WO2022092178A1 - 熱電変換モジュールの製造方法 - Google Patents

熱電変換モジュールの製造方法 Download PDF

Info

Publication number
WO2022092178A1
WO2022092178A1 PCT/JP2021/039751 JP2021039751W WO2022092178A1 WO 2022092178 A1 WO2022092178 A1 WO 2022092178A1 JP 2021039751 W JP2021039751 W JP 2021039751W WO 2022092178 A1 WO2022092178 A1 WO 2022092178A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoelectric conversion
chip
conversion material
type thermoelectric
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/039751
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
佑太 関
邦久 加藤
亘 森田
睦 升本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Priority to JP2022559216A priority Critical patent/JP7770335B2/ja
Priority to CN202180073854.0A priority patent/CN116391458A/zh
Priority to US18/034,430 priority patent/US12114568B2/en
Publication of WO2022092178A1 publication Critical patent/WO2022092178A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/856—Thermoelectric active materials comprising organic compositions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material

Definitions

  • the present invention relates to a method for manufacturing a thermoelectric conversion module.
  • thermoelectric conversion module having a thermoelectric effect such as the Zeebeck effect and the Pelche effect.
  • thermoelectric conversion module As the thermoelectric conversion module, the use of a so-called ⁇ -type thermoelectric conversion element is known.
  • the ⁇ -type thermoelectric conversion element is provided with a pair of electrodes separated from each other on the substrate, for example, the lower surface of the P-type thermoelectric element is provided on one of the electrodes, and the lower surface of the N-type thermoelectric element is provided on the other electrode.
  • the basic unit is a configuration in which the upper surfaces of both types of thermoelectric elements are connected to electrodes on opposite substrates, and usually, the basic units are connected in series in both substrates. Thermally, it is configured to be connected in parallel.
  • Patent Document 1 discloses a thermoelectric conversion module using the above-mentioned ⁇ -type thermoelectric conversion element.
  • thermoelectric conversion module of Patent Document 1 improvement in reliability of the thermoelectric conversion module, such as firmly joining the thermoelectric conversion element and the electrode and preventing diffusion and thermal stress generation, is disclosed.
  • the reduction of the conversion module, the reduction of materials, the improvement of productivity, etc. are not disclosed.
  • the present invention has been made in view of such circumstances, and is a method for manufacturing a thermoelectric conversion module which does not require a support and a solder material and can efficiently manufacture a plurality of thin thermoelectric conversion modules at once.
  • the challenge is to provide.
  • thermoelectric conversion module can be efficiently obtained at once without using a manufacturing method in which chips of thermoelectric conversion materials are mounted one by one on an electrode substrate using a conventional solder material. A method was found and the present invention was completed.
  • thermoelectric conversion module which comprises the following steps (A) to (D).
  • steps (A) to (D) (A) Step of arranging the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material apart on the support (B) The chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material Step (C) Supporting the integrated product obtained in the step (B) above, in which an insulator is filled in between to obtain an integrated product composed of a chip of a P-type thermoelectric conversion material, a chip of an N-type thermoelectric conversion material, and an insulator.
  • Step of peeling from the body In the integrated product after the step of (C), the step of connecting the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material via an electrode [2].
  • step (B') In the integrated product obtained in the step (B), at least the excess portion of the insulator directly in contact with the chip of the P-type thermoelectric conversion material and the region of the upper surface of the chip of the N-type thermoelectric conversion material is removed.
  • Step [3] The method for manufacturing a thermoelectric conversion module according to the above [1] or [2], which comprises the step (E) below after the step (D).
  • (E) Step of laminating an insulating layer on the electrode [4] The method of manufacturing a thermoelectric conversion module according to the above [3], further comprising the following step (F) after the step of (E).
  • thermoelectric conversion module according to the above [5], wherein the insulating resin is selected from a polyimide resin, a silicone resin, a rubber resin, an acrylic resin, an olefin resin, a maleimide resin, and an epoxy resin.
  • Manufacturing method [7] The thermoelectric conversion according to any one of the above [1] to [6], which comprises a fixed layer between the support and the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material. Module manufacturing method. [8] The method for manufacturing a thermoelectric conversion module according to the above [7], wherein the fixed layer is composed of an adhesive layer.
  • thermoelectric conversion module according to any one of the above [1] to [8], wherein the support is selected from glass, plastic and silicon.
  • the thermoelectric semiconductor composition contains a thermoelectric semiconductor material, a heat-resistant resin, and one or both of an ionic liquid and an inorganic ionic compound.
  • thermoelectric conversion module which does not require a support and a solder material and can efficiently manufacture a plurality of thin thermoelectric conversion modules at once.
  • thermoelectric conversion module of this invention It is explanatory drawing which shows an example of the process according to the manufacturing method of the thermoelectric conversion module of this invention in the order of process. It is sectional drawing which shows the embodiment of the thermoelectric conversion module of this invention.
  • thermoelectric conversion module The method for manufacturing a thermoelectric conversion module of the present invention is characterized by including the following steps (A) to (D).
  • Step of peeling from the body (D) In the integrated product after the step of (C), a step of connecting a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material via an electrode.
  • a step of connecting a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material via an electrode In the method of manufacturing a conversion module, for example, a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material are alternately arranged on a support, and the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material are arranged alternately.
