WO2007104603A2 - Tellurides de plomb/germanium destinés à des applications thermoélectriques - Google Patents

Tellurides de plomb/germanium destinés à des applications thermoélectriques Download PDF

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Publication number
WO2007104603A2
WO2007104603A2 PCT/EP2007/050906 EP2007050906W WO2007104603A2 WO 2007104603 A2 WO2007104603 A2 WO 2007104603A2 EP 2007050906 W EP2007050906 W EP 2007050906W WO 2007104603 A2 WO2007104603 A2 WO 2007104603A2
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semiconductor material
thermoelectric
materials
ternary compound
temperature
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PCT/EP2007/050906
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German (de)
English (en)
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WO2007104603A3 (fr
Inventor
Klaus KÜHLING
Frank Haass
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Basf Se
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Publication of WO2007104603A2 publication Critical patent/WO2007104603A2/fr
Publication of WO2007104603A3 publication Critical patent/WO2007104603A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the present invention relates to semiconductor materials containing germanium, lead and tellurium (Ge-Pb-tellurides) as well as thermoelectric generators and deposition arrangements containing them.
  • Thermoelectric generators and Peltier arrangements as such have long been known.
  • P- and n-doped semiconductors which are heated on one side and cooled on the other side, carry electrical charges through an external circuit, and electrical work can be done on a load in the circuit.
  • the achieved conversion efficiency of heat into electrical energy is thermodynamically limited by the C arnot efficiency.
  • an efficiency of (1000 - 400): 1000 60% is possible.
  • efficiencies up to 10% are achieved.
  • Such a Peltier arrangement operates as a heat pump and is therefore suitable for cooling equipment parts, vehicles or buildings.
  • the heating via the Peltier principle is cheaper than a conventional heating, because more and more heat is transported than the supplied energy equivalent corresponds.
  • thermoelectric generators are used in space probes for generating direct currents, for cathodic corrosion protection of pipelines, for powering light and radio buoys, for operating radios and televisions.
  • the advantages of the thermoelectric generators are in their utmost reliability. So they work regardless of atmospheric conditions such as humidity; there is no fault-susceptible mass transfer, but only a charge transport; The fuel is burned continuously - even without catalytic free flame -, whereby only small amounts of CO, NO x and unburned fuel are released; they are Suitable fuels can be used from hydrogen through natural gas, gasoline, kerosene, diesel fuel to biologically produced fuels such as rapeseed oil methyl ester.
  • thermoelectric energy conversion fits extremely flexibly into future needs such as hydrogen economy or energy production from renewable energies.
  • a particularly attractive application would be the use for conversion into electrical energy in electrically powered vehicles. There was no need to change the existing filling station network. However, efficiencies greater than 30% are required for such an application.
  • thermoelectrically active materials are evaluated essentially on the basis of their efficiency. Characteristic of thermoelectric materials in this regard is the so-called Z factor (figure of merit):
  • thermoelectric materials which have the lowest possible thermal conductivity, the highest possible electrical conductivity and the largest possible Seebeck coefficient, so that the figure of merit as high as possible Takes value.
  • thermoelectrically active material which has the highest possible value for Z and a high temperature difference that can be achieved. From the point of view of solid-state physics many problems have to be overcome:
  • a high ⁇ requires a high electron mobility in the material, ie electrons (or holes in p-type materials) should not be strongly bound to the atomic hulls.
  • Materials with high electrical conductivity ⁇ usually have at the same time a high thermal conductivity (Wiedemann - Franz's Law), which means that Z can not be favorably influenced.
  • Currently used materials such as Bi 2 Te 3 are already compromises. Thus, the electrical conductivity is reduced by alloying less than the thermal conductivity. Therefore, alloys are preferably used such as (Bi 2 Te 3 ) 9 o (Sb 2 Te 3 ) s (Sb 2 Se 3 ) 5 or BiI 2 Sb 23 Te 65 , as described in US 5,448,109.
