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WO2014007225A1 - Procédé de production d'un matériau de conversion thermoélectrique - Google Patents

Procédé de production d'un matériau de conversion thermoélectrique Download PDF

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Publication number
WO2014007225A1
WO2014007225A1 PCT/JP2013/068071 JP2013068071W WO2014007225A1 WO 2014007225 A1 WO2014007225 A1 WO 2014007225A1 JP 2013068071 W JP2013068071 W JP 2013068071W WO 2014007225 A1 WO2014007225 A1 WO 2014007225A1
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Prior art keywords
thermoelectric
thermoelectric conversion
conversion material
semiconductor material
porous substrate
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English (en)
Japanese (ja)
Inventor
邦久 加藤
康次 宮崎
豪志 武藤
近藤　健
公市 永元
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Kyushu Institute of Technology NUC
Lintec Corp
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Kyushu Institute of Technology NUC
Lintec Corp
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Priority to JP2014523741A priority Critical patent/JP6167104B2/ja
Publication of WO2014007225A1 publication Critical patent/WO2014007225A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0623—Sulfides, selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions

Definitions

  • the present invention relates to a method for manufacturing a thermoelectric conversion material that performs mutual energy conversion between heat and electricity, and in particular, a thermoelectric film having a thermoelectric thin film in which the composition ratio of a thermoelectric semiconductor material of a deposition source is accurately reflected by an arc plasma deposition method.
  • the present invention relates to a method for producing a thermoelectric conversion material having a high figure of merit.
  • thermoelectric power generation technology that has a simple system and can be reduced in size has attracted attention as a recovery power generation technology for unused waste heat energy generated from fossil fuel resources used in buildings, factories, and the like.
  • thermoelectric power generation generally has poor power generation efficiency, and various companies and research institutions are actively researching and developing power generation efficiency.
  • S the Seebeck coefficient
  • ⁇ the electrical conductivity
  • ⁇ the thermal conductivity.
  • thermoelectric conversion materials for example, in Patent Document 1 and Patent Document 2, physical vapor deposition such as sputtering using a thermoelectric semiconductor material containing two or more elements as a raw material on a substrate such as resin or ceramic. Discloses a p-type thermoelectric thin film and an n-type thermoelectric thin film formed thereon.
  • thermoelectric conversion material to be formed when the thickness of the thermoelectric conversion material to be formed is a nano-order thin film, the composition ratio of raw materials used in sputtering or the like is the composition ratio of the thin film after film formation.
  • thermoelectric conversion efficiency is lowered, and the film is easily peeled off at the interface between the substrate and the thin film.
  • further improvement of the thermoelectric conversion efficiency (as a guide, the dimensionless thermoelectric figure of merit ZT is 1 or more; T is usually 300 K in absolute temperature) has been demanded for practical use.
  • the present invention has been made in view of the above circumstances, and forms a thermoelectric thin film in which the composition ratio of a thermoelectric semiconductor material as a raw material is accurately reflected on a porous substrate, and the porous substrate and the thin film are formed. It is an object of the present invention to provide a method for producing a thermoelectric conversion material that is excellent in adhesiveness and thermoelectric conversion efficiency.
  • thermoelectric conversion material made of a porous structure as a substrate constituting the thermoelectric conversion material, and on the substrate, two types are used.
  • the composition ratio of the deposition source was accurately reflected by forming a thin film of the thermoelectric semiconductor material by arc plasma deposition. It has been found that a thermoelectric conversion material with high thermoelectric conversion efficiency can be obtained by forming a thermoelectric thin film on a substrate and performing a heat treatment during and / or after the film forming step, thereby completing the present invention.
  • the present invention provides the following (1) to (10).
  • (1) In a method for manufacturing a thermoelectric conversion material in which a thin film of a thermoelectric semiconductor material containing two or more elements is formed on a porous substrate, the thermoelectric semiconductor material is converted into the porous material by using an arc plasma deposition method.
