Manufacturing method for thermoelectric conversion modules

Abstract

To provide a manufacturing method of a thermoelectric conversion module capable of an integral multi-bevelling in a thin film without a substrate base material or a solder layer.SOLUTION: A manufacturing method of a thermoelectric conversion module contains steps of (A) to (D): (A) a step of arranging chips of P-type and N-type thermoelectric conversion materials and forming a thermoelectric conversion material layer; (B) a step of forming an insulation layer L1 having P-type and N-type contact holes; (C) a step of forming an insulation layer L2 having P-type and N-type contact holes; and (D) a step of arranging electrode pieces M1 for connecting a pair of P-type and N-type adjacent contact holes onto the insulation layer L1 in a chip arrangement direction with an interval so that the adjacent electrode pieces M1 are not contacted to each other, arranging electrode pieces M2 for connecting a pair of N-type and P-type adjacent contact holes onto the insulation layer L2 in the chip arrangement direction with an interval so that the adjacent electrode pieces M2 are not contacted to each other, and thereby electrically connecting each electrode piece M1, the P-type thermoelectric conversion material, each electrode piece M2, and the N-type thermoelectric conversion material in this order.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a thermoelectric conversion module. [Background technology]

[0002] Conventionally, as one means of efficiently utilizing energy, there are devices that directly convert thermal energy and electrical energy into each other using thermoelectric conversion modules that have thermoelectric effects such as the Seebeck effect and the Peltier effect.

[0003] As the aforementioned thermoelectric conversion module, the use of so-called π-type thermoelectric conversion elements is known. A π-type thermoelectric conversion element has a basic unit consisting of a pair of electrodes spaced apart from each other on a substrate, for example, the lower surface of a P-type thermoelectric element on one electrode and the lower surface of an N-type thermoelectric element on the other electrode, also spaced apart from each other, with the upper surfaces of both types of thermoelectric elements connected to the same electrode on the opposing substrate. Typically, multiple such basic units are configured within both substrates, electrically connected in series and thermally connected in parallel. In recent years, as products using thermoelectric conversion modules, including such π-type thermoelectric conversion elements, are being put into full-scale practical use, there are various demands for thinner thermoelectric conversion modules, reduced material usage, improved productivity, and improved reliability. For example, Patent Documents 1 and 2 disclose thermoelectric conversion modules using the aforementioned π-type thermoelectric conversion elements. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2001-102643 [Patent Document 2] International Publication No. 2017 / 074003 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the thermoelectric conversion module described in Patent Document 1 consists 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 that can be joined in pairs to form a PN junction pair. At least a substrate is used to support the metal electrodes and elements, so no consideration has been given to thinning the thermoelectric conversion module or reducing the number of constituent materials. Similarly, the thermoelectric conversion module described in Patent Document 2 does not include a substrate that serves as a support in its final configuration, but a contact heat conduction layer is provided where a substrate would normally be placed, and moreover, this contact heat conduction layer is made of the same type of substrate as commonly used, such as aluminum nitride, silicon nitride, or alumina, and also functions as a support, so no consideration has been given to thinning the thermoelectric conversion module or reducing the number of constituent materials.

[0006] This invention has been made in view of the above circumstances, and aims to provide a method for manufacturing a thin thermoelectric conversion module that does not have a support substrate and a solder layer, and that can be processed in a single, multi-sided manner. [Means for solving the problem]

[0007] [7] A method for manufacturing a thermoelectric conversion module according to any of [1] to [6] above, comprising the steps (F-1) to (F-2) below after the step (E-3). (F-1) The electrode piece M1 and the protective layer H1 A process of laminating a heat dissipation layer T1' on the surface. (F-2) A process of patterning the heat dissipation layer T1' by etching, thereby forming the extracted electrode and the heat dissipation layer T1 obtained by patterning on the surface of the protective layer H1. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a method for manufacturing a thin thermoelectric conversion module that does not have a support substrate or solder layer and can be processed in a single, multi-sided manner. [Brief explanation of the drawing]

[0009] [Figure 1] It is an explanatory diagram showing Embodiment 1 of the steps according to the manufacturing method of the thermoelectric conversion module of the present invention in the order of steps. [Figure 2] It is an explanatory diagram showing Embodiment 2 of the steps according to the manufacturing method of the thermoelectric conversion module of the present invention in the order of steps. [Figure 3] It is an explanatory diagram showing Embodiment 3 of the steps according to the manufacturing method of the thermoelectric conversion module of the present invention in the order of steps.

