Thermoelectric conversion module and method for manufacturing the same

Abstract

Provided are: a thinner thermoelectric conversion module that has a substrate that has a thermistor for temperature detection embedded therein; and a production method for the thermoelectric conversion module. The thermoelectric conversion module comprises a first substrate that has a first principal surface and a second principal surface that is on the reverse side from the first principal surface, a second substrate that has a third principal surface and a fourth principal surface that is on the reverse side from the third principal surface, the second substrate being arranged such that the third principal surface is opposite the second principal surface, a first electrode that is provided to the second principal surface, a second electrode that is provided to the third principal surface, a p-type thermoelectric element layer and an n-type thermoelectric element layer that are sandwiched and held between the first electrode and the second electrode and run along the second principal surface and the third principal surface, and a thermistor for temperature detection that is embedded in the first substrate and / or the second substrate. An electrification electrode that electrifies the thermistor is provided to at least one of the first principal surface, the second principal surface, the third principal surface, and the fourth principal surface.

Description

[Technical Field]

[0001] The present invention relates to a thermoelectric conversion module and a method for manufacturing the same. [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 a so-called π-type thermoelectric conversion element 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, and the upper surfaces of the P-type thermoelectric element and the N-type thermoelectric element connected to the electrodes on the opposing substrate. Typically, multiple such basic units are configured within both substrates, electrically connected in series and thermally connected in parallel. Here, Patent Document 1 discloses embedding a temperature sensor in a plate installed on a thermoelectric conversion module. Furthermore, Patent Document 2 discloses providing a temperature sensor inside the thermoelectric conversion module. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2002-305275 [Patent Document 2] International Publication No. 2020 / 071036 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, in the thermoelectric conversion module described in Patent Document 1, the temperature sensor is merely embedded in a plate mounted on top of the thermoelectric conversion module (Peltier module) in order to measure the temperature of the optical device (e.g., semiconductor laser) installed on the plate, and no substantial consideration has been given to making the thermoelectric conversion module, including the temperature sensor, thinner. Furthermore, in the thermoelectric conversion module described in Patent Document 2, a temperature sensor is installed inside the module, but the temperature sensor is installed on the substrate that makes up the module. As a result, in reality, the temperature sensor and its energizing electrodes occupy a lot of area, hindering the high integration of thermoelectric elements.

[0006] This invention has been made in view of the above circumstances, and aims to provide a more integrated and thinner thermoelectric conversion module and a method for manufacturing the same, in which a thermistor for temperature detection is embedded inside the substrate constituting the thermoelectric conversion module. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the inventors have discovered that by embedding a thermistor for temperature detection inside the first substrate and / or the second substrate constituting the thermoelectric conversion module, a thinner thermoelectric conversion module can be obtained that does not require the thermistor to be mounted on the heat absorption side and / or heat dissipation side of a conventional thermoelectric conversion module by bonding with a highly thermally conductive adhesive or solder, and have completed the present invention. In other words, the present invention provides the following [1] to [7]. [1] A thermoelectric conversion module comprising: a first substrate having a first main surface and a second main surface opposite to the first main surface; a second substrate having a third main surface and a fourth main surface opposite to the third main surface, arranged such that the second main surface and the third main surface face each other; a first electrode provided on the second main surface; a second electrode provided on the third main surface; a P-type thermoelectric element layer and an N-type thermoelectric element layer sandwiched between the first electrode and the second electrode and arranged along the second main surface and the third main surface; and a thermistor for temperature detection embedded inside the first substrate and / or inside the second substrate, wherein a current-carrying electrode for supplying current to the thermistor is provided on at least one of the first main surface, the second main surface, the third main surface and the fourth main surface. [2] The thermoelectric conversion module according to [1], further comprising a first heat dissipation layer on the first main surface of the first substrate and a second heat dissipation layer on the fourth main surface of the second substrate. [3] The thermoelectric conversion module according to [1] or [2] above, wherein the current-carrying electrodes are arranged on the first main surface of the first substrate or the fourth main surface of the second substrate and provided as a pair of spaced-apart electrodes. [4] The thermoelectric conversion module according to [1] or [2] above, wherein the contact between the thermistor and the energizing electrode is performed along the thickness direction of the first substrate or the second substrate. [5] The thermoelectric conversion module according to [1] or [2] above, wherein the first substrate and the second substrate are made of insulating material. [6]A first substrate having a first main surface and a second main surface opposite to the first main surface, a third main surface, and a fourth main surface opposite to the third main surface, and a second substrate disposed such that the second main surface and the third main surface face each other, a first electrode provided on the second main surface, a second electrode provided on the third main surface, a P-type thermoelectric element layer and an N-type thermoelectric element layer sandwiched between the first electrode and the second electrode and arranged along the second main surface and the third main surface, and a thermistor for temperature detection embedded inside the first substrate and / or inside the second substrate. A thermoelectric conversion module in which a current-carrying electrode for energizing the thermistor is disposed on at least one of the first main surface, the second main surface, the third main surface, and the fourth main surface. Using the second substrate having the second electrode provided on the third main surface, step M of electrically connecting the second electrode onto the P-type thermoelectric element layer and the N-type thermoelectric element layer on the first electrode provided on the second main surface of the first substrate, or using the first substrate having the first electrode provided on the second main surface, step N of electrically connecting the first electrode onto the P-type thermoelectric element layer and the N-type thermoelectric element layer on the second electrode provided on the third main surface of the second substrate. A method for manufacturing a thermoelectric conversion module including [7]The method for manufacturing a thermoelectric conversion module according to [6] above, wherein the step M or the step N includes the following steps (S-1) to (S-3). Step (S-1): A step of providing through holes in the first substrate and / or the second substrate Step (S-2): A step of embedding the thermistor in the through holes Step (S-3): A step of providing a current-carrying electrode for connecting the thermistor on the first substrate and / or the second substrate

Advantages of the Invention

[0008] According to the present invention, it is possible to provide a higher-integration and thinner thermoelectric conversion module in which a thermistor for temperature detection is embedded inside a substrate constituting the thermoelectric conversion module, and a method for manufacturing the same.

