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WO2019088003A1 - Élément thermoélectrique, dispositif de production d'énergie et procédé de production d'élément thermoélectrique - Google Patents

Élément thermoélectrique, dispositif de production d'énergie et procédé de production d'élément thermoélectrique Download PDF

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Publication number
WO2019088003A1
WO2019088003A1 PCT/JP2018/040038 JP2018040038W WO2019088003A1 WO 2019088003 A1 WO2019088003 A1 WO 2019088003A1 JP 2018040038 W JP2018040038 W JP 2018040038W WO 2019088003 A1 WO2019088003 A1 WO 2019088003A1
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Prior art keywords
electrode layer
base material
thermoelectric element
lead
substrate
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PCT/JP2018/040038
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English (en)
Japanese (ja)
Inventor
後藤　博史
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GCE Institute Co Ltd
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GCE Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J45/00—Discharge tubes functioning as thermionic generators
    • 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
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect

Definitions

  • the present invention relates to a thermoelectric element that converts thermal energy into electrical energy, a power generation device, and a method of manufacturing the thermoelectric element.
  • thermoelectric elements that generate electrical energy using thermal energy (absolute temperature) has been actively conducted.
  • a thermoelectric element disclosed in Patent Document 1 has been proposed.
  • Such a thermoelectric element is expected to be used in various applications as compared with a configuration in which electrical energy is generated using a temperature difference given to an electrode.
  • thermoelectric device comprising: insulating spherical nanobeads, wherein a work function of the emitter electrode layer is smaller than a work function of the collector electrode layer, and a particle diameter of the spherical nanobeads is 100 nm or less.
  • Patent No. 6147901 gazette
  • the distance between the electrodes influences the amount of electrical energy generated.
  • the amount of electrical energy generated tends to decrease.
  • spherical nanobeads are used to separate the electrode layers. For this reason, the increase in the variation in the gap between electrodes resulting from the variation in the diameter of the spherical bead is not taken into consideration, and the amount of electrical energy generated is reduced. From the above-mentioned circumstances, it is desired to increase the amount of electrical energy generated.
  • the present invention has been made in view of the above-mentioned problems, and the object of the present invention is to provide a thermoelectric element, a power generation device, and a method of manufacturing the thermoelectric element that can realize an increase in the amount of electrical energy generated. It is to do.
  • thermoelectric device is a thermoelectric device that converts thermal energy into electrical energy, and has an insulating base, an insulating lead-out base laminated on the base, and the insulating base. And a first electrode layer and a second electrode layer provided in the base material and containing nanoparticles and sandwiching the middle portion and having different work functions, and the first electrode layer is used for the extraction.
  • the second electrode layer may be provided in the base in contact with the base.
  • thermoelectric element according to a second aspect of the present invention is characterized in that in the first aspect, the first electrode layer and the second electrode layer are provided in the base material.
  • thermoelectric element in the first invention or the second invention, the first distance between the first electrode layer and the second electrode layer is 10 ⁇ m or less, and the diameter of the nanoparticles is And 1/10 or less of the first distance.
  • the nanoparticles in any one of the first invention to the third invention, have an insulating film provided on the surface, and the thickness of the insulating film is 0.2 nm or more. .0 nm or less.
  • thermoelectric device in any one of the first invention to the fourth invention, the nanoparticles have a work function between a work function of the first electrode layer and a work function of the second electrode layer. It is characterized by having.
  • thermoelectric element according to a sixth aspect is characterized in that, in any one of the first to fifth aspects, the intermediate portion contains a solvent having a boiling point of 60 ° C. or higher.
  • thermoelectric element according to a seventh invention is characterized in that, in any one of the first invention to the fifth invention, the intermediate portion shows a state in which only the nanoparticles are filled.
  • thermoelectric element according to the eighth aspect of the present invention is the lead wire according to any one of the first to seventh aspects, wherein the main surface is in contact with the first electrode layer on the main surface of the lead base and penetrates the lead base;
  • the semiconductor device further includes a wire in contact with the second electrode layer in the material and penetrating the base material.
  • thermoelectric element according to the ninth aspect of the present invention is the thermoelectric element according to any one of the first to eighth aspects, wherein the first electrode layer, the second electrode layer, and the middle portion are parallel to the main surface of the base It is characterized in that a plurality of members are disposed separately from each other in one direction, and intersect in the first direction and extend in a second direction parallel to the main surface of the base.
  • a power generation device is a power generation device for converting thermal energy into electric energy, which comprises an insulating base, an insulating lead-out base laminated on the base, and the insulating base.
  • a first electrode layer and a second electrode layer which are provided in a substrate and have nanoparticles, and have a work function different from each other with the intermediate portion interposed therebetween, and the first electrode layer and the second electrode layer A first wiring and a second wiring electrically connected, wherein the first electrode layer is in contact with the lead-out base material, and the second electrode layer is provided in the base material; Do.
