-sectional diagram showing the state after further forming thermal diffusion layers 7 on the upper and lower surfaces of the insulating layer 6 in the structure obtained in (a) (third embodiment).

[0014] (A) Thermoelectric conversion material chip placement process The method for manufacturing a thermoelectric conversion module of the present invention includes a step of arranging chips of thermoelectric conversion material. The thermoelectric conversion material chip arrangement process is a process of arranging chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material on a support at a distance from each other. For example, in the above-mentioned Figure 1(a), this is a process of arranging chips 2p of P-type thermoelectric conversion material and chips 2n of N-type thermoelectric conversion material alternately at a distance from each other on the support 1. The method for arranging the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material at a distance is not particularly limited, and for example, chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material that have been prepared in advance may be individually arranged at a distance on a fixing layer described below, or chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material that have been prepared in an alternating arrangement may be arranged by, for example, adhering them to a support via an adhesive layer that serves as a fixing layer described below, or further, chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material may be formed directly on a support so that they are arranged at a distance alternately. The chips of P-type thermoelectric conversion material and N-type thermoelectric conversion material can be directly formed by screen printing, coating with a dispenser, or the like.

[0015] 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 thermoelectric element be made of a thin film 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 "chip of thermoelectric conversion material" are synonymous, and also "thermoelectric conversion material layer (including those having voids)".

[0016] (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 measuring with a laser diffraction particle size analyzer (Master Sizer 3000, manufactured by Malvern), and the median value of the particle size distribution was used.

[0017] In the chip of the thermoelectric conversion material used in the present invention, as the thermoelectric semiconductor material 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 that can generate 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; silicide-based thermoelectric semiconductor materials such as β-FeSi2, CrSi2, and MnSi 1.73 Mg2Si; oxide-based thermoelectric semiconductor materials; Heusler materials such as FeVAl, FeVAlSi, and FeVTiAl, and sulfide-based thermoelectric semiconductor materials such as TiS2 are used.

[0018] 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 of 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. It is preferable that when X is greater than 0 and less than or equal to 0.8, the Seebeck coefficient and the electrical conductivity increase, and the characteristics as a P-type thermoelectric conversion material are maintained. Also, the N-type bismuth telluride has electrons as carriers and a negative value of the Seebeck coefficient. For example, Bi2Te 3-Y Se YThose represented by are 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 the electrical conductivity increase, and the characteristics as an N-type thermoelectric conversion material are maintained, which is preferable.

[0019] The content of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. More preferably, it is 50 to 96% by mass, and still more preferably, it is 70 to 95% by mass. If the content of the thermoelectric semiconductor particles is within the above range, the Seebeck coefficient (absolute value of the Peltier coefficient) is large, the decrease in electrical conductivity is suppressed, and only the thermal conductivity decreases, so that high thermoelectric performance is exhibited, and a film having sufficient film strength and flexibility can be obtained, which is preferable.

[0020] Further, the thermoelectric semiconductor particles are preferably those subjected to 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 further, the surface oxide film of the thermoelectric semiconductor particles is removed, so that the Seebeck coefficient (absolute value of the Peltier coefficient) of the thermoelectric conversion material increases, and the thermoelectric performance index can be further improved.

[0021] (Resin) The resin used in the present invention has an action of physically bonding between thermoelectric semiconductor materials (thermoelectric semiconductor particles), can enhance the flexibility of the thermoelectric conversion module, and facilitates the formation of a thin film by coating or the like. As the resin, a heat-resistant resin or a binder resin is preferable.

[0022] When the thin film composed of the thermoelectric semiconductor composition is annealed or the like to cause crystal growth of the thermoelectric semiconductor particles, the mechanical strength and various physical properties such as thermal conductivity of the resin are not impaired and maintained. 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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).

[0027] 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).

[0028] 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.

[0029] 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).

[0030] 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.

[0031] 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.

[0032] 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.

[0033] (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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] (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.

[0041] 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%.

[0042] Methods for applying the P-type and N-type thermoelectric semiconductor compositions onto a support 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, stencil 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 a thin film, and the drying method can be a conventionally known drying method such as hot air drying, hot roll drying, infrared irradiation, etc. The heating temperature is usually 80 to 150°C, and the heating time, which varies depending on the heating method, is usually 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.

