WO2023054583A1 - 熱電体、熱電発電素子、多層熱電体、多層熱電発電素子、熱電発電機、及び熱流センサ - Google Patents

熱電体、熱電発電素子、多層熱電体、多層熱電発電素子、熱電発電機、及び熱流センサ Download PDF

Info

Publication number
WO2023054583A1
WO2023054583A1 PCT/JP2022/036432 JP2022036432W WO2023054583A1 WO 2023054583 A1 WO2023054583 A1 WO 2023054583A1 JP 2022036432 W JP2022036432 W JP 2022036432W WO 2023054583 A1 WO2023054583 A1 WO 2023054583A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoelectric
amorphous
multilayer
magnetization
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/036432
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
健一 内田
ラージクマール モダック
裕弥 桜庭
偉男 周
アミン ホセイン セペリ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute for Materials Science
Original Assignee
National Institute for Materials Science
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute for Materials Science filed Critical National Institute for Materials Science
Priority to US18/695,245 priority Critical patent/US20240284798A1/en
Priority to CN202280064066.XA priority patent/CN117999868A/zh
Priority to JP2023551845A priority patent/JP7669069B2/ja
Publication of WO2023054583A1 publication Critical patent/WO2023054583A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
    • G01K7/04—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples the object to be measured not forming one of the thermoelectric materials