  • a method of manufacturing a thermoelectric device is a method of manufacturing a thermoelectric device for converting thermal energy into electrical energy, comprising: a substrate step of forming a recess in an insulating substrate; A first step of forming a first electrode layer on the main surface of the substrate; a second step of forming a second electrode layer having a work function different from that of the first electrode layer in the recess; and A laminating step of laminating the lead-out base material on the base material at a position where the concave portion and the first electrode layer are stacked, and an intermediate step of forming an intermediate portion containing nanoparticles in the concave portion; And the like.
  • thermoelectric element in a method of manufacturing a thermoelectric element according to a twelfth aspect of the present invention, in the eleventh aspect, the intermediate step is performed after the laminating step.
  • thermoelectric element in accordance with a thirteenth aspect of the present invention is characterized in that, in the eleventh aspect, the intermediate step is performed before the laminating step.
  • the base material step, the first step, and the second step connect the base material and the lead base material.
  • the method is characterized by further comprising a dividing step of dividing the base material and the lead-out base material.
  • the second electrode layer is provided in the base material, and the lead-out base material is laminated on the base material and in contact with the first electrode layer. For this reason, each electrode layer can be disposed with high accuracy, and variations in the gap between electrodes can be suppressed. This makes it possible to realize an increase in the amount of electrical energy generated.
  • the first electrode layer is provided in the substrate. Therefore, the placement accuracy of each electrode layer can be further enhanced. As a result, it is possible to further suppress the inter-electrode gap variation.
  • the first electrode layer, the second electrode layer, and the middle portion are provided in the stacked body, it is possible to suppress deterioration due to the influence of the external environment and deterioration due to the manufacturing process of the power generation device and the like.
  • the diameter of the nanoparticles is 1/10 or less of the first distance. Therefore, an intermediate portion including nanoparticles can be easily formed between the first electrode layer and the second electrode layer. Thereby, when manufacturing a thermoelectric element, it becomes possible to aim at the improvement of workability.
  • the nanoparticles have an insulating film provided on the surface. Therefore, electrons (thermoelectrons) generated from the first electrode layer can easily move between the nanoparticles by the tunnel effect. This makes it possible to further increase the amount of electrical energy generated.
  • the nanoparticles have a work function between the work function of the first electrode layer and the work function of the second electrode layer. For this reason, the thermoelectrons generated from the first electrode layer can easily propagate to the second electrode layer through the nanoparticles. This makes it possible to further increase the amount of electrical energy generated.
  • the middle part contains a solvent having a boiling point of 60 ° C. or higher. For this reason, even when the thermoelectric element is used under an environment of room temperature or more, the vaporization of the solvent can be suppressed. Thereby, it is possible to suppress the deterioration of the thermoelectric element accompanying the vaporization of the solvent.
  • the middle part shows a state in which only the nanoparticles are filled. Therefore, even when the thermoelectric element is used in a high temperature environment, it is not necessary to consider the vaporization of the solvent or the like. This makes it possible to suppress the deterioration of the thermoelectric element under a high temperature environment.
  • the wiring is provided in the base material, and the lead-out wiring is provided in the lead-out base material. For this reason, in the manufacturing process of the electric power generating apparatus using a thermoelectric element, deterioration of wiring can be suppressed. This makes it possible to obtain stable characteristics.
  • a plurality of intermediate portions and the like are disposed apart from each other in the first direction. For this reason, a plurality of independent intermediate portions and the like can be formed in a single base material. This makes it possible to miniaturize the thermoelectric element.
  • the lead-out base material is laminated on the base material at the position where the recess and the first electrode layer are stacked. For this reason, each electrode layer can be disposed with high accuracy, and variations in the gap between electrodes can be suppressed. This makes it possible to realize an increase in the amount of electrical energy generated.
  • the intermediate process is performed after the laminating process. For this reason, an intermediate part can be formed in the state which fixed the gap between electrodes. As a result, it is possible to further suppress the inter-electrode gap variation.
  • the intermediate step is performed before the laminating step. For this reason, the time which forms an intermediate part can be shortened. This makes it possible to shorten the time in the manufacturing process.
  • the base material process, the first process, and the second process are performed in a state where the base material and the lead-out base material are connected. Therefore, it is possible to cope with continuous production processes such as roll-to-roll. This makes it possible to shorten the time in the manufacturing process.
  • FIG. 1 is a schematic cross section which shows an example of a structure of the electric power generating apparatus and thermoelectric element in this embodiment.
  • Fig.2 (a) is a schematic cross section which shows an example of an intermediate part
  • FIG.2 (b) is a schematic cross section which shows the other example of an intermediate part.
  • Fig.3 (a) is a schematic cross section which shows the 1st modification of the 1st electrode layer in an example of composition of a power generator and a thermoelectric element in this embodiment
  • Drawing 3 (b) shows an example of a lamination part. It is a schematic plan view shown.
