WO2004100280A1 - 熱電半導体材料、該熱電半導体材料による熱電半導体素子、該熱電半導体素子を用いた熱電モジュール及びこれらの製造方法 - Google Patents
熱電半導体材料、該熱電半導体材料による熱電半導体素子、該熱電半導体素子を用いた熱電モジュール及びこれらの製造方法 Download PDFInfo
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- WO2004100280A1 WO2004100280A1 PCT/JP2004/006493 JP2004006493W WO2004100280A1 WO 2004100280 A1 WO2004100280 A1 WO 2004100280A1 JP 2004006493 W JP2004006493 W JP 2004006493W WO 2004100280 A1 WO2004100280 A1 WO 2004100280A1
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- thermoelectric semiconductor
- semiconductor material
- alloy
- thermoelectric
- cooling member
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 764
- 239000000463 material Substances 0.000 title claims abstract description 586
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
-
- 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
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
Definitions
- thermoelectric semiconductor material thermoelectric semiconductor device using the thermoelectric semiconductor material
- thermoelectric module using the thermoelectric semiconductor device thermoelectric semiconductor device
- the present invention is used for thermoelectric cooling, thermoelectric heating, thermoelectric power generation, etc.
- the present invention relates to a thermoelectric semiconductor material, a thermoelectric semiconductor element, a thermoelectric module, and a manufacturing method thereof.
- a device for performing thermoelectric cooling, thermoelectric heating, and thermoelectric power generation using the thermoelectric characteristics of a thermoelectric semiconductor has a basic configuration, and as shown in FIG. And a plurality of thermoelectric modules 1 each formed by joining a N-type thermoelectric semiconductor element 3 with a metal electrode 4 to form a PN element pair.
- thermoelectric semiconductor for forming the thermoelectric semiconductor elements 2 and 3 as described above includes one or two elements selected from bismuth (B i) and antimony (Sb), which are group 5B, and 6 B
- the composition is such that the ratio of the number of atoms of the 6B group (6 and 36) is 2: 3, that is, an alloy of (Bi-Sb) 2 (Te-Se) 3 composition is used as the material. .
- thermoelectric semiconductor material described above has a hexagonal structure, and is electrically and thermally anisotropic due to this crystal structure, in the ⁇ 110> direction of the crystal structure, In other words, it is known that by applying electricity or heat along the direction of the C-plane of the hexagonal structure, better thermoelectric performance can be obtained than when applying electricity or heat in the C-axis direction.
- a raw material alloy prepared so as to have the required composition described above is heated and melted to form a molten alloy, and then a direction having good thermoelectric performance is obtained by a unidirectional solidification method such as a zone melt method.
- thermoelectric semiconductor material While controlling the crystal growth direction, a single crystal or polycrystalline ingot is manufactured as a thermoelectric semiconductor material, and the ingot is subjected to necessary processing, such as cutting out a portion with a small composition variation and processing. In this way, devices with good characteristics were manufactured.
- the ingot single crystallized by the zone melt method has a remarkable cleavage property due to its crystal structure, the ingot is cut out using the ingot material as a thermoelectric semiconductor material and the thermoelectric semiconductor element is cut out.
- the mechanical strength was insufficient, cracks and chips occurred, and the yield was reduced. Therefore, it is desired to improve the thermoelectric performance while improving the strength of the thermoelectric semiconductor material processed into the thermoelectric semiconductor element.
- thermoelectric semiconductor One of the methods proposed to improve the strength and thermoelectric performance of a thermoelectric semiconductor in this way is to use a melted material as a thermoelectric semiconductor material produced by a unidirectional solidification method in the same manner as described above, and a hexagonal structure. There is a method to increase the material strength by extrusion or rolling so that a shear force is applied in the direction of the C plane (for example, see Patent Document 1).
- the above metal material shows isotropic properties.However, when the crystal grains are arranged in a specific direction due to processing such as plastic working, individual The crystal anisotropy of the crystal grains appears as a macroscopic property, and the metal material becomes anisotropic as a whole (for example, In view of, for example, Non-Patent Document 1), the ingot material of the alloy raw material is pulverized to be powdered once, and this powder is sintered to form a sintered body, thereby improving the material strength, When the powders are integrated in a random orientation during sintering, the orientation of the crystal orientation in the structure is randomized and the orientation is reduced.
- Patent Document 2 Extrusion molding (for example, see Patent Documents 3 and 4), or plastic deformation by upsetting forging (for example, see Patent Document 5).
- Patent Literature 6 Patent Literature 7, Patent Literature 8, Patent Literature 9, and Patent Literature 10
- techniques for improving the degree of orientation of crystals in a tissue have been proposed.
- the crystal constituting the structure is flatly plastically deformed in a direction orthogonal to the direction in which the pressing force acts, and the cleavage plane is compressed.
- the hexagonal structure C plane is oriented perpendicular to the compression direction (pressing direction) and extrusion molding
- the C-plane of the hexagonal structure is oriented along the extrusion direction (pressing direction) to prepare a thermoelectric semiconductor material in which the crystal is oriented in a direction having good thermoelectric performance.
- thermoelectric performance performance index: ⁇
- ⁇ figure of merit
- ⁇ Seebeck coefficient
- ⁇ electric conductivity
- ⁇ thermal conductivity
- specific resistance specific resistance. Therefore, in order to improve the thermoelectric performance (performance index: ⁇ ) of the thermoelectric semiconductor material, it is necessary to increase the value of the Seebeck coefficient (a) or the electric conductivity ( ⁇ ) or to reduce the thermal conductivity ( ⁇ ). It is understood that an alloy material may be used. Therefore, by reducing the crystal grain size and the thermal conductivity ( ⁇ ), It was considered to improve the thermoelectric performance (performance index: Z).
- thermoelectric semiconductor material which is formed into a thin strip, foil piece or powder is formed by a liquid quenching method such as a gas atomizing method in which the molten alloy is injected into a gas flow of a required gas.
- thermoelectric semiconductor material After forming fine crystal grains in the structure of the material and introducing high-density strains and defects into the structure, the thermoelectric semiconductor material is pulverized into powder, and then the thermoelectric semiconductor material in powder form is formed. Heat-treated and then solidified to produce a thermoelectric semiconductor material, so that when heat-treated or solidified and formed, recrystallized grains are formed using the strain caused by the defects as a driving force, and the presence of grain boundaries Thereby reducing the thermal conductivity of (kappa) thermoelectric performance (performance index: Z) as to improve it has been proposed (e.g., see Patent Document 1 1).
- the rotation speed of the rotating roll used to form a thin strip, foil piece or powdery thermoelectric semiconductor material by quenching the molten alloy as described above has conventionally been the generation of fine crystals by quenching and the direction of heat flow. It has been proposed that the peripheral speed be set to 2 to 80 m / sec in order to make the crystal growth of the crystal effectively (see, for example, Patent Document 12). However, it is reported that a quenching speed cannot be obtained sufficiently if the quenching speed is less than 2 mZ seconds, and that a quenching speed cannot be obtained sufficiently even if it is 8 Om / sec or more.
- Heating conditions for solidification of a thin strip, foil piece and powdery thermoelectric semiconductor material are 200 to 400 ° C or 400 to 600 ° C while applying pressure. It has been proposed that C be held for 5 to 150 minutes (for example, see Patent Document 13).
- a molten alloy of a (Bi-Sb) 2 (Te-Se) 3- based raw material alloy is rapidly cooled by a rotating roll. Ag is added and mixed to the thin ribbon, foil strip or powdered thermoelectric semiconductor material, and then sintered and solidified to disperse Ag at the crystal grain boundaries to increase the specific resistance p.
- thermoelectric performance performance index: Z
- Patent Document 14 It has also been proposed to improve the thermoelectric performance (performance index: Z) by lowering it (for example, see Patent Document 14).
- the molten alloy sprayed on the surface of the rotating roll is melted as it is cooled from the contact surface side with the rotating roll toward the outer periphery of the roll. It is known that solidification of the alloy occurs in the film thickness direction, and as a result, a foil-like thermoelectric semiconductor material in which the C-plane, which is the basal plane of the hexagonal structure of the crystal grains, stands up in the film thickness direction.
- thermoelectric semiconductor material manufactured by the rotating roll method is laminated in a layered manner in the film thickness direction, and this is pressed in parallel with the film thickness direction and fired.
- a method for producing a thermoelectric semiconductor material by sintering has been proposed (for example, see Patent Document 15). Further, in the same manner as described above, the thermoelectric semiconductor material manufactured by the rotating roll method is laminated in a layered manner in the thickness direction, and then pressed in parallel in the laminating direction to form a laminated body orthogonal to the laminating direction.
- thermoelectric conversion materials are required to have higher performance and higher reliability.
- thermoelectric semiconductor when used to cool a laser oscillator, N-type and P-type thermoelectric semiconductor elements having dimensions of 1 mm or less are modularized and used. As a result, there is an increasing demand for such a strength that a thermoelectric semiconductor element having a dimension of lmm or less can be cut out from an ingot-like thermoelectric semiconductor material without any chipping.
- Patent Document 1 JP-A-11-163422
- Patent Document 2 JP-A-63-138789
- Patent document 3 JP-A-2000-124512
- Patent Document 4 JP 2001-345487 A
- Patent Document 5 JP-A-2002-118299
- Patent Document 6 JP-A-10-178218
- Patent document 7 JP-A-2002-151751
- Patent document 8 JP-A-11-261119
- Patent Document 9 JP-A-10-178219
- Patent Document 10 JP-A-2002-111086
- Patent Document 11 JP-A-2000-36627
- Patent Document 12 JP-A-2000-286471
- Patent Document 13 JP-A-2000-332307
- Patent Document 14 JP-A-8-199281
- Patent Document 15 Patent No. 2659309
- Patent Document 16 JP 2001-53344 A
- Patent Document 17 Japanese Patent Application Laid-Open No. 2000-357821
- Non-Patent Document 1 Hiroshi Kato and Keiji Yoshikawa, "Elastic Modulus of A1-Cu Alloy with Columnar Crystal Structure", Materials, April 1981, Vol. 30, No. 331, p.
- the molten material of the thermoelectric semiconductor raw material alloy is plastically deformed. Even if the thermoelectric semiconductor material is manufactured by being deformed, there is a problem that the mechanical strength of the thermoelectric semiconductor material cannot be sufficiently increased. Therefore, it is difficult to overcome the problem that ingots such as single crystal and unidirectional solidified material are easily cracked along the cleavage plane of the material, and even though the crystal orientation is uniform, At present, there are few ways to further improve the performance due to limited manufacturing methods.
- thermoelectric semiconductor material As shown in Patent Documents 2 to 10, after sintering a powder obtained by pulverizing an ingot material of an alloy raw material, it is thought that the technique of causing plastic deformation of the consolidated body by rolling, extrusion forming, or upsetting forging can increase the mechanical strength of the thermoelectric semiconductor material.
