WO2015001865A1 - 熱電変換層の製造方法、熱電変換素子 - Google Patents

熱電変換層の製造方法、熱電変換素子 Download PDF

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WO2015001865A1
WO2015001865A1 PCT/JP2014/063675 JP2014063675W WO2015001865A1 WO 2015001865 A1 WO2015001865 A1 WO 2015001865A1 JP 2014063675 W JP2014063675 W JP 2014063675W WO 2015001865 A1 WO2015001865 A1 WO 2015001865A1
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thermoelectric conversion
layer
thermoelectric
precursor layer
conversion layer
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PCT/JP2014/063675
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English (en)
French (fr)
Japanese (ja)
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林　直之
加納　丈嘉
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富士フイルム株式会社
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Priority to CN201480037691.0A priority Critical patent/CN105359286B/zh
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth
    • 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
    • H10N10/851—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 thermoelectric conversion layer and a thermoelectric conversion element.
  • thermoelectric conversion materials that can mutually convert thermal energy and electrical energy are used in thermoelectric conversion elements such as thermoelectric power generation elements and Peltier elements.
  • Thermoelectric power generation using such thermoelectric conversion materials and thermoelectric conversion elements can directly convert heat energy into electric power, does not require moving parts, operates at body temperature, power supplies for remote areas, power supplies for space, etc. It is used for.
  • a method for producing a thermoelectric conversion layer included in such a thermoelectric conversion element an embodiment in which a heat and baking treatment is performed to form a thermoelectric conversion layer is generally implemented (Patent Document 1). More specifically, Patent Document 1 discloses a method for producing a porous thermoelectric conversion layer containing voids (voids) by performing a heat-firing treatment (heat sintering treatment) when producing the thermoelectric conversion layer. Has been.
  • thermoelectric conversion performance of thermoelectric conversion elements has been demanded in order to improve the performance of equipment in which thermoelectric conversion elements are used.
  • the inventors of the present invention performed a heat-firing process as described in Patent Document 1 to produce a porous thermoelectric conversion layer, and the thermoelectric conversion performance (performance index ZT) of the thermoelectric conversion layer is recently required. It was found that the level was not met and further improvement was necessary. Moreover, in the said heat baking process, the heating time is long and it was not necessarily the method which can be satisfied also from the point of productivity.
  • an object of the present invention is to provide a method for producing a thermoelectric conversion layer capable of efficiently producing a thermoelectric conversion layer having excellent thermoelectric conversion performance.
  • thermoelectric conversion layer comprising a step of forming a thermoelectric conversion layer having voids by subjecting a precursor layer containing an organic material and an inorganic material capable of thermoelectric conversion to light irradiation. Production method.
  • the inorganic material capable of thermoelectric conversion is at least one selected from Bi, Sb, Ag, Pb, Ge, Cu, Sn, As, Se, Te, Fe, Mn, Co, Si, and Zn.
  • thermoelectric conversion layer comprising a thermoelectric conversion material containing an element.
  • Thermoelectric conversion inorganic materials are Zn—Sb thermoelectric conversion material, Pb—Te thermoelectric conversion material, Bi—Se thermoelectric conversion material, Ag—Te thermoelectric conversion material, and Si—Ge thermoelectric
  • a thermoelectric conversion element comprising a thermoelectric conversion layer manufactured by the method for manufacturing a thermoelectric conversion layer according to any one of (1) to (5).
  • thermoelectric conversion layer that can efficiently produce a thermoelectric conversion layer having excellent thermoelectric conversion performance
  • thermoelectric conversion element of this invention It is sectional drawing which shows typically an example of the thermoelectric conversion element of this invention.
  • the arrows in FIG. 1 indicate the direction of the temperature difference applied when the element is used.
  • FIG. 2 shows typically an example of the thermoelectric conversion element of this invention.
  • thermoelectric conversion layer of this invention a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • a photo-baking treatment is performed on a precursor layer containing an organic material.