  • FIG. 1 is a schematic cross section which shows an example of a structure of the electric power generating apparatus and thermoelectric element in this embodiment.
  • Fig.2 (a) is a schematic cross section which shows an example of an intermediate part
  • FIG.2 (b) is a schematic cross section which shows the other example of an intermediate part.
  • Fig.3 (a) is a schematic cross section which shows the 1s
  • FIG. 4 is a schematic cross section which shows the 2nd modification of the 1st electrode layer in an example of a structure of the electric power generating apparatus in this embodiment, and a thermoelectric element.
  • FIG. 5 is a flowchart showing an example of a method of manufacturing a thermoelectric element in the present embodiment.
  • FIG. 6 (a) is a schematic cross-sectional view showing a recess formed in the base, and FIG. 6 (b) is a schematic cross-sectional view showing a wiring formed in the base; 6 is a schematic cross-sectional view showing the first electrode layer formed on the second main surface, and
  • FIG. 6 (d) is a schematic cross-sectional view showing the second electrode layer formed in the recess.
  • FIG.7 (a) is a schematic cross section which shows the divided base material
  • FIG.7 (b) is a schematic cross section which shows the laminated base material.
  • FIGS. 8A to 8D are flowcharts showing first to fourth modified examples of the method of manufacturing a thermoelectric element in the present embodiment.
  • FIG. 9 is a schematic cross-sectional view showing a first modified example of the configuration of the power generation device and the thermoelectric element in the present embodiment.
  • thermoelectric element and a power generation device according to an embodiment of the present invention will be described with reference to the drawings.
  • the direction from the first electrode layer 23 toward the second electrode layer 24 is taken as the height direction Z
  • the directions intersecting with the height direction Z are taken as the first direction X and the second direction Y, respectively.
  • FIG.1 (a) is a schematic cross section which shows an example of the electric power generating apparatus 100 and the thermoelectric element 1 in this embodiment
  • FIG.1 (b) is a schematic plan view which shows an example of the laminated part 20. As shown in FIG.
  • the power generation device 100 includes the thermoelectric element 1, a first wire 101, and a second wire 102.
  • the power generation device 100 supplies the current generated in the thermoelectric element 1 to the load R connected to the first wiring 101 and the second wiring 102.
  • the power generation device 100 is provided, for example, in a mobile device such as an IoT (Internet of Things) device, a wearable device, or a self-supporting sensor terminal in addition to application to solar power generation, and can be used as a substitute or supplement for a battery. .
  • IoT Internet of Things
  • the thermoelectric element 1 can convert thermal energy generated using, for example, a central processing unit (CPU) of an electronic device, an engine of an automobile, a production facility of a factory, or the like as a heat source into electrical energy to generate current.
  • the thermoelectric element 1 includes a stacked unit 20.
  • the thermoelectric element 1 may include, for example, a stacked unit 20 (leader 20n) stacked on the stacked unit 20.
  • the stacked unit 20 includes a base 21, a wire 22, a first electrode layer 23, a second electrode layer 24, and an intermediate portion 25.
  • the stacked unit 20 includes, for example, one first electrode layer 23, a second electrode layer 24, and an intermediate portion 25 for one base material 21.
  • the lead portion 20 n has a lead base 21 n and a lead wire 22 n, and may have, for example, the upper lead electrode layer 26.
  • the lead portion 20 n does not have the middle portion 25.
  • the base 21 has a first major surface 21 a parallel to the first direction X and the second direction Y, and a second major surface 21 b opposite to the first major surface 21 a.
  • the thickness of the base 21 is, for example, 10 ⁇ m or more and 2 mm or less.
  • the thickness of the substrate 21 is smaller than the width of the substrate 21 in the first direction X and smaller than the length of the substrate 21 in the second direction Y.
  • the base 21 preferably has an insulating property and also has excellent properties such as smoothness, heat resistance, or low thermal expansion.
  • the substrate 21 is, for example, a film using a thin plate-like material such as silicon, glass, or resin, and PET (polyethylene terephthalate), PC (polycarbonate), or polyimide is used as the material, for example, single crystal silicon Or glass may be used.
  • the wiring 22 is provided in the base 21.
  • the wiring 22 penetrates the base 21 along the height direction Z.
  • the wiring 22 is exposed from the second main surface 21b, and the exposed surface of the wiring 22 is formed on the same plane as the second main surface 21b.
  • the thickness of the wiring 22 is substantially equal to, for example, the thickness of the base 21.
  • the wiring 22 preferably has conductivity, and also has excellent characteristics such as embedding, heat resistance, or low thermal expansion.
  • nickel, copper, silver, gold, tungsten, or titanium can be used as the wiring 22.
  • the first electrode layer 23 is provided in contact with the lead portion 20 n.
