WO2023054416A1 - 熱電変換素子及びセンサ - Google Patents

熱電変換素子及びセンサ Download PDF

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Publication number
WO2023054416A1
WO2023054416A1 PCT/JP2022/036045 JP2022036045W WO2023054416A1 WO 2023054416 A1 WO2023054416 A1 WO 2023054416A1 JP 2022036045 W JP2022036045 W JP 2022036045W WO 2023054416 A1 WO2023054416 A1 WO 2023054416A1
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Prior art keywords
thermoelectric conversion
conversion element
wiring
less
element according
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PCT/JP2022/036045
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English (en)
French (fr)
Japanese (ja)
Inventor
愛美 黒瀬
陽介 中西
宏和 田中
広宣 待永
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to KR1020247010503A priority Critical patent/KR20240070551A/ko
Priority to US18/695,936 priority patent/US20250008841A1/en
Priority to CN202280065515.2A priority patent/CN118044356A/zh
Priority to EP22876282.9A priority patent/EP4412437A4/en
Priority to JP2023551564A priority patent/JPWO2023054416A1/ja
Publication of WO2023054416A1 publication Critical patent/WO2023054416A1/ja
Anticipated expiration legal-status Critical
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    • 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
    • H10N15/20—Thermomagnetic devices using thermal change of the magnetic permeability, e.g. working above and below the Curie point
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N19/00—Integrated devices, or assemblies of multiple devices, comprising at least one thermoelectric or thermomagnetic element covered by groups H10N10/00 - H10N15/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices

Definitions

  • the present invention relates to thermoelectric conversion elements and sensors.
  • Patent Document 1 describes a thermoelectric power generation device that utilizes the anomalous Nernst effect.
  • the anomalous Nernst effect is a phenomenon in which a voltage is generated in a direction orthogonal to both the magnetization direction and the temperature gradient when a heat flow is applied to a magnetic material and a temperature difference is generated.
  • thermoelectric power generation device has a substrate, a power generation body, and a connection body.
  • the power generating body consists of a plurality of thin wires arranged parallel to each other along the surface of the substrate.
  • the power generator is configured to generate power with a temperature difference in the direction perpendicular to the magnetization direction due to the anomalous Nernst effect.
  • the connector consists of a plurality of thin wires arranged parallel to and between the thin wires of the power generator along the surface of the substrate. Each thin wire of the connector electrically connects one end of each thin wire of the power generating body and the other end of the adjacent thin wire on one side of each thin wire.
  • the connection body electrically connects each thin wire of the power generation body in series.
  • the connector is made of, for example, non-magnetic Cr.
  • thermoelectric conversion elements for heat sensing.
  • thermoelectric conversion elements using magnetic thermoelectric conversion such as the thermoelectric conversion device described in Patent Document 1
  • thermoelectric power generation devices using the Seebeck effect thermoelectric conversion elements using the Seebeck effect
  • thermoelectric conversion device In the thermoelectric conversion device described in Patent Document 1, the power generator is configured to generate power by the temperature difference in the direction perpendicular to the direction of magnetization.
  • a thermoelectric conversion element using magnetic thermoelectric conversion it is assumed that an electromotive force is generated by a mechanism different from that of magnetic thermoelectric conversion.
  • the thermoelectric conversion device described in Patent Document 1 if a temperature gradient occurs in the longitudinal direction of the thin wire of the power generator made of the FePt thin film and the thin wire of the connecting member made of non-magnetic Cr, the Seebeck coefficient of FePt and the Cr Due to the difference from the Seebeck coefficient, a thermoelectromotive force associated with the Seebeck effect may occur in the longitudinal direction.
  • thermoelectromotive force is advantageous from the viewpoint of the accuracy of heat sensing. This is because the electromotive force due to the Seebeck effect is superimposed on the electromotive force due to magneto-thermoelectric conversion.
  • a connection body made up of a plurality of fine wires is electrically connected in series with a power generation body made up of a plurality of fine wires. ing. In such a configuration, the electromotive force associated with the Seebeck effect tends to increase, which may greatly affect the accuracy of heat sensing.
  • the present invention provides a thermoelectric conversion element that is advantageous from the viewpoint of improving the accuracy of heat sensing while using magnetic thermoelectric conversion.
  • the present invention a linearly extending magnetic thermoelectric conversion body; and a wiring electrically connected to the magnetic thermoelectric conversion body,
  • the absolute value of the difference between the Seebeck coefficient Sm in the longitudinal direction of the magnetic thermoelectric converter and the Seebeck coefficient Sc in the longitudinal direction of the wiring is 10 ⁇ V/K or less.