  • the organic material is decomposed and volatilized by the thermal energy generated by the irradiation of light energy, forming voids in the thermoelectric conversion layer. Is prompted.
  • a thermoelectric conversion layer having excellent thermoelectric conversion performance is formed.
  • the light baking treatment is usually performed in a short time by light irradiation with a flash lamp or the like, and instantaneously reaches a high temperature condition, so that voids can be formed more efficiently than in the case of heat baking.
  • heat firing the substrate to be treated is exposed to a high temperature for a long time, so the base material supporting the thermoelectric conversion layer is easily damaged or deformed by heat. Therefore, there is little influence on the base material, and it is excellent in versatility regardless of the type of base material and also in productivity.
  • the organic matter is decomposed and gas is generated over time in the thermal firing, the gas generated from the layer is easily removed and voids are not easily formed.
  • the organic material is decomposed and gasified in a short time, so that a void is easily formed.
  • the method for producing a thermoelectric conversion layer of the present invention includes a step of forming a thermoelectric conversion layer having a void by subjecting a precursor layer containing an organic material and an inorganic material capable of thermoelectric conversion to light irradiation treatment.
  • a precursor layer containing an organic material and an inorganic material capable of thermoelectric conversion to light irradiation treatment.
  • Step A is a step of forming a precursor layer containing an organic material and an inorganic material capable of thermoelectric conversion.
  • a precursor layer to be subjected to a light baking process described later is formed.
  • the components contained in the precursor layer are described in detail, and then the procedure of the process is described in detail.
  • the precursor layer includes an organic material.
  • An organic material decomposes
  • the kind in particular of organic material used is not restrict
  • As the organic material for example, any of a low molecular compound (low molecular organic compound) and a high molecular compound (polymer organic compound) may be used, and a high molecular compound is preferable from the viewpoint of better void formation.
  • a high molecular compound intends a compound with a molecular weight of 1000 or more, and a low molecular compound intends a compound with a molecular weight of less than 1000.
  • a known resin can be used.
  • vinyl resin, acrylic resin, styrene resin, polyolefin resin, polyamide resin, and the like can be given.
  • the polymer compound is preferably a thermoplastic resin in that the thermoelectric conversion performance of the thermoelectric conversion layer is more excellent, and polyvinyl pyrrolidone, polyvinyl alcohol, polyethyleneimine, polyalkylene oxide (polyethylene oxide, polypropylene oxide), and More preferably, it is selected from the group consisting of polyacetals.
  • the content of the organic material in the precursor layer is not particularly limited, but is 5 to 60 parts by mass with respect to 100 parts by mass of an inorganic material capable of thermoelectric conversion, which will be described later, in that the thermoelectric conversion performance of the thermoelectric conversion layer is more excellent.
  • the amount is preferably 10 to 40 parts by mass.
  • only 1 type may be used for an organic material, or 2 or more types may be used for it.
  • the precursor layer includes an inorganic material (inorganic thermoelectric conversion material) capable of thermoelectric conversion.
  • the thermoelectrically convertible inorganic material is an inorganic material that exhibits thermoelectric conversion ability.
  • examples of inorganic materials include semiconductor materials such as compound semiconductor materials and oxide semiconductor materials. Especially, it is selected from Bi, Sb, Ag, Pb, Ge, Cu, Sn, As, Se, Te, Fe, Mn, Co, Si, and Zn in that the thermoelectric conversion performance of the thermoelectric conversion layer is more excellent.
  • a thermoelectric conversion material containing at least one element is preferred.
  • the inorganic materials include Zn—Sb thermoelectric conversion materials, Pb—Te thermoelectric conversion materials, Bi—Se thermoelectric conversion materials, and Ag—Te thermoelectric elements because the thermoelectric conversion performance of the thermoelectric conversion layer is further improved.