  • the first electrode layer 23 contacts, for example, the first major surface 21 a of the base 21.
  • the first electrode layer 23 is provided to be separated from the wiring 22 provided in the base 21 along the height direction Z.
  • the second electrode layer 24 is provided in the base 21.
  • the second electrode layer 24 is in contact with the wiring 22 in the base 21 and is provided between the first electrode layer 23 and the wiring 22.
  • the second electrode layer 24 is separated from the first electrode layer 23.
  • the width of the first electrode layer 23 is larger than the width of the second electrode layer 24.
  • the thickness of the first electrode layer 23 and the second electrode layer 24 is, for example, 1 nm or more and 50 nm or less.
  • the first distance (interelectrode gap) between the first electrode layer 23 and the second electrode layer 24 is, for example, 10 ⁇ m or less, and preferably 10 nm or more and 100 nm or less.
  • the first electrode layer 23 is formed of, for example, one layer other than Refractory Metal.
  • refractory metals refer to niobium, molybdenum, tantalum, tungsten and rhenium.
  • any of carbon-based materials such as aluminum, silicon, lanthanum hexaboride (LaB 6 ), or graphene is used, for example.
  • aluminum is excellent in processability
  • silicon is excellent in productivity
  • lanthanum hexaboride has a low work function, so that materials can be selected according to the application. Further, any of the materials described above can be used under high temperature.
  • the first electrode layer 23 has a work function different from that of the second electrode layer 24.
  • the work function of the first electrode layer 23 is smaller than the work function of the second electrode layer 24.
  • the first electrode layer 23 is described as a cathode (cathode) and the second electrode layer 24 is described as an anode (anode) in the present embodiment, the first electrode layer 23 is an anode and the second electrode layer 24 is a cathode. It is also good. In this case, the work function of the first electrode layer 23 is larger than the work function of the second electrode layer 24.
  • lanthanum hexaboride (work function: 2.50 eV) is used as the first electrode layer 23
  • platinum (work function: 5.65 eV) is used as the second electrode layer 24.
  • a multilayer film may be used as the second electrode layer 24, and a material to be used may be arbitrarily selected according to the work function.
  • formation of the 1st electrode layer 23 and the 2nd electrode layer 24 is realizable by performing vapor deposition of metal material, sputtering, or the inked metal material by methods, such as screen printing and inkjet application.
  • the middle portion 25 is provided in the base 21 and surrounded by the base 21.
  • the intermediate portion 25 is provided in contact with the first electrode layer 23 and the second electrode layer 24. Therefore, the intermediate portion 25 is not exposed to the surface of the thermoelectric element 1.
  • the middle portion 25 includes, for example, nanoparticles 31 and a solvent 32, as shown in FIG. 2 (a).
  • the middle part 25 shows, for example, a state in which the solvent 32 in which the nanoparticles 31 are dispersed is filled.
  • the middle part 25 may not contain the solvent 32, and may show a state in which only the nanoparticles 31 are filled.
  • the nanoparticles 31 have a work function between the work function of the first electrode layer 23 and the work function of the second electrode layer 24, and have a work function of, for example, 3.0 eV or more and 5.5 eV or less.
  • a particle diameter that is 1/10 or less of the first distance is used as the nanoparticles 31, and specifically, a particle diameter of 2 nm or more and 10 nm or less is used.
  • an average particle diameter (D50) is 3 nm or more and 8 nm or less Particle size may be used.
  • the average particle diameter can be measured by a particle size distribution measuring instrument (for example, Nanotrac Wave II-EX 150 manufactured by Microtrac BEL, etc.) using a laser diffraction scattering method.
  • the nanoparticles 31 have, for example, an insulating film 31 a provided on the surface.
  • an insulating film 31a for example, a metal oxide such as silicon oxide or alumina is used.
  • an organic compound such as alkanethiol or a semiconductor such as silicon may be used.
  • the thickness of the insulating film 31a is, for example, 0.2 nm or more and 5.0 nm or less.
  • solvent 32 a liquid having a boiling point of 60 ° C. or higher is used, and for example, at least one of an organic solvent and water is used.
  • organic solvent for example, methanol, ethanol, toluene, xylene, alkanethiol and the like are used.
  • thermoelectrons e when thermal energy is applied to the thermoelectric element 1, the thermoelectrons e are emitted from the first electrode layer 23 and the second electrode layer 24 toward the intermediate portion 25.
  • the emitted thermal electrons e are propagated to the first electrode layer 23 or the second electrode layer 24 via the nanoparticles 31 dispersed in the intermediate portion 25.
  • the amount of thermions e emitted depends on the work function of each of the electrode layers 23 and 24, and the material having a smaller work function tends to be emitted more. That is, more thermal electrons e are emitted from the first electrode layer 23 having a work function smaller than that of the second electrode layer 24. Therefore, the first electrode layer 23 to the second electrode layer are compared to the amount of the thermions e moving from the second electrode layer 24 to the first electrode layer 23 among all the thermions e emitted to the intermediate portion 25. The amount of thermal electrons e moving to 24 tends to be large. As a result, thermal energy is converted into electrical energy, and a current from the second electrode layer 24 to the first electrode layer 23 is generated.
