WO2006089938A1 - Sulfures de bismuth semi-conducteurs aux nouvelles combinaisons de proprietes et leur utilisation dans les domaines thermoelectrique et photovoltaique - Google Patents

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

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WO2006089938A1
WO2006089938A1 PCT/EP2006/060238 EP2006060238W WO2006089938A1 WO 2006089938 A1 WO2006089938 A1 WO 2006089938A1 EP 2006060238 W EP2006060238 W EP 2006060238W WO 2006089938 A1 WO2006089938 A1 WO 2006089938A1
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semiconductor material
thermoelectric
materials
modules
temperature
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Hans-Josef Sterzel
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Basf Aktiengesellschaft
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    • C01—INORGANIC CHEMISTRY
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    • C01G29/00—Compounds of bismuth
    • C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
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    • 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
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    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/6262—Milling of calcined, sintered clinker or ceramics
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    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62665—Flame, plasma or melting treatment
    • 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
    • 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
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    • 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
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    • 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
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon

Definitions

  • thermoelectrics and photovoltaics Semiconducting bismuth sulfides with new property combinations and their use in thermoelectrics and photovoltaics
  • the present invention relates to modified bismuth 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 fits very flexibly into future needs, such as hydrogen economy or energy production from renewable 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 the lowest possible thermal conductivity, a possible have high electrical conductivity and the largest possible Seebeck coefficients, so that the figure of merit assumes the highest possible value.
  • 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 3 ) 9 o (Sb 2 Te 3 ) 5 (Sb 2 Se 3 ) 5 or Bi 12 SB 2S 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 has been achieved in that are used as semiconductor material modified bismuth sulfides.
  • Objects of the invention are modified bismuth sulfides which have a composition according to the following general formula (1)
  • E germanium and / or silicon and the indices x, y, z and u 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 furthermore a process for producing a semiconductor material based on modified bismuth 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 -100 to +600 0 C and visible light directly into electrical energy.
  • Bi 2 S 3 has a very low grating thermal conductivity of 16 mW / cm grad at room temperature for thermoelectric applications.
  • the germanium is preferably used in elemental form.
  • Mg 2 Ge is used.
  • the silicon can also be used in elemental form, but is preferably its use in the form of Mg 2 Si.
  • the index x corresponds to a value of 1.9 to 2.1, preferably 1.95 to 2.05.
  • the index y corresponds to a value from 0.001 to 0.08, preferably from 0.005 to 0.03.
  • the values of the indices x and y do not have to be complementary to 1.
  • the index z corresponds to a value from 2.95 to 3.05, preferably from 2.98 to 3.02.
  • the subscript u corresponds to values from 0 to 2y, preferably from 0 to 0.06.
  • the bismuth 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 mean Seebeck coefficient of up to 500 ⁇ V / degree and an electrical conductivity of up to 450 S / cm are achieved.
  • Advantageously usable modified bismuth sulfides are z. Bi 1i98 Geo , ⁇ 2 S 3 and Bi 1199 Ge 01O2 S 3 . Further exemplified in the examples below.
  • the materials of the present invention are usually prepared by fusing together mixtures of the respective constituent elements or their compounds / alloys. In general, a reaction time of fusion 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 mixed, then this is particularly suitable for a furnace, the can be tilted about its longitudinal axis to ensure the homogeneity of the mixture. If no mixture is made, generally longer melt times of 2 to 100 hours, especially 30 to 100 hours, are required to obtain a homogeneous material.
  • the co-melting is carried out usually at a temperature of at least 800 0 C (melting point of Bi 2 S 3 is approximately 77O 0 C) preferably, at least 850 0 C. In particular, is the melting temperature in the range 850-950 0 C.
  • the preparation of the material according to the invention is generally carried out in a heatable quartz tube.
  • Mixing of the components involved can be ensured by using a rotatable and / or tiltable furnace or an induction furnace, in which the magnetic field ensures thorough mixing of the melt.
  • the furnace is cooled.
  • 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 improve the densification of the material according to the invention can be used in amounts of preferably 0.1 to 5% by volume, particularly preferably 0.2 to 2% by volume, based in each case on the powdered material according to the invention, are 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, if appropriate 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 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 ° C, preferably 400 to 67O 0 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.
  • the sintering is carried out at a tem- perature, the 100 to 600 0 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 bucket density.
  • the semiconductor materials according to the invention are prepared for example by reaction of Bi, Ge and / or Si and sulfur at temperatures of up to 1100 0 C, preferably 850 to 950 0 C, for example in evacuated quartz vessels.
  • Mg 2 Ge and / or Mg 2 Si e.g. B. by reaction of Mg and Ge or Mg and Si at temperatures of preferably 1150 to 1250 ° C, and then admixing Bi and sulfur and the mass again to temperatures above 800 ° C, in particular up to 950 0 C to heat.
  • the materials of the invention have increased Seebeck coefficients and electrical conductivity on the order of magnitude compared to unmodified bismuth 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.
  • thermoelectrics and photovoltaics As a combination with the semiconductors used according to the invention predominantly as n-type material, it is possible to use all p-type materials commonly used in thermoelectrics and photovoltaics. Such suitable p-type materials are Zn 4 Sb 3 and p-type lead or bismuth tellurides in thermoelectrics and p-type ZnTe and p-type CuIn chalcogenides in photovoltaics.
  • modified copper sulfides as p-type 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 copper sulfides have, for example, a composition according to general formula (2)
  • these modified copper sulfides are prepared for example by reaction of Cu, 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 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. They used bismuth with 99.999% purity and sulfur from a tanker delivery of liquid sulfur with a purity of 99.99%. In a tube furnace, the quartz tubes were heated within 10 hours from room temperature to 1,000 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 pure Bi 2 S 3 shows a Seebeck coefficient of 100 to 160 ⁇ V / degree with an electrical conductivity less than 0.01 S / cm.