Mode for Carrying Out the Invention

[0010] [Manufacturing Method of Thermoelectric Conversion Module] The manufacturing method of the thermoelectric conversion module of the present invention is characterized by including the following steps (A) to (D). (A) A step of forming a thermoelectric conversion material layer by arranging chips of a P-type thermoelectric conversion material and chips of an N-type thermoelectric conversion material on a support S (B) A step of forming an insulating layer L1 having P-type contact holes that cover the surface of the thermoelectric conversion material layer opposite to the surface on the support S side and expose a part of each surface of the chips of the P-type thermoelectric conversion material, and N-type contact holes that expose a part of each surface of the chips of the N-type thermoelectric conversion material (C) After peeling the support S, a step of forming an insulating layer L2 having P-type contact holes that cover the surface of the thermoelectric conversion material layer from which the support S has been peeled and expose a part of each surface of the chips of the P-type thermoelectric conversion material, and N-type contact holes that expose a part of each surface of the chips of the N-type thermoelectric conversion material (D) A process in which electrode pieces M1 connecting adjacent pairs of P-type and N-type contact holes are arranged on the insulating layer L1 with spacing between adjacent electrode pieces M1 so that they do not come into contact with each other, and electrode pieces M2 connecting adjacent pairs of N-type and P-type contact holes are arranged on the insulating layer L2 with spacing between adjacent electrode pieces M2 so that they do not come into contact with each other, thereby electrically connecting the electrode pieces M1, the chip of the P-type thermoelectric conversion material, the electrode pieces M2, and the chip of the N-type thermoelectric conversion material in that order. In the method for manufacturing a thermoelectric conversion module of the present invention, a common electrode piece for adjacent P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips is directly formed (wired) on the upper and lower surfaces of the P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips in a shape that straddles the electrode piece via an insulating layer placed in the center of the electrode piece. This allows for the efficient and simultaneous production of a thin thermoelectric conversion module without forming electrodes on a support substrate and without the need for conventionally used solder layers and supports.

[0011] In the following explanation, each of the processes (A), (B), (C), and (D) may also be referred to in this order as "(A) Thermoelectric conversion material chip arrangement process, or (A) process," "(B) Insulating layer L1 formation process, or (B) process," "(C) Insulating layer L2 formation process, or (C) process," and "(D) Electrode piece formation process, or (D) process." Furthermore, other processes such as (E-1) and (F-1) may also be referred to in this order as "(E-1) process," "(F-1) process," etc. Additionally, "P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips" may simply be referred to as "thermoelectric conversion material chips." The manufacturing method of the thermoelectric conversion module of the present invention will be described below with reference to the figures.

[0012] Figure 1 is an explanatory diagram showing an embodiment 1 of the process according to the manufacturing method of the thermoelectric conversion module of the present invention, in order of the process, (a) is a cross-sectional view after forming a thermoelectric conversion material layer 3 by arranging P-type thermoelectric conversion material chips 3p and N-type thermoelectric conversion material chips 3n on a support S having a frame 2, (b) is a cross-sectional view after forming an insulating layer L1' on the upper surface of the thermoelectric conversion material layer 3, (c) is a cross-sectional view after forming an insulating layer L1 with P-type contact holes 5p and N-type contact holes 5n on the insulating layer L1', and (d) is after providing the support S1 on the insulating layer L1, peeling off the support S and the thermoelectric conversion (e) is a cross-sectional view of the material replacement layer 3 after forming an insulating layer L2' on the side opposite to the insulating layer L1, (f) is a cross-sectional view of the insulating layer L2 after forming an insulating layer L2 with P-type contact holes 5p' and N-type contact holes 5n' on the insulating layer L2', (g) is a cross-sectional view of the thermoelectric conversion module 1 manufactured by peeling off the support S1 and then forming electrode piece forming layers M1' and M2' on the insulating layer L1 and M2 in that order, and (g) is a cross-sectional view of the thermoelectric conversion module 1 manufactured by patterning the electrode piece forming layers M1' and M2' to form electrode pieces M1 and M2.

[0013] Figure 2 is an explanatory diagram showing an embodiment 2 of the process according to the manufacturing method of the thermoelectric conversion module of the present invention, where (a) is a cross-sectional view of the thermoelectric conversion module 1 having the configuration of Figure 1(g), after a protective layer H1' is laminated on the surface of electrode piece M1 and insulating layer L1, and a protective layer H2' is laminated on the surface of electrode piece M2 and insulating layer L2, and (b) is a cross-sectional view of the thermoelectric conversion module 11 manufactured by forming a protective layer H1 having a contact hole 12 for an extraction electrode that exposes a part of the surface of electrode piece M1.

[0014] Figure 3 is an explanatory diagram showing the third embodiment of the process according to the manufacturing method of the thermoelectric conversion module of the present invention, in order of the process, where (a) is the surface and protective layer of the electrode piece M1 in the thermoelectric conversion module 11 having the configuration of Figure 2(b), H1(b) is a cross-sectional view of the thermoelectric conversion module 21 after a heat dissipation layer T1' is laminated on the surface of the protective layer H2' and a heat dissipation layer T2' is laminated on the surface of the protective layer H2', and (b) is a cross-sectional view of the thermoelectric conversion module 21 manufactured by patterning the heat dissipation layer T1' and forming the extraction electrode 13 and the heat dissipation layer T1 obtained by patterning on the surface of the protective layer H1.

[0015] (A) Chip arrangement process for thermoelectric conversion materials The method for manufacturing a thermoelectric conversion module of the present invention includes a step of arranging chips of thermoelectric conversion material. The process of arranging thermoelectric materials chips is a process of arranging P-type thermoelectric material chips and N-type thermoelectric material chips on a support S to form a thermoelectric material layer. For example, in Figure 1(a) above, the process involves arranging chips 3p of type P thermoelectric material and chips 3n of type N thermoelectric material on a support S to form a thermoelectric material layer 3. The method for arranging the P-type thermoelectric material chips and the N-type thermoelectric material chips is not particularly limited. For example, the P-type thermoelectric material chips and N-type thermoelectric material chips prepared in advance may be arranged individually, or the P-type thermoelectric material chips and N-type thermoelectric material chips may be arranged by, for example, attaching a pre-fabricated arrangement of the P-type thermoelectric material chips and N-type thermoelectric material chips onto a support S via an adhesive layer. The support S preferably includes an adhesive layer formed from an adhesive on a resin film. The adhesive layer may contain any adhesive resin, and may optionally contain adhesive additives such as crosslinking agents, tackifiers, polymerizable compounds, and polymerization initiators. The adhesive layer can be formed from an adhesive composition containing an adhesive resin by known methods. For example, it can be formed by an application method. Examples of adhesive resins include rubber-based resins such as acrylic resins, urethane resins, and polyisobutylene resins, as well as polyester resins, olefin-based resins, silicone resins, and polyvinyl ether resins. The thickness of the adhesive layer is not particularly limited, but is preferably about 1 to 50 μm, and more preferably 2 to 30 μm.