  • At least one selected from the group consisting of a conversion material and a Si—Ge thermoelectric conversion material is preferable.
  • the Si—Ge-based thermoelectric conversion material is intended to be a thermoelectric conversion material containing a Si element and a Ge element, and the other thermoelectric conversion materials are also intended to be thermoelectric conversion materials containing a predetermined element.
  • inorganic materials capable of thermoelectric conversion include bismuth and tellurium materials (specifically, for example, Bi 2 Te 3 and Bi 2 Te 2.85 Se 0.15 ), bismuth tellurium and antimony materials, and antimony and tellurium materials.
  • Materials specifically, for example, Sb 2 Te 3 ), thallium / tellurium-based materials, bismuth / selenium-based materials (specifically, for example, Bi 2 Se 3 ), lead / tellurium-based materials, tin / tellurium-based materials Materials, silver / tellurium-based materials, germanium / tellurium-based materials, Pb 1-x Sn x Te compounds, bismuth / antimony-based materials, zinc / antimony-based materials (specifically, for example, Zn 4 Sb 3 ), cobalt / (Specifically, for example, CoSb 3) antimony-based material, an iron-cobalt-antimony-based material, silver-antimony-tellurium based material (specifically, for, for
  • the shape of the inorganic material is not particularly limited, but is preferably granular in view of excellent handleability.
  • the size thereof is not particularly limited, but the particle diameter (average particle diameter) of the granular inorganic material is preferably 1 to 10,000 nm from the viewpoint of superior handling properties. It is more preferable.
  • the said particle size measures the particle size (diameter) of at least 20 granular inorganic material using an electron microscope (for example, scanning electron microscope), and arithmetically averages them.
  • the content of the inorganic material in the precursor layer is not particularly limited, but is preferably 50 to 95% by mass, and preferably 70 to 90% by mass with respect to the total mass of the precursor layer in terms of more excellent thermoelectric conversion performance of the thermoelectric conversion layer. Is more preferable.
  • an inorganic material may use only 1 type or may use 2 or more types.
  • the precursor layer may contain other materials other than the organic material and the inorganic material capable of thermoelectric conversion.
  • the precursor layer preferably contains a photothermal conversion material.
  • the photothermal conversion material By including the photothermal conversion material, the efficiency of photobaking is further improved, voids are more efficiently formed, and as a result, a thermoelectric conversion layer having better thermoelectric conversion performance can be obtained.
  • the photothermal conversion material converts light energy into heat energy.
  • a known material can be used as the photothermal conversion material, and it is not particularly limited as long as it can convert light into heat efficiently.
  • carbon black carbon
  • carbon graphite pigment
  • pigment phthalocyanine pigment
  • iron examples thereof include powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, chromium sulfide, and an infrared absorbing dye.
  • infrared absorbing dyes include anthraquinone dyes, dithiol nickel complex dyes, cyanine dyes, azocobalt complex dyes, diimmonium dyes, squarylium dyes, phthalocyanine dyes, and naphthalocyanine dyes.
  • the content of the thermoelectric conversion material is not particularly limited, but is 0.1% with respect to 100 parts by mass of the inorganic material in terms of more excellent thermoelectric conversion performance of the thermoelectric conversion layer. -40 parts by mass is preferable, and 1-20 parts by mass is more preferable.
  • the precursor layer may contain an antioxidant, a light-resistant stabilizer, a heat-resistant stabilizer, a plasticizer, or a dopant in addition to the photothermal conversion material.
  • the procedure is not particularly limited as long as a precursor layer containing an organic material and an inorganic material can be formed.
  • a precursor layer-forming composition containing an organic material and an inorganic material is applied onto a substrate, and a drying treatment is performed as necessary.
  • a method for forming the body layer is preferred.
  • the coating method will be described in detail.
  • the precursor layer forming composition used in the coating method includes the organic material and the inorganic material described above.
