WO2020196709A1 - Procédé pour fabriquer une puce d'un matériau de conversion thermoélectrique - Google Patents

Procédé pour fabriquer une puce d'un matériau de conversion thermoélectrique Download PDF

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Publication number
WO2020196709A1
WO2020196709A1 PCT/JP2020/013547 JP2020013547W WO2020196709A1 WO 2020196709 A1 WO2020196709 A1 WO 2020196709A1 JP 2020013547 W JP2020013547 W JP 2020013547W WO 2020196709 A1 WO2020196709 A1 WO 2020196709A1
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thermoelectric conversion
conversion material
thermoelectric
chip
resin
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PCT/JP2020/013547
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English (en)
Japanese (ja)
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邦久 加藤
亘 森田
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リンテック株式会社
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Priority to JP2021509566A priority Critical patent/JP7458375B2/ja
Priority to CN202080025034.XA priority patent/CN113632253A/zh
Publication of WO2020196709A1 publication Critical patent/WO2020196709A1/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
    • H10N10/01—Manufacture or treatment
    • 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
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

Definitions

  • the present invention relates to a method for manufacturing a chip of a thermoelectric conversion material that performs mutual energy conversion between heat and electricity.
  • thermoelectric conversion module having a thermoelectric effect such as the Seebeck effect and the Peltier effect.
  • thermoelectric conversion module the use of a so-called ⁇ -type thermoelectric conversion element is known.
  • a pair of electrodes separated from each other are provided on the substrate, for example, a P-type thermoelectric element is provided on the-one electrode and an N-type thermoelectric element is provided on the other electrode, also separated from each other.
  • It is configured by connecting the top surfaces of both thermoelectric materials to the electrodes of the opposing substrates.
  • in-plane type thermoelectric conversion element is known.
  • thermoelectric elements and N-type thermoelectric elements are alternately provided in the in-plane direction of the substrate.
  • the lower part of the joint between the two thermoelectric elements is connected in series via electrodes.
  • thermoelectric performance of the thermoelectric conversion module there are demands for improving the flexibility, thinning, and improving thermoelectric performance of the thermoelectric conversion module.
  • a resin substrate such as a polyimide film is used as a substrate used for a thermoelectric conversion module from the viewpoint of heat resistance and flexibility.
  • thermoelectric semiconductor material As the N-type thermoelectric semiconductor material and the P-type thermoelectric semiconductor material, a thin film of a bismuthtellide-based material is used from the viewpoint of thermoelectric performance, and the electrode is a Cu electrode having high thermal conductivity and low resistance. Is used. (Patent Documents 1, 2, etc.).
  • thermoelectric semiconductor material contained in the thermoelectric conversion material formed from the thermoelectric semiconductor composition in response to the demands for improving the flexibility, thinning and thermoelectric performance of the thermoelectric conversion module.
  • a system material a Cu electrode is used as the electrode, and a resin such as polyimide is used as the substrate, for example, in the step of annealing the thermoelectric conversion module at a high temperature of 300 ° C., the thermoelectric semiconductor contained in the thermoelectric conversion material.
  • an alloy layer is formed by diffusion, resulting in cracking and peeling of the electrode, increasing the electrical resistance value between the thermoelectric conversion material and the Cu electrode, and reducing thermoelectric performance.
  • the heat resistant temperature of the substrate may be lower than the optimum annealing temperature of the thermoelectric semiconductor material, and the optimum annealing may not be possible.
  • the present invention enables an annealing treatment of a thermoelectric conversion material in a form having no joint with an electrode in a simple process, and a thermoelectric conversion material capable of annealing a thermoelectric semiconductor material at an optimum annealing temperature. It is an object of the present invention to provide a method for manufacturing a chip.
  • thermoelectric conversion material composed of a thermoelectric semiconductor material and a thermoelectric semiconductor composition containing a resin on a substrate, and then formed them. Chips of a plurality of thermoelectric conversion materials that have been annealed in a form that does not have a joint with an electrode by a simple process of annealing at a temperature equal to or higher than the decomposition temperature of the resin and then peeling from the substrate.
  • the present invention has been completed by finding a method for producing a "thermoelectric conversion material", “self-supporting film of thermoelectric conversion material”, or simply “self-supporting film”). That is, the present invention provides the following (1) to (8).
  • thermoelectric conversion material made of a thermoelectric semiconductor composition, which is obtained in (A) a step of forming the chip of the thermoelectric conversion material on a substrate, and (B) the step (A).
  • the thermoelectric semiconductor composition includes a step of annealing the chip of the thermoelectric conversion material obtained, and (C) a step of peeling off the chip of the thermoelectric conversion material after the annealing treatment obtained in the step (B).
  • a method for producing a chip of a thermoelectric conversion material wherein the product contains a thermoelectric semiconductor material and a resin, and the temperature of the annealing treatment is equal to or higher than the decomposition temperature of the resin.
  • thermoelectric conversion material (2) The method for producing a chip of a thermoelectric conversion material according to (1) above, wherein the decomposition temperature of the resin is 280 to 420 ° C. (3) The method for producing a chip of a thermoelectric conversion material according to (1) or (2) above, wherein the resin is a polyvinyl polymer. (4) The method for producing a chip of a thermoelectric conversion material according to any one of (1) to (3) above, wherein the resin is polyvinylpyrrolidone, polyvinyl alcohol, or polystyrene.
  • thermoelectric semiconductor material is a bismuth-tellu-based thermoelectric semiconductor material, a telluride-based thermoelectric semiconductor material, an antimony-tellu-based thermoelectric semiconductor material, or a bismuth selenide-based thermoelectric semiconductor material.
  • the method for manufacturing a chip of a thermoelectric conversion material according to any one of. (6) The method for producing a chip of a thermoelectric conversion material according to any one of (1) to (5) above, wherein the thermoelectric semiconductor composition further contains an ionic liquid and / or an inorganic ionic compound.
  • thermoelectric conversion material according to any one of (1) to (6) above, wherein the annealing treatment temperature is 280 to 550 ° C.
  • the substrate is a glass substrate.
  • thermoelectric conversion material chip that enables annealing of a thermoelectric conversion material in a form having no joint with an electrode in a simple process and enables annealing of a thermoelectric semiconductor material at an optimum annealing temperature. Manufacturing method can be provided.
  • thermoelectric conversion material of this invention It is sectional drawing for demonstrating an example of embodiment of the method of manufacturing the chip of the thermoelectric conversion material of this invention. It is explanatory drawing which shows an example of the embodiment of the process according to the manufacturing method of the thermoelectric conversion module which combined a plurality of chips of the thermoelectric conversion material obtained from the manufacturing method of the chip of the thermoelectric conversion material of this invention in process order.
  • the method for producing a chip of a thermoelectric conversion material of the present invention is a method for producing a chip of a thermoelectric conversion material made of a thermoelectric semiconductor composition, wherein (A) a step of forming the chip of the thermoelectric conversion material on a substrate, ( B) A step of annealing the chip of the thermoelectric conversion material obtained in the step (A), and (C) peeling off the chip of the thermoelectric conversion material obtained in the step (B) after the annealing treatment.
  • the thermoelectric semiconductor composition comprises a thermoelectric semiconductor material and a resin, and the temperature of the annealing treatment is equal to or higher than the decomposition temperature of the resin.
  • thermoelectric conversion material that is, thermoelectric conversion is performed by annealing the thermoelectric semiconductor material constituting the thermoelectric semiconductor composition at a temperature higher than the decomposition temperature of the resin. A free-standing film of the material can be easily obtained.