[0016] Furthermore, chips of P-type thermoelectric material and chips of N-type thermoelectric material may be formed directly on the support S in an alternating arrangement. Methods for directly forming chips of P-type thermoelectric material and N-type thermoelectric material include screen printing and coating using a dispenser.

[0017] It is preferable to include the following step (Z) before step (A) above. (Z) Step of providing a frame on the outer periphery of the support S. By providing a frame, sealing of the outer periphery of the resulting thermoelectric conversion module becomes unnecessary. The frame is made of metal, ceramics, or resin. From the viewpoint of sealing performance, it is preferable to use metal or ceramics. Furthermore, from the viewpoint of weight reduction, it is preferable to use resin. Examples of metals include gold, silver, copper, nickel, chromium, platinum, palladium, rhodium, molybdenum, aluminum, iron, iron-nickel alloys, or phosphor bronze. Examples of ceramics include materials whose main components are aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicon nitride, silicon carbide, etc. (50% by mass or more in the ceramic). In addition to the above main components, rare earth compounds may also be added. Examples of resins include polyimide resins, polyamide resins, phenolic resins, epoxy resins, maleimide resins, and fluoropolymer resins. When using resins, they may be rigid materials made from hard resins or flexible materials made from flexible resins.

[0018] 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 viewpoint of flexibility, thinness, and thermoelectric performance, it is preferable that the thin film be made of a thermoelectric semiconductor composition containing one or both of a thermoelectric semiconductor material (hereinafter sometimes referred to as "thermoelectric semiconductor particles"), a resin, an ionic liquid, and an inorganic ionic compound. In this specification, "thermoelectric conversion material" and "thermoelectric conversion material chip" are synonymous, and "thermoelectric conversion material layer" is also synonymous.

[0019] (Thermoelectric semiconductor materials) The thermoelectric semiconductor material used in the chip of the thermoelectric conversion material is preferably pulverized to a predetermined size using, for example, a fine pulverization 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 it 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 thermoelectric conversion material chip used in the present invention, the thermoelectric semiconductor material constituting the P-type thermoelectric conversion material chip and the N-type conversion material chip is not particularly limited as long as it is a material that can generate a thermoelectric voltage by applying a temperature difference. Examples include 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; and ZnSb and Zn3Sb. 2、 Zinc-antimony thermoelectric semiconductor materials such as Zn4Sb3; silicon-germanium thermoelectric semiconductor materials such as SiGe; bismuth selenide thermoelectric semiconductor materials such as Bi2Se3; β-FeSi2, CrSi2, MnSi 1.73 Silicide-based thermoelectric semiconductor materials such as 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.

[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 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. When X is greater than 0 and 0.8 or less, the Seebeck coefficient and the electrical conductivity increase, and the characteristics as a P-type thermoelectric conversion material are maintained, which is preferable. In addition, the N-type bismuth telluride has electrons as carriers and a negative value of 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 the 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, it is 50 to 96% by mass, and still more preferably, it is 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, 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 is obtained, which is preferable.

[0023] In addition, 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. Therefore, the Seebeck coefficient (absolute value of the Peltier coefficient) of the thermoelectric conversion material increases, and the thermoelectric performance index can be further improved.

[0024] (resin) The resin used in this invention has the effect of physically bonding thermoelectric semiconductor materials (thermoelectric semiconductor particles), which can improve the flexibility of the thermoelectric conversion module and facilitate the formation of thin films by coating or other means. As the resin, a heat-resistant resin or a binder resin is preferred.

[0025] When a heat-resistant resin is subjected to crystalline growth of thermoelectric semiconductor particles in a thin film made of a thermoelectric semiconductor composition through annealing or other processes, its various physical properties, such as mechanical strength and thermal conductivity, are maintained without being impaired. The heat-resistant resin is preferably polyamide resin, polyamide-imide resin, polyimide resin, or epoxy resin because it has higher heat resistance and does not adversely affect the crystal growth of thermoelectric semiconductor particles in the thin film, and more preferably polyamide resin, polyamide-imide resin, or 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, as will be described later, even when a thin film made of a thermoelectric semiconductor composition is annealed, the binder function is not lost and flexibility can be maintained.

[0027] Furthermore, the heat-resistant resin preferably has a mass loss rate of 10% or less at 300°C as determined by thermogravimetric analysis (TG), more preferably 5% or less, and even more preferably 1% or less. 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 binder function is not lost, 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 with both high thermoelectric performance and film strength can be obtained, and a resin portion is present on the outer surface of the thermoelectric conversion material chip.

[0029] The binder resin also facilitates the removal of the thermoelectric conversion material chips from substrates such as glass, alumina, and silicon after the annealing process (corresponding to "Annealing Process B" described later, and the same applies hereafter).