  • a thermoelectric conversion element is provided.
  • thermoelectric conversion element is advantageous from the viewpoint of improving the accuracy of heat sensing while using magnetic thermoelectric conversion.
  • FIG. 1 is a perspective view showing an example of an embodiment of a thermoelectric conversion element.
  • FIG. 2 is a cross-sectional view of the thermoelectric conversion element taken along plane II shown in FIG.
  • FIG. 3 is a cross-sectional view showing another example of the thermoelectric conversion element.
  • FIG. 4 is a cross-sectional view showing still another example of the thermoelectric conversion element.
  • the thermoelectric conversion element 1 a includes a magnetic thermoelectric conversion body 11 and wiring 12 .
  • the magnetic thermoelectric converter 11 extends linearly.
  • the wiring 12 is electrically connected to the magneto-thermoelectric converter 11 .
  • of the difference between the Seebeck coefficient Sm in the longitudinal direction of the magnetic thermoelectric converter 11 and the Seebeck coefficient Sc in the longitudinal direction of the wiring 12 is 10 ⁇ V/K or less.
  • the Seebeck coefficient Sm and the Seebeck coefficient Sc are, for example, values at 25 to 40° C., and can be measured according to the method described in Examples.
  • the X, Y and Z axes are orthogonal to each other.
  • the magneto-thermoelectric converters 11 and the wirings 12 are arranged, for example, along a plane parallel to the XY plane.
  • thermoelectric conversion element 1a when a temperature gradient occurs in the longitudinal direction (Y-axis direction) of the magnetic thermoelectric conversion body 11, the difference between the Seebeck coefficient Sm and the Seebeck coefficient Sc results in a thermoelectric rise due to the Seebeck effect in the longitudinal direction. Electricity can be generated.
  • is 10 ⁇ V/K or less. tends to be small. Therefore, in sensing using the thermoelectric conversion element 1a, the electromotive force due to the Seebeck effect superimposed on the electromotive force due to magnetic thermoelectric conversion tends to be small. As a result, the thermoelectric conversion element 1a is advantageous from the viewpoint of realizing highly accurate heat sensing using magnetic thermoelectric conversion.
  • may be 9.5 ⁇ V/K or less, 9.0 ⁇ V/K or less, 8.5 ⁇ V/K or less, or 8.0 ⁇ V/K or less. It may be less than or equal to 7.5 ⁇ V/K, or less than or equal to 7.0 ⁇ V/K.
  • may be 6.5 ⁇ V/K or less, 6.0 ⁇ V/K or less, 5.5 ⁇ V/K or less, or 5.0 ⁇ V/K or less. There may be.
  • may be 4.5 ⁇ V/K or less, 4.0 ⁇ V/K or less, 3.5 ⁇ V/K or less, or 3.0 ⁇ V/K or less.
  • may be 1.5 ⁇ V/K or less, 1.0 ⁇ V/K or less, 0.8 ⁇ V/K or less, or 0.5 ⁇ V/K or less. 0.3 ⁇ V/K or less, or 0.2 ⁇ V/K or less.
  • is not limited to a specific value.
  • is, for example, 0.01 ⁇ V/K or more, may be 0.05 ⁇ V/K or more, may be 0.1 ⁇ V/K or more, or may be 0.2 ⁇ V/K or more may be 0.5 ⁇ V/K or more, or 1.0 ⁇ V/K or more.
  • the relationship between the signs of the Seebeck coefficient Sm and the Seebeck coefficient Sc is not limited to a specific relationship as long as the absolute value
  • the Seebeck coefficient Sm and the Seebeck coefficient Sc for example, have values of the same sign. This tends to reduce the absolute value
  • the Seebeck coefficient Sm and the Seebeck coefficient Sc may have values of different signs.
  • the Seebeck coefficient Sc is not limited to a specific value.
  • the Seebeck coefficient Sc has a value of 0 or less, for example.
  • the Seebeck coefficient Sc is, for example, 0 ⁇ V/K or less, may be ⁇ 5 ⁇ V/K or less, may be ⁇ 10 ⁇ V/K or less, may be ⁇ 15 ⁇ V/K or less, may be ⁇ 20 ⁇ V/K or less. It may be K or less.
  • the Seebeck coefficient Sc is, for example, -50 ⁇ V/K or more.
  • the Seebeck coefficient Sc may be a positive value, for example, 1 ⁇ V/K or more, 3 ⁇ V/K or more, 5 ⁇ V/K or more, or 10 ⁇ V/K or more. There may be.