Definitions

  • the present invention relates to thermoelectric bodies and multilayer thermoelectric bodies that are magnetic bodies and are used in thermoelectric power generation elements that utilize the anomalous Nernst effect.
  • the anomalous Nernst effect that appears in ferromagnets is a phenomenon in which an electric field is generated in the direction perpendicular to heat flow and magnetization.
  • the Seebeck effect which has been studied as a thermoelectric power generation technology, is a phenomenon in which a heat flow and an electric field appear in the same direction. are alternately connected in series to form a complex structure arranged in a matrix.
  • thermoelectric power generation using the anomalous Nernst effect has advantages such as easy application to a heat source with no flatness such as a cylindrical shape and low cost of the element.
  • Non-Patent Document 1 describes technical development of a heat flow sensor using the anomalous Nernst effect.
  • some of the inventors of the present invention have proposed novel thermoelectric conversion materials in Patent Documents 1 to 3.
  • Non-Patent Document 2 describes in detail the crystal structure and magnetic properties of various composition ratios of SmCo alloys as rare earth magnets. However, no mention is made of the anomalous Nernst effect.
  • Non-Patent Documents 3 and 4 written by some of the present inventors, report research on the anomalous Nernst effect in SmCo 5 -based magnets, but do not include reports on amorphous magnets.
  • JP 2016-103535 A Japanese Patent Application Laid-Open No. 2018-190780 JP 2021-040066 A
  • thermoelectric conversion materials using the anomalous Nernst effect high anomalous Nernst coefficients have been obtained only in single-crystal bulk materials, epitaxially grown thin films, and crystalline materials that require high-temperature heat treatment. There is a problem that it is inferior to In addition, in conventional thermoelectric conversion materials using the anomalous Nernst effect, excluding bulk permanent magnets, the coercive force and the ratio of residual magnetization to saturation magnetization are small, so there is a problem that an external magnetic field must be applied to operate the anomalous Nernst effect. There is
  • thermoelectric body that can be deposited on any substrate and that exhibits a high coercive force with respect to in-plane magnetization and a high ratio of residual magnetization to saturation magnetization. do.
  • thermoelectric body of the present invention a lamination of a rare earth intermetallic amorphous magnetic alloy material having a large coercive force and remanent magnetization and having an in-plane easy magnetization direction and another ferromagnetic material having a huge anomalous Nernst effect. It is an object of the present invention to provide a multi-layered thermoelectric material that can realize voltage generation by a large anomalous Nernst effect without applying an external magnetic field to a conventional ferromagnetic material by using a structure.
  • the thermoelectric body of the present invention is a thermoelectric body that is a magnetic film used in a thermoelectric power generation element that utilizes the anomalous Nernst effect, It is characterized by having an axis of easy magnetization in the in-plane direction and having an amorphous structure.
  • the thermoelectric element [1] of the present invention is preferably characterized by containing Sm p Co 100-p (0 ⁇ p ⁇ 50).
  • In the thermoelectric element [2] of the present invention preferably 15 ⁇ p ⁇ 35, more preferably 20 ⁇ p ⁇ 30.
  • thermoelectric body [1] of the present invention is preferably characterized by containing Sm p (Fe q Co 100-q ) 100-p (0 ⁇ p ⁇ 50, 0 ⁇ q ⁇ 100) .
  • thermoelectric element [4] of the present invention preferably 15 ⁇ p ⁇ 35 and 5 ⁇ q ⁇ 45, more preferably 20 ⁇ p ⁇ 30 and 10 ⁇ q ⁇ 35. do.
  • the thermoelectric generating element of the present invention preferably comprises the thermoelectric bodies [1] to [5] of the present invention and a substrate supporting the thermoelectric bodies.
  • the multi-layered thermoelectric material of the present invention is a rare earth intermetallic amorphous magnetic alloy that exhibits a large anomalous Nernst effect by having an axis of easy magnetization that exhibits a large coercive force and a large ratio of residual magnetization to saturation magnetization in the in-plane direction. and a second magnetic material layer exhibiting a huge anomalous Nernst effect and made of a magnetic material different from the rare earth intermetallic amorphous magnetic alloy material.
  • the large coercive force is 10 mT or more
  • the large residual magnetization ratio to saturation magnetization is 0.3 or more
  • the large The anomalous Nernst effect means a thermoelectric power of 1 ⁇ V/K or more
  • the huge anomalous Nernst effect means a thermoelectric power of 5 ⁇ V/K or more.
  • the multilayer thermoelectric generating element of the present invention preferably comprises the multilayer thermoelectric element [7] or [8] of the present invention and a substrate supporting the thermoelectric element.
  • thermoelectric generator using the thermoelectric generating elements [1] to [6] or the multilayer thermoelectric generating elements [7] to [9] of the present invention is preferable.
  • a bendable heat flow sensor using the thermoelectric generating elements [1] to [6] or the multilayer thermoelectric generating elements [7] to [9] of the present invention is preferable.
  • thermoelectric power generating element of the present invention is useful for practical application of the horizontal thermoelectric effect by applying the rare earth intermetallic amorphous magnetic alloy to horizontal thermoelectric conversion that operates without an external magnetic field.
  • the multilayer thermoelectric power generation element of the present invention is composed of a rare earth intermetallic amorphous magnetic alloy material that exhibits a large coercive force and remanent magnetization in the in-plane easy magnetization direction and a large anomalous Nernst effect, and other materials that have a huge anomalous Nernst effect.
  • a large anomalous Nernst effect can be realized without applying an external magnetic field to a conventional ferromagnetic material by using a laminated structure with a ferromagnetic material.
  • FIG. 1 is a block diagram showing a typical anomalous Nernst thermopile structure for thermoelectric conversion that produces an electromotive force transverse to the direction of heat flow illustrating one embodiment of the present invention
  • FIG. This shows an example of film formation for examining the optimum composition ratio of the rare earth intermetallic amorphous magnetic alloy showing one embodiment of the present invention .
  • the structure of a gradient film is shown typically, and the top view is shown.
  • the structure of the gradient film is shown schematically, and a cross-sectional view is shown. Fig.
  • FIG. 2 shows XRD patterns at different p-values of amorphous Sm p Co 100-p (0 ⁇ p ⁇ 100) compositionally graded films;
  • FIG. 2A shows a cross-sectional bright-field (BF)-STEM image and a microbeam electron diffraction pattern of the region with a high composition ratio of Sm on the right side indicated by (A) in FIG. 2A.
  • 2B shows a cross-sectional bright-field (BF)-STEM image and a microbeam electron diffraction pattern of a region in which the composition ratio of Co and Sm is roughly the same in the vicinity of the roughly center indicated by (B) in FIG. 2A.
  • FIG. 2A shows a cross-sectional bright field (BF)-STEM image and a microbeam electron diffraction pattern of the region with a high Co composition ratio on the left side indicated by (C) in FIG. 2A.
  • Graph showing composition dependence of temperature change per unit current density due to anomalous Ettingshausen effect (reciprocal phenomenon of anomalous Nernst effect) in amorphous Sm p Co 100-p (0 ⁇ p ⁇ 100) composition gradient film on MgO substrate is.
  • (a) is a cross-sectional schematic diagram showing a laminated structure for producing an amorphous Sm 20 Co 80 film.
  • (b) shows the magnetic field dependence curve (black symbols) of the in-plane magnetization of the deposited amorphous Sm 20 Co 80 film.