  • FIG. 1 is a cross-sectional configuration diagram for explaining an example of an embodiment of a method for manufacturing a chip of a thermoelectric conversion material of the present invention.
  • a P-type thermoelectric conversion material chip 2a and an N-type thermoelectric conversion material chip 2b which are thermoelectric conversion materials 2 composed of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material and a resin, are formed on a substrate 1, and then they are made of a resin.
  • chips of the thermoelectric conversion material can be obtained as a self-supporting film of the thermoelectric conversion material.
  • thermoelectric conversion material is a step of forming a chip of a thermoelectric conversion material on a substrate. For example, in FIG. 1, from a thermoelectric semiconductor composition on a substrate 1. This is a step of applying the chip 2 of the thermoelectric conversion material, that is, the chip 2a of the P-type thermoelectric conversion material and the chip 2b of the N-type thermoelectric conversion material as a thin film.
  • the arrangement of the P-type thermoelectric conversion material chip and the N-type thermoelectric conversion material chip is not particularly limited, but from the viewpoint of thermoelectric performance, the configuration used for the ⁇ -type or in-plane type thermoelectric conversion module is set.
  • thermoelectric conversion module for example, a pair of electrodes that are separated from each other are provided on the substrate, a chip of P-type thermoelectric conversion material is provided on one electrode, and a chip of P-type thermoelectric conversion material is placed on the other electrode.
  • the N-type thermoelectric conversion material chips are also provided apart from each other, and the upper surfaces of the chips of both thermoelectric conversion materials are electrically connected in series to the electrodes on the opposing substrates.
  • thermoelectric conversion material chips a plurality of pairs of P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips interposed at the electrodes of opposite substrates are electrically connected in series and used (described later). (See (f) in FIG. 2) is preferable.
  • an in-plane type thermoelectric conversion module is configured, for example, one electrode is provided on a substrate, a chip of a P-type thermoelectric conversion material is provided on the surface of the electrode, and an N-type is also provided on the surface of the electrode.
  • the chips of the thermoelectric conversion material are provided so that the side surfaces of both chips (for example, the surfaces in the direction perpendicular to the substrate) are in contact with each other or separated from each other, and electrically via the electrodes in the in-plane direction of the substrate. It is configured by connecting in series (for example, in the case of a power generation configuration, a pair of electromotive force extraction electrodes are used together). From the viewpoint of efficiently obtaining high thermoelectric performance, in the configuration, the same number of P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips alternately interpose electrodes and electrically in the in-plane direction of the substrate. It is preferable to use them in series.
  • the substrate examples include glass, silicon, ceramic, metal, plastic and the like. Glass, silicon, ceramic, and metal are preferable from the viewpoint of performing the annealing treatment at a high temperature, and glass, silicon, and ceramic are used from the viewpoint of adhesion to thermoelectric conversion materials, material cost, and dimensional stability after heat treatment. Is more preferable. From the viewpoint of process and dimensional stability, the thickness of the substrate can be 100 to 10000 ⁇ m.
  • a thermoelectric semiconductor composition containing a thermoelectric semiconductor material and a resin.
  • thermoelectric semiconductor material is composed of a thin film composed of a thermoelectric semiconductor composition further containing an ionic liquid and / or an inorganic ionic compound.
  • thermoelectric semiconductor material is preferably used as thermoelectric semiconductor particles (hereinafter, the thermoelectric semiconductor material may be referred to as "thermoelectric semiconductor particles").
  • thermoelectric semiconductor material used in the present invention, that is, the thermoelectric semiconductor material contained in the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material, can generate thermoelectromotive force 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; 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, FeVALSi, FeVTiAl and other Whistler materials, TiS 2 and other sulfide-based thermoelectric semiconductor materials, etc. Be done.
  • a bismuth-tellurium-based thermoelectric semiconductor material such as P-type bismuth telluride or N-type bismuth telluride is more preferable.
  • P-type bismuth telluride those having holes as carriers and a positive Seebeck coefficient, for example, represented by Bi X Te 3 Sb 2-X , are preferably used.
  • X is preferably 0 ⁇ X ⁇ 0.8, more preferably 0.4 ⁇ X ⁇ 0.6.
  • the Seebeck coefficient and the electric conductivity become large, and the characteristics as a P-type thermoelectric element are maintained, which is preferable.
  • the 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 element are maintained, which is preferable.
  • thermoelectric semiconductor particles used in the thermoelectric semiconductor composition are obtained by pulverizing the above-mentioned thermoelectric semiconductor material to a predetermined size by a fine pulverizer or the like.
  • the blending amount 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 Peltier 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.
  • the average particle size of the thermoelectric semiconductor particles is preferably 10 nm to 200 ⁇ m, more preferably 10 nm to 30 ⁇ m, still more preferably 50 nm to 10 ⁇ m, and particularly preferably 1 to 6 ⁇ m. Within the above range, uniform dispersion can be facilitated and the electric conductivity can be increased.
  • the method of pulverizing the thermoelectric semiconductor material to obtain thermoelectric semiconductor particles is not particularly limited, and it may be pulverized to a predetermined size by a known pulverizer such as a jet mill, a ball mill, a bead mill, a colloid mill, a roller mill or the like. ..
  • 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 particles are preferably those that have been heat-treated in advance (the "heat treatment” here is different from the “annealing treatment” performed in the annealing treatment step of the present invention).
  • the heat treatment is not particularly limited, but before preparing the thermoelectric semiconductor composition, the gas flow rate is controlled so as not to adversely affect the thermoelectric semiconductor particles under an atmosphere of an inert gas such as nitrogen or argon.
  • thermoelectric semiconductor particles It is preferably performed in a reducing gas atmosphere such as hydrogen or under vacuum conditions, and more preferably in a mixed gas atmosphere of an inert gas and a reducing gas.
  • a reducing gas atmosphere such as hydrogen or under vacuum conditions
  • a mixed gas atmosphere of an inert gas and a reducing gas The specific temperature condition depends on the thermoelectric semiconductor particles used, but it is usually preferable to carry out the temperature at a temperature equal to or lower than the melting point of the particles and at 100 to 1500 ° C. for several minutes to several tens of hours.
  • the thermoelectric semiconductor composition contains a resin.
  • the resin facilitates peeling of the thermoelectric conversion material from the substrate after the annealing treatment, acts as a binder between the thermoelectric semiconductor materials (thermoelectric semiconductor particles), can enhance the flexibility of the thermoelectric conversion module, and can be applied, etc.
  • the resin is appropriately selected according to the temperature of the annealing treatment on the thermoelectric semiconductor material in the (B) annealing treatment step described later. This is because it is essential to perform the annealing treatment at a temperature higher than the decomposition temperature of the resin from the viewpoint of facilitating the peeling of the thermoelectric conversion material from the substrate. If the annealing treatment is performed at a temperature lower than the decomposition temperature of the resin, it becomes difficult for the thermoelectric conversion material after the annealing treatment to be peeled off from the substrate.
  • the resin is not particularly limited as long as the temperature range of the annealing treatment for the thermoelectric semiconductor material to be used is within the range of the decomposition temperature of the resin or higher, and a thermoplastic resin or a curable resin can be used. ..
  • a resin that maintains various physical properties such as mechanical strength and thermal conductivity as the resin is preferable.
