WO2022092179A1 - Procédé de mise en réseau de puces de matériau de conversion thermoélectrique - Google Patents

Procédé de mise en réseau de puces de matériau de conversion thermoélectrique Download PDF

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Publication number
WO2022092179A1
WO2022092179A1 PCT/JP2021/039752 JP2021039752W WO2022092179A1 WO 2022092179 A1 WO2022092179 A1 WO 2022092179A1 JP 2021039752 W JP2021039752 W JP 2021039752W WO 2022092179 A1 WO2022092179 A1 WO 2022092179A1
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thermoelectric conversion
conversion material
type thermoelectric
fixed layer
chip
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PCT/JP2021/039752
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English (en)
Japanese (ja)
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佑太 関
邦久 加藤
亘 森田
克彦 堀米
睦 升本
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リンテック株式会社
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Priority to JP2022559217A priority Critical patent/JPWO2022092179A1/ja
Publication of WO2022092179A1 publication Critical patent/WO2022092179A1/fr

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

Definitions

  • the present invention relates to a method of arranging chips of a thermoelectric conversion material.
  • thermoelectric conversion module that uses a thermoelectric conversion material having a thermoelectric effect such as the Seebeck effect and the Pelche effect to convert between thermal energy and electrical energy.
  • thermoelectric conversion module the use of a so-called ⁇ -type thermoelectric conversion element is known.
  • the ⁇ -type thermoelectric conversion element is provided with a pair of electrodes separated from each other on the substrate, for example, the lower surface of the P-type thermoelectric element is provided on one of the electrodes, and the lower surface of the N-type thermoelectric element is placed on the other electrode.
  • the basic unit is a configuration in which the upper surfaces of both types of thermoelectric elements are connected to electrodes on opposite substrates, and usually, a plurality of the basic units are electrically connected in series in both substrates.
  • thermoelectric conversion element P-type thermoelectric elements and N-type thermoelectric elements are alternately provided in the in-plane direction of the substrate. It is configured by connecting in series with.
  • Patent Document 1 discloses a method of arranging rectangular parallelepiped P-type semiconductor elements and N-type semiconductor elements constituting a ⁇ -type Pelche module so as to be alternately connected via electrodes. Has been done.
  • both ends of the P-type thermoelectric conversion element and the N-type thermoelectric conversion element in the aspect of a square material in the longitudinal direction are attached to each lattice window of a pair of lattice-shaped jigs.
  • a resin material is filled in the gap between the P-type thermoelectric conversion element and the N-type thermoelectric conversion element by a predetermined method.
  • a method is disclosed in which a plurality of pairs of P-type thermoelectric conversion elements and N-type thermoelectric conversion elements are arranged by forming a block in which the whole is integrated and cutting them to a predetermined thickness using a cutting machine. ..
  • Patent Document 1 it is necessary to individually manufacture a plurality of pairs of rectangular P-type semiconductor elements and N-type semiconductor elements in advance, and to arrange them one by one alternately on an electrode, which is complicated and time-consuming. It was not productive.
  • Patent Document 2 in the final step, P-type thermoelectric conversion elements and N-type thermoelectric conversion elements arranged alternately are collectively obtained by cutting an integrated block molded body, but P-type thermoelectric in the form of a square jig. It is necessary to individually manufacture multiple pairs of conversion elements and N-type thermoelectric conversion elements in advance, and insert P-type thermoelectric conversion elements and N-type thermoelectric conversion elements one by one into a grid-like jig so as to be arranged alternately. There are many complicated and time-consuming processes, which was not sufficient from the viewpoint of productivity.
  • the present inventors have separated the P-type thermoelectric conversion material layer on the fixed layer on the first support into a plurality of pieces, and chipped the P-type thermoelectric conversion material.
  • the adhesive strength of the fixed layer in the region where the chips of some P-type thermoelectric conversion materials are attached is reduced, and only the chips of some P-type thermoelectric conversion materials are selectively placed on the second support.
  • the method of transferring onto the fixed layer and the same operation are applied to the N-type thermoelectric conversion material layer on the fixed layer on the third support, and only some N-type thermoelectric conversion material chips are selected.
  • each support having a chip of a separated P-type thermoelectric conversion material or a chip of a separated N-type thermoelectric conversion material obtained by the method.
  • the chip of the P-type thermoelectric conversion material and the chip of the N-type thermoelectric conversion material are used with the respective supports having the chips of the separated P-type thermoelectric conversion material or the chips of the separated N-type thermoelectric conversion material.
  • a method of arranging chips of a thermoelectric conversion material wherein the chip of the thermoelectric conversion material includes a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material.
  • a step of attaching a P-type thermoelectric conversion material layer to a fixed layer on a first support (B) The P-type thermoelectric conversion material layer attached to the fixed layer on the first support is individualized into P-type thermoelectric conversion material chips to obtain a plurality of P-type thermoelectric conversion material chips.
  • Process (C) A step of reducing the adhesive force between the chip of some P-type thermoelectric conversion materials and the fixed layer among the chips of a plurality of P-type thermoelectric conversion materials.
  • the surface of the N-type thermoelectric conversion material whose adhesive strength was maintained opposite to the attachment surface of the chip was attached to the fixing layer on the second support obtained in the step (D).
  • the fixed layer is a fixed layer capable of absorbing laser light
  • the step (C) and the step (G) are, in this order, a chip of a part of the P-type thermoelectric conversion material, the above-mentioned one.
  • thermoelectric conversion material which is performed by irradiating at least a part of the fixed layer of each region to which the N-type thermoelectric conversion material chip is attached.
  • Arrangement method [3] The method for arranging chips of a thermoelectric conversion material according to the above [1] or [2], wherein the fixed layer includes an adhesive layer.
  • the fixed layer capable of absorbing the laser beam comprises a pressure-sensitive adhesive layer containing a colorant or a metal filler.
  • thermoelectric conversion material [6] The method for arranging chips of a thermoelectric conversion material according to the above [1], wherein a heat-expandable base material is used as the support in one or both of the step (C) and the step (G).
  • a heat-expandable base material is used as the support in one or both of the step (C) and the step (G).
  • the chips of the thermoelectric conversion material are made of a thermoelectric semiconductor composition, and the thermoelectric semiconductor composition contains one or both of a thermoelectric semiconductor material, a resin, and an ionic liquid and an inorganic ionic compound. 7] The method for arranging chips of a thermoelectric conversion material according to any one of.
  • thermoelectric conversion module including a chip of a thermoelectric conversion material, which comprises the step of carrying out the method according to any one of the above [1] to [8].
  • thermoelectric conversion material a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material in a batch of supports.
  • the method of arranging the chips of the thermoelectric conversion material of the present invention is a method of arranging the chips of the thermoelectric conversion material, and the chip of the thermoelectric conversion material includes a chip of a P-type thermoelectric conversion material and a chip of an N-type thermoelectric conversion material.
  • a step of attaching a P-type thermoelectric conversion material layer to a fixed layer on a first support (B) The P-type thermoelectric conversion material layer attached to the fixed layer on the first support is individualized into P-type thermoelectric conversion material chips to obtain a plurality of P-type thermoelectric conversion material chips.