  • (c) shows the dependence of the ANE electric field on the external magnetic field when the heater output is changed.
  • (d) shows the temperature gradient dependence of the ANE electric field.
  • (a) is a diagram showing a schematic structure of a thermopile for heat flux detection using an amorphous Sm 20 Co 80 thin film.
  • (b) shows a schematic experimental set-up for heat flux sensing;
  • (c) is a diagram showing the observation results of the ANE voltage signal of the amorphous Sm 20 Co 80 film deposited on the polyethylene naphthalate (PEN) substrate by the above experimental configuration, where the horizontal axis indicates the strength H of the magnetic field.
  • (d) is similar to (c), and the horizontal axis indicates the heat flow density JQ in the direction penetrating the sample surface.
  • FIG. 1 is a cross-sectional view schematically showing the structure of an amorphous Sm 20 (Fe q Co 100-q ) 80 (0 ⁇ q ⁇ 100) composition gradient film.
  • (b) shows XRD patterns at different q values of FIG. 6(a).
  • (c) shows a cross-sectional bright-field (BF)-STEM image and a microbeam electron diffraction pattern to confirm the results obtained by XRD.
  • Fig. 3 shows the composition dependence of the temperature change per unit current density due to the anomalous Ettingshausen effect in an amorphous Sm 20 (Fe q Co 100-q ) 80 (0 ⁇ q ⁇ 100) compositionally graded film on an MgO substrate.
  • FIG. 2 schematically shows a multilayer thermopile structure using a rare earth intermetallic amorphous magnetic alloy and a different magnetic material having a huge anomalous Nernst effect, showing the multilayer thermopile structure of the present invention
  • Thermoelectric conversion material is a substance that can convert heat into electricity, and is used, for example, in power generation modules and temperature control elements, and is useful for eco-friendly energy and further improvement of energy saving efficiency.
  • the term "Nernst effect” was published in 1886 by E. This is a phenomenon reported by Nernst et al., in which an electric field is generated in the cross product direction of H and ⁇ T when an external magnetic field H is applied to a conductive material subjected to a temperature gradient ⁇ T (see Non-Patent Document 1).
  • the "anomalous Nernst effect” is a phenomenon peculiar to a magnetic material, and is a phenomenon in which an electric field is generated not in an external magnetic field but in the cross product direction of the magnetization M of the magnetic material and the temperature gradient ⁇ T (see Non-Patent Document 1).
  • the anomalous Nernst effect may be abbreviated as ANE (anomalous Nernst effect).
  • a “thermopile” is a structure in which multiple thermoelectric conversion materials are connected in series or in parallel, and is used to boost the thermoelectromotive force.
  • FIG. 1 is a diagram illustrating a typical Nernst thermopile structure for horizontal thermoelectric conversion in which input heat flow and output current are orthogonal, showing an embodiment of the present invention.
  • (b) shows the case where the direction of magnetization M alternates between rightward and leftward directions between adjacent thermoelectric bodies.
  • the thermoelectric material of the present invention is a magnetic film used in a thermoelectric generating element utilizing the anomalous Nernst effect.
  • the thermoelectric element 11 of the present invention is characterized by having an axis of easy magnetization in the in-plane direction and having an amorphous structure. By using this, it is possible to obtain a horizontal thermoelectric conversion element that is free from an external magnetic field and is capable of generating an electromotive force in the in-plane direction.
  • FIG. 1(a) is a diagram illustrating a thermoelectric power generation element 10 using the thermoelectric conversion material of the present invention.
  • the thermoelectric generating element 10 shown in FIG. 1( a ) has a substrate 13 , thermoelectric bodies 11 and connecting bodies 12 arranged (carried) on the substrate 13 , and connection terminals 14 .
  • the material of the thermoelectric element 11 is indicated as Material A
  • the material of the connection body 12 is indicated as Material B.
  • the thermoelectric body 11 is typically composed of a rare earth intermetallic amorphous magnetic alloy film (magnetic film) such as an amorphous Sm 20 Co 80 thin film.
  • the rare earth intermetallic amorphous magnetic alloy film has strong in-plane magnetic anisotropy and has an easy axis of magnetization in the in-plane direction. Therefore, the rare earth intermetallic amorphous magnetic alloy film exhibits a large coercive force and a large residual magnetization with respect to saturation magnetization, and maintains the magnetization even after the external magnetic field is returned to the zero magnetic field.
  • the magnetization direction of the rare-earth intermetallic amorphous magnetic alloy is oriented in the direction of the applied external magnetic field and can be controlled in any direction, so it is suitable for controlling the output of the anomalous Nernst effect.
  • a rare earth intermetallic amorphous magnetic alloy is Sm p Co 100-p (0 ⁇ p ⁇ 50) or Sm p (Fe q Co 100-q ) 100-p (0 ⁇ p ⁇ 50, 0 ⁇ q ⁇ 100), such as Sm p Co 100-p (15 ⁇ p ⁇ 35) or Sm p (F q Co 100-q ) 100-p ( 15 ⁇ p ⁇ 50, 5 ⁇ q ⁇ 45), Sm p Co 100-p (20 ⁇ p ⁇ 30) or Sm p (F q Co 100-q ) 100-p ( 20 ⁇ p ⁇ 30, 10 ⁇ q ⁇ 35).
  • thermoelectric body 11 may be a uniform alloy film, but may also be, for example, a nanoscale multilayer structure in which different single metal layers are alternately laminated, but is not limited thereto.
  • the thickness of the magnetic film can be, for example, about 10 nm to 1 ⁇ m, but is not particularly limited to this.
  • the connector 12 is made of a non-magnetic material (e.g., copper (Cu), chromium (Cr), gold (Au), silver (Ag), platinum (Pt)) that does not exhibit the anomalous Nernst effect as Material B. .
  • the connector 12 may be a ferromagnetic material (e.g., Fe, NdFeB, MnGa) having an anomalous Nernst coefficient opposite in sign to that of the thermoelectric element 11, or a ferromagnetic material Smn having an anomalous Nernst coefficient lower than that of the thermoelectric element 11, as Material B. It may be composed of Fe 1-n (0 ⁇ n ⁇ 100).
  • the substrate 13 is made of MgO, Si—SiO 2 , Al 2 O 3 , AlN, glass, diamond, polyethylene naphthalate (PEN), polyimide film (Kapton (registered trademark of DuPont)), polymer, or the like.
  • connection terminals 14 are made of the same material (Material B) as the connection body 12 and are provided at both ends of the thermoelectric body 11 .
  • the connection terminals 14 may be made of the same material (Material A) as the thermoelectric element 11, and the arrangement of the thermoelectric element 11 and the connection body 12 in FIG. 1 may be exchanged.
  • the thermoelectric element 11 is formed by thinning a rare earth intermetallic amorphous magnetic alloy film such as an amorphous Sm 20 Co 80 thin film formed on a substrate 13, and is oriented in the direction shown in FIG. 1(a). It is magnetized to M. Due to the anomalous Nernst effect, the thermoelectric element 11 responds to the temperature difference in the direction perpendicular to the magnetization direction M (the heat flow direction J Q shown in FIG. 1(a)) by the electric field shown in FIG. 1(a). (longitudinal direction of the thermoelectric element 11 and the connector 12).
  • a rare earth intermetallic amorphous magnetic alloy film such as an amorphous Sm 20 Co 80 thin film formed on a substrate 13, and is oriented in the direction shown in FIG. 1(a). It is magnetized to M. Due to the anomalous Nernst effect, the thermoelectric element 11 responds to the temperature difference in the direction perpendicular to the magnetization direction M (the heat flow direction J Q shown in FIG.
  • connection bodies 12 are arranged on the surface of the substrate 13 in parallel with the thermoelectric bodies 11, 11, .
  • One connecting body 12 is arranged between a pair of adjacent thermoelectric bodies 11, 11, and the connecting body 12 electrically connects one end side of one thermoelectric body 11 and the other end side of the other thermoelectric body 11. connected to. Thereby, the thermoelectric bodies 11 are electrically connected in series by the connecting bodies 12 .