  • thermoelectric materials with high efficiency preferably further boundary conditions are to be met. Above all, they must be temperature-stable in order to be able to work at operating temperatures of up to 1,500 K for years without significant loss of efficiency. This requires a high-temperature-stable phase per se, a stable phase composition and a negligible diffusion of alloy components into the adjacent contact materials. Descriptions of thermoelectric materials can be found in the more recent patent literature, for example in US Pat. No. 6,225,550 and EP-A-1 102 334.
  • the US 6,225,550 relates to materials substantially consisting of Mg x Sb 2, with a further element, preferably a transition metal, are doped.
  • EP-A-1 102 334 discloses p- or n-doped semiconductor materials containing an at least ternary material from the classes of suicides, borides, germanides, tellurides, sulfides, selenides, antimonides, plumbides and semiconducting oxides.
  • the (Pbi_ x Ge x) Te- Blocks are then produced in a melt furnace at 1000 ° C. at a growth rate of 1 mm / min., The ingots are then ground into a powder having a size of 90 to 250 ⁇ m, followed by a reduction treatment at 400 ° C. for 24 hours in a H 2 ZAr atmosphere. The powders are cold and then hot pressed in a vacuum at 650 0 C and 750 0 C. From the materials obtained in this way, it was found that the Seebeck coefficient and the electrical resistance of the thermoelectric materials increases with the GeTe content x in the semiconductor material, while the thermal conductivity decreases as the GeTe content x in the semiconductor material increases. The best Seebeck coefficient obtained is approximately - 150 uV / K, the electric resistance is 1 mQ "cm. The thermal conductivity is in the minimum 2 W / (m ⁇ K).
  • the object of the present invention is to provide semiconductor materials (thermoelectrically active materials) which have a high degree of efficiency and exhibit a suitable property profile for different fields of application.
  • the object is achieved according to the invention by a p-type or n-type semiconductor material containing a ternary compound of the general formula (I)
  • Pb or Te is replaced by Ge or - Ge is added to PbTe or
  • Ge parts of the Pb or Te positions takes over, in each case the ratio of Pb: Te - starting from 1: 1 - changes.
  • the Seebeck coefficients of these materials are generally in the range of -250 to -380 ⁇ V / K for series (Ib) and (Ic).
  • the Seebeck coefficients for the compounds of the series (Ia) are generally up to 500 ⁇ V / K at a temperature of 300 ° C.
  • 0 to 10 wt .-%, preferably 0 to 5 wt .-%, particularly preferably 0 to 1 wt .-%, of the ternary compound by the dopants BiI, SbI, BiTe, SbTe, Sb 2 Te 3 , or Si 2 Te 3 are replaced.
  • Further suitable dopants are familiar to the person skilled in the art.
  • the dopants and the other metals and metal compounds are preferably selected so that the Seebeck coefficient of the materials is not adversely affected.
  • the materials may also contain other compounds or dopants, as far as the aforementioned Seebeck coefficients are retained.
  • the materials of the present invention are generally made by fusing together mixtures of the respective constituent elements or their alloys. In general, a reaction time of melting together of at least one hour has proven to be advantageous.
  • the melting together is preferably carried out for a period of at least 1 hour, more preferably at least 5 hours, in particular at least 10 hours.
  • the melting process can be carried out with or without mixing the starting mixture. If the starting mixture is mixed, then in particular a rotary kiln is suitable for ensuring the homogeneity of the mixture. If no mixture is made, generally longer melt times are required to obtain a homogeneous material. If a mixture is made, the homogeneity in the mixture is obtained earlier.
  • the melting time is generally 2 to 50 hours, especially 30 to 50 hours.
  • the melting temperature is at least 800 ° C., preferably at least 950 ° C.
  • the melting temperature is in a temperature range from 800 to 1100 ° C., preferably 950 to 1100 ° C.
  • the material is annealed at a temperature of generally at least 100 ° C., preferably at least 200 ° C., lower than the melting point of the resulting semiconductor material.
  • the annealing temperature is 450 to 750 0 C, preferably 600 to 700 0 C.
  • the annealing is carried out for a period of preferably at least 0.5 hours, more preferably at least 1 hour, in particular at least 2 hours. Usually, the annealing time is 0.5 to 5 hours, preferably 1 to 3 hours. In one embodiment of the present invention, the annealing is performed at a temperature which is 100 to 500 ° C. lower than the melting temperature of the resulting semiconductor material. A preferred temperature range is 150 to 350 ° C. lower than the melting point of the resulting semiconductor material.