  • (E) A step of attaching the N-type thermoelectric conversion material layer to the fixed layer on the third support
  • (F) The N-type thermoelectric conversion material layer attached to the fixed layer on the third support is individualized into N-type thermoelectric conversion material chips to obtain a plurality of N-type thermoelectric conversion material chips.
  • Process, (G) A step of reducing the adhesive force between the chip of some N-type thermoelectric conversion materials and the fixed layer among the chips of a plurality of N-type thermoelectric conversion materials.
  • (H) The chip of the part of the N-type thermoelectric conversion material having a reduced adhesive force with the fixed layer is peeled off from the fixed layer on the third support, and the chip of the part of the N-type thermoelectric conversion material is peeled off.
  • a step of attaching to a fixed layer between chips of some of the P-type thermoelectric conversion materials is characterized by including.
  • the P-type thermoelectric conversion material layer on the fixed layer on the substrate is separated into a plurality of pieces to form a chip of the P-type thermoelectric conversion material, and a part of the P-type thermoelectric conversion material is used.
  • the chips of some P-type thermoelectric conversion materials are selectively transferred onto the fixed layer on other substrates, and so on.
  • the operation is independently applied to the N-type thermoelectric conversion material layer on the fixed layer on another substrate, and only some N-type thermoelectric conversion material chips are selectively applied to the fixed layer on yet another substrate. Transfer onto and in addition, use a substrate having the resulting isolated P-type thermoelectric conversion material chip or N-type thermoelectric conversion material chip, respectively, and use them as a P-type thermoelectric conversion material chip and an N-type thermoelectric conversion material chip, respectively.
  • the chips of the conversion material are bonded together so as to be arranged alternately, for example.
  • thermoelectric conversion material chips and N-type thermoelectric conversion material chips can be alternately arranged in a batch of supports, and ⁇ -type thermoelectric conversion elements and inplane type thermoelectric conversion elements can be easily arranged. It can be produced in large quantities. This leads to shortening of takt time and improvement of yield by simplifying the manufacturing process, and cost reduction can be expected.
  • Chip transfer process of type thermoelectric conversion material "(E) N-type thermoelectric conversion material layer attachment process”, “(F) Chip formation process of N-type thermoelectric conversion material”, “(G) Adhesive strength reduction process”, It may also be referred to as “(H) chip transfer process of N-type thermoelectric conversion material”, “(I) chip bonding process of thermoelectric conversion material”, and “(J) chip bonding process of thermoelectric conversion material”.
  • the "chip of P-type thermoelectric conversion material and chip of N-type thermoelectric conversion material” may be simply referred to as "chip of thermoelectric conversion material”.
  • FIG. 1 is a schematic cross-sectional view showing one aspect of the process of arranging chips of the thermoelectric conversion material according to one aspect of the present invention.
  • A is a cross-sectional view after the P-type thermoelectric conversion material layer 3p is attached onto the fixed layer 2 on the first support 1a.
  • B is a cross-sectional view after the P-type thermoelectric conversion material layer 3p is fragmented into the chips 3pt of the P-type thermoelectric conversion material to form a plurality of chips 3pt of the P-type thermoelectric conversion material.
  • (C) shows an aspect after reducing the adhesive force between a part of the P-type thermoelectric semiconductor chip 3pt and the fixed layer 2 among the chips 3pt of the plurality of P-type thermoelectric conversion materials formed in (b). It is a cross-sectional view (the space between the fixed layer 2 and the chip 3pt of the P-type thermoelectric conversion material is exaggerated).
  • (d) a part of the P-type thermoelectric semiconductor chip 3pt having a reduced adhesive force with the fixed layer 2 is peeled off from the fixed layer 2 on the second support 1b, and the part of the P-type thermoelectric semiconductor chip 3pt is peeled off.
  • (e) is a cross-sectional view after the N-type thermoelectric conversion material layer 3n is attached onto the fixed layer 2 on the third support 1c.
  • (F) is a cross-sectional view after the N-type thermoelectric conversion material layer 3n is fragmented into N-type thermoelectric conversion material chips 3nt to form a plurality of N-type thermoelectric conversion material chips 3nt.
  • (G) shows an aspect after reducing the adhesive force between a part of the N-type thermoelectric semiconductor chip 3nt and the fixed layer 2 among the chips 3nt of the plurality of N-type thermoelectric conversion materials formed in (f).
  • thermoelectric conversion material layer attachment step In the method of arranging the chips of the thermoelectric conversion material of the present invention, (A) P-type thermoelectric conversion material layer attachment step and (E) N-type thermoelectric conversion material layer attachment step are performed.
  • the thermoelectric conversion material layer attachment step is a step of attaching the thermoelectric conversion material layer to the fixed layer on the support, for example, in FIG. 1A, on the fixed layer 2 on the first support 1a. This is a step of attaching the P-type thermoelectric conversion material layer 3p [(A) step].
  • FIG. 1 (e) it is a step of attaching the N-type thermoelectric conversion material layer 3n onto the fixed layer 2 on the third support 1c [(E) step].
  • the support used in the present invention is not particularly limited, and examples thereof include resin, glass, ceramics, and silicon.
  • a resin film having light transmittance and having a resin-based material as a main material is preferable.
  • the resin film include polyethylene films such as low density polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, and high density polyethylene (HDPE) film, polypropylene film, polybutene film, polybutadiene film, and polymethyl.
  • Polyethylene films such as penten films, ethylene-norbornene copolymer films, and norbornene resin films; ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, and ethylene- (meth) acrylic acids.
  • Ethylene-based copolymer films such as ester copolymer films; polyvinyl chloride-based films such as polyvinyl chloride films and vinyl chloride copolymer films; polyester-based films such as polyethylene terephthalate films and polybutylene terephthalate films; polyurethane films; polyimides Examples thereof include film; polystyrene film; polycarbonate film; fluororesin film and the like. Further, modified films such as these crosslinked films and ionomer films may be used. As the support, one of these resin films may be used alone, or a laminated film in which two or more of these resin films are used in combination may be used.
  • the resin film is a low-density polyethylene (from the viewpoint of versatility, relatively high strength and easy to prevent warpage, heat resistance, and improvement of laser light transmittance described later).
  • LDPE linear low density polyethylene
  • HDPE high density polyethylene
  • the resin film is preferably a single-layer film having one or more layers selected from the group consisting of a polyethylene film, a polyester-based film, and a polypropylene film, or a laminated film in which two or more layers are laminated.
  • the Ra is preferably 0.01 ⁇ m to 0.80 ⁇ m.
  • the arithmetic average roughness Ra is a value measured in accordance with JIS B 0601: 1994.
  • the support may contain a colorant, but when laser light is used in the adhesive force lowering steps of the steps (C) and (G) described later, the support is made to be more excellent in laser light transmission.
  • the content of components such as a colorant that absorbs the laser beam is small.
  • the content of the colorant that absorbs the laser light is preferably less than 0.1% by mass, more preferably less than 0.01% by mass, still more preferably 0.001% by mass based on the total amount of the support. %, More preferably, it does not contain a component that absorbs the wavelength of the laser light used.
  • the support for example, in one or both of the step (C) and the step (G) described later, which is a step of reducing the adhesive strength described later, the pressure-sensitive adhesive layer and the thermoelectric conversion material described later are used.
  • the adhesive force with the chip it is preferable to use a heat-expandable base material.