  • the thermoelectric generating element 10 has the thermoelectric element 11 composed of a rare earth intermetallic amorphous magnetic alloy film such as an amorphous Sm 20 Co 80 thin film.
  • the thermoelectric body 11 composed of a rare earth intermetallic amorphous magnetic alloy film such as an amorphous Sm 20 Co 80 thin film, it is possible to increase the thermoelectromotive force by increasing the effective length in the electric field direction. Therefore, according to this embodiment, by using such a thermoelectric element 11, it is possible to provide the thermoelectric power generation element 10 in a form that is easy to put into practical use.
  • FIG. 1(b) is a diagram illustrating a thermoelectric generation element 20 using the thermoelectric conversion material of the present invention.
  • the thermoelectric generating element 20 shown in FIG. 1(b) has a substrate 23, a thermoelectric element 21 and a reverse magnetization connector 22 arranged (carried) on the substrate 23, and connection terminals 24.
  • the material of both the thermoelectric body 21 and the reverse magnetization connector 22 is indicated as Material A
  • the material of the connection terminal 24 is indicated as Material B.
  • thermoelectric element 21 and the reverse magnetization connector 22 are composed of a rare earth intermetallic amorphous magnetic alloy film such as an amorphous Sm 20 Co 80 thin film, like the thermoelectric element 11 . Even if the thermoelectric bodies 21 and the reverse magnetization connectors 22 are made of the same material, the ANE electric field is generated by alternately arranging the thermoelectric bodies 21 and the reverse magnetization connectors 22 having opposite magnetization directions M. It is boosted without canceling each other out.
  • the substrate 23 is made of silicon, magnesium oxide, or the like, like the substrate 13 described above.
  • connection terminal 24 may be made of the same material as the connection body 12 as Material B, for example, a non-magnetic material that does not exhibit the anomalous Nernst effect (e.g., copper (Cu), chromium (Cr), gold ( Au), silver (Ag), and platinum (Pt)
  • the connection terminals 24 are provided at both ends of the thermoelectric body 21.
  • the connection terminals 24 are connected to the thermoelectric body 21 and the reverse magnetization connection body. It may be the same material as 22 (Material A).
  • the reverse magnetization connectors 22 are arranged on the surface of the substrate 23 in parallel with the thermoelectric bodies 21, 21, .
  • One reverse magnetization connector 22 is arranged between a pair of adjacent thermoelectric bodies 21 , 21 , and the reverse magnetization connector 22 is connected to one end side of one thermoelectric body 1 and the other thermoelectric body 1 . It is electrically connected to the end side.
  • the thermoelectric bodies 21 are electrically connected in series by the reverse magnetization connector 22 .
  • the thermoelectric generating element 20 has the thermoelectric body 21 and the reverse magnetization connector 22 which are composed of a rare earth intermetallic amorphous magnetic alloy film such as an amorphous Sm 20 Co 80 thin film.
  • the thermoelectric body 21 and the reverse magnetization connector 22 composed of the amorphous Sm 20 Co 80 thin film, it is possible to increase the thermoelectromotive force by increasing the effective length in the electric field direction. Therefore, according to the present embodiment, by using such a thermoelectric element 21 and a reverse magnetization connector 22, it is possible to provide a thermoelectric power generation element 20 that is easy to put into practical use.
  • a magnetic film made of a material such as a rare earth intermetallic amorphous magnetic alloy used for the thermoelectric bodies 11 and 21, the connector 12, and the reverse magnetization connector 22 has a strong axis of easy magnetization in the in-plane direction and a thick film. Since it exhibits high coercive force and remanent magnetization ratio to saturation magnetization even in a thinned or thinned shape, it exhibits a large voltage due to the anomalous Nernst effect even in a zero magnetic field, and each wire (thermoelectric bodies 11 and 21, connector 12, opposite direction The magnetization direction of the magnetization connectors 22) can be individually controlled, and the thermopile element can be constructed from a single material.
  • thermoelectric output per unit can be increased.
  • the magnetization of each layer can also be controlled using a local magnetic field or an exchange bias effect by adding a pinning layer such as Cr.
  • amorphous composition gradient material with p of Sm p Co 100-p varied from 0 to 100 was prepared. (hereinafter also simply referred to as “amorphous Sm p Co 100-p (0 ⁇ p ⁇ 100) compositionally graded film”) was fabricated, and its physical properties (structure and thermoelectric performance) were evaluated.
  • FIG. 2A schematically shows the structure of an amorphous Sm p Co 100-p (0 ⁇ p ⁇ 100) compositionally graded film, showing a plan view.
  • FIG. 2B shows a cross-sectional view thereof.
  • 100 layers of a laminated body made of a compositionally graded material of Sm and Co, with a total thickness of 1 nm of Sm and Co per layer, are laminated, and the uppermost layer is an aluminum thin film for oxidation prevention. is evaporated.
  • the laminate with a thickness of 1 nm is a composition gradient layer in which the composition ratio of Sm increases from 0 at % to 100 at % in the x-axis direction in FIGS.
  • the right side of the figure is a region where the Sm composition ratio is high
  • the approximate center area shown by (B) in FIG. 2A is a region where the Co and Sm composition ratios are roughly equal
  • FIG. 2C shows XRD patterns at different p-values of amorphous Sm p Co 100-p (0 ⁇ p ⁇ 100) compositionally graded films.
  • the XRD pattern confirmed that most of the Sm—Co binary alloy phase was amorphous except for pure Sm and Co rich regions.
  • FIG. 2D shows a cross-sectional bright-field (BF)-STEM image and a microbeam electron diffraction pattern of the region with a high composition ratio of Sm on the right side of (A) in FIG. 2A.
  • TEM images confirm the results obtained by XRD. In the Sm-rich region, a diffraction image showing the crystal structure is obtained.
  • FIG. 2E shows a cross-sectional bright-field (BF)-STEM image and a microbeam electron diffraction pattern of a region in which the composition ratio of Co and Sm is roughly equal in the vicinity of (B) in FIG. 2A. It was confirmed that most of the Sm--Co binary alloy phase was amorphous.
  • FIG. 2D shows a cross-sectional bright-field (BF)-STEM image and a microbeam electron diffraction pattern of the region with a high composition ratio of Sm on the right side of (A) in FIG. 2A.
  • TEM images confirm the results obtained by X
  • 2F shows a cross-sectional bright-field (BF)-STEM image and a microbeam electron diffraction pattern of the region with a high Co composition ratio on the left side of (C) in FIG. 2A.
  • BF bright-field
  • C Co composition ratio
  • FIG. 3 is a diagram showing the composition dependence of the temperature change per unit charge current density due to the anomalous Ettingshausen effect in an amorphous Sm p Co 100-p (0 ⁇ p ⁇ 100) compositionally graded film on an MgO substrate. .
  • the alloy composition range suitable for thermoelectric applications should be 0 ⁇ p ⁇ 50, which exhibits at least a large anomalous Nernst effect.
  • a thermoelectric body composed of an amorphous Sm 20 Co 80 film was fabricated as an amorphous Sm p Co 100-p (0 ⁇ p ⁇ 50) film with a preferred composition range, and its thermoelectric performance was evaluated.
  • FIG. 4(a) is a schematic cross-sectional view showing the laminated state of the amorphous Sm 20 Co 80 film.
  • 100 stacked layers each having a total thickness of 1 nm of Sm layer and Co layer are stacked, and aluminum is vapor-deposited as the uppermost layer as a cap layer.
  • FIG. 4(b) shows the magnetic field dependence curve (black data points) of the in-plane magnetization of the deposited amorphous Sm 20 Co 80 film. From FIG.