  • the degree of thermions e emitted from the first electrode layer 23 mainly depends on the thermal energy, and also depends on the work function of the first electrode layer 23 and the work function of the second electrode layer 24 and the interelectrode gap Do. Therefore, by shortening the distance between the first electrode layer 23 and the second electrode layer 24, it is possible to increase the amount of generation of electrical energy.
  • the inventors have found that when the thermal electrons e move from the first electrode layer 23 to the second electrode layer 24, the amount of generation of electrical energy is increased by utilizing the tunnel effect or the nano hopping effect.
  • the tunnel effect or the like the first electrode layer 23 to the second electrode layer can be easily obtained even when the thermal electron e does not have energy corresponding to the work function of each of the electrode layers 23 and 24 and the nanoparticles 31. You can move up to 24.
  • the lead-out substrate 21 n has a main surface parallel to the first direction X and the second direction Y.
  • the lead-out base 21 n is laminated on the base 21.
  • the main surface of the lead-out base 21 n is in contact with the first electrode layer 23.
  • the lead-out base 21 n is separated from the base 21 via, for example, the first electrode layer 23.
  • the thickness of the lead-out substrate 21n, the configuration of the material, and the like are the same as those of the substrate 21.
  • the lead-out wiring 22n is provided in the lead-out base material 21n, and is electrically connected to the wiring 22 of the stacked unit 20.
  • the lead-out wiring 22n is in contact with the first electrode layer 23 on the main surface of the lead-out base 21n, and penetrates the lead-out base 21n along the height direction Z.
  • the thickness, material, and the like of the lead-out wiring 22 n are the same as the wiring 22.
  • the lead interconnection 22 n may be provided thicker than the interconnection 22.
  • the upper layer lead-out electrode layer 26 is in contact with the lead-out wiring 22 n and, for example, in contact with the first wiring 101.
  • the upper layer lead-out electrode layer 26 may be provided on the main surface opposite to the main surface of the lead-out substrate 21n in contact with the first electrode layer 23, or may be provided in the lead-out substrate 21n.
  • the thickness, the material, and the like of the upper layer lead-out electrode layer 26 are the same as those of any of the electrode layers 23 and 24.
  • the upper extraction electrode layer 26 may be provided thicker than each electrode layer 23 and 24.
  • the stacked unit 20 includes, for example, a lower layer lead-out electrode layer 27 provided on the second major surface 21 b of the base 21.
  • the lower layer lead-out electrode layer 27 is in contact with the wiring 22, for example, in contact with the second wiring 102.
  • the thickness and the material configuration of the lower layer extraction electrode layer 27 are the same as those of any of the electrode layers 23 and 24.
  • the second electrode layer 24 is provided in the base 21, and the lead-out base 21 n is stacked on the base 21 and in contact with the first electrode layer 23. For this reason, each electrode layer 23 and 24 can be arrange
  • the first electrode layer 23 is provided in the base 21. For this reason, the arrangement
  • the first electrode layer 23, the second electrode layer 24, and the intermediate portion 25 are provided in the base 21, the deterioration due to the influence of the external environment and the deterioration due to the manufacturing process of the power generation device 100 and the like are suppressed. can do.
  • the diameter of the nanoparticles 31 is 1/10 or less of the first distance. Therefore, the intermediate portion 25 including the nanoparticles 31 can be easily formed between the first electrode layer 23 and the second electrode layer 24. Thereby, when manufacturing the thermoelement 1, it becomes possible to aim at the improvement of workability.
  • the nanoparticles 31 have the insulating film 31 a provided on the surface. For this reason, electrons (thermal electrons e) generated from the first electrode layer 23 can easily move between the nanoparticles 31 by the tunnel effect. This makes it possible to further increase the amount of electrical energy generated.
  • the nanoparticles 31 have a work function between the work function of the first electrode layer 23 and the work function of the second electrode layer 24. Therefore, the thermoelectrons e generated from the first electrode layer 23 can be easily propagated to the second electrode layer 24 through the nanoparticles 31. This makes it possible to further increase the amount of electrical energy generated.
  • the middle portion 25 includes the solvent 32 having a boiling point of 60 ° C. or higher. For this reason, even when the thermoelectric element 1 is used in an environment of room temperature or more, the vaporization of the solvent 32 can be suppressed. This makes it possible to suppress the deterioration of the thermoelectric element 1 caused by the vaporization of the solvent 32.