  • a method for producing a thermoelectric conversion material comprising a step of forming a film on a substrate and a step of performing a heat treatment during and / or after the film forming step.
  • (2) The method for producing a thermoelectric conversion material according to (1), wherein the heat treatment is performed under an atmospheric pressure of an inert gas or under vacuum conditions.
  • thermoelectric conversion material (1) or (2), wherein the porous substrate is formed by self-organization of a block copolymer.
  • thermoelectric semiconductor material any one of (1) to (3), wherein the thermoelectric semiconductor material is any one selected from a bismuth-tellurium-based thermoelectric semiconductor material, a silicide-based thermoelectric semiconductor material, and a Heusler-based thermoelectric semiconductor material. Manufacturing method of thermoelectric conversion material.
  • block copolymer is a block copolymer composed of a hydrophilic unit and a hydrophobic unit.
  • the hydrophilic unit includes at least one selected from methacrylate, butadiene, vinyl acetate, acrylate, acrylamide, acrylonitrile, and acrylic acid
  • the hydrophobic unit includes styrene, xylylene, ethylene, and helical oligomeric silyl.
  • thermoelectric conversion material the bismuth - telluride thermoelectric semiconductor material, p-type bismuth telluride (Bi X Te 3 Sb 2- X (0 ⁇ X ⁇ 0.6)), n -type bismuth telluride (Bi 2 Te 3-Y Se Y (0 ⁇ Y ⁇ 3)), the method for producing a thermoelectric conversion material according to (4) above, comprising at least one selected from Bi 2 Te 3 .
  • the silicide-based thermoelectric semiconductor material contains at least one selected from ⁇ -FeSi 2 , CrSi 2 , MnSi 1.73 , and Mg 2 Si.
  • thermoelectric conversion material (9) The method for producing a thermoelectric conversion material according to (4), wherein the Heusler-based thermoelectric semiconductor material includes at least one selected from Fe 2 VAl, FeVAlSi, and FeVTiAl. (10) The method for producing a thermoelectric conversion material according to any one of (1) to (9), wherein the thin film of the thermoelectric semiconductor material is formed on the porous substrate with a film thickness of 10 nm to 10 ⁇ m.
  • thermoelectric thin film the composition of the thin film of semiconductor material (hereinafter sometimes simply referred to as “thermoelectric thin film”) and the composition of the raw material hardly change, and the ionized vapor-deposited particles are formed at a high output.
  • thermoelectric thin film the composition of the thin film of semiconductor material
  • the ionized vapor-deposited particles are formed at a high output.
  • thermoelectric semiconductor materials can be deposited efficiently and accurately, and heat loss due to heat conduction of the substrate occurs by using a porous substrate. Therefore, it is possible to provide a method for easily and inexpensively manufacturing a thin-film thermoelectric conversion material having improved thermoelectric characteristics and excellent thermoelectric conversion efficiency by crystal growth of the thermoelectric thin film by heat treatment.
  • FIG. 2 shows an example of a thermoelectric conversion material manufactured according to the manufacturing method of the present invention, and is a cross-sectional view of a thermoelectric conversion material having a thermoelectric thin film formed on the porous substrate of FIG. 1 by an arc plasma deposition method.
  • An example of the coaxial type vacuum arc plasma deposition apparatus used in the embodiment of the present invention is shown, (a) is a schematic view of the deposition apparatus, (b) is a conceptual diagram for explaining the operation of the arc plasma deposition source. is there. It is the schematic which shows an example of the heat processing apparatus used by the Example and comparative example of this invention.
  • the method for producing a thermoelectric conversion material of the present invention is a method for producing a thermoelectric conversion material in which a thin film of a thermoelectric semiconductor material containing two or more elements is formed on a porous substrate, using an arc plasma deposition method, The method includes a step of forming the thermoelectric semiconductor material on the porous substrate and a step of performing a heat treatment during and / or after the film formation step.