  • thermoelectric conversion material By filling an insulator between the chip of the conversion material and the chip of the conversion material, a self-standing integrated product consisting of the chip of the P-type thermoelectric conversion material, the chip of the N-type thermoelectric conversion material and the insulator is formed, and the integrated product after the support is peeled off.
  • electrodes By directly forming the electrodes on the group, a plurality of thin thermoelectric conversion modules that do not require the conventionally used solder materials and supports can be efficiently manufactured at once.
  • each of the steps (A), (B), (C) and (D) will be described in this order as "(A) Chip placement step of thermoelectric conversion material or (A) step". Both “(B) insulator filling step or (B) step”, “(C) support peeling step or (C) step”, “(D) electrode forming step or (D) step” There is something to say. Further, each of the steps (B'), (E) and (F) is performed in this order as “(B') Insulator surplus portion removing step or (B') step", "(E) Insulation. It may also be referred to as a layer forming step, or (E) step, or (F) heat diffusion layer forming step.
  • the "chip of P-type thermoelectric conversion material and chip of N-type thermoelectric conversion material” may be simply referred to as "chip of thermoelectric conversion material”.
  • the "surplus portion of the insulator” or the “surplus portion of the insulator” is used between the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material in the step (B). It means a layer of the insulator extending to the region of the upper surface of the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material when the insulator is filled.
  • FIG. 1 is an explanatory diagram showing an example of a process according to the manufacturing method of the thermoelectric conversion module of the present invention in the order of steps
  • FIG. 1A shows a chip 2p of a P-type thermoelectric conversion material and an N-type thermoelectric conversion on a support 1. It is sectional drawing which shows the aspect after arranging the chip 2n of a material apart from each other, (b) is an insulator 3 between a chip 2p of a P-type thermoelectric conversion material and a chip 2n of an N-type thermoelectric conversion material.
  • FIG. 1 It is a cross-sectional view which shows the aspect after being filled and made into the integrated body 4a which consists of a chip 2p of a P-type thermoelectric conversion material, a chip 2n of an N-type thermoelectric conversion material, and an insulator 3, and (c) is P in (b).
  • (D) is a cross-sectional view showing an embodiment in which the obtained integrated product 4b is peeled off from the support 1.
  • thermoelectric conversion module After the electrodes 5 are formed on the upper and lower surfaces of the chip 2p of the P-type thermoelectric conversion material and the chip 2n of the N-type thermoelectric conversion material in the integrated body 4b so as to form a ⁇ -type thermoelectric conversion element.
  • FIG. 1 It is sectional drawing which shows the aspect of, and the said structure is the basic structure (1st Embodiment) of the thermoelectric conversion module of this invention.
  • FIG. 2 is a cross-sectional configuration diagram showing an embodiment of the thermoelectric conversion module of the present invention
  • FIG. 2A shows an insulating layer 6 formed on the upper and lower surfaces of the electrode 5 in the basic configuration obtained in FIG. 1E.
  • thermoelectric conversion material The method for manufacturing a thermoelectric conversion module of the present invention includes a chip placement step of a thermoelectric conversion material.
  • the chip placement step of the thermoelectric conversion material is a step of arranging the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material on the support in a separated manner. For example, in FIG. 1 (a) described above. This is a step of alternately arranging the chips 2p of the P-type thermoelectric conversion material and the chips 2n of the N-type thermoelectric conversion material on the support 1.
  • the method of arranging the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material apart from each other is not particularly limited.
  • the chips may be placed on the support by interposing a pressure-sensitive adhesive layer as a fixed layer, which will be described later, and further, a chip of a P-type thermoelectric conversion material and an N-type thermoelectric conversion material. It may be formed directly on the support so that the chips of the above are alternately arranged apart from each other.
  • a method of directly forming the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material it can be performed by screen printing, coating with a dispenser or the like.
  • the chip of the thermoelectric conversion material used in the present invention is not particularly limited, and may be a thermoelectric semiconductor material or a thin film made of a thermoelectric semiconductor composition. From the viewpoint of flexibility, thinness, and thermoelectric performance, it comprises a thermoelectric semiconductor composition containing one or both of a thermoelectric semiconductor material (hereinafter, may be referred to as "thermoelectric semiconductor particles"), a resin, an ionic liquid, and an inorganic ionic compound. It is preferably composed of a thin film.
  • thermoelectric conversion material or “chip of a thermoelectric conversion material” is synonymous, and also is synonymous with “thermoelectric conversion material layer (however, including those having voids)".
  • thermoelectric semiconductor material used for the chip of the thermoelectric conversion material is preferably pulverized to a predetermined size by, for example, a fine pulverizer or the like and used as the thermoelectric semiconductor particles (hereinafter, the thermoelectric semiconductor material is referred to as "thermoelectric semiconductor particles"). There is.).
  • the particle size of the thermoelectric semiconductor particles is preferably 10 nm to 100 ⁇ m, more preferably 20 nm to 50 ⁇ m, and even more preferably 30 nm to 30 ⁇ m.
  • the average particle size of the thermoelectric semiconductor particles was obtained by measuring with a laser diffraction type particle size analyzer (Mastersizer 3000 manufactured by Malvern), and was used as the median value of the particle size distribution.
  • thermoelectric semiconductor material constituting the P-type thermoelectric conversion material chip and the N-type conversion material chip may generate thermoelectromotive power by imparting a temperature difference.
  • the material is not particularly limited as long as it can be used, and for example, a bismuth-tellu-based thermoelectric semiconductor material such as P-type bismasterlide and N-type bismasterlide; a telluride-based thermoelectric semiconductor material such as GeTe and PbTe; an anti-Mont-tellu-based thermoelectric semiconductor material; Zinc-antimony thermoelectric semiconductor materials such as ZnSb, Zn 3 Sb 2, Zn 4 Sb 3 ; silicon-germanium thermoelectric semiconductor materials such as SiGe; bismus selenide thermoelectric semiconductor materials such as Bi 2 Se 3 ; ⁇ -FeSi 2 , CrSi 2 , MnSi 1.73 , Mg 2 Si and other silicide-based thermoelectric semiconductor materials; oxide-based thermoelectric semiconductor materials; FeVAL, Fe