  • the Seebeck coefficient Sm is not limited to a specific value.
  • the Seebeck coefficient Sm is, for example, 0 ⁇ V/K or less, may be ⁇ 5 ⁇ V/K or less, may be ⁇ 10 ⁇ V/K or less, or may be ⁇ 15 ⁇ V/K or less.
  • the Seebeck coefficient Sm is -50 ⁇ V/K or more, for example.
  • the Seebeck coefficient Sm may be a positive value, for example, 1 ⁇ V/K or more, 3 ⁇ V/K or more, 5 ⁇ V/K or more, or 10 ⁇ V/K or more. There may be.
  • of the Seebeck coefficient Sm is desirably 10 ⁇ V or more.
  • the magnetic thermoelectric coefficient tends to increase, and the thermoelectric conversion performance of the thermoelectric conversion element 1a tends to increase.
  • may be 15 ⁇ V or more, or may be 20 ⁇ V or more.
  • the resistivity of the wiring 12 is not limited to a specific value.
  • the wiring 12 has a specific resistance of 8 to 200 ⁇ cm, for example. This facilitates adjustment of the Seebeck coefficient Sc to a desired range. In addition, even if the wiring 12 is made thin, it is easy to reduce the resistance.
  • the specific resistance of the wiring 12 may be 10 ⁇ cm or more, 15 ⁇ cm or more, 20 ⁇ cm or more, 25 ⁇ cm or more, or 30 ⁇ cm. or more.
  • the specific resistance of the wiring 12 may be 180 ⁇ -cm or less, 150 ⁇ -cm or less, 140 ⁇ -cm or less, 130 ⁇ -cm or less, or 120 ⁇ -cm. or less, 110 ⁇ cm or less, or 100 ⁇ cm or less.
  • the material forming the wiring 12 is not limited to a specific material.
  • the wiring 12 contains at least one metal selected from the group consisting of Cu, Ag, Au, Al, Ni, and Co, for example.
  • the content of these metals in the wiring 12 is 50% or more based on the number of atoms.
  • the total content of Cu, Ag, Au, Al, Ni, and Co in the wiring 12 is 50% or more based on the number of atoms.
  • the wiring 12 may be made of a single metal, or may be made of an alloy.
  • the wiring 12 is composed of at least one metal selected from the group consisting of Cu, Ag, Au, and Al, and at least one metal selected from the group consisting of Group 8 elements, Group 9 elements, and Group 10 elements. element.
  • the Seebeck coefficient Sc of the alloy tends to fluctuate over a wide range from positive values to negative values depending on the composition, and the Seebeck coefficient Sc is easily adjusted to a desired value.
  • the Group 8 element is, for example, Fe.
  • a group 9 element is Co, for example.
  • Group 10 elements are, for example, Ni or Pt.
  • the content of at least one element selected from the group consisting of Group 8 elements, Group 9 elements, and Group 10 elements in the wiring 12 is not limited to a specific value. The content may be 1% or more, 3% or more, 5% or more, 10% or more, or 20% or more based on the number of atoms. may be 30% or more, 40% or more, or 50% or more.
  • the magnetic thermoelectric converter 11 is not limited to a specific material.
  • the magneto-thermoelectric converter 11 generates an electromotive force by the magneto-thermoelectric effect.
  • the magneto-thermoelectric effect is, for example, the anomalous Nernst effect or the spin Seebeck effect.
  • the magneto-thermoelectric converter 11 contains, for example, a material exhibiting the anomalous Nernst effect. Substances exhibiting the anomalous Nernst effect are not limited to specific substances. A material exhibiting the anomalous Nernst effect is, for example, a magnetic material having a saturation magnetic susceptibility of 5 ⁇ 10 ⁇ 3 T or more or a material having a band structure having a Weyl point near the Fermi energy.
  • the magneto-thermoelectric converter 11 includes at least one substance selected from the group consisting of the following (i), (ii), (iii), (iv), and (v) as the substance exhibiting the anomalous Nernst effect. contains.
  • a stoichiometric substance having a composition represented by Fe 3 X (ii) an off-stoichiometric substance in which the composition ratio of Fe and X deviates from the substance (i) above (iii) the above ( A substance (iv) Fe 3 M1 1-x M2 x (iv) in which a part of the Fe site of the substance i) or part of the Fe site of the substance (ii) is replaced with a typical metal element other than X or a transition element (v) a substance having a composition represented by 0 ⁇ x ⁇ 1), wherein M1 and M2 are different representative elements; , a substance in which a part of the X site of the substance (i) above is replaced with a main group metal element other than X
  • X is a typical element or a transition element.