  • the thermoelectric conversion material refers to a material obtained by forming a thermoelectric semiconductor material as a raw material on a porous substrate.
  • the porous substrate used in the present invention has very fine pores, and the fine pores are arranged independently of each other at a predetermined shape and interval (hereinafter referred to as “nanostructure”). And the nanostructure is formed, the thermal conductivity of the thermoelectric conversion material can be reduced.
  • the material of the porous substrate used in the present invention is not particularly limited, and examples thereof include ceramic substrates such as alumina oxide, silica, and zirconia, glass substrates, silicon substrates, and resin substrates. Among these, a resin substrate is preferable from the viewpoint of flexibility and low thermal conductivity.
  • the resin substrate is not particularly limited.
  • a thermosetting resin such as polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyethylene terephthalate, and polyethylene.
  • a polyolefin such as polyimide, polyamide, polyamideimide, polyphenylene ether, polyetherketone, polyetheretherketone, polyethylene terephthalate, and polyethylene.
  • Polystyrene polyester, polycarbonate, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic polymer, and other thermoplastic resins, and from hydrophilic and hydrophobic units
  • the block copolymer etc. which are comprised are mentioned.
  • hydrophilic unit of the block copolymer examples include methacrylate, butadiene, vinyl acetate, acrylate, acrylamide, acrylonitrile, acrylic acid and the like, and examples of the hydrophobic unit include styrene, xylylene, ethylene, and helical oligomeric silsesquioxane. Examples thereof include polymethacrylate containing.
  • the porous substrate may be produced by a known method. For example, there are a method for forming a porous layer by etching or the like on a substrate having no pores, a method for forming a porous layer by anodizing such as an aluminum substrate, and a method for forming a porous layer by imprinting. Can be mentioned. In particular, when a resin substrate is used as the porous substrate, a method of forming a porous layer by a method using self-organization of the block copolymer can be mentioned.
  • the block copolymer porous substrate comprises a step of forming a block copolymer layer, a phase separation step in which the block copolymer layer is annealed in a solvent atmosphere to perform microphase separation, and a part of the hydrophilic unit phase of the block copolymer layer subjected to microphase separation. Or it can form by passing through the etching process which removes all and forms nanostructure.
  • the combination of hydrophilic units and hydrophobic units and the molecular weight of each unit, the solvent and annealing conditions in the phase separation step, and the etching method and etching conditions in the etching step are appropriately selected or adjusted.
  • a porous substrate having a desired nanostructure can be formed.
  • FIG. 1 is a cross-sectional view showing an example of a porous substrate used in the present invention.
  • 1 is a support
  • 2 is a porous substrate
  • 3 is a nanostructure.
  • the porous substrate 2 is formed by utilizing the self-organization of the block copolymer
  • 4 is a hydrophobic unit phase
  • 5 is a hydrophilic unit phase.
  • the porous substrate 2 does not have self-supporting properties, it may be laminated on the support 1 as shown in FIG.
  • the support 1 may be omitted.
  • the support 1 used in the present invention is not particularly limited as long as it does not adversely affect the electrical conductivity and thermal conductivity, and examples thereof include glass, silicon, and a plastic substrate.
  • the average pore diameter of the pores of the nanostructure 3 of the porous substrate 2 is preferably 5 to 1000 nm, more preferably 10 to 300 nm, and still more preferably 30 to 150 nm.
  • the average pore diameter is 5 nm or more, for example, after the thermoelectric semiconductor material described later is deposited on the porous substrate, the thermoelectric semiconductor material does not block the pores, and the average pore diameter is 1000 nm or less. It is preferable because the mechanical strength of the conversion material can be secured and the thermal conductivity is sufficiently lowered.
  • the average hole diameter is determined by reading the maximum and minimum diameters of the individual holes present in the field of view from the SEM photograph at a measurement magnification of 30,000 times. And then simple averaging over the total number measured.
  • the depth of the hole is preferably 5 to 1000 nm, more preferably 10 to 300 nm.