  • thermoplastic resin examples include acrylic resins such as methyl poly (meth) acrylate, ethyl poly (meth) acrylate, methyl (meth) butyl acrylate- (meth) butyl acrylate copolymer, polyethylene, polypropylene, polyisobutylene, and the like.
  • Polypropylene resin such as polymethylpentene, polycarbonate resin, thermoplastic polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polystyrene, acrylonitrile-styrene copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride, polyvinyl Examples thereof include polyvinyl polymers such as pyridine, polyvinyl alcohol and polyvinylpyrrolidone, polyurethane and ethyl cellulose.
  • methyl poly (meth) acrylate means methyl polyacrylate or polymethyl methacrylate, and (meth) has the same meaning.
  • the curable resin include thermosetting resins and photocurable resins.
  • thermosetting resin examples include epoxy resin and phenol resin.
  • photocurable resin examples include a photocurable acrylic resin, a photocurable urethane resin, and a photocurable epoxy resin.
  • Thermoplastic resin is preferable, and polyvinyl polymer, polyisobutylene, polymethyl methacrylate and the like can be mentioned.
  • the polyvinyl polymer is preferably a water-soluble polyvinyl polymer, and examples thereof include polyvinylpyrrolidone and polyvinyl alcohol.
  • the thermoplastic resin is more preferably polyvinylpyrrolidone, polyvinyl alcohol, or polystyrene.
  • the resin may be used alone or in combination of two or more, and the thermoelectric conversion material after the annealing treatment can be easily peeled off from the substrate and the thermoelectric performance is impaired.
  • a resin whose decomposition temperature exceeds the annealing treatment temperature may be combined as long as it does not exist.
  • the resin is not particularly limited and is selected depending on the annealing treatment temperature.
  • a heat-resistant resin having a high decomposition temperature which will be described later, can be mentioned.
  • a resin having a decomposition temperature equal to or lower than the annealing treatment temperature is referred to as a resin
  • a resin having a decomposition temperature exceeding the annealing treatment temperature is referred to as a heat-resistant resin.
  • the decomposition temperature in the present specification means a temperature at which the mass reduction rate at the annealing temperature by thermogravimetric analysis (TG) is 10%.
  • thermoelectric semiconductor composition used in the present invention may further contain a heat-resistant resin.
  • the heat-resistant resin acts as a binder between thermoelectric semiconductor materials (thermoelectric semiconductor particles), can increase the mechanical strength of the thermoelectric conversion module, and facilitates the formation of a thin film by coating or the like.
  • the heat-resistant resin is not particularly limited as long as the decomposition temperature exceeds the annealing treatment temperature, but the heat-resistant resin has higher heat resistance and does not adversely affect the crystal growth of the thermoelectric semiconductor particles in the thin film.
  • a polyamide resin, a polyamideimide resin, a polyimide resin, and an epoxy resin are preferable, and from the viewpoint of excellent flexibility, a polyamide resin, a polyamideimide resin, and a polyimide resin are more preferable.
  • the polyimide resin is more preferable as the heat-resistant resin from the viewpoint of adhesion to the polyimide film and the like.
  • the polyimide resin is a general term for polyimide and its precursor.
  • the blending ratio [heat-resistant resin / resin] of the resin and the heat-resistant resin contained in the thermoelectric semiconductor composition is preferably 0.01 or more and 0.5 or less from the viewpoint of good peelability from the substrate. It is more preferably 0.1 or more and 0.4 or less, and most preferably 0.15 or more and 0.3 or less.
  • the decomposition temperature of the resin is selected depending on the temperature of the annealing treatment of the thermoelectric semiconductor material, but is usually 260 to 450 ° C., preferably 280 to 420 ° C., more preferably 300 to 400 ° C., still more preferably 320 to 380 ° C. °C. If the resin having a decomposition temperature in this range is used, the thermoelectric conversion material after the annealing treatment can be easily peeled off from the substrate, the function as a binder is not lost, the thermoelectric performance is improved, and the flexibility is maintained. can do. Further, the mass reduction rate of the resin at 150 ° C. by thermogravimetric analysis (TG) is preferably 10% or less, more preferably 5% or less, and further preferably 1% or less. When the mass reduction rate is within the above range, the flexibility can be maintained without losing the function as a binder.
  • TG thermogravimetric analysis
  • the blending amount of the 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% by mass. is there.
  • the thermoelectric conversion material after the annealing treatment can be easily peeled off from the substrate, functions as a binder for the thermoelectric semiconductor material, and a thin film can be easily formed. A film having both high thermoelectric performance and film strength can be obtained.
  • the ionic liquid used in the present invention 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 to 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.
  • Ionic liquids have features such as extremely low vapor pressure, non-volatility, excellent thermostability 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 electric conductivity between the thermoelectric semiconductor particles. Further, since the ionic liquid exhibits high polarity based on the aprotic ionic structure and has excellent compatibility with the resin, the electric conductivity of the chip of the thermoelectric conversion material can be made uniform.
  • ionic liquid known or commercially available ones can be used.
  • nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and their derivatives; amine-based cations of tetraalkylammonium and their derivatives; phosphine such as phosphonium, trialkylsulfonium, tetraalkylphosphonium. systems cations and their derivatives; and cationic components, such as lithium cations and derivatives thereof, Cl -, AlCl 4 -, Al 2 Cl 7 -, ClO 4 - chloride or ion, Br -, etc.
  • 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 particles and resins, and suppression of decrease in electrical conductivity between thermoelectric semiconductor particle gaps.
  • At least one selected from imidazolium cations and derivatives thereof is preferably contained.
  • Anionic component of the ionic liquid preferably contains a halide anion, Cl -, Br - and I - is more preferably contains at least one selected from.
  • an ionic liquid in which the cation component contains a pyridinium cation and a derivative thereof include 4-methyl-butylpyridinium chloride, 3-methyl-butylpyridinium chloride, 4-methyl-hexylpyridinium chloride, and 3-methyl-hexylpyridinium.
  • Chloride 4-methyl-octylpyridinium chloride, 3-methyl-octylpyridinium chloride, 3,4-dimethyl-butylpyridinium chloride, 3,5-dimethyl-butylpyridinium chloride, 4-methyl-butylpyridinium tetrafluoroborate, 4- Methyl-butylpyridinium hexafluorophosphate, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium iodide, etc. Be done.
  • 1-butylpyridinium bromide 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, and 1-butyl-4-methylpyridinium iodide are preferable.
  • the ionic liquid in which the cation component contains an imidazolium cation and a derivative thereof [1-butyl-3- (2-hydroxyethyl) imidazolium bromide] and [1-butyl-3- (2) -Hydroxyethyl) imidazolium tetrafluoroborate], 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3 -Methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-Tetradecyl-3-methylimidazolium chloride, 1-ethyl-3- (2-hydroxyeth
  • the above-mentioned ionic liquid preferably has an electric conductivity of 10-7 S / cm or more, and more preferably 10-6 S / cm or more.
  • the electric conductivity is in the above range, the reduction of the electric conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductivity auxiliary agent.
  • 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 above-mentioned ionic liquid 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 blending amount 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 blending amount 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.
  • the inorganic ionic compound used in the present invention is a compound composed of at least cations and anions.
  • the inorganic ionic compound is solid at room temperature, has a melting point in any temperature in the temperature range of 400 to 900 ° C., and has characteristics such as high ionic conductivity. Therefore, it can be used as a conductive auxiliary agent. It is possible to suppress a decrease in electrical conductivity between thermoelectric semiconductor particles.
