WO2024048473A1 - 熱電変換素子及び熱電変換素子の製造方法 - Google Patents

熱電変換素子及び熱電変換素子の製造方法 Download PDF

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Publication number
WO2024048473A1
WO2024048473A1 PCT/JP2023/030824 JP2023030824W WO2024048473A1 WO 2024048473 A1 WO2024048473 A1 WO 2024048473A1 JP 2023030824 W JP2023030824 W JP 2023030824W WO 2024048473 A1 WO2024048473 A1 WO 2024048473A1
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Prior art keywords
conversion element
thermoelectric
thermoelectric conversion
conductive member
heat insulating
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English (en)
French (fr)
Japanese (ja)
Inventor
宏平 高橋
正樹 藤金
邦彦 中村
敦史 姫野
尚基 反保
浩之 田中
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to JP2024544214A priority Critical patent/JPWO2024048473A1/ja
Publication of WO2024048473A1 publication Critical patent/WO2024048473A1/ja
Priority to US19/046,241 priority patent/US20250185512A1/en
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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
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment

Definitions

  • the present disclosure relates to a thermoelectric conversion element and a method for manufacturing the thermoelectric conversion element.
  • Thermoelectric conversion is a technology that directly converts thermal energy into electrical energy by utilizing the Seebeck effect, which generates an electromotive force in proportion to the temperature difference applied to both ends of a substance.
  • it is a technology that converts electrical energy into thermal energy by utilizing the Peltier effect, which creates a temperature difference between the two ends of a material due to an electric current generated in the material.
  • thermoelectric conversion element The performance of the thermoelectric conversion element is evaluated by the figure of merit Z or the dimensionless figure of merit ZT, which is the product of the figure of merit Z and the absolute temperature T.
  • thermoelectric conversion element A ⁇ -type thermoelectric conversion element is known as a thermoelectric conversion element.
  • a p-type thermoelectric member having a positive Seebeck coefficient and an n-type thermoelectric member having a negative Seebeck coefficient are electrically connected in series and thermally connected in parallel to form a thermocouple. It is configured.
  • Unileg type thermoelectric conversion elements are also known as thermoelectric conversion elements.
  • a unireg type thermoelectric conversion element only one of a p-type thermoelectric member and an n-type thermoelectric member is used as a thermoelectric member, and each thermoelectric member is electrically connected in series by a metal plate, and thermally connected in parallel.
  • Patent Documents 1 and 2 describe Unileg type thermoelectric conversion elements.
  • a ⁇ -type thermoelectric conversion element it is important to use a p-type thermoelectric member and an n-type thermoelectric member that have similar characteristics such as electrical resistivity, thermal conductivity, and Seebeck coefficient.
  • the Unileg type thermoelectric conversion element only one of the p-type thermoelectric member and the n-type thermoelectric member is used as the thermoelectric member, so there are fewer restrictions regarding the selection of the thermoelectric member.
  • thermoelectric conversion element is constructed using a thin film thermoelectric member.
  • the present disclosure provides a technique that is advantageous from the viewpoint of thermoelectric conversion performance while using a thin film thermoelectric member in a Unileg type thermoelectric conversion element.
  • thermoelectric conversion element A substrate and a thermocouple including a thin film thermoelectric member and a conductive member arranged along the main surface of the substrate; a heat insulating material in contact with the conductive member,
  • the conductive member includes at least one selected from the group consisting of metals and metal compounds,
  • the thermal conductivity of the heat insulating material is lower than the thermal conductivity of the electrically conductive member.
  • thermoelectric conversion element of the present disclosure is configured as a unileg type thermoelectric conversion element including a thin film thermoelectric member, and is advantageous from the viewpoint of thermoelectric conversion performance.
  • FIG. 1A is a cross-sectional view schematically showing an example of the thermoelectric conversion element of Embodiment 1.
  • FIG. 1B is a cross-sectional view schematically showing another example of the thermoelectric conversion element of Embodiment 1.
  • FIG. 2A is a plan view showing an example of the thermoelectric member of Embodiment 1.
  • FIG. 2B is a plan view showing another example of the thermoelectric member of Embodiment 1.
  • FIG. 2C is a plan view showing still another example of the thermoelectric member of Embodiment 1.
  • FIG. 2D is a plan view showing still another example of the thermoelectric member of Embodiment 1.
  • FIG. 2E is a plan view showing still another example of the thermoelectric member of Embodiment 1.
  • FIG. 1A is a cross-sectional view schematically showing an example of the thermoelectric conversion element of Embodiment 1.
  • FIG. 1B is a cross-sectional view schematically showing another example of the thermoelectric conversion element of Embodiment 1.
  • FIG. 2F is a plan view showing still another example of the thermoelectric member of Embodiment 1.
  • FIG. 3A is a plan view showing an example of the conductive member of Embodiment 1.
  • FIG. 3B is a plan view showing another example of the conductive member of Embodiment 1.
  • FIG. 3C is a plan view showing still another example of the conductive member of Embodiment 1.
  • FIG. 3D is a plan view showing still another example of the conductive member of Embodiment 1.
  • FIG. 3E is a plan view showing still another example of the conductive member of Embodiment 1.
  • FIG. 3F is a plan view showing still another example of the conductive member of Embodiment 1.
  • FIG. 3G is a plan view showing yet another example of the conductive member of Embodiment 1.
  • FIG. 3A is a plan view showing an example of the conductive member of Embodiment 1.
  • FIG. 3B is a plan view showing another example of the conductive member of Embodiment 1.
  • FIG. 4A is a cross-sectional view of the thermocouple taken along line IVA-IVA in FIG. 1A.
  • FIG. 4B is a cross-sectional view showing another example of the arrangement of the thermoelectric member and the conductive member in the thermocouple of Embodiment 1.
  • FIG. 4C is a cross-sectional view showing still another example of the arrangement of the thermoelectric member and the conductive member in the thermocouple of Embodiment 1.