  • the average interval between the holes (the average value of the center-to-center distance between adjacent holes) is preferably 10 to 1500 nm, more preferably 10 to 300 nm, and further preferably 10 to 150 nm. .
  • the average interval is 10 nm or more, it becomes longer than the mean free path of electrons, and it becomes difficult to become an electron scattering factor.
  • the average interval is 1500 nm or less, it becomes shorter than the mean free path of phonons and becomes a phonon scattering factor, which is preferable because the thermal conductivity is reduced.
  • the shape of the hole of the nanostructure 3 is not particularly limited, and is, for example, a columnar shape such as a columnar shape or a prismatic shape; an inverted conical shape such as an inverted cone or an inverted pyramid; an inverted frustum shape such as an inverted pyramid or an inverted truncated cone; Groove shape etc. are mentioned and these combinations may be sufficient.
  • Occupation ratio of the nanostructure 3 in the porous substrate 2 (the opening area of the holes of the nanostructure 3 relative to the sum of the area of the openings of the holes of the nanostructure 3 on the porous substrate 2 and the area other than the openings of the holes) Is generally from 5 to 90%, preferably from 10 to 50%.
  • the thickness of the porous substrate 2 is preferably 0.1 to 500 ⁇ m, more preferably 0.1 to 100 ⁇ m. A thickness within the above range is preferable because the thermal conductivity of the substrate is low, heat loss can be suppressed, and handling is easy.
  • thermoelectric semiconductor material contains two or more elements having thermoelectric performance.
  • thermoelectric semiconductor material specifically, p-type bismuth telluride (Bi X Te 3 Sb 2- X (0 ⁇ X ⁇ 0.6)), n -type bismuth telluride (Bi 2 Te 3-Y Se Y (0 ⁇ Y ⁇ 3)), Bi 2 Te 3 and other bismuth-tellurium-based thermoelectric semiconductor materials; GeTe, PbTe and other telluride-based thermoelectric semiconductor materials; Antimony-tellurium-based thermoelectric semiconductor materials; ZnSb, Zn 3 Sb 2 , Zinc-antimony-based thermoelectric semiconductor materials such as Zn 4 Sb 3 ; Silicon-germanium-based thermoelectric semiconductor materials such as SiGe; Bismuth selenide-based thermoelectric semiconductor materials such as Bi 2 Se 3 ; ⁇ -FeSi 2 , CrSi 2 , MnSi 1.73 , silicide-based thermoelectric semiconductor
  • FIG. 2 shows an example of a thermoelectric conversion material manufactured according to the manufacturing method of the present invention, and is a cross-sectional view of a thermoelectric conversion material having a thin film (hereinafter referred to as a thermoelectric thin film) formed on the porous substrate of FIG. 1 by an arc plasma deposition method. It is.
  • 6 is a thermoelectric thin film formed on the top of the nanostructure 3 of the porous substrate 2
  • 7 is a thermoelectric thin film formed on the inner bottom of the nanostructure 3 of the porous substrate 2.
  • thermoelectric semiconductor material film forming process forms a thin film of thermoelectric semiconductor material by depositing a thermoelectric semiconductor material containing two or more elements on the porous substrate described above by arc plasma deposition. It is a process to do.
  • the arc plasma vapor deposition method which will be described in detail later, is a film formation method in which ionized vapor deposition particles are deposited on a substrate by using a pulsed arc discharge as a raw material, which is a vapor deposition source, instantaneously converted into plasma.
  • a pulsed arc discharge as a raw material
  • the thermoelectric semiconductor material is instantaneously converted into plasma, and the ionized deposition particles adhere to the porous substrate, and the raw material scatters and the residual non-evaporated material is small.
  • the composition of the deposited film is more accurate, and a uniform thin film that hardly changes from the composition of the raw material is formed, suppressing the decrease in Seebeck coefficient and electrical conductivity.