  • thermoelectric semiconductor material used in the present invention is preferably a bismuth-tellurium-based thermoelectric semiconductor material such as P-type bismuthellide or N-type bismuthellide.
  • P-type bismuth telluride one having a hole as a carrier and a positive Seebeck coefficient, for example, represented by Bi X Te 3 Sb 2-X is preferably used.
  • X is preferably 0 ⁇ X ⁇ 0.8, more preferably 0.4 ⁇ X ⁇ 0.6.
  • X is larger than 0 and 0.8 or less, the Seebeck coefficient and the electric conductivity become large, and the characteristics as a P-type thermoelectric conversion material are maintained, which is preferable.
  • N-type bismuth telluride one having an electron carrier and a negative Seebeck coefficient, for example, represented by Bi 2 Te 3-Y Se Y is preferably used.
  • the Seebeck coefficient and the electric conductivity become large, and the characteristics as an N-type thermoelectric conversion material are maintained, which is preferable.
  • the content of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. It is more preferably 50 to 96% by mass, and even more preferably 70 to 95% by mass.
  • the Seebeck coefficient absolute value of the Perche coefficient
  • the decrease in the electric conductivity is suppressed, and only the thermal conductivity is decreased, so that high thermoelectric performance is exhibited.
  • a film having sufficient film strength and flexibility can be obtained, which is preferable.
  • thermoelectric semiconductor particles are annealed (hereinafter, may be referred to as "annealing treatment A").
  • annealing treatment A By performing the annealing treatment A, the crystallinity of the thermoelectric semiconductor particles is improved, and further, the surface oxide film of the thermoelectric semiconductor particles is removed, so that the Seebeck coefficient (absolute value of the Perche coefficient) of the thermoelectric conversion material is increased. , The thermoelectric performance index can be further improved.
  • the resin used in the present invention has a function of physically bonding thermoelectric semiconductor materials (thermoelectric semiconductor particles), can enhance the flexibility of the thermoelectric conversion module, and facilitates the formation of a thin film by coating or the like. ..
  • a heat-resistant resin or a binder resin is preferable.
  • the heat-resistant resin is maintained without impairing various physical properties such as mechanical strength and thermal conductivity as the resin when the thin film made of the thermoelectric semiconductor composition is subjected to crystal growth such as annealing treatment.
  • the heat-resistant resin is preferably a polyamide resin, a polyamideimide resin, a polyimide resin, or an epoxy resin, and has excellent flexibility, because it has higher heat resistance and does not adversely affect the crystal growth of thermoelectric semiconductor particles in the thin film. From this point of view, polyamide resin, polyamideimide resin, and polyimide resin are more preferable.
  • the heat-resistant resin preferably has a decomposition temperature of 300 ° C. or higher. As long as the decomposition temperature is within the above range, the flexibility can be maintained without losing the function as a binder even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the heat-resistant resin preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and further preferably 1% or less at 300 ° C. by thermogravimetric analysis (TG). ..
  • TG thermogravimetric analysis
  • 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, still more preferably 2 to 15. It is mass%.
  • the content of the heat-resistant resin is within the above range, it functions as a binder for the thermoelectric semiconductor material, facilitates the formation of a thin film, and obtains a film having both high thermoelectric performance and film strength, and thermoelectric conversion.
  • the binder resin can be easily peeled off from a substrate such as glass, alumina, or silicon used for producing chips of a thermoelectric conversion material after firing (annealing) treatment (corresponding to "annealing treatment B" described later, the same applies hereinafter).
  • a substrate such as glass, alumina, or silicon used for producing chips of a thermoelectric conversion material after firing (annealing) treatment (corresponding to "annealing treatment B" described later, the same applies hereinafter).
  • the binder resin refers to a resin that decomposes in an amount of 90% by mass or more at a firing (annealing) temperature or higher, more preferably a resin that decomposes in an amount of 95% by mass or more, and a resin that decomposes in an amount of 99% by mass or more. Is particularly preferable. Further, when a coating film (thin film) made of a thermoelectric semiconductor composition is subjected to crystal growth such as firing (annealing) treatment, a resin that maintains various physical properties such as mechanical strength and thermal conductivity without being impaired. More preferred.
  • a resin that decomposes by 90% by mass or more at a firing (annealing) temperature or higher that is, a resin that decomposes at a lower temperature than the heat-resistant resin described above. Since the content of the binder resin, which is an insulating component contained therein, is reduced and the crystal growth of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is promoted, the voids in the thermoelectric conversion material layer are reduced and the filling rate is increased. Can be improved.
  • Whether or not the resin decomposes at a predetermined value (for example, 90% by mass) or more at the firing (annealing) temperature or higher is determined by the mass reduction rate (before decomposition) at the firing (annealing) temperature by thermogravimetric analysis (TG). Judgment is made by measuring (the value obtained by dividing the mass after decomposition by the mass).
  • a predetermined value for example, 90% by mass
  • TG thermogravimetric analysis
  • thermoplastic resin examples include polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polymethylpentene; polycarbonate; thermoplastic polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polystyrene, acrylonitrile-styrene copolymer, and polyacetic acid.
  • Examples thereof include polyvinyl polymers such as vinyl, ethylene-vinyl acetate copolymers, vinyl chloride, polyvinylpyridine, polyvinyl alcohol, and polyvinylpyrrolidone; polyurethanes; cellulose derivatives such as ethyl cellulose; and the like.
  • the curable resin include thermosetting resins and photocurable resins.