- the size of the powder is the crystal grain size, there is a limit to the miniaturization of the crystal grains, which is disadvantageous in reducing the thermal conductivity ( ⁇ ), and therefore, the thermoelectric performance cannot be improved so much.
- the sintering of the powder is performed in a state where the orientation of the tissue is randomly arranged for each powder, so that even if the sintered body in the state where the texture orientation is disordered is plastically deformed, Within the structure of the resulting thermoelectric semiconductor material That the crystal orientation of the there is a problem that can not be made too high. Further, according to the method disclosed in Patent Document 11, heat treatment and sintering are performed to remove defects in the grains to improve the electrical conductivity ( ⁇ ), and the thermal conductivity is reduced by scattering of phonons at grain boundaries.
- Patent Document 12 discloses that the peripheral speed of the rotating roll is set to 2 to 80 m / sec.
- Patent Document 1 and 2 disclose a rotation in which the peripheral speed is set as described above.
- thermoelectric semiconductor material manufactured by the liquid quenching method is set at a temperature range of 200 to 60 Ot: as a heating condition when sintering. This is to set a temperature condition for enabling sintering without disturbing the crystal orientation in the structure in the thermoelectric semiconductor material, and is used when solidifying and molding the thermoelectric semiconductor material of the present invention described later. Temperature range that completely prevents segregation of low melting point Te-rich phase, phase separation, and liquid precipitation during solidification and molding of thermoelectric semiconductor material It is.
- Patent Document 14 in a method for improving thermoelectric performance by dispersing Ag at crystal grain boundaries to lower the specific resistance ( ⁇ ), Ag is (B i- In order to become a dopant in the Sb) 2 (T e — S e) 3 type thermoelectric semiconductor, there is a problem that the addition amount must be strictly adjusted and a problem with time change.
- the foil-like thermoelectric semiconductor material manufactured by the rotating roll method since the foil-like thermoelectric semiconductor material manufactured by the rotating roll method is laminated and solidified in the film thickness direction, it is pressed in parallel with the film thickness direction. At times, there is a problem that the crystal orientation at the interface between the layers of the laminated thermoelectric semiconductor material is disturbed.
- a direction perpendicular to the laminating direction as shown in Patent Document 16, or As shown in Patent Document 17, it is considered that the crystal orientation of the structure can be improved by pressing from at least three directions orthogonal to the laminating direction.
- the orientation is improved by erecting the direction of the C-plane of the hexagonal structure in the laminating direction of the thermoelectric semiconductor material, and the C-axis direction of the hexagonal structure of each crystal grain can be aligned.
- thermoelectric semiconductor material in a foil form manufactured by a rotating roll method is laminated in layers, solidification molding is performed.
- fine materials are used as the foil-like thermoelectric semiconductor material.However, the densification of the structure after sintering by hot pressing depends on the flow of the powder and the plastic deformation of the powder itself.
- the present invention provides a thermoelectric semiconductor material which has a high orientation of crystal grains in a tissue, can reduce the concentration of oxygen contained therein, and can further improve thermoelectric performance. It is an object of the present invention to provide a thermoelectric semiconductor element made of a material, a thermoelectric module using the thermoelectric element, and a method for manufacturing these.
- the present invention provides a plate-shaped thermoelectric semiconductor material composed of a raw material alloy having a required thermoelectric semiconductor composition, which is substantially layered and filled and solidified and molded to form a molded body.
- a plastic deformation process is performed such that a shear force is applied in a uniaxial direction substantially parallel to the main laminating direction of the thermoelectric semiconductor material by pressing from a uniaxial direction that is perpendicular or nearly perpendicular to the main laminating direction of the thermoelectric semiconductor material.
- Thermoelectric semiconductor material is performed such that a shear force is applied in a uniaxial direction substantially parallel to the main laminating direction of the thermoelectric semiconductor material by pressing from a uniaxial direction that is perpendicular or nearly perpendicular to the main laminating direction of the thermoelectric semiconductor material.
- thermoelectric semiconductor material When the raw material alloy is brought into contact with the surface of the cooling member during the production of the thermoelectric semiconductor material, a thermoelectric semiconductor material is obtained in which the C-plane of the hexagonal structure of the crystal grains is oriented so as to extend substantially parallel to the thickness direction. .
- thermoelectric semiconductor material When the thermoelectric semiconductor material is laminated in a substantially layered manner in the plate thickness direction and solidified and formed, the direction in which the C-plane of the crystal grains extends in the formed compact is maintained while being oriented in the laminating direction.
- the molded body is plastically deformed by pressing so as to apply a shearing force in a uniaxial direction substantially parallel to a main laminating direction of the thermoelectric semiconductor, which substantially coincides with a direction in which the C plane of the crystal grain extends
- the crystal grains are flattened in the direction in which the shearing force acts, and the direction in which the C plane extends is maintained and aligned with the direction in which the shearing force acts during the plastic deformation.
- thermoelectric semiconductor material the direction in which the C plane of the hexagonal structure of the crystal grains extends and the direction of the C axis are both aligned in the structure, so that the current flows in the direction in which the C plane extends. If heat and heat are set, high thermoelectric performance can be obtained. Therefore, after melting a raw material alloy having a required composition of the thermoelectric semiconductor, the molten alloy is brought into contact with the surface of the cooling member to form a plate-like thermoelectric semiconductor material. A molded body is formed by laminating and solidifying in parallel to form a molded body. Next, the molded body is formed in one of two axial directions intersecting in a plane substantially orthogonal to the main laminating direction of the thermoelectric semiconductor material.
- thermoelectric element is pressed from the other axial direction in a state where the deformation is restricted, and a shear force is applied in a uniaxial direction substantially parallel to the main laminating direction of the thermoelectric semiconductor material to form a thermoelectric semiconductor material by plastic working.
- a thermoelectric semiconductor material having good thermoelectric performance can be obtained.
- thermoelectric semiconductor material having a composite phase of a composite compound semiconductor phase having a stoichiometric composition of a required compound thermoelectric semiconductor and a Te rich phase containing an excess of Te in the above composition is also be used.
- thermoelectric semiconductor material at the same time as the grain boundaries of the crystal grains are present, a crystal strain can be generated due to the presence of the composite phase of the composite compound semiconductor phase and the Te-rich phase. Since the thermal conductivity can be reduced by the introduction, the performance index can be improved by reducing the thermal conductivity. Further, an excess of Te is added to the stoichiometric composition of the required compound thermoelectric semiconductor, and a plate-like thermoelectric semiconductor material made of the obtained raw material alloy is laminated and filled in a substantially layered form and solidified to form a molded body.
- thermoelectric semiconductor material When the thermoelectric semiconductor material is processed, it can have high crystal orientation in which the C-plane extending direction and the C-axis direction of the hexagonal structure of the crystal grains described above are substantially aligned, and the composite compound semiconductor phase and T Since the thermal conductivity can be reduced by the presence of the composite phase of the e-rich phase, it is possible to further improve the figure of merit.
- the composition of the raw material alloy is a thermoelectric semiconductor material manufacturing method in which an excess Te is added to the stoichiometric composition of the required compound thermoelectric semiconductor, the above-described high crystal orientation and The composite phase of the composite compound semiconductor phase and the Te It is possible to obtain a thermoelectric semiconductor having a high figure of merit with both of them.
- the composition of the raw material alloy is defined as the composition obtained by adding an excess of Te to the stoichiometric composition of the (Bi—Sb) 2 Te 3 system, specifically, the composition of the raw material alloy is 7 to 10 atomic%.
- a compound consisting of B i, 30-33 atomic% S b, and 60 atomic% Te a composition obtained by adding 0.1-5% of excess Te to the stoichiometric composition of a thermoelectric semiconductor.
- a P-type thermoelectric semiconductor material having high thermoelectric performance as described above can be obtained.
- the composition of the raw material alloy is a composition obtained by adding an excess of Te to the stoichiometric composition of the Bi 2 (Te-Se) 3 system, specifically, the composition of the raw material alloy is 40 atomic%. : 61, 50 to 59 atomic% of Te, and 1 to 10 atomic% of e.
- thermoelectric semiconductor material having high thermoelectric performance as described above can be obtained.
- solidification molding of the thermoelectric semiconductor material is performed by applying pressure and heating the material temperature to a temperature of 380 ° C or more and 500 or less, so that the Te-rich phase in the thermoelectric semiconductor material becomes a liquid phase.
- thermoelectric semiconductor material having a multiphase structure structure in which the Te rich phases containing the above are each finely dispersed can be formed. Furthermore, when the molten alloy of the raw material alloy is brought into contact with the surface of the cooling member to form a plate-like thermoelectric semiconductor material, 90% or more of the thickness of the formed plate-like thermoelectric semiconductor material does not become rapidly cooled.
- the thickness of the plate-like thermoelectric semiconductor material is at least By using a rotating roll rotated at a speed of 30 or more, fine crystal nuclei are formed on the side of the molten alloy of the raw material alloy that contacts the cooling member, and the thickness is
- the crystal can be slowly solidified to form large crystal grains in the direction, and the thermoelectric semiconductor material can be formed as a material having a thickness of 30 or more. In this case, the crystal grains are formed with the C-plane of the hexagonal structure as described above.
- thermoelectric semiconductor material can be formed so as to extend over almost the entire length in the thickness direction, and when the composition of the raw material alloy is a composition containing an excessive amount of Te, extremely (B i—S b) 2 Te 3 P-type compound compound semiconductor phase or Bi 2 (T e -S e) 3 N-type compound semiconductor phase Without amorphizing the Te rich phase containing excess Te
- the thermoelectric semiconductor material having a structure in which the Te-rich phase precipitates or forms as a heterophase nucleus in a crystal grain or a grain boundary of the composite compound semiconductor due to the phase separation can be obtained.
- thermoelectric semiconductor material is thicker and wider at the same time as the molten alloy of the raw material alloy is slowly cooled, the volume of each thermoelectric semiconductor material can be increased. Therefore, the specific surface area can be made smaller than that of a powder having a small size, so that the possibility that the surface is oxidized can be reduced, so that a decrease in the electrical conductivity of the thermoelectric semiconductor material can be prevented.
- thermoelectric semiconductor material if the method of solidifying and molding the thermoelectric semiconductor material is performed by a multi-stage heating method, if the heating position of the heating source is biased when heating to solidify and mold the thermoelectric semiconductor material, In addition, the temperature of the laminated thermoelectric semiconductor material can be uniformly increased as a whole to reach a desired temperature at the time of the solidification molding. As a result, the molded body formed by solidification molding of the thermoelectric semiconductor material can be made uniform throughout, so that the thermoelectric semiconductor material produced by plastic deformation processing of the molded body can be uniformly homogenized throughout. It can be.
- the composition of the raw material alloy is a composition containing an excessive amount of Te
- the excess component can be melted at the grain boundaries, and the bonding at the grain boundaries can be improved.
- one or more omnidirectional hydrostatic pressure processes should be performed during the plastic working process.
