WO2023190633A1 - Module de conversion thermoélectrique - Google Patents

Module de conversion thermoélectrique Download PDF

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Publication number
WO2023190633A1
WO2023190633A1 PCT/JP2023/012719 JP2023012719W WO2023190633A1 WO 2023190633 A1 WO2023190633 A1 WO 2023190633A1 JP 2023012719 W JP2023012719 W JP 2023012719W WO 2023190633 A1 WO2023190633 A1 WO 2023190633A1
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WIPO (PCT)
Prior art keywords
thermoelectric conversion
conversion material
chip
type thermoelectric
insulating layer
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PCT/JP2023/012719
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English (en)
Japanese (ja)
Inventor
晴樹 末吉
佑太 関
邦久 加藤
睦 升本
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リンテック株式会社
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Publication of WO2023190633A1 publication Critical patent/WO2023190633A1/fr

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    • 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
    • H10N10/13—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 heat-exchanging means at the junction
    • 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 thermoelectric conversion module.
  • thermoelectric conversion module having a thermoelectric effect such as the Seebeck effect or the Peltier effect.
  • thermoelectric conversion module it is known to use a so-called ⁇ -type thermoelectric conversion element.
  • a ⁇ -type thermoelectric conversion element has a pair of electrodes spaced apart from each other on a substrate, for example, the lower surface of a P-type thermoelectric element is placed on one electrode, the lower surface of an N-type thermoelectric element is placed on the other electrode,
  • the basic unit is a configuration in which the top surfaces of both types of thermoelectric elements are connected to the same electrode on the opposing substrate, which are also spaced apart from each other, and usually a plurality of the basic units are connected electrically in series on both substrates. The connections are configured so that they are thermally connected in parallel.
  • thermoelectric conversion modules including such ⁇ -type thermoelectric conversion elements
  • various efforts have been made to make thermoelectric conversion modules thinner, reduce the amount of constituent materials, and improve reliability. I have a request.
  • Patent Documents 1 and 2 disclose thermoelectric conversion modules using the aforementioned ⁇ -type thermoelectric conversion elements.
  • thermoelectric conversion module of Patent Document 1 has a P-type element made of a P-type thermoelectric material, an N-type element made of an N-type thermoelectric material, and a metal that can form a PN junction pair by bonding these dissimilar elements one by one. It consists of two substrates with electrodes, etc., and at least a base material that supports metal electrodes and elements is used, so no consideration has been given to making the thermoelectric conversion module thinner or reducing the number of constituent materials. Not yet.
  • thermoelectric conversion module of Patent Document 2 does not include a base material that serves as a support in the final configuration, but a contact heat conduction layer is provided at a location where a substrate is normally placed, and the contact heat conduction layer is provided at a location where a substrate is normally placed.
  • the layer is made of the same materials as commonly used base materials, such as aluminum nitride, silicon nitride, alumina, etc., and also functions as a support, so it is important to consider ways to make the thermoelectric conversion module thinner and reduce the number of constituent materials. Not real.
  • the present invention has been made in view of these circumstances, and an object of the present invention is to provide a thin thermoelectric conversion module that does not have a support base material or a solder layer.
  • thermoelectric conversion module having a structure in which an insulating layer is interposed and straddled, and the present invention was completed. That is, the present invention provides the following [1] to [15].
  • thermoelectric conversion module comprising:
  • the first insulating layer includes a chip of the P-type thermoelectric conversion material on a first surface side of the chip of the P-type thermoelectric conversion material and a first surface side of the chip of the N-type thermoelectric conversion material adjacent to the first surface side of the chip of the P-type thermoelectric conversion material. provided so as to straddle the gap between the adjacent chips of the N-type thermoelectric conversion material,
  • the second insulating layer includes a chip of the P-type thermoelectric conversion material on a second surface side of the chip of the P-type thermoelectric conversion material and a second surface side of the chip of the N-type thermoelectric conversion material adjacent to the second surface side of the chip of the P-type thermoelectric conversion material.
  • the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material are: The first surface side of the chip of the P-type thermoelectric conversion material and the first surface side of the chip of the N-type thermoelectric conversion material adjacent to the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material in the arrangement direction.