  • examples of the thermosetting resin include epoxy resin and phenol resin.
  • Examples of the photocurable resin include a photocurable acrylic resin, a photocurable urethane resin, and a photocurable epoxy resin. These may be used alone or in combination of two or more.
  • thermoplastic resin a thermoplastic resin is preferable, a cellulose derivative such as polycarbonate and ethyl cellulose is more preferable, and polycarbonate is particularly preferable.
  • the binder resin is appropriately selected according to the temperature of the firing (annealing) treatment of the thermoelectric semiconductor material in the firing (annealing) treatment step. It is preferable to perform the firing (annealing) treatment at a temperature equal to or higher than the final decomposition temperature of the binder resin from the viewpoint of the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer.
  • the "final decomposition temperature” is a temperature at which the mass reduction rate at the firing (annealing) temperature by thermogravimetric analysis (TG) is 100% (the mass after decomposition is 0% of the mass before decomposition).
  • the final decomposition temperature of the binder resin is usually 150 to 600 ° C, preferably 200 to 560 ° C, more preferably 220 to 460 ° C, and particularly preferably 240 to 360 ° C. If a binder resin having a final decomposition temperature in this range is used, it functions as a binder for the thermoelectric semiconductor material, and it becomes easy to form a thin film at the time of printing.
  • 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%. It is mass%.
  • the content of the binder resin is within the above range, the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer can be reduced.
  • the content of the binder resin 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.
  • the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer can be reduced.
  • the ionic liquid that can be contained in the thermoelectric semiconductor composition is a molten salt formed by combining a cation and an anion, and refers to a salt that can exist as a liquid in any temperature range of ⁇ 50 ° C. or higher and lower than 400 ° C.
  • the ionic liquid is an ionic compound having a melting point in the range of ⁇ 50 ° C. or higher and lower than 400 ° C.
  • the melting point of the ionic liquid is preferably ⁇ 25 ° C. or higher and 200 ° C. or lower, and more preferably 0 ° C. or higher and 150 ° C. or lower.
  • the ionic liquid has features such as extremely low vapor pressure, non-volatileity, excellent thermal stability and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, as a conductive auxiliary agent, it is possible to effectively suppress the reduction of the electrical conductivity between the thermoelectric semiconductor materials. Further, since the ionic liquid exhibits high polarity based on the aprotic ionic structure and has excellent compatibility with the heat-resistant resin, the electric conductivity of the thermoelectric conversion material can be made uniform.
  • the ionic liquid a known or commercially available one can be used.
  • nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and their derivatives; tetraalkylammonium-based amine-based cations and their derivatives; phosphonium, trialkylsulfonium, tetraalkylphosphonium and the like.
  • Phosphonic cations and their derivatives Phosphonic cations and their derivatives; cation components such as lithium cations and their derivatives, Cl- , Br- , I- , AlCl 4- , Al 2 Cl 7- , BF 4- , PF 6- , ClO 4- , NO 3- , CH 3 COO- , CF 3 COO- , CH 3 SO 3- , CF 3 SO 3- , (FSO 2 ) 2 N- , (CF 3 SO 2 ) 2 N- , (CF 3 SO 2 ) 3 C- , AsF 6- , SbF 6- , NbF 6- , TaF 6- , F (HF) n- , (CN) 2 N- , C 4 F 9 SO 3- , (C 2 F 5 SO 2 ) Examples thereof include those composed of anionic components such as 2 N ⁇ , C 3 F 7 COO ⁇ , and (CF 3 SO 2 ) (CF 3 CO) N ⁇ .
  • the cation component of the ionic liquid is a pyridinium cation and its derivatives from the viewpoints of high temperature stability, compatibility with thermoelectric semiconductor materials and resins, and suppression of decrease in electrical conductivity between thermoelectric semiconductor material gaps.
  • 1-butyl-4-methylpyridinium bromide, 1-butylpyridinium bromide, and 1-butyl-4-methylpyridinium hexafluorophosphart are preferable.
  • the cation component is [1-butyl-3- (2-hydroxyethyl) imidazolium bromide], [1-butyl-3- (2-hydroxyethyl) imidazole].
  • Rium tetrafluoroborate] is preferred.
  • the above-mentioned ionic liquid preferably has a decomposition temperature of 300 ° C. or higher. As long as the decomposition temperature is within the above range, the effect as a conductive auxiliary agent can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • 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 further preferably 1.0 to 20% by mass.
  • the content of the ionic liquid is within the above range, the decrease in electrical conductivity is effectively suppressed, and a film having high thermoelectric performance can be obtained.
  • thermoelectric semiconductor composition (Inorganic ionic compound)
  • the inorganic ionic compound that can be contained in the thermoelectric semiconductor composition is a compound composed of at least cations and anions.
  • Inorganic ionic compounds exist as solids in a wide temperature range of 400 to 900 ° C. and have characteristics such as high ionic conductivity. Therefore, as a conductive auxiliary agent, the electrical conductivity between thermoelectric semiconductor materials is reduced. Can be suppressed.
  • the content of the inorganic ionic compound in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 10% by mass.
  • the content of the inorganic ionic compound is within the above range, the decrease in electrical conductivity can be effectively suppressed, and as a result, a film having improved thermoelectric performance can be obtained.
  • the total content of the inorganic ionic compound and the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably. Is 0.5 to 30% by mass, more preferably 1.0 to 10% by mass.
  • thermoelectric semiconductor compositions As a method of applying the P-type and N-type thermoelectric semiconductor compositions on the support, a screen printing method, a flexographic printing method, a gravure printing method, a spin coating method, a dip coating method, a die coating method, a spray coating method, and a bar.
  • Known methods such as a coating method and a doctor blade method can be mentioned and are not particularly limited.
  • the coating film is formed into a pattern, screen printing, stencil printing, slot die coating, etc., which can easily form a pattern using a screen plate having a desired pattern, are preferably used.
  • a thin film is formed by drying the obtained coating film, and as the drying method, conventionally known drying methods such as a hot air drying method, a hot roll drying method, and an infrared irradiation method can be adopted.
  • 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.