- buckling can be prevented when the molded body is plastically deformed, and the deformation speed at the time of plastic deformation can be made uniform. Therefore, the thermoelectric semiconductor formed by the above plastic deformation can be formed.
- the structure of the material can be made uniform.
- thermoelectric semiconductor material having good crystal orientation in which the direction of extension of the C-plane of the hexagonal structure of crystal grains and the C-axis direction are both aligned, is plastically deformed to form the thermoelectric semiconductor material
- thermoelectric semiconductor element By applying a shearing force to the thermoelectric semiconductor element that is cut out so that a surface almost perpendicular to the uniaxial direction can be used as the electrode joining surface, current and heat can be applied to the C-plane of the crystal grains. Since they can act substantially parallel to the extending direction, the thermoelectric performance of the thermoelectric semiconductor element can be enhanced.
- thermoelectric semiconductor element is cut out from the thermoelectric semiconductor material as described above so that a surface substantially perpendicular to the uniaxial direction on which a shearing force acts upon plastic deformation of the molded body can be used as an electrode joining surface.
- a thermoelectric semiconductor element with improved thermoelectric performance can be obtained.
- P-type and N-type thermoelectric semiconductor elements are formed as thermoelectric semiconductor elements having the same crystal orientation and high thermoelectric performance as described above.
- thermoelectric semiconductor elements are When the molded body is plastically deformed to form a thermoelectric semiconductor material, the molded body is arranged side by side in a direction substantially perpendicular to both the axial direction in which the pressing force is applied and the direction in which the shearing force is applied by the pressing.
- a thermoelectric module having a PN element pair formed by joining P-type and N-type thermoelectric semiconductor elements via metal electrodes is provided, the above-mentioned metal electrodes generated due to a temperature change when the thermoelectric module is used.
- thermoelectric semiconductor elements Since the stress due to the elongation and shrinkage deformation can act on each of the P-type and N-type thermoelectric semiconductor elements in a direction parallel to the C-plane of the hexagonal structure of each crystal grain, the metal electrode is elongated. , Shrinkage deformation Even in this case, the risk of crystal delamination occurring in the structure of each of the thermoelectric semiconductor elements can be prevented, and the strength and durability of the thermoelectric module can be improved. Therefore, P-type and N-type thermoelectric semiconductor elements are prepared as the thermoelectric semiconductor elements as described above, and a pressing force is applied to each of the P-type and N-type thermoelectric semiconductor elements during plastic deformation processing of the molded body.
- thermoelectric module that forms a thermoelectric module
- a thermoelectric module with improved durability and strength can be obtained. According to the present invention, the following excellent effects are exhibited.
- thermoelectric semiconductor material made of a raw material alloy having a required thermoelectric semiconductor composition is laminated and filled in a substantially layered form and solidified and molded to form a molded body.
- thermoelectric semiconductor material which is plastically deformed in such a way that it is pressed from a uniaxial direction that is perpendicular or nearly perpendicular to the laminating direction and a shearing force is applied in a uniaxial direction substantially parallel to the main laminating direction of the thermoelectric semiconductor material Therefore, it is possible to increase the strength by further pressing the molded body formed by solidifying the plate-shaped thermoelectric semiconductor material and deforming it plastically, and to reduce the crystal grains in the structure by its hexagonal C-plane.
- the direction of the C-axis as well as the direction in which the crystal grains extend can be made uniform, and the crystal orientation can be made extremely high.
- Ri it is possible to improve the thermoelectric performance.
- thermoelectric semiconductor material After melting a raw material alloy having a required composition of the thermoelectric semiconductor, the molten alloy is brought into contact with the surface of the cooling member to form a plate-like thermoelectric semiconductor material.
- the molded body is formed by laminating the molded body substantially parallel to the thickness direction and solidifying and forming the molded body. Then, the molded body is formed in one of two axial directions crossing in a plane substantially orthogonal to the main laminating direction of the thermoelectric semiconductor material. While the deformation of the thermoelectric semiconductor material is restrained in the axial direction, the material is pressed from the other axial direction to apply a shearing force in a uniaxial direction substantially parallel to the main laminating direction of the thermoelectric semiconductor material, and plastically process the thermoelectric semiconductor material.
- thermoelectric semiconductor material having good thermoelectric performance By using the method for producing a thermoelectric semiconductor material for forming the above, the thermoelectric semiconductor material having good thermoelectric performance can be obtained. (3) Further, a thermoelectric semiconductor material having a composite phase of a composite compound semiconductor phase having a stoichiometric composition of a required compound thermoelectric semiconductor and a Te-rich phase containing excess Te in the above composition Then, in the thermoelectric semiconductor material, at the same time as the grain boundaries of the crystal grains are present, crystal distortion can be generated due to the presence of the composite phase of the composite compound semiconductor phase and the Te-rich phase. Since the thermal conductivity can be reduced by introducing the strain, the performance index can be improved by reducing the thermal conductivity.
- thermoelectric semiconductor material composed of the obtained raw material alloy is laminated and filled in a substantially laminar form, solidified and molded.
- the molded body is pressed from a uniaxial direction perpendicular or nearly perpendicular to the laminating direction of the thermoelectric semiconductor material so that a shear force is applied in a uniaxial direction substantially parallel to the main laminating direction of the thermoelectric semiconductor material.
- thermoelectric semiconductor material When the thermoelectric semiconductor material is formed by plastic deformation processing, it can have high crystal orientation in which the C-plane extending direction and the C-axis direction of the hexagonal structure of the crystal grains are substantially aligned, and the composite compound semiconductor phase Since the thermal conductivity can be reduced due to the presence of the composite phase of the Ti and Te rich phases, it is possible to further improve the figure of merit.
- thermoelectric semiconductor material in which the composition of the raw material alloy is obtained by adding an excess of Te to the stoichiometric composition of the required compound thermoelectric semiconductor. It is possible to obtain a thermoelectric semiconductor having a high figure of merit having both properties and a composite phase of a composite compound semiconductor phase and a Te-rich phase.
- the composition of the raw material alloy is defined as the composition obtained by adding excess Te to the stoichiometric composition of the (B i—Sb) 2 Te 3 system.
- a compound consisting of ⁇ 10 atomic% Bi, 30-33 atomic% Sb, and 60 atomic% Te The stoichiometric composition of thermoelectric semiconductors is obtained by adding 0.1-5% excess Te. With the added composition, a P-type thermoelectric semiconductor material having high thermoelectric performance as described above can be obtained.
- the composition of the raw material alloy is a composition obtained by adding excess Te to the stoichiometric composition of the Bi 2 (Te-Se) 3 system, specifically, the composition of the raw material alloy is 40 atoms. % 8i,
- thermoelectric semiconductor material having high thermoelectric performance as described above can be obtained.
- the solidification molding of the thermoelectric semiconductor material is performed by applying pressure and heating the material temperature to a temperature of 380 ° C or more and 500 ° C or less, so that the thermoelectric semiconductor material can be solidified. Since the Te-rich phase can be solidified or formed in a liquid phase, or even if it becomes a liquid phase, it can be solidified and formed in a small amount. It is possible to form a P-type or N-type thermoelectric semiconductor material having a multiphase structure in which the Te rich phases each containing excess Te in each composition are finely dispersed.
- the thickness of the plate-like thermoelectric semiconductor material is 90% or more.
- thermoelectric semiconductor material can be formed as a material having a thickness of 30 m or more.
- the crystal grains are The hexagonal C-plane can be formed so as to extend over almost the entire length in the thickness direction of the thermoelectric semiconductor material, and when the composition of the raw material alloy is a composition excessively containing Te. Is, at the very minimum, a phase of a P-type compound compound semiconductor of the (Bi—Sb) 2 Te 3 system or an N-type compound of the B i 2 (Te—Se) 3 system.
- the Te rich phase containing excess Te in each composition can be phase-separated without becoming amorphous, and the Te rich phase is a crystal of the composite compound semiconductor. It is possible to obtain a thermoelectric semiconductor material having a structure that precipitates as a heterophase or forms as a heterophase nucleus in a grain or a grain boundary and includes crystal distortion.
- thermoelectric semiconductor material is thicker and wider at the same time as the molten alloy of the raw material alloy is slowly cooled, the volume of each thermoelectric semiconductor material can be increased. Therefore, the specific surface area can be made smaller than that of a powder having a small size, so that the possibility that the surface is oxidized can be reduced, so that a decrease in the electrical conductivity of the thermoelectric semiconductor material can be prevented.
- thermoelectric semiconductor material if the method of solidifying and molding the thermoelectric semiconductor material is performed by a multi-stage heating method, the heating position of the heating source is biased when the thermoelectric semiconductor material is solidified and molded. Even if the temperature rises, the temperature of the laminated thermoelectric semiconductor material can be evenly increased so as to reach a desired temperature at the time of the solidification molding. As a result, the molded body formed by solidification molding of the thermoelectric semiconductor material can be made uniform over the entire body, so that the thermoelectric semiconductor material produced by plastic deformation processing of the molded body can be entirely used. It can be homogeneous throughout. Further, when the composition of the raw material alloy is a composition containing an excessive amount of Te, the excess component can be melted at the grain boundaries, and the bonding at the grain boundaries can be improved.
- thermoelectric semiconductor material having good crystal orientation in which the extending direction of the C-plane and the C-axis direction of the hexagonal structure of the crystal grains are both aligned, is formed by plasticizing the molded body to form the thermoelectric semiconductor material.
- a thermoelectric semiconductor element that is cut out so that a surface that is almost perpendicular to the uniaxial direction to which a shear force is applied during deformation processing can be used as an electrode bonding surface. This allows current and heat to act substantially parallel to the direction in which the C-plane of the crystal grains extends, so that the thermoelectric performance of the thermoelectric semiconductor element can be enhanced.
- thermoelectric semiconductor material as described above is cut out so that a surface almost perpendicular to the uniaxial direction on which a shearing force acts upon plastic deformation of the molded body can be used as an electrode joining surface, and the thermoelectric semiconductor material is thermoelectrically processed.
- thermoelectric semiconductor element and an N-type thermoelectric semiconductor element are formed as thermoelectric semiconductor elements having a well-defined crystal orientation and high thermoelectric performance, and each of the P-type and N-type thermoelectric semiconductor elements is formed.
- the elements are arranged side by side in a direction substantially orthogonal to both the axial direction in which the pressing force is applied and the direction in which the shearing force is applied by the pressing when plastically deforming the molded body to form the thermoelectric semiconductor material.
- a thermoelectric module having a configuration including a PN element pair formed by joining the P-type and N-type thermoelectric semiconductor elements via a metal electrode is provided, the above-mentioned metal electrode generated due to a temperature change when the thermoelectric module is used.
- the stress caused by the elongation and shrinkage of the metal electrode can be applied to each of the P-type and N-type thermoelectric semiconductor elements in a direction parallel to the C-plane of the hexagonal structure of each crystal grain. Expands and contracts Even if it is deformed, the risk of delamination of crystals in the structure of each thermoelectric semiconductor element can be prevented, and the strength and durability of the thermoelectric module can be improved.