  • the intermediate portion 25 shows a state in which only the nanoparticles 31 are filled. Therefore, even when the thermoelectric element 1 is used in a high temperature environment, it is not necessary to consider the vaporization of the solvent 32 and the like. Thereby, it is possible to suppress the deterioration of the thermoelectric element 1 under a high temperature environment.
  • the wiring 22 is provided in the base material 21, and the lead-out wiring 22n is provided in the lead-out base material 21n. For this reason, in the manufacturing process of the electric power generating apparatus 100 using the thermoelectric element 1, deterioration of the wiring 22 and the lead wiring 22n can be suppressed. This makes it possible to obtain stable characteristics.
  • the base 21 may be in contact with the lead-out base 21n.
  • the first electrode layer 23 is provided in the base 21.
  • the side surface of the first electrode layer 23 may be in contact with the base 21, or may be in contact with the intermediate portion 25 apart from the base 21 as shown in FIG. 4, for example. Even with such a configuration, it is possible to realize an increase in the amount of electrical energy generated.
  • the first electrode layer 23, the second electrode layer 24, and the intermediate portion 25 are disposed one by one or more than one for one substrate 21, for example. May be In this case, the first electrode layer 23, the second electrode layer 24, and the intermediate portion 25 can extend in, for example, the second direction Y, and can be disposed in plurality and spaced in the first direction X, respectively. Thereby, the thermoelectric element 1 can be miniaturized. Also, the electrode layers 23 and 24 sandwiching the plurality of independent intermediate portions 25 can be connected in parallel. As a result, the current can be increased, that is, the output can be increased.
  • thermoelectric element 1 a plurality of stacked portions 20 may be stacked and then the lead portion 20 n may be stacked.
  • the electrode layers 23 and 24 sandwiching the plurality of intermediate portions 25 can be connected in series. Thereby, it is possible to realize the improvement of the voltage obtained from the thermoelectric element 1.
  • FIG. 5 is a flowchart showing an example of a method of manufacturing the thermoelectric element 1 in the present embodiment.
  • FIG.6 and FIG.7 is a schematic cross section which shows an example of the manufacturing method of the thermo-element 1 in this embodiment.
  • the method of manufacturing the thermoelectric element 1 in the present embodiment includes a pre-process S110 and a post-process S120.
  • the base 21 is processed to form the wiring 22 and the like.
  • the wiring 22 and the like may be formed in a state in which the base material 21 and the lead-out base material 21n are connected.
  • the previous process S110 includes, for example, a base process S111, a wiring process S112, a first process S113, and a second process S114.
  • the lead-out base 21n is stacked on the base 21.
  • the post-process S120 includes, for example, a dividing process S121, a stacking process S122, and an intermediate process S123.
  • Forming Recess 21c Substrate Step S111
  • the recess 21c is formed in the first major surface 21a of the base 21 (base step S111).
  • a plurality of recesses 21 c are formed spaced apart in the first direction X and extend in the second direction Y.
  • the recess 21c is not formed in a portion where the lead-out wiring 22n is formed (the left side in FIG. 6A).
  • the recess 21 c is formed by, for example, a thermal transfer process using a metal mold.
  • the depth of the recess 21c is, for example, 50 nm to 500 nm
  • the width in the first direction X is preferably 10 times to 1000 times the depth.
  • the width is preferably 1 ⁇ m to 100 ⁇ m.
  • Wiring Step S112 the wiring 22 penetrating from the bottom of the recess 21c to the second main surface 21b is formed (wiring step S112).
  • the wiring 22 is formed on the bottom of each recess 21 c and extends in the second direction Y.
  • a plurality of the wirings 22 may be formed spaced apart in the second direction Y.
  • the lead wire 22n may be formed simultaneously with the wire 22.
  • the lead interconnection 22 n is formed at a position separated from the interconnection 22 along the first direction X.
  • the lead-out wiring 22n is formed penetrating the base 21 of the portion formed as the lead-out base 21n.
  • the wiring 22 is formed, for example, by forming a through hole by laser processing on the bottom surface of the recess 21 c and embedding a metal by a plating method. At this time, metal is embedded to such an extent that the recess 21 c is not filled.
  • the first electrode layer 23 in contact with the wiring 22 and the lead wiring 22n is formed on the second major surface 21b of the base 21 (first step S113).
  • the first electrode layers 23 are formed in contact with the respective wirings 22 in a state of being separated in the first direction X, respectively.
  • the first electrode layer 23 is formed to overlap the recess 21 c.
  • the first electrode layer 23 may be formed only on the main surface of the drawn base 21 n.
  • the first electrode layer 23 for example, a material other than the refractory metal is used. In this case, it can be processed more easily than the high melting point metal, and the in-plane precision and the precision of thickness can be dramatically improved.
  • the first electrode layer 23 is formed of one layer. For this reason, compared with the case where it comprises from a multilayer, the fall of the generation amount of the electrical energy resulting from the contact resistance between layers can be suppressed.