  • the heating temperature is not particularly limited as long as the used solvent can be dried.
  • the thickness of the chip of the thermoelectric conversion material is not particularly limited, and is preferably 100 nm to 1000 ⁇ m, more preferably 300 nm to 600 ⁇ m, and further preferably 5 to 400 ⁇ m from the viewpoint of thermoelectric performance and film strength.
  • the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material made of the thermoelectric semiconductor composition are further subjected to an annealing treatment (hereinafter, may be referred to as "annealing treatment B").
  • annealing treatment B By performing the annealing treatment B, the thermoelectric performance can be stabilized, and the thermoelectric semiconductor particles in the thermoelectric conversion material chip can be crystal-grown, so that the thermoelectric performance can be further improved.
  • the 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 a vacuum condition in which the gas flow rate is controlled, and the thermoelectric semiconductor composition to be used is supported. It is carried out at 100 to 500 ° C. for several minutes to several tens of hours, depending on the heat-resistant temperature of the body or the like.
  • the support used in the present invention is not particularly limited, and examples thereof include glass, silicon, ceramics, metal, and plastic. It is preferably selected from glass, plastic and silicon. When the annealing treatment or the like is performed at a high temperature, glass, silicon, ceramics, or metal is preferable.
  • the thickness of the support is preferably 100 to 1200 ⁇ m, more preferably 200 to 800 ⁇ m, still more preferably 400 to 700 ⁇ m from the viewpoint of process and dimensional stability.
  • the fixing layer is used to fix the support and the chip of the thermoelectric conversion material when the chips of the thermoelectric conversion material are arranged apart from each other in the step (A).
  • the fixed layer is not particularly limited as long as the support and the chip of the thermoelectric conversion material can be adhered to each other, but it is preferable to use an adhesive layer as one embodiment.
  • a pressure-sensitive adhesive layer containing an energy ray-curable adhesive resin having a polymerizable functional group introduced in the side chain From the viewpoint of adhesiveness and curing by energy rays such as ultraviolet rays to reduce the adhesive strength, it is more preferable to use a pressure-sensitive adhesive layer containing an energy ray-curable adhesive resin having a polymerizable functional group introduced in the side chain.
  • the pressure-sensitive adhesive layer may contain any pressure-sensitive adhesive resin, and may contain additives for pressure-sensitive adhesive such as a cross-linking agent, a pressure-sensitive adhesive, a polymerizable compound, and a polymerization initiator, if necessary.
  • the pressure-sensitive adhesive layer can be formed from a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive resin by a known method. For example, it can be formed by a coating method.
  • the adhesive resin examples include rubber resins such as acrylic resins, urethane resins and polyisobutylene resins, polyester resins, olefin resins, silicone resins, polyvinyl ether resins and the like.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably about 1 to 50 ⁇ m, and more preferably 2 to 30 ⁇ m.
  • thermoelectric conversion module of the present invention includes an insulator filling step.
  • an insulator is filled between the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material, and the chip of the P-type thermoelectric conversion material, the chip of the N-type thermoelectric conversion material and the insulator are used.
  • FIG. 1B for example, in FIG. 1B, an insulator 3 is filled between a chip 2p of a P-type thermoelectric conversion material and a chip 2n of an N-type thermoelectric conversion material, and a P-type thermoelectric product is obtained.
  • This is a step of obtaining a self-supporting integrated product 4a composed of a chip 2p of a conversion material, a chip 2n of an N-type thermoelectric conversion material, and an insulator 3.
  • the insulator used in the present invention is not particularly limited as long as the insulation between the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material can be maintained and the mechanical strength can be maintained when they are integrated. Examples include ceramics.
  • the insulating resin examples include a polyimide resin, a silicone resin, a rubber resin, an acrylic resin, an olefin resin, a maleimide resin, an epoxy resin and the like. From the viewpoint of heat resistance and mechanical strength, it is preferably selected from a polyimide resin, a silicone resin, an acrylic resin, a maleimide resin and an epoxy resin.
  • the insulating resin is preferably a curable resin or a foamable resin.
  • the insulating resin may further contain a filler. As the filler, a hollow filler is preferable. The hollow filler is not particularly limited, and known ones can be used.
  • an inorganic hollow which is a balloon (hollow body) such as a glass balloon, a silica balloon, a silas balloon, a fly ash balloon, or a metal silicate.
  • a balloon high body
  • examples thereof include fillers and organic resin-based hollow fillers which are balloons (hollow bodies) such as acrylonitrile, vinylidene chloride, phenol resin, epoxy resin, and urea resin.
  • the thermal conductivity of the insulating resin is lowered, and the thermoelectric performance is further improved.
  • the ceramics include materials containing aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicon carbide and the like as main components (50% by mass or more in the ceramics).
  • a rare earth compound may be added.
  • a known method can be used. For example, a method of using a liquid resin and spreading and filling the resin on a support surface in which chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material are alternately arranged using a coating member such as a squeegee. Further, a method of dropping the support from substantially the center to the outside and then filling the support by a spin coat method, a method of immersing the support in a liquid resin storage tank or the like and then pulling it up to fill the support, and further.
  • the sheet-shaped insulating resin is attached onto the support surface in which the chips of the P-type thermoelectric conversion material and the chips of the N-type thermoelectric conversion material are alternately arranged, and heated and / or Examples thereof include a method of melting and filling a sheet-shaped insulating resin by pressurization. After filling, thermosetting or the like is performed.
  • the insulator surplus portion removing step is a chip of at least a P-type thermoelectric conversion material in the integrated product obtained in the step (B) after the step (B) and before the step (C).