  • the composition for forming a precursor layer may contain other components (for example, the photothermal conversion material), and from the viewpoint of handleability of the composition, a solvent is included. May be.
  • the solvent should just be able to disperse
  • organic solvents for example, alcohols; halogen solvents such as chloroform; aprotic polar solvents such as dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO); chlorobenzene, dichlorobenzene Aromatic solvents such as benzene, toluene, xylene, mesitylene, tetralin, tetramethylbenzene and pyridine; ketone solvents such as cyclohexanone, acetone and methylethylkenton; diethyl ether, tetrahydrofuran (THF), t-butyl methyl ether, And ether solvents such as dimethoxyethane and diglyme.
  • halogen solvents such as chloroform
  • aprotic polar solvents such as dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO)
  • the composition for forming a precursor layer can be prepared by mixing each component described above. There is no restriction
  • an organic material and an inorganic material may be prepared by stirring, shaking, or kneading in a solvent and dissolving or dispersing them. Sonication may be performed to promote dissolution and dispersion.
  • the type of the substrate that supports the precursor layer is not particularly limited, and examples thereof include glass, transparent ceramics, metal, and plastic film. Among these, organic substrates are preferable from the viewpoint of cost and flexibility, and plastic film. Is more preferable.
  • Specific examples of the plastic film include polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-phthalenedicarboxylate, and bisphenol A.
  • Polyester films such as polyester films with iso and terephthalic acid; polycycloolefin films such as ZEONOR film (manufactured by Nippon Zeon), ARTON film (manufactured by JSR), Sumilite FS1700 (manufactured by Sumitomo Bakelite); Kapton (Toray DuPont) Polyimide film such as Apical (manufactured by Kaneka), Ubilex (manufactured by Ube Industries), Pomilan (manufactured by Arakawa Chemical); Pure Ace (manufactured by Teijin Chemicals), Polyether ether ketone film, such as (manufactured by Sumitomo Bakelite) SUMILITE FS1100;; Rumekku polycarbonate film (such as manufactured by Kaneka Corporation) TORELINA (manufactured by Toray Industries, Inc.) and the like polyphenyl sulfide film such.
  • ZEONOR film manufactured by Nippon Zeon
  • polyethylene terephthalate polyethylene naphthalate
  • stacked 2 types of materials may be sufficient as a base material,
  • positioned the electrode previously on the resin base material can also be used as a base material.
  • the coating method (film forming method) of the precursor layer forming composition is not particularly limited.
  • Known coating methods such as a coating method, a curtain coating method, a spray coating method, a dip coating method, and an ink jet method can be used.
  • a drying process is performed as needed.
  • the solvent can be volatilized and dried by blowing hot air.
  • the average thickness of the precursor layer is not particularly limited, and an optimum thickness is selected according to the use of the thermoelectric conversion layer, but is usually 0.5 to 1000 ⁇ m in many cases.
  • the average thickness of a precursor layer measures the thickness of the precursor layer in arbitrary 10 points
  • the precursor layer includes an embodiment in which the photothermal conversion material is unevenly distributed on the side of the precursor layer irradiated with light. More specifically, the precursor layer includes a first precursor layer containing at least an organic material and a thermoelectrically convertible inorganic material, and a photothermal conversion material disposed on the first precursor layer. A laminated precursor layer having two precursor layers is preferable. In this embodiment, when the second precursor layer is irradiated with light, decomposition and volatilization of the organic material proceeds more efficiently during the step B, and as a result, a thermoelectric conversion layer that is superior in thermoelectric conversion performance is formed.
  • the first precursor layer includes the organic material and the inorganic material capable of thermoelectric conversion described above.
  • the content of the organic material in the first precursor layer is preferably 5 to 60 parts by mass and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the thermoelectrically convertible inorganic material as described above.
  • other components for example, photothermal conversion material
  • the 1st precursor layer since the light with which the 2nd precursor layer mentioned later is irradiated absorbs and converts into heat energy, the 1st precursor layer does not need to contain the photothermal conversion material substantially.
