WO2006089936A1 - Sulfures de cuivre semi-conducteurs aux nouvelles combinaisons de proprietes et leur utilisation dans les domaines thermoelectrique et photovoltaique - Google Patents

Sulfures de cuivre semi-conducteurs aux nouvelles combinaisons de proprietes et leur utilisation dans les domaines thermoelectrique et photovoltaique Download PDF

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WO2006089936A1
WO2006089936A1 PCT/EP2006/060236 EP2006060236W WO2006089936A1 WO 2006089936 A1 WO2006089936 A1 WO 2006089936A1 EP 2006060236 W EP2006060236 W EP 2006060236W WO 2006089936 A1 WO2006089936 A1 WO 2006089936A1
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semiconductor material
thermoelectric
materials
modules
temperature
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English (en)
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Hans-Josef Sterzel
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Basf Aktiengesellschaft
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/12—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3891—Silicides, e.g. molybdenum disilicide, iron silicide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/405—Iron group metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/40—Metallic constituents or additives not added as binding phase
    • C04B2235/407—Copper
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Definitions

  • thermoelectrics and photovoltaics Semiconducting copper sulphides with new property combinations and their use in thermoelectrics and photovoltaics
  • the present invention relates to modified copper sulfides, semiconductor materials for thermoelectrics and photovoltaics containing them, to processes for producing these semiconductor materials and to their use.
  • thermoelectric generators and Peltier devices have long been known, p- and n-doped semiconductors heated on one side and cooled on the other side carry electrical charges through an external circuit. These thermoelectric generators electrical work can be done on a consumer in the circuit.
  • thermoelectric materials can be used to convert thermal energy to electricity.
  • the reverse process which is called the Peltier effect, is also possible using thermoelectric materials with the application of an electric current to generate temperature differences.
  • 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 effects and materials are z. B. Cronin B Vining, ITS Short Course on Thermoelectricity, 08.11.93, Yokohama, Japan, 1997 Proceedings, Sixth International Conference on Thermoelectrics (ICT), CRC Handbook of Thermoelectrics, CRC-Press 1995, and Materials Research Society Symposium Proceedings Volume 545 : Thermoelectric Materials 1998 - The next generation materials for small-scale refrigeration and power generation applications.
  • thermoelectric generators are used in modules for controlling the temperature of microprocessors or optoelectronic components, in space probes and satellites for generating direct currents, for cathodic corrosion protection of pipelines, for powering radio and radio buoys, for operating radios and television sets, and as cooling units in coolers used.
  • the advantages of thermoelectric generators and Peltier arrangements lie in their high reliability.
  • thermoelectric energy conversion adapts extremely flexibly to future needs, such as hydrogen economy or energy generation from regenerative energies.
  • thermoelectrically active materials are essentially evaluated on the basis of their efficiency. Characteristic of thermoelectric materials in this regard is the so-called Z factor (figure of merit)
  • thermoelectric materials have maximum values of Z • T of about 1 at an optimum temperature. Beyond this optimum temperature, the values of Z • T are often lower than 1. Materials such as Bi 2 Te 3 , PbTe and the antimonides Zn 4 Sb 3 and CoSb 3 are currently the best known in the art.
  • thermoelectric semiconductor material with the highest possible value for Z and high temperature difference achievable. From the point of view of solid-state physics many problems have to be overcome: Materials with high electrical conductivity usually have at the same time a high thermal conductivity (Wiedemann-Franz's law), whereby the figure of merit Z is adversely affected. Currently used materials such as Bi 2 Te 3 , PbTe or SiGe are already compromises. Thus, the electrical conductivity is reduced by alloying less than the thermal conductivity. Therefore, it is preferable to use alloys, such. B. (Bi 2 Te S ) 90 (Sb 2 Te 3 ) S (Sb 2 Se 3 ) S or Bi 12 SB 23 Te 65 , as described in US 5,448,109.
  • thermoelectric materials with high efficiency preferably further boundary conditions are to be met. So they must be temperature stable, to work at working temperatures of 700 to 1000 K over years without significant loss of efficiency. This requires both high-temperature stable phases per se, a stable phase composition, as well as a negligible diffusion of alloying components in the adjacent contact materials.
  • the electrical conductivity decreases in the order from telluride via the selenide to the sulfide in the expected order, giving 300, 67 and 25 S / cm, conversely, the band gap increases between valence band and conduction band of 0.28 eV for the telluride over 0.48 eV of the selenide to 0.54 eV for the sulfide It is generally expected that with a larger band gap a lower electrical conductivity will be obtained Semiconductors are indeed excited by heat, which requires low band gaps of 0.1 to usually 0.4 eV.
  • thermoelectric applications essentially Bi 2 Te 3 (by 0.3 eV) and PbTe (0.25 eV).
  • the object of the invention was to provide a thermoelectric semiconductor material with the highest possible value for Z and high realizable temperature difference, which show a suitable property profile for different applications.
  • the object is achieved in that are used as semiconductor material modified copper sulfides.
  • Objects of the invention are modified copper sulphides which have a composition according to general formula (1)
  • Me denotes Co and / or Bi and the indices x, y, z and v correspond to one of the following values:
  • thermoelectric modules and photovoltaic cells or modules thermoelectric modules and photovoltaic cells or modules.
  • Objects of the invention are also a method for producing a semiconductor material based on modified copper sulfides.
  • high-band-gap sulfides known per se can be modified in a previously unknown manner in such a way that they can be used both in thermoelectric applications and in photovoltaic applications. They are excited by both heat and light and are thus able to convert both temperature differences in the range of about -100 to + 800 ° C and visible light directly into electrical energy.
  • Cu 2 S (chalcocite) with a band gap of 1.2 eV.
  • Cu 2 S exhibits a very low thermal conductivity of the crystal lattice of approx. 5 mW / cm • degree for thermoelectric applications at room temperature up to approx. 600 ° C.
  • Cu 2 S obtains completely new properties when it is modified according to the invention according to the general formula (1) (Cu x Mey) 2 S z - (Mg 2 SiJv (1).
  • Me means cobalt and / or bismuth.
  • bismuth is used in elemental form.
  • mixtures of cobalt and bismuth are also possible.
  • the index x corresponds to a value of 0.95 to 1.00, preferably 0.98 to 0.998.