  • FIG. 4(c) is a diagram showing the dependence of the ANE electric field on the external magnetic field when the heater output is changed.
  • FIG. 4(c) that the ANE electric field exhibits an odd dependence on the magnetic field, and that the electric field is saturated when the magnetization of the amorphous Sm 20 Co 80 film is saturated.
  • the electric field increased in FIG. 4(c), the lightest colored line indicates the result when the heater output is high, and the darkest colored line indicates the result when the heater output is low).
  • FIG. 4(d) is a diagram showing the temperature gradient dependence of the ANE electric field.
  • thermoelectric body composed of the amorphous Sm p Co 100-p (0 ⁇ p ⁇ 50) film of the present invention has a relatively high thermoelectric power due to the anomalous Nernst effect.
  • thermoelectric performance was evaluated when the thermoelectric body composed of the amorphous Sm 20 Co 80 film produced above was used as a thermopile for heat flux detection (thermoelectric power generating element 10).
  • FIG. 5(a) is a diagram showing a schematic structure of a thermopile for heat flux sensing using an amorphous Sm 20 Co 80 thin film, which is the same as that shown in FIG. 1(a).
  • FIG. 5(b) shows a schematic experimental setup for heat flux sensing.
  • An amorphous Sm 20 Co 80 thin film and a heat flow sensor are laminated between the heat source and the heat sink.
  • FIG. 5(c) is a diagram showing the observation result of the ANE voltage signal by the above experimental configuration of the amorphous Sm 20 Co 80 film deposited on the PEN substrate. ing.
  • a signal showing odd dependence on the magnetic field which is a characteristic of the ANE electric field, was obtained .
  • the results obtained reflect the large coercive force and remanent magnetization of the film. That is, a finite ANE electric field is observed even at zero magnetic field.
  • FIG. 5(c) shows a schematic experimental setup for heat flux sensing.
  • An amorphous Sm 20 Co 80 thin film and a heat flow sensor are laminated between the heat source and the heat sink.
  • FIG. 5(c) is a diagram showing the observation result of the ANE voltage signal by the above experimental configuration of the a
  • FIG. 5 (d) is a diagram showing the observation results of the ANE voltage signal in the above experimental configuration of the amorphous Sm20Co80 film deposited on the PEN substrate.
  • FIG. 5(d) shows that the output voltage V ANE increases in proportion to the heat flow density J Q , and V ANE /J Q represents the sensitivity of the heat flow sensor. It was found from this that a heat flow sensor with good sensitivity and operating in zero magnetic field was obtained.
  • p _ _ _ _ is 20 and q is varied from 0 to 100 (hereinafter simply referred to as “amorphous Sm 20 (Fe q Co 100-q ) 80 composition gradient film”). (Structure and thermoelectric performance) were evaluated.
  • FIG. 6A is a schematic cross-sectional view showing a lamination state of amorphous Sm 20 (Fe q Co 100-q ) 80 (0 ⁇ q ⁇ 100) compositionally graded films, showing an embodiment of the present invention.
  • a stack having a total thickness of 1 nm in which an Sm layer with a thickness of 0.37 nm per layer and a compositionally graded layer of a compositionally graded material of Fe and Co with a thickness of 0.63 nm are laminated on an MgO substrate.
  • the body consists of 100 layers, and the uppermost layer is vapor-deposited with an aluminum thin film to prevent oxidation.
  • the composition ratio of the amorphous Sm 20 (Fe q Co 100-q ) 80 (0 ⁇ q ⁇ 100) composition gradient film changed from Sm 20 Co 80 to Sm 17 Fe 83 due to manufacturing errors.
  • FIG. 6(b) shows XRD patterns of amorphous Sm 20 (Fe q Co 100-q ) 80 (0 ⁇ q ⁇ 100) compositionally graded films at different q values.
  • the XRD patterns at this different q value confirmed the amorphous phase for all compositions.
  • FIG. 6(c) shows a cross-sectional bright field (BF)-STEM image to confirm the XRD results shown in FIG. 6(b).
  • FIG. 6(d) shows a microbeam electron diffraction pattern confirming the XRD results shown in FIG. 6(b). Also from FIGS. 6(c) and 6(d), it was confirmed that all the amorphous Sm 20 (Fe q Co 100-q ) 80 (0 ⁇ q ⁇ 100) compositionally graded films were amorphous phases.
  • the alloy composition range suitable for thermoelectric applications may be in the range of 0 ⁇ q ⁇ 100 where at least a large anomalous Nernst effect is exhibited. , the range of 0 ⁇ q ⁇ 90, which suggests the presence of a sufficiently large anomalous Nernst effect, is preferred, the range of 5 ⁇ q ⁇ 45 is more preferred, and the range of 10 ⁇ q ⁇ 35 is even more preferred.
  • an amorphous Sm 20 (Fe 23 Co 77 ) 80 film (thermoelectric) was produced as an amorphous Sm 20 (Fe q Co 100-q ) 80 (0 ⁇ q ⁇ 100) film within a preferred composition range, The thermoelectric performance of the thermoelectric generator using this was evaluated.
  • FIG. 8(a) shows a schematic diagram of the amorphous Sm20 ( Fe23Co77 ) 80 film fabrication process.
  • FIG. 8(b) shows the magnetic field dependence curve of the in-plane magnetization of the deposited Sm 20 (Fe 23 Co 77 ) 80 film. From FIG. 8B, it can be seen that the Sm 20 (Fe 23 Co 77 ) 80 film also exhibits a large coercive force and a large residual magnetization ratio to saturation magnetization when a magnetic field is applied in the plane.
  • FIG. 8(c) shows the dependence of the ANE voltage on the external magnetic field when the heater output is changed.
  • FIG. 8(d) shows the temperature gradient dependence of the ANE voltage.
  • the anomalous Nernst coefficient of the thin film of Sm 20 (Fe 23 Co 77 ) 80 composition is 1.55 ⁇ V/K. From the above, the thermoelectric body composed of the amorphous Sm p (Fe q Co 100-q ) 100-p (0 ⁇ p ⁇ 50, 0 ⁇ q ⁇ 100) film of the present invention can obtain a high thermoelectric power. I understand.
  • FIG. 9 shows a schematic of a multilayer thermopile structure using this material and another magnetic material with a giant anomalous Nernst effect, representing a second embodiment of the invention.
  • FIG. 9(a) is a diagram illustrating a multi-layer thermoelectric power generation element 30 using the thermoelectric conversion material of the present invention.
  • the multilayer thermoelectric generating element 30 shown in FIG. 9A has a substrate 33 , multilayer thermoelectric elements 31 and connecting bodies 32 arranged on the substrate 33 , and connection terminals 34 .
  • the multilayer thermoelectric body 31 is different from the first magnetic material layer 311 made of a rare earth intermetallic amorphous magnetic alloy, which is the same material as the thermoelectric body 11, and the rare earth intermetallic amorphous magnetic alloy constituting the thermoelectric body 11. It has a laminated structure including a second magnetic material layer 312 made of a magnetic material having an anomalous Nernst effect.
  • the first magnetic material layer 311 exhibits a large anomalous Nernst effect.
  • the anomalous Nernst coefficient (thermoelectric power) of the first magnetic material layer 311 is preferably 1 ⁇ V/K or more, and the anomalous Nernst coefficient need not necessarily be huge.
  • the first magnetic material layer 311 Since the first magnetic material layer 311 has a strong magnetic anisotropy in the in-plane direction of the thin film, it has a magnetization easy axis showing a large coercive force and residual magnetization ratio with respect to the in-plane magnetic field. Therefore, the first magnetic material layer 311 can generate a thermoelectromotive force with zero magnetic field. In such a first magnetic material layer 311, the coercive force is preferably 10 mT or more, and the residual magnetization ratio is preferably 0.3 or more.
  • the second magnetic material layer 312 exhibits a huge anomalous Nernst effect and is composed of a magnetic material with a huge anomalous Nernst coefficient.
  • the anomalous Nernst coefficient (thermoelectric power) of the second magnetic material layer 312 is larger than the anomalous Nernst coefficient (thermoelectric power) of the first magnetic material layer 311, and is preferably 5 ⁇ V/K or more, for example. Since the second magnetic material layer 312 has weak magnetic anisotropy in the in-plane direction, the remanent magnetization is remarkably reduced by increasing the film thickness or thinning the wire alone. Therefore, the second layer of magnetic material 312 no longer operates at zero magnetic field.