  • content of a photothermal conversion material is 0.5 mass% or less with respect to the 1st precursor layer total mass that it is not contained substantially.
  • the second precursor layer contains at least the photothermal conversion material described above.
  • a photothermal conversion material is contained as a main component. More specifically, the content of the photothermal conversion material in the second precursor layer is 50 to 95% by mass with respect to the total mass of the second precursor layer because the thermoelectric conversion performance of the thermoelectric conversion layer is more excellent. 60 to 90% by mass is more preferable.
  • Components other than the photothermal conversion material may be included in the second precursor layer, for example, the organic material may be included, and a thermoplastic resin is preferably included.
  • thermoelectric conversion layer When an organic material (preferably a thermoplastic resin) is contained in the second precursor layer, its content is 5 with respect to 100 parts by mass of the photothermal conversion material from the viewpoint that the thermoelectric conversion performance of the thermoelectric conversion layer is more excellent. -50 parts by mass is preferable, and 10-40 parts by mass is more preferable.
  • the ratio of the thickness of the first precursor layer to the thickness of the second precursor layer is not particularly limited, but the thermoelectric conversion performance of the thermoelectric conversion layer is more excellent. From the viewpoint, 2 to 50 is preferable, and 5 to 30 is more preferable.
  • the method for producing the laminated precursor layer is not particularly limited, and a first precursor layer forming composition containing an organic material and a thermoelectrically convertible inorganic material is applied onto a substrate and dried as necessary.
  • the first precursor layer is formed by performing the treatment, and then the second precursor layer-forming composition containing the photothermal conversion material is applied onto the first precursor layer, and if necessary, a drying treatment is performed.
  • a method of forming a second precursor layer application method
  • a method of laminating a separately prepared second precursor layer on a separately prepared first precursor layer and the like.
  • a coating method is preferable because the thickness of each layer can be easily controlled.
  • the solvent mentioned above may be contained in the composition for 1st precursor layer formation, and the composition for 2nd precursor layer formation.
  • Step B is a step of forming a thermoelectric conversion layer having voids by subjecting the precursor layer to a light baking treatment for irradiating light.
  • a light baking treatment for irradiating light.
  • the type of light source used for the light baking treatment is not particularly limited, and examples thereof include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, and a carbon arc lamp.
  • Examples of radiation include electron beams, X-rays, ion beams, and far infrared rays.
  • g-line, i-line, deep-UV light, and high-density energy beam are used.
  • Specific examples of preferred embodiments include scanning exposure with an infrared laser, high-illuminance flash exposure such as a xenon discharge lamp, and infrared lamp exposure, and particularly high-illuminance flash exposure of a xenon discharge lamp from the viewpoint of emission wavelength. preferable.
  • a pulsed light irradiation process for example, a pulsed light irradiation process using a flash lamp
  • Irradiation with high-energy pulsed light can concentrate and heat the irradiated portion in a very short time, and therefore the influence of heat on the base material supporting the precursor layer can be extremely reduced.
  • the irradiation energy of the pulse light is preferably 1 ⁇ 100J / cm 2, more preferably 1 ⁇ 30J / cm 2, preferably from 1 ⁇ sec ⁇ 100 m sec as a pulse width, and more preferably 10 ⁇ sec ⁇ 10 m sec.
  • the irradiation time of the pulsed light is preferably 1 to 100 milliseconds, more preferably 1 to 50 milliseconds, and further preferably 1 to 20 milliseconds.
  • the atmosphere for performing the pulsed light irradiation treatment is not particularly limited, and examples thereof include an air atmosphere, an inert atmosphere, and a reducing atmosphere.
  • the inert atmosphere is, for example, an atmosphere filled with an inert gas such as argon, helium, neon, or nitrogen
  • the reducing atmosphere is a reduction of hydrogen, carbon monoxide, formic acid, alcohol, or the like. It refers to the atmosphere in which sex gas exists.