Brief Description of the Drawings

[0009] [Figure 1] It is a cross-sectional configuration diagram showing a first embodiment of a thermoelectric conversion module of the present invention. [Figure 2] It is a cross-sectional configuration diagram showing a second embodiment of a thermoelectric conversion module of the present invention. [Figure 3] It is an explanatory diagram showing an example of steps according to a method for manufacturing a thermoelectric conversion module of the present invention in the order of steps.

Embodiments for Carrying Out the Invention

[0010] [Thermoelectric Conversion Module] The thermoelectric conversion module of the present invention includes a first substrate having a first main surface and a second main surface on the opposite side of the first main surface, a third main surface and a fourth main surface on the opposite side of the third main surface, and the second substrate is arranged such that the second main surface and the third main surface face each other, a first electrode provided on the second main surface, a second electrode provided on the third main surface, a P-type thermoelectric element layer and an N-type thermoelectric element layer sandwiched between the first electrode and the second electrode and arranged along the second main surface and the third main surface, and a thermistor for temperature detection embedded inside the first substrate and / or inside the second substrate, and is characterized in that a current-carrying electrode for supplying current to the thermistor is arranged on at least one of the first main surface, the second main surface, the third main surface, and the fourth main surface. In the thermoelectric conversion module of the present invention, by embedding a thermistor for temperature detection inside the first substrate and / or inside the second substrate constituting the thermoelectric conversion module, a thinner thermoelectric conversion module can be realized without mounting the thermistor on the heat absorption side and / or the heat dissipation side of the thermoelectric conversion module by joining using, for example, a highly thermally conductive adhesive or solder. Also, since a current-carrying electrode for supplying current to the thermistor can be arranged on at least one of the first main surface, the second main surface, the third main surface, and the fourth main surface above and / or below the thermistor embedded inside the substrate, for example, compared to the case where the thermistor is mounted on the substrate, the wiring length from the terminal electrodes at both ends of the thermistor to the current-carrying electrode can be shortened, and the area of the current-carrying electrode can be reduced.

[0011] Figure 1 is a cross-sectional view showing a first embodiment of the thermoelectric conversion module of the present invention, and the thermoelectric conversion module 11 comprises a first substrate 1 having a first main surface 1a and a second main surface 1b opposite to the first main surface 1a, a second substrate 2 having a third main surface 2a and a fourth main surface 2b opposite to the third main surface 2a, and arranged so that the second main surface 1b and the third main surface 2a face each other, a first electrode 3 provided on the second main surface 1b, a second electrode 4 provided on the third main surface 2a, and the first electrode 3 and the second electrode The device comprises a P-type thermoelectric element layer 6p and an N-type thermoelectric element layer 6n, which are sandwiched between electrodes 4 and arranged along the second main surface 1b and the third main surface 2a, and a thermistor 7, which has terminal electrodes 7a and 7b for temperature detection, embedded inside the second substrate 2. Spaced current-carrying electrodes 8v and 8w for supplying current to the thermistor 7 are located on the fourth main surface 2b, and spaced current-carrying electrodes 8x and 8y for supplying current to the thermistor 7 are located on the third main surface 2a. The upper surfaces of the P-type thermoelectric element layer 6p and the N-type thermoelectric element layer 6n are joined to the second electrode 4 via a solder layer 5u, and the lower surfaces of the P-type thermoelectric element layer 6p and the N-type thermoelectric element layer 6n are joined to the first electrode 3 via a solder layer 5d. In this first embodiment, since the thermistor 7 for temperature detection is embedded inside the second substrate 2, it is not necessary to join the thermistor to the fourth main surface 2b (for example, the heat absorption side) of the thermoelectric conversion module 11 using a high thermal conductivity adhesive or solder. Furthermore, since the current-carrying electrodes that supply current to the thermistor can be positioned directly above and below the thermistor body embedded in the substrate, the wiring length from the terminal electrodes at both ends of the thermistor to the current-carrying electrodes can be shortened, and the area of ​​the current-carrying electrodes can be reduced. The substrate in which the thermistor 7 is embedded can be used on either the heat-generating or heat-absorbing side, but it is preferable to position it on the side that controls the temperature of the object (for example, the heat-absorbing side). This makes it possible to sensitively detect heat conduction from the object and perform a fast-responding, fine-grained heat absorption and heating action on the object.

[0012] Figure 2 is a cross-sectional view showing a second embodiment of the thermoelectric conversion module of the present invention, wherein the thermoelectric conversion module 12 has a configuration in which a heat dissipation layer 9a is further provided on the first main surface 1a and a heat dissipation layer 9b is further provided on the fourth main surface 2b, compared to the configuration in Figure 1. In this embodiment, as is the case with the first embodiment, the thermistor 7 for temperature detection is embedded inside the second substrate 2. Therefore, it is not necessary to join the thermistor to the fourth main surface 2b (for example, the heat absorption side) of the thermoelectric conversion module 11 using a high thermal conductivity adhesive or solder. Furthermore, since the current-carrying electrodes that supply power to the thermistor can be positioned directly above and below the thermistor body embedded inside the circuit board, the wiring length from the terminal electrodes at both ends of the thermistor to the current-carrying electrodes can be shortened, and the area of ​​the current-carrying electrodes can be reduced.