[0043] The thickness of the thermoelectric conversion material chip is not particularly limited, but is preferably 100 nm to 1000 μm, more preferably 300 nm to 600 μm, and even more preferably 5 to 400 μm, from the viewpoint of thermoelectric performance and film strength.

[0044] The chips of P-type thermoelectric conversion material and N-type thermoelectric conversion material made of the thermoelectric semiconductor composition are preferably further subjected to an annealing treatment (hereinafter, sometimes referred to as "annealing treatment B"). By performing annealing treatment B, the thermoelectric performance can be stabilized and the thermoelectric semiconductor particles in the thermoelectric conversion material chips can undergo crystal growth, thereby further improving the thermoelectric performance. Annealing treatment B is not particularly limited, but is usually performed in an inert gas atmosphere such as nitrogen or argon, in a reducing gas atmosphere, or under vacuum conditions with a controlled gas flow rate. The annealing treatment is performed at 100 to 500°C for several minutes to several tens of hours, depending on the heat resistance temperature of the thermoelectric semiconductor composition, support, etc. used.

[0045] (Support) The support used in the present invention is not particularly limited, and examples thereof include glass, silicon, ceramics, metals, and plastics. Preferably, the support is selected from glass, plastics, and silicon. When annealing or the like is performed at high temperatures, glass, silicon, ceramics, and metals are 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.

[0046] (fixed layer) It is preferable to include an anchoring layer between the support and the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material. The anchoring layer is used to anchor the support and the chips of thermoelectric conversion material when the chips of thermoelectric conversion material are spaced apart in step (A). The anchoring layer is not particularly limited as long as it can bond the support and the chips of thermoelectric conversion material, but in one embodiment, it is preferable to use an adhesive layer. From the viewpoints of adhesiveness and curing with energy rays such as ultraviolet rays to reduce adhesive strength, it is more preferable to use an adhesive layer containing an energy ray-curable adhesive resin having a polymerizable functional group introduced into its side chain.

[0047] The adhesive layer may contain any adhesive resin, and may contain adhesive additives such as a crosslinking agent, a tackifier, a polymerizable compound, and a polymerization initiator, as needed. The pressure-sensitive adhesive layer can be formed from a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive resin by a known method, for example, by a coating method.

[0048] 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 pressure-sensitive adhesive layer is not particularly limited, but is preferably about 1 to 50 μm, and more preferably 2 to 30 μm.

[0049] (B) Insulator filling process The method for manufacturing a thermoelectric conversion module of the present invention includes a step of filling with an insulator. The insulator filling step is a step of filling an insulator between a chip of P-type thermoelectric conversion material and a chip of N-type thermoelectric conversion material to obtain an integrated product consisting of a chip of P-type thermoelectric conversion material, a chip of N-type thermoelectric conversion material, and an insulator. For example, in Figure 1(b), this is a step of filling an insulator 3 between a chip 2p of P-type thermoelectric conversion material and a chip 2n of N-type thermoelectric conversion material to obtain a self-standing integrated product 4a consisting of a chip 2p of P-type thermoelectric conversion material, a chip 2n of N-type thermoelectric conversion material, and an insulator 3.

[0050] (insulator) The insulator used in the present invention is not particularly limited as long as it can maintain the insulation between the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material and the mechanical strength when integrated, and examples of the insulator include insulating resins and ceramics.

[0051] 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.

[0052] 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.

[0053] (B') Excess insulation removal process The method for manufacturing a thermoelectric conversion module of the present invention preferably includes a step of removing excess insulator. The step of removing excess insulator is a step performed after step (B) and before step (C) to remove excess insulator in the integrated product obtained in step (B), which is in direct contact with at least the upper surface regions of the P-type thermoelectric conversion material chip and the N-type thermoelectric conversion material chip. In this step, excess insulator extending in the thickness direction in the remaining insulator present in the region between the P-type thermoelectric conversion material chip and the N-type thermoelectric conversion material chip may also be removed. For example, in the integrated product 4a shown in FIG. 1(b), excess insulator 3' located on the upper surface of the P-type thermoelectric conversion material chip 2p, the upper surface of the N-type thermoelectric conversion material chip 2n, and the region between the P-type thermoelectric conversion material chip 2p and the N-type thermoelectric conversion material chip 2n is removed to obtain the integrated product 4b shown in FIG. 1(c).