  • the heat-expandable base material is a non-adhesive base material containing a resin and heat-expandable particles.
  • the resin include acrylic urethane-based resins and olefin-based resins.
  • the heat-expandable particles are microencapsulated foaming agents composed of an outer shell made of a thermoplastic resin and an inner shell component contained in the outer shell and vaporized when heated to a predetermined temperature. It is preferable to have.
  • thermoplastic resin constituting the outer shell of the microencapsulated foaming agent examples include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethylmethacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone. ..
  • the contained component contained in the outer shell examples include propane, butane, pentane, hexane, heptane, octane, nonane, decane, and isobutane. These inclusion components may be used alone or in combination of two or more.
  • the average particle size of the heat-expandable particles before expansion at 23 ° C. is preferably 3 to 100 ⁇ m, more preferably 4 to 70 ⁇ m, still more preferably 6 to 60 ⁇ m, still more preferably 10 to 50 ⁇ m.
  • the average particle size of the heat-expandable particles before expansion is the volume medium particle size (D50), and a laser diffraction type particle size distribution measuring device (for example, manufactured by Malvern, product name “Mastersizer 3000”) is used.
  • D50 volume medium particle size
  • a laser diffraction type particle size distribution measuring device for example, manufactured by Malvern, product name “Mastersizer 3000”
  • the particle distribution of the heat-expandable particles before expansion measured using the particle size it means the particle size corresponding to the cumulative volume frequency of 50% calculated from the smaller particle size of the heat-expandable particles before expansion.
  • the thickness of the support is not particularly limited, but is preferably in the range of 20 ⁇ m to 450 ⁇ m, more preferably 25 ⁇ m to 400 ⁇ m.
  • the fixed layer used in the present invention adheres the support to the chip of the thermoelectric conversion material layer or the thermoelectric conversion material layer, and is a part of the chips of a plurality of thermoelectric conversion materials due to the physicochemical action described later.
  • a material having a function of selectively reducing the adhesive force of the thermoelectric conversion material with the chip is used.
  • the fixed layer a layer containing a thermosetting resin, a photocurable resin, or the like can be used as long as the above conditions are satisfied.
  • a pressure-sensitive adhesive layer containing a colorant or a metal filler from the viewpoint of adhesiveness and light absorption.
  • thermoelectric conversion material from the viewpoint of chip retention and transferability of the thermoelectric conversion material, it is preferable to use a pressure-sensitive adhesive layer containing an energy ray-curable pressure-sensitive adhesive resin having a polymerizable functional group introduced in the side chain. .. Furthermore, as another aspect, from the viewpoint of easy peeling of the chip of the thermoelectric conversion material, it is preferable that the pressure-sensitive adhesive layer contains the heat-expandable particles.
  • the pressure-sensitive adhesive layer may contain any pressure-sensitive adhesive resin, and may contain additives for pressure-sensitive adhesive such as a cross-linking agent, a pressure-sensitive adhesive, a polymerizable compound, and a polymerization initiator, if necessary.
  • the pressure-sensitive adhesive layer can be formed from a pressure-sensitive adhesive composition containing a pressure-sensitive adhesive resin.
  • each component contained in the pressure-sensitive adhesive composition which is a material for forming the pressure-sensitive adhesive layer, will be described.
  • the adhesive resin is preferably a polymer having adhesiveness by itself and having a mass average molecular weight (Mw) of 10,000 or more.
  • the mass average molecular weight (Mw) of the adhesive resin is more preferably 10,000 to 2,000,000, still more preferably 20,000 to 1.5 million, and even more preferably 30,000 to 1,000,000 from the viewpoint of improving the adhesive strength. ..
  • the glass transition temperature (Tg) of the adhesive resin is preferably ⁇ 60 ° C. to ⁇ 10 ° C., more preferably ⁇ 50 ° C. to ⁇ 20 ° C.
  • the adhesive resin examples include rubber resins such as acrylic resins, urethane resins and polyisobutylene resins, polyester resins, olefin resins, silicone resins, polyvinyl ether resins and the like. These adhesive resins may be used alone or in combination of two or more. Further, when these adhesive resins are copolymers having two or more kinds of structural units, the form of the copolymer is not particularly limited, and the block copolymer, the random copolymer, and the graft can be used together. It may be any of the polymers.
  • the adhesive resin may be an energy ray-curable adhesive resin in which a polymerizable functional group is introduced into the side chain.
  • a photopolymerization initiator described later.
  • the polymerizable functional group include (meth) acryloyl group and vinyl group.
  • the energy ray include ultraviolet rays and electron beams.
  • the step (C) or the step (G) which is a step of reducing the adhesive force described later, the adhesive layer and the chip of the thermoelectric conversion material are bonded to each other.
  • ultraviolet rays As one embodiment.
  • the content of the pressure-sensitive adhesive resin is preferably 30 to 99.99% by mass, more preferably 40 to 99.95% by mass, still more preferably, based on the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition. It is 50 to 99.90% by mass, more preferably 55 to 99.80% by mass, and even more preferably 60 to 99.50% by mass.
  • the content of each component with respect to the total amount of the active ingredient of the pressure-sensitive adhesive composition is "the content of each component in the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition”. Is synonymous with.
  • the adhesive resin preferably contains an acrylic resin.
  • the content ratio of the acrylic resin in the pressure-sensitive adhesive resin is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total amount (100% by mass) of the pressure-sensitive adhesive resin contained in the pressure-sensitive adhesive composition. %, More preferably 70 to 100% by mass, still more preferably 85 to 100% by mass.
  • Acrylic resins that can be used as adhesive resins include, for example, a polymer containing a structural unit derived from an alkyl (meth) acrylate having a linear or branched alkyl group, and a (meth) acrylate having a cyclic structure. Examples thereof include a polymer containing a structural unit thereof.
  • the mass average molecular weight (Mw) of the acrylic resin is preferably 100,000 to 1,500,000, more preferably 200,000 to 1,300,000, and even more preferably 350,000 to 1,200,000.
  • the acrylic resin includes a structural unit (a1) derived from an alkyl (meth) acrylate (a1') (hereinafter, also referred to as “monomer (a1')”) and a functional group-containing monomer (a2') (hereinafter, “monomer”).
  • (A2') ”) an acrylic copolymer (A1) having a structural unit (a2) is more preferable.
  • the number of carbon atoms of the alkyl group of the monomer (a1') is preferably 1 to 24, more preferably 1 to 12, still more preferably 2 to 10, and even more preferably 4 to 8 from the viewpoint of improving the adhesive properties.
  • the alkyl group of the monomer (a1') may be a linear alkyl group or a branched chain alkyl group.
  • Examples of the monomer (a1') include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (). Examples thereof include meth) acrylate and stearyl (meth) acrylate. These monomers (a1') may be used alone or in combination of two or more.
  • the monomer (a1') one or more selected from methyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable, and from methyl (meth) acrylate and butyl (meth) acrylate. One or more selected are more preferable.
  • the content of the structural unit (a1) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 70 to 97.0% by mass, still more preferably 80 to 95.0% by mass.
