WO2024071419A1 - 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
WO2024071419A1
WO2024071419A1 PCT/JP2023/035777 JP2023035777W WO2024071419A1 WO 2024071419 A1 WO2024071419 A1 WO 2024071419A1 JP 2023035777 W JP2023035777 W JP 2023035777W WO 2024071419 A1 WO2024071419 A1 WO 2024071419A1
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Prior art keywords
thermoelectric conversion
conversion element
conductive layer
conductive
seebeck coefficient
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English (en)
French (fr)
Japanese (ja)
Inventor
宏和 田中
陽介 中西
愛美 黒瀬
孝洋 中井
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to JP2024550523A priority Critical patent/JPWO2024071419A1/ja
Priority to US19/116,186 priority patent/US20260107687A1/en
Priority to CN202380067930.6A priority patent/CN120694002A/zh
Publication of WO2024071419A1 publication Critical patent/WO2024071419A1/ja
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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
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions

Definitions

  • the present invention relates to a thermoelectric conversion element and a sensor.
  • Patent Document 1 describes a thermoelectric power generation device that utilizes the anomalous Nernst effect.
  • the anomalous Nernst effect is a phenomenon in which, when a heat flow is passed through a magnetic material, causing a temperature difference, a voltage is generated in a direction perpendicular to both the magnetization direction and the temperature gradient.
  • thermoelectric power generation device has a substrate, a power generation body, and a connection body.
  • the power generation body is made of a number of thin wires arranged parallel to each other along the surface of the substrate, and each thin wire is formed by thinning a thin FePt film formed on the substrate, and is magnetized in the width direction.
  • the power generation body is configured to generate electricity with a temperature difference perpendicular to the direction of magnetization due to the anomalous Nernst effect.
  • the connection body is made of a number of thin wires arranged parallel to and between each thin wire of the power generation body along the surface of the substrate.
  • Each thin wire of the connection body electrically connects one end of each thin wire of the power generation body to the other end of the thin wire adjacent to that side of each thin wire.
  • the connection body electrically connects each thin wire of the power generation body in series.
  • the connection body is made of, for example, non-magnetic Cr.
  • thermoelectric conversion elements for heat sensing.
  • thermoelectric conversion elements that utilize magneto-thermoelectric conversion such as the thermoelectric conversion device described in Patent Document 1
  • thermoelectric conversion elements that utilize magneto-thermoelectric conversion can be fabricated more easily than thermoelectric generation devices that utilize the Seebeck effect.
  • thermoelectric conversion elements that utilize magneto-thermoelectric conversion for thermal sensing.
  • thermoelectric conversion device described in Patent Document 1 the power generating body is configured to generate electricity with a temperature difference in a direction perpendicular to the magnetization direction.
  • thermoelectric conversion element using magneto-thermoelectric conversion it is assumed that an electromotive force is generated by a mechanism different from magneto-thermoelectric conversion.
  • a thermoelectric conversion device described in Patent Document 1 when a temperature gradient occurs in the longitudinal direction of the thin wires of the power generating body made of FePt thin film and the thin wires of the connecting body made of non-magnetic Cr, a thermoelectromotive force due to the Seebeck effect may be generated in the longitudinal direction due to the difference between the Seebeck coefficient of FePt and the Seebeck coefficient of Cr.
  • thermoelectromotive force is advantageous from the viewpoint of the accuracy of thermal sensing.
  • the electromotive force due to the Seebeck effect is superimposed on the electromotive force due to the magneto-thermoelectric conversion.
  • the connecting body made of multiple thin wires is electrically connected in series with the power generating body made of multiple thin wires. In such a configuration, the electromotive force due to the Seebeck effect is also likely to be large, which may have a significant effect on the accuracy of thermal sensing.
  • thermoelectric conversion element that is advantageous from the standpoint of improving the accuracy of thermal sensing while utilizing magnetic thermoelectric conversion.
  • thermoelectric converter including a conductive magnetic body having a ferromagnetic body or an antiferromagnetic body that exhibits the anomalous Nernst effect and extending linearly; a connection portion including a conductor and electrically connected to the thermoelectric conversion element; the connection portion has a laminated structure of a plurality of conductive layers,
  • the laminated structure includes a first conductive layer having a Seebeck coefficient lower than the Seebeck coefficient of the conductive magnetic material, and a second conductive layer having a Seebeck coefficient higher than the Seebeck coefficient of the conductive magnetic material.
  • a thermoelectric conversion element is provided.
  • the present invention relates to a thermoelectric converter including a conductive magnetic body having a ferromagnetic body or an antiferromagnetic body that exhibits the anomalous Nernst effect and extending linearly; a connection portion including a conductor and electrically connected to the thermoelectric conversion element; the connection portion has a laminated structure of a plurality of conductive layers, The absolute value of the difference between the Seebeck coefficient of the connection portion and the Seebeck coefficient of the conductive magnetic body is 5 ⁇ V/K or less.