  • FIG. 4D is a cross-sectional view showing still another example of the arrangement of the thermoelectric member and the conductive member in the thermocouple of Embodiment 1.
  • FIG. 4A is a cross-sectional view of the thermocouple taken along line IVA-IVA in FIG. 1A.
  • FIG. 4B is a cross-sectional view showing another example of the arrangement of the thermoelectric member and the conductive member in the thermocouple of Embodiment 1.
  • FIG. 4C is a cross-sectional view showing still another example of the arrangement of the thermo
  • FIG. 4E is a cross-sectional view showing yet another example of the arrangement of the thermoelectric member and the conductive member in the thermocouple of Embodiment 1.
  • FIG. 5A is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5B is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5C is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5D is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5E is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5A is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5B is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5F is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5G is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5H is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5I is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5J is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5K is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5L is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5M is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5N is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 5O is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 1.
  • FIG. 6A is a cross-sectional view schematically showing an example of the thermoelectric conversion element of Embodiment 2.
  • FIG. 6B is a cross-sectional view schematically showing another example of the thermoelectric conversion element of Embodiment 2.
  • FIG. 7A is a cross-sectional view of the thermocouple taken along line VIIA-VIIA in FIG. 6A.
  • FIG. 7B is a cross-sectional view showing another example of the arrangement of the thermoelectric member and the conductive member in the thermocouple of Embodiment 2.
  • FIG. 7C is a cross-sectional view showing still another example of the arrangement of the thermoelectric member and the conductive member in the thermocouple of Embodiment 2.
  • FIG. 7D is a cross-sectional view showing still another example of the arrangement of the thermoelectric member and the conductive member in the thermocouple of Embodiment 2.
  • FIG. 8A is a cross-sectional view showing a method for manufacturing a thermoelectric conversion element according to Embodiment 2.
  • FIG. 8A is a cross-sectional view showing a method for manufacturing a thermoelectric conversion element according to Embodiment 2.
  • FIG. 8A is a cross-sectional view showing a method for manufacturing a thermoelectric conversion element according to Embodi
  • FIG. 8B is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8C is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8D is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8E is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8F is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8G is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8H is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8I is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8J is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8K is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • FIG. 8L is a cross-sectional view showing the method for manufacturing the thermoelectric conversion element of Embodiment 2.
  • thermoelectric conversion element In the Unileg type thermoelectric conversion element, the metal plate for electrically connecting the thermoelectric member is considered to have high thermal conductance with respect to the thermoelectric member. For this reason, the thermal conductance of the entire element tends to be higher in the Unileg type thermoelectric conversion element than in the ⁇ type thermoelectric conversion element. This cannot be said to be advantageous from the viewpoint of thermoelectric conversion performance.
  • the thermal conductance G m of the metal plate that constitutes the thermocouple together with the thermoelectric member is determined by the thermal conductivity ⁇ m of the material of the metal plate, the area A m of the end face forming one end of the metal plate in the heat flow direction, and the heat flow direction of the metal plate.
  • the dimension L m ⁇ m ⁇ A m /L m .
  • the dimension L t and the dimension L m can be adjusted to be the same or close to each other.
  • thermoelectric member which is a member that constitutes the thermocouple together with the thermoelectric member in the Unileg type thermoelectric conversion element, is lowered.
  • Cheap the thermal conductance of the conductive member, which is a member that constitutes the thermocouple together with the thermoelectric member in the Unileg type thermoelectric conversion element
  • thermoelectric conversion element equipped with a thermoelectric member made of a bulk obtained through a manufacturing process that includes cutting, it is difficult to produce a metal plate that constitutes a thermocouple together with the thermoelectric member with a fine structure. Therefore, it is conceivable to manufacture a thermoelectric conversion element including a thin film thermoelectric member using a semiconductor manufacturing process or the like. In this case, a fine structure can easily be obtained by a method such as lithography. Therefore, instead of a metal plate, a conductive member that has a small end face that forms one end in the heat flow direction and that contains at least one member selected from the group consisting of metals and metal compounds is used to conduct each thin-film thermoelectric member. It is conceivable to connect electrically.
  • thermoelectric conversion element of the present disclosure was finally completed.
  • FIG. 1A is a cross-sectional view schematically showing an example of the thermoelectric conversion element of Embodiment 1.
  • the thermoelectric conversion element 1a includes a substrate 20, a thermocouple 10t, and a heat insulating material 11.
  • the thermocouple 10t includes a thin film thermoelectric member 10g and a conductive member 10m.
  • the thermoelectric member 10g and the conductive member 10m are arranged along the main surface of the substrate 20.
  • Each of the thermoelectric member 10g and the conductive member 10m extends along the main surface of the substrate 20, for example.
  • the conductive member 10m includes at least one selected from the group consisting of metals and metal compounds.
  • the heat insulating material 11 is in contact with the conductive member.
  • the thermal conductivity of the heat insulating material 11 is lower than that of the conductive member 10m. Due to the heat insulating material 11, the volume of the conductive member 10m tends to be reduced, for example, even if the conductive member 10m is not formed as a fine structure having a dimension of 1 ⁇ m or less in the direction parallel to the main surface of the substrate 20. Therefore, the thermal conductance of the conductive member 10m tends to be low. As a result, the thermoelectric conversion performance of the thermoelectric conversion element 1a tends to be high. In this specification, thermal conductivity means a value at 25°C. Note that the formation of fine structures with dimensions of 1 ⁇ m or less may require process node processes that involve high manufacturing costs.
  • the material forming the thermoelectric member 10g is not limited to a specific material.
  • the material may be a thermoelectric material with a positive Seebeck coefficient or a thermoelectric material with a negative Seebeck coefficient.
  • the material forming the thermoelectric member 10g is preferably a semiconductor material in which carriers responsible for electrical conduction can be adjusted to either holes or electrons by doping. Examples of such semiconductor materials are Si, SiGe, SiC, GaAs, InAs, InSb, InP, GaN, ZnO, and BiTe.
  • the thermoelectric member 10g may be made of other materials.