[0013] <Circuit board> The thermoelectric conversion module of the present invention includes a first substrate and a second substrate. A thermistor for temperature detection is provided inside the first substrate and / or the second substrate. The first substrate and the second substrate also function as supports for the P-type thermoelectric element layer and the N-type thermoelectric element layer. The first and second substrates used in the present invention are preferably made of an insulating material. Examples of insulating materials include known substrates such as glass substrates, ceramic substrates, and resin substrates. Alternatively, lead frames, CCL (Copper Clad Laminate), etc., may be used.

[0014] Examples of ceramic substrates include materials whose main components are aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicon carbide, etc. (at least 50% by mass in the ceramic). In addition to the above main components, rare earth compounds, for example, can also be added.

[0015] As a resin substrate, a heat-resistant resin substrate (film) is preferred from the viewpoint of being easy to process, having excellent flexibility, and having high heat resistance and dimensional stability. The heat-resistant resin substrate (film) has sufficient heat resistance to maintain its shape even in high-temperature environments. Specifically, the melting point of the heat-resistant resin substrate (film) is above 130°C or it has no melting point, and the thermal shrinkage rate of the heat-resistant film when heated at 130°C for 2 hours is -1 to +1%. More preferably, the melting point of the heat-resistant resin substrate (film) is 140°C or higher or it has no melting point, and particularly preferably it is 200°C or higher or it has no melting point. By using such a heat-resistant substrate (film), it is possible to manufacture thermoelectric conversion modules with excellent dimensional accuracy even after undergoing high-temperature manufacturing processes, such as bonding the thermoelectric element layer and electrodes. Here, the thermal shrinkage rate is defined as follows. Heat shrinkage rate (%) = {(Area of ​​heat-resistant film before processing) - (Area of ​​heat-resistant film after processing)} / Area of ​​heat-resistant film before processing × 100 Examples of heat-resistant resin substrates (films) include polyester film, polycarbonate film, polyphenylene sulfide film, cycloolefin resin film, polyimide resin film, film obtained by casting and curing UV-curing resin, and laminates of two or more of these. Cycloolefin resin film and polyimide resin film may be uniaxially oriented or biaxially oriented.

[0016] The thickness of the first substrate and the second substrate are, independently of the viewpoint of the thickness of the thermistor for temperature detection, heat resistance, and dimensional stability, preferably 10 to 3000 μm, more preferably 100 to 1000 μm, and particularly preferably 150 to 600 μm.

[0017] <Thermistor> In this invention, a thermistor is used to detect the temperature of the first substrate and the second substrate. Furthermore, since it is embedded inside the first substrate and the second substrate, a thermistor thinner than the thickness of the first substrate and the second substrate is used. As for the thermistor, there are no particular restrictions as long as it is thinner than the thickness of the first and second substrates, and NTC (Negative Temperature Coefficient) thermistors with a negative temperature coefficient, PTC (Positive Temperature Coefficient) thermistors with a positive temperature coefficient, etc., can be used. Among these, NTC thermistors are preferable because their resistance changes uniformly and smoothly over a wide temperature range, making them suitable for applications that detect and control temperature as a value. Furthermore, chip-type NTC thermistors are even more preferable from the viewpoint of enabling miniaturization, weight reduction, and thinning. Materials used to construct an NTC thermistor include ceramics produced by firing oxides containing manganese (Mn), nickel (Ni), cobalt (Co), and other elements.

[0018] Examples of commercially available thin NTC thermistors include the following: • NTC thermistor (manufactured by Mitsubishi Materials Corporation, model number: "VH05-6D103F", 0.21mm (length) x 0.21mm (width) x 0.20mm (thickness)) • NTC thermistor (Mitsubishi Materials Corporation, Model: "TZ05-3H103D", 1.0mm (length) x 0.50mm (width) x 0.55mm (thickness)) • NTC thermistor (Murata Manufacturing Co., Ltd., Model: "NCP02WF104F05RH", 0.4mm (length) x 0.2mm (width) x 0.2mm (thickness))

[0019] <Electrified electrodes> The thermoelectric conversion module of the present invention includes a current-carrying electrode that supplies current to a thermistor. The current-carrying electrodes are preferably arranged on the first main surface of the first substrate or the fourth main surface of the second substrate, and are provided as a pair of spaced-apart electrodes. The current-carrying electrodes are wired to terminal electrodes provided at both ends of a thermistor that is embedded inside the first and / or second substrate. The contact between the thermistor and the energizing electrode is preferably performed along the thickness direction of the first or second substrate. In Figure 1, for example, the current-carrying electrodes 8v and 8w are provided spaced apart from each other on the fourth main surface 2b and are simultaneously wired to the terminal electrodes 7a and 7b provided at both ends of the thermistor 7 embedded inside the second substrate, for example, by electroplating. Similarly, the current-carrying electrodes 8x and 8y are provided spaced apart from each other on the third main surface 2a and are simultaneously wired to the terminal electrodes 7a and 7b provided at both ends of the thermistor 7 embedded inside the second substrate, for example, by electroplating. In this way, by providing the current-carrying electrodes on the substrate surface above and / or below the thermistor, the wiring length can be shortened compared to when the thermistor is mounted on the substrate. Furthermore, by wiring to the terminal electrodes, a four-terminal connection, a wiring method used to measure the resistance value of a thermistor for accurate temperature detection, can be easily implemented, enabling highly accurate temperature control. There are no particular restrictions on the metal material used for the conductive electrodes, and examples include copper, gold, nickel, rhodium, platinum, palladium, or alloys thereof. Among these, copper is particularly preferred because it has low electrical resistance, low material cost, and can be easily wired using plating or vapor deposition methods.