[0030] The binder resin refers to a resin that decomposes by 90% or more by mass at temperatures above the annealing temperature, more preferably a resin that decomposes by 95% or more by mass, and particularly preferably a resin that decomposes by 99% or more by mass. Furthermore, it is more preferable to use a resin that maintains various physical properties such as mechanical strength and thermal conductivity without being impaired when growing thermoelectric semiconductor particles in a coated film (thin film) made of a thermoelectric semiconductor composition through annealing or other processes. If a resin that decomposes by 90% or more by mass at temperatures above the annealing temperature, that is, a resin that decomposes at a lower temperature than the aforementioned heat-resistant resin, is used as the binder resin, the binder resin decomposes during firing. This reduces the amount of binder resin, which is an insulating component in the fired body, and promotes the crystal growth of thermoelectric semiconductor particles in the thermoelectric semiconductor composition. As a result, the voids in the thermoelectric conversion material layer can be reduced, and the packing density can be improved. Furthermore, whether or not a resin decomposes by a predetermined amount (for example, 90% by mass) or more above the firing (annealing) temperature is determined by measuring the mass loss rate at the firing (annealing) temperature (the value obtained by dividing the mass after decomposition by the mass before decomposition) using thermogravimetric analysis (TG).

[0031] Examples of such binder resins include thermoplastic resins and curable 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 ethylcellulose. 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 may be used individually or in combination of two or more. Among these, from the viewpoint of the electrical resistivity of the thermoelectric material in the thermoelectric 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 according to the annealing temperature of the thermoelectric semiconductor material in the annealing process. Annealing at a temperature above the final decomposition temperature of the binder resin is preferable from the viewpoint of the electrical resistivity of the thermoelectric material in the thermoelectric material layer. In this specification, "final decomposition temperature" refers to the temperature at which the mass reduction rate at the annealing temperature, as determined by thermogravimetric analysis (TG), reaches 100% (the mass after decomposition is 0% of the mass before decomposition).

[0033] The final decomposition temperature of the binder resin is typically 150 to 600°C, preferably 200 to 560°C, more preferably 220 to 460°C, and particularly preferably 240 to 360°C. Using a binder resin with a final decomposition temperature within this range allows it to function as a binder for thermoelectric semiconductor materials, facilitating the formation of thin films during printing.

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

[0035] The binder resin content in the thermoelectric conversion material is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass. If the binder resin content 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) Ionic liquids that may be included in thermoelectric semiconductor compositions are molten salts formed by combining cations and anions, and are salts that can exist as liquids in any temperature range between -50°C and 400°C. In other words, ionic liquids are ionic compounds with a melting point in the range of -50°C to 400°C. The melting point of ionic liquids is preferably between -25°C and 200°C, more preferably between 0°C and 150°C. Because ionic liquids have characteristics such as extremely low vapor pressure and non-volatility, excellent thermal and electrochemical stability, low viscosity, and high ionic conductivity, they can effectively suppress the reduction of electrical conductivity between thermoelectric semiconductor materials when used as a conductivity enhancer. Furthermore, ionic liquids exhibit high polarity based on their aprotic ionic structure and have excellent compatibility with heat-resistant resins, thus enabling the electrical conductivity of thermoelectric conversion materials to be made uniform.

[0037] Ionic liquids that are known or commercially available can be used. For example, nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium, and their derivatives; tetraalkylammonium-based amine cations and their derivatives; phosphine-based cations such as phosphonium, trialkylsulfonium, tetraalkylphosphonium, and their derivatives; cation components such as lithium cation and its derivatives, and Cl - , 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 - etc. composed of anion components can be mentioned.

[0038] Among the above ionic liquids, from the viewpoints of high-temperature stability, compatibility with thermoelectric semiconductor materials and resins, suppression of reduction in electrical conductivity in the thermoelectric semiconductor material gap, etc., it is preferable that the cation component of the ionic liquid contains at least one selected from pyridinium cation and its derivatives, imidazolium cation and its derivatives.

[0039] The cationic component is preferably 1-butyl-4-methylpyridinium bromide, 1-butylpyridinium bromide, or 1-butyl-4-methylpyridinium hexafluorophosphate, as an ionic liquid containing pyridinium cations and their derivatives.

[0040] Furthermore, as the cationic component, [1-butyl-3-(2-hydroxyethyl)imidazolium bromide] and [1-butyl-3-(2-hydroxyethyl)imidazolium tetrafluoroborate] are preferred as ionic liquids containing imidazolium cations and their derivatives.

[0041] Furthermore, it is preferable that the above-mentioned ionic liquid has a decomposition temperature of 300°C or higher. If the decomposition temperature is within the above range, the effect as a conductive additive can be maintained even when a thin film made of a thermoelectric semiconductor composition is annealed, as will be described later.

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

[0043] (Inorganic ionic compounds) Inorganic ionic compounds that may be included in thermoelectric semiconductor compositions are compounds composed of at least a cation and anion. Inorganic ionic compounds exist as solids over a wide temperature range of 400 to 900°C and have characteristics such as high ionic conductivity, and can therefore be used as conductivity enhancers to suppress the reduction of electrical conductivity between thermoelectric semiconductor materials.

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

[0045] Methods for applying P-type and N-type thermoelectric semiconductor compositions 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, and doctor blade coating. When forming a patterned coating, screen printing, stencil printing, slot die coating, etc., which allow for easy pattern formation using a screen plate with the desired pattern, are preferably used. Next, a thin film is formed by drying the obtained coating. Conventional drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used. The heating temperature is usually 80 to 150°C, and the heating time varies depending on the heating method, but is usually several seconds to several tens of minutes. Furthermore, when a solvent is used in the preparation of a thermoelectric semiconductor composition, there are no particular restrictions on the heating temperature, as long as it is within a temperature range that allows the solvent used to dry.

