WO2002021608A1 - Thermocouple - Google Patents

Thermocouple Download PDF

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Publication number
WO2002021608A1
WO2002021608A1 PCT/JP2001/007362 JP0107362W WO0221608A1 WO 2002021608 A1 WO2002021608 A1 WO 2002021608A1 JP 0107362 W JP0107362 W JP 0107362W WO 0221608 A1 WO0221608 A1 WO 0221608A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoelectric
temperature side
electrodes
wiring
thermoelectric element
Prior art date
Application number
PCT/JP2001/007362
Other languages
English (en)
Japanese (ja)
Inventor
Takao Abe
Original Assignee
Shin-Etsu Handotai Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shin-Etsu Handotai Co., Ltd. filed Critical Shin-Etsu Handotai Co., Ltd.
Publication of WO2002021608A1 publication Critical patent/WO2002021608A1/fr

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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
    • H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device

Definitions

  • the present invention relates to a connection structure between a thermoelectric material electrode and a wiring in a thermoelectric element, and particularly to a connection structure and a wiring suitably used for a thermoelectric element using a silicon-germanium (SiGe) -based thermoelectric material.
  • the present invention relates to a thermoelectric element having a material.
  • thermoelectric power is generated between the two locations due to the so-called Seebeck effect. I do.
  • thermoelectric elements that apply this principle have no moving parts and have a simple structure.Therefore, there is a high possibility that a thermoelectric element with high reliability, a long service life, and easy maintenance can be used. . For this purpose, various thermoelectric element materials have been conventionally manufactured and developed.
  • SiGe is known as a chemically stable and typical thermoelectric element material, and many proposals have been made for improving its performance and manufacturing methods [JP-A-6-11-1].
  • No. 494553 U.S. Pat.No. 4,711,971; European Patent No. 1,849,499); Japanese Unexamined Patent Publication No. H8-56020; Patent No. 2623 No.172 publication etc.].
  • thermoelectric element thermoelectric conversion module
  • the Voyager launched in 1981 was made of a thermoelectric material made by sintering Si and Ge powder by hot pressing.
  • the formed thermoelectric element uses fission as a heat source Used for space applications.
  • ground-based applications have been developed for thermal power generation, or as thermoelectric generators that use vehicle exhaust heat or combustion heat as a heat source.
  • FIG. 2 is a schematic explanatory view showing a general cross-sectional structure of such a conventional thermoelectric element (thermoelectric conversion module).
  • reference numeral 30 denotes a conventional thermoelectric element, in which a plurality of thermoelectric materials, that is, a p-type thermoelectric semiconductor 32 and an n-type thermoelectric semiconductor 34 are electrically connected via a high-temperature side wiring 36 and a low-temperature side wiring 38.
  • High-temperature side connections 32a, 34a and high-temperature side electrodes 33a, 35a, and low-temperature side connections 32b, 34b and low-temperature side electrodes 33b, 35 has b.
  • 40 is a high-temperature side substrate
  • 42 is a low-temperature side substrate
  • 44 is a bonding agent and a bonding agent for bonding the wirings 36, 38 and the connecting portions 32a, 34a and 32b, 34b.
  • Numeral 6 denotes a heat insulating insulator such as silicate glass for welding between the p-type thermoelectric semiconductor 32 and the n-type thermoelectric semiconductor 34.
  • thermoelectric material conventionally intensification of S i G e based material, tellurium materials and such B i 2 T e 3 P b T e, such as iron Kei Motokei material such as F e S i 2 is used Diffusion bonding, brazing, soldering, or bonding using a bonding agent made of a specific alloy can be used as a method of connecting the electrodes and wiring of these thermoelectric materials (Japanese Patent Application Laid-Open No. H11-16881). 72) was commonly used.
  • thermoelectric material having a large coefficient of thermal expansion
  • SiGe despite its high thermoelectric performance, there was a problem in the durability of such a connection due to a large coefficient of thermal expansion, which hindered its practical use. Disclosure of the invention
  • the present invention has been made in view of such a problem, and the present invention has been made in consideration of a heat cycle applied to a high temperature side when used as a terrestrial thermoelectric element, in which a connection between an electrode of thermoelectric material and a wiring is provided.
  • An object of the present invention is to provide a thermoelectric element having a structure capable of improving durability and having excellent thermoelectric performance.
  • thermoelectric element of the present invention has a connection portion in which electrodes and wires of a plurality of thermoelectric materials are electrically connected, and the electrodes, the wires and the connection portions are connected to a low-temperature side.
  • a thermoelectric element having a structure divided into a high-temperature side and a high-temperature side at least a high-temperature-side connection portion of the connection portions is electrically connected by contact without integrating the wiring and the electrode. It is characterized by the following.
  • thermoelectric material and the wiring are not integrated, and the contact is made to be in a uniform contact state, even if subjected to a thermal cycle, no destruction due to a difference in thermal expansion coefficient occurs. A stable conduction can be obtained.
  • PBN pyroboron nitride
  • PBN pyroboron nitride
  • thermoelectric material constituting the thermoelectric element it is preferable to use a silicon-germanium-based material capable of obtaining high thermoelectric performance.
  • the silicon-germanium-based material is preferably a polycrystal having a large particle size, and more preferably a single crystal.
  • FIG. 1 is a schematic explanatory view showing a cross-sectional structure of one embodiment of the thermoelectric element of the present invention.
  • FIG. 2 is a schematic explanatory view showing an example of a cross-sectional structure of a conventional thermoelectric element.