[0020] The thickness of the current-carrying electrode is not particularly limited as long as the resistance change of the thermistor can be detected accurately, but from the viewpoint of a thin thermoelectric conversion module, it is preferably 3 to 500 μm, more preferably 5 to 300 μm, and particularly preferably 10 to 100 μm.

[0021] <Thermoelectric element layer> The thermoelectric element layer used in the present invention is not particularly limited and may be made of a bulk 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.

[0022] (Thermoelectric semiconductor materials) The thermoelectric semiconductor material constituting the thermoelectric element layer 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, and 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.

[0023] The thermoelectric semiconductor material constituting the P-type thermoelectric element layer and N-type thermoelectric element layer used in the present invention 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.

[0024] The content of thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass, more preferably 70 to 95% by mass. When the content of 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, resulting in a film that exhibits high thermoelectric performance, as well as sufficient film strength and flexibility, which is preferable.

[0025] Furthermore, it is preferable that the thermoelectric semiconductor particles are annealed (hereinafter sometimes referred to as "annealing treatment A"). By performing annealing treatment A, the crystallinity of the thermoelectric semiconductor particles is improved, and the surface oxide film of the thermoelectric semiconductor particles is removed, thereby increasing the Seebeck coefficient (absolute value of the Peltier coefficient) of the thermoelectric element layer and further improving the thermoelectric figure of merit.

[0026] (resin) The resin used in the thermoelectric semiconductor composition 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.

[0027] 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.

[0028] 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.

[0029] The content of the heat-resistant resin in the thermoelectric semiconductor composition is preferably 0.1 to 40% by mass, 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.

[0030] The binder resin refers to a resin that decomposes by 90% or more by mass at temperatures above the annealing temperature, and is particularly preferred to be a resin that decomposes by 99% or more by mass. If a resin that decomposes by 90% or more by mass at temperatures above the annealing temperature is used as the binder resin, that is, a resin that decomposes at a lower temperature than the heat-resistant resin mentioned above, 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 element layer can be reduced, and the packing efficiency 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.

[0032] The binder resin is appropriately selected according to the annealing temperature of the thermoelectric semiconductor material in the annealing process. It is preferable to perform the annealing process at a temperature above the final decomposition temperature of the binder resin. 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 220 to 460°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 10% by mass.

[0035] (Ionic liquid) Ionic liquids that may be included in thermoelectric semiconductor compositions are molten salts composed of a combination of cations and anions, and are salts that can exist as a liquid in any temperature range between -50°C and 400°C. Ionic liquids have characteristics such as extremely low vapor pressure and nonvolatility, excellent thermal and electrochemical stability, low viscosity, and high ionic conductivity, and can effectively suppress the reduction of electrical conductivity between thermoelectric semiconductor materials when used as a conductivity enhancer. In addition, ionic liquids exhibit high polarity based on their aprotic ionic structure and have excellent compatibility with heat-resistant resins, which can make the electrical conductivity of thermoelectric conversion materials uniform.

[0036] Known or commercially available ionic liquids 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<00所00017>, (CF3SO2)3C - , AsF6 - , SbF6 - , NbF6 - , TaF6 - , F(HF) n - , (CN)2N - , C4F9SO3 - , (C2F5SO2)2N - , C3F7COO[[ID=5所]] - , (CF3SO2)(CF3CO)N - and the like composed of anion components.

[0037] Further, the above ionic liquid preferably has a decomposition temperature of 300 °C or higher. If the decomposition temperature is within the above range, as described later, even when a thin film composed of a thermoelectric semiconductor composition is annealed, the effect as a conductive auxiliary agent can be maintained.

[0038] The content of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 1.0 to 20% by mass. When the ionic liquid content is within the above range, the decrease in electrical conductivity is effectively suppressed, and a film with high thermoelectric performance can be obtained.

[0039] (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.

[0040] 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. 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.

[0041] There are no particular limitations on the method for preparing the thermoelectric semiconductor composition. For example, the thermoelectric semiconductor particles, the ionic liquid, the inorganic ionic compound (when used in combination with the ionic liquid), the heat-resistant resin, and any other additives as needed, as well as a solvent, may be mixed and dispersed using known methods such as an ultrasonic homogenizer, spiral mixer, planetary mixer, disperser, or hybrid mixer to prepare the thermoelectric semiconductor composition. Examples of the aforementioned solvents include toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve. These solvents may be used individually or in mixtures of two or more. The solid content concentration of the thermoelectric semiconductor composition is not particularly limited, as long as the composition has a viscosity suitable for coating.

[0042] The thermoelectric element layer made of the thermoelectric semiconductor composition is not particularly limited, but can be obtained by coating the thermoelectric semiconductor composition onto a substrate to obtain a coating film and then drying it. Known methods for applying a thermoelectric semiconductor composition to obtain a thermoelectric element layer include 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 and slot die coating methods, which allow for easy pattern formation using a screen plate with the desired pattern, are preferred. Next, the obtained coating film is dried to form the thermoelectric element layer. 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.

[0043] There are no particular restrictions on the thickness of the thermoelectric element layer, 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.