  • X is, for example, Al, Ga, Ge, Sn, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Sc, Ni, Mn, or Co.
  • the combination of M1 and M2 is not limited to a specific combination as long as M1 and M2 are representative elements different from each other.
  • the combination of M1 and M2 is Ga and Al, Si and Al, or Ga and B, for example.
  • the magneto-thermoelectric converter 11 may contain Co 2 MnGa as a substance exhibiting the anomalous Nernst effect, and may contain Mn 3 Sn, which is an antiferromagnetic substance.
  • the magneto-thermoelectric converter 11 may be an alloy containing Fe and having a body-centered cubic crystal structure. In this case, the magneto-thermoelectric converter 11 tends to generate a large electromotive force based on the anomalous Nernst effect.
  • the magneto-thermoelectric converter 11 is an alloy containing Fe and having a body-centered cubic lattice crystal structure
  • the content of Fe and the content of elements other than Fe in the alloy are not limited to specific values.
  • the content of Fe in the alloy is, for example, 50% or more based on the number of atoms
  • the content of elements other than Fe in the alloy is, for example, 10% or more based on the number of atoms.
  • the magneto-thermoelectric converter 11 tends to generate a large electromotive force based on the anomalous Nernst effect.
  • the content of Fe in the above alloy may be 55% or more, 60% or more, 65% or more, or 70% or more, based on the number of atoms. .
  • the content of Fe in the above alloy is 90% or less, may be 85% or less, or may be 80% or less, based on the number of atoms.
  • the content of elements other than Fe in the above alloy may be 15% or more, or 20% or more, based on the number of atoms.
  • the content of elements other than Fe in the above alloy is 50% or less, may be 40% or less, or may be 30% or less, based on the number of atoms.
  • the magnetic thermoelectric coefficient S NE of the magnetic thermoelectric converter 11 is not limited to a specific value.
  • the absolute value of the magnetic thermoelectric coefficient S NE of the magnetic thermoelectric converter 11 is, for example, 0.5 ⁇ V/K or more. As a result, a large electromotive force is likely to be generated by the magnetic thermoelectric conversion in the magnetic thermoelectric converter 11, and the accuracy of sensing using the thermoelectric conversion element 1a is likely to be improved. Therefore, minute heat is easily detected.
  • the absolute value of the magnetic thermoelectric coefficient S NE of the magnetic thermoelectric converter 11 is preferably 1.0 ⁇ V/K or more, more preferably 1.5 ⁇ V/K or more, and still more preferably 2.0 ⁇ V/K or more. .
  • the absolute value of the magnetic thermoelectric coefficient S NE of the magnetic thermoelectric converter 11 may be 3.0 ⁇ V/K or more, 4.0 ⁇ V/K or more, or 5.0 ⁇ V/K or more. It may be 6.0 ⁇ V/K or more, 7.0 ⁇ V/K or more, or 8.0 ⁇ V/K or more.
  • the magnetic thermoelectric converter 11 has a plurality of first thin wires 11a.
  • the wiring 12 has a plurality of second thin wires 12a.
  • the thermoelectric conversion element 1a the plurality of first fine wires 11a and the plurality of second fine wires 12a are electrically connected in series. According to such a configuration, the electromotive forces accompanying the magnetic thermoelectric conversion generated in the plurality of first fine wires 11a are synthesized, and a large output can be easily obtained from the thermoelectric conversion element 1a.
  • thermoelectric conversion element 1a the plurality of first thin wires 11a and the plurality of second thin wires 12a form, for example, a plurality of thin wire pairs 15.
  • Each thin line pair 15 consists of a first thin line 11a and a second thin line 12a.
  • each thin wire pair 15 consists of one first thin wire 11a and one second thin wire 12a.
  • the number of thin wire pairs 15 in thermoelectric conversion element 1a is not limited to a specific value.
  • the plurality of first fine wires 11a and the plurality of second fine wires 12a form 50 or more fine wire pairs 15, for example.
  • the electromotive force due to the Seebeck effect increases as the number of pairs of joined dissimilar materials increases.
  • thermoelectric conversion element 1a the absolute value
  • the plurality of first fine lines 11a and the plurality of second fine lines 12a form a meander pattern. According to such a configuration, even if the area of the plane on which the plurality of first fine wires 11a and the plurality of second fine wires 12a are arranged is small, it is easy to obtain a large output from the thermoelectric conversion element 1a.