  • FIG. 1 is a schematic explanatory view showing a cross-sectional structure of a thermoelectric element of the present invention.
  • the same or similar members as those in FIG. 2 are denoted by the same reference numerals.
  • reference numeral 10 denotes a thermoelectric element according to the present invention, in which a plurality of thermoelectric materials, that is, P-type thermoelectric semiconductors 32 and n-type thermoelectric semiconductors 34 are electrically connected to the high-temperature side wiring 36 and the low-temperature side wiring 38.
  • the basic structure in which a high-temperature side substrate 40 is connected to the high-temperature side wiring 36 and a low-temperature side substrate 42 is connected to the low-temperature side wiring 38 is shown in FIG. There is no difference from the structure of the conventional thermoelectric element.
  • the P-type thermoelectric semiconductor 32 and the n-type thermoelectric semiconductor 34 alternate between the high-temperature side substrate 40 and the low-temperature side substrate 42 via the high-temperature side wiring 36 and the low-temperature side wiring 38.
  • the thermoelectric material in the present invention that is, the p-type thermoelectric semiconductor 32 and the n-type thermoelectric semiconductor 34, SiGe crystals are suitably used.
  • the S i G e crystals used are prepared by Chiyokurarusuki method, p-type or Formula was contained n-type dopant preparative S i t.
  • X G e ⁇ S i represented by (0 ⁇ X ⁇ 1) It is a G e crystal.
  • the Chiyokurarusuki method approximately the size of the crystal grains over the entire X has a 5 X 1 0- 5 mm 3 or more, the number of performance finger high crystallinity as thermoelectric elements (polycrystalline or monocrystalline) is obtained (Japanese Patent Application No. 10-33 358 904).
  • the obtained crystal is divided into, for example, a size of about 2 ⁇ 2 ⁇ 2 mm, and n-type SiGe crystal (n-type thermoelectric semiconductor) 32 and p-type SiGe crystal (p-type thermoelectric semiconductor) 34 Used as
  • thermoelectric element 30 In the structure of the conventional thermoelectric element 30 as shown in FIG. 2, the P-type and n-type thermoelectric semiconductors 32 and 34 are welded and fixed by a heat insulating insulator 54 such as silicate glass. ing.
  • thermoelectric semiconductors 32 and 34 As in the conventional structure of FIG. It has a structure in which the n-type thermoelectric semiconductors 32 and 34 are not fixed, for example, a structure in which a cavity 12 is provided.
  • Reference numeral 14 denotes a hollow portion provided in the low-temperature substrate 42, and the temperature of the low-temperature substrate 42 can be adjusted by introducing a fluid, for example, air.
  • a fluid for example, air.
  • thermoelectric material that is, the electrode portions 33a, 35a and 33b, 35b at both ends of the p-type and n-type thermoelectric semiconductors 32, 34 are formed.
  • the high-temperature side wiring and low-temperature side wiring 36, 38 are joined together with a bonding agent 44 as in the conventional structure shown in Fig. 2, they can be fixed without being integrated. it can.
  • the electrodes 33a, 33b and 35a, 35b of the thermoelectric materials 32, 34 and the wirings 36, 38 are not integrated with the wirings 36, 38, but the ohmic contact is obtained by contact.
  • the contact portion relaxes the thermal stress, so that the effect of the present invention that stable conduction can be obtained without causing destruction due to a difference in thermal expansion coefficient is obtained.
  • thermoelectric material in contact with the high-temperature side wiring 36 that is, the surface of the p-type thermoelectric semiconductor 32 and the surface of the n-type thermoelectric semiconductor 34
  • a high melting point metal such as Ti, W, Mo and Ta
  • a laminated film, a silicide or the like as an electrode.
  • thermoelectric material that is, a p-type thermoelectric semiconductor 32 and an n-type thermoelectric semiconductor 34
  • the surface can be directly contacted with the wiring as an electrode without forming such a film.
  • thermoelectric material that is, the p-type thermoelectric semiconductor 32 and the n-type thermoelectric semiconductor 34
  • a good ohmic contact is obtained. Therefore, it is desirable to remove the natural oxide film on the surface as much as possible by hydrofluoric acid treatment or the like.
  • a PG film As a material for forming the high-temperature side wiring 36, a PG film is preferable.
  • PG Polyrographite
  • PG is a pyrolytic graphiteite obtained by laminating multiple graphiteite layers by chemical vapor deposition, and it is a good electrical conductor at high temperatures and therefore reduces thermoelectric efficiency. Since it is a low heat absorber, it can efficiently transfer external heat. It is appropriate that the thickness of the PG film used is about 0.1 to 1 mm.If PG is also used for the wiring 38 on the low temperature side, the thickness on the high temperature side should be considered in consideration of heat conduction. It is preferable that the thickness be smaller.
  • PBN pyroboron nitride
  • PBN pyroboron nitride
  • pyrolytic boron nitride layer obtained by stacking multiple boron nitride layers by chemical vapor deposition, and is stable at high temperatures up to 180 ° C.
  • thermoelectric semiconductor 34 can be efficiently heated to a high temperature.
  • the thickness of the PBN plate to be used is preferably from 0.1 to: Lmm. '
  • PG and PBN can be used as the material of the low-temperature side wiring 38 and the low-temperature side substrate 42 as in the case of the high-temperature side, but the high melting point metal such as Ti, W, Mo, and Ta described above is used.
  • the high melting point metal such as Ti, W, Mo, and Ta described above is used.
  • metals such as Cu, Al, Au, Ni, and Pt can also be used.
  • thermoelectric material since the thermal strain at the low temperature side is smaller than that at the high temperature side, it can be integrated as in the past depending on the combination and temperature of the thermoelectric material, electrode material and wiring material. Industrial applicability
  • thermoelectric element having a structure and excellent thermoelectric performance can be obtained, and the use of the thermoelectric element can be expanded.