[0046] The thickness of the thermoelectric conversion material chip 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.

[0047] It is preferable to further anneal the chips of P-type thermoelectric conversion material and N-type thermoelectric conversion material made of a thermoelectric semiconductor composition. By performing annealing B, the thermoelectric performance can be stabilized and the thermoelectric semiconductor particles in the thermoelectric conversion material chip can be grown crystallized, thereby further improving the thermoelectric performance. Annealing B is not particularly limited, but is usually performed under an inert gas atmosphere such as nitrogen or argon, a reducing gas atmosphere, or under vacuum conditions with controlled gas flow rate, and 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 used.

[0048] (B) Insulating layer L1 formation process The method for manufacturing a thermoelectric conversion module of the present invention includes a step of forming an insulating layer L1. The insulating layer L1 formation step involves forming an insulating layer that covers the side of the thermoelectric conversion material layer opposite to the side facing the support S, and then forming an insulating layer L1 on the insulating layer that has P-type contact holes that expose a portion of the surface of each chip of the P-type thermoelectric conversion material, and N-type contact holes that expose a portion of the surface of each chip of the N-type thermoelectric conversion material.

[0049] Step (B) preferably includes steps (B-1) and (B-2).

[0050] (B-1) is a process of forming an insulating layer L1' on the surface of the P-type thermoelectric material chip and the N-type thermoelectric material chip that is opposite to the surface facing the support S. For example, in Figure 1(b), the process involves forming an insulating layer L1' on the upper surface of a thermoelectric material layer 3, which is formed by arranging P-type thermoelectric material chips 3p and N-type thermoelectric material chips 3n. A preferred method for forming the insulating layer L1' is one in which the gaps between the chips of the P-type thermoelectric material and the chips of the N-type thermoelectric material, and the gaps around them, are not filled. For example, known methods such as lamination can be used. The insulating layer L1' is preferably selected from polyimide resin, silicone resin, rubber resin, acrylic resin, olefin resin, maleimide resin, and epoxy resin. The thickness of the insulating layer L1' is preferably 5 to 200 μm, more preferably 10 to 100 μm, and even more preferably 15 to 30 μm. When the thickness of the insulating layer L1' is within this range, insulation between adjacent electrode pieces can be ensured, and it does not increase the thickness of the thermoelectric conversion module.

[0051] (B-2) Step (B-2) is a step in which the insulating layer L1' is patterned by performing an exposure development process or laser irradiation on the insulating layer L1' to form the insulating layer L1. For example, in Figure 1(c), the insulating layer L1 is formed by providing P-type contact holes 5p and N-type contact holes 5n in the insulating layer L1'. While known methods can be used to form the insulating layer L1 and are not particularly limited, it is preferable to provide P-type and N-type contact holes in the insulating layer L1' by exposure development or laser irradiation. In exposure and development processing methods, for example, when a photosensitive resin is used as the insulating layer L1', the method involves exposing it by irradiating it with ultraviolet light or the like through a desired photomask for forming contact holes, and then processing it using a developer or the like. Furthermore, laser irradiation can be performed using methods such as carbon dioxide lasers or ultraviolet lasers.

[0052] The following step (B') may be included after step (B) and before step (C). (B') A step of laminating a support S1 on the insulating layer L1 obtained in step (B) above. For example, in Figure 1(c), this is the process of laminating the support S1 onto the insulating layer L1. Support S1 may be made of the same material as or different from support S.

[0053] (C) Insulating layer L2 formation process The method for manufacturing a thermoelectric conversion module of the present invention includes a step of forming an insulating layer L2. The insulating layer L2 formation step involves peeling off the support S, forming an insulating layer that covers the surface of the thermoelectric conversion material layer from which the support S was peeled off, and then forming contact holes for P-type thermoelectric conversion material chips and contact holes for N-type thermoelectric conversion material chips in the insulating layer, exposing a portion of the surface of each chip.

[0054] Step (C) preferably includes steps (C-1) and (C-2) below.

[0055] Step (C-1) is a step in which an insulating layer L2' is formed on the surface of the P-type thermoelectric material chip and the N-type thermoelectric material chip that has been peeled off from the support S side. For example, in Figure 1(d), the process involves providing a support S1 on the insulating layer L1, then peeling off the support S, and forming an insulating layer L2' on the side of the thermoelectric conversion material layer 3 opposite to the insulating layer L1. The method for forming the insulating layer L2', the material used for the insulating layer L2', and the thickness of the insulating layer L2' are the same as those for the insulating layer L1' described above.

[0056] (C-2) Step (C-2) is a step in which the insulating layer L2' is patterned by exposure development or laser irradiation to form the insulating layer L2'. For example, in Figure 1(e), the process involves forming the insulating layer L2 by providing P-type contact holes 5p' and N-type contact holes 5n' in the insulating layer L2'. The exposure and development process or laser irradiation is the same as described above for the insulating layer L1'.