  • This is a step of removing the excess portion of the insulator that is in direct contact with the region of the upper surface of the chip of the N-type thermoelectric conversion material.
  • the insulator extending excessively in the thickness direction is further removed. It is also good.
  • the upper surface of the chip 2p of the P-type thermoelectric conversion material, the upper surface of the chip 2n of the N-type thermoelectric conversion material, and the chip 2p of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material is a step of removing the insulator surplus portion 3'located on the upper portion of the insulator 3, which is a region between the chip 2n and the chip 2n, to form the embodiment of the integrated product 4b of (c).
  • a known method can be used. For example, the upper part of the insulator 3 in the region between the chip 2p of the P-type thermoelectric conversion material, the chip 2n of the N-type thermoelectric conversion material, and the chip 2p of the P-type thermoelectric conversion material and the chip 2n of the N-type thermoelectric conversion material.
  • the insulator surplus portion 3'located in the above is irradiated with plasma or the like, or the insulator surplus portion 3'is removed by mechanical polishing or the like, so that the chip 2p of the P-type thermoelectric conversion material and the chip 2n of the N-type thermoelectric conversion material are used.
  • the top surface can be exposed.
  • the method for manufacturing a thermoelectric conversion module of the present invention includes a support peeling step.
  • the support peeling step is a step of peeling the integrated product obtained in the step (B) (or (B')) from the support.
  • the support 1 is integrated. This is a step of peeling off the compound 4b.
  • a known method can be used. For example, when the support is fixed by interposing and fixing the chip of the thermoelectric conversion material constituting the integrated product and the pressure-sensitive adhesive layer, the adhesiveness of the pressure-sensitive adhesive layer is deactivated and the integrated material is peeled off from the support. The residue of the pressure-sensitive adhesive layer is removed by pickling or the like. Alternatively, the support itself is directly polished until the lower surface of the chip of the thermoelectric conversion material is exposed to obtain an integrated product as a single molded body.
  • Electrode forming step The method for manufacturing a thermoelectric conversion module of the present invention includes an electrode forming step.
  • electrodes are directly provided (formed) on the chips of the P-type thermoelectric conversion material and the chips of the N-type thermoelectric conversion material on the upper and lower surfaces, and the P-type thermoelectric conversion material is formed. It is a step of connecting the chip of the N-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material by interposing an electrode. This is a step of directly forming and arranging electrodes on the chip of the N-type thermoelectric conversion material 2n so that the ⁇ -type thermoelectric conversion element operates.
  • Electrode examples of the metal material of the electrode of the thermoelectric conversion module used in the present invention include copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, solder, or an alloy containing any of these metals. Be done.
  • the thickness of the electrode layer is preferably 10 nm to 200 ⁇ m, more preferably 30 nm to 150 ⁇ m, and further preferably 50 nm to 120 ⁇ m. When the thickness of the electrode layer is within the above range, the electric conductivity is high and the resistance is low, and sufficient strength as an electrode can be obtained.
  • the electrode is formed using the metal material described above.
  • a method for forming the electrode after providing an electrode having no pattern formed on the support, a known physical treatment or chemical treatment mainly based on a photolithography method, or a combined use thereof is performed.
  • a method of processing into the pattern shape of the above, a method of directly forming an electrode pattern by a screen printing method, an inkjet method, or the like can be mentioned.
  • PVD Physical Vapor Deposition
  • CVD chemical vapor deposition
  • thermal CVD and atomic layer deposition (ALD) can be used to form electrodes that do not have a pattern.
  • Electrolytic plating method electroless plating method, laminating of metal foil and the like, and are appropriately selected according to the material of the electrode. Since the electrode used in the present invention is required to have high conductivity and high thermal conductivity from the viewpoint of maintaining thermoelectric performance, it is preferable to use an electrode formed by a plating method or a vacuum film forming method.
  • a vacuum film forming method such as a vacuum vapor deposition method and a sputtering method, and an electrolytic plating method and an electroless plating method are preferable. Although it depends on the dimensions of the forming pattern and the requirement of dimensional accuracy, the pattern can be easily formed by interposing a hard mask such as a metal mask.
  • the thickness of the layer of the metal material is preferably 10 nm to 200 ⁇ m, more preferably 30 nm to 150 ⁇ m, and further preferably 50 nm to 120 ⁇ m. When the thickness of the layer of the metal material is within the above range, the electric conductivity is high and the resistance is low, and sufficient strength as an electrode can be obtained.
  • the insulating layer forming step is a step of laminating an insulating layer on the upper and lower surfaces of the electrode obtained in the step (D).
  • the insulating layer 6 is formed on the upper and lower surfaces of the electrode 5. This is the process of forming.
  • the insulating layer is not particularly limited, but is not particularly limited. It is possible to suppress a short circuit with the above.
  • the insulating layer is not particularly limited as long as it has an insulating property, but is preferably a resin for forming an insulating layer or an inorganic material, and a resin for forming an insulating layer is more preferable from the viewpoint of flexibility.
  • Resins for forming an insulating layer include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulphon, polyethersulphon, polyphenylene sulfide, polyarylate, nylon, and acrylic. Examples thereof include resins, cycloolefin polymers, and aromatic polymers.
  • polyester include polyethylene terephthalate (PET) polybutylene terephthalate, polyethylene naphthalate (PEN), polyarylate and the like.
  • cycloolefin-based polymer examples include norbornene-based polymers, monocyclic cyclic olefin-based polymers, cyclic conjugated diene-based polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof.
  • the resins for forming an insulating layer polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and nylon are preferable from the viewpoint of cost and heat resistance.