  • the plurality of first thin wires 11a are, for example, separated at predetermined intervals in the X-axis direction and arranged parallel to each other.
  • the plurality of first thin wires 11a are arranged at regular intervals in the X-axis direction.
  • the plurality of second thin wires 12a electrically connect, for example, first thin wires 11a adjacent to each other in the X-axis direction.
  • the second thin line 12a electrically connects, for example, one end of the first thin line 11a in the Y-axis direction and the other end in the Y-axis direction of another first thin line 11a adjacent to the first thin line 11a. ing.
  • One end of the plurality of first fine lines 11a in the Y-axis direction is located at the end of the first fine line 11a on the same side in the Y-axis direction, and the other end of the plurality of first fine lines 11a in the Y-axis direction is located at , at the end opposite to the one end in the Y-axis direction of the first thin wire 11a.
  • the thickness of the first fine wire 11a is not limited to a specific value.
  • the first thin wire 11a has a thickness of 1000 nm or less, for example. This makes it possible to reduce the amount of material used for forming the magnetic thermoelectric converter in the thermoelectric conversion element 1a, thereby easily reducing the manufacturing cost of the thermoelectric conversion element 1a. In addition, disconnection of the conductive paths formed by the plurality of first fine wires 11a and the plurality of second fine wires 12a in the thermoelectric conversion element 1a is less likely to occur.
  • the thickness of the first fine wire 11a may be 750 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, or 200 nm or less.
  • the thickness of the first thin wire 11a is, for example, 5 nm or more. This makes it easy for the thermoelectric conversion element 1a to exhibit high durability.
  • the thickness of the first thin wire 11a may be 10 nm or more, 20 nm or more, 30 nm or more, or 50 nm or more.
  • the width which is the dimension of the first thin wire 11a in the X-axis direction, is not limited to a specific value.
  • the width of the first thin wire 11a is, for example, 500 ⁇ m or less. This makes it possible to reduce the amount of material used for forming the magnetic thermoelectric converter in the thermoelectric conversion element 1a, thereby easily reducing the manufacturing cost of the thermoelectric conversion element 1a. In addition, it is easy to arrange a large number of first thin wires 11a in the X-axis direction, and the electromotive force generated by magneto-thermoelectric conversion in the thermoelectric conversion element 1a tends to increase.
  • the width of the first thin wire 11a may be 400 ⁇ m or less, 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, or 50 ⁇ m or less.
  • the width of the first thin wire 11a is, for example, 0.1 ⁇ m or more.
  • the width of the first fine line 11a may be 0.5 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more, It may be 20 ⁇ m or more, or may be 30 ⁇ m or more.
  • the thickness of the second fine wire 12a is not limited to a specific value.
  • the thickness of the second thin wire 12a is, for example, 1000 nm or less.
  • the thickness of the second thin wire 12a may be 750 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, or 100 nm or less. may be
  • the thickness of the second fine wire 12a is, for example, 5 nm or more. This makes it easy for the thermoelectric conversion element 1a to exhibit high durability.
  • the thickness of the second thin wire 12a may be 10 nm or more, 20 nm or more, 30 nm or more, or 50 nm or more.
  • the width which is the maximum dimension in the X-axis direction of the second thin wire 12a, is not limited to a specific value.
  • the width of the second fine line 12a is, for example, 500 ⁇ m or less.
  • the amount of material used for forming the wiring 12 in the thermoelectric conversion element 1a can be reduced, and the manufacturing cost of the thermoelectric conversion element 1a can be easily reduced.
  • the width of the second thin wire 12a may be 400 ⁇ m or less, 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, or 50 ⁇ m or less.
  • the width of the second fine line 12a is, for example, 0.1 ⁇ m or more. As a result, disconnection of the conductive path is less likely to occur in the thermoelectric conversion element 1a, and the thermoelectric conversion element 1a tends to exhibit high durability.
  • the width of the second fine line 12a may be 0.5 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more, It may be 20 ⁇ m or more, or may be 30 ⁇ m or more.
  • thermoelectric conversion element 1a further includes a substrate 20 as shown in FIG.
  • the magneto-thermoelectric converter 11 and the wiring 12 are arranged on the substrate 20 .
  • the material forming the base material 20 is not limited to a specific material.
  • the base material 20 does not contain MgO in the surface layer, for example. As a result, it is not necessary to add MgO to the surface layer of the base material 20, so the production of the thermoelectric conversion element 1a is less complicated, and acid resistance is easily obtained.