  • the second magnetic material layer 312 exhibiting a huge anomalous Nernst coefficient is formed by exchange coupling. Since it can be magnetized in one direction even in zero magnetic field, it is possible to achieve both zero magnetic field operation and a large anomalous Nernst coefficient.
  • Magnetic materials for the second magnetic material layer 312 include Fe—Ga alloys, Fe—Al alloys, Heusler alloys such as Co 2 MnGa, and antiferromagnetic materials such as YbMnBi 2 .
  • connection body 32 a rare earth intermetallic amorphous magnetic alloy such as Sm p Co 100-p (0 ⁇ p ⁇ 50) may be used. If the magnetization direction of the connection body 32 can be made opposite to the magnetization direction of the multilayer thermoelectric body 31, the connection body 32 may be composed of the same laminate as the multilayer thermoelectric body 31. In addition, the arrangement of the multilayer thermoelectric element 31 and the connector 32 may be exchanged. On the other hand, the substrate 33 is made of the same material as the substrate 13 .
  • the connection terminals 34 are made of the same material as the connection body 32 here, and are provided at both ends of the multilayer thermoelectric body 31 .
  • connection terminal 34 may be composed of the same laminate as the multilayer thermoelectric element 31 .
  • the material of the first magnetic material layer 311 is denoted as Material A
  • the material of the second magnetic material layer 312 is denoted as Material C
  • the material of the connector 32 is denoted as Material B. It is written.
  • the multilayer thermoelectric element 31 is formed by thinning a film made of a rare earth intermetallic amorphous magnetic alloy such as amorphous Sm 20 Co 80 and a different magnetic material formed on the substrate 33 . Therefore, the device shown in FIG. 9(a) is magnetized in the same direction as shown in FIG. 1(a). Therefore, due to the anomalous Nernst effect, the multilayer thermoelectric element 31 responds to the temperature difference in the direction perpendicular to the direction of magnetization (the direction of the heat flow shown in FIG. 1(a)) by the electric field shown in FIG. 1(a). (longitudinal direction of the multilayer thermoelectric element 31 and the connector 32).
  • the connecting bodies 32 are arranged on the surface of the substrate 33 in parallel with the multilayer thermoelectric bodies 31, 31, .
  • One connector 32 is arranged between a pair of adjacent multilayer thermoelectric bodies 31, 31, and the connector 32 connects one end side of one multilayer thermoelectric body 31 and the other end side of the other multilayer thermoelectric body 31. are electrically connected.
  • the multilayer thermoelectric bodies 31 are electrically connected in series by the connector 32 .
  • the multilayer thermoelectric generating element 30 has the multilayer thermoelectric element 31 composed of a rare earth intermetallic amorphous magnetic alloy such as amorphous Sm 20 Co 80 and a different magnetic material.
  • the multilayer thermoelectric body 31 composed of a rare earth intermetallic amorphous magnetic alloy such as amorphous Sm 20 Co 80 and a different magnetic material, the effective length in the electric field direction is increased to increase the thermoelectromotive force. is possible. Therefore, according to the present embodiment, by using such a multilayer thermoelectric element 31, it is possible to provide a multilayer thermoelectric generating element 30 that is easy to put into practical use.
  • FIG. 9(b) is a diagram illustrating a multi-layer thermoelectric power generation element 40 using the thermoelectric conversion material of the present invention.
  • the multilayer thermoelectric generating element 40 shown in FIG. 9B has a substrate 43 , multilayer thermoelectric bodies 41 and connecting bodies 42 arranged on the substrate 43 , and connection terminals 44 .
  • the multilayer thermoelectric element 41 includes a first magnetic material layer 412 using the same material as the thermoelectric element 11 and a second magnetic material layer using a magnetic material having a huge anomalous Nernst effect different from the thermoelectric element 11. layer 411; In the embodiment shown in FIG. 9(b), the stacking order of the first magnetic material layer 412 and the second magnetic material layer 411 is reversed compared to the embodiment shown in FIG. 9(a).
  • connection body 42 A material similar to that of the connecting body 32 is used for the connecting body 42 .
  • a material similar to that of the substrate 13 is used for the substrate 43 .
  • the connection terminals 44 are made of the same material as the connection body 42 here, and are provided at both ends of the multilayer thermoelectric body 41 .
  • the connection terminal 44 may be composed of the same laminate as the multilayer thermoelectric element 41 .
  • the connecting bodies 42 are arranged on the surface of the substrate 43 in parallel with the multilayer thermoelectric bodies 41, 41, .
  • One connecting body 42 is arranged between a pair of adjacent multilayer thermoelectric bodies 41, 41, and the connecting body 42 electrically connects one end side of one thermoelectric body 1 and the other end side of the other thermoelectric body 1. properly connected.
  • the multilayer thermoelectric elements 41 are electrically connected in series by the connector 42 .
  • the multilayer thermoelectric generating element 40 has the multilayer thermoelectric element 42 composed of a rare earth intermetallic amorphous magnetic alloy such as amorphous Sm 20 Co 80 and a different magnetic material.
  • the multilayer thermoelectric body 41 composed of amorphous Sm 20 Co 80 and a different magnetic material, it is possible to increase the thermoelectromotive force by increasing the effective length in the electric field direction. Therefore, according to the present embodiment, by using such a multilayer thermoelectric element 41, it is possible to provide a multilayer thermoelectric generating element 40 that is easy to put into practical use.
  • thermoelectric bodies 31, 41 and connecting bodies 32, 42 and other magnetic materials exhibit finite coercive force and residual magnetization.
  • a thermopile element made of a single material can be realized.
  • the magnetization of each layer can be controlled using a local magnetic field or an exchange bias effect by adding a pinning layer such as Cr.
  • thermoelectric element of the present invention by connecting the magnetic material exhibiting the anomalous Nernst effect and the connector in a zigzag pattern, the effective length in the electric field direction can be lengthened and the thermoelectromotive force can be boosted. It is suitable for use in a thermoelectric generator utilizing the anomalous Nernst effect.
  • the thermoelectric body of the present invention uses a rare earth intermetallic amorphous magnetic alloy that can be produced on any kind of substrate including flexible substrates at room temperature using magnetron sputtering, vapor deposition, or the like. Therefore, it can be used universally for various types of thermopile structures.
  • Thermoelectric bodies of the present invention can also be used to implement bendable thermoelectric generators and bendable heat flow sensors.
  • the magnetic material exhibiting the anomalous Nernst effect and the second magnetic material layer are connected in a zigzag manner to increase the effective length in the electric field direction and boost the thermoelectromotive force. is possible, and it is suitable for use in thermoelectric generation elements and heat flow sensors that utilize the anomalous Nernst effect.
  • thermoelectric generating elements 10
  • thermoelectric element 12 connecting bodies 13, 23 substrates 14, 24 terminals 22 reverse magnetization connecting bodies 30, 40 multilayer thermoelectric generating elements 31, 41, 51 multilayer thermoelectric elements 311, 412 first magnetism Material layers 312, 411 Second magnetic material layers 32, 42 Connectors 33, 43 Substrates 34, 44 Terminals