  • the arc plasma deposition method is suitable as a method for forming a film on a resin substrate or film because it does not require the use of argon gas or the like to generate plasma and the temperature of the substrate hardly increases. Furthermore, in the arc plasma vapor deposition method, the straightness of the material during vapor deposition is maintained within a predetermined range. Therefore, in particular, when a film is formed on a porous substrate, the inner structure of the nanostructure is smaller than other vapor deposition methods. The material is difficult to deposit on the wall surface, and the thermoelectric performance is unlikely to deteriorate.
  • FIG. 3 is an example of a coaxial vacuum arc plasma deposition apparatus used in the embodiment of the present invention, (a) is a schematic view of the deposition apparatus, and (b) is for explaining the operation of the arc plasma deposition source.
  • FIG. 3 (a) and 3 (b) 11 is a porous substrate, 12 is a vacuum exhaust port, 13 is a cathode electrode (evaporation source; target), 14 is a trigger electrode, 15 is a power supply unit, 16 is an anode electrode, 17 Is a trigger power source, 18 is an arc power source, 19 is a capacitor, 20 is an insulator, and 21 is an arc plasma.
  • 11 is a porous substrate
  • 12 is a vacuum exhaust port
  • 13 is a cathode electrode (evaporation source; target)
  • 14 is a trigger electrode
  • 15 is a power supply unit
  • 16 is an anode electrode
  • 18 is an arc power source
  • 19 is a capacitor
  • the coaxial vacuum arc plasma deposition source in the arc plasma deposition apparatus is a deposition source in which a cylindrical trigger electrode 14 and a tip portion are made of a raw material of a thermoelectric semiconductor material.
  • a cylindrical cathode electrode 13 is arranged adjacent to each other with a disc-shaped insulator 20 interposed therebetween, and a cylindrical anode electrode 16 is coaxially arranged around the cathode electrode 13 and the trigger electrode 14.
  • the cathode electrode 13 is formed by forming the above-described thermoelectric semiconductor material into a cylindrical shape by a known method such as a hot press method.
  • the actual vapor deposition uses a coaxial vacuum arc plasma vapor deposition apparatus equipped with the coaxial vacuum arc plasma vapor deposition source, and generates an arc discharge between the trigger electrode 14 and the anode electrode 16 in a pulsed manner to produce thermoelectric power.
  • the semiconductor material is instantly turned into plasma, and the arc plasma 21 is intermittently induced between the cathode electrode 13 and the anode electrode 16, and ionized deposition is performed on the porous substrate 11 disposed immediately above the arc plasma 21. Film formation is performed by attaching particles.
  • the porous substrate 11 may be at room temperature or heated.
  • the arc voltage for generating the arc plasma 21 is usually 50 to 400 V, preferably 70 to 100 V, and the capacity of the discharging capacitor 19 is usually 360 to 8800 ⁇ F, preferably 360 to 1080 ⁇ F. Further, the number of generations of the arc plasma 21 is usually 50 to 50,000 times. Furthermore, the deposition range can be controlled by appropriately adjusting the distance between the porous substrate 11 and the arc plasma 21.
  • the distance between the cathode electrode (deposition source; target) and the porous substrate was 150 mm.
  • the degree of vacuum in the chamber is preferably 10 ⁇ 2 Pa or less.
  • the temperature of the porous substrate 11 in the chamber may be room temperature as long as heat treatment is performed after the film forming step. When the heat treatment is performed during the film forming step, the temperature of the porous substrate 11 is usually 50 to 1000 ° C. Deposition may be performed by heating at 50 to 600 ° C., more preferably 100 to 250 ° C. By performing the heat treatment described later during the film forming step, the thermoelectric semiconductor material can be deposited on the porous substrate 11 and at the same time, a thin film made of the thermoelectric semiconductor material can be grown and stabilized.
  • Manufacturing time can be shortened. If the temperature is too low, a sufficient heat treatment effect cannot be obtained, and if the temperature is too high, the composition may change due to volatilization of the constituent elements, and if the porous substrate is a plastic substrate, problems such as thermal deformation may occur. Therefore, it is not preferable.