  • a thermoelectric conversion element is provided.
  • thermoelectric conversion element is advantageous in terms of improving the accuracy of thermal sensing while utilizing magneto-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 a thermoelectric conversion element.
  • FIG. 4 is a cross-sectional view showing still another example of a thermoelectric conversion element.
  • FIG. 5 is a cross-sectional view showing still another example of a thermoelectric conversion element.
  • the thermoelectric conversion element 1a includes a thermoelectric conversion body 11 and a connection portion 12.
  • the thermoelectric conversion body 11 includes a conductive magnetic material having a ferromagnetic material or an antiferromagnetic material that exhibits the anomalous Nernst effect, and extends linearly.
  • the connection portion 12 includes a conductor and is electrically connected to the thermoelectric conversion body 11.
  • the connection portion 12 has a laminated structure 12k of a plurality of conductive layers.
  • the laminated structure 12k includes, for example, a first conductive layer 12p and a second conductive layer 12q.
  • the first conductive layer 12p has a Seebeck coefficient lower than the Seebeck coefficient S m of the conductive magnetic material included in the thermoelectric conversion body 11.
  • the second conductive layer 12q has a Seebeck coefficient higher than the Seebeck coefficient S m .
  • the Seebeck coefficient and the Seebeck coefficient S m of each conductive layer of the laminated structure 12k are, for example, values at 25 to 40° C., and can be measured according to the method described in the Examples.
  • the thermoelectric converter 11 and the connection portion 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 thermoelectric conversion body 11, a thermoelectromotive force due to the Seebeck effect may occur in the longitudinal direction due to the difference between the Seebeck coefficient S L of the connection part 12 and the Seebeck coefficient S m . Since the connection part 12 has a laminated structure 12k including the first conductive layer 12p and the second conductive layer 12q, the Seebeck coefficient S L of the connection part 12 can take a value between the Seebeck coefficient of the first conductive layer 12p and the Seebeck coefficient of the second conductive layer 12q.
  • thermoelectric conversion element 1a is advantageous in terms of achieving highly accurate thermal sensing by utilizing magneto-thermoelectric conversion.
  • thermoelectric converter including a conductive magnetic material When a connection part electrically connected to a thermoelectric converter including a conductive magnetic material consists of only a single conductive layer, it is possible to make the Seebeck coefficient of the conductor constituting the conductive layer closer to the Seebeck coefficient of the conductive magnetic material. For example, it is possible to adjust the Seebeck coefficient of the conductive layer by adjusting the composition of the components contained in the single conductive layer. However, in this case, the Seebeck coefficient of the conductive layer may vary significantly due to fluctuations in the composition of the components contained in the single conductive layer, and good robustness may not be achieved.
  • the composition of the conductive layer is uniquely determined, which may impose restrictions on realizing other properties such as the durability of the conductive layer.
  • the Seebeck coefficient of the laminated structure can be roughly predicted based on the Seebeck coefficient, resistivity, and thickness of each layer of the laminated structure.
  • the Seebeck coefficient S L of the connection portion 12 can take a value between the Seebeck coefficient of the first conductive layer 12p and the Seebeck coefficient of the second conductive layer 12q.
  • the difference between the Seebeck coefficient S L and the Seebeck coefficient S m of the connection portion 12 can be reduced.
  • thermoelectric conversion element 1a there are few restrictions on the conductor in adjusting the Seebeck coefficient S L of the connection portion 12, and the Seebeck coefficient S L is easily adjusted, and good robustness is exhibited.
  • of the difference between the Seebeck coefficient S L of the connection portion 12 and the Seebeck coefficient S m is not limited to a specific value.
  • is, for example, 5 ⁇ V/K or less.
  • the thermoelectric conversion element 1a is advantageous from the viewpoint of realizing high-precision thermal sensing by utilizing magneto-thermoelectric conversion.
  • the Seebeck coefficient S L of the connection portion 12 is, for example, a value at 25 to 40° C., and can be measured according to the method described in the examples.
  • thermoelectric conversion element 1a In the thermoelectric conversion element 1a,
  • the number n of the multiple conductive layers included in the laminated structure 12k is not limited to a specific value. As shown in FIG. 2, in the laminated structure 12k, n may be 2, and the laminated structure 12k may be composed of only two conductive layers, the first conductive layer 12p and the second conductive layer 12q.
  • FIG. 3 is a cross-sectional view showing another example of a thermoelectric conversion element.
  • the thermoelectric conversion element 1b shown in FIG. 3 is configured in the same manner as the thermoelectric conversion element 1a, except for the parts that are particularly described.
  • n in the laminated structure 12k, n may be 3, and the laminated structure 12k may further include a third conductive layer 12r.
