WO2007023548A1 - Matériau thermoélectrique et procédé d'élaboration - Google Patents

Matériau thermoélectrique et procédé d'élaboration Download PDF

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Publication number
WO2007023548A1
WO2007023548A1 PCT/JP2005/015432 JP2005015432W WO2007023548A1 WO 2007023548 A1 WO2007023548 A1 WO 2007023548A1 JP 2005015432 W JP2005015432 W JP 2005015432W WO 2007023548 A1 WO2007023548 A1 WO 2007023548A1
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WIPO (PCT)
Prior art keywords
mnsi
manganese
thermoelectric
single crystal
base material
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PCT/JP2005/015432
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English (en)
Japanese (ja)
Inventor
Ikuto Aoyama
Mikhail Ivanovich Fedorov
Vladimir Konstantinovich Zaitsev
Fedor Yurievich Solomkin
Ivan Sergeevich Eremin
Aleksandr Yurievich Samunin
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Komatsu Ltd.
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Priority to PCT/JP2005/015432 priority Critical patent/WO2007023548A1/fr
Publication of WO2007023548A1 publication Critical patent/WO2007023548A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/003—Heating or cooling of the melt or the crystallised material
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/34—Silicates
    • 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
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen

Definitions

  • the present invention relates to a thermoelectric material having thermoelectric performance including a Thomson effect, a Peltier effect, and a Seebeck effect, and a method for manufacturing the thermoelectric material.
  • the present invention relates to a p-type thermoelectric material, which is a semiconductor using holes as carriers, and a method for manufacturing the same.
  • thermoelectric modules that convert thermal energy and electrical energy to each other are configured by combining two types of thermoelectric elements using the thermoelectric effect called the Thomson effect, Peltier effect, Seebeck effect, and so on. This also applies to elements.
  • thermoelectric effect called the Thomson effect, Peltier effect, Seebeck effect, and so on.
  • semiconductors are used as thermoelectric materials, P-type semiconductors and N-type semiconductors are combined.
  • thermoelectric material In general, the performance of a thermoelectric material is characterized by a figure of merit Z expressed by the following equation (1).
  • oc is the Seebeck constant
  • ⁇ is the electrical conductivity
  • ⁇ is the thermal conductivity
  • thermoelectric material As shown in Equation (1), the larger the Seebeck constant ⁇ and the electrical conductivity ⁇ , and the smaller the thermal conductivity ⁇ , the higher the figure of merit of the thermoelectric material. Therefore, semiconductor materials are generally suitable as thermoelectric materials.
  • thermoelectric materials are produced by adding appropriate impurities to a semiconductor material as a base material and optimizing thermoelectric characteristics such as the Seebeck constant. These thermoelectric properties are closely related to the carrier concentration, and the energy gap of the base material is one factor that determines the carrier concentration along with the environmental temperature.
  • the temperature characteristic of the figure of merit ⁇ has a maximum value, and the temperature region that gives this maximum value depends greatly on the energy gap of the base material. That is, there is an optimum temperature range for each base material.
  • manganese silicide MnSi manganese silicide MnSi
  • 1.7 ⁇ y ⁇ 1.8 has an energy gap of 0.67eV and a medium temperature range (about 300 ° C to 550 ° C) The degree of performance is high.
  • Figure 1 is a binary phase diagram of Mn—Si
  • Figure 2 shows the crystallization of MnSi (1.7 ⁇ y ⁇ 1.8).
  • FIG. 1 It is a schematic diagram which shows the process to advance.
  • symbols (a) to (d) shown in FIG. 1 correspond to the crystallization processes (a) to (d) shown in FIG.
  • the MnSi (1.7 ⁇ y ⁇ 1.8) crystal has a stoichiometric composition (stoichiometry) y as shown in Fig. 2 (a).
  • the melt containing Mn and Si adjusted so as to satisfy the above conditions is produced by cooling and crystallizing while controlling the cooling rate as shown in (b) to (d) of FIG.
  • M nSi (1.7 ⁇ y ⁇ 1.8) is crystallized while undergoing peritectic reaction as shown in Fig. 2 (c).