[0057] (D) Electrode piece formation process The method for manufacturing a thermoelectric conversion module of the present invention includes an electrode piece formation step. The electrode piece formation process involves arranging electrode pieces M1 on an insulating layer L1, which connect adjacent pairs of P-type and N-type contact holes, with spacing between them so that adjacent electrode pieces M1 do not come into contact with each other, in the chip arrangement direction, and arranging electrode pieces M2 on an insulating layer L2, which connect adjacent pairs of N-type and P-type contact holes, with spacing between them so that adjacent electrode pieces M2 do not come into contact with each other, thereby electrically connecting the electrode pieces M1, the chip of the N-type thermoelectric conversion material, the electrode pieces M2, and the chip of the P-type thermoelectric conversion material in that order.

[0058] Step (D) preferably includes the following steps (D-1) to (D-4).

[0059] Step (D-1) is a step in which an electrode piece forming layer M1' is formed on the surface of the insulating layer L1, the chip of the P-type thermoelectric conversion material, and the chip of the N-type thermoelectric conversion material. For example, in Figure 1(e), after peeling the support S1 from the insulating layer L1, the process involves forming an electrode piece forming layer M1' on the insulating layer L1, as shown in (f).

[0060] Step (D-2) is a step in which the electrode piece forming layer M1' is patterned to form the electrode piece M1. For example, in Figure 1(f), the electrode piece forming layer M1' is patterned to form the electrode piece M1 as shown in (g).

[0061] Step (D-3) is a step in which an electrode piece forming layer M2' is formed on the surface of the insulating layer L2, the chip of the P-type thermoelectric conversion material, and the chip of the N-type thermoelectric conversion material. For example, in Figure 1(e), after peeling off the support S1, the process involves forming an electrode piece forming layer M2' on the insulating layer L2, as shown in (f).

[0062] Step (D-4) is a step of patterning the electrode piece forming layer M2' to form the electrode piece M2. For example, in Figure 1(f), the electrode piece forming layer M2' is patterned to form the electrode piece M2 as shown in (g).

[0063] The electrode piece forming layers M1' and M2' (hereinafter sometimes simply referred to as "electrode forming layers") used in the present invention require high electrical conductivity and high thermal conductivity from the viewpoint of maintaining thermoelectric performance. Therefore, the electrode piece forming layer, that is, electrode pieces M1 and M2 (hereinafter sometimes simply referred to as "electrode pieces"), is formed independently of at least one film preferably selected from the group consisting of sputtered films, vapor-deposited films, and plating films. The electrode forming layer, i.e., the electrode material constituting the electrode piece, is independently selected, preferably from gold, silver, copper, nickel, chromium, platinum, palladium, rhodium, molybdenum, aluminum, or an alloy containing any of these metals.

[0064] Methods for patterning the electrode formation layer to form electrode pieces include known physical or chemical treatments, primarily photolithography, or methods that combine these to process the material into a predetermined pattern shape. Specific methods for processing into a predetermined pattern shape include, for example, methods of direct formation by exposure and development, methods of formation by etching after exposure and development, and methods of direct formation by laser processing. Among these, the method of formation by etching after exposure and development is particularly preferred from the viewpoint of pattern accuracy and cycle time.

[0065] The thickness of the electrode-forming layer depends on the thickness of the insulating layers L1 and L2 used, but is preferably 5 to 200 μm, more preferably 8 to 150 μm, and even more preferably 10 to 120 μm. If the thickness of the electrode-forming layer is within the above range, the electrical conductivity will be high and the resistance low, and sufficient strength as an electrode piece can be obtained.

[0066] It is preferable to include the following steps (E-1) to (E-3) after step (D).

[0067] Step (E-1) is a step in which a protective layer H1' is laminated onto the surface of the electrode piece M1 and the insulating layer L1. For example, as shown in Figure 2(a), this is a step of laminating a protective layer H1' onto the surface of the electrode piece M1 and insulating layer L1 of the thermoelectric conversion module 1 having the configuration shown in Figure 1(g).

[0068] (E-2) Step is a process of laminating a protective layer H2' onto the surface of the electrode piece M2 and the insulating layer L2. That is the case. For example, as shown in Figure 2(a), this is a step of laminating a protective layer H2' onto the surface of the electrode piece M2 and insulating layer L2 of the thermoelectric conversion module 1 having the configuration shown in Figure 1(g).

[0069] Step (E-3) is a step of forming a protective layer H1 having a contact hole for an extraction electrode that exposes a part of the surface of the electrode piece M1 or the electrode piece M2. For example, in Figure 2(b), the process involves forming a protective layer H1 having a contact hole 12 for an extraction electrode that exposes a portion of the surface of the electrode piece M1.

[0070] The materials used for protective layers H1' and H2' are not particularly limited, and known materials can be used. Protective layers H1' and H2' are each independently selected, preferably from insulating resins and ceramics. Examples of insulating resins include polyimide resins, polyamide resins, phenolic resins, epoxy resins, maleimide resins, fluoropolymer resins, polyester resins, polyurethane resins (especially two-component curable resins of polyacrylic polyols, polyester polyols, polyether polyols, etc., and isocyanate compounds), acrylic resins, polycarbonate resins, vinyl chloride / vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, and other resins; alkyl titanates; ethyleneimines; and the like. These may be used individually or in combination of two or more. Examples of ceramics include materials whose main components are aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicon nitride, silicon carbide, etc. (50% by mass or more in the ceramic). In addition to the above main components, rare earth compounds may also be added.