  • the laminated structure 12k may include four or more conductive layers.
  • the number n of conductive layers included in the laminated structure 12k may be, for example, 10 or less, or 5 or less.
  • thermoelectric conversion element 1a satisfies the conditions shown in the following formulas (1), (2), and (3), for example.
  • n is an integer of 2 or more, which is the number of multiple conductive layers in the laminated structure 12k.
  • i is an integer from 1 to n.
  • t i is the thickness [m] of the i-th conductive layer in the order of stacking in the laminated structure 12k.
  • ⁇ i is the resistivity [ ⁇ m] of the i-th conductive layer.
  • S i is the Seebeck coefficient [V/K] of the i-th conductive layer, and S m is the Seebeck coefficient of the conductive magnetic material.
  • the first term on the left side is based on the new knowledge obtained by the present inventors that the Seebeck coefficient S L of the laminated structure 12k can be predicted based on the thickness and resistivity of each conductive layer.
  • the first term on the left side corresponds to the predicted value of the Seebeck coefficient S L of the laminated structure 12k. Since the thermoelectric conversion element 1a satisfies these conditions, the thermoelectric conversion element 1a is more advantageous in terms of achieving highly accurate thermal sensing by utilizing magneto-thermoelectric conversion.
  • the left side of formula (1) may be 4.8 ⁇ V/K or less, 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.
  • This left side may be 2.5 ⁇ V/K or less, 2.0 ⁇ V/K or less, 1.0 ⁇ V/K or less, 0.5 ⁇ V/K or less, or 0.3 ⁇ V/K or less.
  • thermoelectric conversion element 1a satisfies the conditions shown in the following formulas (4) and (5), for example.
  • n is an integer of 2 or more, which is the number of the plurality of conductive layers in the laminate structure 12k.
  • i is an integer from 1 to n.
  • t i is the thickness [m] of the i-th conductive layer in the order of stacking in the laminate structure 12k.
  • ⁇ i is the resistivity [ ⁇ m] of the i-th conductive layer.
  • ⁇ i is the electrical conductivity [S/m] of the i-th conductive layer.
  • thermoelectric conversion element 1a When such conditions are satisfied in the thermoelectric conversion element 1a, it is possible to prevent the thicknesses of the plurality of conductive layers of the laminate structure 12k from differing greatly from each other while adjusting the Seebeck coefficient S L of the connection portion 12 to a desired range. In this case, the thermoelectric conversion element 1a is advantageous from the viewpoint of robustness.
  • the value of the central physical quantity in formula (4) may be 0.12 or more, 0.15 or more, or 0.18 or more.
  • the value of the central physical quantity in formula (4) may be 8 or less, 6 or less, 4 or less, or 2 or less.
  • of the difference between the arithmetic average value S AVG of the Seebeck coefficients of the multiple conductive layers of the laminated structure 12k and the Seebeck coefficient S m of the conductive magnetic material contained in the thermoelectric conversion body 11 is not limited to a specific value.
  • is, for example, 10 ⁇ V/K or less.
  • the Seebeck coefficient S L of the connection portion 12 can be easily adjusted to a desired range, and the thermoelectric conversion element 1a is advantageous in terms of robustness.
  • may be 8 ⁇ V/K or less, 6 ⁇ V/K or less, 4 ⁇ V/K or less, 2 ⁇ V/K or less, or 1 ⁇ V/K or less.
  • the laminated structure 12k satisfies the conditions shown in the following formulas (6), (7), and (8), for example.
  • n is an integer of 2 or more, which is the number of multiple conductive layers in the laminated structure 12k.
  • i is an integer from 1 to n.
  • t i is the thickness [m] of the i-th conductive layer in the order of stacking in the laminated structure 12k.
  • ⁇ i is the resistivity [ ⁇ m] of the i-th conductive layer.
  • G m is the longitudinal conductance [S] of the conductive magnetic body. If these conditions are met, the laminated structure 12k is likely to have high conductivity.
  • thermoelectric conversion element 1a when performing thermal sensing using magneto-thermoelectric conversion with the thermoelectric conversion element 1a, a large output is likely to be obtained, and the sensitivity of thermal sensing is likely to be high. Whether the condition of formula (6) is satisfied is determined, for example, by comparing the laminated structure 12k and the thermoelectric conversion body 11 of the same length in the longitudinal direction (Y-axis direction).
  • the left side of formula (6) may be 3.5 or more, 4.0 or more, or 4.5 or more.
  • the left side of formula (6) is, for example, 20 or less.
  • the material forming the conductive layer of the laminated structure 12k is not limited to a specific material.
  • the content of at least one element selected from the group consisting of Ti, Cr, Ni, Al, Zn, Nb, Pd, Ag, Ta, W, Pt, and Au is 10% or more based on the atomic number.