  • thermoelectric conversion layer having voids can be formed.
  • the average thickness of the thermoelectric conversion layer is preferably 0.1 to 1000 ⁇ m and more preferably 1 to 100 ⁇ m from the viewpoint of imparting a temperature difference.
  • the average thickness of a thermoelectric conversion layer measures the thickness of the thermoelectric conversion layer in arbitrary 10 points
  • voids voids
  • the ratio of voids (void ratio) in the thermoelectric conversion layer is not particularly limited, but is preferably 20% or more, more preferably 30% or more, from the viewpoint that the thermoelectric conversion performance of the thermoelectric conversion layer is more excellent. Although an upper limit in particular is not restrict
  • the cross section of the thermoelectric conversion layer is measured with an electron microscope (for example, a scanning electron microscope), and the void area ratio in at least three observation regions (10 ⁇ m ⁇ 10 ⁇ m) ( %) [(Total area of voids / area of observation area) ⁇ 100] and the arithmetic average of them.
  • thermoelectric conversion element of this invention is equipped with the thermoelectric conversion layer obtained from the manufacturing method mentioned above.
  • a preferred embodiment of the thermoelectric conversion element is an element having a base material, the thermoelectric conversion layer provided on the base material, and an electrode for electrically connecting them, and more preferably provided on the base material.
  • the device has a pair of electrodes and the thermoelectric conversion layer between the electrodes.
  • the thermoelectric conversion layer may be one layer or two or more layers. Preferably, there are two or more layers.
  • thermoelectric conversion element 10 shown in FIG. 1 is an element having a first base material 11, a first electrode 12, a thermoelectric conversion layer 14, a second electrode 13, and a second base material 15 in this order. It is.
  • the thermoelectric conversion element 10 shown in FIG. 1 is an aspect which obtains an electromotive force (voltage) using the temperature difference of the direction shown by the arrow.
  • thermoelectric conversion element 20 shown in FIG. 2 is an aspect which obtains an electromotive force (voltage) using the temperature difference of the direction shown by the arrow.
  • thermoelectric conversion layer 34 is disposed between the first electrode 32 and the second electrode 33.
  • thermoelectric power generation article of the present invention is a thermoelectric power generation article using the thermoelectric conversion element of the present invention.
  • generators such as a hot spring thermal generator, a solar thermal generator, a waste heat generator, a power supply for wristwatches, a semiconductor drive power supply, a power supply for small sensors, etc. are mentioned. That is, the thermoelectric conversion element of the present invention described above can be suitably used for these applications.
  • Example 1 A sputter target made of Zn 4 Sb 3 was prepared, and coarse particles were produced using a mortar. Thereafter, a solution consisting of the coarse particles (5 g), polyethylene oxide (1 g), and Isopar C (20 g) was prepared and subjected to bead mill dispersion. As a result, a dispersion 1 of Zn 4 Sb 3 particles having a particle size of about 400 nm was obtained. Next, 0.3 g of carbon was added to the obtained dispersion 1, and beads 1 were dispersed to prepare solution 1. A Teflon frame was pasted on the polyimide substrate, the solution 1 was poured into the frame, and dried on a hot plate at 110 ° C. for 1 hour to form a precursor layer.
  • the obtained precursor layer is subjected to light firing using flash lamp exposure (Xenon's photosintering apparatus Sinteron 2000, irradiation energy: 5 J / cm 2 , pulse width: 2 msec), and voids
  • flash lamp exposure Xenon's photosintering apparatus Sinteron 2000, irradiation energy: 5 J / cm 2 , pulse width: 2 msec
  • voids A Zn 4 Sb 3 layer (thermoelectric conversion layer, average thickness: 1.1 ⁇ m) was obtained.