  • the film thickness of the thermoelectric semiconductor material formed by the above-described method is usually 10 nm to 10 ⁇ m, more preferably 10 nm to 1 ⁇ m, more preferably so as not to fill the holes of the porous substrate 11 with the thermoelectric semiconductor material. Preferably, it is 50 to 500 nm. When the film thickness is in the above range, a thin film having excellent thermoelectric performance and flexibility can be obtained.
  • thermoelectric conversion material The heat treatment step is a step of crystal-growing the thermoelectric thin film by performing heat treatment on the thermoelectric thin film constituting the thermoelectric conversion material during and / or after the film formation step in (1). It is a process. By growing and stabilizing the thermoelectric thin film, a thin film of thermoelectric semiconductor material having high thermoelectric characteristics can be obtained.
  • the porous substrate 11 may be vapor-deposited by heating as described above.
  • the heat treatment method is not particularly limited, and a publicly known method is used. Can be used. Further, although heat treatment may be performed both during and after the film formation step, it is preferable to perform the heat treatment after the film formation step because crystal growth of the thermoelectric thin film can be facilitated. Furthermore, it is more preferable to perform the heat treatment only after the film-forming process from the viewpoint that a thermoelectric conversion material having high thermoelectric characteristics can be obtained by forming a film with as little variation in the composition of the thermoelectric semiconductor material.
  • FIG. 4 is a schematic view showing an example of a heat treatment apparatus used in Examples and Comparative Examples of the present invention.
  • 31 is a thermoelectric conversion material
  • 32 is a heater
  • 33 is a thermocouple
  • 34 is a vacuum exhaust port
  • 35 is an introduction gas exhaust port
  • 36 is a hydrogen gas introduction port
  • 37 is an argon gas introduction port.
  • the heat treatment has different processing conditions such as temperature and time depending on the material used and the type of processing apparatus.
  • the temperature does not change in composition, that is, usually 50 to 50. It is preferably performed at 1000 ° C. for about 1 to 2 hours.
  • the temperature is preferably 50 to 600 ° C, more preferably 100 to 250 ° C. If the temperature is too low, a sufficient heat treatment effect cannot be obtained, and if the temperature is too high, the crystal state of the thermoelectric semiconductor material may be lost, or the composition may change due to volatilization of the constituent elements.
  • the heat treatment is preferably performed under an atmospheric pressure atmosphere of an inert gas or under vacuum conditions. Under an inert gas atmosphere, the composition of the thermoelectric semiconductor material does not vary due to oxidation, and a high-performance thin film can be easily produced.
  • thermoelectric thin film having a desired composition can be accurately formed on a substrate composed of a porous structure.
  • thermoelectric conversion materials prepared in Examples and Comparative Examples were performed by the following methods.
  • A Thermal conductivity The 3omega method was used for the measurement of the thermal conductivity of the thermoelectric conversion material produced by the Example and the comparative example.
  • B Electric conductivity The surface resistance value of the sample was measured by a four-terminal method using a surface resistance measuring device (trade name: Loresta GP MCP-T600, manufactured by Mitsubishi Chemical Corporation), and the electric conductivity was calculated.
  • thermocouple Seebeck coefficient
  • the thermoelectromotive force was measured from the electrode adjacent to the thermocouple installation position. Specifically, the distance between both ends of the sample for measuring the temperature difference and the electromotive force is 25 mm, one end is kept at 20 ° C., and the other end is heated from 25 ° C. to 50 ° C. in 1 ° C. increments. The power was measured and the Seebeck coefficient was calculated from the slope.
  • the positions of the thermocouple and the electrode are symmetrical with respect to the center line of the thin film, and the distance between the thermocouple and the electrode is 1 mm.