- FIG. 1 is a view showing a flow in one embodiment of a method for producing a thermoelectric semiconductor material according to the present invention.
- FIG. 2 is a diagram showing an outline of an apparatus used in the annealing foil manufacturing process of FIG.
- FIG. 3 is a schematic perspective view showing a thermoelectric semiconductor material formed in the annealing step of FIG.
- FIG. 4 is a diagram showing a correlation between the thickness of the thermoelectric semiconductor material formed in the annealing step of FIG. 1 and the peripheral speed of the cooling roll.
- FIG. 5 is a diagram showing the correlation between the width of the thermoelectric semiconductor material formed in the annealing step of FIG. 1 and the peripheral speed of the cooling hole.
- FIG. 6A is a drawing-substituting photograph showing a cross-sectional view of the structure of the formed body formed in the solidification forming step of FIG. 1.
- FIG. 6B is a drawing substitute photograph showing the structure of the compact formed in the solidification molding step of FIG. 1 and showing the surface on the side of the anti-rotating roll contact surface.
- FIG. 7A is a schematic perspective view showing a molded body formed in the solidification molding step of FIG.
- FIG. 7B shows a compact formed in the solidification molding step of FIG. 1, and is a perspective view schematically showing a laminated structure of a thermoelectric semiconductor material.
- FIG. 7C is an enlarged perspective view showing a part of FIG. 7B.
- FIG. 8A shows a plastic working apparatus used in the plastic deformation step of FIG. 1, and is a schematic cut side view showing an initial state before plastic deformation of a compact.
- FIG. 8B is a view taken in the direction of arrows AA in FIG. 8A.
- FIG. 8C shows a plastic working apparatus used in the plastic deformation step of FIG. 1, and is a schematic cut side view showing a state in which a thermoelectric semiconductor material is formed by plastic deformation of a compact.
- FIG. 8D shows a plastic working apparatus used in the plastic deformation step of FIG. 1, and corresponds to FIG. 8B showing a type having a position fixing ring.
- FIG. 9A is a schematic perspective view showing a thermoelectric semiconductor material formed in the plastic deformation step of FIG.
- FIG. 9B shows a thermoelectric semiconductor material formed in the plastic deformation step of FIG. 1, and is a perspective view schematically showing the orientation of crystal grains.
- FIG. 10 shows the peripheral speed of the cooling roll in the annealing foil manufacturing process of FIG. 1 and the thermoelectric material formed in the plastic deformation process of FIG. 1 using the thermoelectric semiconductor material formed in the annealing foil manufacturing process.
- FIG. 4 is a diagram showing a correlation with the thermal conductivity of a semiconductor material.
- FIG. 11 shows the peripheral speed of the cooling roll in the annealing foil manufacturing process of FIG. 1 and the thermoelectric material formed in the plastic deformation process of FIG. 1 using the thermoelectric semiconductor material formed in the annealing foil manufacturing process.
- FIG. 3 is a diagram showing a correlation with the electrical conductivity of a semiconductor material.
- FIG. 12 shows the peripheral speed of the cooling roll in the annealing foil manufacturing process in FIG. 1 and the thermoelectric semiconductor material formed in the plastic deformation process in FIG. 1 using the thermoelectric semiconductor material formed in the annealing foil manufacturing process.
- FIG. 3 is a diagram showing a correlation with a Seebeck coefficient of a semiconductor material.
- FIG. 13 shows the peripheral speed of the cooling roll in the annealing step of FIG. 1 and the thermoelectric material formed in the plastic deformation step of FIG. 1 using the thermoelectric semiconductor material formed in the annealing step.
- FIG. 3 is a diagram showing a correlation with a carrier concentration of a semiconductor material.
- FIG. 14 shows the peripheral speed of the cooling roll in the annealing foil manufacturing process of FIG. 1 and the thermoelectric material formed in the plastic deformation process of FIG. 1 using the thermoelectric semiconductor material formed in the annealing foil manufacturing process.
- FIG. 4 is a diagram showing a correlation with a figure of merit of a semiconductor material.
- FIG. 15 is a diagram showing the correlation between the thickness of the thermoelectric semiconductor material formed in the annealing step of FIG. 1 and the oxygen concentration.
- FIG. 16 is a diagram showing the correlation between the width dimension of the thermoelectric semiconductor material formed in the annealing step of FIG. 1 and the oxygen concentration.
- FIG. 17 is a diagram showing the correlation between the peripheral speed of the cooling roll in the step of producing the slowly cooled foil of FIG. 1 and the oxygen concentration of the thermoelectric semiconductor material formed in the step of producing the slowly cooled foil.
- FIG. 18 is a diagram showing the correlation between the oxygen concentration in the thermoelectric semiconductor material produced in the annealing step of FIG. 1 and the figure of merit of the thermoelectric semiconductor material formed using the thermoelectric semiconductor material. It is.
- FIG. 19 is a flowchart showing another embodiment of the method for producing a thermoelectric semiconductor material according to the present invention.
- FIG. 20A shows a plastic working apparatus used for performing the omnidirectional hydrostatic pressure process of FIG. Therefore, it is a schematic cut side view showing an initial state before plastic deformation of a formed body.
- FIG. 20B is a view as seen in the direction of arrows B—B in FIG. 2OA.
- Fig. 20C shows the plastic working device used to carry out the omnidirectional hydrostatic pressure step of Fig. 19, and shows the state in which the omnidirectional hydrostatic pressure is applied to the required amount of plastically deformed compact. It is a cutting
- FIG. 21 shows a procedure of a method for manufacturing a thermoelectric semiconductor device of the present invention, showing a state in which a thermoelectric semiconductor material is sliced, a sliced wafer, and a thermoelectric semiconductor device cut out from a wafer 81. It is a schematic perspective view.
- FIG. 22 is a schematic perspective view showing one embodiment of the thermoelectric module of the present invention.
- FIG. 23 is a schematic perspective view showing a comparative example of the thermoelectric module of FIG.
- FIG. 24A is a schematic cross-sectional side view showing another example of the plastic working device used in the plastic deformation step of FIG.
- FIG. 24B is a view as seen in the direction of arrows CC in FIG. 24A.
- FIG. 25A shows an example in which the plastic deformation step in FIG. 1 is performed by another device, and is a schematic diagram showing a state in which a compact is plastically deformed by a large-pressure pressing device.
- FIG. 25B shows an example in which the plastic deformation step of FIG. 1 is performed by another apparatus, and is a schematic diagram showing a state in which a compact is plastically deformed by a rolling machine.
- FIG. 26 is a diagram showing a result of comparing the thermoelectric performance of a thermoelectric module manufactured by the manufacturing method of the present invention with a thermoelectric module manufactured by another manufacturing method.
- FIG. 27 is a perspective view schematically showing an example of a conventional thermoelectric module. BEST MODE FOR CARRYING OUT THE INVENTION
- FIGS. 1 to 18 show an embodiment of a method for producing a thermoelectric semiconductor material according to the present invention.
- a flow chart of a thermoelectric semiconductor material alloy is basically formed. After mixing the metal at a required ratio and preparing an alloy, it is melted to form a molten alloy, and the molten alloy is not rapidly cooled by 90% or more of the thickness of a thermoelectric semiconductor material formed by a cooling method described later. Slow cooling (slow cooling) at a high speed A thin plate-like foil (annealed foil) as a material is manufactured. Then, the manufactured annealed foil as a thermoelectric semiconductor material is laminated and filled in a mold in a direction substantially parallel to the thickness direction.
- thermoelectric semiconductor material is manufactured by being plastically deformed by pressing. Specifically, the method for producing an N-type thermoelectric semiconductor material and an N-type semiconductor element will be described.
- the component adjustment step I in order to prepare a stoichiometric composition of a raw material alloy of the N-type thermoelectric semiconductor, , And Se and Te are weighed so as to have compositions of Bi: 40 atomic%, Se: 1 to 10 atomic%, and Te: 50 to 59 atomic%, respectively.
- the composition of the Bi 2 (T e — S e) 3 system is obtained, and the mass is calculated with respect to the total amount of the above composition of the Bi 2 (T e — S e) 3 system.
- An alloy is prepared by adding an excess of 0.11 to 10% by weight to the composition so as to have a non-stoichiometric composition in excess of Te.
- a necessary amount of a dopant for forming an N-type thermoelectric semiconductor for example, a dopant such as Hg, Ag, Cu, or halogen may be added.
- the metal mixture mixed and charged in the above component preparation process I is mixed with a reducing gas atmosphere, an inert gas atmosphere, or a low oxygen concentration atmosphere such as vacuum.
- a quartz melting crucible 6 installed in a container 5 capable of holding the molten alloy and being heated by a heating coil 7 to be melted into a molten alloy 8
- the molten alloy 8 is cooled by a cooling member.
- the molten crucible 6 is formed so as to form a thermoelectric semiconductor material 10 having a material thickness of at least 30 or more by being supplied to the surface of a rotating roll 9 such as a water-cooled roll and solidified.
- thermoelectric semiconductors material 1 0-mentioned thin plate shown in FIG. 1 A rotating port that rotates the molten alloy 8 in the melting crucible 6 at a low speed so that the peripheral speed is 5 mZ seconds or less from a nozzle with a required diameter provided at the lower end, for example, 0.5 mm in diameter.
- the rotation speed of the rotating roll 9 can be set to a peripheral speed of 2 m / sec or less. desirable. This is because when the peripheral speed of the rotating roll 9 is set to 5 m / sec or less, as shown in the graph of FIG. 4, the thickness of the gradually cooled foil as the thermoelectric semiconductor material 10 to be manufactured is 30 or more.
- the thickness of the thermoelectric semiconductor material 10 to be formed is 90%. % Or more can be solidified at a rate that does not cause rapid cooling, and therefore, as shown in FIG. 3, the crystal grains 11 formed in the structure of the thermoelectric semiconductor material 10 are referred to as thermoelectric semiconductor material 10.
- the length of the annealed foil can be almost the entire length in the plate thickness direction, a thermoelectric semiconductor material 10 with good crystal orientation can be formed, and the peripheral speed of the rotating roll 9 is 2 mZ If it is less than seconds, the thickness of the thermoelectric semiconductor material 10 can be efficiently increased to about 70 im or more. This makes it possible to further increase the length of the crystal grains 11 and further improve the crystal orientation.
- the thermoelectric semiconductor material 10 is manufactured. Since the width dimension of all the gradually cooled foils can be made large, the volume of each thermoelectric semiconductor material 10 can be increased. In FIG.
- the crystal grains 11 in the structure of the thermoelectric semiconductor material 10 are schematically shown as hexagons.
- the hexagons represent the actual crystal lattice of the hexagonal structure of the crystal grains 11 described above.
- the orientation of the C-plane of the hexagonal structure of the crystal grains 11 is schematically indicated by the hexagonal faces, and the crystal grains 1 are determined by the flattening directions of the hexagons.