[0071] The protective layers H1' and H2' can be formed by laminating a protective layer-forming solution obtained by dissolving or dispersing the material in a suitable solvent, applying it by a known method, drying the resulting coating, and optionally heating or irradiating it with light. Alternatively, a protective layer-forming film may be formed separately and laminated using a roll laminator or flatbed press to form protective layers H1' and H2'. Lamination may be performed at room temperature or while heating. The thicknesses of protective layers H1' and H2' are determined appropriately from the viewpoint of thermoelectric performance, but are preferably 5 to 300 μm, more preferably 25 to 200 μm, and even more preferably 50 to 100 μm, respectively. When protective layers H1' and H2' are formed by coating, the thickness of each protective layer is preferably 5 to 150 μm, more preferably 10 to 100 μm, and even more preferably 15 to 50 μm, independently of each other. When protective layers H1' and H2' are formed by lamination, the thickness of each protective layer is preferably 20 to 300 μm, more preferably 40 to 200 μm, and even more preferably 50 to 100 μm, independently of each other.

[0072] It is preferable to include the following steps (F-1) to (F-2) after step (E-3).

[0073] (F-1) Step involves the electrode piece M1 and the protective layer H1 This is a process of laminating a heat dissipation layer T1' onto the surface. For example, as shown in Figure 3(a), the surface and protective layer of the electrode piece M1 of the thermoelectric conversion module 11 having the configuration shown in Figure 2(b) H1 This is a process of laminating a heat dissipation layer T1' onto the surface.

[0074] Step (F-2) is a process in which the heat dissipation layer T1' is patterned by etching, and the extracted electrode and the heat dissipation layer T1 obtained by patterning are formed on the surface of the protective layer H1. For example, as shown in Figure 3(b), in (a), the heat dissipation layer T1' is patterned to form the extraction electrode 13 and the heat dissipation layer T1 obtained by patterning on the surface of the protective layer H1.

[0075] The following step (F-2) may be included after step (E-3). (F-2) Process of laminating a heat dissipation layer T2' on the surface of the protective layer H2'. For example, as shown in Figure 3(b), this is a process of laminating a heat dissipation layer T2' onto the surface of a protective layer H2'.

[0076] The materials used for the heat dissipation layers T1' and T2' are not particularly limited, and known materials can be used. Preferably, each is independently selected from gold, silver, copper, nickel, tin, iron, chromium, platinum, palladium, rhodium, iridium, ruthenium, osmium, indium, zinc, molybdenum, manganese, titanium, aluminum, stainless steel, and brass.

[0077] There are no particular limitations on the method for laminating the heat dissipation layers T1' and T2', but examples include PVD (physical vapor deposition) such as vacuum deposition, sputtering, and ion plating, or dry processes such as CVD (chemical vapor deposition) such as thermal CVD and atomic layer deposition (ALD), or wet processes such as various coating methods such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade methods, or electrodeposition, as well as silver salt methods, electrolytic plating, and electroless plating. Furthermore, the patterning of the heat dissipation layers T1' and T2' can be carried out by known physical or chemical treatments, primarily photolithography, or by a combination of these. The thermal conductivity of heat dissipation layers T1' and T2' 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), respectively.

[0078] The thickness of the heat dissipation layers T1' and T2' is determined appropriately from the viewpoint of thermoelectric performance, but is preferably 5 to 550 μm, more preferably 40 to 530 μm, and even more preferably 80 to 510 μm.

[0079] The total thickness of the thermoelectric conversion module manufactured by the method for manufacturing a thermoelectric conversion module of the present invention is preferably 150 to 5,000 μm.

[0080] The thermoelectric conversion module of the present invention does not require a substrate and solder layer as support structures, which were used in conventional designs, and allows for a thinner thermoelectric conversion module. [Industrial applicability]

[0081] According to the thermoelectric conversion module of the present invention, it is expected that conventional thermoelectric conversion modules can be made thinner, leading to lighter weight, smaller size, and higher integration. [Explanation of symbols]

[0082] 1,11,21: Thermoelectric conversion module 2: Frame 3p: P-type thermoelectric conversion material chip 3n:N type thermoelectric conversion material chip 3: Thermoelectric conversion material layer L1, L2: Insulating layer (with contact holes) L1', L2': Insulating layer S, S1: Support 5p, 5p': Contact holes for P-type 5n, 5n': Contact holes for N-type M1',M2': Electrode piece forming layer M1, M2: Electrode pieces (with patterns) H1',H2': Protective layer H1, H2: Protective layer (with contact holes) T1',T2': Heat dissipation layer T1, T2: Heat dissipation layer (with pattern) 12: Contact hole for extraction electrode 13: Extraction electrode