  • thermoelectric materials 3 X 10 _4 K- 1 to 4 X 10 _4 _1 _1 ( (Page 69).
  • the area fraction of MnSi is reported to be 2vol.% To 3vol.% According to microscopic observation.
  • Such layered MnSi may increase to about 10 vol.% Depending on the crystal production conditions.
  • HMS p-type Higher Mnganese Silicide
  • MnSi manganese monosilicide
  • MnSi is a P-type good conductor having metallic characteristics and is not suitable for thermoelectric materials. Therefore, MnSi where MnSi is deposited (1.7 ⁇ y ⁇ 1.8) is
  • the figure of merit Z is expected to decline.
  • Kawasumi, et al. “Manganese 'Silicide MnSi Crystal Growth and Mn Si Semiconductor Properties (Crystal growth of manga)
  • JP-A Japanese Patent Application Publication
  • thermoelectric material is made into ultrafine particles, and ultrafine particles that do not react with the base material are added to the uniformly distributed state and sintered to produce ultrafine crystal grains.
  • a thermoelectric material is disclosed. Also, JP-A-9
  • JP-A-7 38156 discloses a composite composed of silicon (Si) and silicon carbide (SiC) as a thermoelectric material having high thermoelectric conversion efficiency, low density, and low thermal conductivity at high temperatures.
  • a thermoelectric power generation material having a silicon average particle size of 10 m or less and a silicon carbide average particle size of 1 ⁇ m or less is disclosed.
  • the second phase (MnSi), which has inferior thermoelectric properties than the base material (MnSi (1.7 ⁇ y ⁇ 1.8)
  • RNAL OF APPLIED PHYSICS No. 14 (1975), No. 1, p. 141-142), MnSi is not present by chemical transport growth method.
  • MnSi (1.7 ⁇ y ⁇ l. 8) Synthesize y
  • JP-A-2002-3325008 Japanese Patent Application Publication JP-A-2002-332508 analyzes the synthesized MnSi sintered body by powder X-ray diffraction, and the MnSi peak scale of the matrix MnSi is analyzed. Since no peak is observed, it is claimed that a single phase structure can be synthesized by sintering without the presence of a second phase.
  • JP-A-2002-332508 contains raw materials for producing MnSi-based thermoelectric materials in a short time and at a low cost, since the crystal grains with less prejudice are fine and impurities are mixed.
  • a melting process for melting the material a raw material melted by the melting process is dropped, spray gas is sprayed on the raw material being dripped, rapidly cooled and pulverized to obtain a MnSi-based thermoelectric material,
  • the MnSi system including a molding process in which the powdered MnSi thermoelectric material obtained in the cooling / powdering process is formed into a desired shape by pressing, sintering, or pressure sintering.
  • a method for manufacturing a thermoelectric material is disclosed!
  • thermoelectric characteristic of a MnSi—MnSi (1.7 ⁇ y ⁇ 1.8) composite material In contrast, the inventors of the present application have proposed a thermoelectric characteristic of a MnSi—MnSi (1.7 ⁇ y ⁇ 1.8) composite material.
  • the present invention provides a high figure of merit (MnSi (1.7 ⁇ y ⁇ 1.8
  • thermoelectric material -Based thermoelectric material.
  • thermoelectric material according to the first aspect of the present invention includes a single crystal to which impurities are added with manganese silicide MnSi (1.7 ⁇ y ⁇ 1.8) as a base material.
  • the peak of manganese monosilicide MnSi is not detected by powder X-ray diffraction or the peak of manganese monosilicide MnSi is detected by powder X-ray diffraction.
  • the value is less than 10% of the integrated average noise level in the range of 44 ° ⁇ 2 ⁇ ⁇ 45 °.
  • thermoelectric material according to the second aspect of the present invention is manganese silicide MnSi (1.7 ⁇ y
  • the area occupation ratio of the region is less than 1% of manganese silicide MnSi (1.7 ⁇ y ⁇ 1.8).