  • the material forming the thermoelectric member 10g may be a single crystal material, a polycrystalline material, or an amorphous material.
  • the thickness of the thermoelectric member 10g in the direction perpendicular to the main surface of the substrate 20 is not limited to a specific thickness.
  • the thickness is, for example, 100 nm or more and 10 ⁇ m or less.
  • the carrier density of the thermoelectric member 10g is not limited to a specific value.
  • the carrier density is, for example, in the range of 1 ⁇ 10 19 cm ⁇ 3 to 1 ⁇ 10 21 cm ⁇ 3 .
  • the metal or metal compound contained in the conductive member 10m is not limited to a specific metal or metal compound.
  • Examples of metals and metal compounds are materials used in semiconductor manufacturing processes such as Al, Cu, TiN, and TaN.
  • the thermal conductivity of the conductive member 10m is not limited to a specific value as long as the thermal conductivity of the heat insulating material 11 is lower than the thermal conductivity of the conductive member 10m.
  • the thermal conductivity of the conductive member 10m is, for example, 15 Wm -1 K -1 or more and 400 Wm -1 K -1 or less.
  • the dimension of the conductive member 10m in the direction perpendicular to the main surface of the substrate 20 is not limited to a specific value. Its dimensions may vary depending on the thickness of the thermoelectric member 10g. Its dimensions are, for example, 100 nm or more and 10 ⁇ m or less.
  • the maximum dimension of the conductive member 10m in the direction parallel to the main surface of the substrate 20 is not limited to a specific value. Its maximum dimension is, for example, 2 ⁇ m or more and 50 ⁇ m or less. According to such a configuration, the conductive member 10m can be formed without using a process node process that involves high manufacturing costs, and the manufacturing cost of the thermoelectric conversion element 1a is unlikely to increase.
  • the thermal conductivity of the heat insulating material 11 is not limited to a specific value as long as it is lower than the thermal conductivity of the conductive member 10m.
  • the thermal conductivity of the heat insulating material 11 is, for example, 10 Wm ⁇ 1 K ⁇ 1 or less. In this case, the thermal conductance of the structure including the conductive member 10m and the heat insulating material 11 tends to be low, and the thermal conductance of the entire thermoelectric conversion element 1a tends to be low. Therefore, the thermoelectric conversion performance of the thermoelectric conversion element 1a tends to be higher.
  • the thermal conductivity of the heat insulating material 11 may be 20 Wm -1 K -1 or less, or may be 10 Wm -1 K -1 or less.
  • the thermal conductivity of the heat insulating material 11 is, for example, 0.1 Wm ⁇ 1 K ⁇ 1 or more.
  • the heat insulating material 11 includes, for example, an amorphous material. In this case, the thermal conductivity of the heat insulating material 11 tends to decrease, and the thermal conductance of the structure including the conductive member 10m and the heat insulating material 11 tends to decrease.
  • the heat insulating material 11 may include a polycrystalline material.
  • the material forming the heat insulating material 11 is not limited to a specific material as long as the thermal conductivity of the heat insulating material 11 is lower than the thermal conductivity of the conductive member 10m. Examples of materials forming the heat insulating material 11 are oxides such as SiO 2 and Al 2 O 3 and metallic glass.
  • the ratio of the volume of the heat insulating material 11 to the sum of the volumes of the conductive member 10m and the heat insulating material 11 is not limited to a specific value.
  • the ratio is, for example, 50% to 90%. According to such a configuration, the thermal conductance of the structure including the conductive member 10m and the heat insulating material 11 tends to be lower, and the overall thermal conductance of the thermoelectric conversion element 1a tends to be lower.
  • the conductive member 10m tends to have desired electrical conductivity.
  • the substrate 20 includes, for example, a base 20a and a base insulating film 20b.
  • a first wiring 30a is arranged on the base insulating film 20b.
  • a thermoelectric member 10g and a conductive member 10m are arranged on the first wiring 30a.
  • a second wiring 30b is arranged on the thermoelectric member 10g and the conductive member 10m.
  • One end surface of the thermoelectric member 10g and the conductive member 10m in the direction perpendicular to the main surface of the substrate 20 is electrically connected to the first wiring 30a.
  • the other end surfaces of the thermoelectric member 10g and the conductive member 10m in the direction perpendicular to the main surface of the substrate 20 are electrically connected to the second wiring 30b.
  • FIG. 1A the heat insulating material 11 is covered with, for example, the second wiring 30b.
  • FIG. 1B is a cross-sectional view schematically showing another example of the thermoelectric conversion element of Embodiment 1.
  • the thermoelectric conversion element 1b shown in FIG. 1B has the same structure as the thermoelectric conversion element 1a except for the parts to be particularly described.
  • the heat insulating material 11 does not need to be covered by the second wiring 30b.
  • thermoelectric member 10g and the conductive member 10m are electrically connected in series by a first wiring 30a and a second wiring 30b.
  • a thermocouple 10t is configured by the thermoelectric member 10g and the conductive member 10m.
  • the thermoelectric conversion element 1a further includes, for example, a first interlayer insulating film 41 and a second interlayer insulating film 42.
  • the first interlayer insulating film 41 is arranged between the first wiring 30a and the second wiring 30b in a direction perpendicular to the main surface of the substrate 20.
  • the first interlayer insulating film 41 is formed to fill the gap between the thermoelectric member 10g and the conductive member 10m and the periphery of the thermoelectric member 10g and the conductive member 10m.
  • the second interlayer insulating film 42 is formed to cover the second wiring 30b.
  • the thermoelectric conversion element 1a includes, for example, a plurality of plugs 53.
  • Plug 53 extends through second interlayer insulating film 42 in a direction perpendicular to the main surface of substrate 20 .
  • the plug 53 is placed on the second wiring 30b and is electrically connected to the second wiring 30b.