  • a metal cation is used as the cation.
  • the metal cation include alkali metal cations, alkaline earth metal cations, typical metal cations and transition metal cations, and alkali metal cations or alkaline earth metal cations are more preferable.
  • the alkali metal cation include Li + , Na + , K + , Rb + , Cs +, Fr + and the like.
  • Examples of the alkaline earth metal cation include Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ .
  • the anion such as, F -, Cl -, Br -, I -, OH -, CN -, NO 3 -, NO 2 -, ClO -, ClO 2 -, ClO 3 -, ClO 4 -, CrO 4 2 -, HSO 4 -, SCN - , BF 4 -, PF 6 - , and the like.
  • a cation component such as potassium cation, sodium cation, or lithium cations, Cl -, AlCl 4 -, Al 2 Cl 7 -, ClO 4 - chloride or ion, Br -, etc. of bromide ion, I -, etc. iodide ion, BF 4 -, PF 6 - fluoride ions, F (HF) n, such as - such as halide anions of, NO 3 -, OH -, CN - and the ones mentioned consists the anion component of such Be done.
  • a cation component such as potassium cation, sodium cation, or lithium cations
  • the cationic component of the inorganic ionic compound is potassium from the viewpoints of high temperature stability, compatibility with thermoelectric semiconductor particles and resins, and suppression of decrease in electrical conductivity between thermoelectric semiconductor particle gaps.
  • Sodium, and lithium are preferably included.
  • the anion component of the inorganic ionic compound preferably contains a halide anion, and more preferably contains at least one selected from Cl ⁇ , Br ⁇ , and I ⁇ .
  • Cationic component is, as a specific example of the inorganic ionic compound containing a potassium cation, KBr, KI, KCl, KF , KOH, K 2 CO 3 and the like. Of these, KBr and KI are preferable.
  • Specific examples of the inorganic ionic compound whose cation component contains a sodium cation include NaBr, NaI, NaOH, NaF, Na 2 CO 3 and the like. Of these, NaBr and NaI are preferable.
  • Specific examples of the inorganic ionic compound whose cation component contains a lithium cation include LiF, LiOH, and LiNO 3 . Of these, LiF and LiOH are preferable.
  • the above-mentioned inorganic ionic compound preferably has an electric conductivity of 10-7 S / cm or more, and more preferably 10-6 S / cm or more.
  • the electric conductivity is within the above range, the reduction of the electric conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductivity auxiliary agent.
  • the decomposition temperature of the above-mentioned inorganic ionic compound is preferably 400 ° 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 above-mentioned inorganic ionic compound preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and preferably 1% or less at 400 ° C. by thermogravimetric analysis (TG). More preferred. As long as the mass reduction rate 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.
  • TG thermogravimetric analysis
  • the blending amount 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, still more preferably 1.0 to 10% by mass. ..
  • the blending amount 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. It is preferably 0.5 to 30% by mass, more preferably 1.0 to 10% by mass.
  • thermoelectric semiconductor composition used in the present invention further contains, if necessary, a dispersant, a film-forming auxiliary, a light stabilizer, an antioxidant, a tackifier, a plasticizer, a colorant, and the like. It may contain other additives such as resin stabilizers, fillers, pigments, conductive fillers, conductive polymers and hardeners. These additives can be used alone or in combination of two or more.
  • thermoelectric semiconductor composition used in the present invention is not particularly limited, and the thermoelectric semiconductor particles, the resin, and the thermoelectric semiconductor particles can be prepared by a known method such as an ultrasonic homogenizer, a spiral mixer, a planetary mixer, a disperser, or a hybrid mixer.
  • a known method such as an ultrasonic homogenizer, a spiral mixer, a planetary mixer, a disperser, or a hybrid mixer.
  • One or both of the ionic liquid and the inorganic ionic compound, if necessary, the other additives and a solvent may be added and mixed and dispersed to prepare the thermoelectric semiconductor composition.
  • the solvent examples include solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve.
  • solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve.
  • solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve.
  • One of these solvents may be used alone, or two or more of these solvents may be mixed and used.
  • the solid content concentration of the thermoelectric semiconductor composition is not particularly limited as long as the composition has a viscosity suitable for coating.
  • the thin film made of the thermoelectric semiconductor composition can be formed by applying the thermoelectric semiconductor composition on the substrate used in the present invention and drying it.
  • thermoelectric semiconductor composition As a method of applying the thermoelectric semiconductor composition on a substrate, 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, a bar coating method, a doctor blade method, etc.
  • a known method is mentioned, and is 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 a 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 thin film made of the thermoelectric semiconductor composition is not particularly limited, but 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 annealing treatment step is a step of forming chips of a thermoelectric conversion material on a substrate and then heat-treating the chips of the thermoelectric conversion material at a predetermined temperature while holding the substrate.
  • the chip of the thermoelectric conversion material is formed as a thin film and then annealed.
  • the annealing treatment is not particularly limited, but is usually carried out under an atmosphere of an inert gas such as nitrogen or argon, in which the gas flow rate is controlled, in a reducing gas atmosphere, or under vacuum conditions.
  • the temperature of the annealing treatment depends on the thermoelectric semiconductor material, resin, ionic liquid, inorganic ionic compound, etc. used in the thermoelectric semiconductor composition and is appropriately adjusted. However, in the present invention, as described above, at least above the decomposition temperature of the resin. It is essential to carry out, usually at 260 to 600 ° C., preferably 280 to 550 ° C.
  • the difference between the decomposition temperature of the resin and the temperature of the annealing treatment described above is usually 0 to 200 ° C., preferably 0 to 170 ° C., more preferably 5 to 150 ° C., and even more preferably 10 to 80 ° C.
  • the annealing treatment time is not particularly limited as long as it functions as a binder for the thermoelectric semiconductor material and the flexibility is maintained, but it is usually carried out for several minutes to several tens of hours, preferably several minutes to several hours.
  • the chip peeling step of the thermoelectric conversion material is a step of annealing the chip of the thermoelectric conversion material and then peeling the chip of the thermoelectric conversion material from the substrate.
  • the method for peeling the chips is not particularly limited as long as the chips of the thermoelectric conversion material can be annealed and then the chips of the thermoelectric conversion material can be peeled from the substrate, and one plurality of chips of the thermoelectric conversion material can be peeled from the substrate. It may be peeled off in the form of a single piece, or may be peeled off in the form of a plurality of chips as described later.
  • thermoelectric conversion material of the present invention chips of thermoelectric conversion material can be produced by a simple method. Further, since the thermoelectric conversion material and the electrode are bonded to each other and are not annealed, the electric resistance value between the thermoelectric conversion material and the electrode increases and the thermoelectric performance deteriorates as described above. Problem does not occur.
  • thermoelectric conversion module A method for manufacturing a thermoelectric conversion module in which a plurality of thermoelectric conversion material chips obtained by the method for producing chips of a thermoelectric conversion material of the present invention are combined, and includes the following steps (i) to (vii).
  • the other surface of the chip of the thermoelectric conversion material obtained by peeling in the step (vi) is joined to the electrode of the second layer prepared in the step (iv).
  • thermoelectric conversion module is manufactured in the form of a chip of a thermoelectric conversion material obtained by going through each of the steps (i) and (ii).
  • steps (i) and (ii) is the step of forming the chip of the thermoelectric conversion material (A) and the step of annealing (B) in the method for producing the chip of the thermoelectric conversion material of the present invention described above.