  • thermoelectric materials according to the invention is generally carried out in a heatable quartz tube.
  • a mixing of the components involved can be ensured by using a rotatable and / or tiltable furnace. After completion of the reaction, the furnace is cooled. Subsequently, the quartz tube is removed from the oven and sliced in the form of blocks semiconductor material. These disks are now cut into pieces of about 1 to 5 mm in length, from which thermoelectric modules can be produced.
  • quartz tube and pipes made of other materials can be used instead of a quartz tube and pipes made of other materials, such as tantalum. This is preferred because the thermal conductivity of this material is higher than that of quartz.
  • tubes instead of tubes, other containers of suitable shape can be used. Other materials, such as graphite, can be used as container material.
  • the cooled material can be ground at a suitable temperature, so that the semiconductor material according to the invention in conventional particle sizes smaller than 10 microns is obtained.
  • the milled material according to the invention is then preferably pressed into shaped parts which have the desired shape.
  • the bulk density of the moldings pressed in this way should preferably be greater than 50%, particularly preferably greater than 80%, than the bulk density of the raw material in the mold. be pressed state.
  • Compounds which improve the densification of the material according to the invention can be added in quantities of preferably 0.1 to 5% by volume, more preferably 0.2 to 2% by volume, based in each case on the powdered material according to the invention.
  • Additives which are added to the materials of the invention should preferably be inert to the semiconductor material and preferably to be dissolved out of the inventive material during heating to temperatures below the sintering temperature of the materials of the invention, optionally under inert conditions and / or vacuum. After pressing, the pressed parts are preferably placed in a sintering furnace in which they are heated to a temperature of preferably at most 20 0 C below the melting point
  • the pressed parts are sintered at a temperature of generally at least 100 ° C., preferably at least 200 ° C., lower than the melting point of the resulting semiconductor material.
  • the sintering temperature is 350 to 750 0 C, preferably 600 to 700 pre 0 C.
  • the sintering is carried out for a period of preferably at least 0.5 hours, particularly preferably at least 1 hour, in particular at least 2 hours. Normally, the annealing time is 0.5 to 5 hours, preferably 1 to 3 hours. In one embodiment of the present invention, the sintering is performed at a temperature which is 100 to 600 ° C lower than the melting temperature of the resulting semiconductor material. A preferred temperature range is 150 to 350 ° C. lower than the melting point of the resulting semiconductor material.
  • the sintering is preferably carried out under hydrogen or a protective gas atmosphere, for example of argon.
  • the pressed parts are preferably sintered to 95 to 100% of their theoretical bulk density.
  • the present invention also relates to a p-type or n-type semiconductor material of a ternary compound of the general formula (I)
  • Another object of the present invention is the use of the semiconductor material described above and the semiconductor material obtainable by the method described above as a thermoelectric generator or Peltier arrangement.
  • thermoelectric generators or Peltier arrangements which contain the semiconductor material described above and / or the semiconductor material obtainable by the method described above.
  • Another object of the present invention is a method for producing thermoelectric generators or Peltier arrangements, in which series-connected thermo-electrically active blocks (“legs") are used with thin layers of the previously described thermoelectric materials.
  • thermoelectric generators or Peltier arrangements In a first embodiment of this method, the production of the thermoelectric generators or Peltier arrangements takes place as follows:
  • the semiconductors of the invention according to a first conductivity type are applied to a substrate by means of conventional semiconductor fabrication techniques, in particular CVD, sputtering technique or molecular beam epitaxy.
  • the semiconductors according to the invention are likewise applied to a further substrate by means of sputtering technique or molecular beam epitaxy, but the conductivity type of this semiconductor material is inverse to the first-used semiconductor material (n- or p-doped).
  • thermoelectrically active building blocks each of a different charge type are arranged alternately.