  • the thermoelectric conversion element 1a includes, for example, a first electrode pad 51 and a second electrode pad 52. Each of the first electrode pad 51 and the second electrode pad 52 is electrically connected to a different plug 53. Thereby, the thermocouple 10t is electrically connected to the first electrode pad 51 and the second electrode pad 52 between the first electrode pad 51 and the second electrode pad 52.
  • thermoelectric member 10g is not limited to a specific shape.
  • 2A to 2F are plan views showing examples of the thermoelectric member 10g.
  • the thermoelectric member 10g may have a quadrilateral shape such as a square or a rectangle, a pentagonal shape, a hexagonal shape, or any other shape in a plan view. It may be polygonal.
  • the thermoelectric member 10g may be circular or oval.
  • the arrangement of the heat insulator 11 and the conductive member 10m is not limited to a specific embodiment.
  • the heat insulating material 11 is surrounded by, for example, a conductive member 10m. According to such a configuration, the thermal conductance of the structure including the conductive member 10m and the heat insulating material 11 tends to be low, and the conductive member 10m tends to have desired electrical conductivity.
  • the conductive member 10m may be configured to have at least one selected from the group consisting of a cavity and a recess.
  • the heat insulating material 11 may be arranged to fill at least a portion of the cavity or at least a portion of the recess.
  • FIGS. 3A to 3H are plan views showing examples of the conductive member 10m.
  • the conductive member 10m has, for example, a cavity 10j.
  • the cavity 10j extends, for example, in a direction perpendicular to the main surface of the substrate 20.
  • the cavity 10j may extend through the conductive member 10m in the direction perpendicular to the main surface of the substrate 20, or the cavity 10j may extend through at least both ends of the conductive member 10m in the direction perpendicular to the main surface of the substrate 20. It may extend away from one.
  • the conductive member 10m may include a plurality of cavities 10j. As shown in FIGS.
  • the conductive member 10m may have a quadrilateral outline such as a square or a rectangle, a pentagonal outline, or a hexagonal outline in a plan view. It may have a contour of the shape.
  • the conductive member 10m may have another polygonal contour in plan view.
  • the conductive member 10m may have a circular outline or an elliptical outline in plan view.
  • the cavity 10j of the conductive member 10m has, for example, a polygonal shape such as a quadrangle in plan view.
  • the cavity 10j of the conductive member 10m may be, for example, circular or elliptical in plan view.
  • the conductive member 10m has, for example, a recess 10k.
  • the conductive member 10m may have a plurality of recesses 10k.
  • the recess 10k may be separated from one of the ends of the conductive member 10m in the direction parallel to the main surface of the substrate 20.
  • the recess 10k may extend through the conductive member 10m in a direction parallel to the main surface of the substrate 20.
  • the ratio of the volume of the cavity 10j and the recess 10k to the sum of the volume of the conductive member 10m and the volume of the cavity 10j and the recess 10k is not limited to a specific value.
  • the ratio is, for example, 50% or more and 90% or less. According to such a configuration, the thermal conductance of the structure including the conductive member 10m and the heat insulating material 11 tends to be lower, and the overall thermal conductance of the thermoelectric conversion element 1a tends to be lower.
  • the conductive member 10m tends to have desired electrical conductivity.
  • FIG. 4A is a cross-sectional view of the thermocouple taken along the line IVA-IVA in FIG. 1A.
  • 4B to 4E are cross-sectional views showing another example of the arrangement of the thermoelectric member 10g and the conductive member 10m in the thermocouple 10t of the first embodiment.
  • the outer dimensions of the thermoelectric member 10g and the conductive member 10m in plan view may be the same or different.
  • the side surfaces of the thermoelectric member 10g and the side surfaces of the conductive member 10m may face each other in one direction, as shown in FIGS. 4A and 4B, or may face each other in a plurality of different directions, as shown in FIGS. 4C, 4D, and 4E. You can face each other.
  • the material forming the base 20a is not limited to a specific material.
  • the base 20a is, for example, a Si substrate.
  • the base 20a may be made of a semiconductor other than Si or a material other than a semiconductor.
  • the material forming the base insulating film 20b is not limited to a specific material.
  • the base insulating film 20b may contain an oxide insulator such as silicon oxide and aluminum oxide, or may contain a nitride insulator such as silicon nitride and aluminum nitride. When the base 20a has electrical insulation, the underlying insulating film 20b may be omitted.
  • the thickness of the base insulating film 20b is not limited to a specific value. Its thickness is, for example, 50 nm to 1 ⁇ m.
  • the material forming the first wiring 30a and the second wiring 30b is not limited to a specific material as long as it has a predetermined conductivity.
  • the first wiring 30a and the second wiring 30b include, for example, a metal or a metal compound. Examples of metals and metal compounds are materials used in semiconductor manufacturing processes such as Al, Cu, TiN, and TaN.
  • the thicknesses of the first wiring 30a and the second wiring 30b are not limited to specific values. Its thickness is, for example, 100 nm to 1 ⁇ m.
  • the materials forming the first interlayer insulating film 41 and the second interlayer insulating film 42 are not limited to specific materials.
  • the first interlayer insulating film 41 and the second interlayer insulating film 42 may contain an oxide insulator such as silicon oxide and aluminum oxide, or may contain a nitride insulator such as silicon nitride and aluminum nitride. Good too.
  • the material forming the first interlayer insulating film 41 and the second interlayer insulating film 42 may be a single crystal material, a polycrystalline material, or an amorphous material.
  • the materials forming the first interlayer insulating film 41 and the second interlayer insulating film 42 may be the same type of material, or may be different types of materials.
  • the thickness of the first interlayer insulating film 41 can vary depending on the thickness of the thermoelectric member 10g. Its thickness is, for example, from 100 nm to 10 ⁇ m.
  • the thickness of the second interlayer insulating film 42 is not limited to a specific value as long as it can cover the second wiring 30b. Its thickness is, for example, 100 nm to 2 ⁇ m.
  • the materials forming the plug 53, the first electrode pad 51, and the second electrode pad 52 are not limited to specific materials.
  • the material is, for example, a metal or a metal compound.