  • Examples of the functional group of the monomer (a2') include a hydroxyl group, a carboxy group, an amino group, an epoxy group and the like. That is, examples of the monomer (a2') include a hydroxyl group-containing monomer, a carboxy group-containing monomer, an amino group-containing monomer, and an epoxy group-containing monomer. These monomers (a2') may be used alone or in combination of two or more. Among these, as the monomer (a2'), a hydroxyl group-containing monomer and a carboxy group-containing monomer are preferable, and a hydroxyl group-containing monomer is more preferable.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl (meth).
  • Acrylate and hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate; unsaturated alcohols such as vinyl alcohol and allyl alcohol can be mentioned.
  • 2-hydroxyethyl (meth) acrylate is preferable.
  • carboxy group-containing monomer examples include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid and their anhydrides.
  • monocarboxylic acids such as (meth) acrylic acid and crotonic acid
  • dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, and citraconic acid and their anhydrides.
  • 2- (acryloyloxy) ethyl succinate, 2-carboxyethyl (meth) acrylate and the like examples include 2- (acryloyloxy) ethyl succinate, 2-carboxyethyl (meth) acrylate and the like.
  • the content of the structural unit (a2) is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, based on the total structural unit (100% by mass) of the acrylic copolymer (A1). %, More preferably 1.0 to 30% by mass, still more preferably 3.0 to 25% by mass.
  • the acrylic copolymer (A1) may further have a structural unit (a3) derived from a monomer (a3') other than the monomers (a1') and (a2').
  • the content of the structural units (a1) and (a2) is preferably 70 with respect to the total structural units (100% by mass) of the acrylic copolymer (A1). It is -100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.
  • Examples of the monomer (a3') include olefins such as ethylene, propylene, and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; diene monomers such as butadiene, isoprene, and chloroprene; cyclohexyl (meth). Cyclic such as acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and imide (meth) acrylate.
  • olefins such as ethylene, propylene, and isobutylene
  • halogenated olefins such as vinyl chloride and vinylidene chloride
  • diene monomers such as butadiene, isoprene, and chloro
  • Structural (meth) acrylates styrene, ⁇ -methylstyrene, vinyltoluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholine, N-vinylpyrrolidone and the like. Be done.
  • the acrylic copolymer (A1) may be an energy ray-curable acrylic copolymer having a polymerizable functional group introduced in the side chain.
  • the polymerizable functional group include (meth) acryloyl group and vinyl group.
  • the energy ray include ultraviolet rays and electron beams, but ultraviolet rays are preferable.
  • the polymerizable functional group is a substituent capable of binding to the acrylic copolymer having the above-mentioned structural units (a1) and (a2) and the functional group having the structural unit (a2) of the acrylic copolymer. It can be introduced by reacting with a compound having a polymerizable functional group. Examples of the compound include (meth) acryloyloxyethyl isocyanate, (meth) acryloyl isocyanate, and glycidyl (meth) acrylate.
  • the pressure-sensitive adhesive composition preferably further contains a cross-linking agent.
  • the cross-linking agent like the above-mentioned acrylic copolymer (A1), reacts with a pressure-sensitive adhesive resin having a functional group and cross-links the pressure-sensitive resins with the functional group as a starting point for cross-linking.
  • cross-linking agent examples include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, an aziridine-based cross-linking agent, a metal chelate-based cross-linking agent, and the like. These cross-linking agents may be used alone or in combination of two or more. Among these cross-linking agents, isocyanate-based cross-linking agents are preferable from the viewpoint of increasing the cohesive force to improve the adhesive force and the availability.
  • the content of the cross-linking agent is appropriately adjusted depending on the number of functional groups of the adhesive resin, and is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the adhesive resin having functional groups. It is more preferably 0.03 to 7 parts by mass, and further preferably 0.05 to 5 parts by mass.
  • the pressure-sensitive adhesive composition may further contain a pressure-sensitive adhesive from the viewpoint of further improving the pressure-sensitive adhesive strength.
  • a pressure-sensitive adhesive refers to an oligomer having a mass average molecular weight (Mw) of less than 10,000, which is a component that supplementarily improves the adhesive strength of the above-mentioned adhesive resin, and refers to the above-mentioned adhesion. It is distinguished from the sex resin.
  • the mass average molecular weight (Mw) of the tackifier is preferably 400 to less than 10000, more preferably 500 to 8000, and even more preferably 800 to 5000.
  • C5 distillates such as rosin-based resin, terpene-based resin, styrene-based resin, pentene, isoprene, piperin, and 1,3-pentadiene produced by thermal decomposition of petroleum naphtha are copolymerized.
  • Examples thereof include a C5 petroleum resin obtained, a C9 petroleum resin obtained by copolymerizing a C9 distillate such as inden and vinyl toluene produced by thermal decomposition of petroleum naphtha, and a hydride resin obtained by hydrogenating these.
  • the softening point of the tackifier is preferably 60 to 170 ° C, more preferably 65 to 160 ° C, and even more preferably 70 to 150 ° C.
  • the "softening point" of the tackifier means a value measured according to JIS K 2531.
  • the tackifier one type may be used alone, or two or more types having different softening points, structures, etc. may be used in combination.
  • the weighted average of the softening points of the plurality of tackifiers belongs to the above range.
  • the content of the tackifier is preferably 0.01 to 65% by mass, more preferably 0.05 to 55% by mass, still more preferably, based on the total amount (100% by mass) of the active ingredient of the pressure-sensitive adhesive composition. It is 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, and even more preferably 1.0 to 40% by mass.
  • the pressure-sensitive adhesive composition contains an energy ray-curable pressure-sensitive adhesive resin as the pressure-sensitive adhesive resin
  • the pressure-sensitive adhesive composition further contains a photopolymerization initiator.
  • the curing reaction can be sufficiently advanced even by irradiation with relatively low energy energy rays.
  • photopolymerization initiator examples include 1-hydroxy-cyclohexyl-phenyl-ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzylphenyl sulfide, tetramethylthium monosulfide, and azobisisobutyrol. Examples thereof include nitrile, dibenzyl, diacetyl, 8-chloranthraquinone and the like. These photopolymerization initiators may be used alone or in combination of two or more.
  • the content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and further preferably 0. It is 05 to 2 parts by mass.
  • the pressure-sensitive adhesive layer may contain a colorant that absorbs laser light of a specific wavelength and generates heat.
  • the colorant include one or more selected from pigments and dyes.
  • the pigment may be an organic pigment or an inorganic pigment.
  • the dye include basic dyes, acid dyes, disperse dyes, direct dyes and the like.
  • the black pigment include carbon black, copper oxide, iron tetraoxide, manganese dioxide, aniline black, activated carbon and the like.
  • yellow pigment examples include chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, nables ero, naphthol ero S, hansa ero, benzine ero G, benzine ero GR, quinoline ero lake, and the like. Permanent yellow NCG, tartrazine lake and the like can be mentioned.
  • orange pigment examples include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, induthren brilliant orange RK, benzidine orange G, and induslen brilliant orange GKM.
  • red pigments include red iron oxide, cadmium red, lead tan, mercury sulfide, cadmium, permanent red 4R, resole red, pyrozolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, eosin lake, and rhodamine. Examples thereof include Lake B, Alizarin Lake, Brilliant Carmine 3B and the like. Examples of the purple pigment include manganese purple, fast violet B, methyl violet lake and the like. Examples of the blue pigment include dark blue, cobalt blue, alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and induslen blue BC.