  • thermoelectric material containing a manganese silicide MnSi (1.7 ⁇ y ⁇ 1.8) -based single crystal, wherein
  • germanium to be added to the base material and impurities to be added to the base material the germanium is 0.3at.% To lat.% Of the sum of silicon and germanium which are group 4 elements
  • a step of preparing an amount corresponding to the above a step of melting the raw material into a melt, and cooling the melt at a cooling rate greater than 0 ° CZ and not more than 1.5 ° CZ And a step of crystal growth.
  • manganese silicide is added to the MnSi (1.7 ⁇ y ⁇ 1.8) single crystal. Since the amount of impurities is controlled and the melt is crystallized at a cooling rate within a predetermined range, the content of manganese monosilicide MnSi in the crystal can be kept extremely low. Therefore, a high figure of merit can be obtained by using single crystals as P-type thermoelectric materials.
  • thermoelectric material according to an embodiment of the present invention is manganese silicide MnSi (1.7 ⁇ y ⁇ 1.8
  • Manganese monosilicide M a MnSi-based single crystal with a p-type good conductor
  • MnSi hardly contained means that MnSi is not detected by a predetermined inspection. For example, as will be described in detail later, as a result of analysis by X-ray diffraction, the (2 1 0) peak of MnSi is not detected, or the value of the detected peak is less than 10% of the noise level In some cases, MnSi is not observed by microscopic observation, or the observed area occupancy of MnSi is MnSi (1.
  • the inventors of the present application made an MnSi (1.7 ⁇ y ⁇ 1.8) single crystal containing almost no MnSi.
  • MnSi 1.7 ⁇ y ⁇ 1.8
  • thermoelectric material A method for producing a thermoelectric material according to an embodiment of the present invention will be described.
  • the raw material must satisfy the stoichiometric composition of the base material MnSi (1.7 ⁇ y ⁇ 1.8).
  • Manganese (Mn) and silicon (Si) thus prepared, germanium added to the base material, and impurities are prepared.
  • germanium an amount corresponding to 0.3at.% To lat.% Of the sum of silicon and germanium, group 4 elements, is prepared. Mix these ingredients thoroughly. In that case, the raw materials are once melted and then cooled. An alloy may be produced by the above and pulverized. Furthermore, a melt (melt) is produced by melting the mixed raw materials, and the melt is cooled at a cooling rate greater than 0 ° CZ and not more than 1.5 ° C / min. To grow a crystal. As a method for crystal growth, a known method such as the Bridgman method can be used.
  • thermoelectric material having a basic composition of Mn (Si Ge 2) was produced using the method for producing a thermoelectric material according to the present embodiment.
  • this alloy was pulverized, put in a quartz tube ( ⁇ 32 mm ⁇ L 200 mm) charged with MnSi seed crystal at the tip, and MnSi single crystal was grown in a Bridgman furnace in an argon atmosphere.
  • the seed crystal an MnSi single crystal previously grown without a seed and without bridgman was used by cutting out the crystal orientation by X-ray pole analysis.
  • the melting temperature when melting the alloy is 1250 ° C
  • the temperature gradient near the solid-liquid interface is 3 ° CZmm
  • the growth rate is 0.5mmZmin (that is, the cooling rate of the melt (melt)) 1 5 ° CZmin).
  • the growth start position of the quartz tube tip was adjusted so that the solid-liquid interface came near the center of the L20mm seed. That is, by adjusting the position so that the distance from the bottom of the seed is 10 mm! /, 1428K (1155 ° C), the lower half of the seed is in the solid state and the upper half is in the molten state. In this way, crystal growth was performed so as to inherit the crystal orientation of the lower half of the seed.
  • a crystal growth rate of about 60 gZh was achieved by increasing the diameter of the quartz tube to ⁇ 32. This growth rate corresponds to about 10,000 times the crystal growth rate reported by Kojima et al. (0.01 mgZh to 5 mgZh).
  • Figure 3 shows a photograph of the MnSi (1.7 ⁇ y ⁇ l. 8) single crystal ingot fabricated in this way.