  • the conductive layer forming the surface tends to have high durability.
  • the thermoelectric conversion element 1a is manufactured by a method including lithography, the conductive layer forming the surface is less likely to corrode even in the strong alkaline environment associated with lithography.
  • the content of at least one element selected from the group consisting of Cu, Al, Ag, and Au in at least one of the multiple conductive layers is 50% or more based on the atomic number.
  • the laminated structure 12k tends to have high conductivity. Therefore, when performing thermal sensing using the thermoelectric conversion element 1a by utilizing magneto-thermoelectric conversion, a large output is likely to be obtained, and the sensitivity of thermal sensing is likely to be high.
  • At least one of the multiple conductive layers may contain a single metal.
  • the precursor of the conductive layer is easily etched by a commercially available etching solution, which may facilitate the manufacture of the thermoelectric conversion element 1a.
  • an alloy of multiple metals may have corrosion resistance, the chemical solutions that can be used for etching may be limited. For this reason, it is difficult to achieve etching selectivity with the magnetic material, which may easily result in restrictions on the element formation process.
  • the multiple conductive layers may contain an alloy.
  • the thermoelectric converter 11 includes, for example, a substance exhibiting the anomalous Nernst effect.
  • the substance exhibiting the anomalous Nernst effect is not limited to a specific substance.
  • the substance 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 with a Weyl point in the vicinity of the Fermi energy.
  • the thermoelectric converter 11 contains, as the substance exhibiting the anomalous Nernst effect, at least one substance selected from the group consisting of the following (i), (ii), (iii), (iv), and (v).
  • a stoichiometric substance having a composition represented by Fe3X (i) a stoichiometric substance having a composition represented by Fe3X ; (ii) an off-stoichiometric substance in which the composition ratio of Fe and X deviates from that of the substance (i) above; (iii) a substance in which part of the Fe sites of the substance (i) above or part of the Fe sites of the substance (ii) above is substituted with a typical metal element or transition element other than X; (iv) a substance having a composition represented by Fe3M11 -xM2x ( 0 ⁇ x ⁇ 1), in which M1 and M2 are different typical elements; (v) a substance in which part of the Fe sites of the substance (i) above is substituted with a transition element other than X, and part of the X sites of the substance (i) above is substituted with a typical 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 different typical elements.
  • the combination of M1 and M2 is, for example, Ga and Al, Si and Al, or Ga and B.
  • the thermoelectric converter 11 may contain Co 2 MnGa as a substance exhibiting the anomalous Nernst effect, or may contain an antiferromagnetic material, such as Mn 3 Sn.
  • Thermoelectric converter 11 may be an alloy containing Fe and having a body-centered cubic crystal structure. In this case, a large electromotive force is likely to be generated in the thermoelectric converter 11 due to the anomalous Nernst effect.
  • the thermoelectric converter 11 is an alloy containing Fe and having a body-centered cubic crystal structure
  • the Fe content and the content of elements other than Fe in the alloy are not limited to specific values.
  • the Fe content in the alloy is, for example, 50% or more based on the atomic number
  • the content of elements other than Fe in the alloy is, for example, 10% or more based on the atomic number. In this case, a large electromotive force based on the anomalous Nernst effect is likely to be generated in the thermoelectric converter 11.
  • the Fe content in the above alloy may be, based on atomic number, 55% or more, 60% or more, 65% or more, or 70% or more.
  • the Fe content in the above alloy may be, based on atomic number, 90% or less, 85% or less, or 80% or less.
  • the content of elements other than Fe in the above alloy may be 15% or more, or 20% or more, based on the atomic number.
  • the content of elements other than Fe in the above alloy may be 50% or less, or 40% or less, or 30% or less, based on the atomic number.
  • the magneto-thermoelectric coefficient S NE of the thermoelectric converter 11 is not limited to a specific value.
  • the absolute value of the magneto-thermoelectric coefficient S NE of the thermoelectric converter 11 is, for example, 0.5 ⁇ V/K or more. This makes it easier for a large electromotive force to be generated by magneto-thermoelectric conversion in the thermoelectric converter 11, and the accuracy of sensing using the thermoelectric conversion element 1a is easily improved. For this reason, minute heat is easily detected.
  • the absolute value of the magneto-thermoelectric coefficient S NE of the thermoelectric converter 11 is preferably 1.0 ⁇ V/K or more, more preferably 1.5 ⁇ V/K or more, and even more preferably 2.0 ⁇ V/K or more.
  • the absolute value of the magneto-thermoelectric coefficient S NE of the thermoelectric converter 11 may be 3.0 ⁇ V/K or more, 4.0 ⁇ V/K or more, 5.0 ⁇ V/K or more, 6.0 ⁇ V/K or more, 7.0 ⁇ V/K or more, or 8.0 ⁇ V/K or more.