[0054] The excess insulator portion can be removed by a known method. For example, the excess insulator portion 3' located on the P-type thermoelectric conversion material chip 2p, the N-type thermoelectric conversion material chip 2n, and the insulator excess portion 3' located on the insulator 3 in the region between the P-type thermoelectric conversion material chip 2p and the N-type thermoelectric conversion material chip 2n can be removed by irradiating plasma or the like or mechanical polishing or the like to expose the top surfaces of the P-type thermoelectric conversion material chip 2p and the N-type thermoelectric conversion material chip 2n. By performing such a process, the electrical connection between the electrode obtained in step (D) described below and the thermoelectric conversion material chip can be improved.

[0055] (C) Support peeling process The method for producing a thermoelectric conversion module of the present invention includes a support peeling step. The support peeling step is a step of peeling the integrated product obtained in the step (B) (or step (B')) from the support, for example, in Figure 1(d), it is a step of peeling the integrated product 4b from the support 1.

[0056] The peeling can be performed by a known method. For example, when the support and the thermoelectric conversion material chips constituting the integrated product are fixed to each other via an adhesive layer, the adhesive layer is deactivated to peel the integrated product from the support, and then residues of the adhesive layer are removed by acid washing or the like. Alternatively, the support itself can be directly polished until the underside of the thermoelectric conversion material chips is exposed, thereby obtaining the integrated product as a single molded product.

[0057] (D) Electrode formation process The method for manufacturing a thermoelectric conversion module of the present invention includes an electrode formation step. The electrode formation process is a process in which electrodes are provided (formed) directly on the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material on the upper and lower surfaces of the integrated product after the process (C), and the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material are connected via the electrodes. For example, in Figure 1(e), this is a process in which electrodes are formed directly on the chips of P-type thermoelectric conversion material 2p and the chips of N-type thermoelectric conversion material 2n on the upper and lower surfaces of the integrated product 4b, and arranged so that the π-type thermoelectric conversion elements operate.

[0058] (electrode) Examples of metal materials for the electrodes of the thermoelectric conversion module used in the present invention include copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, solder, and alloys containing any of these metals. 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.

[0059] The electrodes are formed using the above-mentioned metal materials. Examples of methods for forming an electrode include a method in which an electrode without a pattern is provided on a support, 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. 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, electrolytic plating, electroless plating, and metal foil lamination, and the like, and these methods are selected appropriately depending on the material of the electrode. 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 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.

[0060] The thickness of the metal material layer is preferably 10 nm to 200 μm, more preferably 30 nm to 150 μm, and even more preferably 50 nm to 120 μm. If the thickness of the metal material 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.

[0061] (E) Insulation layer formation process The method for producing a thermoelectric conversion module of the present invention preferably includes an insulating layer forming step, which is a step of laminating insulating layers on the upper and lower surfaces of the electrode obtained in step (D), for example, a step of forming insulating layer 6 on the upper and lower surfaces of electrode 5 in the above-mentioned FIG. The insulating layer is not particularly limited, but for example, it can be provided on an electrode to prevent short circuits between the chip of thermoelectric conversion material and the conductive portion of the thermal diffusion layer described below and / or the conductive portion on the surface on which the thermoelectric conversion module is placed.

[0062] The insulating layer is not particularly limited as long as it has insulating properties, but is preferably made of a resin for forming an insulating layer or an inorganic material, and from the viewpoint of flexibility, a resin for forming an insulating layer is more preferred.