  • the base material 20 has flexibility, for example. In this case, the shape of the object to which the thermoelectric conversion element 1a can be attached is less likely to be restricted.
  • the substrate 20 contains at least an organic polymer, for example. Thereby, it is easy to reduce the manufacturing cost of the thermoelectric conversion element 1a.
  • organic polymers are polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin (PMMA), polycarbonate (PC), polyimide (PI) or cycloolefin polymer (COP).
  • Substrate 20 may be ultra-thin glass.
  • An example of ultra-thin glass is G-Leaf (registered trademark) manufactured by Nippon Electric Glass Co., Ltd.
  • thermoelectric conversion element 1a An example of a method for manufacturing the thermoelectric conversion element 1a will be described.
  • a precursor of the magnetic thermoelectric converter 11 is applied to one main surface of the base material 20 by a method such as sputtering, chemical vapor deposition (CVD), pulsed laser deposition (PLD), ion plating, and plating.
  • CVD chemical vapor deposition
  • PLD pulsed laser deposition
  • ion plating ion plating
  • a thin film of a precursor of the wiring 12 is formed on one main surface of the substrate 20 by sputtering, CVD, PLD, ion plating, plating, or the like.
  • a photoresist is applied on the thin film of the precursor of the wiring 12, a photomask is placed on the thin film of the precursor of the wiring 12, exposure is performed, and then wet etching is performed.
  • the wiring 12 is obtained, and the linear patterns of the precursor of the magnetic thermoelectric converter 11 are electrically connected to each other.
  • the magnetic thermoelectric converter 11 is formed by magnetizing the precursor of the magnetic thermoelectric converter 11 .
  • the thermoelectric conversion element 1a is obtained.
  • the precursor of wiring 12 may be magnetized to form wiring 12 .
  • the thermoelectric conversion element 1a may be provided with, for example, an adhesive layer.
  • the substrate 20 is arranged between the magnetic thermoelectric converter 11 and the adhesive layer in the thickness direction of the substrate 20 .
  • the thermoelectric conversion element 1a can be attached to the article by pressing the adhesive layer against the article.
  • the adhesive layer contains, for example, a rubber-based adhesive, an acrylic adhesive, a silicone-based adhesive, or a urethane-based adhesive.
  • Thermoelectric conversion element 1a may be provided with an adhesive layer and a release liner.
  • the release liner covers the adhesive layer.
  • a release liner is typically a film that can retain the adhesive strength of the adhesive layer when covering the adhesive layer and that can be easily peeled from the adhesive layer.
  • the release liner is, for example, a film made of polyester resin such as PET. By peeling off the release liner, the adhesive layer is exposed, and the thermoelectric conversion element 1a can be attached to the article.
  • thermoelectric conversion element 1a A sensor equipped with the thermoelectric conversion element 1a can be provided.
  • this sensor for example, when a temperature gradient occurs in the thickness direction of the base material 20, an electromotive force is generated in the longitudinal direction of the magneto-thermoelectric converter 11 due to the magneto-thermoelectric effect.
  • the sensor can sense heat by processing the electric signal output to the outside of the thermoelectric conversion element 1a based on this electromotive force.
  • thermoelectric conversion element 1a can be changed from various points of view.
  • the thermoelectric conversion element 1a may be changed, for example, into a thermoelectric conversion element 1b shown in FIG. 3 or a thermoelectric conversion element 1c shown in FIG.
  • the thermoelectric conversion elements 1b and 1c are constructed in the same manner as the thermoelectric conversion element 1a, except for the parts that are particularly described.
  • Components of the thermoelectric conversion elements 1b and 1c that are the same as or correspond to the components of the thermoelectric conversion element 1a are denoted by the same reference numerals, and detailed description thereof will be omitted.
  • the description regarding the thermoelectric conversion element 1a also applies to the thermoelectric conversion elements 1b and 1c unless technically contradictory.
  • the magnetic thermoelectric conversion body 11 extends continuously on the same plane, for example.
  • the wiring 12 is arranged on part of the magneto-thermoelectric converter 11 .
  • the plurality of second fine wires 12a are arranged on the magnetic thermoelectric converter 11 at predetermined intervals.
  • the magnetic thermoelectric conversion body 11 has, for example, a meander pattern.
  • the thermoelectric conversion element 1b is configured such that a single layer of the magnetic thermoelectric conversion body 11 and a laminated body including the magnetic thermoelectric conversion body 11 and the second fine wire 12a appear alternately in the X-axis direction.