  • the first electrode layer 23 is formed by, for example, a vapor deposition method or an inkjet method in addition to the spray printing method.
  • the width of the first electrode layer 23 in the first direction X is wider than the width of the wiring 22 and equal to the width of the recess 21 c.
  • Second Step S114 Next, the second electrode layer 24 separated from the first electrode layer 23 and having a work function larger than that of the first electrode layer 23 is formed (second step S114). As shown in FIG. 6D, the second electrode layer 24 in contact with the wiring 22 is formed in the recess 21c. The second electrode layer 24 is formed apart from each of the main surfaces 21a and 21b. Note that the second electrode layer 24 may be formed before the first electrode layer 23 is formed. Further, the upper extraction electrode layer 26 may be formed simultaneously with the second electrode layer 24. In this case, the upper layer lead-out electrode layer 26 is in contact with the lead-out wiring 22 n.
  • the first electrode layer 23 is formed by, for example, a vapor deposition method or an inkjet method in addition to the spray printing method.
  • the width of the second electrode layer 24 in the first direction X is equal to the width of the first electrode layer 23.
  • the base material 21 may be divided (division step S121).
  • the substrate 21 is divided into a plurality of substrates 21 in the first direction X.
  • the base 21 is divided at positions separated from the wiring 22, the first electrode layer 23, and the second electrode layer 24. Thereby, the base 21 separates from the lead-out base 21 n.
  • the base material 21 is laminated (lamination process S122).
  • the drawn substrate 21 n is laminated on the substrate 21.
  • the lead-out base 21 n is laminated on the base 21 at a position where the recess 21 c and the first electrode layer 23 overlap.
  • the first electrode layer 23 may be arranged on the first major surface 21a as shown in FIG. 1, for example.
  • the first electrode layer 23 is disposed apart from the second electrode layer 24 and an unfilled portion is left in the recess 21 c.
  • An arbitrary number of substrates 21 may be laminated between the substrate 21 and the drawn substrate 21 n. Further, the first electrode layer 23 formed on the second major surface 21 b of the base material 21 is used as the lower layer lead-out electrode layer 27.
  • the base 21 and the drawn-out base 21n are, for example, activated by plasma cleaning or UV cleaning of the respective main surfaces 21a and 21b, and then the first main surface 21a of the base 21 and the second main surface of the drawn-out base 21n It is laminated by pasting 21b.
  • Intermediate Step S123 an intermediate portion 25 including the nanoparticles 31 and the solvent 32 is formed in the recess 21 c (intermediate step S123).
  • the intermediate portion 25 is filled in the unfilled portion of the recess 21 c between the first electrode layer 23 and the second electrode layer 24.
  • the intermediate portion 25 can be filled in the recess 21c by capillary action.
  • the middle portion 25 is filled in the recess 21 c from the side surface of the base 21 in the second direction Y. Thereafter, for example, by covering the side surface of the base 21 with an insulating material or the like, it is possible to suppress the filling failure of the intermediate portion 25 and the like.
  • thermoelectric element 1 in the present embodiment is formed through the steps described above.
  • the first wiring 101 connected to the upper layer lead electrode layer 26 formed and the second wiring 102 connected to the lower layer lead electrode layer 27 are formed, and the load R is connected to the first wiring 101 and the second wiring 102.
  • the power generation device 100 in the present embodiment can be formed.
  • the lead-out base material 21n is stacked on the base material 21 at the position where the recess 21c and the first electrode layer 23 are stacked. For this reason, each electrode layer 23 and 24 can be arrange
  • the wiring 22 and the intermediate portion 25 are formed in the base 21. For this reason, in the manufacturing process of the electric power generating apparatus 100 using the thermoelement 1, deterioration of the wiring 22 can be suppressed. This makes it possible to obtain stable characteristics.
  • the intermediate step S123 is performed after the stacking step S122. For this reason, the intermediate part 25 can be formed in the state which fixed the gap between electrodes. As a result, it is possible to further suppress the inter-electrode gap variation.
  • the dividing step S121 is performed prior to the stacking step S122. For this reason, it is possible to accurately set the stacking position at which the lead-out base 21n is stacked on the base 21. This makes it possible to obtain more stable characteristics.
  • thermoelectric element 1 it is not necessary to use an etching method, for example, as a method of forming the recess 21 c. For this reason, it is possible to realize the reduction of equipment investment, the reduction of the manufacturing cost, and the improvement of the task associated with the manufacture of the thermoelectric element 1.
  • the base material process S111, the first process S113, and the second process S114 are performed in a state in which the base 21 and the drawn base 21n are connected. Therefore, it is possible to cope with continuous production processes such as roll-to-roll. This makes it possible to shorten the time in the manufacturing process.
  • the recess 21 c can be formed by a fine transfer method using a mold. Therefore, the processing area can be easily expanded without the need to use a vacuum process.