[0044] The thermoelectric element layer, which is a thin film made of a thermoelectric semiconductor composition, is preferably subjected to further annealing (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 thin film can be grown crystal-like, thereby further improving the thermoelectric performance. Annealing treatment 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 rates, and is performed at 100 to 500°C for several minutes to several tens of hours, depending on the heat resistance temperature of the resin and ionic compound used. Furthermore, in annealing treatment B, the thermoelectric semiconductor composition may be pressed to improve the density of the thermoelectric semiconductor composition.

[0045] <Electrode> The thermoelectric conversion module of the present invention includes a first electrode and a second electrode (hereinafter sometimes simply referred to as "electrodes"). The electrode is preferably formed of at least one film selected from the group consisting of a vapor-deposited film, a plated film, a conductive composition, and a metal foil. The metal material used for the electrodes is not particularly limited, but examples include copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, solder, or alloys containing any of these metals.

[0046] Methods for forming electrodes include a method in which an electrode without a pattern is provided and then processed into a predetermined pattern shape by a known physical or chemical treatment, mainly photolithography, or a combination thereof; or a method in which a conductive paste made of a conductive composition containing the aforementioned metal material is used to directly form the electrode pattern by screen printing, inkjet printing, or the like. Methods for forming electrodes without a pattern include PVD (Physical Vapor Deposition) such as vacuum deposition, sputtering, and ion plating; dry processes such as CVD (Chemical Vapor Deposition) such as thermal CVD and atomic layer deposition (ALD); wet processes such as various coatings and electrodeposition methods such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade coating; silver halide method; electrolytic plating; electroless plating; and metal foil lamination, which are selected appropriately depending on the electrode material. For metal foil lamination, solder material may be used to bond it with thermoelectric materials, etc. The electrodes used in this invention require high conductivity and high thermal conductivity to maintain thermoelectric performance; therefore, it is more preferable to use electrodes formed by plating or vacuum deposition. Vacuum deposition methods such as vacuum evaporation and sputtering, as well as electroplating and electroless plating, are preferred because they can easily achieve high conductivity and high thermal conductivity. Depending on the required dimensions and dimensional accuracy of the formed pattern, a hard mask such as a metal mask can be used to easily form the pattern.

[0047] 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. If the thickness of the electrode layer is within the above range, the electrical conductivity will be high and the resistance low, and sufficient strength as an electrode can be obtained.

[0048] <Solder layer> In the thermoelectric conversion module of the present invention, a solder layer made of solder material may be used to join the electrodes with the P-type thermoelectric element layer and the N-type thermoelectric element layer. While solder materials are not particularly limited, examples of solder materials with relatively low melting points from the viewpoint of being lead-free and / or cadmium-free include Sn-In based In52Sn48 [melting temperature: solidus temperature (approx. 119°C), liquidus temperature (approx. 119°C)], Sn-Bi based Bi58Sn42 [melting temperature: solidus temperature (approx. 139°C), liquidus temperature (approx. 139°C)], Sn-Zn-Bi based Sn89Zn8Bi3 [melting temperature: solidus temperature (approx. 190°C), liquidus temperature (approx. 196°C)], and Sn-Zn based Sn91Zn9 [melting temperature: solidus temperature (approx. 198°C), liquidus temperature (approx. 198°C)]. Furthermore, as solder materials with relatively high melting points, from the viewpoint of being lead-free and / or cadmium-free, for example, Sn-Sb type Sn95Sb5 [Melting temperature: Solidus temperature (approx. 238°C), Liquidus temperature (approx. 241°C)], Sn-Cu type Sn99.3Cu0.7 [Melting temperature: Solidus temperature (approx. 227°C), Liquidus temperature (approx. 228°C)], Sn-Cu-Ag type Sn99Cu0.7Ag0.3 [Melting temperature: Solidus temperature (approx. 217°C), Liquidus temperature (approx. 226°C)], Sn-Ag type Examples include Sn97Ag3 [Melting temperature: Solidus temperature (approx. 221°C), Liquidus temperature (approx. 222°C)], Sn-Ag-Cu type Sn96.5Ag3Cu0.5 [Melting temperature: Solidus temperature (approx. 217°C), Liquidus temperature (approx. 219°C)], Sn95.5Ag4Cu0.5 [Melting temperature: Solidus temperature (approx. 217°C), Liquidus temperature (approx. 219°C)], and Sn-Ag-Cu type Sn95.8Ag3.5Cu0.7 [Melting temperature: Solidus temperature (approx. 217°C), Liquidus temperature (approx. 217°C)]. Considering the heat resistance of the substrate, electrodes, etc. that make up the thermoelectric conversion module, the above solder material can be used as appropriate.

[0049] The thickness of the solder layer containing the solder material (after heating and cooling) is preferably 10 to 200 μm, more preferably 30 to 130 μm, and particularly preferably 40 to 120 μm. A solder layer thickness within this range facilitates bonding with the thermoelectric element layer and electrodes.

[0050] Methods for applying solder material to a substrate include known methods such as stencil printing, screen printing, and dispensing. The heating temperature varies depending on the solder material and substrate used, but is usually 100-280°C for 0.5-20 minutes.

[0051] Examples of commercially available soldering materials include the following: For example, 42Sn / 58Bi alloy [manufactured by Tamura Corporation, product name: SAM10-401-27, melting temperature: solidus temperature (approx. 139°C), liquidus temperature (approx. 139°C)], 96.5Sn3.0Ag0.5Cu alloy [manufactured by Nihon Handa Co., Ltd., product name: PF305-153TO, melting temperature: solidus temperature (approx. 217°C), liquidus temperature (approx. 219°C)], Sn / 57Bi alloy [manufactured by Nihon Handa Co., Ltd., product name: PF141-LT7H0, melting temperature: solidus temperature (approx. 137°C)], etc. can be used.