  • thermoelectrically active building blocks have a diameter of preferably less than 100 .mu.m, more preferably less than 50 .mu.m, in particular less than 20 microns and a thickness of preferably 5 to 100 .mu.m, more preferably 10 to 50 .mu.m, in particular 15 to
  • the area occupied by a thermoelectrically active building block is preferably less than 1 mm, particularly preferably less than 0.5 mm, in particular less than 0.4 mm 2 .
  • thermoelectric generators or Peltier arrangements are produced in such a way that layers of semiconductor materials of different charge types (p- and n-doped) according to the invention are produced alternately on a substrate by suitable deposition methods, for example molecular beam epitaxy.
  • the layer thickness is in each case preferably 5 to 100 nm, more preferably 5 to 50 nm, in particular 5 to 20 nm.
  • thermoelectric generators or Peltier arrangements, which are known per se to the person skilled in the art and are described, for example, in WO 98/44562, US Pat. No. 5,448,109, EP-A-1 102 334 or US Pat. No. 5,439,528.
  • thermoelectric generators or Peltier arrangements according to the invention generally expand the available range of thermoelectric generators and Peltier arrangements. By varying the chemical composition of the thermoelectric generators or Peltier arrangements, it is possible to provide different systems that meet different requirements in a variety of applications. Thus, the thermoelectric generators or Peltier arrangements according to the invention expand the range of applications of these systems.
  • the present invention also relates to the use of a thermoelectric generator according to the invention or a Peltier arrangement according to the invention
  • the present invention relates to a heat pump, a refrigerator, a tumble dryer or a generator for using heat sources, comprising at least one thermoelectric generator according to the invention or a Peltier arrangement according to the invention, via the or in the (laundry) dryer a material to be dried directly or heated indirectly and is cooled directly or indirectly over the or the incurred during the drying water or solvent vapor.
  • the dryer is a clothes dryer and the material to be dried is laundry.
  • the thermal energy is determined by the fact that the material to be examined between a hot and a cold contact, which are each electrically heated, is placed, wherein the hot contact has a temperature of 200 to 300 0 C.
  • the cold side is kept at room temperature so that a ⁇ T of typically 150 to 280 0 C results.
  • the measured voltage at the respective temperature difference between hot and cold contact provides the respectively specified Seebeck coefficient.
  • the total amount of material was 17 g.
  • the quartz tube was evacuated, sealed and then heated for 20 hours under agitation in a rotary furnace for mixing at 1,050 0 C. Subsequently, the quartz tube was cooled in an upright position.
  • any other inert material can be used in this melting process.
  • the resulting material showed no phase transition.
  • the melting point was 928 0 C.
  • the Seebeck coefficient was -320 to -342 uV / K at 300 0 C and -330 to -355 uV / K at 200 0 C on the hot side.
  • thermoelectric material obtained had a Seebeck coefficient of -350 to - 360 uV / K at 300 0 C.
  • the melting point was 920 0 C.
  • Example 2 The procedure described in Example 1 was repeated, now as sample (Id) Pbö, 97 Geö, ö 3 Te 1; ö 2 was used and the total amount of material was 16.8 g.
  • thermoelectric material had a Seebeck coefficient of 330 to 350 ⁇ V / K at 300 ° C.
  • the melting point was 925 ° C.
  • Example 2 The procedure described in Example 1 was repeated, now as sample (Id) Pbö, 97 Geö, ö 3 Te 1; ö 3 was used and the total amount of material was 16.7 g.
  • thermoelectric material obtained had a Seebeck coefficient of 335 to 342 microvolts / K at 300 0 C and 257 to 352 microvolts / K at 200 0 C.
  • the melting point was 924 0 C.
  • Example 2 The procedure described in Example 1 was repeated, using now as sample (Ic) PbGeo, o3Te and the total amount of material was 10.8 g.
  • thermoelectric material was ground and pressed into 7 or 13 mm diameter pressings.
  • the pellets were sintered in an evacuated quartz glass tube or under protective gas (argon) at 700 ° C. for 2 h. Only a slight shrinkage ( ⁇ 0.2%) was observed.
  • thermoelectric material was ground and pressed to a 7 mm diameter crimp.