[0063] Examples of resins for forming the insulating layer include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, nylon, acrylic resins, cycloolefin polymers, and aromatic polymers. Among these, polyesters include polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polyarylate, etc. Cycloolefin polymers include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated versions of these. Among the resins for forming the insulating layer, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and nylon are preferred from the viewpoints of cost and heat resistance. The resin for forming the insulating layer may contain a filler from the viewpoint of controlling the elastic modulus and the thermal conductivity. Examples of fillers to be added to the resin film include magnesium oxide, anhydrous magnesium carbonate, magnesium hydroxide, aluminum oxide, boron nitride, aluminum nitride, silicon oxide, etc. Among these, aluminum oxide, boron nitride, aluminum nitride, and silicon oxide are preferred from the viewpoints of elastic modulus control, thermal conductivity, etc. The insulating layer-forming resin used for the insulating layer is preferably in a sheet form, which allows the insulating layer to be easily formed.

[0064] The inorganic material is not particularly limited, and examples thereof include silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, boron nitride, aluminum nitride, silicon carbide, etc. Among these, silicon oxide and aluminum oxide are preferred from the viewpoints of cost, stability, and ease of availability.

[0065] The thickness of the insulating layer is preferably 1 to 150 μm, more preferably 2 to 140 μm, even more preferably 3 to 120 μm, and particularly preferably 5 to 100 μm. When the thickness of the insulating layer is within this range, the conductive portion of the thermal diffusion layer is less likely to penetrate the insulating layer, which prevents short circuits with the thermoelectric conversion material chip and maintains thermoelectric performance. The same applies when the mounting surface of the thermoelectric conversion module has a conductive portion.

[0066] In order to ensure insulation, the insulating layer preferably has a volume resistivity of 1.0×10 8 Ω·cm or more, preferably 1.0×10 9 Ω·cm or more, more preferably 1.0×10 10 Ω·cm or more. The volume resistivity is a value measured using a resistivity meter (MCP-HT450, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) after leaving the insulating layer in an environment of 23° C. and 50% RH for one day.

[0067] The insulating layer can be formed by a known method, for example, it may be formed directly on the surface of the electrode, or it may be formed by attaching an insulating layer previously formed on a release sheet to the electrode and transferring it to the electrode by lamination. In addition, two or more types of insulating layers may be laminated.

[0068] (F) Thermal diffusion layer formation process The method for manufacturing a thermoelectric conversion module of the present invention preferably includes a thermal diffusion layer forming step, which is a step of laminating thermal diffusion layers on the upper and lower surfaces of the insulating layer obtained in step (E), for example, a step of forming thermal diffusion layers 7 on the upper and lower surfaces of insulating layer 6 in the above-mentioned FIG. The thermal diffusion layer is provided on one or both sides of the thermoelectric conversion module and functions as a heat dissipation layer. From the viewpoint of thermoelectric performance, it is preferable to provide the thermal diffusion layer on both sides. In the present invention, for example, by using the thermal diffusion layer, it is possible to efficiently apply a sufficient temperature difference in the thickness direction to the chip of thermoelectric conversion material inside the thermoelectric conversion module.

[0069] (thermal diffusion layer) The thermal diffusion layer is made of a highly thermally conductive material. Examples of highly thermally conductive materials used for the thermal diffusion layer include simple metals such as copper, silver, iron, nickel, chromium, and aluminum, and alloys such as stainless steel and brass. Among these, copper (including oxygen-free copper), stainless steel, and aluminum are preferred, and copper is even more preferred because of its high thermal conductivity and ease of processability. Representative high thermal conductive materials 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 (18% Cr, 12% Ni, containing molybdenum (Mo)) stainless steel

[0070] The method for forming the thermal diffusion layer is not particularly limited, but examples thereof include a method for directly forming a pattern of the thermal diffusion layer by screen printing, ink jet printing, or the like. Further, there is also mentioned a method of processing a thermal diffusion layer made of a highly thermally conductive material without a pattern formed thereon, such as a rolled metal foil or an electrolytic metal foil, obtained by dry processes such as PVD (physical vapor deposition) processes, such as vacuum deposition, sputtering, and ion plating, or CVD (chemical vapor deposition) processes, such as thermal CVD and atomic layer deposition (ALD), or by various coating processes, such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade, or wet processes such as electrodeposition, silver halide plating, electrolytic plating, and electroless plating, or by other processes, into a predetermined pattern shape by known physical or chemical treatments, mainly based on the above-mentioned photolithography method, or a combination of these.