  • thermoelectric element 1 by using a resin film as the base material 21, base materials 21 comrades can be bonded easily and the space which fills the intermediate part 25 can be controlled easily. Therefore, in addition to the improvement of the productivity of the thermoelectric element 1 and the reduction of the manufacturing cost, it becomes possible to suppress the characteristic variation of the thermoelectric element 1.
  • FIG. 8 is a flowchart showing first to fourth modified examples of the method of manufacturing the thermoelectric element 1 in the present modified example.
  • the lamination process S122 may be performed.
  • the intermediate portion 25 can be formed using, for example, a continuous coating method such as roll-to-roll. For this reason, the time which forms intermediate part 25 can be shortened. This makes it possible to shorten the time in the manufacturing process.
  • the intermediate portion 25 can be formed only by filling the nanoparticles 31 without using the solvent 32 in order to form the intermediate portion 25. As a result, it is possible to suppress the deterioration of the thermoelectric element 1 caused by the vaporization and the like of the solvent 32.
  • the division process S121 may be performed after the lamination process S122. For this reason, in a state where the drawn-out base 21n is laminated on the base 21, the base 21 and the drawn-out base 21n can be divided at one time. This makes it possible to shorten the time in the manufacturing process.
  • FIG. 9 is a schematic cross-sectional view showing a modified example of the thermoelectric element 1 in the present embodiment.
  • the second electrode layer 24 is exposed from the second main surface 21b, and the exposed surface of the second electrode layer 24 is formed on the same plane as the second main surface 21b. Be done.
  • the second electrode layer 24 contacts, for example, the second wiring 102.
  • the second electrode layer 24 is provided in the base 21, and the lead-out base 21 n is stacked on the base 21 and in contact with the first electrode layer 23. .
  • each electrode layer 23 and 24 can be arrange
  • the stacked unit 20 does not have the wiring 22. For this reason, it is possible to suppress an increase in the amount of electrical energy generated due to the contact resistance between the wiring 22 and the second electrode layer 24.
  • Thermoelectric element 20 Layered portion 20n: Lead portion 21: Base 21a: First main surface 21b: Second main surface 21c: Concave portion 21n: Lead base 22: Wiring 22n: Lead wiring 23: First electrode layer 24 : Second electrode layer 25: middle portion 26: upper layer extraction electrode layer 27: lower layer extraction electrode layer 31: nanoparticles 31a: insulating film 32: solvent 100: power generating device 101: first wiring 102: second wiring R: load S110 : Front step S120: Back step X: first direction Y: second direction Z: height direction e: thermal electron

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Abstract

Le problème décrit par la présente invention est de fournir un élément thermoélectrique, un dispositif de production d'énergie et un procédé de production d'élément thermoélectrique capables d'augmenter la quantité de production d'énergie électrique. La solution selon l'invention porte sur un élément thermoélectrique 1 qui convertit une énergie thermique en énergie électrique, et qui est caractérisé en ce qu'il comprend un matériau de base 21 ayant des propriétés isolantes, un matériau de base de sortie 21n stratifié sur le matériau de base 21 et ayant des propriétés isolantes, une partie intermédiaire 25 contenant des nanoparticules 31 et disposée à l'intérieur du matériau de base 21, et une première couche d'électrode 23 et une seconde couche d'électrode 24 prenant en sandwich la partie intermédiaire 25 et ayant des fonctions de travail mutuellement différentes, la première couche d'électrode 23 étant en contact avec le matériau de base de sortie 21n, et la seconde couche d'électrode 24 étant disposée à l'intérieur du matériau de base 21.
PCT/JP2018/040038 2017-10-31 2018-10-29 Élément thermoélectrique, dispositif de production d'énergie et procédé de production d'élément thermoélectrique Ceased WO2019088003A1 (fr)

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US10559864B2 (en) 2014-02-13 2020-02-11 Birmingham Technologies, Inc. Nanofluid contact potential difference battery
US11244816B2 (en) 2019-02-25 2022-02-08 Birmingham Technologies, Inc. Method of manufacturing and operating nano-scale energy conversion device
US11101421B2 (en) 2019-02-25 2021-08-24 Birmingham Technologies, Inc. Nano-scale energy conversion device
US11124864B2 (en) 2019-05-20 2021-09-21 Birmingham Technologies, Inc. Method of fabricating nano-structures with engineered nano-scale electrospray depositions
US11649525B2 (en) 2020-05-01 2023-05-16 Birmingham Technologies, Inc. Single electron transistor (SET), circuit containing set and energy harvesting device, and fabrication method
US11417506B1 (en) 2020-10-15 2022-08-16 Birmingham Technologies, Inc. Apparatus including thermal energy harvesting thermionic device integrated with electronics, and related systems and methods
US11616186B1 (en) 2021-06-28 2023-03-28 Birmingham Technologies, Inc. Thermal-transfer apparatus including thermionic devices, and related methods

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