  • first electrode provided on the front surface side with the first insulating layer interposed therebetween and further spanning the first insulating layer;
  • a second electrode provided on the surface side with the second insulating layer interposed therebetween and further spanning the second insulating layer;
  • the chips of the P-type thermoelectric conversion material and the chips of the N-type thermoelectric conversion material are electrically connected in this order alternately in the arrangement direction, A gap formed between the first insulating layer, the second insulating layer, the P-type thermoelectric conversion material chip, and the N-type thermoelectric conversion material chip is maintained.
  • Thermoelectric conversion module [2]
  • a first protective layer is provided on the first electrode and the first insulating layer, and a second protective layer is provided on the second electrode and the second insulating layer.
  • thermoelectric conversion module according to [1] above, wherein the thermoelectric conversion module is provided with: [3] The thermoelectric conversion module according to [2] above, further comprising a heat dissipation layer provided on the first protective layer and the second protective layer. [4] The thermoelectric conversion module according to any one of [1] to [3] above, wherein a frame is provided around the thermoelectric conversion module. [5] The thermoelectric conversion module according to [4] above, wherein the frame is made of metal, ceramics, or resin. [6] The first insulating layer and the second insulating layer are each independently selected from polyimide resin, silicone resin, rubber resin, acrylic resin, olefin resin, maleimide resin, and epoxy resin, as described above.
  • thermoelectric conversion module according to any one of [1] to [5]. [7] The thermoelectric conversion module according to [2] or [3], wherein the first protective layer and the second protective layer are each independently selected from insulating resins and ceramics. [8] The heat dissipation layer is made of gold, silver, copper, nickel, tin, iron, chromium, platinum, palladium, rhodium, iridium, ruthenium, osmium, indium, zinc, molybdenum, manganese, titanium, aluminum, stainless steel, and brass. The thermoelectric conversion module according to [3] above, selected from.
  • thermoelectric conversion module according to any one of [1] to [8] above, wherein the first insulating layer and the second insulating layer each independently have a thickness of 5 to 200 ⁇ m.
  • thermoelectric device according to any one of [2], [3] and [7] above, wherein the first protective layer and the second protective layer each independently have a thickness of 5 to 300 ⁇ m.
  • Conversion module [11] The thermoelectric conversion module according to [3] or [8] above, wherein the heat dissipation layer has a thickness of 5 to 550 ⁇ m.
  • the first electrode and the second electrode are each independently made of gold, silver, copper, nickel, chromium, platinum, palladium, rhodium, molybdenum, aluminum, or an alloy containing any of these metals.
  • the thermoelectric conversion module according to any one of [1] to [11] above, selected from. [13]
  • the first electrode and the second electrode are each independently formed of at least one type of film selected from the group consisting of a sputtered film, a vapor deposited film, and a plated film, [1] to [ above]. 12].
  • the thermoelectric conversion module according to any one of [12].
  • thermoelectric conversion module according to any one of [1] to [13] above, wherein the P-type thermoelectric conversion material chip and the N-type thermoelectric conversion material chip are made of a thermoelectric semiconductor composition.
  • thermoelectric semiconductor composition contains a thermoelectric semiconductor material, a resin, and one or both of an ionic liquid and an inorganic ionic compound.
  • thermoelectric conversion module that does not have a support base material and a solder layer.
  • FIG. 1 is a cross-sectional configuration diagram showing a first embodiment of a thermoelectric conversion module of the present invention.
  • FIG. 2 is a cross-sectional configuration diagram showing a second embodiment of the thermoelectric conversion module of the present invention.
  • FIG. 3 is a cross-sectional configuration diagram showing a third embodiment of a thermoelectric conversion module of the present invention.
  • thermoelectric conversion module includes chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material arranged in a spaced manner alternately, a first insulating layer, a second insulating layer, a first electrode, and A thermoelectric conversion module including a second electrode,
  • the first insulating layer includes a chip of the P-type thermoelectric conversion material on a first surface side of the chip of the P-type thermoelectric conversion material and a first surface side of the chip of the N-type thermoelectric conversion material adjacent to the first surface side of the chip of the P-type thermoelectric conversion material.
  • the second insulating layer includes a chip of the P-type thermoelectric conversion material on a second surface side of the chip of the P-type thermoelectric conversion material and a second surface side of the chip of the N-type thermoelectric conversion material adjacent to the second surface side of the chip of the P-type thermoelectric conversion material.
  • the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material are: The first surface side of the chip of the P-type thermoelectric conversion material and the first surface side of the chip of the N-type thermoelectric conversion material adjacent to the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material in the arrangement direction.