  • FIG. 4 and FIG. 5 are diagrams showing that MnSi (1.7 ⁇ y ⁇ l. 8) single crystal containing almost no MnSi can be produced by adding a predetermined amount of Ge. .
  • y As a comparative example, y
  • MnSi single crystals (0 ⁇ x ⁇ 0.3 at.%) With varying amounts of Ge addition (X) were produced by the same method as in the examples.
  • Fig. 4 shows a structure observation photograph of an Mn (Si Ge) (1.7 ⁇ y ⁇ 1. 8) single crystal ingot with varying Ge content (X) by an optical microscope. Yes. These photographs show the MnSi precipitated in the MnSi crystal by chemical etching with hydrofluoric acid on the polished surface of the single crystal ingot obtained in the examples and comparative examples. Table y
  • MnSi is more susceptible to corrosion than MnSi (1.7 ⁇ y ⁇ l. 8).
  • FIG. 5 shows the results of powder X-ray diffraction performed on the Mn (Si Ge 2) (1.7 ⁇ y ⁇ l. 8) single crystal samples produced in the examples and comparative examples.
  • M nSi 1.7 ⁇ v ⁇ l. 8
  • Mn Si Mn Si
  • the relative intensity is expressed by being standardized by the intensity of the peak.
  • Figure 6 shows the relative strength of the (2 1 0) peak of MnSi present in MnSi (1. 7 ⁇ y ⁇ l. 8).
  • Figure 7 shows the rocking force of the (1 0 15) peak at room temperature when Ge-doped Mn Si is assumed to be Mn Si.
  • the half width (FWHM) of the probe is shown. As shown in Fig. 7, it was confirmed that the crystallinity of MnSi was improved by decreasing the FWHM as the Ge addition amount X increased. In other words, the crystallinity of MnSi improves due to the dispersion and reduction of MnSi.
  • the thickness of the MnSi layer is within the range of 0.2 m to 0.3 m, regardless of the composition (the amount of added Ge). Therefore, it can be said that the increase in the number of MnSi layers corresponds to the increase in the volume of MnSi.
  • the discontinuity of the MnSi layer is considered to correspond to the decrease in the volume of MnSi. Considering this correspondence, the analysis results shown in Fig.
  • FIG. 10 shows the composition dependence of the electrical conductivity ⁇ , Seebeck constant a, and output factor ⁇ 2 ⁇ in the c-axis direction of the Ge-doped MnSi single crystal and the Al-doped MnSi single crystal, that is, The dependence of Ge or A1 on the amount of added X is shown in comparison.
  • the electrical conductivity ⁇ of the Ge-doped MnSi single crystal increases within the range of ⁇ 0.0000133 with an inclination of about twice the electrical conductivity ⁇ of the A1-doped MnSi single crystal (or Seebeck constant a decreases), but when X becomes larger than 0.000133, it turns to a gradual decrease.
  • the gradual decrease in the electrical conductivity ⁇ of the Ge-doped MnSi single crystal is related to the disappearance of MnSi. It is considered a thing.
  • Figure 11 shows the composition dependency (Ge addition amount dependency) of hole density and mobility (mobility) in the c-axis direction of Ge-doped MnSi single crystals. This hole density was determined by hole measurement at room temperature.
  • the hole density (concentration) of the Ge-added MnSi single crystal has a maximum value.
  • Such a result is considered to be related to the existence of the MnSi layer. That is, as described above with reference to FIG. 9, since the MnSi layer has almost the same thickness, it is difficult to increase the number of MnSi layers in the range of 0.00027 ⁇ x ⁇ 0.0025. (See Fig. 4), corresponding to an increase in hole concentration in the entire MnSi. On the other hand, the fact that the MnSi layer breaks in the range of 0.00265 ⁇ x (see Fig. 4) corresponds to a decrease in the hole concentration in the entire MnSi.
  • MnSi itself or the interface between MnSi and MnSi becomes a scattering source for the carrier is thought to be a factor that reduces mobility.
  • the MnSi layer breaks and disappears, and as shown in Fig. 7, the mobility is recovered by improving the crystallinity of the MnSi single crystal. .