  • green pigment examples include chrome green, chromium oxide, pigment green B, malachite green lake, final yellow green G and the like.
  • dye examples include niglocin, methylene blue, rose bengal, quinoline yellow, ultramarine blue and the like.
  • the content of the colorant can be appropriately adjusted depending on the wavelength, output, irradiation time, etc. of the laser beam, but is usually preferably 0.01 to 10% by mass, more preferably 0.01 to 10% by mass, based on the total amount of the pressure-sensitive adhesive composition. It is 0.05 to 7% by mass, more preferably 0.1 to 5% by mass.
  • the adhesive layer may contain a metal filler or the like that absorbs laser light of a specific wavelength and generates heat. good.
  • the metal filler is not particularly limited, and examples thereof include a metal filler made of copper, silver, gold, zinc, nickel, or palladium.
  • the content of the metal filler can be appropriately adjusted depending on the wavelength, output, irradiation time, etc. of the laser beam, but is usually preferably 0.01 to 10% by mass, more preferably 0.01 to 10% by mass, based on the total amount of the pressure-sensitive adhesive composition. It is 0.05 to 5% by mass, more preferably 0.1 to 3% by mass.
  • the colorant and the metal filler may be used in combination.
  • thermoelectric conversion material layer used in the present invention (hereinafter, may be referred to as “thin film of thermoelectric conversion material layer” or “chip of thermoelectric conversion material”) is not particularly limited and is made of a thermoelectric semiconductor material. It may also be a thin film made of a thermoelectric semiconductor composition. From the viewpoint of flexibility and thinness, it is composed of a thin film made of a thermoelectric semiconductor composition containing one or both of a thermoelectric semiconductor material (hereinafter, may be referred to as "thermoelectric semiconductor particles”), a resin, an ionic liquid and an inorganic ionic compound. Is preferable.
  • thermoelectric semiconductor material used for the thermoelectric conversion material layer is preferably pulverized to a predetermined size by, for example, a fine pulverizer or the like, and used as thermoelectric semiconductor particles (hereinafter, the thermoelectric semiconductor material is referred to as "thermoelectric semiconductor particles". be.).
  • the particle size of the thermoelectric semiconductor particles is preferably 10 nm to 100 ⁇ m, more preferably 20 nm to 50 ⁇ m, and even more preferably 30 nm to 30 ⁇ m.
  • the average particle size of the thermoelectric semiconductor fine particles was obtained by measuring with a laser diffraction type particle size analyzer (Mastersizer 3000 manufactured by Malvern), and was used as the median value of the particle size distribution.
  • thermoelectric semiconductor material constituting the P-type thermoelectric conversion material layer and the N-type conversion material layer is a material capable of generating thermoelectromotive force by imparting a temperature difference.
  • the present invention is not particularly limited, and for example, a bismuth-tellu-based thermoelectric semiconductor material such as P-type bismasterlide and N-type bismasterlide; a telluride-based thermoelectric semiconductor material such as GeTe and PbTe; an antimony-tellu-based thermoelectric semiconductor material; ZnSb, Zn.
  • Zinc-antimony thermoelectric semiconductor materials such as 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 the like, silicide-based thermoelectric semiconductor materials; oxide-based thermoelectric semiconductor materials; FeVAL, FeVALSi, FeVTiAl and the like, whisler materials, TiS 2 and the like, sulfide-based thermoelectric semiconductor materials and the like are used.
  • thermoelectric semiconductor material used in the present invention is preferably a bismuth-tellurium-based thermoelectric semiconductor material such as P-type bismuthellide or N-type bismuthellide.
  • P-type bismuth telluride one having a hole as a carrier and a positive Seebeck coefficient, for example, represented by Bi X Te 3 Sb 2-X is preferably used.
  • X is preferably 0 ⁇ X ⁇ 0.8, more preferably 0.4 ⁇ X ⁇ 0.6.
  • X is larger than 0 and 0.8 or less, the Seebeck coefficient and the electric conductivity become large, and the characteristics as a P-type thermoelectric conversion material are maintained, which is preferable.
  • N-type bismuth telluride one having an electron carrier and a negative Seebeck coefficient, for example, represented by Bi 2 Te 3-Y Se Y is preferably used.
  • the Seebeck coefficient and the electric conductivity become large, and the characteristics as an N-type thermoelectric conversion material are maintained, which is preferable.
  • the content of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. It is more preferably 50 to 96% by mass, and even more preferably 70 to 95% by mass.
  • the Seebeck coefficient absolute value of the Perche coefficient
  • the decrease in the electric conductivity is suppressed, and only the thermal conductivity is decreased, so that high thermoelectric performance is exhibited.
  • a film having sufficient film strength and flexibility can be obtained, which is preferable.
  • thermoelectric semiconductor particles are annealed (hereinafter, may be referred to as "annealing treatment A").
  • annealing treatment A By performing the annealing treatment A, the crystallinity of the thermoelectric semiconductor particles is improved, and further, the surface oxide film of the thermoelectric semiconductor particles is removed, so that the Seebeck coefficient (absolute value of the Perche coefficient) of the thermoelectric conversion material is increased. , The thermoelectric performance index can be further improved.
  • the resin used in the present invention has a function of physically bonding thermoelectric semiconductor materials (thermoelectric semiconductor particles), can enhance the flexibility of the thermoelectric conversion module, and facilitates the formation of a thin film by coating or the like. ..
  • a heat-resistant resin or a binder resin is preferable.
  • the heat-resistant resin is maintained without impairing various physical properties such as mechanical strength and thermal conductivity as the resin when the thin film made of the thermoelectric semiconductor composition is subjected to crystal growth such as annealing treatment.
  • the heat-resistant resin is preferably a polyamide resin, a polyamideimide resin, a polyimide resin, or an epoxy resin, and has excellent flexibility, because it has higher heat resistance and does not adversely affect the crystal growth of thermoelectric semiconductor particles in the thin film. From this point of view, polyamide resin, polyamideimide resin, and polyimide resin are more preferable.
  • the heat-resistant resin preferably has a decomposition temperature of 300 ° C. or higher. As long as the decomposition temperature is within the above range, the flexibility can be maintained without losing the function as a binder even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the heat-resistant resin preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and further preferably 1% or less at 300 ° C. by thermogravimetric analysis (TG). ..
  • TG thermogravimetric analysis
  • the content of the heat-resistant resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15. It is mass%.
  • the content of the heat-resistant resin is within the above range, it functions as a binder for the thermoelectric semiconductor material, facilitates the formation of a thin film, and obtains a film having both high thermoelectric performance and film strength, and thermoelectric conversion.
  • the binder resin can be easily peeled off from the base material such as glass, alumina, silicon, etc. used for manufacturing chips of thermoelectric conversion materials after firing (annealing) treatment (corresponding to "annealing treatment B" described later, the same applies hereinafter).
  • annealing treatment B thermoelectric conversion materials after firing
  • the binder resin refers to a resin that decomposes in an amount of 90% by mass or more at a firing (annealing) temperature or higher, more preferably a resin that decomposes in an amount of 95% by mass or more, and a resin that decomposes in an amount of 99% by mass or more. Is particularly preferable. Further, when a coating film (thin film) made of a thermoelectric semiconductor composition is subjected to crystal growth such as firing (annealing) treatment, a resin that maintains various physical properties such as mechanical strength and thermal conductivity without being impaired. More preferred.