  • the resin for forming an insulating layer may contain a filler from the viewpoint of controlling the elastic modulus and the thermal conductivity.
  • Examples of the filler added to the resin film include magnesium oxide, anhydrous magnesium carbonate, magnesium hydroxide, aluminum oxide, boron nitride, aluminum nitride, silicon oxide and the like.
  • aluminum oxide, boron nitride, aluminum nitride, and silicon oxide are preferable from the viewpoint of elastic modulus control, thermal conductivity, and the like.
  • the resin for forming the insulating layer used for the insulating layer is preferably in the form of a sheet. Since it is in the form of a sheet, an insulating layer can be easily formed.
  • the inorganic material is not particularly limited, and examples thereof include silicon oxide, aluminum oxide, magnesium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, hafnium oxide, barium oxide, boron nitride, aluminum nitride, and silicon carbide.
  • silicon oxide and aluminum oxide are preferable from the viewpoint of cost, stability, and availability.
  • the thickness of the insulating layer is preferably 1 to 150 ⁇ m, more preferably 2 to 140 ⁇ m, still more preferably 3 to 120 ⁇ m, and particularly preferably 5 to 100 ⁇ m.
  • the thickness of the insulating layer is within this range, the conductive portion of the heat diffusion layer is less likely to penetrate the insulating layer, short-circuiting of the thermoelectric conversion material with the chip is suppressed, and the thermoelectric performance is maintained. Further, the same applies to the case where the surface to be installed of the thermoelectric conversion module has a conductive portion.
  • the insulating layer has a volume resistivity of preferably 1.0 ⁇ 10 8 ⁇ ⁇ cm or more, more preferably 1.0 ⁇ 10 9 ⁇ ⁇ cm or more, still more preferably 1.0, from the viewpoint of ensuring the insulating property. ⁇ 10 10 ⁇ ⁇ cm or more.
  • the volume resistivity is a value measured by a resistivity meter (MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd.) after the insulating layer is left in an environment of 23 ° C. and 50% RH for one day.
  • the insulating layer can be formed by a known method.
  • the insulating layer may be formed directly on the surface of the electrode, or the insulating layer previously formed on the release sheet may be attached to the electrode and attached to the electrode. It may be formed by transferring by laminating. Further, two or more types of insulating layers may be laminated.
  • the method for manufacturing a thermoelectric conversion module of the present invention preferably includes a heat diffusing layer forming step.
  • the heat diffusion layer forming step is a step of laminating the heat diffusion layer on the upper and lower surfaces of the insulating layer obtained in the step (E).
  • the heat diffusion layer is formed on the upper and lower surfaces of the insulating layer 6.
  • This is a step of forming the heat diffusion layer 7.
  • the heat diffusion layer is provided on one side or both sides of the thermoelectric conversion module and functions as a heat dissipation layer. From the viewpoint of thermoelectric performance, it is preferable to provide the heat diffusion layer on both sides.
  • the thermal diffusion layer is formed from a highly thermally conductive material.
  • the high heat conductive material used for the heat diffusion layer include single metals such as copper, silver, iron, nickel, chromium and aluminum, and alloys such as stainless steel and brass (brass).
  • copper (including oxygen-free copper), stainless steel, and aluminum are preferable, and copper is more preferable because it has high thermal conductivity and is easy to process.
  • typical materials of the high thermal conductive material used in the present invention are shown below.
  • -Oxygen-free copper Oxygen-free copper generally refers to high-purity copper of 99.95% (3N) or more that does not contain oxides.
  • JIS H 3100, C1020 oxygen-free copper
  • JIS H 3510, C1011 oxygen-free copper for electron tubes
  • the method for forming the heat diffusion layer is not particularly limited, and examples thereof include a method for directly forming a pattern of the heat diffusion layer by a screen printing method, an inkjet method, or the like.
  • PVD physical vapor deposition method
  • CVD chemical vapor deposition method
  • ALD atomic layer vapor deposition
  • Wet processes such as various coating methods such as dip coating method, spin coating method, spray coating method, gravure coating method, die coating method, doctor blade method, electrodeposition method, silver salt method, electrolytic plating method, electroless plating method, etc.
  • a heat diffusion layer made of a highly thermally conductive material having no pattern formed is subjected to a known physical treatment or chemical treatment mainly based on the above-mentioned photolithography method. Examples thereof include a method of processing into a predetermined pattern shape by processing or using them in combination.
  • the thermal conductivity of the heat diffusion layer made of the high thermal conductive material used in the present invention is preferably 5 to 500 W / (m ⁇ K), more preferably 8 to 500 W / (m ⁇ K), and even more preferably 10 to 450 W /. (M ⁇ K), particularly preferably 12 to 420 W / (m ⁇ K), most preferably 15 to 400 W / (m ⁇ K).
  • the thickness of the heat diffusion layer is preferably 40 to 550 ⁇ m, more preferably 60 to 530 ⁇ m, and even more preferably 80 to 510 ⁇ m.
  • thermoelectric conversion module cutting process In the method for manufacturing a thermoelectric conversion module of the present invention, it is preferable to include a thermoelectric conversion module cutting step.
  • the thermoelectric conversion module cutting step is, for example, a step of cutting the obtained thermoelectric conversion module in FIG. 1 (e), FIG. 2 (a) or (b) described above to obtain a plurality of thermoelectric conversion modules having predetermined specifications. Is.
  • the method for cutting the thermoelectric conversion module is not particularly limited, and a known method can be used. For example, a dicing method can be mentioned.
  • the dicing method is not particularly limited, and known methods such as blade dicing and laser dicing can be adopted.
  • thermoelectric conversion module of the present invention does not require a solder material or a support that has been conventionally used, and a plurality of thin thermoelectric conversion modules can be efficiently manufactured at once by a simple method.
  • thermoelectric conversion module of the present invention According to the method for manufacturing a thermoelectric conversion module of the present invention, it is expected to provide an inexpensive and downsized thermoelectric conversion module because a thin and high-density thermoelectric conversion module can be mass-produced in a batch.