- the flattening direction of 1, that is, the directionality of the orientation of the crystal grains 11 is schematically shown. The same applies to the following drawings.
- the molten alloy 8 of the raw material alloy is supplied onto the rotating roll 9 and gradually cooled, so that the molten alloy 8 is slowly moved in the thickness direction of the molten alloy 8 from the contact surface side with the rotating roll 9 toward the outer periphery of the mouth. It is sequentially cooled, Thus as shown in FIG.
- thermoelectric semiconductor material 10 which is considered to have a structure including the above is obtained.
- FIGS. 6A and 6B show scanning electron microscope (SEM) images of the microstructure of the thermoelectric semiconductor material 10 manufactured in the above-described annealing foil manufacturing process II.
- FIG. 6A shows the thermoelectric semiconductor material. 10 shows a state in which the contact surface side with the rotating roll 9 is arranged on the upper side
- FIG. 6B shows the surface structure of the thermoelectric semiconductor material 10 on the non-rotating roll contact surface side.
- thermoelectric semiconductor material 10 having a thickness of 30 m or more can be formed, and the contact surface side with the rotating roll 9 can be formed.
- small crystal grains generated by the rapid cooling of the molten alloy 8 due to the contact with the rotary port 9 are seen, and the small crystal grains are formed in the surface layer on the contact surface side with the rotary roll 9.
- the sheet thickness of the thermoelectric semiconductor material 10 extends over almost the entire length of the sheet pressure dimension of the thermoelectric semiconductor material 10. Large crystal grains 11 oriented in the direction can be formed.
- thermoelectric semiconductor material 10 is such that a Bi 2 (Te—Se) 3 composite compound that is flat and oriented so as to extend in the plate pressure direction.
- Heterogeneous phase (Te-rich phase) crystal grains 11a are formed in the crystal grains 11 of semiconductors and the like and in the grain boundaries.
- thermoelectric semiconductor material 10 manufactured in the above-described slow cooling foil manufacturing process II is formed by solidification molding:! : Before sending to III, powder with small particle size may be sieved and removed in advance.
- the annealing foil is placed in a container (not shown) capable of holding a low oxygen concentration atmosphere such as a reducing gas atmosphere, an inert gas atmosphere, or a vacuum of 10 Pa or less.
- the annealed foil of the thermoelectric semiconductor material 10 manufactured in the manufacturing process II is filled in a mold (not shown) so as to be laminated and arranged almost in parallel in the thickness direction (direction of arrow t), and then sintered and pressed.
- 7A, FIG. 7B, and FIG. 7C as shown in FIG. 7A, FIG. 7B, and FIG. 7C, the width between the restraining members 15 in the plastic working device 13 used in the plastic deformation process IV described later.
- a rectangular parallelepiped molded body 12 having a corresponding required width dimension is manufactured.
- FIG. 7B schematically shows a laminated structure of a slow cooling foil as a thermoelectric semiconductor material 10 which is a basic structure of the structure of the molded body 12.
- FIG. This is an enlarged view of a part of the laminated structure of the thermoelectric semiconductor material 10 of FIG.
- the reaction conditions at the time of sintering are as follows: a given pressure, for example, a pressure of 14.7 MPa or more, is applied to the thermoelectric semiconductor material 6 produced in the slow cooling foil production step II.
- 420 Temperature lower than 500 ° C to prevent complete segregation, phase separation, and liquid precipitation of the low melting point Te-rich phase, which may become liquid at around 200 ° C.
- Conditions preferably, heating to a temperature of 420 ° C. or more and 450 ° C. or less, and holding at that temperature for a short time, for example, about 5 seconds to 5 minutes to perform sintering.
- a given pressure for example, a pressure of 14.7 MPa or more
- the lower limit of the temperature condition range for this sintering is set at 380 ° C or more. This is because if the sintering temperature is lower than 380 ° C, the density of the molded body 12 does not increase. Furthermore, during the sintering, the sintering object is allowed to reach the required sintering temperature condition almost uniformly over the whole without causing a bias in the temperature distribution of the object. The multi-stage heating should be performed.
- the multi-stage heating means that when the object to be sintered is heated to the above-mentioned required sintering temperature condition using a required heating source (not shown), the heating is performed once or more in the middle for a required period, for example, 10 times.
- the heating by the above heating source is temporarily stopped for more than 2 seconds, or by the heating source.
- the heat conduction of the sintering object itself is used during the above-mentioned heating stop period or the period during which the heating rate is reduced to reduce the sintering object.
- the temperature of the entire product is made uniform, the temperature of the whole is made uniform at the temperature in the process of raising the temperature, and then the sintering object is further heated, so that the sintering * f
- This is a method of raising the temperature of the material almost uniformly to the above-mentioned sintering temperature condition which is the ultimate temperature.
- the temperature of the sintering object uniform on the way, it is possible to suppress the uneven distribution of the temperature distribution when the sintering temperature is reached even if the heating location by the heating source is uneven.
- a heating device heating furnace
- a normal hot press an energized hot press, a pulsed hot press, or the like may be used.
- the above-mentioned heating stop period and the period of decreasing the heating rate are not limited to 10 seconds or more, but may be set arbitrarily according to the heating capacity of the heating source, the size of the sintering object, and the like. Good.
- the annealed foil as the thermoelectric semiconductor material 10 formed in the annealed foil manufacturing step II has a large width and a large thickness.
- the respective thermoelectric semiconductor materials 10 are filled so as to fill the gaps between the thermoelectric semiconductor materials 10.
- the thermoelectric semiconductor materials 10 are plastically deformed so that the gaps between the thermoelectric semiconductor materials 10 are filled with the movement of the atoms, so that the thermoelectric semiconductor materials 10 are brought into contact with each other. The interfaces of the thermoelectric semiconductor materials 10 are joined.
- thermoelectric semiconductor material 10 due to the deformation of the thermoelectric semiconductor material 10, the orientation of the C-plane of the crystal grain 11 that has been oriented so as to be substantially aligned in the thickness direction of the thermoelectric semiconductor material 10 is somewhat disturbed, but in terms of volume. For the most part, there is no collapse, and therefore, as shown in FIG. 7B, in the slowly cooled foil of each thermoelectric semiconductor material 10 constituting the molded body 12, the orientation of the crystal grains 11 is The orientation (arrow t direction) is substantially the same as that of the thermoelectric semiconductor material 10 shown in FIG. Therefore, it is possible to prevent the orientation of the c-plane of the crystal grains from being largely disturbed as in the case where a fine thermoelectric semiconductor material is sintered as in the past.
- the molded body 12 is formed by laminating annealed foil having a large thickness and a large width as the thermoelectric semiconductor material 10 substantially in parallel with the thickness direction, and then solidifying and molding,
- the gap between the semiconductor materials 10 can be easily reduced, and the density of the formed body 12 can be compared with the density of a composite compound semiconductor having the same composition as an ideal crystal structure. 99.8% or more can be improved.
- thermoelectric semiconductor material 1 in 0, since either not a liquid phase during sintering, or limited to a small amount even if was in the liquid phase, the B i 2 T e 3 and B i 2 S e and complex compound semiconductor phase having a composition of 3, T e Ritsuchi phase while carrying a tissue structure with finely dispersed shaped body containing these excess T e and against the composition 1 2 Is formed, and a part of the Te-rich phase is present at the interface between the slowly cooled foils as the thermoelectric semiconductor material 10 with the heating during the sintering.
- a reducing gas atmosphere, an inert gas atmosphere, or a low oxygen concentration such as a vacuum for example, in a sealed container (not shown) capable of maintaining an atmosphere having an oxygen partial pressure of 0.2 Pa or less.
- a pair of plate-like restraining members 15 having substantially parallel opposing surfaces are provided at the left and right positions on the base 14 with the molded body 12 Dimensions in the width direction (dimensions in one of the two axial directions that intersect in a plane perpendicular to the main laminating direction of the thermoelectric semiconductor material 10 forming the molded body 12) and a corresponding required interval
- the punch 16 is vertically slidably disposed inside the left and right restraining members 15, and the punch 16 is positioned above the left and right restraining members 15 by a lifting drive (not shown).
- each restraining member 15 To the lower position inside each restraining member 15 In addition, a plastic working device 13 having a heating device (not shown) at required positions of the base 14, the restraining member 15, and the punch 16 is prepared. As shown in FIG. 8A, in a state where the punch 16 is lifted to the upper position of the restraining member 15, the punch 16 is positioned at the center inside the restraining members 15 in the solidification molding step III.
- the formed body 12 is formed such that the longitudinal direction of the formed body 12 is arranged along the vertical direction, and the formed body 12 is The lamination direction of the thermoelectric semiconductor material 10 to be composed (the same arrow t direction in the thickness direction of the thermoelectric semiconductor material 10) is arranged in parallel with the left and right restraining members 15 and the width of the molded body 12 The both sides in the direction are arranged so as to contact the inner surfaces of the left and right restraining members 15, and then the molded body 12 is heated by a heating device at a temperature of 470 ° C. or less, preferably 450 ° C. or less.
- the punch 16 is lowered by a lifting drive device to apply a pressing force of a required load to the molded body 12 from above, as indicated by a two-dot chain line in FIG. 8A.
- the molded body 12 is plastically deformed so as to be spread in a uniaxial direction parallel to the lamination direction of the thermoelectric semiconductor material 10, thereby producing a rectangular parallelepiped thermoelectric semiconductor material 17 as shown in FIG. 8C.
- the pressing force of the punch 16 is applied to the compact 12 from above by the plastic working device 13, the compact 12 is deformed in the width direction by the right and left restraining members 15.
- thermoelectric semiconductor material 10 in the molded body 12 Due to the restraint, only deformation in the direction parallel to the restraining member 15, that is, in the lamination direction (the direction of the arrow t) of the thermoelectric semiconductor material 10 in the molded body 12 is allowed.
- the shearing force is applied in a uniaxial direction parallel to the direction, whereby the gradually cooled foil of the thermoelectric semiconductor material 10 constituting the molded body 12 before the plastic deformation has an adjacent lamination interface broken.
- the crystal grains 11 are oriented such that the C-plane of the hexagonal structure extends in a direction parallel to the thickness direction of the thermoelectric semiconductor material 10 in the molded body 12. Is that the cleavage plane is flattened plastically in the direction in which the above-mentioned shearing force acts. Yuku is oriented so as to be perpendicular to the pressure direction.
- each crystal grain 11 1 Has its hexagonal structure.
- the surface is deformed so as to extend parallel to the extending direction of the molded body 12, that is, the laminating direction (arrow t direction) of the thermoelectric semiconductor material 10 in the molded body 12 before deformation, and at the same time, most of the crystal grains 11 is oriented so that its C-axis direction is aligned with the compression direction (the direction indicated by the arrow P in the figure) during the plastic working.
- the hexagons in FIG. 9B merely indicate the orientation of the crystal grains 11 and do not reflect the actual size of the crystal grains 11.