  • a resin that decomposes by 90% by mass or more at a firing (annealing) temperature or higher that is, a resin that decomposes at a lower temperature than the heat-resistant resin described above. Since the content of the binder resin, which is an insulating component contained therein, is reduced and the crystal growth of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is promoted, the voids in the thermoelectric conversion material layer are reduced and the filling rate is increased. Can be improved.
  • Whether or not the resin decomposes at a predetermined value (for example, 90% by mass) or more at the firing (annealing) temperature or higher is determined by the mass reduction rate (before decomposition) at the firing (annealing) temperature by thermogravimetric analysis (TG). Judgment is made by measuring (the value obtained by dividing the mass after decomposition by the mass).
  • a predetermined value for example, 90% by mass
  • TG thermogravimetric analysis
  • thermoplastic resin examples include polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polymethylpentene; polycarbonate; thermoplastic polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polystyrene, acrylonitrile-styrene copolymer, and polyacetic acid.
  • Examples thereof include polyvinyl polymers such as vinyl, ethylene-vinyl acetate copolymers, vinyl chloride, polyvinylpyridine, polyvinyl alcohol, and polyvinylpyrrolidone; polyurethanes; cellulose derivatives such as ethyl cellulose; and the like.
  • the curable resin include thermosetting resins and photocurable resins.
  • examples of the thermosetting resin include epoxy resin and phenol resin.
  • Examples of the photocurable resin include a photocurable acrylic resin, a photocurable urethane resin, and a photocurable epoxy resin. These may be used alone or in combination of two or more.
  • thermoplastic resin a thermoplastic resin is preferable, a cellulose derivative such as polycarbonate and ethyl cellulose is more preferable, and polycarbonate is particularly preferable.
  • the binder resin is appropriately selected according to the temperature of the firing (annealing) treatment of the thermoelectric semiconductor material in the firing (annealing) treatment step. It is preferable to perform the firing (annealing) treatment at a temperature equal to or higher than the final decomposition temperature of the binder resin from the viewpoint of the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer.
  • the "final decomposition temperature” is a temperature at which the mass reduction rate at the firing (annealing) temperature by thermogravimetric analysis (TG) is 100% (the mass after decomposition is 0% of the mass before decomposition).
  • the final decomposition temperature of the binder resin is usually 150 to 600 ° C, preferably 200 to 560 ° C, more preferably 220 to 460 ° C, and particularly preferably 240 to 360 ° C. If a binder resin having a final decomposition temperature in this range is used, it functions as a binder for the thermoelectric semiconductor material, and it becomes easy to form a thin film at the time of printing.
  • the content of the binder resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 5%. It is mass%.
  • the content of the binder resin is within the above range, the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer can be reduced.
  • the content of the binder resin in the thermoelectric conversion material is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass.
  • the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer can be reduced.
  • the ionic liquid that can be contained in the thermoelectric semiconductor composition is a molten salt formed by combining a cation and an anion, and refers to a salt that can exist as a liquid in any temperature range of ⁇ 50 ° C. or higher and lower than 400 ° C.
  • the ionic liquid is an ionic compound having a melting point in the range of ⁇ 50 ° C. or higher and lower than 400 ° C.
  • the melting point of the ionic liquid is preferably ⁇ 25 ° C. or higher and 200 ° C. or lower, and more preferably 0 ° C. or higher and 150 ° C. or lower.
  • the ionic liquid has features such as extremely low vapor pressure, non-volatileity, excellent thermal stability and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, as a conductive auxiliary agent, it is possible to effectively suppress the reduction of the electrical conductivity between the thermoelectric semiconductor materials. Further, since the ionic liquid exhibits high polarity based on the aprotic ionic structure and has excellent compatibility with the heat-resistant resin, the electric conductivity of the thermoelectric conversion material can be made uniform.
  • the ionic liquid a known or commercially available one can be used.
  • nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and their derivatives; tetraalkylammonium-based amine-based cations and their derivatives; phosphonium, trialkylsulfonium, tetraalkylphosphonium and the like.
  • Phosphonic cations and their derivatives Phosphonic cations and their derivatives; cation components such as lithium cations and their derivatives, Cl- , Br- , I- , AlCl 4- , Al 2 Cl 7- , BF 4- , PF 6- , ClO 4- , NO 3- , CH 3 COO- , CF 3 COO- , CH 3 SO 3- , CF 3 SO 3- , (FSO 2 ) 2 N- , (CF 3 SO 2 ) 2 N- , (CF 3 SO 2 ) 3 C- , AsF 6- , SbF 6- , NbF 6- , TaF 6- , F (HF) n- , (CN) 2 N- , C 4 F 9 SO 3- , (C 2 F 5 SO 2 ) Examples thereof include those composed of anionic components such as 2 N ⁇ , C 3 F 7 COO ⁇ , and (CF 3 SO 2 ) (CF 3 CO) N ⁇ .
  • the cation component of the ionic liquid is a pyridinium cation and its derivatives from the viewpoints of high temperature stability, compatibility with thermoelectric semiconductor materials and resins, and suppression of decrease in electrical conductivity between thermoelectric semiconductor material gaps.
  • 1-butyl-4-methylpyridinium bromide, 1-butylpyridinium bromide, and 1-butyl-4-methylpyridinium hexafluorophosphart are preferable.
  • the cation component is [1-butyl-3- (2-hydroxyethyl) imidazolium bromide], [1-butyl-3- (2-hydroxyethyl) imidazole].
  • Rium tetrafluoroborate] is preferred.
  • the above-mentioned ionic liquid preferably has a decomposition temperature of 300 ° C. or higher. As long as the decomposition temperature is within the above range, the effect as a conductive auxiliary agent can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the content of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 20% by mass.
  • the content of the ionic liquid is within the above range, the decrease in electrical conductivity is effectively suppressed, and a film having high thermoelectric performance can be obtained.
  • thermoelectric semiconductor composition (Inorganic ionic compound)
  • the inorganic ionic compound that can be contained in the thermoelectric semiconductor composition is a compound composed of at least cations and anions.
  • Inorganic ionic compounds exist as solids in a wide temperature range of 400 to 900 ° C. and have characteristics such as high ionic conductivity. Therefore, as a conductive auxiliary agent, the electrical conductivity between thermoelectric semiconductor materials is reduced. Can be suppressed.
  • the content of the inorganic ionic compound in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 10% by mass.
  • the content of the inorganic ionic compound is within the above range, the decrease in electrical conductivity can be effectively suppressed, and as a result, a film having improved thermoelectric performance can be obtained.
  • the total content of the inorganic ionic compound and the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably. Is 0.5 to 30% by mass, more preferably 1.0 to 10% by mass.
  • thermoelectric conversion material layer is formed by being attached to a fixed layer on a support.
  • a thermoelectric conversion material layer prepared on a pre-peelable substrate is used. From the viewpoint of thermoelectric performance, when the annealing treatment B described later is performed, it is preferable to perform the annealing treatment B before the attachment.
  • the thermoelectric semiconductor composition is formed by applying the thermoelectric semiconductor composition on a known substrate such as glass or silicon and drying it. Can be done. By forming in this way, a large number of thermoelectric conversion material layers can be easily obtained at low cost.