  • Each step corresponds to this order, and the steps are exactly the same. For example, an embodiment as described with reference to FIG. 1 can be mentioned.
  • the substrate to be used, the thin film of the thermoelectric semiconductor composition, the preferable material, the thickness, the forming method, and the like constituting them are all the same as those described in the above-mentioned method for manufacturing a chip of a thermoelectric conversion material.
  • the step (iv) is a step of preparing a second layer having a second resin film and a second electrode in this order.
  • the step (vii) is the other surface of the chip of the thermoelectric conversion material obtained by peeling off in the step (vi), and the second electrode of the layer 2A prepared in the step (iv). It is preferable that this is a step of joining with the bonding material layer 2 interposed therebetween.
  • the thermoelectric conversion module obtained in the above step corresponds to the above-mentioned ⁇ -type thermoelectric conversion module.
  • the step (iv) prepares a second layer having a second resin film and no electrodes. It is a step, and the step (vii) is the other surface of the chip of the thermoelectric conversion material obtained by peeling in the step (vi), and the second layer B prepared in the step (iv). It is preferable that this is a step of joining with the bonding material layer 3 interposed therebetween.
  • the thermoelectric conversion module obtained in the above step corresponds to the above-mentioned inplane type thermoelectric conversion module.
  • thermoelectric conversion module in which a plurality of chips of a thermoelectric conversion material obtained from the method for manufacturing chips of a thermoelectric conversion material of the present invention are combined will be described with reference to the drawings.
  • FIG. 2 shows an example of an embodiment of a process according to a method for manufacturing a thermoelectric conversion module in which a plurality of chips of a thermoelectric conversion material obtained from the method for producing chips of a thermoelectric conversion material of the present invention are combined ( ⁇ -type thermoelectric conversion module).
  • A is a sectional view after forming a solder receiving layer described later on one surface (upper surface) of a chip of a thermoelectric conversion material, and (b) is an electrode on a resin film. And is a cross-sectional view after forming the solder layer,
  • (c) is one of the chips of the thermoelectric conversion material with the electrode on the resin film obtained in (b) interposed below the solder layer and the solder receiving layer of (a).
  • (C') is a cross-sectional view after the solder layers are joined by heating and cooling, and (d) is the other side of the chip of the thermoelectric conversion material from the substrate. It is a cross-sectional view after peeling off the surface (lower surface), and (e) is after forming the solder receiving layer on the other surface (lower surface) of the chip of the thermoelectric conversion material on the resin film obtained in (d).
  • (F) is a cross-sectional view of (f), in which the electrode on the resin film obtained in (b) is attached to the other surface (lower surface) of the chip of the thermoelectric conversion material via the solder layer and the solder receiving layer of (e). It is a cross-sectional view after joining and joining.
  • the electrode forming step is a step of preparing a first layer having the first resin film and the first electrode in this order in the above (iii) of the method for manufacturing a thermoelectric conversion module, and the first step is on the first resin film.
  • This is a step of forming the electrode of 1.
  • it is a step of forming the second electrode on the second resin film.
  • a metal layer is formed on the resin film 4 and processed into a predetermined pattern to form an electrode 5.
  • thermoelectric conversion module in the method for manufacturing the thermoelectric conversion module, a first resin film and a second resin film that do not affect the decrease in the electric conductivity and the increase in the thermal conductivity of the thermoelectric conversion material are used.
  • the first resin film and the second resin film may be the same or different. It has excellent flexibility, and even when a thin film made of a thermoelectric semiconductor composition is annealed, the performance of the thermoelectric element can be maintained without thermal deformation of the substrate, and heat resistance and dimensional stability are high.
  • a polyimide film, a polyamide film, a polyetherimide film, a polyaramid film, and a polyamideimide film are preferable, and a polyimide film is particularly preferable from the viewpoint of high versatility.
  • the thickness of the first resin film and the second resin film is preferably 1 to 1000 ⁇ m, more preferably 5 to 500 ⁇ m, and 10 to 100 ⁇ m independently from the viewpoint of flexibility, heat resistance, and dimensional stability. Is even more preferable.
  • the 5% weight loss temperature measured by thermogravimetric analysis is preferably 300 ° C. or higher, more preferably 400 ° C. or higher.
  • the heating dimension change rate measured at 200 ° C. in accordance with JIS K7133 (1999) is preferably 0.5% or less, and more preferably 0.3% or less.
  • the coefficient of linear expansion in the plane direction measured in accordance with JIS K7197 (2012) is 0.1 ppm ⁇ °C -1 to 50 ppm ⁇ °C -1 , and 0.1 ppm ⁇ °C -1 to 30 ppm ⁇ °C -1. Is more preferable.
  • the metal materials of the first electrode and the second electrode of the thermoelectric conversion module are independently copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, or any of these metals. Examples include alloys containing.
  • the thickness of the electrode layer is preferably 10 nm to 200 ⁇ m, more preferably 30 nm to 150 ⁇ m, and even more 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 a predetermined method is performed by providing an electrode having no pattern formed on the resin film, and then performing a known physical treatment or chemical treatment mainly based on a photolithography method, or using them in combination.
  • 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 Method
  • CVD Chemical Vapor Deposition
  • thermal CVD thermal CVD
  • atomic layer deposition ALD
  • various coating methods such as dip coating method, spin coating method, spray coating method, gravure coating method, die coating method, doctor blade method, wet process such as electrodeposition method, silver salt method , Electrolytic plating method, electroless plating method, laminating of metal foil, etc., and are appropriately selected according to the material of the electrode.
  • an electrode formed by a plating method or a vacuum film forming method Since high conductivity and high thermal conductivity are required for the electrode 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. Since high conductivity and high thermal conductivity can be easily realized, 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 requirements for 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 electrode bonding step 1 is the step (v) of the method for manufacturing a thermoelectric conversion module of the present invention, and is formed on one surface of the chip of the thermoelectric conversion material after the annealing treatment obtained in the step (ii). , Is a step of joining the first electrode of the first layer prepared in the step (iii) with the bonding material layer 1 interposed therebetween.
  • the electrode joining step 1 for example, in FIG. 2C, the solder layer 6 on the electrode 5 of the resin film 4, the P-type thermoelectric conversion material chip 2a, and the N-type thermoelectric conversion material chip 2b, respectively.
  • a solder receiving layer 3 formed on one surface is interposed, a P-type thermoelectric conversion material chip 2a and an N-type thermoelectric conversion material chip 2b are bonded to an electrode 5, and the solder layer 6 is heated to a predetermined temperature to be predetermined.
  • This is a step of joining the chip 2a of the P-type thermoelectric conversion material and the chip 2b of the N-type thermoelectric conversion material to the electrode 5 by returning the temperature to room temperature after holding the above time. The heating temperature, holding time, etc. will be described later.
  • FIG. 2C' is an embodiment after the solder layer 6 is returned to room temperature (the solder layer 6'is solidified by heating and cooling and its thickness is reduced).
  • the electrode bonding step 1 includes a bonding material layer 1 forming step.
  • the bonding material layer 1 forming step is a step of forming the bonding material layer 1 on the first electrode obtained in the step (iii) in the step (v) of the method for manufacturing the thermoelectric conversion module.
  • the bonding material layer 1 forming step is, for example, in FIG. 2B, a step of forming the solder layer 6 on the electrode 5.