  • the dimensionless thermoelectric figure of merit is defined as the product of the thermoelectric figure of merit Z calculated above and the absolute temperature T. In the present invention, the dimensionless thermoelectric figure of merit was calculated as a value at room temperature (T: 300K).
  • EDS energy dispersive X-ray analyzer
  • Adhesion test (cross-cut method) The adhesion of the produced thermoelectric thin film is determined by the JIS K5600 cross-cut method, and the evaluation is according to the number of peeled masses, that is, when no peeling is observed at all, the number of peeling is 1% or more and less than 5%. In some cases, ⁇ was given, ⁇ was given when the number of peeled pieces was 5% or more and less than 50%, and x was given when the number of peeled pieces was 50% or more.
  • Example 1 Preparation of porous substrate
  • a block copolymer manufactured by Polymer Source, product name “P9695-MMAPOSSSMA” methyl methacrylate unit composed of a hydrophilic unit (methyl methacrylate) and a hydrophobic unit (polymethacrylate containing a helical oligomeric silsesquioxane)
  • a polymer having a concentration of 3% by mass in cyclopentanone manufactured by Tokyo Chemical Industry Co., Ltd.
  • a solution was prepared.
  • the prepared polymer solution was applied onto a glass substrate (support 1) by a spin coating method to produce a block copolymer layer having a thickness of 200 nm.
  • the produced block copolymer layer was annealed in a carbon sulfide solvent atmosphere for 20 hours, thereby microphase-separating into a poly (methacrylate) phase and a polymethyl methacrylate phase containing a helical oligomeric silsesquioxane. Then, using a reactive ion etching apparatus (Samco, UV-zone dry stripper), the polymethylmethacrylate phase was etched to obtain a porous substrate 2 (average pore diameter: 80 nm, pore depth: 120 nm). .
  • a cylindrical cathode electrode (deposition source; target: ⁇ 10 ⁇ 17 mm) of a thermoelectric semiconductor material to be a coaxial vacuum arc plasma deposition source is obtained by placing in a mold and holding at a sintering temperature of 200 ° C. for 1 hour by hot pressing. It was. Next, when the degree of vacuum in the chamber reaches 5.0 ⁇ 10 ⁇ 3 Pa or less using the coaxial vacuum arc plasma deposition apparatus shown in FIGS.
  • the arc voltage is set to 80V.
  • Discharge was performed 300 times at a film rate of 0.33 nm / discharge (one discharge per second) to form a thin film (100 nm) of p-type bismuth telluride on the porous substrate 2 (11).
  • the porous substrate 2 (11) in the chamber was deposited at room temperature without heating. After that, the obtained thermoelectric conversion material is installed in the center of the heat treatment apparatus shown in FIG. 4, evacuated to 1.0 Pa by a rotary pump, purged with argon gas three times, and then mixed with hydrogen and argon mixed gas.
  • thermoelectric conversion material in which a thermoelectric thin film was grown.
  • thermoelectric conversion material was produced in the same manner as in Example 1 except that p-type bismuth telluride was formed by flash vapor deposition.
  • Table 1 shows the evaluation results of the thermal conductivity, electrical conductivity, Seebeck coefficient, element composition, and adhesion test of the thermoelectric conversion materials obtained in Example 1 and Comparative Example 1.
  • Table 1 shows the results of thermal conductivity, electrical conductivity, Seebeck coefficient, element composition, and adhesion test of the thermoelectric conversion materials obtained in Example 3 and Comparative Example 3.
  • Table 1 shows the results of thermal conductivity, electrical conductivity, Seebeck coefficient, element composition, and adhesion test of the thermoelectric conversion materials obtained in Example 4 and Comparative Example 4.
  • Table 1 shows the thermal conductivity, electrical conductivity, Seebeck coefficient, element composition, and adhesion test results of the thermoelectric conversion materials obtained in Example 5 and Comparative Example 5.
  • Table 1 shows the results of thermal conductivity, electrical conductivity, Seebeck coefficient, element composition and adhesion test of the thermoelectric conversion materials obtained in Example 6 and Comparative Example 6.