  • thermoelectric semiconductor composition As a method of applying a thermoelectric semiconductor composition to obtain a thermoelectric conversion material layer, 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, and a doctor Known methods such as the blade method can be mentioned, and the present invention is not particularly limited. Then, the obtained coating film is dried to form a thermoelectric conversion material layer.
  • the thickness of the thermoelectric conversion material layer is not particularly limited, and is preferably 100 nm to 1000 ⁇ m, more preferably 300 nm to 600 ⁇ m, and further preferably 5 to 400 ⁇ m from the viewpoint of thermoelectric performance and film strength.
  • the P-type thermoelectric conversion material layer and the N-type thermoelectric conversion material layer as a thin film made of the thermoelectric semiconductor composition are further subjected to an annealing treatment (hereinafter, may be referred to as "annealing treatment B").
  • annealing treatment B By performing the annealing treatment B, the thermoelectric performance can be stabilized, and the thermoelectric semiconductor particles in the thin film can be crystal-grown, so that the thermoelectric performance can be further improved.
  • the annealing treatment B is not particularly limited, but is usually carried out under an inert gas atmosphere such as nitrogen or argon, a reducing gas atmosphere, or a vacuum condition in which the gas flow rate is controlled, and the thermoelectric semiconductor composition and the group to be used are used. Although it depends on the heat-resistant temperature of the material, it is carried out at 100 to 500 ° C. for several minutes to several tens of hours.
  • thermoelectric conversion material In the method of arranging chips of thermoelectric conversion material of the present invention, (B) chip forming step of P-type thermoelectric conversion material and (F) chip forming step of N-type thermoelectric conversion material are performed.
  • the chip forming step of the thermoelectric conversion material is a step of individualizing the thermoelectric conversion material layer to obtain a chip of the thermoelectric conversion material.
  • the P-type thermoelectric conversion material layer 3p is individualized. This is a step of obtaining a chip 3pt of a P-type thermoelectric conversion material [step (B)].
  • the N-type thermoelectric conversion material layer 3n is fragmented to obtain a chip 3nt of the N-type thermoelectric conversion material [(F) step].
  • the method for individualizing the thermoelectric conversion material layer is not particularly limited, and a known method can be used.
  • a dicing method can be mentioned.
  • the dicing method is not particularly limited, but known methods such as blade dicing and laser dicing can be adopted.
  • the dicing method is performed by providing a notch so as to penetrate the thermoelectric conversion material layer.
  • the adhesive strength reducing step relating to the chip of the P-type thermoelectric conversion material and (G) relating to the chip of the N-type thermoelectric conversion material.
  • the adhesive strength lowering step is a step of lowering the adhesive strength between the fixed layer and the chip of the thermoelectric conversion material.
  • a part of the P-type thermoelectric conversion material chip 3pt is attached.
  • This is a step of reducing the adhesive strength of the fixed layer 2 in the region [(C) step].
  • FIG. 1 (g) it is a step of reducing the adhesive force of the fixed layer 2 in the region to which the chip 3nt of a part of the N-type thermoelectric conversion material is attached [(G) step].
  • the fixed layer is made into a fixed layer capable of absorbing laser light, and the step (C) and the step (G) are, in this order, a part of the P-type thermoelectric. It is preferably performed by irradiating at least a part of the fixed layer of each region to which the chip of the conversion material and the chip of the part of the N-type thermoelectric conversion material are attached with the laser beam.
  • FIG. 2 is a schematic cross-sectional view showing one aspect of the adhesive force reducing step in the present invention, and is among the chips 3pt of a plurality of P-type thermoelectric conversion materials attached to the fixed layer 2 on the first support 1a.
  • a mode in which the adhesive force between the chip 3pt of some P-type thermoelectric conversion materials and the fixed layer 2 is reduced is schematically shown.
  • the adhesive force between the fixed layer and the chip of the thermoelectric conversion material is reduced by irradiation with laser light in the step (C) or the step (G), for example, with the chip 3pt of the P-type thermoelectric conversion material of the fixed layer 2.
  • laser light 4 is applied to at least a part of the fixed layer 2 in the region where the chip 3pt of a part of the P-type thermoelectric conversion material is attached from the surface opposite to the attachment surface of the above.
  • a part of the fixed layer 2 is ablated to generate sublimation gas 6, and the contact area between the chip 3pt of a part of the P-type thermoelectric conversion material and the fixed layer 2 around the irradiated portion of the laser beam 4 is generated. Decreases.
  • the fixed layer 2 is ablated over a wide range to generate sublimation gas, and a part of the P-type thermoelectric is generated.
  • the adhesive force between the chip 3pt of some P-type thermoelectric conversion materials and the fixed layer 2 is further reduced. Even if the sublimation gas 6 leaks around the chip 3pt of the P-type thermoelectric conversion material, the leaked sublimation gas 6 is released from the gap 7 between the chips 3pt of the P-type thermoelectric conversion material.
  • the lasers are multi-arrayed and collectively performed according to the arrangement and number of chips of some thermoelectric conversion materials.
  • thermoelectric conversion material it is preferable to reduce the adhesive force between the fixed layer and the chip of the thermoelectric conversion material by irradiation with ultraviolet rays.
  • all the chips of the thermoelectric conversion material that do not want to reduce the adhesive strength are masked together with the support from the surface opposite to the surface on which the fixed layer is attached to the chip of the thermoelectric conversion material.
  • the fixed layer and some thermoelectrics are applied.
  • Adhesion to all of the conversion material chips can be reduced, and all of the thermoelectric conversion material chips of some of the plurality of thermoelectric conversion material chips can be selectively and easily peeled off at once on the support. Can be done.
  • the masking material is not particularly limited as long as it is a material that does not transmit ultraviolet rays and has a small temperature rise, and a metal plate having high thermal conductivity such as aluminum can be used.
  • the support is made of the above-mentioned heat-expandable base material, and a part of the corresponding P-type thermoelectrics is used in one or both of the steps (C) and the step (G).
  • the chip of the corresponding N-type thermoelectric conversion material is attached. It is preferable to be carried out by.
  • the heat-expandable base material By heating a part of the heat-expandable base material to a temperature higher than the temperature at which the heat-expandable particles expand, the heat-expandable base material follows the volume expansion of the heat-expandable particles at a temperature at which the heat-expandable particles are expanded.
  • the chips of some thermoelectric conversion materials among the chips of a plurality of thermoelectric conversion materials are selectively selected. It can be easily peeled off.
  • the means for heating the heat-expandable base material as a support is not particularly limited as long as it can selectively heat the heat-expandable particles in the heat-expandable base material to a temperature higher than the temperature at which the heat-expandable particles expand.
  • Heating by electromagnetic waves such as near-infrared rays, mid-infrared rays, and far-infrared rays can be used as appropriate.
  • the heating method may be either a direct heating method or an indirect heating method.
  • a chip of a part of the corresponding P-type thermoelectric conversion material and a part of the corresponding N-type thermoelectric conversion is preferably carried out by selectively heating at least a part of the heat-expandable particles of the fixed layer of the fixed layer to which the chip of the material is attached.
  • the step (C) and the step (G) a fixed layer (adhesive layer) containing heat-expandable particles and a heat-expandable base material as a support may be used in combination.