  • first electrode provided on the front surface side with the first insulating layer interposed therebetween and further spanning the first insulating layer;
  • thermoelectric conversion module of the present invention the P-type thermoelectric conversion material is connected so that the common electrode of the adjacent P-type thermoelectric conversion material chip and the N-type thermoelectric conversion material chip is straddled with an insulating layer disposed in the center of the electrode.
  • thermoelectric conversion module By placing (wiring) directly on the upper and lower surfaces of the chip of type thermoelectric conversion material and the chip of N type thermoelectric conversion material, it is no longer necessary to provide electrodes on the support base material, and the support base material and solder layer used in the past can be used. This can be omitted, and the thermoelectric conversion module can be made thinner.
  • support base material refers to a substrate material used as a support for thermoelectric conversion materials, electrodes, etc., including, but not limited to, glass, silicon, and ceramics commonly used in the thermoelectric field. , resin, etc.
  • thermoelectric conversion module of the present invention will be explained using the drawings.
  • FIG. 1 is a cross-sectional configuration diagram showing a first embodiment of a thermoelectric conversion module of the present invention, and the thermoelectric conversion module 1 includes: Chips 3p of P-type thermoelectric conversion material and chips 3n of N-type thermoelectric conversion material arranged in an alternately spaced manner, the first insulating layer L1, the second insulating layer L2, the first electrode M1, and the second A thermoelectric conversion module including an electrode M2,
  • the first insulating layer L1 has a P-type thermoelectric conversion material on the first surface 3p 1 side of the chip 3p made of P-type thermoelectric conversion material and the first surface 3n 1 side of the chip 3n made of N-type thermoelectric conversion material adjacent to the first surface 3p 1 side of the chip 3p made of P-type thermoelectric conversion material.
  • the second insulating layer L2 has a P-type thermoelectric conversion material on the second surface 3p2 side of the chip 3P made of P-type thermoelectric conversion material and the second surface 3n2 side of the chip 3n made of N-type thermoelectric conversion material adjacent to the second surface 3p2 side of the chip 3P made of P-type thermoelectric conversion material.
  • the chip 3p of P-type thermoelectric conversion material and the chip 3n of N-type thermoelectric conversion material are: A first insulating layer is provided on the first surface 3p 1 side of the chip 3p made of P-type thermoelectric conversion material and on the first surface 3n 1 side of the chip 3n made of N-type thermoelectric conversion material adjacent to the chip arrangement direction 4.
  • a first electrode M1 provided to interpose L1 and further straddle the first insulating layer L1;
  • a second insulating layer L2 is provided on the second surface 3n 2 side of the chip made of N-type thermoelectric conversion material and on the second surface 3p 2 side of the chip made of P-type thermoelectric conversion material adjacent to the chip arrangement direction 4.
  • a second electrode M2 interposed and further provided to straddle the second insulating layer L2, They are electrically connected in this order alternately in the chip arrangement direction 4, A gap formed between the first insulating layer L1, the second insulating layer L2, the chip 3p of the P-type thermoelectric conversion material, and the chip 3n of the N-type thermoelectric conversion material is maintained.
  • 2 indicates a frame that also has the function of sealing the outer periphery of the thermoelectric conversion module. This embodiment does not have a supporting base material or a solder layer used for bonding the electrodes.
  • FIG. 2 is a cross-sectional configuration diagram showing a second embodiment of the thermoelectric conversion module of the present invention, in which the thermoelectric conversion module 11 has the structure shown in FIG. , a first protective layer H1 is provided, and a second protective layer H2 is provided on the second electrode M2 and the second insulating layer L2. 12 indicates a contact hole for an extraction electrode.
  • this embodiment also does not have a supporting base material and a solder layer used for bonding the electrodes.
  • FIG. 3 is a cross-sectional configuration diagram showing a third embodiment of the thermoelectric conversion module of the present invention.
  • a second heat dissipation layer T2 is provided on the second protective layer H2. 13 indicates an extraction electrode.
  • this embodiment also does not have a supporting base material and a solder layer used for bonding the electrodes.
  • the thermoelectric conversion module of the present invention includes a first insulating layer and a second insulating layer.
  • the insulating layer has the function of maintaining insulation between adjacent chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material, and gaps between chips of P-type thermoelectric conversion material and chips of N-type thermoelectric conversion material.