- the plastic working device 13 applies a large outward stress to the left and right binding members 15 at the time of plastic deformation of the molded body 12, as shown in FIG.
- a series of position fixing rings 15a are provided so as to surround the outer peripheral side of the restraining member 15 of the above, the stress acting on the left and right restraining members 15 is applied to the position fixing ring 15a. You may make it receive.
- the crystal grain 11 is oriented in the thickness direction by gradually cooling and solidifying the molten alloy 8 of the raw material alloy using the rotating roll 9.
- thermoelectric semiconductor material 10 is made to maintain the crystal structure while maintaining the crystal orientation, and retain the microstructure of the Bi 2 (T e -S e) 3 type compound semiconductor phase in which the above-mentioned Te rich phase is finely dispersed.
- the molded body 12 is formed by solidification and molding while the molded body 12 is formed only in the uniaxial direction substantially parallel to the thickness direction of the thermoelectric semiconductor material 10 which is the laminating direction of the thermoelectric semiconductor material 10.
- thermoelectric semiconductor material 17 Since the direction in which the C-plane of the hexagonal structure extends and the direction of the C-axis can be almost aligned, setting the direction of current and heat flow in the direction in which the C-plane of each of the crystal grains 11 extends allows the thermoelectric performance ( The figure of merit: Z) can be improved. That is, as described in FIG.
- the peripheral speed of the rotating roll 9 is set to a low speed of 5 seconds so that the thermoelectric semiconductor material 10 having a thickness of 30 / im or more can be obtained. Therefore, the rotational speed of the rotating roll 9 during the production of the gradually cooled foil as the thermoelectric semiconductor material 10 as shown in FIG. 10 and the thermoelectric semiconductor material produced from the thermoelectric semiconductor material 10 through the above steps As is clear from the relationship with the thermal conductivity ( ⁇ ) of 17, the thermal conductivity (/ c) of the manufactured thermoelectric semiconductor material 17 is reduced by reducing the rotation speed of the rotating roll 9 as described above. When the rotating speed of the rotating roll 9 is high Can be increased as compared with the case where the thermoelectric semiconductor material 10 is used. Also, as shown in FIG.
- thermoelectric semiconductor material 17 the relationship between the rotation speed of the rotating roll 9 during the production of the slowly cooled foil as the thermoelectric semiconductor material 10 and the electric conductivity ( ⁇ ) of the thermoelectric semiconductor material 17 produced
- the rotation speed of the rotating roll 9 as described above the electric conductivity ( ⁇ ) of the manufactured thermoelectric semiconductor material ⁇ fl 7 is reduced when the rotating speed of the rotating roll 9 is high. This can be increased as compared with the case where the thermoelectric semiconductor material 10 is used.
- the rotation speed of the rotating roll 9 during the production of the slowly cooled foil as the thermoelectric semiconductor material 10 as shown in FIG. 12 and the Seebeck coefficient (a) of the produced thermoelectric semiconductor material 17 are shown in FIG.
- thermoelectric semiconductor material 17 to be manufactured is reduced when the rotation speed of the rotary roll 9 is high. This can be increased as compared with the case where the thermoelectric semiconductor material 10 is used. Furthermore, from the relationship between the rotation speed of the rotating roll 9 during the production of the gradually cooled foil as the thermoelectric semiconductor material 10 as shown in FIG. 13 and the carrier concentration in the produced thermoelectric semiconductor material 17. As is evident, the carrier concentration in the manufactured thermoelectric semiconductor material 17 is reduced by reducing the rotation speed of the rotating roll 9, and the thermoelectric semiconductor material 10 when the rotation speed of the rotating port 9 is high is used.
- thermoelectric semiconductor material 11 of the present invention As shown in FIG. 4, by reducing the rotation speed of the rotating hole 9, the gradually cooled foil as the thermoelectric semiconductor material 10 to be manufactured is manufactured.
- the thickness can be increased, the specific surface area can be reduced. For this reason, the thickness of the gradually cooled foil as the thermoelectric semiconductor material 10 shown in FIG. 15 and the thermoelectric semiconductor material 10 measured by the infrared absorption method can be reduced. As is clear from the relationship with the oxygen concentration contained in the thermoelectric semiconductor material 10, the oxidation of the thermoelectric semiconductor material 10 can be suppressed, and the oxygen concentration in the thermoelectric semiconductor material 17 produced from the thermoelectric semiconductor material 10 can be reduced. Reduction can be achieved. Further, as shown in FIG. 5, by reducing the rotation speed of the rotating roll 9, the width of the gradually cooled foil as the thermoelectric semiconductor material 10 to be manufactured can be increased.
- the specific surface area can be reduced, and therefore, the width of the slowly cooled foil as the thermoelectric semiconductor material 10 shown in FIG. 16 and the oxygen concentration contained in the thermoelectric semiconductor material 10 measured by the infrared absorption method are reduced.
- the oxidation of the thermoelectric semiconductor material 10 can be suppressed in the same manner as described above, and the oxygen concentration in the manufactured thermoelectric semiconductor material 17 can be reduced. Therefore, as is clear from the relationship between the rotation speed of the rotating roll 9 as shown in FIG. 17 and the oxygen concentration in the thermoelectric semiconductor material 17, the manufacturing is performed by reducing the rotating speed of the rotating roll 9 described above.
- thermoelectric semiconductor material 17 Since the concentration of oxygen contained in the thermoelectric semiconductor material 17 can be reduced, it is possible to prevent a decrease in electric conductivity ( ⁇ ) due to oxidation. Therefore, as is clear from the relationship between the oxygen concentration in the gradually cooled foil as the thermoelectric semiconductor material 10 and the figure of merit as shown in FIG. 18, the oxygen concentration contained in the manufactured thermoelectric semiconductor material 17 Thus, the thermoelectric performance of the thermoelectric semiconductor material 17 can be improved.
- the electrical conductivity ( ⁇ ) of the ⁇ -type thermoelectric semiconductor material 17 manufactured above and the Seebeck coefficient (H) are Bi 2 (T e ⁇ S e) Series 3 Can be controlled by adjusting the ratio of Te and Se in the composition of Further, as another embodiment of the method for producing a thermoelectric semiconductor material of the present invention, as shown in FIG.
- a plastic deformation step IV in the same procedure for producing a thermoelectric semiconductor material as described above,
- a shear force is applied in a uniaxial direction parallel to the laminating direction of the annealed foil of the thermoelectric semiconductor material 10 by pressing 1 2 to plastically deform to a required shape, the uniaxial shear force for performing the plastic deformation itself
- One or more omnidirectional hydrostatic pressure steps IV-2 may be performed during the action step IV-1, for example, when the deformation rate is low.
- the omnidirectional hydrostatic pressure step IV-2 refers to a state in which, during plastic deformation of the molded body 12, the molded body 12 being deformed is brought into contact with a surface in the deformation direction to temporarily restrain the deformation, This is the process of applying pressure for a certain period of time. Therefore, when performing the above-mentioned omnidirectional hydrostatic pressure process IV-2, as shown in FIGS. 20A, 20B and 20C, the plasticity shown in FIGS. 8A, 8B and 8C is obtained.
- a pair of front and rear restraining members 18 having substantially parallel opposing surfaces is provided at a required interval at both sides in the front-rear direction between the left and right restraining members 15, As a configuration in which the front and rear sides of the region between the left and right restraining members 15 are respectively closed, the molded body 12 formed in the solidification molding process III is placed at the center of the inner side of the left and right restraining members 15.
- thermoelectric semiconductor material 10 forming the molded body 12 When the thermoelectric semiconductor material 10 forming the molded body 12 is arranged so that the lamination direction of the thermoelectric semiconductor material 10 is parallel to the left and right constraint members 15, the molded body 12 and the front and rear constraint members 18 are Between them, a required gap that is a deformation allowance of the molded body 12 is formed, and The punch 16a having a plane shape corresponding to the space surrounded by the front and rear restraint members 15 and 18 is moved up and down in the space by a lifting drive device (not shown).
- a plastic working device 13a equipped with a heating device (not shown) at required positions of the base 14, the restraint members 15, 18 and the punch 16a is prepared.
- B and the plastic working device 13 shown in Fig. 8C are also prepared.
- a shear force is applied in one axial direction before and after, and the plastic deformation is performed so as to flatten forward and backward, and a uniaxial shear force action process IV-1 is performed. Thereafter, the plastic deformation in the forward and backward direction proceeds.
- the deformed object of the molded body 12 is simultaneously restrained by the left and right restraining members 15 on both sides in the width direction and simultaneously in the front-rear direction.
- the pressing force given by the punch 16a acts as a hydrostatic pressure in all directions on the deformed product of the molded body 12. This causes the omnidirectional hydrostatic pressure process IV-2 to be performed. Thereafter, the plastic deformation of the molded body 12 that has been extended (plastically deformed) in the front-rear direction until it comes into contact with the restraining members 18 in front of and behind the plastic working device 13a is taken out, and the plastic deformation of the molded body 12 is taken out.
- the object is placed at the center between the left and right restraining members 15 of the plastic working device 13 in the same manner as described with reference to FIGS. 8A, 8B, and 8C.
- a uniaxial shearing force acting step IV-1 is performed by applying a shearing force in the front-back direction, which is a uniaxial direction substantially parallel to the laminating direction, to perform a thermoelectric semiconductor material 17.
- the above omnidirectional hydrostatic pressure step IV-2 may be performed two or more times. In this case, a plurality of plastic working devices 13 in which the distance between the restraining members 18 in the front-rear direction is gradually increased.
- a pressing force is applied from above to apply a shearing force in a uniaxial direction substantially parallel to the laminating direction of the thermoelectric semiconductor material 10, and the plastic deformation is performed so that the deformation amount from the initial state gradually increases.
- the omnidirectional hydrostatic pressure is applied while the deformation is restrained by the front and rear restraining members 18, and finally the plastic working device 13 without the front and rear restraining members 18 is plastically deformed to extend in the front and rear directions. You can make it deform.
- the above-mentioned omnidirectional hydrostatic pressure step IV-2 is performed on the molded body 12 which is undergoing plastic deformation in the uniaxial shearing force acting step IV-1, so that the molded body 12 which is undergoing plastic deformation is dense. Therefore, it is possible to prevent the possibility that buckling will occur in the molded body 12 finally subjected to the plastic deformation processing by the plastic working device 13 and to prevent both ends in the front-rear direction which are the front ends in the plastic deformation direction.
- the shape of the front and rear ends of the molded body 12 can be adjusted at the stage of plastic deformation, so that the deformation speed of the molded body 12 is made uniform. Therefore, the uniformity of the structure of the manufactured thermoelectric semiconductor material 17 can be improved.
- the front and rear ends of the molded body 12 abut against the front and rear restraining members 18, so that the crystal grains 11 are formed at the front and rear ends of the molded body 12.