  • Examples of the bonding material constituting the bonding material layer 1 include a solder material, a conductive adhesive, and a sintered bonding agent, which are formed on the electrodes as a solder layer, a conductive adhesive layer, and a sintered bonding layer, respectively. It is preferable to be done.
  • the solder material constituting the solder layer may be appropriately selected in consideration of the heat-resistant temperature of the resin film, the heat-resistant resin contained in the chip of the thermoelectric conversion material, and the conductivity and heat conductivity.
  • Lead-free and / or cadmium-free from the viewpoint of melting point, conductivity, thermal conductivity, 43Sn / 57Bi alloy, 42Sn / 58Bi alloy, 40Sn / 56Bi / 4Zn alloy, 48Sn / 52In alloy, 39.8Sn / 52In / 7Bi / Alloys such as 1.2 Zn alloys are preferred.
  • Commercially available products of solder materials include the following.
  • the thickness of the solder layer (after heating and cooling) is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, still more preferably 30 to 130 ⁇ m, and particularly preferably 40 to 120 ⁇ m. When the thickness of the solder layer is within this range, it becomes easy to obtain the adhesion of the thermoelectric conversion material to the chip and the electrode.
  • Examples of the method of applying the solder material on the substrate include known methods such as stencil printing, screen printing, and dispensing method.
  • the heating temperature varies depending on the solder material used, the resin film, etc., but is usually carried out at 150 to 280 ° C. for 3 to 20 minutes.
  • the conductive adhesive constituting the conductive adhesive layer is not particularly limited, and examples thereof include a conductive paste.
  • the conductive paste include copper paste, silver paste, nickel paste and the like, and when a binder is used, epoxy resin, acrylic resin, urethane resin and the like can be mentioned.
  • the method of applying the conductive adhesive on the resin film include known methods such as screen printing and a dispensing method.
  • the thickness of the conductive adhesive layer is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, still more preferably 30 to 130 ⁇ m, and particularly preferably 40 to 120 ⁇ m.
  • the sintered bonding agent constituting the sintered bonding agent layer is not particularly limited, and examples thereof include a sintered paste.
  • the sintering paste is composed of, for example, micron-sized metal powder and nano-sized metal particles, and unlike the conductive adhesive, the metal is directly bonded by sintering, and is made of epoxy resin, acrylic resin, urethane, or the like. It may contain a binder such as a resin.
  • Examples of the sintering paste include silver sintering paste and copper sintering paste.
  • Examples of the method of applying the sintered bonding agent layer on the resin film include known methods such as screen printing, stencil printing, and dispensing method. Sintering conditions vary depending on the metal material used and the like, but are usually 100 to 300 ° C.
  • the sintered bonding agent include, for example, as a silver sintered paste, a sintered paste (manufactured by Kyocera, product name: CT2700R7S), a sintered metal bonding material (manufactured by Nihon Handa, product name: MAX102) and the like. Can be used.
  • the thickness of the sintered bonding agent layer is preferably 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, further preferably 30 to 130 ⁇ m, and particularly preferably 40 to 120 ⁇ m.
  • solder layer When a solder layer is used, it is preferable to join the solder layer via a solder receiving layer, which will be described later, from the viewpoint of improving the adhesion of the thermoelectric conversion material to the chip.
  • thermoelectric after annealing treatment obtained in the step (ii) is further performed. It is preferable to include a step of forming a solder receiving layer on one surface of the chip of the conversion material.
  • the solder receiving layer forming step is a step of forming a solder receiving layer on a chip of a thermoelectric conversion material.
  • a thermoelectric conversion material chip 2a For example, in FIG. 2A, a P-type thermoelectric conversion material chip 2a and an N-type thermoelectric conversion material. This is a step of forming the solder receiving layer 3 on one surface of the chip 2b.
  • the solder receiving layer preferably contains a metal material.
  • the metal material is preferably at least one selected from an alloy containing gold, silver, aluminum, rhodium, platinum, chromium, palladium, tin, and any of these metal materials.
  • a two-layer structure of gold, silver, aluminum, or tin and gold is more preferable, and silver and aluminum are further preferable from the viewpoint of material cost, high thermal conductivity, and bonding stability.
  • the solder receiving layer may be formed by using a paste material containing a solvent or a resin component in addition to the metal material. When a paste material is used, it is preferable to remove the solvent and the resin component by firing or the like as described later.
  • As the paste material silver paste and aluminum paste are preferable.
  • the thickness of the solder receiving layer is preferably 10 nm to 50 ⁇ m, more preferably 50 nm to 16 ⁇ m, further preferably 200 nm to 4 ⁇ m, and particularly preferably 500 nm to 3 ⁇ m.
  • the adhesion of the thermoelectric conversion material containing resin to the chip surface and the adhesion to the surface of the solder layer on the electrode side are excellent, and a highly reliable bond can be obtained. Be done. Further, since the thermal conductivity can be maintained high as well as the conductivity, the thermoelectric performance as a thermoelectric conversion module is not deteriorated as a result and is maintained.
  • the metal material may be formed as it is and used as a single layer, or two or more metal materials may be laminated and used in multiple layers. Further, a film may be formed as a composition in which a metal material is contained in a solvent, a resin or the like. However, in this case, from the viewpoint of maintaining high conductivity and high thermal conductivity (maintaining thermoelectric performance), as the final form of the solder receiving layer, the resin component including the solvent may be removed by firing or the like. preferable.
  • the solder receiving layer is preferably formed using the above-mentioned metal material.
  • a method of forming the solder receiving layer after providing a solder receiving layer having no pattern formed on the thermoelectric element layer, a known physical treatment or chemical treatment mainly based on a photolithography method, or a combination thereof is used. Examples thereof include a method of processing into a predetermined pattern shape, a method of directly forming a pattern of a solder receiving layer by a screen printing method, a stencil printing method, an inkjet method, or the like.
  • Examples of the method for forming the solder receiving layer in which the pattern is not formed include PVD (Physical Vapor Deposition) such as vacuum deposition, sputtering, and ion plating, or CVD such as thermal CVD and atomic layer deposition (ALD).
  • Vacuum film deposition method such as (chemical vapor deposition method), various coating methods such as dip coating method, spin coating method, spray coating method, gravure coating method, die coating method, doctor blade method, and wet process such as electrodeposition method.
  • Silver salt method, electrolytic plating method, electroless plating method, laminating of metal foil, etc. and are appropriately selected depending on the material of the solder receiving layer.
  • the solder receiving layer is required to have high conductivity and high thermal conductivity from the viewpoint of maintaining thermoelectric performance, it is formed by screen printing method, stencil printing method, electrolytic plating method, electroless plating method or vacuum film formation method. It is preferable to use a filmed solder receiving layer.
  • the chip batch peeling step is the step (vi) of the method for manufacturing a thermoelectric conversion module, and is a step of peeling the other surface of the chip of the thermoelectric conversion material after the step (v) from the substrate.
  • the chip batch peeling step is, for example, in FIG. 2D, a step of collectively peeling the other surfaces of the P-type thermoelectric conversion material chip 2a and the N-type thermoelectric conversion material chip 2b from the substrate 1. .
  • the method for peeling the thermoelectric conversion material is not particularly limited as long as it can peel off all the chips of the thermoelectric conversion material from the substrate at once.
  • the electrode joining step 2 is included in the step (vii) of the method for manufacturing a thermoelectric conversion module, and includes the other surface of the chip of the thermoelectric conversion material obtained by peeling in the step (vi) and the above (. This is a step of joining the second electrode of the second layer prepared in step iv) with the bonding material layer 2 interposed therebetween.