  • the first insulating layer and the second insulating layer are each independently preferably selected from polyimide resin, silicone resin, rubber resin, acrylic resin, olefin resin, maleimide resin, and epoxy resin, although they are not particularly limited. .
  • the insulating layer it is preferable to form the insulating layer so that the gaps between and around the chips of the P-type thermoelectric conversion material and the N-type thermoelectric conversion material are not filled.
  • known methods such as lamination can be used.
  • a method for patterning the insulating layer a known method can be used and is not particularly limited, but for example, by exposure and development treatment or laser irradiation, each chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material are patterned. It is preferable to provide the contact holes so that the upper and lower surfaces are exposed.
  • a photosensitive resin for example, when a photosensitive resin is used, a desired photomask for forming a contact hole is interposed, the resin is exposed to ultraviolet rays, etc., and then processed using a developer or the like.
  • examples include methods.
  • examples of laser irradiation include processing methods using carbon dioxide laser, ultraviolet laser, and the like.
  • each insulating layer is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and still more preferably 15 to 30 ⁇ m. When the thickness of the insulating layer is within this range, insulation between adjacent electrodes can be ensured, and the thickness of the thermoelectric conversion module will not increase.
  • the thermoelectric conversion module of the present invention includes a first electrode and a second electrode.
  • the electrode covers the insulating layer and the upper and lower surfaces of the P-type thermoelectric conversion material chip and the N-type conversion material chip, and is not directly formed using a support base material or the like.
  • the electrode materials are each independently preferably selected from gold, silver, copper, nickel, chromium, platinum, palladium, rhodium, molybdenum, aluminum, or an alloy containing any of these metals.
  • the electrode covers the insulating layer and the upper and lower surfaces of the P-type thermoelectric conversion material chip and the N-type conversion material chip, and is made of a sputtered film, a vapor deposited film, and a plated film from the viewpoint of maintaining high thermoelectric performance. It is preferable that the film is formed of at least one kind of film selected from the group.
  • Examples of methods for patterning the electrode material to form electrodes include methods of processing the material into a predetermined pattern shape by known physical or chemical treatments, mainly photolithography, or a combination thereof.
  • Specific methods for processing into a predetermined pattern include, for example, a method of directly forming by exposure and development, a method of forming by etching after exposure and development, a method of directly forming by laser processing, and the like.
  • a method of directly forming by exposure and development processing is particularly preferable.
  • the thickness of the electrode depends on the thickness of the insulating layer used, but is preferably 5 to 200 ⁇ m, more preferably 8 to 150 ⁇ m, and still more preferably 10 to 120 ⁇ m. If the thickness of the electrode is within the above range, the electrical conductivity will be high and the resistance will be low, and sufficient strength as an electrode will be obtained.
  • thermoelectric conversion material used in the present invention is not particularly limited, and may be made of a thermoelectric semiconductor material or a thin film made of a thermoelectric semiconductor composition. From the viewpoints of flexibility, thinness, and thermoelectric performance, it consists 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. Preferably, it is made of a thin film.
  • thermoelectric semiconductor particles 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.
  • thermoelectric conversion material or “chip of thermoelectric conversion material” have the same meaning, and also have the same meaning as “thermoelectric conversion material layer.”
  • thermoelectric semiconductor material used for the thermoelectric conversion material chip is preferably ground to a predetermined size using a pulverizer or the like and used as thermoelectric semiconductor particles (hereinafter, the thermoelectric semiconductor material is referred to as "thermoelectric semiconductor particles"). ).
  • the particle size of the thermoelectric semiconductor particles is preferably 10 nm to 100 ⁇ m, more preferably 20 nm to 50 ⁇ m, 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 particle size analyzer (Mastersizer 3000, manufactured by Malvern), and was taken as the median of the particle size distribution.
  • thermoelectric semiconductor material constituting the P-type thermoelectric conversion material chip and the N-type conversion material chip can generate thermoelectromotive force by applying a temperature difference.
  • bismuth-tellurium thermoelectric semiconductor materials such as P-type bismuth telluride and N-type bismuth telluride; telluride thermoelectric semiconductor materials such as GeTe and PbTe; antimony-tellurium thermoelectric semiconductor materials; Zinc-antimony thermoelectric semiconductor materials such as ZnSb, Zn 3 Sb 2, Zn 4 Sb 3 ; silicon-germanium thermoelectric semiconductor materials such as SiGe; bismuth 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; Heusler materials such as FeVAl, FeVAlSi, and FeVTiAl, and
  • thermoelectric semiconductor material used in the present invention is preferably a bismuth-tellurium thermoelectric semiconductor material such as P-type bismuth telluride or N-type bismuth telluride.