  • thermoelectric conversion body 11 has a plurality of first thin wires 11a.
  • connection portion 12 has a plurality of second thin wires 12a.
  • the plurality of first thin wires 11a and the plurality of second thin wires 12a are electrically connected in series. With this configuration, the electromotive forces associated with the magnetic thermoelectric conversion generated in the plurality of first thin wires 11a are combined, making it easier to obtain a large output from the thermoelectric conversion element 1a.
  • the multiple first thin wires 11a and the multiple second thin wires 12a form, for example, multiple pairs of thin wires 15.
  • Each pair of thin wires 15 consists of a first thin wire 11a and a second thin wire 12a.
  • each pair of thin wires 15 consists of one first thin wire 11a and one second thin wire 12a.
  • the number of thin wire pairs 15 in the thermoelectric conversion element 1a is not limited to a specific value.
  • the multiple first thin wires 11a and the multiple second thin wires 12a form, for example, 50 or more pairs of thin wires 15.
  • the electromotive force due to the Seebeck effect increases as the number of pairs of joined dissimilar materials increases.
  • thermoelectric conversion element 1a even if the thermoelectric conversion element 1a has 50 or more pairs of fine wires 15, when a temperature gradient occurs in the longitudinal direction of the thermoelectric conversion body 11, the thermoelectromotive force caused by the Seebeck effect in that longitudinal direction tends to be small.
  • the multiple first thin wires 11a and the multiple second thin wires 12a form a meander pattern. With this configuration, even if the area of the plane on which the multiple first thin wires 11a and the multiple second thin wires 12a are arranged is small, it is easy to obtain a large output from the thermoelectric conversion element 1a.
  • the first thin lines 11a are, for example, spaced apart at a predetermined interval in the X-axis direction and arranged parallel to each other.
  • the first thin lines 11a are arranged at equal intervals in the X-axis direction.
  • the second thin lines 12a for example, electrically connect the first thin lines 11a adjacent to each other in the X-axis direction.
  • the second thin lines 12a for example, electrically connect one end of the first thin line 11a in the Y-axis direction to the other end of another first thin line 11a adjacent to the first thin line 11a in the Y-axis direction.
  • One end of the first thin lines 11a in the Y-axis direction is located at the end on the same side of the first thin line 11a in the Y-axis direction, and the other end of the first thin lines 11a in the Y-axis direction is located at the end opposite to the one end of the first thin line 11a in the Y-axis direction.
  • the thickness of the first thin wire 11a is not limited to a specific value.
  • the first thin wire 11a has a thickness of, for example, 1000 nm or less. This makes it possible to reduce the amount of material used to form the magnetic thermoelectric converter in the thermoelectric conversion element 1a, which makes it easier to reduce the manufacturing cost of the thermoelectric conversion element 1a. In addition, breaks in the conductive path formed by the multiple first thin wires 11a and the multiple second thin wires 12a in the thermoelectric conversion element 1a are less likely to occur.
  • the thickness of the first thin 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 easier 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 in the X-axis direction of the first thin wire 11a, 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 to form the magnetic thermoelectric converter in the thermoelectric conversion element 1a, which makes it easier to reduce 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, which makes it easier to increase the electromotive force generated by magnetic thermoelectric conversion in the thermoelectric conversion element 1a.
  • 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. This makes it difficult for the conductive path in the thermoelectric conversion element 1a to break, and makes it easier for the thermoelectric conversion element 1a to exhibit high durability.
  • the width of the first thin wire 11a may be 0.5 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more.
  • the thickness of the second thin wire 12a is not limited to a specific value.
  • the thickness of the second thin wire 12a is, for example, 1000 nm or less. This allows the amount of material used to form the connection portion 12 to be reduced, making it easier to reduce the manufacturing cost of the thermoelectric conversion element 1a. In addition, breaks in the conductive path are less likely to occur in the thermoelectric conversion element 1a.
  • 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.
  • the thickness of the second thin wire 12a is, for example, 5 nm or more. This makes it easier 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 thin wire 12a is, for example, 500 ⁇ m or less. This makes it possible to reduce the amount of material used to form the connection portion 12 in the thermoelectric conversion element 1a, making it easier to reduce the manufacturing cost of the thermoelectric conversion element 1a. In addition, it is easy to arrange a large number of second connection portions 12a in the X-axis direction, making it easier to increase the electromotive force generated by magneto-thermoelectric conversion in the thermoelectric conversion element 1a.
  • 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 thin wire 12a is, for example, 0.1 ⁇ m or more. This makes it difficult for the conductive path in the thermoelectric conversion element 1a to break, and the thermoelectric conversion element 1a is likely to exhibit high durability.
  • the width of the second thin wire 12a may be 0.5 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more.
  • thermoelectric conversion element 1a further includes a substrate 20.