  • the electrode joining step 2 for example, in FIG. 2F, the other surfaces of the chip 2a of the P-type thermoelectric conversion material and the chip 2b of the N-type thermoelectric conversion material, and the solder receiving layer 3 and the solder layer 6 are interposed. This is a step of joining the electrode 5 on the resin film 4.
  • the same materials as those described in the electrode bonding step 1 can be used, and the bonding method is also the same. It is preferable to bond the electrodes with the solder layer, the conductive adhesive layer, or the sintered bonding agent layer described above.
  • the electrode bonding step 2 includes a bonding material layer 2 forming step.
  • the bonding material layer 2 is placed on the second electrode of the layer 2A prepared in the step (iv). Is the process of forming.
  • the bonding material layer 2 the same material as the bonding material layer 1 described above can be used, and the forming method, thickness, and the like are all the same.
  • solder is further applied to the other surface of the chip of the thermoelectric conversion material obtained by peeling in the step (vi). It is preferable to include a step of forming a receiving layer.
  • a step of forming a receiving layer For example, in FIG. 2E, it is a step of forming the solder receiving layer 3 on the other surface of the chip 2a of the P-type thermoelectric conversion material and the chip 2b of the N-type thermoelectric conversion material.
  • the resin film joining step is included in the step (vii) of the method for manufacturing the thermoelectric conversion module of the present invention, and is combined with the other surface of the chip of the thermoelectric conversion material obtained by peeling in the step (vi).
  • This is a step of joining the second B layer having the second resin film and having no electrode prepared in the step (iv) above via the bonding material layer 3.
  • the second resin film is as described above.
  • the bonding material layer 3 is used for bonding with the second layer B having the second resin film and having no electrodes.
  • the bonding material constituting the bonding material layer 3 is preferably a resin material, and is formed on the resin film as the resin material layer.
  • the resin material preferably contains a polyolefin-based resin, an epoxy-based resin, or an acrylic-based resin. Further, it is preferable that the resin material has adhesiveness and low water vapor permeability.
  • having adhesiveness means that the resin material has adhesiveness, adhesiveness, and pressure-sensitive adhesiveness that can be adhered by pressure at the initial stage of sticking.
  • the resin material layer can be formed by a known method.
  • the thickness of the resin material layer is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, and even more preferably 5 to 30 ⁇ m.
  • thermoelectric conversion module except when the electrodes are not provided on any of the pair of resin films
  • thermoelectric conversion is performed. From the viewpoint of preventing mechanical deformation of the module and suppressing deterioration of thermoelectric performance, it is preferable to use a combination of solder layers, conductive adhesive layers, or sintered bonding agent layers.
  • thermoelectric conversion module using a chip obtained by the method for manufacturing a chip for a thermoelectric conversion material of the present invention is as follows. Specifically, a plurality of chips of the thermoelectric conversion material are peeled off from the above-mentioned substrate for each chip to obtain a plurality of chips, and the plurality of chips are placed on a predetermined electrode on the resin film. This is a method of forming a thermoelectric conversion module by going through the steps of arranging them one by one. As a method of arranging a plurality of chips of the thermoelectric conversion material on the electrodes, a known method such as handling each chip with a robot or the like, aligning with a microscope or the like, and arranging the chips can be used.
  • thermoelectric conversion material of the present invention a chip of a thermoelectric conversion material can be formed by a simple method, and a thermoelectric conversion module in which a plurality of chips of a thermoelectric conversion material are combined is conventional. It is possible to prevent deterioration of thermoelectric performance due to formation of an alloy layer due to diffusion between the thermoelectric conversion material and the electrode in the annealing treatment step.
  • thermoelectric conversion material chip from the glass substrate was evaluated by the following method in the test pieces having the thermoelectric conversion material chip prepared in Examples and Comparative Examples.
  • Category 2 The coating is peeling off along the edges of the cut and / or at the intersection. The cross-cut area is clearly affected by more than 5%, but not more than 15%.
  • Category 3 The coating film is partially or wholly peeled off along the edges of the cut, and / or various parts of the eye are partially or wholly peeled off. The cross-cut area is clearly affected by more than 15% but not more than 35%.
  • Category 4 The coating film has partially or wholly peeled off along the edges of the cut, and / or some eyes have partially or wholly peeled off. The cross-cut portion is clearly not affected by more than 65%.
  • Category 5 Any degree of peeling that cannot be classified even in Category 4.
  • thermoelectric conversion material peeled off from the test piece was measured at 25 ° C. and 60% RH. It was measured in the environment of.
  • the total peelability was evaluated (comprehensive evaluation) according to the following criteria.
  • thermoelectric semiconductor composition production of thermoelectric semiconductor particles
  • P-type bismuth tellurium Bi 0.4 Te 3.0 Sb 1.6 manufactured by High Purity Chemical Laboratory, particle size: 180 ⁇ m
  • Thermoelectric semiconductor particles having an average particle size of 2.0 ⁇ m were produced by pulverizing in a nitrogen gas atmosphere using line P-7).
  • the particle size distribution of the thermoelectric semiconductor particles obtained by pulverization was measured by a laser diffraction type particle size analyzer (Mastersizer 3000 manufactured by Malvern).
  • thermoelectric semiconductor composition P-type bismuth sterlide Bi 0.4 Te 3 Sb 1.6 particles 82.5% by mass obtained above, polyvinyl pyrrolidone aqueous solution as a resin (manufactured by Sigma Aldrich, solvent: water, solid content concentration: 18% by mass, decomposition)
  • thermoelectric conversion material On a glass substrate (soda lime glass, 100 mm x 100 mm x thickness 0.7 mm), a metal mask (material: magnetic SUS, pattern area: 70 mm x 70 mm, pattern specifications; width : 1.5 mm, length: 1.5 mm, interval: 0.2 mm), the coating solution prepared in (1) above is applied by the screen printing method, and argon at a temperature of 150 ° C. for 10 minutes. It was dried in an atmosphere to form a thin film (thermoelectric conversion material before annealing treatment) having a thickness of 200 ⁇ m.
  • thermoelectric conversion material after annealing treatment was produced to prepare a test piece having a chip of the thermoelectric conversion material.
  • Example 2 N-type bismuth sterlide Bi 2 Te 3 particles 91.6% by mass as the thermoelectric semiconductor material, polyvinylpyrrolidone aqueous solution as the resin (manufactured by Sigma Aldrich, solvent: water, solid content concentration: 18% by mass, decomposition temperature 300).
  • a test piece was prepared in the same manner as in Example 1 except that (° C.) 3.6% by mass (solid content), 4.8% by mass of 1-butylpyridinium bromide was used as the ionic liquid, and the annealing treatment temperature was 400 ° C. did.
  • the obtained test piece was evaluated for peelability (comprehensive evaluation) in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 Example 1 except that polyvinyl alcohol (manufactured by Sigma-Aldrich, solvent: water, solid content concentration: 18% by mass, decomposition temperature 300 ° C.) 3.2% by mass (solid content) was used as the resin in Example 1.
  • a test piece was prepared in the same manner as in the above. The obtained test piece was evaluated for peelability (comprehensive evaluation) in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 Example 1 and Example 1 except that polystyrene (manufactured by Sigma-Aldrich, solvent: methyl ethyl ketone, solid content concentration: 15% by mass, decomposition temperature 364 ° C.) 3.2% by mass (solid content) was used as the resin.