  • the metals and metal compounds may be materials used in semiconductor manufacturing processes, such as Al, Cu, W, TiN, and TaN, for example.
  • the thermoelectric conversion element 1a includes, for example, a plurality of thermocouples 10t.
  • the plurality of thermocouples 10t are electrically connected in series between the first electrode pad 51 and the second electrode pad 52.
  • thermoelectric conversion element of Embodiment 1 when a temperature difference occurs in a direction perpendicular to the main surface of the substrate 20, an electromotive force is generated between the first electrode pad 51 and the second electrode pad 52 due to the Seebeck effect. This electromotive force is output to the outside of the thermoelectric conversion element by the conductive wires connected to the first electrode pad 51 and the second electrode pad 52. Thereby, the thermoelectric conversion element can be used as a power generation device and a heat flow sensor.
  • thermoelectric conversion element of Embodiment 1 by connecting conductive wires to the first electrode pad 51 and the second electrode pad 52 to generate a current, a heat flow is generated in a direction perpendicular to the main surface of the substrate 20 due to the Peltier effect. be able to. The direction of heat flow can change depending on the direction of the current. Thereby, the thermoelectric conversion element of Embodiment 1 can be used as a temperature control device for cooling or heating.
  • the method for manufacturing the thermoelectric conversion element of Embodiment 1 includes arranging the heat insulating material 11 along the main surface of the substrate 10 together with the thin film thermoelectric member 10g and in contact with the conductive member 10m containing a metal or a metal compound. including.
  • the conductive member 10m has at least one selected from the group consisting of a cavity and a recess, the heat insulating material 11 is arranged so as to fill the cavity or the recess.
  • a base insulating film 20b made of an electrical insulator such as SiO 2 is formed on the surface of a base 20a such as a Si substrate by a method such as sputtering or chemical vapor deposition (CVD), thereby obtaining a substrate 20.
  • a first wiring 30a made of a conductor such as Al is formed.
  • a pattern forming the first wiring 30a is formed by photolithography and etching or lift-off from a film of Al or the like formed by a method such as sputtering.
  • a first interlayer insulating film 41 is formed by a method such as sputtering or CVD so as to cover the first wiring 30a.
  • a recess 15 is formed in the first interlayer insulating film 41 by photolithography and etching. At this stage, a portion of the first wiring 30a is exposed to form the bottom surface of the recess 15.
  • a thermoelectric material thin film 12 made of a semiconductor such as polycrystalline Si is formed from above the first interlayer insulating film 41 by a method such as sputtering or CVD. filled by.
  • FIG. 5C a first interlayer insulating film 41 is formed by a method such as sputtering or CVD so as to cover the first wiring 30a.
  • a recess 15 is formed in the first interlayer insulating film 41 by photolithography and etching. At this stage, a portion of the first wiring 30a is exposed to form the bottom surface of the recess 15.
  • thermoelectric member 10g the thermoelectric material thin film 12 outside the recess 15 is removed by a method such as chemical mechanical polishing (CMP).
  • CMP chemical mechanical polishing
  • a predetermined region is doped to obtain a thermoelectric member 10g.
  • a method such as ion implantation is used for doping.
  • An annealing treatment may be additionally performed to adjust the carrier density to a desired range.
  • the thermoelectric member 10g may be formed as an n-type thermoelectric member having a negative Seebeck coefficient, or may be formed as a p-type thermoelectric member having a positive Seebeck coefficient.
  • Si trivalent elements
  • a thermoelectric member 10g that is an n-type thermoelectric member can be obtained.
  • Si doping Si with pentavalent elements such as boron and gallium, a thermoelectric member 10g which is a p-type thermoelectric member is obtained.
  • a recess 16 is formed in the first interlayer insulating film 41 by photolithography and etching. At this stage, a portion of the first wiring 30a is exposed to form the bottom surface of the recess 16.
  • a metal thin film 13 containing a metal such as Al is formed from above the first interlayer insulating film 41 by methods such as sputtering and CVD.
  • the metal thin film 13 covers the bottom and side surfaces of the recess 16 .
  • the metal thin film 13 outside the recess 16 is removed by photolithography and etching to form a conductive member 10m having a cavity 10j.
  • the cavity 10j is filled from above the first interlayer insulating film 41 with a heat insulating material 11 made of amorphous material such as SiO 2 by sputtering or CVD.
  • a heat insulating material 11 made of amorphous material such as SiO 2 by sputtering or CVD.
  • the heat insulating material 11 outside the cavity 10j is removed by a method such as CMP.
  • a second wiring 30b containing a conductor such as Al is formed.
  • a pattern forming the second wiring 30b is formed from a film of Al or the like formed by a method such as sputtering by photolithography, etching, or lift-off.
  • a second interlayer insulating film 42 is formed of an electrical insulator such as SiO 2 so as to cover the second wiring 30b by a method such as sputtering or CVD.
  • the second wiring 30b and the conductive member 10m may include the same type of material.
  • the second wiring 30b and the conductive member 10m having the cavity 10j may be formed in the same process by photolithography and etching or lift-off.
  • a second interlayer insulating film 42 containing an electrical insulator such as SiO 2 the formation of the second interlayer insulating film 42 and the filling of the heat insulating material 11 into the cavity 10j of the conductive member 10m are performed at the same time. It can be carried out in a process.
  • the second interlayer insulating film 42 and the heat insulating material 11 may be made of the same type of material.
  • a recess 53h is formed in the second interlayer insulating film 42 by photolithography and etching. At this stage, a portion of the second wiring 30b is exposed to form the bottom surface of the recess 53h.
  • thermoelectric conversion element of Embodiment 1 is obtained.
  • the base insulating film 20b, the first interlayer insulating film 41, and the second interlayer insulating film 42 may be formed of different materials, and only the first interlayer insulating film 41 may be removed by etching at the end.
  • the first interlayer insulating film 41 is made of SiO 2
  • the base insulating film 20b and the second interlayer insulating film 42 are made of Al 2 O 3 . Thereafter, the first interlayer insulating film 41 may be removed by etching the SiO 2 with gaseous hydrofluoric acid.