Claims

1. A method for manufacturing a thermoelectric conversion module, comprising the following steps (A), (B), (B'), (C), and (D): (A) A step of forming a thermoelectric material layer by arranging chips of P-type thermoelectric material and chips of N-type thermoelectric material on a support S. (B) A step of forming an insulating layer L1 that covers the surface of the thermoelectric conversion material layer opposite to the surface on the support S side, and has P-type contact holes that expose a portion of the surface of each of the P-type thermoelectric conversion material chips and N-type contact holes that expose a portion of the surface of each of the N-type thermoelectric conversion material chips. (B') A step of laminating a support S1 on the insulating layer L1 obtained in step (B) above. (C) After peeling off the support S, a step of forming an insulating layer L2 which covers the surface of the thermoelectric conversion material layer from which the support S was peeled off and has P-type contact holes that expose a portion of the surface of each of the P-type thermoelectric conversion material chips and N-type contact holes that expose a portion of the surface of each of the N-type thermoelectric conversion material chips. (D) After peeling off the support S1, the process of electrically connecting the electrode pieces M1, the chip of the P-type thermoelectric conversion material, the electrode pieces M2, and the chip of the N-type thermoelectric conversion material in the order of: (D) After peeling off the support S1, the electrode pieces M1 connecting a pair of adjacent P-type contact holes and N-type contact holes are arranged on the insulating layer L1 with spacing between them so that adjacent electrode pieces M1 do not come into contact with each other in the chip arrangement direction; and the electrode pieces M2 connecting a pair of adjacent N-type contact holes and P-type contact holes are arranged on the insulating layer L2 with spacing between them so that adjacent electrode pieces M2 do not come into contact with each other in the chip arrangement direction. The above step (B) includes the following steps (B-1) and (B-2): (B-1) A step of forming an insulating layer L1' on the surface of the P-type thermoelectric material chip and the N-type thermoelectric material chip opposite to the surface facing the support S, such that the gap between the P-type thermoelectric material chip and the N-type thermoelectric material chip is not filled. (B-2) A step of forming the insulating layer L1 by patterning the insulating layer L1' by performing an exposure and development process or laser irradiation on the insulating layer L1'. The method for manufacturing a thermoelectric conversion module, wherein step (C) above includes steps (C-1) and (C-2) below. (C-1) A step of forming an insulating layer L2' on the surface of the P-type thermoelectric material chip and the N-type thermoelectric material chip that has been peeled off from the support S side, such that the gap between the P-type thermoelectric material chip and the N-type thermoelectric material chip is not filled. (C-2) A step of forming the insulating layer L2 by patterning the insulating layer L2' by performing an exposure and development process or laser irradiation on the insulating layer L2'.

2. A method for manufacturing a thermoelectric conversion module according to claim 1, comprising the step (Z) below before the step (A) described above. (Z) Step of providing a frame on the outer periphery of the support S.

3. The method for manufacturing a thermoelectric conversion module according to claim 1 or 2, wherein step (D) includes the following steps (D-1) to (D-4). (D-1) A step of forming an electrode piece forming layer M1' on the surface of the insulating layer L1, the chip of the P-type thermoelectric conversion material, and the chip of the N-type thermoelectric conversion material. (D-2) A step of patterning the electrode piece forming layer M1' to form the electrode piece M1. (D-3) A step of forming an electrode piece forming layer M2' on the surface of the insulating layer L2, the chip of the P-type thermoelectric conversion material, and the chip of the N-type thermoelectric conversion material. (D-4) Step of patterning the electrode piece forming layer M2' to form the electrode piece M2.

4. A method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 3, comprising the following steps (E-1) to (E-3) after step (D). (E-1) A step of laminating a protective layer H1' onto the surface of the electrode piece M1 and the insulating layer L1. (E-2) A step of laminating a protective layer H2' onto the surface of the electrode piece M2 and the insulating layer L2. (E-3) A step of forming a protective layer H1 having a contact hole for an extraction electrode that exposes a part of the surface of the electrode piece M1 or the electrode piece M2.

5. A method for manufacturing a thermoelectric conversion module according to claim 4, comprising the following steps (F-1) to (F-2) after step (E-3). (F-1) A step of laminating a heat dissipation layer T1' on the surface of the electrode piece M1 and the protective layer H1. (F-2) A step of patterning the heat dissipation layer T1' by etching, thereby forming the extracted electrode and the heat dissipation layer T1 obtained by patterning on the surface of the protective layer H1.

6. The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 5, wherein the support S has an adhesive layer formed from an adhesive on a resin film.

7. The method for manufacturing a thermoelectric conversion module according to claim 2, wherein the frame is made of metal, ceramics, or resin.

8. The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 7, wherein the insulating layers L1' and L2' are each independently selected from polyimide resin, silicone resin, rubber-based resin, acrylic resin, olefin-based resin, maleimide resin, and epoxy resin.

9. The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 8, wherein the thickness of the insulating layers L1' and L2' is independently 5 to 200 μm.

10. The method for manufacturing a thermoelectric conversion module according to claim 4 or 5, wherein the protective layer H1' and the protective layer H2' are each independently selected from an insulating resin and a ceramic.

11. The method for manufacturing a thermoelectric conversion module according to claim 4, 5, or 10, wherein the thickness of the protective layer H1' and the protective layer H2' is independently 5 to 300 μm.

12. The method for manufacturing a thermoelectric conversion module according to claim 5, wherein the heat dissipation layer T1' is selected from gold, silver, copper, nickel, tin, iron, chromium, platinum, palladium, rhodium, iridium, ruthenium, osmium, indium, zinc, molybdenum, manganese, titanium, aluminum, stainless steel, and brass.

13. The method for manufacturing a thermoelectric conversion module according to claim 5 or 12, wherein the thickness of the heat dissipation layer T1' is 5 to 550 μm.

14. A method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 13, wherein the electrode material constituting the electrode piece M1 and electrode piece M2 is independently selected from gold, silver, copper, nickel, chromium, platinum, palladium, rhodium, molybdenum, aluminum, or an alloy containing any of these metals.

15. The method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 14, wherein the electrode piece M1 and the electrode piece M2 are each independently formed of at least one film selected from the group consisting of a sputtered film, a vapor-deposited film, and a plated film.

16. A method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 15, wherein the total thickness of the thermoelectric conversion module is 150 to 5,000 μm.

17. A method for manufacturing a thermoelectric conversion module according to any one of claims 1 to 16, 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.

18. The method for manufacturing a thermoelectric conversion module according to claim 17, 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.

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