  • Example 7 (Preparation of porous substrate) An aluminum substrate (manufactured by Nilaco Corporation, 10 ⁇ 100 ⁇ 0.5 mm, purity 99.9%) is anodized to form a porous alumina substrate (porous substrate, average pore diameter: 80 nm, pore depth: 120 nm). Produced. A thermoelectric conversion material was produced in the same manner as in Example 1 except that the obtained porous substrate was used.
  • thermoelectric conversion material was produced in the same manner as in Comparative Example 1 except that the porous substrate was used.
  • Table 1 shows the thermal conductivity, electrical conductivity, Seebeck coefficient, element composition, and adhesion test results of the thermoelectric conversion materials obtained in Example 7 and Comparative Example 7.
  • Example 8 In Example 1, the heat treatment after the film forming process was not performed, but instead it was performed at the time of the film forming process, that is, while the porous substrate 2 (11) in the vacuum chamber was heated to 230 ° C., the film forming rate P-type bismuth telluride thin film on the porous substrate 2 (11) in the same manner as in Example 1 except that the discharge was performed 1200 times at 0.08 nm / discharge (one discharge per second). 100 nm) to form a thermoelectric conversion material.
  • Table 1 shows the thermal conductivity, electrical conductivity, Seebeck coefficient, elemental composition, and adhesion test results of the thermoelectric conversion material obtained in Example 8.
  • Example 9 In Example 1, except that heat treatment was also performed during the film formation process, that is, the film formation rate was 0.08 nm / time (1 second while heating the porous substrate 2 (11) in the vacuum chamber to 230 ° C. A p-type bismuth telluride thin film (100 nm) was formed on the porous substrate 2 (11) in the same manner as in Example 1 except that the discharge was performed 1200 times per discharge). Was made. Table 1 shows the thermal conductivity, electrical conductivity, Seebeck coefficient, elemental composition, and adhesion test results of the thermoelectric conversion material obtained in Example 9.
  • thermoelectric conversion materials of Examples 1 to 9 in which a thermoelectric semiconductor material was formed by arc plasma deposition and heat-treated, the composition ratio of the thermoelectric thin film was controlled to be almost the same as that of the evaporation source composed of the raw material. Compared with the thermoelectric conversion materials of Comparative Examples 1 to 7 formed by flash evaporation using the same raw material, the thermoelectric performance was greatly improved. In particular, the thermoelectric conversion material of Example 1 that was heat-treated only after film formation had an excellent dimensionless thermoelectric performance index. Further, in all of Examples 1 to 9, the adhesion between the porous substrate and the thermoelectric thin film was excellent.
  • thermoelectric conversion material that is excellent in workability, can be imparted flexibility, can be produced at a low cost, and can be reduced in size can be obtained.
  • Support 2 Porous substrate 3: Nanostructure 4: Hydrophobic unit phase 5: Hydrophilic unit phase 6: Thermoelectric thin film (upper part) 7: Thermoelectric thin film (inner bottom) 11: Porous substrate 12: Vacuum exhaust port 13: Cathode electrode (deposition source; target) 14: Trigger electrode 15: Power supply unit 16: Anode electrode 17: Trigger power supply 18: Arc power supply 19: Capacitor 20: Insulator 21: Arc plasma 31: Thermoelectric conversion material 32: Heater 33: Thermocouple 34: Vacuum exhaust port 35: Introduction gas exhaust port 36: Hydrogen gas introduction port 37: Argon gas introduction port

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JP2018516457A (ja) * 2015-04-14 2018-06-21 エルジー エレクトロニクス インコーポレイティド 熱電素材及びこれを含む熱電素子と熱電モジュール
CN111234688A (zh) * 2020-03-26 2020-06-05 清华大学 热电材料浆料及制备方法
CN115014438A (zh) * 2022-06-06 2022-09-06 中国科学技术大学 一种仿生多功能传感器及其制备方法、应用

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