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2021/039751 2020-10-30 2021-10-28 熱電変換モジュールの製造方法 Ceased WO2022092178A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2022559216A JP7770335B2 (ja) 2020-10-30 2021-10-28 熱電変換モジュールの製造方法
CN202180073854.0A CN116391458A (zh) 2020-10-30 2021-10-28 热电转换组件的制造方法
US18/034,430 US12114568B2 (en) 2020-10-30 2021-10-28 Method for manufacturing thermoelectric conversion module

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020182610 2020-10-30
JP2020-182610 2020-10-30

Publications (1)

Publication Number Publication Date
WO2022092178A1 true WO2022092178A1 (ja) 2022-05-05

Family

ID=81382558

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/039751 Ceased WO2022092178A1 (ja) 2020-10-30 2021-10-28 熱電変換モジュールの製造方法

Country Status (5)

Country Link
US (1) US12114568B2 (https=)
JP (1) JP7770335B2 (https=)
CN (1) CN116391458A (https=)
TW (1) TWI895533B (https=)
WO (1) WO2022092178A1 (https=)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09293909A (ja) * 1996-02-26 1997-11-11 Matsushita Electric Works Ltd 熱電モジュール及びその製造方法
JP2016500201A (ja) * 2013-10-18 2016-01-07 コリア・アドバンスト・インスティテュート・オブ・サイエンス・アンド・テクノロジー メッシュ状基板を用いたフレキシブル熱電素子およびその製造方法
WO2018139475A1 (ja) * 2017-01-27 2018-08-02 リンテック株式会社 フレキシブル熱電変換素子及びその製造方法
JP2019500757A (ja) * 2015-10-27 2019-01-10 コリア アドバンスト インスティチュート オブ サイエンス アンド テクノロジー 柔軟な熱電素子及びその製造方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4459428A (en) * 1982-04-28 1984-07-10 Energy Conversion Devices, Inc. Thermoelectric device and method of making same
JP2001102643A (ja) * 1999-09-27 2001-04-13 Seiko Instruments Inc 熱電素子の製造方法
JP2001352107A (ja) * 2000-06-07 2001-12-21 Nissan Motor Co Ltd 熱電変換モジュールの製造方法
JP2003258323A (ja) * 2002-03-07 2003-09-12 Citizen Watch Co Ltd 熱電素子
JP4345279B2 (ja) * 2002-09-13 2009-10-14 ソニー株式会社 熱電変換装置の製造方法
JP4275938B2 (ja) * 2002-12-25 2009-06-10 岡野電線株式会社 熱電変換モジュールの製造方法
JP2005019767A (ja) * 2003-06-27 2005-01-20 Yamaha Corp 熱電変換モジュールの製造方法
TWI405361B (zh) * 2008-12-31 2013-08-11 財團法人工業技術研究院 熱電元件及其製程、晶片堆疊結構及晶片封裝結構
JP2010161297A (ja) * 2009-01-09 2010-07-22 Toshiba Corp 熱電変換モジュールおよびその製造方法
JP2011176073A (ja) * 2010-02-24 2011-09-08 Aisin Seiki Co Ltd 高密度熱電変換素子の製造方法
JP5928599B2 (ja) * 2012-09-19 2016-06-01 富士通株式会社 発電装置、測定装置及び測定システム
JP6047413B2 (ja) * 2013-01-29 2016-12-21 富士フイルム株式会社 熱電発電モジュール
KR20160028697A (ko) * 2014-09-04 2016-03-14 한국전기연구원 벌크형 소면적 열전모듈 및 그 제조방법
KR20170019109A (ko) * 2015-08-11 2017-02-21 홍익대학교 산학협력단 열전모듈의 제조방법 및 이에 의해 제조된 열전모듈
JP6750404B2 (ja) 2015-09-18 2020-09-02 三菱マテリアル株式会社 熱電変換モジュール及び熱電変換装置並びに熱電変換モジュールの製造方法
WO2017052646A1 (en) * 2015-09-25 2017-03-30 Intel Corporation Island transfer for optical, piezo and rf applications
JP6709040B2 (ja) * 2015-11-18 2020-06-10 日東電工株式会社 半導体装置の製造方法
CN110494997A (zh) * 2017-03-30 2019-11-22 琳得科株式会社 热电转换模块及其制造方法
JP7200616B2 (ja) * 2017-12-06 2023-01-10 三菱マテリアル株式会社 絶縁伝熱基板、熱電変換モジュール、及び、絶縁伝熱基板の製造方法
JP7346427B2 (ja) * 2018-08-28 2023-09-19 リンテック株式会社 熱電変換材料のチップの製造方法及びその製造方法により得られたチップを用いた熱電変換モジュールの製造方法
JP7543140B2 (ja) * 2018-10-05 2024-09-02 リンテック株式会社 熱電変換材料のチップ
WO2020196709A1 (ja) * 2019-03-28 2020-10-01 リンテック株式会社 熱電変換材料のチップの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09293909A (ja) * 1996-02-26 1997-11-11 Matsushita Electric Works Ltd 熱電モジュール及びその製造方法
JP2016500201A (ja) * 2013-10-18 2016-01-07 コリア・アドバンスト・インスティテュート・オブ・サイエンス・アンド・テクノロジー メッシュ状基板を用いたフレキシブル熱電素子およびその製造方法
JP2019500757A (ja) * 2015-10-27 2019-01-10 コリア アドバンスト インスティチュート オブ サイエンス アンド テクノロジー 柔軟な熱電素子及びその製造方法
WO2018139475A1 (ja) * 2017-01-27 2018-08-02 リンテック株式会社 フレキシブル熱電変換素子及びその製造方法

Also Published As

Publication number Publication date
TW202226625A (zh) 2022-07-01
CN116391458A (zh) 2023-07-04
US20240023441A1 (en) 2024-01-18
US12114568B2 (en) 2024-10-08
JP7770335B2 (ja) 2025-11-14
JPWO2022092178A1 (https=) 2022-05-05
TWI895533B (zh) 2025-09-01

Similar Documents

Publication Publication Date Title
US12408551B2 (en) Thermoelectric conversion module
JPWO2020045376A1 (ja) 熱電変換材料のチップの製造方法及びその製造方法により得られたチップを用いた熱電変換モジュールの製造方法
KR20210062022A (ko) 열전 변환 모듈용 중간체의 제조 방법
JP7401361B2 (ja) 熱電変換モジュール
WO2022092178A1 (ja) 熱電変換モジュールの製造方法
JP7207858B2 (ja) 熱電変換モジュール
US11882766B2 (en) Thermoelectric conversion module
JP7854327B2 (ja) 熱電変換モジュールの製造方法
US20230200240A1 (en) Thermoelectric conversion module and manufacturing method therefor
WO2023190633A1 (ja) 熱電変換モジュール
CN118742180A (zh) 帕尔贴冷却热电转换模块
US20260090272A1 (en) Pi-type thermoelectric conversion module
JP2022057937A (ja) 熱電変換モジュール用電極
JP7760277B2 (ja) 熱電変換材料層
US20250311631A1 (en) Thermoelectric conversion module
JP2025154927A (ja) 熱電変換モジュール
TW202614906A (zh) 熱電轉換模組
WO2024204850A1 (ja) 熱電変換モジュール
JP2024146619A (ja) 熱電変換モジュール
WO2021193357A1 (ja) 熱電変換モジュール
WO2023276559A1 (ja) 半導体封止体
WO2022210996A1 (ja) 熱電変換モジュール
CN120018755A (zh) 制造热电发电机的方法
JP2023006278A (ja) 半導体装置、及び、半導体装置の製造方法
JP2022157777A (ja) 熱電変換モジュール

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21886295

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022559216

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 18034430

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21886295

Country of ref document: EP

Kind code of ref document: A1