  • thermoelectric conversion element By removing the first interlayer insulating film 41 around the thermoelectric member 10g and the conductive member 10m, the space between one end surface and the other end surface in the direction perpendicular to the main surface of the substrate 20 in the thermoelectric member 10g and the conductive member 10m is removed.
  • the temperature difference that occurs tends to become large. As a result, the performance of the thermoelectric conversion element tends to be higher.
  • FIG. 6A is a cross-sectional view schematically showing an example of the thermoelectric conversion element of Embodiment 2.
  • the thermoelectric conversion element of Embodiment 2 is configured in the same manner as the thermoelectric conversion element of Embodiment 1, except for particularly explained parts.
  • Components of Embodiment 2 that are the same as or correspond to components of the thermoelectric conversion element of Embodiment 1 are given the same reference numerals, and detailed description thereof will be omitted.
  • the description regarding the thermoelectric conversion element of Embodiment 1 also applies to the thermoelectric conversion element of Embodiment 2, unless technically contradictory.
  • thermoelectric member 10g has a first portion 10q and a second portion 10r.
  • First portion 10q has a first thickness.
  • the second portion 10r has a second thickness smaller than the first thickness.
  • a step is formed by the first portion 10q and the second portion 10r. According to such a configuration, for example, the configuration corresponding to the first wiring 30a of the thermoelectric conversion element of Embodiment 1 can be omitted, and the configuration of the thermoelectric conversion element can be easily simplified.
  • the thermoelectric member 10g may include a p-type thermoelectric material having a positive Seebeck coefficient, or may include an n-type thermoelectric material having a negative Seebeck coefficient.
  • the conductive member 10m is placed, for example, on the second portion 10r. According to such a configuration, even if the configuration corresponding to the first wiring 30a of the thermoelectric conversion element of Embodiment 1 is omitted, the electrical connection between the conductive member 10m and the thermoelectric member 10g can be ensured.
  • the second portion 10r plays the same role as the first wiring 30a in the thermoelectric conversion element of the first embodiment.
  • the second thickness of the second portion 10r is not limited to a specific value as long as it is smaller than the first thickness.
  • the second thickness is, for example, 10 nm or more, and preferably 100 nm or more.
  • FIG. 6A the wiring 30 is arranged on the thermoelectric member 10g and the conductive member 10m. Thereby, the thermoelectric member 10g and the conductive member 10m are electrically connected to form a thermocouple 10t.
  • the heat insulating material 11 is covered with, for example, a wiring 30.
  • FIG. 6B is a cross-sectional view schematically showing another example of the thermoelectric conversion element of Embodiment 2.
  • the thermoelectric conversion element 1d shown in FIG. 6B has the same structure as the thermoelectric conversion element 1c except for the parts to be particularly described. As shown in FIG. 6B, the heat insulating material 11 does not need to be covered by the wiring 30.
  • thermoelectric conversion element 1c further includes a first interlayer insulating film 41 and a second interlayer insulating film 42.
  • the first interlayer insulating film 41 is formed to fill the gap between the thermoelectric member 10g and the conductive member 10m and the space around the thermoelectric member 10g and the conductive member 10m.
  • the second interlayer insulating film 42 is formed on the first interlayer insulating film 41 and covers the wiring 30.
  • the thermoelectric conversion element 1c includes a plurality of plugs 53.
  • the plug 53 penetrates the second interlayer insulating film 42 and is arranged on the wiring 30.
  • the plug 53 is electrically connected to the wiring 30.
  • a first electrode pad 51 and a second electrode pad 52 are arranged on the second interlayer insulating film 42 .
  • the first electrode pad 51 and the second electrode pad 52 are electrically connected to different plugs 53.
  • the thermocouple 10t is electrically connected to the first electrode pad 51 and the second electrode pad 52 between the first electrode pad 51 and the second electrode pad 52.
  • FIG. 7A is a cross-sectional view of the thermocouple 10t taken along line VIIA-VIIA in FIG. 6A.
  • 7B to 7D are cross-sectional views showing another example of the arrangement of the thermoelectric member 10g and the conductive member 10m in the thermocouple 10t of the second embodiment.
  • the side surface of the thermoelectric member 10g and the side surface of the conductive member 10m may face each other in one direction, or may face each other in a plurality of different directions as shown in FIGS. 7B, 7C, and 7D. It's okay.
  • thermoelectric conversion element of Embodiment 2 An example of a method for manufacturing the thermoelectric conversion element of Embodiment 2 will be described.
  • the method for manufacturing the thermoelectric conversion element of Embodiment 2 is not limited to the following method.
  • a base insulating film 20b is formed on one main surface of the base 20a.
  • the base 20a is, for example, a Si substrate.
  • the base insulating film 20b is, for example, an electrical insulator such as SiO 2 and is formed by a method such as sputtering or CVD.
  • a thermoelectric material thin film 18 is formed on the base insulating film 20b.
  • the thermoelectric material thin film 18 is, for example, a semiconductor such as polycrystalline Si, and is formed by a method such as sputtering or CVD.
  • the laminated body of the base 20a, the base insulating film 20b, and the thermoelectric material thin film 18 may be replaced by a silicon-on-insulator (SOI) substrate.
  • SOI silicon-on-insulator
  • the layer corresponding to the base insulating film 20b is a layer of SiO2
  • the layer corresponding to the thermoelectric material thin film 18 is a layer of single crystal Si.
  • impurity ions are doped into the thermoelectric material thin film 18, and the carrier density of electrons or holes is adjusted to a range of 1 ⁇ 10 19 cm ⁇ 3 to 1 ⁇ 10 21 cm ⁇ 3 .
  • Doping is performed, for example, by methods such as ion implantation and thermal diffusion. An additional annealing treatment may be performed to adjust the carrier density to a desired value. Doping may be performed on the entire surface of the thin film 18 for thermoelectric material, or may be performed on a predetermined region using photolithography.