  • the P-type bismuth telluride has holes as carriers and a positive Seebeck coefficient, and is preferably represented by, for example, Bi X Te 3 Sb 2-X .
  • X preferably satisfies 0 ⁇ X ⁇ 0.8, more preferably 0.4 ⁇ X ⁇ 0.6.
  • X is greater than 0 and less than or equal to 0.8, the Seebeck coefficient and electrical conductivity become large, and the properties as a P-type thermoelectric conversion material are maintained, which is preferable.
  • the N-type bismuth telluride has an electron as a carrier and a negative Seebeck coefficient, and for example, one represented by Bi 2 Te 3-Y Se Y is preferably used.
  • the content of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. More preferably, it is 50 to 96% by mass, and even more preferably 70 to 95% by mass. If the content of thermoelectric semiconductor particles is within the above range, the Seebeck coefficient (absolute value of the Peltier coefficient) is large, and the decrease in electrical conductivity is suppressed, and only the thermal conductivity decreases, resulting in high thermoelectric performance. At the same time, a film having sufficient film strength and flexibility can be obtained, which is preferable.
  • thermoelectric semiconductor particles are those that have been subjected to an annealing treatment (hereinafter sometimes referred to as "annealing treatment A").
  • 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, so the Seebeck coefficient (absolute value of the Peltier coefficient) of the thermoelectric conversion material increases. , the thermoelectric figure of merit can be further improved.
  • the resin used in the present invention has the effect of physically bonding between thermoelectric semiconductor materials (thermoelectric semiconductor particles), can increase the flexibility of the thermoelectric conversion module, and facilitates the formation of a thin film by coating etc. .
  • a heat-resistant resin or a binder resin is preferable.
  • the heat-resistant resin maintains its physical properties such as mechanical strength and thermal conductivity as a resin when crystal-growing thermoelectric semiconductor particles by annealing a thin film made of a thermoelectric semiconductor composition or the like.
  • the heat-resistant resin is preferably a polyamide resin, a polyamide-imide resin, a polyimide resin, or an epoxy resin because it has higher heat resistance and does not adversely affect the crystal growth of the thermoelectric semiconductor particles in the thin film, and has excellent flexibility. 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. If the decomposition temperature is within the above range, even when a thin film made of the thermoelectric semiconductor composition is annealed, it will not lose its function as a binder and will maintain its flexibility, as will be described later.
  • the heat-resistant resin preferably has a mass reduction rate at 300°C measured by thermogravimetry (TG) of 10% or less, more preferably 5% or less, and even more preferably 1% or less. . If the mass reduction rate is within the above range, even when a thin film made of a thermoelectric semiconductor composition is annealed, the flexibility of the thermoelectric conversion material chip can be maintained without losing its function as a binder, as described later. I can do it.
  • TG thermogravimetry
  • the content of the heat-resistant resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 15% by mass. 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 provides a film that has both high thermoelectric performance and film strength, and is effective in thermoelectric conversion.
  • a resin portion is present on the outer surface of the material chip.
  • the binder resin can be easily peeled off from the base material such as glass, alumina, silicon, etc. used in the production of thermoelectric conversion material chips after firing (annealing) treatment (corresponds to "annealing treatment B" described later, the same applies hereinafter). Make it.
  • the binder resin refers to a resin that decomposes at least 90% by mass at a firing (annealing) temperature or higher, more preferably a resin that decomposes at least 95% by mass, and a resin that decomposes at least 99% by mass. is particularly preferred.
  • a coating film (thin film) made of a thermoelectric semiconductor composition is subjected to a baking (annealing) treatment or the like to cause crystal growth of thermoelectric semiconductor particles, a resin that maintains various physical properties such as mechanical strength and thermal conductivity without loss is required. More preferred.
  • the binder resin If a resin that decomposes at least 90% by mass at a temperature equal to or higher than the sintering (annealing) temperature is used as the binder resin, in other words, a resin that decomposes at a lower temperature than the aforementioned heat-resistant resin, the binder resin will decompose during sintering, so the sintered product will The content of the binder resin, which is an insulating component, is reduced, and the crystal growth of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is promoted, so the voids in the thermoelectric conversion material layer are reduced and the filling rate is increased. can be improved.