  • the wiring 12 extends continuously on the same plane, for example.
  • the magneto-thermoelectric converter 11 is arranged on part of the wiring 12 .
  • the plurality of first thin wires 11a are arranged on the wiring 12 at predetermined intervals from each other. With such a configuration, the thermoelectromotive force associated with the Seebeck effect tends to be small. Moreover, it is easy to reduce the manufacturing cost.
  • the wiring 12 forms, for example, a meander pattern.
  • the thermoelectric conversion element 1c is configured such that a single layer of the wiring 12 and a laminated body including the wiring 12 and the first thin wires 11a appear alternately in the X-axis direction.
  • thermoelectric conversion element A thermoelectric conversion element according to each example and each comparative example was fixed between a pair of Cu plates having dimensions of 30 mm, 30 mm, and 5 mm using Shin-Etsu Chemical Co., Ltd.'s silicone grease KS609, and the thermoelectric properties were measured. A sample for evaluation was produced. The sample was placed on the cooling plate SCP-125 from AS ONE. A film heater manufactured by Shinwa Kiseki Co., Ltd. was fixed on the upper Cu plate with double-sided tape No. 5000NS manufactured by Nitto Denko. The heater had dimensions of 30 mm square and an electrical resistance of 20 ohms.
  • thermoelectric conversion element In the plane of the thermoelectric conversion element according to each example and each comparative example, one longitudinal end of the thermoelectric conversion thin wire and wiring was heated by a heater, and the temperature between both ends of the thermoelectric conversion thin wire and wiring in the longitudinal direction was 1°C. of temperature difference. In this state, the electromotive force Vs associated with the Seebeck effect was measured. In this measurement, the temperature of both surfaces of the thermoelectric conversion element was kept constant so as not to generate a temperature gradient in the thickness direction of the thermoelectric conversion element except at one end in the longitudinal direction of the thermoelectric conversion fine wire and wiring. Table 1 shows the results.
  • PET polyethylene terephthalate
  • a CuNi thin film having a thickness of 100 nm was formed by DC magnetron sputtering using a target material containing Cu and Ni.
  • the atomic ratio of Cu content:Ni content was 95:5.
  • a photoresist was applied on the CuNi thin film, a photomask was placed on the CuNi thin film, exposure was performed, and then wet etching was performed. Thereby, a wiring having a width of 40 ⁇ m was formed.
  • a plurality of thin wires for magnetic thermoelectric conversion were electrically connected in series.
  • the plurality of thin wires for magneto-thermoelectric conversion and this wiring formed a meander pattern.
  • thermoelectric conversion element according to Example 1 was obtained by magnetizing the thin wire for magnetic thermoelectric conversion in a direction parallel to the plane of the PET film and perpendicular to the longitudinal direction of the thin wire for magnetic thermoelectric conversion. This thermoelectric conversion element generated an electromotive force based on the anomalous Nernst effect.
  • thermoelectric conversion element according to Example 5 was produced in the same manner as in Example 1, except that the wiring was formed using Ni as a target material.
  • a thermoelectric conversion element according to Example 12 was produced in the same manner as in Example 1 except for the above.
  • a thermoelectric conversion element according to Example 13 was produced in the same manner as in Example 1 except for the above.
  • thermoelectric conversion element according to Comparative Example 1 was produced in the same manner as in Example 1, except that the wiring was formed using Cu as a target material.
  • thermoelectric conversion element according to Comparative Example 2 was produced in the same manner as in Example 1, except that a thin wire for thermoelectric conversion was formed using a target material containing Fe and Pt, and wiring was formed using Cr as a target material. .
  • This thermoelectric conversion element generated an electromotive force based on the anomalous Nernst effect.
  • thermoelectric conversion element according to Comparative Example 3 was produced in the same manner as in Example 1, except that the wiring was formed using Au as a target material.
  • thermoelectric conversion element according to Comparative Example 4 was fabricated in the same manner as in Example 1, except that a Co 2 MnGa target was used instead of the target material containing Fe and Ga, and the wiring was formed using Au as the target material. made.
  • the Seebeck electromotive force Vs in the thermoelectric conversion element according to each example was lower than the Seebeck electromotive force Vs in the thermoelectric conversion element according to each comparative example. Since the absolute value of the difference between the Seebeck coefficient Sm in the longitudinal direction of the thin wire for magnetic thermoelectric conversion and the Seebeck coefficient Sc in the longitudinal direction of the wiring is 10 ⁇ V/K or less, the Seebeck electromotive force Vs can be reduced, and the thickness direction of the thermoelectric conversion element can be reduced. It is understood to be advantageous from the point of view of increasing the accuracy of the measurement of the temperature difference in .