  • the index y corresponds to a value of 0 to 0.05, preferably 0.002 to 0.01.
  • the sum of the indices x + y is 0.98 to 1.02, preferably 0.99 to 1.01.
  • the index z corresponds to a value of 0.95 to 1.05, preferably 0.98 to 1.02.
  • the index v corresponds to a value of 0 to 0.01, preferably from 0 to 0.005. In a particularly advantageous embodiment, v has a value of 0.
  • the copper sulfides modified according to the invention have a Seebeck coefficient of more than 300 ⁇ V / degree and an electrical conductivity of more than 150 S / cm.
  • a Seebeck coefficient of up to 500 ⁇ V / degree and an electrical conductivity of up to 450 S / cm are achieved.
  • modified copper sulfides are outstandingly suitable for use as semiconductor material, in particular as p-conductive materials.
  • modified copper sulfide use.
  • Other modified copper sulfides are exemplified in the examples.
  • the materials of the present invention are usually prepared by fusing together mixtures of the respective constituent elements or their compounds / alloys.
  • a reaction time of fusion of at least one hour has proven to be advantageous.
  • the fusion is preferably carried out for a period of at least 1 hour, particularly preferably at least 5 hours, in particular at least 10 hours.
  • the melting process can be carried out with or without mixing of the starting done. If mixed, then in particular a rotary kiln is suitable for ensuring the homogeneity of the mixture.
  • the magnetic field ensures thorough mixing of the melt. If no mixing is carried out, generally longer melting times of 2 to 100 hours, in particular 30 to 100 hours, are required to obtain a homogeneous material.
  • the co-melting is carried out usually at a temperature of at least 1,150 0 C (melting point of Cu 2 S), preferably at least 1,200 0 C. In particular, is the melting temperature in a range of 1200-1300 0 C.
  • the preparation of the material 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 tubes of other materials such as graphite
  • tubes other containers of suitable shape can be used.
  • the cooled material can be ground at a suitable temperature, so that the semiconductor material according to the invention is obtained in conventional particle sizes smaller than 50 ⁇ m.
  • the milled material of the invention is then preferably pressed to the desired moldings.
  • the bulk density of the pressed moldings should preferably be greater than 50%, particularly preferably greater than 80%, than the raw density of the raw material in the unpressed state.
  • Compounds which enhance the compression of the inventive material to improve, can be added in amounts of preferably 0.1 to 5 vol .-%, particularly preferably 0.2 to 2 vol .-%, each based on the powdered material according to the invention added.
  • Additives which are added to the material according to the invention should preferably be inert to the semiconductor material and preferably dissolve out of the material according to the invention during heating to temperatures below the sintering temperature of the material according to the invention, optionally under inert conditions and / or vacuum.
  • the pressed parts are preferably placed in a sintering furnace in which they are heated to a temperature of preferably at most 100 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 900 0 C, preferably 500 to 700 ° C.
  • the sintering 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.
  • the sintering time is 0.5 to 5 hours, preferably 1 to 3 hours.
  • sintering is performed at a temperature that is 100 to 600 ° C. lower than the melting temperature of the resulting semiconductor material.
  • a preferred temperature range is 150-350 ° 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 bucket density.
  • the semiconductor materials according to the invention are prepared for example by reaction of Cu 1 Co and / or Bi, sulfur and optionally Mg 2 Si at temperatures of up to 1300 0 C, preferably from 1200 to 1250 0 C, for example in evacuated quartz vessels ,
  • the materials of the invention have increased Seebeck coefficients and electrical conductivity on the order of magnitude compared to unmodified copper sulfides, as set forth above. They are thus outstandingly suitable for applications in thermoelectrics and in photovoltaics, in particular as active semiconductors in thermoelectric modules and in photovoltaic cells or modules. Their use in modules for solar cells and thermoelectric generators and Peltier arrangements, in tumble dryers or air conditioning systems is particularly advantageous.
  • thermoelectric methods In thermoelectric methods, p- and n-type materials are connected in series to avoid thermal losses. In photovoltaics, a p-n junction is used, with charge separation occurring in the boundary layer.
  • n-type materials commonly used in thermoelectrics and photovoltaics.
  • suitable n-type materials are for example n-doped Bi 2 Te 3 and n-doped PbTe in thermoelectrics, n-type chalcopyrites of the type (Cu, In, Ga) x (S, Se, Te) y in photovoltaics.
  • modified bismuth sulfides as n-conductive material, which likewise have a Seebeck coefficient of more than 300 ⁇ V / degree and an electrical conductivity of more than 150 S / cm in the temperature range from room temperature to 130 ° C.
  • modified bismuth sulfides have, for example, a composition according to the following general formula (2)
  • these modified Bismutsulfide be prepared for example by reaction of Bi, Ge and sulfur at temperatures of up to 1100 0 C, preferably from 850 to 95O 0 C, for example in evacuated quartz vessels.
  • the component weights given in the following table were filled into quartz tubes with a 10 mm internal diameter. Subsequently, the quartz tubes were heated for 5 min to about 100 ° C in vacuo and then sealed in vacuo. The following were used: copper from 2.5 mm copper wires of an electric cable and sulfur from a tanker delivery of liquid sulfur. In a tube furnace, the quartz tubes were heated within 10 hours from room temperature to 1,200 0 C. This temperature was maintained for another 5 hours. During the entire heating time, the furnace was tilted about the longitudinal axis over a period of about 2 minutes by means of a drive in order to achieve good mixing of the melt.
  • the Seebeck coefficients found in the temperature range of 30 to 130 0 C and the average electrical conductivity in this temperature range are given in the table.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Electromagnetism (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne des sulfures de cuivre modifiés ayant une composition de la formule générale (1) (CuxMey)2Sz - (Mg2Si)v (1 ), Me représentant Co et/ou Bi et les indices x, y, z et v correspondant à une des valeurs suivantes: x = 0,95 bis 1,00, y = 0 à 0,05 ; x + y représentant une somme de 0,98 à 1,02 ; z = 0,95 à 1,05, v = 0 à 0,01. L'invention concerne également un matériau semi-conducteur contenant ces sulfures de cuivre modifiés ainsi que l'utilisation d'un tel matériau semi-conducteur dans des modules thermoélectriques et piles photovoltaïques ou des modules.
PCT/EP2006/060236 2005-02-24 2006-02-23 Sulfures de cuivre semi-conducteurs aux nouvelles combinaisons de proprietes et leur utilisation dans les domaines thermoelectrique et photovoltaique WO2006089936A1 (fr)