  • thermoelectric conversion material In the method of arranging chips of thermoelectric conversion material of the present invention, (D) chip transfer step of P-type thermoelectric conversion material and (H) chip transfer step of N-type thermoelectric conversion material are performed.
  • the chip transfer step of the thermoelectric conversion material is a step of selectively transferring and adhering only a part of the chips of the thermoelectric conversion material having reduced adhesive strength onto a fixed layer on another support, for example, FIG. 1.
  • (d) only the chip 3pt of a part of the P-type thermoelectric conversion material is selectively peeled from the fixed layer 2 on the first support 1a and transferred to the fixed layer 2 on the second support 1b. It is a step of sticking [(D) step].
  • thermoelectric conversion material only the chip 3nt of a part of the N-type thermoelectric conversion material is selectively peeled from the fixing layer 2 on the third support 1c and fixed on the fourth support 1d. It is a step of transferring and sticking to the layer 2 [step (H)].
  • the method of transferring the chip of the thermoelectric conversion material from the fixed layer having reduced adhesive strength onto the fixed layer on another support is not particularly limited, and a known method can be used.
  • the chip arranging method of the thermoelectric conversion material of the present invention includes (I) a chip bonding step of the thermoelectric conversion material and (J) a chip bonding step of the thermoelectric conversion material.
  • the chip bonding step of the thermoelectric conversion material is a chip of a separated P-type thermoelectric conversion material (or an N-type thermoelectric conversion material) attached to a fixed layer on a support obtained in the chip transfer step of the thermoelectric conversion material. Thermoelectric conversion on both supports so that the chip) and the chip of the N-type thermoelectric conversion material (or the chip of the P-type thermoelectric conversion material) separated on the fixed layer on the other support have a predetermined arrangement.
  • the method of laminating the chips of the N-type thermoelectric conversion material (or the chips of the P-type thermoelectric conversion material) separated on the layer so as to have a predetermined arrangement is not particularly limited, and is performed by a known method. Can be done.
  • the separated N-type thermoelectric conversion material chips 3nt transferred to the fixed layer 2 on the fourth support 1d obtained in the transfer step and the separated Ps on the fixed layer 2 on the first support 1a.
  • the chip 3pt of the type thermoelectric conversion material When the chip 3pt of the type thermoelectric conversion material is bonded, the chip 3pt of the separated P-type thermoelectric conversion material on the fixed layer 2 on the first support 1a is attached to the fixed layer 2 on the fourth support 1d.
  • Alignment marks are provided in advance on the first support and the second support in order to accurately place them at predetermined positions between the chips 3nt of the separated N-type thermoelectric conversion material transferred to the above, and with a microscope or the like. Align and bond by a known method.
  • the method for arranging chips of a thermoelectric conversion material of the present invention further includes a step of peeling one of the supports having a fixed layer from the chips of the thermoelectric conversion material.
  • the N-type thermoelectric conversion material chips 3nt and the P-type thermoelectric conversion material chips 3pt alternately arranged on the fixed layer 2 on the fourth support 1d are the first. This is a step of peeling off the fixed layer on the support 1a of 1.
  • a chip of a thermoelectric conversion material whose adhesive strength is not reduced by the same method as in step (C) or step (G) [for example, FIG. 1 (i').
  • the adhesive force of the fixed layer on one support to be peeled off (for example, the adhesive force of the pressure-sensitive adhesive layer) is fixed on the other support which is not the object to be peeled off. It is preferable that the adhesive strength of the layer is lower than that of the adhesive layer (for example, the adhesive strength of the pressure-sensitive adhesive layer).
  • the method for producing a chip array of a thermoelectric conversion material of the present invention is a step of arranging chips of the thermoelectric conversion material of the present invention including steps (A) to (J) or a step of carrying out an arrangement method of one aspect of the present invention. including.
  • the method for producing a chip array of a thermoelectric conversion material of the present invention is a step of carrying out a method of arranging chips of a thermoelectric conversion material according to one aspect of the present invention, which includes steps (A) to (J) in this order.
  • thermoelectric conversion module The method for manufacturing a thermoelectric conversion module of the present invention includes a step of arranging chips of the thermoelectric conversion material of the present invention including steps (A) to (J) or a step of carrying out an arrangement method of one aspect of the present invention. Therefore, all of the chips of the plurality of P-type and N-type thermoelectric conversion materials arranged alternately in the support batch can be used in the process of assembling the thermoelectric conversion module. Specifically, all of the chips of a plurality of P-type and N-type thermoelectric conversion materials arranged alternately in a support can be used in the process of assembling the thermoelectric conversion module, and the yield of the thermoelectric conversion module can be improved. Contributes to improving productivity.
  • the chips of the P-type conversion material and the chips of the N-type thermoelectric conversion material can be efficiently and alternately arranged in a support. Therefore, by using this in the process of assembling the thermoelectric conversion module, it is possible to improve the productivity of the thermoelectric conversion module.
  • thermoelectric conversion material which comprises a step of arranging the chip of the thermoelectric conversion material of the present invention
  • a plurality of P-type and N-type thermoelectric conversion material chips arranged alternately in a support batch are used. All of them can be used in the process of assembling the thermoelectric conversion module, which leads to the improvement of productivity including the improvement of the yield of the thermoelectric conversion module. Therefore, it can be expected to provide a large amount of inexpensive thermoelectric conversion modules.

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Abstract

La présente invention concerne un procédé de mise en réseau efficace d'une puce d'un matériau de conversion thermoélectrique de type P et d'une puce d'un matériau de conversion thermoélectrique de type N collectivement sur un support. Procédé de mise en réseau de puces d'un matériau de conversion thermoélectrique, dans lequel les puces du matériau de conversion thermoélectrique comprennent une puce d'un matériau de conversion thermoélectrique de type P et une puce d'un matériau de conversion thermoélectrique de type N, le procédé comprenant les étapes (A) à (J) (voir la description).
PCT/JP2021/039752 2020-10-30 2021-10-28 Procédé de mise en réseau de puces de matériau de conversion thermoélectrique WO2022092179A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003105244A1 (fr) * 2002-01-01 2003-12-18 古河電気工業株式会社 Module a elements thermoelectriques et son procede de fabrication
JP2004221109A (ja) * 2003-01-09 2004-08-05 Furukawa Electric Co Ltd:The 熱電素子モジュール及びその製造方法
JP2005019767A (ja) * 2003-06-27 2005-01-20 Yamaha Corp 熱電変換モジュールの製造方法
WO2018139475A1 (fr) * 2017-01-27 2018-08-02 リンテック株式会社 Élément de conversion thermoélectrique flexible, et procédé de fabrication de celui-ci

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003105244A1 (fr) * 2002-01-01 2003-12-18 古河電気工業株式会社 Module a elements thermoelectriques et son procede de fabrication
JP2004221109A (ja) * 2003-01-09 2004-08-05 Furukawa Electric Co Ltd:The 熱電素子モジュール及びその製造方法
JP2005019767A (ja) * 2003-06-27 2005-01-20 Yamaha Corp 熱電変換モジュールの製造方法
WO2018139475A1 (fr) * 2017-01-27 2018-08-02 リンテック株式会社 Élément de conversion thermoélectrique flexible, et procédé de fabrication de celui-ci

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