  • thermoplastic resins 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.
  • Polyvinyl polymers such as vinyl, ethylene-vinyl acetate copolymer, vinyl chloride, polyvinylpyridine, polyvinyl alcohol, and polyvinylpyrrolidone; polyurethane; cellulose derivatives such as ethylcellulose; and the like.
  • thermosetting resins examples include epoxy resins and phenol resins.
  • thermosetting resins examples include epoxy resins and phenol resins.
  • photocurable resin examples include photocurable acrylic resin, photocurable urethane resin, and photocurable epoxy resin. These may be used alone or in combination of two or more. Among these, from the viewpoint of electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer, thermoplastic resins are preferred, cellulose derivatives such as polycarbonate and ethyl cellulose are more preferred, and polycarbonate is particularly preferred.
  • the binder resin is appropriately selected depending on the temperature of the firing (annealing) process for the thermoelectric semiconductor material in the firing (annealing) process. 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 electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer.
  • the "final decomposition temperature” refers to the temperature at which the mass reduction rate at the calcination (annealing) temperature as measured by thermogravimetry (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, particularly preferably 240 to 360°C. If a binder resin with a final decomposition temperature within this range is used, it will function as a binder for the thermoelectric semiconductor material and will facilitate the formation of a thin film during 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, particularly preferably 0.5 to 5% by mass. 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, particularly preferably 0 to 1% by mass. If the content of the binder resin in the thermoelectric conversion material is within the above range, the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer can be reduced.
  • the ionic liquid that can be contained in the thermoelectric semiconductor composition is a molten salt formed by combining a cation and an anion, and refers to a salt that can exist in a liquid state in a temperature range of -50°C or higher and lower than 400°C.
  • an ionic liquid is an ionic compound having a melting point in the range of -50°C or more and less than 400°C.
  • the melting point of the ionic liquid is preferably -25°C or more and 200°C or less, more preferably 0°C or more and 150°C or less.
  • Ionic liquids have characteristics such as extremely low vapor pressure, non-volatility, excellent thermal stability and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, as a conductivity auxiliary agent, it is possible to effectively suppress reduction in electrical conductivity between thermoelectric semiconductor materials. Furthermore, the ionic liquid exhibits high polarity based on its aprotic ionic structure and has excellent compatibility with heat-resistant resins, so that the electrical conductivity of the thermoelectric conversion material can be made uniform.
  • ionic liquids can be used.
  • nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, and imidazolium and their derivatives; tetraalkylammonium-based amine cations and their derivatives; phosphonium, trialkylsulfonium, tetraalkylphosphonium, etc.
  • Phosphine cations and derivatives thereof Phosphine cations and derivatives thereof; cationic components such as lithium cations and derivatives thereof; 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 ) 2 N - , C 3 F 7 COO - , (CF
  • the cation component of the ionic liquid is pyridinium cation and its derivatives. , imidazolium cations and derivatives thereof.
  • ionic liquid whose cation component includes a pyridinium cation and its derivatives
  • 1-butyl-4-methylpyridinium bromide, 1-butylpyridinium bromide, and 1-butyl-4-methylpyridinium hexafluorophosphate are preferred.
  • the above ionic liquid has a decomposition temperature of 300° C. or higher. If the decomposition temperature is within the above range, the effect as a conductive aid can be maintained even when a 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 even more preferably 1.0 to 20% by mass.
  • the content of the ionic liquid is within the above range, a decrease in electrical conductivity is effectively suppressed, and a film having high thermoelectric performance can be obtained.
  • the inorganic ionic compound that can be contained in the thermoelectric semiconductor composition is a compound that is composed of at least a cation and an anion.
  • Inorganic ionic compounds exist as solids in a wide temperature range of 400 to 900°C and have characteristics such as high ionic conductivity, so they can be used as conductive aids to reduce the electrical conductivity between thermoelectric semiconductor materials. 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 even more preferably 1.0 to 10% by mass.
  • the content of the inorganic ionic compound is within the above range, a decrease in electrical conductivity can be effectively suppressed, and as a result, a membrane with 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 weight, more preferably 1.0 to 10% by weight.
  • Methods for applying P-type and N-type thermoelectric semiconductor compositions include screen printing, flexographic printing, gravure printing, spin coating, dip coating, die coating, spray coating, bar coating, and doctor coating.