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  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
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  • Silicon Compounds (AREA)

Abstract

L'invention concerne des sulfures de bismuth modifiés ayant une composition conforme à la formule générale suivante (1) Bi<SUB>x</SUB>E<SUB>y</SUB>S<SUB>z</SUB>Mg<SUB>u</SUB> (1 ), E représentant du germanium et/ou du silicium et les indices x, y, z et u ayant les valeurs suivantes: x = 1,9 à 2,1, y = 0,001 à 0,08, z = 2,95 à 3,05, u = 0 à 2y. L'invention concerne également un matériau semi-conducteur contenant ces sulfures de bismuth modifiés ainsi que l'utilisation d'un tel matériau semi-conducteur dans des modules thermoélectriques et des piles photovoltaïques ou des modules.
PCT/EP2006/060238 2005-02-24 2006-02-23 Sulfures de bismuth semi-conducteurs aux nouvelles combinaisons de proprietes et leur utilisation dans les domaines thermoelectrique et photovoltaique WO2006089938A1 (fr)

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DE102005008865A DE102005008865A1 (de) 2005-02-24 2005-02-24 Halbleitende Bismutsulfide mit neuen Eigenschaftskombinationen und deren Verwendung in der Thermoelektrik und Photovoltaik
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN102443848A (zh) * 2012-01-29 2012-05-09 北京科技大学 一种提高硫化铋多晶热电性能的方法
CN102992400A (zh) * 2011-09-13 2013-03-27 郴州市金贵银业股份有限公司 一种利用含铋烟尘湿法制备硫化铋的工艺

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DE102012022686A1 (de) 2012-11-21 2014-05-22 Hans-Josef Sterzel Elektrische Doppelschichten enthaltende Kondensatoren hoher Energiedichte auf der Basis von Ionenleiter-Halbleiter-Übergängen
CN112939078B (zh) * 2021-01-26 2023-02-28 昆明理工大学 一种提高硫化铋基热电材料性能的方法

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WO2005114755A2 (fr) * 2004-05-18 2005-12-01 Basf Aktiengesellschaft Tellurures presentant de nouvelles combinaisons de proprietes

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CN102992400A (zh) * 2011-09-13 2013-03-27 郴州市金贵银业股份有限公司 一种利用含铋烟尘湿法制备硫化铋的工艺
CN102443848A (zh) * 2012-01-29 2012-05-09 北京科技大学 一种提高硫化铋多晶热电性能的方法

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