Landscapes

  • Thin Magnetic Films (AREA)
  • Hall/Mr Elements (AREA)
PCT/JP2022/036432 2021-09-30 2022-09-29 熱電体、熱電発電素子、多層熱電体、多層熱電発電素子、熱電発電機、及び熱流センサ Ceased WO2023054583A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US18/695,245 US20240284798A1 (en) 2021-09-30 2022-09-29 Thermoelectric body, thermoelectric generation element, multilayer thermoelectric body, multilayer thermoelectric generation element, thermoelectric generator, and heat flow sensor
CN202280064066.XA CN117999868A (zh) 2021-09-30 2022-09-29 热电体、热电发电元件、多层热电体、多层热电发电元件、热电发电机以及热流传感器
JP2023551845A JP7669069B2 (ja) 2021-09-30 2022-09-29 熱電体、熱電発電素子、多層熱電体、多層熱電発電素子、熱電発電機、及び熱流センサ

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021160834 2021-09-30
JP2021-160834 2021-09-30

Publications (1)

Publication Number Publication Date
WO2023054583A1 true WO2023054583A1 (ja) 2023-04-06

Family

ID=85782891

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/036432 Ceased WO2023054583A1 (ja) 2021-09-30 2022-09-29 熱電体、熱電発電素子、多層熱電体、多層熱電発電素子、熱電発電機、及び熱流センサ

Country Status (4)

Country Link
US (1) US20240284798A1 (https=)
JP (1) JP7669069B2 (https=)
CN (1) CN117999868A (https=)
WO (1) WO2023054583A1 (https=)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025047008A1 (ja) * 2023-08-25 2025-03-06 国立研究開発法人物質・材料研究機構 ハイブリッド横型熱電温度変調素子およびこれを用いた温度変調方法
WO2025047007A1 (ja) * 2023-08-25 2025-03-06 国立研究開発法人物質・材料研究機構 ハイブリッド横型熱電発電素子およびこれを用いた発電方法
JPWO2025062936A1 (https=) * 2023-09-19 2025-03-27
WO2025115805A1 (ja) * 2023-12-01 2025-06-05 Ｓｅｍｉｔｅｃ株式会社 熱電デバイス及び積層体
WO2025159210A1 (ja) * 2024-01-27 2025-07-31 国立大学法人東北大学 デバイス、評価方法、評価装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018180800A1 (ja) * 2017-03-31 2018-10-04 日本電気株式会社 温度拡散係数計測装置、それを用いた深部体温計、深部体温計測装置、および深部体温計測方法
WO2019064972A1 (ja) * 2017-09-28 2019-04-04 日本電気株式会社 熱電変換素子
WO2020218613A1 (ja) * 2019-04-26 2020-10-29 国立大学法人東京大学 熱電変換素子及び熱電変換装置