  • the press was sintered in an evacuated quartz glass tube or under protective gas (argon) at 700 ° C. for 2 hours. Only a slight shrinkage ( ⁇ 0.2%) was observed.
  • thermoelectric material was ground and pressed to a 13 mm diameter crimp.
  • the press was sintered in an evacuated quartz glass tube or under protective gas (argon) at 700 ° C. for 2 hours. Only a slight shrinkage ( ⁇ 0.2%) was observed.
  • the reaction temperature is 1000 ° C.
  • the Seebeck coefficient is 311 to 347 ⁇ V / K at 300 ° C. on the hot side.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne un matériau semiconducteur à conductivité p ou n, constitué d'un composé ternaire représenté par la formule (I) Pb<SUB>x</SUB>Ge<SUB>y</SUB>Te<SUB>z</SUB>, dans laquelle x, y et z obéissent à une des relations suivantes: (a) x = 1 - y; z = 1; 0,05 < y < 0,1; (b) z = 1 - y; x = 1; 0 < y < 0,1; (c) x = z = 1; 0 < y 0,05; (d) 0,8 = x =1,2; 0 < y = 0,05; 0,8 = z = 1,2.
PCT/EP2007/050906 2006-03-16 2007-01-30 Tellurides de plomb/germanium destinés à des applications thermoélectriques WO2007104603A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06111284.3 2006-03-16
EP06111284 2006-03-16

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WO2007104603A2 true WO2007104603A2 (fr) 2007-09-20
WO2007104603A3 WO2007104603A3 (fr) 2007-12-13

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010115776A1 (fr) 2009-04-02 2010-10-14 Basf Se Matériau thermoélectrique recouvert d'une couche de protection
WO2010115792A1 (fr) 2009-04-02 2010-10-14 Basf Se Module thermoélectrique à substrat isolé
US8772622B2 (en) 2008-02-07 2014-07-08 Basf Se Doped tin tellurides for thermoelectric applications

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3652421A (en) * 1968-08-01 1972-03-28 Gen Electric N-type lead telluride
US20040200519A1 (en) * 2003-04-11 2004-10-14 Hans-Josef Sterzel Pb-Ge-Te-compounds for thermoelectric generators or Peltier arrangements
WO2005114755A2 (fr) * 2004-05-18 2005-12-01 Basf Aktiengesellschaft Tellurures presentant de nouvelles combinaisons de proprietes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3652421A (en) * 1968-08-01 1972-03-28 Gen Electric N-type lead telluride
US20040200519A1 (en) * 2003-04-11 2004-10-14 Hans-Josef Sterzel Pb-Ge-Te-compounds for thermoelectric generators or Peltier arrangements
WO2005114755A2 (fr) * 2004-05-18 2005-12-01 Basf Aktiengesellschaft Tellurures presentant de nouvelles combinaisons de proprietes

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHOI J-S ET AL: "Thermoelectric properties of n-type (Pb1-xGex)Te fabricated by hot pressing method" THERMOELECTRICS, 1997. PROCEEDINGS ICT '97. XVI INTERNATIONAL CONFERENCE ON DRESDEN, GERMANY 26-29 AUG. 1997, NEW YORK, NY, USA,IEEE, US, 26. August 1997 (1997-08-26), Seiten 228-231, XP002296046 ISBN: 0-7803-4057-4 in der Anmeldung erwähnt *
KOHRI H ET AL: "IMPROVEMENT OF THERMOELECTRIC PROPERTIES FOR N-TYPE PBTE BY ADDING GE" MATERIALS SCIENCE FORUM, AEDERMANNSFDORF, CH, Bd. 423-425, 2003, Seiten 381-384, XP008035344 ISSN: 0255-5476 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8772622B2 (en) 2008-02-07 2014-07-08 Basf Se Doped tin tellurides for thermoelectric applications
WO2010115776A1 (fr) 2009-04-02 2010-10-14 Basf Se Matériau thermoélectrique recouvert d'une couche de protection
WO2010115792A1 (fr) 2009-04-02 2010-10-14 Basf Se Module thermoélectrique à substrat isolé

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WO2007104603A3 (fr) 2007-12-13

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