- the plastic working apparatus 13 is almost parallel to the laminating direction of the thermoelectric semiconductor material 10 forming the molded body 12 without restraining the front and rear directions. Since the thermoelectric semiconductor material 17 is made to spread while applying a shearing force in a single axial direction, the C-plane direction and the C-axis direction of the crystal grains 11 can be changed at both ends in the front-rear direction. It can be almost aligned.
- a stress-strain processing step V is provided as a step subsequent to the plastic deformation step IV, and the plastic deformation is performed in the stress-strain processing step V.
- the thermoelectric semiconductor material 17 produced by plastically deforming to the required shape in step IV is placed at a predetermined temperature, for example, 350 ° C to 500 ° C, 30 minutes to 24 hours, etc. By holding for a certain period of time, the dislocation of the crystal lattice, the reduction by heat treatment of vacancies, etc., and the rearrangement are performed, which are caused by the plastic deformation processing in the plastic deformation step IV.
- the stress strain remaining in the structure may be eliminated.
- a defect concentration control step VII is provided as a step subsequent to the stress distortion processing step VI.
- the thermoelectric semiconductor from which the residual stress distortion has been removed in the stress distortion processing step VI is provided.
- the defect concentration in the thermoelectric semiconductor material 17 is changed, thereby controlling the electric conductivity ( ⁇ ) and the Seebeck coefficient (a). Is also good.
- thermoelectric semiconductor material 17 produced in the plastic deformation step IV has the structure of the thermoelectric semiconductor material 10 constituting the molded body 12, that is, the composite of the Bi 2 (Te-Se) 3 system. Heterogeneous phase (Te-rich phase) is maintained in the crystal grains of compound semiconductors and in grain boundaries. Since this excess Te is a component of the Bi 2 (Te—Se) 3 system thermoelectric semiconductor, when the thermoelectric semiconductor material 17 is heat-treated, the Bi 2 (Te—Se) 3 system The effect of reacting with the component part and filling the defect of the main component is obtained.
- thermoelectric semiconductor element of the present invention a case where the N-type thermoelectric semiconductor element 3a is manufactured using the N-type thermoelectric semiconductor material 17 manufactured in the embodiment of FIGS. Will be described. In this case, the N-type thermoelectric semiconductor material 17 has crystal grains throughout its structure.
- thermoelectric semiconductor element 3a is formed by cutting out so that the current and heat flow directions can be set in the direction in which the C plane extends.
- the C-plane of the hexagonal structure of each crystal grain is oriented in the direction of the plastic deformation of the molded body 12 (arrow). (t direction) and the C axis is almost aligned with the pressing direction (arrow p direction) during the plastic deformation.
- the material 17 is sliced on a plane perpendicular to the spreading direction at a required interval position in the spreading direction (the direction of the arrow t) at the time of plastic deformation, as shown in the middle part of FIG. Cut out wafer 19.
- the C-plane of the hexagonal structure of the crystal grains 11 is oriented in a state of extending in the thickness direction. Therefore, the conductive material treated surface 20 was formed on the both end surfaces in the thickness direction of the wafer 19 by performing plating or the like using a plating device (not shown).
- a plating device not shown.
- the wafer 19 has a surface perpendicular to the pressing direction (arrow p direction) of the molded body 12 during the production of the thermoelectric semiconductor material 17 and the pressing direction (arrow).
- (p direction) and thermoelectric semiconductor material 17 Cut along a plane defined by two axes in the spreading direction (arrow t direction) at the time of manufacture, and cut out (diced) into a rectangular parallelepiped shape as shown in the lower part of Fig. 21
- an N-type thermoelectric semiconductor element 3a is manufactured.
- the N-type thermoelectric semiconductor element 3 a is a set in which the conductive material processing corresponding to the conductive material processing surface 20 of the wafer 19 subjected to the conductive material processing is performed.
- the C-plane of the hexagonal structure of the crystal grains 11 extends in the direction of the opposing surface 20 of the crystal grains 11 (the same direction as the spreading direction at the time of production of the thermoelectric semiconductor material 17 indicated by the arrow t in the figure), and the crystal grains 11
- the crystal structure has a C-axis aligned with the pressing direction (the direction of the arrow p in the figure) of the thermoelectric semiconductor material 17 among the biaxial directions perpendicular to the conductive material treated surface 20. Therefore, by attaching a metal electrode (not shown) to the conductive material treated surface 20, a texture structure having crystal grains 11 with well-aligned orientation not only in the C-plane direction of the hexagonal structure but also in the C-axis direction can be obtained.
- thermoelectric semiconductor element 3a having good thermoelectric performance can be obtained as a current and heat acting in the C-plane direction of the hexagonal structure of the crystal grains 11 described above.
- a case of manufacturing a P-type thermoelectric semiconductor material will be described.
- B i, Sb and Te are used, and B i: 7 to 10 respectively.
- the metal mixture mixed in the component adjustment step I was melted using the apparatus shown in FIG. 2.
- the alloy 8 is supplied from a 0.5 mm diameter nozzle of the melting crucible 6 to the surface of a rotating roll 9 rotated at a low speed at a peripheral speed of 5 mZ seconds or less, preferably at a peripheral speed of 2 m / s or less, and gradually.
- a plate-like thermoelectric semiconductor material 10 (slowly cooled foil) is manufactured.
- the peripheral speed of the rotating roll 9 is set to 5 m / sec or less, preferably 2 mZ sec or less, as in the case of forming the N-type thermoelectric semiconductor material 10 described above. Is preferably increased to 30 or more, and a gradually cooled foil having a thickness of 70 im or more is formed.
- the width of the gradually cooled foil as the manufactured thermoelectric semiconductor material 10 is increased to increase the volume of a single thermoelectric semiconductor material 10, This is because the specific surface area can be reduced.
- the P-type thermoelectric semiconductor material 10 has the same crystal orientation as the N-type thermoelectric semiconductor material 10 in the thickness direction when cooled on the rotating roll 9 like the N-type thermoelectric semiconductor material 10 described above.
- thermoelectric semiconductor material 10 that is considered to have a structure that includes heterogeneous nuclei and includes crystal strain is obtained, and the thermoelectric semiconductor material 10 Similar to that shown in FIG. 3, it is a state in which crystal grains 11 extend substantially as in the thickness direction reaches the thickness dimension longer.
- the thermoelectric semiconductor material 10 may be pre-sieved to remove powder before a solidification molding step III described later.
- the slowly cooled foils of the P-type thermoelectric semiconductor material 10 produced in the above-described slowly cooled foil production step II are stacked and arranged substantially parallel to the thickness direction to form a mold (not shown).
- each laminated thermoelectric semiconductor material 10 is The thermoelectric semiconductor materials 10 are solidified and molded while being plastically worked so as to be in contact with each other so as to be in contact with each other, thereby producing a rectangular parallelepiped molded body 12 similar to that shown in FIGS. 7A, 7B and 7C.
- the Te-rich phase formed in the P-type thermoelectric semiconductor material 10 does not become a liquid phase during sintering, or is limited to a small amount even if it becomes a liquid phase.
- the molded body 12 is formed while maintaining a microstructure in which the Te phase and the Te rich phase containing excess Te with respect to these compositions are finely dispersed. Then, in the plastic deformation step IV, as in the case of manufacturing the N-type thermoelectric semiconductor material 17 described above, the plastic working apparatus 13 shown in FIGS. 8A, 8B, 8C, and 8D is used. Thus, in a state where the molded body 12 is heated to 500 ° C. or less, preferably 350 ° C. or less, only the uniaxial direction substantially parallel to the laminating direction of the thermoelectric semiconductor material 10 is developed. The P-type thermoelectric semiconductor material 17 is manufactured by plastic deformation so as to be extended.
- the heating temperature conditions vary depending on the excess amount of Te, and the smaller the excess amount of Te, the higher the temperature.
- a shearing force is applied only in the laminating direction of the thermoelectric semiconductor material 10, so that the thermoelectric semiconductor material is formed inside the molded body 12 in the same manner as shown in FIGS. 9A and 9B.
- the crystal grains 11 of the material 10 oriented in the plate thickness direction are oriented so that the cleavage plane is substantially perpendicular to the pressing direction while being flatly plastically deformed in the uniaxial direction where the above-mentioned shearing force acts.
- the C-plane of the hexagonal structure of each crystal grain 11 is deformed so as to extend in the spreading direction (the direction of the arrow t in FIGS.
- thermoelectric performance performance index: Z
- thermoelectric semiconductor material 10 having a large thickness and a width, and therefore a small specific surface area, is manufactured, and then solidified and formed to produce a P-type thermoelectric semiconductor material 17.
- concentration of oxygen contained in the thermoelectric semiconductor material 17 can be reduced, and a decrease in electric conductivity ( ⁇ ) due to oxidation can be prevented.
- ⁇ electric conductivity
- the electric conductivity ( ⁇ ) of the ⁇ -type thermoelectric semiconductor material 17 ⁇ Seebeck coefficient () is the standard of the composition of the ⁇ -type semiconductor, ie, B (B i — S b) 2 Te 3 system composition. It can be controlled by adjusting the ratio between i and Sb.
- the omnidirectional hydrostatic pressure step IV-2 in the plastic deformation step IV shown in FIG. 19 and the stress-strain processing as a post-step of the plastic deformation step IV Step V and defect concentration control step VI may be performed.
- the case where the P-type thermoelectric semiconductor element 2a is manufactured using the P-type thermoelectric semiconductor material 17 manufactured by the above method will be described.
- the P-type thermoelectric semiconductor material 17 also in the P-type thermoelectric semiconductor material 17, as in the case of the N-type thermoelectric semiconductor material 17 shown in FIGS.
- the C-plane of the crystal structure extends in the spreading direction during plastic deformation of the molded body 12 (the direction of the arrow t in FIGS.
- the P-type thermoelectric semiconductor material 17 is replaced with the N-type thermoelectric semiconductor element 3a shown in FIG.
- First as shown in the upper part of FIG. 21, first, as shown in the upper portion of FIG. After slicing the wafer 19 and cutting it out as a wafer 19 as shown in the middle section of FIG. 21, both ends of the wafer 19 in the thickness direction are treated with a conductive material. To form a conductive material treated surface 20, and then, the wafer 19 is cut out to form a rectangular parallelepiped P similar to the N-type thermoelectric semiconductor element 3 a as shown in the lower part of FIG.
- thermoelectric semiconductor element 2a is manufactured.
- the P-type thermoelectric semiconductor element 2a is, like the N-type thermoelectric semiconductor element 3a described above, oriented in the direction of the set of facing surfaces 20 on which the conductive material treatment has been performed. Pressing direction during production of the thermoelectric semiconductor material 17 (in the direction of arrow p) in the biaxial direction in which the C-plane of the crystal structure is elongated and the C-axis of the crystal grains 11 is perpendicular to the conductive material treated surface 20 Since the crystal structure is uniform, the thermoelectric performance can be improved.
- FIG. 22 shows a thermoelectric module 1 a of the present invention.