  • Example 2 Dispersion 1 produced in Example 1 was applied onto a Teflon framed polyimide substrate to produce a first precursor layer.
  • a dispersion composed of carbon (1 g), polyethylene oxide (0.3 g), and Isopar C (1 g) is applied onto the first precursor layer, and a second precursor layer (hereinafter referred to as “first precursor layer”) is applied to the first precursor layer.
  • first precursor layer also referred to as a photothermal conversion layer.
  • the obtained laminated precursor layer (first precursor layer and second precursor layer) is subjected to photo-baking in the same procedure as in Example 1, and a Zn 4 Sb 3 layer having voids. (Thermoelectric conversion layer, average thickness: 1.3 ⁇ m) was obtained.
  • Example 3 Instead of polyethylene oxide (1 g), except for using the polyvinyl pyrrolidone (1 g) according to the same procedure as in Example 1, Zn 4 Sb 3 layer having a void (thermoelectric conversion layer, the average thickness: 0.9 .mu.m) Got.
  • Example 4 A Zn 4 Sb 3 layer having a void (thermoelectric conversion layer, average thickness: 1.3 ⁇ m) was obtained according to the same procedure as in Example 2 except that polyvinyl alcohol was used instead of polyethylene oxide.
  • Example 5 Instead the coarse particles of Zn 4 Sb 3, PdTe except for using the coarse particles (Aldrich) according to the same procedure as in Example 1, PDTE layer having a void (thermoelectric conversion layer, the average thickness: 1. 2 ⁇ m) was obtained.
  • Example 6 A Bi 2 Se 3 layer (a thermoelectric conversion layer, a void) was formed in the same manner as in Example 2 except that Bi 2 Se 3 (Aldrich) coarse particles were used instead of Zn 4 Sb 3 coarse particles. Average thickness: 1.0 ⁇ m) was obtained.
  • Example 7 An Ag 2 Te layer having a void (thermoelectric conversion layer, average thickness) according to the same procedure as in Example 1 except that Ag 2 Te (Aldrich) coarse particles were used instead of the Zn 4 Sb 3 coarse particles. Obtained: 1.3 ⁇ m).
  • Example 8 A Zn 4 Sb 3 layer having a void (thermoelectric conversion layer, average thickness: 0.9 ⁇ m) was obtained according to the same procedure as in Example 1 except that a glass substrate was used instead of the polyimide substrate.
  • thermoelectric conversion material A target made of Zn 4 Sb 3 (purity 4N) was prepared as a thermoelectric conversion material, and film formation was performed using a magnetron sputtering apparatus while maintaining the temperature of the polyimide substrate at 150 ° C. At this time, the film thickness of the thermoelectric conversion layer (Zn 4 Sb 3 layer) was 200 nm. Further, using an electric furnace substituted with argon gas, annealing treatment was performed at 350 ° C. for 2 hours to produce a thermoelectric conversion layer (average thickness: 0.2 ⁇ m) with few voids.
  • thermoelectric conversion layer (average thickness: 0.65 ⁇ m).
  • thermoelectric conversion layers obtained in the respective Examples and Comparative Examples were cut, and the cross sections thereof were observed with a scanning electron microscope to obtain the void ratio, and evaluated according to the following criteria.
  • the results are summarized in Table 1.
  • the cross section of the thermoelectric conversion layer was measured with a scanning electron microscope, and the void area ratio (%) [% of voids in at least three observation regions (10 ⁇ m ⁇ 10 ⁇ m). Total area / observation area area) ⁇ 100], and arithmetically averaged them.
  • C Void ratio is less than 20%
  • thermoelectric conversion performance measuring device MODEL RZ2001i product name, manufactured by Ozawa Science Co., Ltd.
  • Measurement of figure of merit ZT Using a thermoelectric conversion performance measuring device MODEL RZ2001i (product name, manufactured by Ozawa Science Co., Ltd.), measurement was performed in an air atmosphere at a temperature of 100 ° C., and the thermoelectromotive force (Seebeck) of the thermoelectric conversion layer produced in each example and comparative example Coefficient: ⁇ V / k) was measured.