  • Fig. 12 shows the composition dependence of thermal conductivity ⁇ and lattice thermal conductivity ⁇ in the c-axis direction of Ge-added MnSi single crystals and A1-added MnSi single crystals, that is, elements other than the base metal.
  • Both of the conductivities ⁇ are simply hindered by an increase in the amount of A1 additive due to phonon scattering by A1 impurities.
  • the thermal conductivity ⁇ and lattice thermal conductivity ⁇ of the Ge-doped MnSi single crystal increase.
  • the decrease is thought to be due to an increase in phonon scattering by Ge.
  • FIG. 13 shows the composition of the figure of merit Z in the c-axis direction of the Ge-added MnSi single crystal and the A1-added MnSi single crystal. It shows the dependency, that is, the dependency on the added amount X of elements other than the base metal.
  • the figure of merit Z is calculated using the output factor 2 ⁇ shown in FIG. 10 and the thermal conductivity ⁇ shown in FIG.
  • the Z value of the Ge-added MnSi single crystal increases as the Ge-added amount x increases.
  • the maximum value of the figure of merit Z in the sample with A1 added is considered to reflect the maximum value of the output factor ⁇ 2 ⁇ in Fig. 10.
  • the effect of Ge addition in Ge-doped MnSi single crystals is due to the dispersion and disappearance of MnSi and This is thought to be an increase in mobility due to improved crystallinity.
  • thermoelectric material according to an embodiment of the present invention is MnSi (1.7 ⁇ y ⁇ y
  • thermoelectric material that is carrier-doped using 8) as a base material.
  • MnSi for example, less than 1% area fraction
  • the N-type thermoelectric material used in the manufacture of the thermoelectric module includes high thermoelectricity y in the temperature range similar to that of the thermoelectric material MnSi (1.7 ⁇ y ⁇ l. 8) according to this embodiment.
  • V and displacement can be applied to any material that exhibits performance.
  • thermoelectric module using a thermoelectric material according to an embodiment of the present invention will be described.
  • thermoelectric module (silicide 'module). This thermoelectric module is manufactured as follows.
  • Mg 2 Si Sn is prepared as an N-type thermoelectric material.
  • each of these P-type and N-type thermoelectric materials is cut into a rectangular parallelepiped shape to produce a P-type element and an N-type element.
  • electrodes 3 to 5 are alternately formed on the upper and lower surfaces of P-type element 1 and N-type element 2 so as to bridge P-type element 1 and N-type element 2.
  • the electrodes 3 to 5 are formed, for example, by spraying aluminum (A1).
  • These P-type element 1, N-type element 2, and electrodes 3 to 5 form the basic structure ( ⁇ set) of the thermoelectric module.
  • thermoelectric module shown in Fig. 14 is completed by drawing the wiring from both ends of the ⁇ -pair structure connected in series.
  • FIG. 16 shows the output power P (W) of the thermoelectric module shown in FIG. 14, and FIG. The energy conversion efficiency (%) of the thermoelectric module shown in Fig. 14 is shown.
  • the output power is 5.5 W.
  • the energy conversion efficiency of 7.3% was extremely high.
  • FIG. 18 shows the appearance of another example of manufacturing a thermoelectric module using a thermoelectric material according to an embodiment of the present invention.
  • This thermoelectric module is manufactured as follows.
  • a single crystal of MnSi (1.7 ⁇ y ⁇ l. 8) was prepared by adding lat.% Ge and crystal growth at a cooling rate of 1.5 minutes Z. prepare.
  • Co (Pt Pd) Sb is prepared as an N-type thermoelectric material.
  • each of these P-type and N-type thermoelectric materials is cut into a rectangular parallelepiped shape to produce a P-type element and an N-type element.
  • the A1 electrode is formed by thermal spraying on the upper surface and the lower surface of the saddle-shaped element and the saddle-shaped element so that the structure of ⁇ pairs shown in FIG.
  • the thermoelectric module shown in FIG. 18 is completed by connecting a plurality of such ⁇ pairs in series, placing a heat exchange board, and drawing out the wiring.