  • Known methods such as the blade method may be used, but are not particularly limited.
  • the obtained coating film is dried to form a thin film, and conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be employed.
  • the heating temperature is usually 80 to 150°C, and the heating time varies depending on the heating method, but is usually from several seconds to several tens of minutes. Furthermore, when a solvent is used in preparing the thermoelectric semiconductor composition, the heating temperature is not particularly limited as long as it is within a temperature range that can dry the used solvent.
  • the thickness of the thermoelectric conversion material chip is not particularly limited, and from the viewpoint of thermoelectric performance and film strength, it is preferably 100 nm to 1000 ⁇ m, more preferably 300 nm to 600 ⁇ m, and even more preferably 5 to 400 ⁇ m.
  • thermoelectric conversion material and the chips of the N-type thermoelectric conversion material made of the thermoelectric semiconductor composition are further subjected to an annealing treatment (hereinafter sometimes 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.
  • annealing treatment B is usually performed under an inert gas atmosphere such as nitrogen or argon, under a reducing gas atmosphere, or under vacuum conditions with a controlled gas flow rate. Although it depends on the heat resistance temperature, it is carried out at 100 to 500°C for several minutes to several tens of hours.
  • thermoelectric conversion module of the present invention a first protective layer is provided on the first electrode and the first insulating layer, and a second protective layer is provided on the second electrode and the second insulating layer.
  • a layer is provided.
  • the materials used for the first protective layer and the second protective layer are not particularly limited, and known materials can be used.
  • the first protective layer and the second protective layer are each independently preferably selected from insulating resins and ceramics.
  • insulating resins examples include polyimide resins, polyamide resins, phenol resins, epoxy resins, maleimide resins, fluorine resins, polyester resins, polyurethane resins (especially polyacrylic polyols, polyester polyols, polyether polyols, etc., and isocyanate compounds).
  • Resins such as acrylic resin, polycarbonate resin, vinyl chloride/vinyl acetate copolymer, polyvinyl butyral resin, and nitrocellulose resin; alkyl titanate; ethyleneimine; and the like. These may be used alone or in combination of two or more.
  • Ceramics include materials whose main components (50% by mass or more in ceramics) include aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicon nitride, silicon carbide, and the like.
  • main components for example, a rare earth compound can also be added.
  • a protective layer forming solution prepared by dissolving or dispersing the above materials in an appropriate solvent is applied by a known method, the resulting coating is dried, and if desired, heated or It can be formed by irradiating light.
  • the protective layer may be formed by separately forming a film for forming a protective layer and laminating it with a roll laminator or a flat press machine. Lamination may be performed at room temperature or may be performed while heating.
  • the thickness of the first protective layer and the second protective layer is appropriately determined from the viewpoint of thermoelectric performance, but each independently preferably has a thickness of 5 to 300 ⁇ m, more preferably 25 to 200 ⁇ m, and even more preferably 50 to 300 ⁇ m. It is 100 ⁇ m.
  • the thickness of each protective layer is preferably 5 to 150 ⁇ m, more preferably 10 to 100 ⁇ m, and still more preferably 15 to 50 ⁇ m.
  • the thickness of the protective layer is preferably 20 to 300 ⁇ m, more preferably 40 to 200 ⁇ m, and even more preferably 50 to 100 ⁇ m. .
  • thermoelectric conversion module of the present invention from the viewpoint of thermoelectric performance, it is preferable to further provide a heat dissipation layer on the first protective layer and the second protective layer.
  • the materials used for the first heat dissipation layer and the second heat dissipation layer are not particularly limited, and known materials can be used.
  • the method of laminating the heat dissipation layer is not particularly limited, but may include PVD (physical vapor deposition) such as vacuum evaporation, sputtering, and ion plating, or CVD (such as thermal CVD and atomic layer deposition (ALD)).
  • PVD physical vapor deposition
  • CVD thermal CVD and atomic layer deposition
  • dry processes such as chemical vapor deposition (chemical vapor deposition); various coating methods such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade methods; wet processes such as electrodeposition; Examples include salt method, electrolytic plating method, electroless plating method, and the like.
  • patterning of the heat dissipation layer can be performed by known physical processing or chemical processing mainly based on photolithography, or a combination thereof.