  • a first aspect of the present invention is a linearly extending magnetic thermoelectric conversion body; and a wiring electrically connected to the magnetic thermoelectric conversion body,
  • the absolute value of the difference between the Seebeck coefficient Sm in the longitudinal direction of the magnetic thermoelectric converter and the Seebeck coefficient Sc in the longitudinal direction of the wiring is 10 ⁇ V/K or less.
  • a thermoelectric conversion element is provided.
  • a second aspect of the present invention is The absolute value of the Seebeck coefficient Sm is 10 ⁇ V / K or more, A thermoelectric conversion element according to the first aspect is provided.
  • a third aspect of the present invention is The Seebeck coefficient Sm and the Seebeck coefficient Sc have values of the same sign, A thermoelectric conversion element according to the first aspect or the second aspect is provided.
  • a fourth aspect of the present invention is The Seebeck coefficient Sc has a value of 0 or less, A thermoelectric conversion element according to any one of the first side to the third side is provided.
  • a fifth aspect of the present invention is The wiring has a specific resistance of 8 to 200 ⁇ cm, A thermoelectric conversion element according to any one of the first side to the fourth side is provided.
  • a sixth aspect of the present invention is the wiring contains at least one metal selected from the group consisting of Cu, Ag, Au, Al, Ni, and Co;
  • the content of the metal in the wiring is 50% or more based on the number of atoms,
  • a thermoelectric conversion element according to any one of the first side to the fifth side is provided.
  • a seventh aspect of the present invention is The wiring includes at least one metal selected from the group consisting of Cu, Ag, Au, and Al, and at least one metal selected from the group consisting of Group 8 elements, Group 9 elements, and Group 10 elements. including elements and A thermoelectric conversion element according to any one of the first side to the sixth side is provided.
  • the eighth aspect of the present invention is
  • the magneto-thermoelectric converter is an alloy containing Fe and having a body-centered cubic lattice crystal structure, A thermoelectric conversion element according to any one of the first side to the seventh side is provided.
  • a ninth aspect of the present invention is The content of Fe in the alloy is 50% or more based on the number of atoms, The content of elements other than Fe in the alloy is 10% or more based on the number of atoms.
  • a thermoelectric conversion element according to the eighth aspect is provided.
  • a tenth aspect of the present invention is
  • the magnetic thermoelectric conversion body has a plurality of first thin wires
  • the wiring has a plurality of second thin wires
  • the plurality of first thin wires and the plurality of second thin wires are electrically connected in series
  • a thermoelectric conversion element according to any one of the first side to the ninth side is provided.
  • the eleventh aspect of the present invention is The plurality of first thin wires and the plurality of second thin wires form 50 or more thin wire pairs, Each of the 50 or more thin wire pairs consists of the first thin wire and the second thin wire, A thermoelectric conversion element according to the tenth aspect is provided.
  • a twelfth aspect of the present invention is The plurality of first fine lines and the plurality of second fine lines form a meander pattern, A thermoelectric conversion element according to the tenth or eleventh aspect is provided.
  • thermoelectric conversion element according to any one of the first to twelfth sides.

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US18/695,936 US20250008841A1 (en) 2021-09-29 2022-09-27 Thermoelectric conversion element and sensor
CN202280065515.2A CN118044356A (zh) 2021-09-29 2022-09-27 热电转换元件及传感器
EP22876282.9A EP4412437A4 (en) 2021-09-29 2022-09-27 THERMOELECTRIC CONVERSION ELEMENT AND SENSOR
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019009308A1 (ja) * 2017-07-03 2019-01-10 国立大学法人東京大学 熱電変換素子及び熱電変換デバイス
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

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WO2002017406A1 (fr) * 2000-08-24 2002-02-28 Sumitomo Special Metals Co., Ltd. Matiere de conversion thermoelectrique du groupe bi et element de conversion thermoelectrique
JP6079995B2 (ja) 2012-09-28 2017-02-15 国立大学法人東北大学 熱電発電デバイス
JP7679881B2 (ja) * 2021-06-30 2025-05-20 株式会社村田製作所 熱電変換デバイス

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Publication number Priority date Publication date Assignee Title
WO2019009308A1 (ja) * 2017-07-03 2019-01-10 国立大学法人東京大学 熱電変換素子及び熱電変換デバイス
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

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Title
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US20250008841A1 (en) 2025-01-02

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