  • thermoelectric conversion layer produced in each example and comparative example was determined by using “low resistivity meter: Loresta GP” (device name, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and surface resistivity (unit: ⁇ / ⁇ ) was measured, and the electrical conductivity (S / cm) was calculated from the following formula using the average thickness (unit: cm) of the thermoelectric conversion layer.
  • Conductivity 1 / ((Surface resistivity) ⁇ (Average thickness))
  • the thermal conductivity (unit: W / mK) of the thermoelectric conversion layer produced in each example and comparative example was measured using a thermal conductivity measuring device (manufactured by ULVAC-RIKO, Inc .: TCN-2 ⁇ ).
  • thermoelectromotive force S conductivity ⁇
  • thermal conductivity ⁇ a ZT value at 100 ° C. was calculated according to the following formula (A), and this value was defined as a thermoelectric conversion performance value.
  • “PEO” represents polyethylene oxide
  • “PVP” represents polyvinylpyrrolidone
  • “PVA” represents polyvinyl alcohol.
  • “Substrate” column indicates the type of base material used
  • “PI substrate” intends a polyimide substrate.
  • the “baking method” column indicates the type of baking treatment, and indicates “light” in the case of light baking, and “heat” in the case of heat baking.
  • thermoelectric conversion layer obtained from the production method of the present invention was excellent in thermoelectric conversion performance.
  • thermoelectric conversion performance was more excellent when the photothermal conversion layer was used.
  • Comparative Examples 1 and 2 where the heat-firing treatment was performed the thermoelectric conversion efficiency of the thermoelectric conversion layer was inferior compared to Example 1.
  • thermoelectric conversion layer was produced on the glass substrate on which the gold electrode was formed, according to the same procedure as in Example 1.
  • a counter electrode was formed on the obtained thermoelectric conversion layer using a conductive paste (Dotite manufactured by Fujikura Kasei) to produce a thermoelectric conversion element.
  • the manufactured thermoelectric conversion element also shows excellent thermoelectric conversion performance.

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WO2018056368A1 (ja) * 2016-09-21 2018-03-29 日産化学工業株式会社 熱電変換層形成用組成物及び熱電変換層の製造方法
WO2018159696A1 (ja) * 2017-03-03 2018-09-07 浩明 中弥 光熱変換基板を備えた熱電変換モジュール
KR102121436B1 (ko) * 2017-06-27 2020-06-10 주식회사 엘지화학 칼코겐 화합물, 이의 제조 방법, 및 이를 포함하는 열전소자
WO2019004613A1 (ko) * 2017-06-30 2019-01-03 주식회사 엘지화학 칼코겐 화합물, 이의 제조 방법, 및 이를 포함하는 열전소자
KR102138937B1 (ko) 2017-09-29 2020-07-28 주식회사 엘지화학 칼코겐 화합물, 이의 제조 방법, 및 이를 포함하는 열전소자
WO2019066580A2 (ko) * 2017-09-29 2019-04-04 주식회사 엘지화학 칼코겐 화합물, 이의 제조 방법, 및 이를 포함하는 열전소자
WO2019181960A1 (ja) * 2018-03-20 2019-09-26 日産化学株式会社 熱電変換層形成用組成物及び熱電変換層の製造方法
CN108807654B (zh) * 2018-06-15 2020-08-14 同济大学 高性能低成本MnGeTe2基热电材料及其制备
CN109755377A (zh) * 2018-12-17 2019-05-14 新奥科技发展有限公司 一种方钴矿基热电材料及其制备方法
CN110061121A (zh) * 2019-03-27 2019-07-26 同济大学 一种聚乙烯吡咯烷酮/银/碲化银三元柔性复合热电薄膜的制备方法

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