  • the thermal conductivity of the heat dissipation layer is preferably 5 to 500 W/(m K), more preferably 8 to 500 W/(m K), even more preferably 10 to 450 W/(m K), each independently. Particularly preferably 12 to 420 W/(m ⁇ K), most preferably 15 to 400 W/(m ⁇ K).
  • the thickness of the heat dissipation layer is determined as appropriate from the viewpoint of thermoelectric performance, but is preferably 5 to 550 ⁇ m, more preferably 40 to 530 ⁇ m, and even more preferably 80 to 510 ⁇ m.
  • a frame may be provided around the thermoelectric conversion module of the present invention. Providing the frame eliminates the need to seal the outer periphery of the thermoelectric conversion module.
  • the frame is made of metal, ceramics, or resin. From the viewpoint of sealing performance, it is preferable to use metal or ceramics. Further, from the viewpoint of weight reduction, it is preferable to use resin. Examples of the metal include gold, silver, copper, nickel, chromium, platinum, palladium, rhodium, molybdenum, aluminum, iron, iron-nickel alloy, and phosphor bronze.
  • Ceramics include materials whose main components (50% by mass or more in ceramics) include aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicon nitride, silicon carbide, and the like.
  • main components for example, a rare earth compound can also be added.
  • the resin include polyimide resin, polyamide resin, phenol resin, epoxy resin, maleimide resin, fluorine resin, and the like. Note that when resin is used, a rigid material using a hard resin may be used, or a flexible material using a flexible resin may be used.
  • thermoelectric conversion module of the present invention does not use a base material as a support and a solder layer that have been conventionally used, the thermoelectric conversion module can be made thin.
  • thermoelectric conversion module of the present invention it is expected that the conventional thermoelectric conversion module can be made thinner, leading to lighter weight, smaller size, and higher integration.
  • Thermoelectric conversion module 2 Frame 3p: Chip 3n of P-type thermoelectric conversion material: Chip 3p of N-type thermoelectric conversion material 1 : First surface 3p of chip 3p of P-type thermoelectric conversion material 2 : P Second surface 3n 1 of chip 3n of N-type thermoelectric conversion material: First surface 3n 2 of chip 3n of N-type thermoelectric conversion material: Second surface 4 of chip 3n of N-type thermoelectric conversion material: Chip arrangement direction L1: First insulating layer L2: Second insulating layer M1: First electrode M2: Second electrode H1: First protective layer H2: Second protective layer T1: First heat dissipation layer T2: First 2 heat dissipation layer 12: contact hole for extraction electrode 13: extraction electrode

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  • Measuring Temperature Or Quantity Of Heat (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

L'invention concerne un module de conversion thermoélectrique mince qui n'a pas de substrat de support et de couche de brasure, des électrodes M1 ou M2 qui sont partagées entre des puces de matériau de conversion thermoélectrique de type p adjacentes 3p et des puces de matériau de conversion thermoélectrique de type n 3n sont agencées (câblées) directement sur des surfaces supérieure / inférieure des puces de matériau de conversion thermoélectrique de type p 3p et des puces de matériau de conversion thermoélectrique de type n 3n de façon à chevaucher des couches d'isolation opposées L1, L2 qui couvrent des espaces entre les puces de matériau de conversion thermoélectrique de type p 3p et les puces de matériau de conversion thermoélectrique de type n 3n.
PCT/JP2023/012719 2022-03-31 2023-03-29 Module de conversion thermoélectrique WO2023190633A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019525456A (ja) * 2016-06-23 2019-09-05 スリーエム イノベイティブ プロパティズ カンパニー フレキシブル熱電モジュール
WO2020166647A1 (fr) * 2019-02-15 2020-08-20 パナソニックＩｐマネジメント株式会社 Substrat de conversion thermoélectrique et module de conversion thermoélectrique
WO2020196001A1 (fr) * 2019-03-25 2020-10-01 リンテック株式会社 Module de conversion thermoélectrique et procédé de production de module de conversion thermoélectrique

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019525456A (ja) * 2016-06-23 2019-09-05 スリーエム イノベイティブ プロパティズ カンパニー フレキシブル熱電モジュール
WO2020166647A1 (fr) * 2019-02-15 2020-08-20 パナソニックＩｐマネジメント株式会社 Substrat de conversion thermoélectrique et module de conversion thermoélectrique
WO2020196001A1 (fr) * 2019-03-25 2020-10-01 リンテック株式会社 Module de conversion thermoélectrique et procédé de production de module de conversion thermoélectrique

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