  • FIG. 19 shows the maximum output power P (W) and the high temperature side temperature max in the thermoelectric module shown in FIG.
  • the present invention can be used in a thermoelectric material having thermoelectric performance including the Thomson effect, the Peltier effect, and the Seebeck effect, and a method for manufacturing the thermoelectric material.
  • FIG. 1 is a binary phase diagram of Mn—Si.
  • FIG. 2 is a schematic diagram showing the process of crystallization of MnSi (1.7 ⁇ y ⁇ 1.8).
  • FIG. 4 A photograph showing the microstructure (10 Zd iv) of MnSi in a single crystal of Mn (Si_Ge) (1.7 ⁇ y ⁇ 1.8).
  • FIG. 4 is a diagram showing a relationship with a performance index Z.
  • FIG. 8 is a graph showing the Ge addition amount dependence of the spacing between MnSi layers in a Ge-doped MnSi single crystal.
  • FIG. 9 is a diagram showing the width of the MnSi stripe (the thickness of the MnSi layer) in the Ge-doped MnSi single crystal.
  • FIG. Ll is a diagram showing the composition (Ge addition amount) dependence of hole (hole) density and mobility (mobility) in the c-axis direction of Ge-doped MnSi single crystals.
  • FIG. 12 is a graph showing the dependence of the thermal conductivity K and lattice thermal conductivity ⁇ in the c-axis direction (addition amount of elements other than the base material) on Ge-doped MnSi single crystals and A1-doped MnSi single crystals. h
  • FIG. 13 is a graph showing the dependence of the performance index in the c-axis direction (addition amount of elements other than the base material) on Ge-added MnSi single crystals and A1-added MnSi single crystals.
  • thermoelectric module 14 A photograph showing an external appearance of a production example of a thermoelectric module using a thermoelectric material according to an embodiment of the present invention.
  • FIG. 15 is a diagram showing a basic structure ( ⁇ set) of a thermoelectric module.
  • FIG. 16 is a diagram showing the I-characteristic and IV characteristic of the thermoelectric module shown in FIG.
  • FIG. 17 is a diagram showing the I 7? Characteristics and IV characteristics of the thermoelectric module shown in FIG. 18] A photograph showing the appearance of another example of manufacturing a thermoelectric module using a thermoelectric material according to an embodiment of the present invention.
  • FIG. 19 is a diagram showing the relationship between the maximum output power ⁇ and the high temperature side temperature ⁇ of the thermoelectric module shown in FIG.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

Matériau thermoélectrique de type P à base de MnSiy (1,7 ≤ y ≤1,8) à indice de performance élevé, et procédé d'élaboration. Procédé : fourniture, comme matières premières, de manganèse et de silicium répondant à la composition stoechiométrique de siliciure de manganèse MnSiy comme matériau de base, avec adjonction de germanium à ce matériau, et adjonction d'impuretés, le germanium en quantité comprise entre 0,3 et 1 % de la somme du silicium et du germanium comme éléments du groupe 4, puis fusion des matières premières pour donner un produit fondu qui est ensuite refroidi à un taux de refroidissement supérieur à 0 °C/min et qui ne dépasse pas 1,5 °C/min pour le développement de cristaux.
PCT/JP2005/015432 2005-08-25 2005-08-25 Matériau thermoélectrique et procédé d'élaboration WO2007023548A1 (fr)

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JP2011210845A (ja) * 2010-03-29 2011-10-20 Ibaraki Univ ＧａあるいはＳｎでドーピングされたバルク状マンガンシリサイド単結晶体あるいは多結晶体およびその製造方法
JP2018148037A (ja) * 2017-03-06 2018-09-20 昭和電線ケーブルシステム株式会社 熱電変換モジュール

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011210845A (ja) * 2010-03-29 2011-10-20 Ibaraki Univ ＧａあるいはＳｎでドーピングされたバルク状マンガンシリサイド単結晶体あるいは多結晶体およびその製造方法
JP2018148037A (ja) * 2017-03-06 2018-09-20 昭和電線ケーブルシステム株式会社 熱電変換モジュール

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