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DE112006000265T DE112006000265A5 (de) 2005-02-24 2006-02-23 Halbleitende Kupfersulfide mit neuen Eigenschaftskombinationen und deren Verwendung in der Thermoelektrik und Photovoltaik

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DE102005008867A DE102005008867A1 (de) 2005-02-24 2005-02-24 Halbleitende Kupfersulfide mit neuen Eigenschaftskombinationen und deren Verwendung in der Thermoelektrik und Photovoltaik
DE102005008867.8 2005-02-24

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Publication number Priority date Publication date Assignee Title
WO1999065086A1 (fr) * 1998-06-08 1999-12-16 Ormet Corporation Production de modules thermoelectriques hautes performances et compositions thermoelectriques a cet effet frittables a basse temperature

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999065086A1 (fr) * 1998-06-08 1999-12-16 Ormet Corporation Production de modules thermoelectriques hautes performances et compositions thermoelectriques a cet effet frittables a basse temperature

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE INSPEC [online] THE INSTITUTION OF ELECTRICAL ENGINEERS, STEVENAGE, GB; 16 March 1993 (1993-03-16), MANSOUR B A: "Electrical and thermoelectric properties of In and Cd doped Cu1.8S", XP002379634, Database accession no. 4402234 *
DATABASE INSPEC [online] THE INSTITUTION OF ELECTRICAL ENGINEERS, STEVENAGE, GB; 1968, ABDULLAEV G B ET AL: "Investigation of the electric properties of Cu2S single crystals", XP002379633, Database accession no. 1968A22585 *
HASAKA M ET AL: "Thermoelectric properties of Cu-Sn-S", ENERGY CONVERSION AND MANAGEMENT, ELSEVIER SCIENCE PUBLISHERS, OXFORD, GB, vol. 38, no. 9, June 1997 (1997-06-01), pages 855 - 859, XP004056692, ISSN: 0196-8904 *
PHYSICA STATUS SOLIDI A GERMANY, vol. 136, no. 1, 16 March 1993 (1993-03-16), pages 153 - 159, ISSN: 0031-8965 *
PHYSICA STATUS SOLIDI GERMANY, vol. 26, no. 1, 1968, pages 65 - 68 *

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DE112006000265A5 (de) 2007-10-31
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