  • the thermoelectric conversion body 11 and the connection portion 12 are disposed on the substrate 20.
  • the material constituting the substrate 20 is not limited to a specific material.
  • the substrate 20 does not contain MgO in the surface layer. This eliminates the need to include MgO in the surface layer of the substrate 20, making the manufacture of the thermoelectric conversion element 1a less complicated and making it easier to achieve acid resistance.
  • the substrate 20 is, for example, flexible. In this case, the shape of the object to which the thermoelectric conversion element 1a can be attached is less restricted.
  • the substrate 20 contains, for example, at least an organic polymer. This makes it easier 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).
  • the 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 manufacturing method of the thermoelectric conversion element 1a will be described.
  • a thin film of the precursor of the thermoelectric conversion body 11 is formed on one main surface of the substrate 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
  • plating plating
  • a photoresist is applied onto the thin film, a photomask is placed on the thin film, exposure is performed, and then wet etching is performed. This forms a linear pattern of the precursors of the multiple thermoelectric conversion bodies 11 arranged at a predetermined interval.
  • a thin film of the precursor of the laminated structure 12k is formed on one main surface of the substrate 20 by a method such as sputtering, CVD, PLD, ion plating, and plating.
  • a method such as sputtering, CVD, PLD, ion plating, and plating.
  • a thin film of the precursor of the laminated structure 12k for example, after a thin film of the precursor of the first conductive layer 12p is formed, a thin film of the precursor of the second conductive layer 12p is formed on the thin film.
  • a photoresist is applied onto the thin film of the precursor of the laminated structure 12k, a photomask is placed on the thin film of the precursor of the laminated structure 12k, exposure is performed, and then wet etching is performed.
  • connection portion 12 having the laminated structure 12k, and the linear patterns of the precursor of the thermoelectric converter 11 are electrically connected to each other.
  • the precursor of the thermoelectric converter 11 is magnetized to form the thermoelectric converter 11. In this way, the thermoelectric conversion element 1a is obtained.
  • the precursor of the connection portion 12 may be magnetized to form the connection portion 12.
  • wet etching may be performed on the thin film of the precursor of the conductive layer for each conductive layer in the laminated structure 12k.
  • thermoelectric conversion element 1a may be provided, for example, together with an adhesive layer.
  • the substrate 20 is disposed between the thermoelectric conversion body 11 and the adhesive layer in the thickness direction of the substrate 20. This allows the adhesive layer to be pressed against an article to attach the thermoelectric conversion element 1a to the article.
  • the adhesive layer contains, for example, a rubber-based adhesive, an acrylic-based adhesive, a silicone-based adhesive, or a urethane-based adhesive.
  • the thermoelectric conversion element 1a may be provided together with the adhesive layer and a release liner.
  • the release liner covers the adhesive layer.
  • the release liner is typically a film that can maintain the adhesive force of the adhesive layer when covering the adhesive layer, and can be easily peeled off from the adhesive layer.
  • the release liner is, for example, a film made of a polyester resin such as PET. The adhesive layer is exposed by peeling off the release liner, and the thermoelectric conversion element 1a can be attached to an article.
  • thermoelectric conversion element 1a A sensor equipped with a thermoelectric conversion element 1a can be provided.
  • this sensor for example, when a temperature gradient occurs in the thickness direction of the substrate 20, an electromotive force is generated in the longitudinal direction of the thermoelectric conversion body 11 due to the magneto-thermoelectric effect.
  • the sensor can sense the heat flux by processing an electrical signal output to the outside of the thermoelectric conversion element 1a based on this electromotive force.
  • Thermoelectric conversion element 1a can be modified from various viewpoints.
  • Thermoelectric conversion element 1a may be modified, for example, to thermoelectric conversion element 1c shown in FIG. 4 or thermoelectric conversion element 1d shown in FIG. 5.
  • Thermoelectric conversion elements 1c and 1d are configured in the same manner as thermoelectric conversion element 1a, except for parts that will be specifically described.
  • the components of thermoelectric conversion elements 1c and 1d that are the same as or correspond to the components of thermoelectric conversion element 1a are given the same reference numerals, and detailed description will be omitted.
  • the description of thermoelectric conversion element 1a also applies to thermoelectric conversion elements 1c and 1d, unless there is a technical contradiction.
  • thermoelectric conversion body 11 extends continuously on the same plane, for example.
  • the laminated structure 12k of the connection portion 12 is disposed on a part of the thermoelectric conversion body 11.
  • the multiple second fine wires 12a are disposed on the thermoelectric conversion body 11 at a predetermined distance from each other.
  • thermoelectric conversion body 11 has, for example, a meander pattern.
  • the thermoelectric conversion element 1c is configured such that single layers of the thermoelectric conversion body 11 and laminates including the thermoelectric conversion body 11 and the second fine wire 12a appear alternately in the X-axis direction.