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2909891A1 (de) * 1979-03-14 1980-09-25 Basf Ag Magnetischer aufzeichnungstraeger
US20080236441A1 (en) * 2006-10-13 2008-10-02 Ken Nobe Aqueous eletrodeposition of magnetic cobalt-samarium alloys
US9242295B2 (en) * 2007-12-21 2016-01-26 The Univeristy Of Texas At Arlington Bulk nanocomposite magnets and methods of making bulk nanocomposite magnets
US20120024333A1 (en) * 2010-07-29 2012-02-02 The Regents Of The University Of California Thermoelectric material deformed by cryogenic impact and method of preparing the same
JP2014216333A (ja) * 2013-04-22 2014-11-17 株式会社東芝 熱電変換素子
WO2021187347A1 (ja) * 2020-03-19 2021-09-23 国立研究開発法人物質・材料研究機構 垂直型熱電変換素子、並びにこれを用いた熱電発電応用機器又は熱流センサー

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018180800A1 (ja) * 2017-03-31 2018-10-04 日本電気株式会社 温度拡散係数計測装置、それを用いた深部体温計、深部体温計測装置、および深部体温計測方法
WO2019064972A1 (ja) * 2017-09-28 2019-04-04 日本電気株式会社 熱電変換素子
WO2020218613A1 (ja) * 2019-04-26 2020-10-29 国立大学法人東京大学 熱電変換素子及び熱電変換装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANDO RYO, TAKASHI KOMINE: "Composition dependence of transport properties in TbFeCo magnetic thin films", THE 66TH JSAP SPRING MEETING 2019 [LECTURE PREPRINTS], 1 January 2019 (2019-01-01), pages 10, XP093054483 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025047008A1 (ja) * 2023-08-25 2025-03-06 国立研究開発法人物質・材料研究機構 ハイブリッド横型熱電温度変調素子およびこれを用いた温度変調方法
WO2025047007A1 (ja) * 2023-08-25 2025-03-06 国立研究開発法人物質・材料研究機構 ハイブリッド横型熱電発電素子およびこれを用いた発電方法
JPWO2025062936A1 (https=) * 2023-09-19 2025-03-27
WO2025062936A1 (ja) * 2023-09-19 2025-03-27 国立研究開発法人物質・材料研究機構 熱電積層体及び熱電装置
WO2025115805A1 (ja) * 2023-12-01 2025-06-05 Ｓｅｍｉｔｅｃ株式会社 熱電デバイス及び積層体
WO2025159210A1 (ja) * 2024-01-27 2025-07-31 国立大学法人東北大学 デバイス、評価方法、評価装置

Also Published As

Publication number Publication date
JP7669069B2 (ja) 2025-04-28
US20240284798A1 (en) 2024-08-22
CN117999868A (zh) 2024-05-07
JPWO2023054583A1 (https=) 2023-04-06

Similar Documents

Publication Publication Date Title
JP7669069B2 (ja) 熱電体、熱電発電素子、多層熱電体、多層熱電発電素子、熱電発電機、及び熱流センサ
Mizuguchi et al. Energy-harvesting materials based on the anomalous Nernst effect
JP6233320B2 (ja) 熱電変換素子及びその製造方法
CN103081109B (zh) 自旋器件、其驱动方法及其制造方法
KR20140021544A (ko) 조셉슨 자기 스위치
WO2021187347A1 (ja) 垂直型熱電変換素子、並びにこれを用いた熱電発電応用機器又は熱流センサー
WO2017082266A1 (ja) 熱電変換素子用起電膜及び熱電変換素子
WO2018146713A1 (ja) 熱電変換素子およびその製造方法
JP6066091B2 (ja) 熱電変換素子及びその製造方法
JP6565689B2 (ja) 熱電変換素子、熱電変換素子モジュールおよび熱電変換素子の製造方法
US9306153B2 (en) Thermoelectric conversion element and method for manufacturing the same
Liu et al. Thermally assisted electric field control of magnetism in flexible multiferroic heterostructures
Dabas et al. Cutting-edge technologies and recent modernization on multifunctional perovskite materials for green energy conversion and spintronic applications
WO2022264940A1 (ja) 熱電発電デバイス
JP2014072250A (ja) 熱電変換素子及びその製造方法
JP6349863B2 (ja) スピン流熱電変換素子とその製造方法および熱電変換装置
JP7815834B2 (ja) 熱電変換素子
WO2019124257A1 (ja) 熱電変換素子
Kurokawa et al. All chemically fabricated Co-Pt nanoparticle spin thermoelectric generator on plastic sheet
JP2008071720A (ja) バッテリー、バッテリーシステムおよびマイクロ波発信装置
Uchida et al. Spin Seebeck Effect in Ni $ _ {81} $ Fe $ _ {19} $/Pt Thin Films With Different Widths
Daqiq Thermopower of double-barrier magnetic tunnel junctions with a middle La0. 7Sr0. 3MnO3 layer
JP6172439B2 (ja) スピン流熱電変換素子
JP2015185778A (ja) 熱電変換素子及びその製造方法
Modak et al. Large Anomalous Nernst Conductivity in Pt2CoNi Permanent Magnet Films with High In‐Plane and Out‐Of‐Plane Coercivities

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22876447

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202280064066.X

Country of ref document: CN

Ref document number: 2023551845

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 18695245

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22876447

Country of ref document: EP

Kind code of ref document: A1