  • a recess 19 is formed in a predetermined region of the thermoelectric material thin film 18 by photolithography and etching.
  • the depth of the recess 19 is adjusted in consideration of the second thickness of the second portion 10r. For example, by measuring the etching rate of the thin film 18 for thermoelectric material in advance and adjusting the etching time based on the measurement result, the depth of the recess 19 can be adjusted to a range suitable for the second thickness of the second portion 10r. Can be adjusted.
  • thermoelectric member 10g is formed by photolithography and etching.
  • a first interlayer insulating film 41 made of a material such as SiO 2 is formed from above the thermoelectric member 10g by a method such as sputtering or CVD so as to cover the thermoelectric member 10g.
  • a portion of the first interlayer insulating film 41 above the thermoelectric member 10g is removed by a method such as CMP.
  • a recess 16 is formed in a predetermined region of the first interlayer insulating film 41 by photolithography and etching. At this stage, a portion of the second portion 10r is exposed so as to form the bottom surface of the recess 16.
  • a metal thin film 13 containing a metal such as Al is formed from above the first interlayer insulating film 41 by methods such as sputtering and CVD. The metal thin film 13 covers the bottom and side surfaces of the recess 16 .
  • the metal thin film 13 outside the recess 16 is removed by photolithography and etching to form a conductive member 10m having a cavity 10j.
  • the cavity 10j is filled from above the first interlayer insulating film 41 with a heat insulating material 11 made of amorphous material such as SiO 2 by sputtering or CVD.
  • a heat insulating material 11 made of amorphous material such as SiO 2 by sputtering or CVD.
  • the heat insulating material 11 outside the cavity 10j is removed by a method such as CMP.
  • wiring 30 containing a conductor such as Al is formed.
  • a pattern forming the wiring 30 is formed by photolithography and etching or lift-off from a film of Al or the like formed by a method such as sputtering.
  • a second interlayer insulating film 42 is formed of an electrical insulator such as SiO 2 so as to cover the wiring 30 by a method such as sputtering or CVD.
  • the wiring 30 and the conductive member 10m include the same type of material
  • the wiring 30 and the conductive member 10m having the cavity 10j are formed in the same process by photolithography and etching or lift-off after the metal thin film 13 is formed. may be done.
  • a second interlayer insulating film 42 containing an electrical insulator such as SiO 2 the formation of the second interlayer insulating film 42 and the filling of the heat insulating material 11 into the cavity 10j of the conductive member 10m are performed at the same time. It can be carried out in a process.
  • the second interlayer insulating film 42 and the heat insulating material 11 may be made of the same type of material.
  • a recess 53h is formed in the second interlayer insulating film 42 by photolithography and etching. At this stage, a portion of the wiring 30 is exposed to form the bottom surface of the recess 53h.
  • thermoelectric conversion element of the second embodiment is obtained.
  • thermocouple including a thin film thermoelectric member and a conductive member arranged along the main surface of the substrate; a heat insulating material in contact with the conductive member,
  • the conductive member includes at least one selected from the group consisting of metals and metal compounds,
  • the thermal conductivity of the heat insulating material is lower than the thermal conductivity of the electrically conductive member.
  • Thermoelectric conversion element
  • thermoelectric conversion performance of the Unileg type thermoelectric conversion element including the thin-film thermoelectric member tends to be high.
  • thermoelectric conversion performance of the thermoelectric conversion element tends to be higher.
  • the thermal conductivity of the heat insulating material is 10 Wm -1 K -1 or less, Thermoelectric conversion element according to technology 1 or 2.
  • thermoelectric conversion performance of the thermoelectric conversion element 1a tends to be higher.
  • the heat insulating material includes an amorphous material.
  • the thermoelectric conversion element according to any one of Techniques 1 to 3.
  • thermoelectric conversion performance of the thermoelectric conversion element tends to be higher.
  • thermoelectric conversion element according to any one of Techniques 1 to 4.
  • thermoelectric conversion performance of the thermoelectric conversion element tends to be higher.
  • thermoelectric member includes a first portion having a first thickness and a second portion having a second thickness smaller than the first thickness, A step is formed by the first part and the second part, The thermoelectric conversion element according to any one of Techniques 1 to 5.
  • thermoelectric conversion element With this configuration, the configuration corresponding to the first wiring 30a of the thermoelectric conversion element of Embodiment 1 can be omitted. Therefore, the configuration of the thermoelectric conversion element tends to be simple.
  • thermoelectric conversion element of Embodiment 1 Even if the configuration corresponding to the first wiring 30a of the thermoelectric conversion element of Embodiment 1 is omitted, the electrical connection between the conductive member and the thermoelectric member can be ensured.
  • a heat insulating material is arranged along the main surface of the substrate together with a thin film thermoelectric member, and includes arranging a heat insulating material so as to be in contact with a conductive member containing at least one selected from the group consisting of a metal and a metal compound, The thermal conductivity of the heat insulating material is lower than the thermal conductivity of the electrically conductive member.
  • the thermal conductance of the conductive member can be lowered by the heat insulating material. Therefore, it is easy to improve the thermoelectric conversion performance of the thermoelectric conversion element while suppressing manufacturing costs.
  • thermoelectric conversion element of Embodiment 1 is not limited to each aspect shown in the following examples.
  • Example A-1 to Sample A-10> A 100 nm thick Al thin film was formed on a 100 nm thick SiO 2 thin film formed on a Si substrate. Photolithography and etching were performed on this Al thin film to form a pattern that would become the first wiring. Next, a SiO 2 film with a thickness of 1.1 ⁇ m was formed to cover the first wiring to obtain a first interlayer insulating film. Photolithography and etching were performed on the first interlayer insulating film to form recesses in the first interlayer insulating film. At this time, a part of the first wiring was exposed so as to form the bottom surface of the recess.
  • thermoelectric member a thin film of polycrystalline Si was formed, and the polycrystalline Si outside the recess was removed by CMP to form a thin film for thermoelectric material in the recess.