[0052] <Heat dissipation layer> A heat dissipation layer may be used in the thermoelectric conversion module of the present invention. The heat dissipation layer is disposed on the first substrate and / or second substrate of the thermoelectric conversion module. It is preferable that the first substrate includes a first heat dissipation layer on its first main surface and the second substrate includes a second heat dissipation layer on its fourth main surface. For example, in Figure 2, the first heat dissipation layer 9a and the second heat dissipation layer 9b are provided on the first main surface 1a and the fourth main surface 2b in this order. The first heat dissipation layer and the second heat dissipation layer can be, independently, a metal material, a ceramic material, or a mixture of these materials and a resin. Among these, it is preferable that at least one is selected from the metal material and the ceramic material. Examples of metallic materials include single metals such as gold, silver, copper, nickel, tin, iron, chromium, platinum, palladium, rhodium, iridium, ruthenium, osmium, indium, zinc, molybdenum, manganese, titanium, and aluminum, as well as alloys containing two or more metals such as stainless steel and brass. Examples of ceramic materials include barium titanate, aluminum nitride, boron nitride, aluminum oxide, silicon carbide, and silicon nitride. Among these, metal materials are preferred from the viewpoint of high thermal conductivity, workability, and flexibility. Among metal materials, copper (including oxygen-free copper) and stainless steel are preferred, with copper being more preferred because it has high thermal conductivity and is even easier to work with. The resin used as a mixture with metal or ceramic materials is not particularly limited, but examples include polyimide, polyamide, polyamide-imide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, nylon, acrylic resin, cycloolefin polymer, aromatic polymer, etc.

[0053] Herein, typical examples of metal materials with high thermal conductivity used in the present invention are shown below. (Oxygen-free copper) Oxygen-free copper (OFC) generally refers to high-purity copper with a purity of 99.95% (3N) or higher, free of oxides. The Japanese Industrial Standards (JIS) specify oxygen-free copper (JIS H 3100, C1020) and oxygen-free copper for electron tubes (JIS H 3510, C1011). Stainless steel (JIS standard) SUS304: 18Cr-8Ni (contains 18% Cr and 8% Ni) SUS316:18Cr-12Ni (Stainless steel containing 18% Cr, 12% Ni, and molybdenum (Mo))

[0054] The method for forming the heat dissipation layer used in the present invention is not particularly limited, but examples include processing a sheet-like heat dissipation layer to a predetermined size, or processing it into a predetermined pattern shape by a known physical or chemical treatment mainly using photolithography, or by using a combination of the above.

[0055] The thermal conductivity of the heat dissipation layer is preferably 15 to 500 W / (m·K), more preferably 100 to 450 W / (m·K), and even more preferably 250 to 420 W / (m·K). When the thermal conductivity of the heat dissipation layer is within the above range, a temperature difference can be efficiently created.

[0056] The thickness of the heat dissipation layer is preferably 15 to 550 μm, and more preferably 70 to 510 μm. When the thickness of the heat dissipation layer is within this range, for example, a temperature difference can be efficiently applied in the thickness direction of the P-type thermoelectric element layer and the N-type thermoelectric element layer.

[0057] The thermoelectric conversion module of the present invention can be made thinner because the thermistor for temperature detection is embedded inside the substrate that makes up the thermoelectric conversion module.

[0058] [Manufacturing method for thermoelectric conversion modules] A method for manufacturing a thermoelectric conversion module of the present invention comprises: a first substrate having a first main surface and a second main surface opposite to the first main surface; a second substrate having a third main surface and a fourth main surface opposite to the third main surface, arranged such that the second main surface and the third main surface face each other; a first electrode provided on the second main surface; a second electrode provided on the third main surface; a P-type thermoelectric element layer and an N-type thermoelectric element layer sandwiched between the first electrode and the second electrode and arranged along the second main surface and the third main surface; and a thermistor for temperature detection embedded inside the first substrate and / or inside the second substrate, wherein the current-carrying electrodes for supplying current to the thermistor are located on at least the first main surface, the second main surface, the third main surface and the A thermoelectric conversion module disposed on any of the fourth main surfaces, preferably comprising the steps of: using a second substrate having the second electrode provided on the third main surface and having the thermistor for temperature detection embedded inside, and electrically connecting the second electrode to the P-type thermoelectric element layer and the N-type thermoelectric element layer on the first electrode provided on the second main surface of the first substrate; or preferably using a first substrate having the first electrode provided on the second main surface and having the thermistor for temperature detection embedded inside, and electrically connecting the first electrode to the P-type thermoelectric element layer and the N-type thermoelectric element layer on the second electrode provided on the third main surface of the second substrate. The manufacturing method of the thermoelectric conversion module of the present invention will be described below with reference to the figures.