  • a test piece was prepared in the same manner. The obtained test piece was subjected to a peelability evaluation (comprehensive evaluation) in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 In Example 1, polystyrene (manufactured by Sigma Aldrich, solvent: methyl ethyl ketone, solid content concentration: 18% by mass, decomposition temperature 364 ° C.) 2.88% by mass (solid content) was used as the resin, and a polyimide precursor was used as the heat-resistant resin.
  • Example 1 and Example 1 except that a certain polyamic acid (manufactured by Kawamura Sangyo Co., Ltd., KPI-MX300F, solvent: methyl ethyl ketone, solid content concentration: 18% by mass, decomposition temperature 530 ° C.) 0.32% by mass (solid content) was used.
  • a test piece was prepared in the same manner. The obtained test piece was evaluated for peelability (comprehensive evaluation) in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 Polyamic acid which is a polyimide precursor as a resin (manufactured by Ube Industries, Ltd., U-varnish A, solvent: N-methylpyrrolidone, solid content concentration: 18% by mass, decomposition temperature 500 ° C.) 3.2% by mass A test piece was prepared in the same manner as in Example 1 except that% (solid content) was used. The obtained test piece was evaluated for peelability (comprehensive evaluation) in the same manner as in Example 1. The results are shown in Table 1.
  • Example 2 In Example 1, a test piece was prepared in the same manner as in Example 1 except that the firing temperature was set to 250 ° C. The obtained test piece was evaluated for peelability (comprehensive evaluation) in the same manner as in Example 1. The results are shown in Table 1.
  • thermoelectric conversion material of Examples 1 to 4 formed on the glass substrate and annealed at an annealing temperature equal to or higher than the decomposition temperature of the resin and comprising the resin-containing thermoelectric semiconductor composition are peelable from the glass substrate. Is good. Further, it can be seen that the same applies to the chip of the thermoelectric conversion material of Example 5, which further contains a heat-resistant resin. On the other hand, the chips of the thermoelectric conversion material of Comparative Examples 1 and 2 formed on the glass substrate and treated at an annealing temperature lower than the decomposition temperature of the resin and composed of the thermoelectric semiconductor composition containing the resin are from the glass substrate. It can be seen that the peelability of is poor.
  • thermoelectric conversion material made of a thermoelectric semiconductor composition containing a resin, which has been treated at an annealing temperature equal to or higher than the decomposition temperature of the resin, can be formed as a self-supporting film. It was.
  • thermoelectric conversion module According to the method for manufacturing a chip of a thermoelectric conversion material of the present invention and the method for manufacturing a thermoelectric conversion module using the chip obtained by the manufacturing method, it is possible to prevent the formation of an alloy phase due to diffusion between the electrode and the thermoelectric conversion material. As a result, problems such as deterioration of thermoelectric performance can be solved. At the same time, it can be expected that the yield in the manufacturing process will be improved. In addition, the thermoelectric conversion module has flexibility and has the possibility of being thin (small and lightweight).
  • the thermoelectric conversion module using the chips obtained by the above-mentioned method for producing chips of thermoelectric conversion materials can be used for exhaust heat from various combustion furnaces such as factories, waste combustion furnaces, cement combustion furnaces, automobile combustion gas exhaust heat, and automobile combustion gas exhaust heat.
  • Substrate 2 Chip of thermoelectric conversion material 2a: Chip of P-type thermoelectric conversion material 2b: Chip of N-type thermoelectric conversion material 3: Solder receiving layer 4: Resin film 5: Electrode 6: Solder layer (at the time of formation) 6': Solder layer (after joining)

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  • Chemical & Material Sciences (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé pour fabriquer une puce d'un matériau de conversion thermoélectrique. Le procédé permet d'effectuer, par une étape simple, le recuit du matériau de conversion thermoélectrique d'une manière qui n'implique pas de jonction à une électrode, et permet de recuire un matériau semi-conducteur thermoélectrique à une température de recuit optimale, le matériau de conversion thermoélectrique comprenant une composition semi-conductrice thermoélectrique. Le procédé consiste : (A) en une étape de formation d'une puce du matériau de conversion thermoélectrique sur un substrat ; (B) en une étape de recuit de la puce du matériau de conversion thermoélectrique obtenue à l'étape (A) ; et (C) en une étape de pelage de la puce du matériau de conversion thermoélectrique après recuit obtenue à l'étape (B). La composition semi-conductrice thermoélectrique comprend un matériau semi-conducteur thermoélectrique et une résine, et la température du recuit n'est pas inférieure à la température de décomposition de la résine.
PCT/JP2020/013547 2019-03-28 2020-03-26 Procédé pour fabriquer une puce d'un matériau de conversion thermoélectrique WO2020196709A1 (fr)

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JP2021509566A JP7458375B2 (ja) 2019-03-28 2020-03-26 熱電変換材料のチップの製造方法
CN202080025034.XA CN113632253A (zh) 2019-03-28 2020-03-26 热电转换材料的芯片的制造方法

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000183412A (ja) * 1998-12-16 2000-06-30 Sharp Corp 積層材料の製造方法および製造装置
US20030041892A1 (en) * 1998-08-07 2003-03-06 California Institute Of Technology Microfabricated thermoelectric power-generation devices
US7531739B1 (en) * 2004-10-15 2009-05-12 Marlow Industries, Inc. Build-in-place method of manufacturing thermoelectric modules
WO2013069347A1 (fr) * 2011-11-08 2013-05-16 富士通株式会社 Élément de conversion thermoélectrique et son procédé de fabrication
JP2013251333A (ja) * 2012-05-30 2013-12-12 Fujifilm Corp 熱電変換素子の製造方法
JP2017041540A (ja) * 2015-08-20 2017-02-23 リンテック株式会社 ペルチェ冷却素子及びその製造方法
JP2017098283A (ja) * 2015-11-18 2017-06-01 日東電工株式会社 半導体装置の製造方法
WO2020045379A1 (fr) * 2018-08-28 2020-03-05 リンテック株式会社 Procédé de production de puce constituée d'un matériau de conversion thermoélectrique et procédé de fabrication de module de conversion thermoélectrique utilisant une puce obtenue au moyen dudit procédé de production

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030041892A1 (en) * 1998-08-07 2003-03-06 California Institute Of Technology Microfabricated thermoelectric power-generation devices
JP2000183412A (ja) * 1998-12-16 2000-06-30 Sharp Corp 積層材料の製造方法および製造装置
US7531739B1 (en) * 2004-10-15 2009-05-12 Marlow Industries, Inc. Build-in-place method of manufacturing thermoelectric modules
WO2013069347A1 (fr) * 2011-11-08 2013-05-16 富士通株式会社 Élément de conversion thermoélectrique et son procédé de fabrication
JP2013251333A (ja) * 2012-05-30 2013-12-12 Fujifilm Corp 熱電変換素子の製造方法
JP2017041540A (ja) * 2015-08-20 2017-02-23 リンテック株式会社 ペルチェ冷却素子及びその製造方法
JP2017098283A (ja) * 2015-11-18 2017-06-01 日東電工株式会社 半導体装置の製造方法
WO2020045379A1 (fr) * 2018-08-28 2020-03-05 リンテック株式会社 Procédé de production de puce constituée d'un matériau de conversion thermoélectrique et procédé de fabrication de module de conversion thermoélectrique utilisant une puce obtenue au moyen dudit procédé de production

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JPWO2020196709A1 (fr) 2020-10-01
CN113632253A (zh) 2021-11-09

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