  • the layered structure 12k of the connection portion 12 extends continuously on the same plane, for example.
  • the thermoelectric conversion body 11 is disposed on a part of the layered structure 12k of the connection portion 12.
  • the first fine wires 11a are disposed on the layered structure 12k of the connection portion 12 at a predetermined distance from each other.
  • thermoelectric conversion element 1d the laminated structure 12k of the connection portion 12 has, for example, a meandering pattern.
  • Thermoelectric conversion element 1c is configured such that connection portions 12 and laminates including connection portions 12 and first fine wires 11a appear alternately in the X-axis direction.
  • Each Seebeck coefficient was determined based on the electromotive force and temperature difference induced between two thermometers attached to the sample when a heat flow was generated by a heater attached to one end of each sample.
  • the Seebeck coefficients at 27 to 37 ° C of the material alone constituting each conductive layer constituting the wiring are shown in Table 1.
  • the arithmetic average value S AVG of the Seebeck coefficients of the conductive layers constituting the wiring are shown in Table 2.
  • the Seebeck coefficients S m and Seebeck coefficients S L are shown in Table 2.
  • the Nernst coefficient of the thin film of the thermoelectric conversion body forming the magnetic thermoelectric conversion thin wire in each of the thermoelectric conversion elements according to each Example and Comparative Example was measured at 27 to 37° C. using a small refrigerant-free physical property measurement system PPMS VersaLab manufactured by Quantum Design.
  • the Nernst coefficient S NE was 2.0 ⁇ V/K.
  • thermoelectric conversion wire and wiring (connection portion) in the longitudinal direction was heated by a heater to generate a temperature difference of 1°C between both ends of the thermoelectric conversion wire and wiring in the longitudinal direction.
  • the electromotive force Vs associated with the Seebeck effect was measured.
  • the temperature of both sides of the thermoelectric conversion element was kept constant so that no temperature gradient would occur in the thickness direction of the thermoelectric conversion element, except for the one end of the thermoelectric conversion wire and wiring in the longitudinal direction. The results are shown in Table 2.
  • the processability was evaluated based on whether or not the film could be etched in wet etching.
  • a chemical solution was prepared by mixing Cu etching solution SF-5420 manufactured by MEC, nickel selective etching solution NC manufactured by Nippon Kagaku Sangyo Co., Ltd., or Melstrip TI-3991 manufactured by Meltex Co., Ltd., hydrogen peroxide solution, and water in a volume ratio of 1:2:2. If the laminated film consisting of the first conductive layer and the second conductive layer can be dissolved in these chemical solutions, the processability was evaluated as "A”, and if the laminated film cannot be dissolved in these chemical solutions, the processability was evaluated as "X”. In addition, if the evaluation of the processability was "X", a lithography process was performed using a liquid in which nitric acid and hydrogen peroxide solution were mixed in a predetermined ratio.
  • PET polyethylene terephthalate
  • a first conductive layer having a thickness of 10 nm was formed by DC magnetron sputtering using a Cu target material.
  • a second conductive layer having a thickness of 101 nm was formed on the first conductive layer by DC magnetron sputtering using a Ni target material.
  • a photoresist was applied on a laminate film consisting of a first conductive layer and a second conductive layer, a photomask was placed on this laminate film and exposed to light, and then wet etching was performed. This resulted in the formation of wiring (connection portion) having a width of 40 ⁇ m.
  • the wiring electrically connected the multiple magnetic thermoelectric conversion wires in series.
  • the multiple magnetic thermoelectric conversion wires and the wiring formed a meander pattern.
  • thermoelectric conversion wires were magnetized in a direction parallel to the plane of the PET film and perpendicular to the longitudinal direction of the magnetic thermoelectric conversion wires, to obtain a thermoelectric conversion element according to Example 1.
  • This thermoelectric conversion element generated an electromotive force based on the anomalous Nernst effect.
  • thermoelectric conversion element according to Example 7 was produced in the same manner as in Example 2.
  • thermoelectric conversion element according to Comparative Example 2 was produced in the same manner as in Example 1, except for the following points.
  • thermoelectric conversion element according to Comparative Example 3 was produced in the same manner as in Example 2, except for the following points.
  • the electromotive force due to the Seebeck effect in the thermoelectric conversion element according to each embodiment was smaller than that due to the Seebeck effect in the thermoelectric conversion element according to the comparative example. Therefore, it was suggested that the electromotive force due to the Seebeck effect can be reduced by having a structure in which a conductive layer having a Seebeck coefficient lower than that of the thermoelectric conversion body and a conductive layer having a Seebeck coefficient higher than that of the thermoelectric conversion body are laminated.