[0059] Figure 3 is an explanatory diagram showing an example of the process according to the manufacturing method of the thermoelectric conversion module of the present invention, in order of process: (a) is a cross-sectional view after a through-hole 22 is formed inside the substrate 21; (b) is a cross-sectional view after an adhesive tape 23 is formed on the lower surface of the substrate 21; (c) is a cross-sectional view after a thermistor 7 having terminal electrodes 7a and terminal electrodes 7b at both ends is provided in the through-hole 22 of the substrate 21; (d) is a cross-sectional view after an insulating material layer 24 is provided on the through-hole 22 and the upper surface of the substrate 21; (e) is a cross-sectional view after the adhesive tape 23 is peeled off from the lower surface of the substrate 21; and (f) is a cross-sectional view after an insulating material layer 25 is provided on the lower surface of the substrate 21. (g) is a cross-sectional view after forming a hole 26u from the upper surface of the insulating material layer 24 to the upper surfaces of the terminal electrodes 7a and 7b of the thermistor 7, and a hole 26d from the lower surface of the insulating material layer 25 to the lower surfaces of the terminal electrodes 7a and 7b of the thermistor 7. (h) is a cross-sectional view after forming copper electrodes 28v, 28w, 28x, and 28y by forming a metal material layer, for example, preferably a copper layer, inside the holes 26u and 26d formed in (g), and on the surfaces of the insulating material layer 24 and the insulating material layer 25, and simultaneously forming a second heat dissipation layer 27 on the upper surface of the insulating material layer 24 and a second electrode 29 on the lower surface of the insulating material layer 25. Note that the current-carrying electrodes may be arranged only on one side of the substrate 21, such as current-carrying electrodes 28v and 28w, or on the other side of the substrate 21, such as current-carrying electrodes 28x and 28y. Next, (i) is a cross-sectional view of the thermoelectric conversion module after the second electrode 29 provided on the thermistor embedded substrate 30 obtained in (h) is electrically connected to the P-type thermoelectric element layer 36p and N-type thermoelectric element layer 36n on the first electrode 33 provided on the second main surface 31b of the first substrate 31, which has a first heat dissipation layer 37 on its first main surface 31a. Note that 32a is the third main surface, 32b is the fourth main surface, and 35u and 35d are solder layers.

[0060] Process M or process N preferably includes the following processes (S-1) to (S-3). Process (S-1): Process of creating through-holes in the first substrate and / or the second substrate. Process (S-2): Process of embedding thermistors in through-holes Step (S-3): Step of providing energizing electrodes to which the thermistor is connected on the first substrate and / or the second substrate.

[0061] • Process (S-1) Through-hole formation process Step (S-1) is a step of forming through-holes inside the substrates that constitute the thermoelectric conversion module, and is a step of forming through-holes in the first substrate and / or the second substrate. The method for forming the through-hole can be any known method and is not particularly limited. Examples include laser processing and drilling.

[0062] • Process (S-2) <Thermistor embedding process> Step (S-2) is the process of embedding a thermistor inside the substrate that constitutes the thermoelectric conversion module, and is the process of placing the thermistor in the through-holes of the first substrate and / or second substrate formed in step (S-1). The method for arranging the thermistor is not particularly limited and any known method can be used. For example, one method involves laminating adhesive tape to the underside of a substrate, temporarily fixing the substrate in place, then placing the thermistor on the adhesive tape, and then sealing the entire through-hole containing the thermistor by filling it with an insulating material such as resin.

[0063] ·Process (S-3) <Electrifying electrode formation process> Step (S-3) is a step in which current-carrying electrodes are formed on the surface of the substrate constituting the thermoelectric conversion module to supply current to the thermistor. This step involves forming current-carrying electrodes on the surface of the first substrate and / or the second substrate via the wiring layer from the terminal electrodes at both ends of the thermistor in the through-holes of the first substrate and / or the second substrate sealed in step (S-2). Known methods can be used to form the current-carrying electrodes, and are not particularly limited. For example, a method can be used in which holes are made from the surface of the first substrate and / or the second substrate to the terminal electrode portions at both ends of the thermistor by laser processing, and the aforementioned metal material is deposited in the holes and on the surface of the first substrate and / or the second substrate by, for example, plating or vapor deposition, and then the metal material layer formed on the surface is formed into a predetermined electrode pattern by photolithography or the like.

[0064] Process M or process N further preferably includes any of processes (S-4) to (S-6).

[0065] ·Process (S-4) <Electrode formation process> Step (S-4) is a step in which electrodes constituting the thermoelectric conversion module are formed. Specifically, this involves the steps of providing a second electrode on the third main surface of the second substrate and providing a first electrode on the second main surface of the first substrate. The electrodes can be formed on the second main surface of the first substrate and the third main surface of the second substrate using the aforementioned forming method with the metal material used for the electrodes. Furthermore, from the viewpoint of bonding with the thermoelectric element layer, it is preferable that step (S-4) includes a step of forming a solder layer as a bonding layer on the obtained electrode. The solder layer can be formed on the first electrode and the second electrode using the solder material described above and the formation method described above. The solder layer may also be formed on the P-type thermoelectric element layer and the N-type thermoelectric element layer.

[0066] ·Process (S-5) <Thermoelectric element layer formation process> Step (S-5) is a step of forming thermoelectric element layers that constitute a thermoelectric conversion module. Specifically, this is a step of providing a P-type thermoelectric element layer and an N-type thermoelectric element layer on the first electrode on the second main surface of the first substrate, or a step of providing a P-type thermoelectric element layer and an N-type thermoelectric element layer on the second electrode on the third main surface of the second substrate. A method for forming a P-type thermoelectric element layer and an N-type thermoelectric element layer can be used, for example, by using the thermoelectric semiconductor composition described above and forming them on the first electrode on the second main surface of the first substrate, or on the second electrode on the third main surface of the second substrate, using the formation method described above.