- the P-type thermoelectric semiconductor element 2a and the N-type thermoelectric semiconductor element 3a are arranged side by side in the direction in which the C-plane of the hexagonal structure of the crystal grains 11 extends, and in the direction orthogonal to both the C-axis directions.
- thermoelectric module 1 a of the present invention the P-type thermoelectric semiconductor element 2 a and the N-type thermoelectric Current and heat can be applied to a in the direction in which the C-plane of the crystal grains 11 extends, so that a thermoelectric module 1a having good thermoelectric performance can be obtained.
- the metal electrodes 4 expand and contract with a change in temperature.
- thermoelectric semiconductor elements 2a and 3a A stress in a direction of approaching or separating from the P-type and N-type thermoconductive semiconductor elements 2a and 3a acts on the thermoelectric semiconductor elements 2a and 3a.
- adjacent thermoelectric semiconductor elements 2a and 3a joined by one metal electrode 4 are arranged in the same plane in the C-plane direction of crystal grains 11 when forming
- the metal electrode 4 is stretched and contracted Stress can be applied to each crystal grain 11 only in a direction parallel to the C-plane. Therefore, even if the above-mentioned stress is applied, the stress is applied to the structure of each of the thermoelectric semiconductor elements 2a and 3a.
- thermoelectric module 1a since the risk of delamination between layers of the crystal grains 11 having a hexagonal structure can be prevented, damage due to cleavage of the thermoelectric semiconductor elements 2a and 3a can be prevented, and the strength and durability of the thermoelectric module 1a can be reduced. It can be improved. That is, as shown in FIG. 23 as a comparative example, in a state where the P-type and N-type thermoelectric semiconductor elements 2 a and 3 a are arranged side by side in the C-axis direction of the hexagonal structure of the crystal grains 11. When the thermoelectric semiconductor elements 2a and 3a are joined via the metal electrode 4 to form a PN element pair, the stress due to the elongation and shrinkage deformation of the metal electrode 4 due to the temperature change is as described above.
- thermoelectric semiconductor elements 2 a and 3 a acts on each of the thermoconductive semiconductor elements 2 a and 3 a along the C-axis direction of the crystal grain 11, and thus acts to peel off the hexagonal structure of the crystal grain 11, In such a case, it is considered that the thermoelectric semiconductor elements 2a and 3a are easily damaged by cleavage, but the thermoelectric module 1a of the present invention can prevent such damage.
- thermoelectric semiconductor material 10 in the solidifying and molding step III of the method for producing a thermoelectric semiconductor material are as follows: 380 t: not more than 500 t: not more than, preferably, not less than 420 ° C and not more than 450 ° C, but it is shown as holding for 5 seconds to 5 minutes, but time is not more than 400 ° C. It is also possible to perform sintering while applying a temperature to prevent complete segregation, phase separation, and liquid precipitation of the low melting point Te-rich phase dispersed in the composite compound semiconductor phase.
- the plastic working device 13 used in the plastic deformation step IV includes: Punch 16 can be raised and lowered inside left and right restraining members 15 The molded body 12 is disposed in the center of the inside of the left and right restraining members 15, and the molded body 12 is pressed from above by a punch 16, thereby forming the molded body 12. Although it is shown that it is spread on both front and rear sides, which are uniaxial directions parallel to the lamination direction of the thermoelectric semiconductor material 10, the plastic working device 13 is mounted on the base as shown in FIGS. 24A and 24B.
- a restraint member 15b that can restrain the deformation (extension) of the molded body 12 in one of the front-rear directions is further provided at the first position when the molded body 12 is plastically deformed.
- the molded body 12 is disposed so as to be in contact with the left and right restraining members 15 and the restraining members 15b, and thereafter, the molded body 12 is pressed from above by a punch 16 as shown by a two-dot chain line in the upper part of FIG.
- the molded body 12 may be extended only in one direction on the anti-restraining member 15b side.
- the plastic working device 13a used is provided with a position fixing ring 15a similar to that shown in FIG.8D on the outer peripheral side of the left and right restraining members 15 and the front and rear restraining members 18, and the plastic deformation of the molded body 12 is performed.
- the above-mentioned restraining members 15, 18 are subjected to stress acting outward.
- the A plastic working device 13a of a type capable of adjusting the restraining member 18 at an arbitrary interval may be used, and the composition of the raw material alloy of the thermoelectric semiconductor may be any of the P-type and the N-type. It is shown that an excess of Te is added to the stoichiometric composition of the composite compound.Instead of Te, any of Bi, Se, and Sb is replaced with a thermoelectric semiconductor composite. The composition may be an excessively added composition to the stoichiometric composition of the compound.
- thermoelectric semiconductor elements and thermoelectric modules may be applied.
- the improvement of the thermoelectric performance accompanying the improvement of the orientation of the crystal grains 11 in the structure of the thermoelectric semiconductor material 17 can be expected.
- the stoichiometric composition of the raw material alloy of the N-type thermoelectric semiconductor is, B i 2 (Te-S e) it showed a three-element 3 -based, B i 2 Te 3 system 2-element, or (B i-Sb) of the small amount of 2 Te 3 system S
- the method for producing a thermoelectric semiconductor material, a thermoelectric semiconductor element, and a thermoelectric module of the present invention may be applied to a four-element stoichiometric raw material alloy obtained by adding e.
- thermoelectric semiconductor material As the stoichiometric composition of the composite compound, the composition of a three-element system of (B i — Sb) 2 Te 3 was shown, but a small amount of Sb was added to the Bi 2 (Te-Se) 3 system.
- the method for producing a thermoelectric semiconductor material, a thermoelectric semiconductor element, and a thermoelectric module of the present invention may be applied to a raw material alloy having a stoichiometric composition of a four-element system.
- Thermoelectric semiconductor Plasticity is obtained by applying a shearing force in a uniaxial direction substantially parallel to the laminating direction of the thermoelectric semiconductor material 10 on a molded body 12 obtained by laminating the annealed foil of the material 10 in the thickness direction and solidifying and forming the same.
- the thermoelectric semiconductor material 17 is manufactured by deforming, it is shown that the plastic working devices 13 and 13a are used, but as shown in FIG. 25A, the thermoelectric semiconductor material 17 can be moved in directions close to and away from each other.
- the green compact 12 is formed into a thermoelectric semiconductor material 10 by a large pressing machine 21 having a pair of dies 22 and a rolling machine 23 having a rolling roll 24 as shown in FIG. 25B.
- pressing While proceeding in the main laminating direction, pressing may be performed in a uniaxial direction perpendicular to the laminating direction. In this case, friction is applied in a direction perpendicular to both the laminating direction and the pressing direction of the thermoelectric semiconductor material 10. Does not spread due to the action of Since it is possible to suppress, in particular, that it does not restraining member required, other, it is a matter of course that within the scope not departing from the gist of the present invention achieve various changes example pressurized.
- thermoelectric semiconductor elements 2a and 3a produced based on the method for producing a thermoelectric semiconductor element of the present invention form a PN element pair to produce a thermoelectric module 1a.
- the thermoelectric performance was compared with that of a thermoelectric module manufactured by the company. As a result, the thermoelectric performance of the thermoelectric module 1a manufactured according to the present invention was obtained as shown in FIG.
- thermoelectric semiconductor element 2a is manufactured based on the thermoelectric semiconductor element manufacturing method of the present invention, while the P-type thermoelectric semiconductor element is manufactured only by hot pressing of thermoelectric semiconductor material (indicated by ⁇ and ⁇ in FIG. 26). In comparison, high thermoelectric performance was found to be obtained.
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US10/555,855 US20060243314A1 (en) | 2003-05-08 | 2004-05-07 | Thermoelectric semiconductor material, thermoelectric semiconductor element therefrom, thermoelectric module including thermoelectric semiconductor element and process for producing these |
CN2004800193530A CN1816919B (zh) | 2003-05-08 | 2004-05-07 | 热电半导体材料及其制造方法 |
US13/083,666 US8692103B2 (en) | 2003-05-08 | 2011-04-11 | Thermoelectric semiconductor material, thermoelectric semiconductor element using thermoelectric semiconductor material, thermoelectric module using thermoelectric semiconductor element and manufacturing method for same |
US14/187,858 US8884152B2 (en) | 2003-05-08 | 2014-02-24 | Thermoelectric semiconductor material, thermoelectric semiconductor element using thermoelectric semiconductor material, thermoelectric module using thermoelectric semiconductor element and manufacturing method for same |
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JP2003130618A JP4286053B2 (ja) | 2003-05-08 | 2003-05-08 | 熱電半導体材料、該熱電半導体材料による熱電半導体素子、該熱電半導体素子を用いた熱電モジュール及びこれらの製造方法 |
JP2003-130618 | 2003-05-08 |
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US10555855 A-371-Of-International | 2004-05-07 | ||
US13/083,666 Continuation US8692103B2 (en) | 2003-05-08 | 2011-04-11 | Thermoelectric semiconductor material, thermoelectric semiconductor element using thermoelectric semiconductor material, thermoelectric module using thermoelectric semiconductor element and manufacturing method for same |
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RU2470414C1 (ru) * | 2011-06-28 | 2012-12-20 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | СПОСОБ ПОЛУЧЕНИЯ ТЕРМОЭЛЕКТРИЧЕСКОГО МАТЕРИАЛА p-ТИПА НА ОСНОВЕ ТВЕРДЫХ РАСТВОРОВ Bi2Te3-Sb2Te3 |
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Publication number | Priority date | Publication date | Assignee | Title |
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RU2470414C1 (ru) * | 2011-06-28 | 2012-12-20 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | СПОСОБ ПОЛУЧЕНИЯ ТЕРМОЭЛЕКТРИЧЕСКОГО МАТЕРИАЛА p-ТИПА НА ОСНОВЕ ТВЕРДЫХ РАСТВОРОВ Bi2Te3-Sb2Te3 |
CN114406217A (zh) * | 2022-01-10 | 2022-04-29 | 燕山大学 | 基于热电效应的内部快冷内冷型轧辊及其温控方法 |
CN115141018A (zh) * | 2022-07-15 | 2022-10-04 | 湖北赛格瑞新能源科技有限公司 | 一种利用累积热镦制备n型碲化铋基热电材料的方法 |
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Also Published As
Publication number | Publication date |
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US20060243314A1 (en) | 2006-11-02 |
CN1816919A (zh) | 2006-08-09 |
RU2005137862A (ru) | 2006-06-10 |
US20140170794A1 (en) | 2014-06-19 |
RU2326466C2 (ru) | 2008-06-10 |
JP4286053B2 (ja) | 2009-06-24 |
US20110180121A1 (en) | 2011-07-28 |
KR100749122B1 (ko) | 2007-08-13 |
US8884152B2 (en) | 2014-11-11 |
JP2004335796A (ja) | 2004-11-25 |
KR20050121272A (ko) | 2005-12-26 |
US8692103B2 (en) | 2014-04-08 |
CN1816919B (zh) | 2012-05-09 |
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