  • thermoelectric conversion element according to comparative example 3 the electromotive force due to the Seebeck effect was reduced by using a single conductive layer close to the Seebeck coefficient of the thermoelectric conversion body, but the durability was poor.
  • the first aspect of the present invention is a thermoelectric converter including a conductive magnetic body having a ferromagnetic body or an antiferromagnetic body that exhibits the anomalous Nernst effect and extending linearly; a connection portion including a conductor and electrically connected to the thermoelectric conversion element; the connection portion has a laminated structure of a plurality of conductive layers,
  • the laminated structure includes a first conductive layer having a Seebeck coefficient lower than the Seebeck coefficient of the conductive magnetic material, and a second conductive layer having a Seebeck coefficient higher than the Seebeck coefficient of the conductive magnetic material.
  • a thermoelectric conversion element is provided.
  • a second aspect of the present invention is a thermoelectric converter including a conductive magnetic body having a ferromagnetic body or an antiferromagnetic body that exhibits the anomalous Nernst effect and extending linearly; a connection portion including a conductor and electrically connected to the thermoelectric conversion element; the connection portion has a laminated structure of a plurality of conductive layers, The absolute value of the difference between the Seebeck coefficient of the connection portion and the Seebeck coefficient of the conductive magnetic body is 5 ⁇ V/K or less.
  • a thermoelectric conversion element is provided.
  • a third aspect of the present invention is The laminated structure satisfies the conditions shown in the following formulas (1), (2), and (3),
  • n is an integer of 2 or more which is the number of the conductive layers in the laminate structure
  • i is an integer from 1 to n
  • t i is a thickness of the i-th conductive layer in the laminate structure in the stacking order
  • ⁇ i is a resistivity of the i-th conductive layer
  • S i is a Seebeck coefficient of the i-th conductive layer
  • S m is a Seebeck coefficient of the conductive magnetic body.
  • a thermoelectric conversion element according to a first or second aspect is provided.
  • a fourth aspect of the present invention is The laminated structure satisfies the conditions shown in the following formulas (4) and (5),
  • n is an integer of 2 or more which is the number of the conductive layers in the laminate structure
  • i is an integer from 1 to n
  • t i is a thickness of the i-th conductive layer in the laminate structure in the stacking order
  • ⁇ i is a resistivity of the i-th conductive layer
  • ⁇ i is an electrical conductivity of the i-th conductive layer.
  • a fifth aspect of the present invention is an absolute value of a difference between an arithmetic average value of the Seebeck coefficients of the plurality of conductive layers and a Seebeck coefficient of the conductive magnetic body is 10 ⁇ V/K or less;
  • a thermoelectric conversion element according to any one of the first to fourth aspects is provided.
  • a sixth aspect of the present invention is the conductive layer forming a surface layer in the laminated structure has a content of at least one element selected from the group consisting of Ti, Cr, Ni, Al, Zn, Nb, Pd, Ag, Ta, W, Pt, and Au of 10% or more based on the number of atoms;
  • the present invention provides a thermoelectric conversion element according to any one of the first to fifth aspects.
  • a seventh aspect of the present invention is a content of at least one selected from the group consisting of Cu, Al, Ag, and Au in at least one of the plurality of conductive layers is 50% or more based on the number of atoms;
  • a thermoelectric conversion element according to any one of the first to sixth aspects is provided.
  • An eighth aspect of the present invention is The laminated structure satisfies the conditions shown in the following formulas (6), (7), and (8),
  • n is an integer of 2 or more that is the number of the conductive layers in the laminated structure
  • i is an integer from 1 to n
  • t i is a thickness of the i-th conductive layer in the laminated order in the laminated structure
  • ⁇ i is a resistivity of the i-th conductive layer in the laminated order in the laminated structure
  • G m is a longitudinal conductance of the conductive magnetic body.
  • a ninth aspect of the present invention is At least one of the conductive layers comprises an elemental metal.
  • a thermoelectric conversion element according to any one of the first to eighth aspects is provided.
  • thermoelectric converter has a plurality of first thin wires,
  • connection portion has a plurality of second thin wires, the first thin wires and the second thin wires are electrically connected in series;
  • thermoelectric conversion element according to any one of the first to ninth aspects is provided.
  • An eleventh aspect of the present invention is a method for producing a semiconductor device comprising the steps of: the first thin wires and the second thin wires form 50 or more thin wire pairs, Each of the 50 or more fine wire pairs is composed of the first fine wire and the second fine wire.
  • a thermoelectric conversion element according to a tenth aspect is provided.
  • a twelfth aspect of the present invention is a method for producing a method for manufacturing a semiconductor device comprising the steps of: The first thin lines and the second thin lines form a meander pattern.
  • a thermoelectric conversion element according to a tenth or eleventh aspect is provided.
  • thermoelectric conversion element according to any one of the first to twelfth sides is provided.
  • a sensor is provided.

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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

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