[0067] • Process (S-6) <Thermoelectric Conversion Module Assembly Process> Step (S-6) is a step of assembling a thermoelectric conversion module by electrically connecting the second electrode on the third main surface of the second substrate obtained in step (S-4) to the P-type thermoelectric element layer and the N-type thermoelectric element layer on the first electrode on the second main surface of the first substrate obtained in step (S-5), or a step of assembling a thermoelectric conversion module by electrically connecting the first electrode on the second main surface of the first substrate obtained in step (S-4) to the P-type thermoelectric element layer and the N-type thermoelectric element layer on the second electrode on the third main surface of the second substrate obtained in step (S-5). The method for electrically connecting the electrodes to the surfaces of the P-type thermoelectric element layer and the N-type thermoelectric element layer to assemble the thermoelectric conversion module can be carried out by known methods.

[0068] The process may further include a heat dissipation layer formation step after step (S-3) and / or after step (S-6). The heat dissipation layer formation process is, for example, the process of providing a second heat dissipation layer on the fourth main surface of a second substrate constituting a thermoelectric conversion module and / or a first heat dissipation layer on the first main surface of a first substrate. The formation of the heat dissipation layer is not particularly limited, but as mentioned above, examples include processing a sheet-like heat dissipation layer to a predetermined size, or processing it into a predetermined pattern shape by a known physical or chemical treatment, mainly using photolithography, or by using a combination of these methods.

[0069] According to the manufacturing method of the present invention, a thin thermoelectric conversion module can be manufactured in which a thermistor for temperature detection is embedded inside the substrate constituting the thermoelectric conversion module. [Industrial applicability]

[0070] 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 and smaller size. [Explanation of symbols]

[0071] 1,31: First board 1a, 31a: 1st main surface 1b, 31b: 2nd principal surface 2,32: Second board 2a, 32a: 3rd principal surface 2b, 32b: 4th principal surface 3,33: 1st electrode 4,29:Second electrode 5u, 5d, 35u, 35d: Solder layer 6p, 36p: P-type thermoelectric element layer 6n,36n: N-type thermoelectric element layer 7: Thermistor 7a: Terminal electrode 7b: Terminal electrode 8v, 8w: Current-carrying electrode (4th principal surface) 8x,8y: Current-carrying electrode (3rd principal surface) 9a,37: 1st heat dissipation layer 9b,27: Second heat dissipation layer 11,12: Thermoelectric conversion module 21: Circuit board 22: Through-hole 23: Adhesive tape 24,25: Insulating material layer 26u,26d: Hall 28v, 28w: Current-carrying electrode 28x,28y: Current-carrying electrode 30: Thermistor embedded substrate

Claims

1. A first substrate having a first main surface and a second main surface opposite to the first main surface, A second substrate having a third main surface and a fourth main surface opposite to the third main surface, and arranged such that the second main surface and the third main surface face each other, The first electrode provided on the second main surface, The second electrode provided on the third main surface, A P-type thermoelectric element layer and an N-type thermoelectric element layer are sandwiched between the first electrode and the second electrode and arranged along the second main surface and the third main surface, The device comprises a thermistor for temperature detection embedded inside the first substrate or the second substrate, The first or second substrate, in which the thermistor for temperature detection is embedded, is the side that controls the temperature of the object. The current-carrying electrodes that supply current to the thermistor are arranged on at least one of the first main surface, second main surface, third main surface, and fourth main surface. A thermoelectric conversion module in which the connection between the thermistor and the energizing electrode is made along the thickness direction of the first substrate or the second substrate.

2. The thermoelectric conversion module according to claim 1, further comprising a first heat dissipation layer on the first main surface of the first substrate and a second heat dissipation layer on the fourth main surface of the second substrate.

3. The thermoelectric conversion module according to claim 1 or 2, wherein the current-carrying electrodes are arranged on the first main surface of the first substrate or the fourth main surface of the second substrate and provided as a pair of spaced-apart electrodes.

4. The thermoelectric conversion module according to claim 1 or 2, wherein the first substrate and the second substrate are insulating materials.

5. A first substrate having a first main surface and a second main surface opposite to the first main surface, A second substrate having a third main surface and a fourth main surface opposite to the third main surface, and arranged such that the second main surface and the third main surface face each other, The first electrode provided on the second main surface, The second electrode provided on the third main surface, A P-type thermoelectric element layer and an N-type thermoelectric element layer are sandwiched between the first electrode and the second electrode and arranged along the second main surface and the third main surface, The device comprises a thermistor for temperature detection embedded inside the first substrate or the second substrate, The first or second substrate, in which the thermistor for temperature detection is embedded, is the side that controls the temperature of the object. The current-carrying electrodes that supply current to the thermistor are arranged on at least one of the first main surface, second main surface, third main surface, and fourth main surface. A method for manufacturing a thermoelectric conversion module, wherein the connection between the thermistor and the energizing electrode is made along the thickness direction of the first substrate or the second substrate, A step M is to use the second substrate having the second electrode provided on the third main surface, and electrically connect the second electrode to the P-type thermoelectric element layer and the N-type thermoelectric element layer on the first electrode provided on the second main surface of the first substrate, or A method for manufacturing a thermoelectric conversion module, comprising step N of electrically connecting the first electrode to the P-type thermoelectric element layer and the N-type thermoelectric element layer on the second electrode provided on the third main surface of the second substrate, using the first substrate having the first electrode provided on the second main surface of the second substrate.

6. The method for manufacturing a thermoelectric conversion module according to claim 5, wherein step M or step N includes the following steps (S-1) to (S-3). Step (S-1): Step of providing through holes in the first substrate or the second substrate. Step (S-2): Step of embedding the thermistor in the through-hole. Step (S-3): Step of providing energizing electrodes to which the thermistor is connected on the first substrate and / or the second substrate.

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