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  • Measuring Temperature Or Quantity Of Heat (AREA)

Abstract

L'invention porte sur un thermocouple d'une structure permettant d'accroître la durabilité des connexions entre des électrodes et des conducteurs, faits de matériaux thermoélectriques, sous l'effet des cycles thermiques appliqués côté haute température, alors que le thermocouple est à la masse, et qui présente d'excellentes performances thermoélectriques. Lesdites connexions reliant entre eux des éléments de plusieurs matériaux différents, c.-à-d. les électrodes, les conducteurs et les connexions, forment une structure dont les éléments sont répartis en deux positions: l'une du côté basse température et l'autre du côté haute température. Les connexions du côté haute température au moins sont conçues pour que les conducteurs et les électrodes soient reliés par contact sans être intégrés les uns aux autres.
PCT/JP2001/007362 2000-09-04 2001-08-28 Thermocouple WO2002021608A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000-266610 2000-09-04
JP2000266610A JP2002076448A (ja) 2000-09-04 2000-09-04 熱電素子

Publications (1)

Publication Number Publication Date
WO2002021608A1 true WO2002021608A1 (fr) 2002-03-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2001/007362 WO2002021608A1 (fr) 2000-09-04 2001-08-28 Thermocouple

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JP (1) JP2002076448A (fr)
WO (1) WO2002021608A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4488778B2 (ja) * 2003-07-25 2010-06-23 株式会社東芝 熱電変換装置
JP5105718B2 (ja) * 2005-05-27 2012-12-26 株式会社東芝 熱−電気直接変換装置
JP5881066B2 (ja) * 2010-11-30 2016-03-09 学校法人東京理科大学 熱電変換素子及び熱電変換モジュール
JP5954103B2 (ja) * 2012-10-19 2016-07-20 トヨタ自動車株式会社 熱電発電装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04325685A (ja) * 1991-04-24 1992-11-16 Shin Etsu Chem Co Ltd 薄膜の製造方法
JPH10144969A (ja) * 1996-11-08 1998-05-29 Sumitomo Special Metals Co Ltd 熱電変換素子
JPH10213360A (ja) * 1997-01-30 1998-08-11 Yamaha Corp 熱電変換装置
JPH1155974A (ja) * 1997-07-28 1999-02-26 Gastar Corp 熱発電ユニット
JPH11220184A (ja) * 1998-02-02 1999-08-10 Natl Aerospace Lab 熱電変換装置
JPH11307825A (ja) * 1998-04-21 1999-11-05 Yamaha Corp 熱電モジュール及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04325685A (ja) * 1991-04-24 1992-11-16 Shin Etsu Chem Co Ltd 薄膜の製造方法
JPH10144969A (ja) * 1996-11-08 1998-05-29 Sumitomo Special Metals Co Ltd 熱電変換素子
JPH10213360A (ja) * 1997-01-30 1998-08-11 Yamaha Corp 熱電変換装置
JPH1155974A (ja) * 1997-07-28 1999-02-26 Gastar Corp 熱発電ユニット
JPH11220184A (ja) * 1998-02-02 1999-08-10 Natl Aerospace Lab 熱電変換装置
JPH11307825A (ja) * 1998-04-21 1999-11-05 Yamaha Corp 熱電モジュール及びその製造方法

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