[0071] The thermal conductivity of the thermal diffusion layer made of a highly thermally conductive material used in the present invention is preferably 5 to 500 W / (m·K), more preferably 8 to 500 W / (m·K), even more preferably 10 to 450 W / (m·K), particularly preferably 12 to 420 W / (m·K), and most preferably 15 to 400 W / (m·K). When the thermal conductivity is within the above range, a temperature difference can be efficiently created in the thickness direction of the thermoelectric conversion material. The thickness of the thermal diffusion layer is preferably from 40 to 550 μm, more preferably from 60 to 530 μm, and even more preferably from 80 to 510 μm.

[0072] <Thermoelectric conversion module cutting process> The method for producing a thermoelectric conversion module of the present invention preferably includes a thermoelectric conversion module cutting step. The thermoelectric conversion module cutting step is a step of cutting the thermoelectric conversion module obtained, for example, in the above-described FIG. 1(e), FIG. 2(a), or FIG. 2(b) to obtain a plurality of thermoelectric conversion modules with predetermined specifications. The method for cutting the thermoelectric conversion module is not particularly limited and can be performed by a known method. For example, a dicing method can be used. The dicing method is not particularly limited, and known methods such as blade dicing and laser dicing can be used.

[0073] The method for manufacturing a thermoelectric conversion module of the present invention does not require the solder material or support that have been used conventionally, and can efficiently manufacture a plurality of thin thermoelectric conversion modules in a single operation using a simple method. [Industrial Applicability]

[0074] According to the method for manufacturing a thermoelectric conversion module of the present invention, thin, high-density thermoelectric conversion modules can be mass-produced in one go, and it is therefore expected that inexpensive, downsized thermoelectric conversion modules can be provided. [Explanation of symbols]

[0075] 1:Support 2p:P-type thermoelectric conversion material chip 2n:N-type thermoelectric conversion material chip 3: Insulator 3': Excess insulator 4a: Integrated product (with excess insulation) 4b: Integrated product (after removing excess insulation) 5: Electrode 6: Insulating layer 7: Thermal diffusion layer

Claims

1. A method for producing a thermoelectric conversion module, comprising the following steps (A) to (D): (A) A step of arranging a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material on a support at a distance from each other. (B) A step of filling an insulator between the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material to obtain an integrated product consisting of the chip of P-type thermoelectric conversion material, the chip of N-type thermoelectric conversion material, and the insulator. (C) A step of peeling off the integrated product obtained in the step (B) from the support. (D) A step of connecting the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material via electrodes in the integrated product after the step (C). A method for manufacturing a thermoelectric conversion module, comprising: a fixing layer between the support body and the chip of P-type thermoelectric conversion material and the chip of N-type thermoelectric conversion material; and the fixing layer being made of an adhesive layer.

2. 2. The method for producing a thermoelectric conversion module according to claim 1, further comprising the following step (B') after the step (B) and before the step (C): (B') a step of removing excess portions of the insulator that are in direct contact with at least the upper surface regions of the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material in the integrated product obtained in the step (B).

3. The method for producing a thermoelectric conversion module according to claim 1 or 2, further comprising the following step (E) after the step (D): (E) A step of laminating an insulating layer on the electrode.

4. The method for producing a thermoelectric conversion module according to claim 3 , further comprising the following step (F) after the step (E): (F) A step of laminating a thermal diffusion layer on the insulating layer.

5. The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 4, wherein the insulator is selected from the group consisting of insulating resin and ceramics.

6. 6. The method for producing a thermoelectric conversion module according to claim 5, 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.

7. 7. The method for producing a thermoelectric conversion module according to claim 1, wherein the support is selected from the group consisting of glass, plastic, and silicon.

8. The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 7, wherein the chips of P-type thermoelectric conversion material and the chips of N-type thermoelectric conversion material are made of a thermoelectric semiconductor composition.

9. 9. The method for producing a thermoelectric conversion module according to claim 8, wherein the thermoelectric semiconductor composition contains a thermoelectric semiconductor material, a heat-resistant resin, and one or both of an ionic liquid and an inorganic ionic compound.

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