  • boron ions were implanted as an impurity into the thin film for thermoelectric material at a dose of 1 ⁇ 10 16 cm ⁇ 2 to obtain a Si thermoelectric member.
  • the bottom surface of the Si thermoelectric member had a square shape with a side length of 100 ⁇ m, and the thickness of the Si thermoelectric member was 1 ⁇ m.
  • a recessed portion was formed in a region of the first interlayer insulating film adjacent to the Si thermoelectric member by photolithography and etching.
  • an Al thin film was formed on the first interlayer insulating film.
  • the Al thin film was formed to cover the bottom and side surfaces of the recess.
  • the Al thin film existing in the area away from the recess is removed, leaving a part of the Al thin film around the recess and the Al thin film on the Si thermoelectric member, and forming the second wiring. Obtained.
  • an Al member having a cavity surrounded by an Al thin film corresponding to the recess in plan view was formed.
  • the bottom surface of the Al member had a square shape with a side length of 100 ⁇ m, and the height, which is the dimension of the Al member in the direction perpendicular to the main surface of the Si substrate, was 1 ⁇ m.
  • the ratio of the volume of the cavity to the sum of the volume of the Al member and the volume of the cavity was 90%.
  • a SiO 2 thin film was formed from above the cavity to fill the entire cavity with SiO 2 .
  • SiO 2 around the Si thermoelectric member and Al member was removed by photolithography and etching to expose a portion of the second wiring. In this way, an element of sample A-1 was obtained.
  • Sample A-1 except that the conditions for forming the Al thin film for producing the Al member were adjusted so that the ratio of the volume of the cavity to the sum of the volume of the Al member and the volume of the cavity was the value shown in Table 1.
  • elements of samples A-2 to A-10 were obtained.
  • the Al member was formed so that no cavities were formed.
  • Sample B-1 to Sample B-10 Elements of samples B-1 to B-10 were fabricated in the same manner as sample A-1 except for the following points.
  • the bottom surface of the Al member had a square shape with a side length of 30 ⁇ m.
  • the conditions for forming the Al thin film for producing the Al members were such that the ratio of the volume of the cavity to the sum of the volume of the Al member and the volume of the cavity was the value shown in Table 2. has been adjusted.
  • Sample C-1 to Sample C-10 Elements of samples C-1 to C-10 were fabricated in the same manner as sample A-1 except for the following points.
  • the bottom surface of the Al member had a square shape with a side length of 20 ⁇ m.
  • the conditions for forming the Al thin film for producing the Al members were set such that the ratio of the volume of the cavity to the sum of the volume of the Al member and the volume of the cavity became the value shown in Table 3. has been adjusted.
  • thermoelectric performance of each sample element was evaluated, and the dimensionless figure of merit ZT at 300K was determined.
  • the electrical resistance of each sample element was measured according to the four-terminal method via the first wiring.
  • the thermal conductance of each sample element was measured according to the thermoreflectance method. Note that a sample containing a polycrystalline Si thin film and an Al thin film fabricated on different substrates was separately fabricated, and the Seebeck coefficient of the Si thermoelectric member was determined using a measuring device ZEM3 manufactured by ULVAC Riko Co., Ltd. and this sample. The value of this Seebeck coefficient was used to determine the dimensionless figure of merit ZT.
  • the dimensionless figure of merit ZT of the element of sample A-4 was more than twice that of the element of sample A-10, which had no cavity in the Al member.
  • the ratio of the volume of the cavity to the sum of the volume of the Al member and the volume of the cavity was 60%, and the cavity was filled with SiO 2 .
  • the thermal conductivity of SiO 2 is lower than that of Al.
  • the dimensionless figure of merit ZT of the element of sample B-3 was more than twice that of the element of sample B-10, which had no cavity in the Al member.
  • the ratio of the volume of the cavity to the sum of the volume of the Al member and the volume of the cavity was 70%, and the cavity was filled with SiO 2 .
  • the dimensionless figure of merit ZT of the element of sample C-2 was more than twice that of the element of sample C-10, which had no cavity in the Al member.
  • the ratio of the volume of the cavity to the sum of the volume of the Al member and the volume of the cavity was 80%, and the cavity was filled with SiO 2 .
  • thermoelectric conversion element of the present disclosure can be used for various purposes including, for example, power generation and temperature control.

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JP2015115590A (ja) * 2013-12-16 2015-06-22 日本特殊陶業株式会社 熱電変換モジュール
JP2017135278A (ja) * 2016-01-28 2017-08-03 積水化学工業株式会社 熱電変換デバイス
JP2017152691A (ja) * 2016-02-24 2017-08-31 三菱マテリアル株式会社 マグネシウム系熱電変換材料の製造方法、マグネシウム系熱電変換素子の製造方法、マグネシウム系熱電変換材料、マグネシウム系熱電変換素子、熱電変換装置
WO2019171915A1 (ja) * 2018-03-08 2019-09-12 住友電気工業株式会社 熱電材料素子、発電装置、光センサおよび熱電材料の製造方法
WO2022092177A1 (ja) * 2020-10-30 2022-05-05 リンテック株式会社 熱電変換モジュール

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JP2015115590A (ja) * 2013-12-16 2015-06-22 日本特殊陶業株式会社 熱電変換モジュール
JP2017135278A (ja) * 2016-01-28 2017-08-03 積水化学工業株式会社 熱電変換デバイス
JP2017152691A (ja) * 2016-02-24 2017-08-31 三菱マテリアル株式会社 マグネシウム系熱電変換材料の製造方法、マグネシウム系熱電変換素子の製造方法、マグネシウム系熱電変換材料、マグネシウム系熱電変換素子、熱電変換装置
WO2019171915A1 (ja) * 2018-03-08 2019-09-12 住友電気工業株式会社 熱電材料素子、発電装置、光センサおよび熱電材料の製造方法
WO2022092177A1 (ja) * 2020-10-30 2022-05-05 リンテック株式会社 熱電変換モジュール

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