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DE1278111B - Semiconductor material made of p-conductive lead telluride, suitable as a limb for thermocouples - Google Patents

Semiconductor material made of p-conductive lead telluride, suitable as a limb for thermocouples

Info

Publication number
DE1278111B
DE1278111B DEM29059A DEM0029059A DE1278111B DE 1278111 B DE1278111 B DE 1278111B DE M29059 A DEM29059 A DE M29059A DE M0029059 A DEM0029059 A DE M0029059A DE 1278111 B DE1278111 B DE 1278111B
Authority
DE
Germany
Prior art keywords
semiconductor material
lead telluride
thermocouples
limb
conductive lead
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
DEM29059A
Other languages
German (de)
Inventor
Robert Washburn Fritts
Elm Grove Wis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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 Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of DE1278111B publication Critical patent/DE1278111B/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00—Machines, plants or systems, using electric or magnetic effects
    • F25B21/02—Machines, plants or systems, using electric or magnetic effects using Peltier effect; using Nernst-Ettinghausen effect
    • 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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
    • F25B2321/02—Details of machines, plants or systems, using electric or magnetic effects using Peltier effects; using Nernst-Ettinghausen effects
    • F25B2321/021—Control thereof
    • F25B2321/0212—Control thereof of electric power, current or voltage

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Conductive Materials (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. Cl.:Int. Cl .:

C22cC22c

Deutsche Kl.: 40 b-11/00German class: 40 b-11/00

Nummer: 1278111Number: 1278111

Aktenzeichen: P 12 78 111.2-24 (M 29059)File number: P 12 78 111.2-24 (M 29059) Anmeldetag: 14. Dezember 1955 Filing date: December 14, 1955 Auslegetag: 19. September 1968Opening day: September 19, 1968

Die Erfindung betrifft p-leitendes dotiertes Bleitellurid als Halbleitermaterial für die Herstellung von Schenkeln von Thermoelementen für Wärmepumpen u. dgl.The invention relates to p-type doped lead telluride as a semiconductor material for the manufacture of legs of thermocouples for heat pumps and the like

Es sind bereits Wärmepumpen aus thermoelek-Irischem Halbleitermaterial auf der Basis von dotierten Bleisulfiden bekannt; jedoch zeigte sich, daß diese Halbleitermaterialien eine für großtechnische Anwendung unzureichende Effektivität besitzen. Darüber hinaus ist für thermoelektrische Kühlung unter Ausnutzung des Peltiereffekts eine Vorrichtung bekanntgeworden, in welcher als thermoelektrisches Halbleitermaterial eine Cadmium-Antimon-Legierung mit einem Antimongehalt von 48 bis 54% angewandt wurde. Zur Erhöhung der Leitfähigkeit konnte diese Legierung bis zu 2% Übergangsmetalle enthalten. There are already heat pumps made of thermoelectronic semiconductor material on the basis of doped Known lead sulfides; however, it has been found that these semiconductor materials are ones for industrial use have insufficient effectiveness. In addition, thermoelectric cooling is being used the Peltier effect became known a device in which as a thermoelectric semiconductor material a cadmium-antimony alloy with an antimony content of 48 to 54% was used. To increase the conductivity could this alloy contains up to 2% transition metals.

Die Erfindung bringt nun ein hochleistungsfähiges Halbleitermaterial für p-leitende Schenkel in Thermoelementen, die zur Herstellung von Wärmepumpen verwendet werden sollen. Die erfindungsgemäßen Halbleitermaterialien auf der Basis von Bleitellurid haben einen Tellurüberschuß über das stöchiometrische Verhältnis und sind bis zu gewissen maximalen Anteilen mit Natrium, Kalium oder Thallium p-leitend dotiert.The invention now brings a high-performance semiconductor material for p-conducting legs in thermocouples, which are to be used to manufacture heat pumps. The invention Semiconductor materials based on lead telluride have a tellurium excess over the stoichiometric one Ratio and are up to certain maximum proportions with sodium, potassium or thallium p-type doped.

Die Erfindung betrifft somit p-leitendes Bleitellurid für Thermoelementschenkel, bestehend aus 59 bis 61,8% Blei, Rest 41 bis 38,2% Tellur und bis 0,001% Verunreinigungen, dem als Akzeptor 0,007 bis 0,14% Natrium, 0,012 bis 0,23% Kalium oder 0,18 bis 0,6% Thallium zulegiert sind, wobei der Gehalt an dem Akzeptor in Gewichtsprozent des Bleitellurids ausgedrückt ist.The invention thus relates to p-type lead telluride for thermocouple legs, consisting of 59 to 61.8% lead, the remainder 41 to 38.2% tellurium and up to 0.001% Impurities that are used as the acceptor 0.007 to 0.14% sodium, 0.012 to 0.23% potassium or 0.18 to 0.6% Thallium are added, the content of the acceptor being expressed in percent by weight of the lead telluride is.

Es zeigte sich, daß das so dotierte Bleitellurid infolge hoher Thermokraft und geringer Wärmeleitfähigkeit ein sehr geeignetes Halbleitermaterial mit hohem Nutzeffekt in Wärmepumpen darstellt. Der Peltierkoeffizient für dotiertes Material bei 300° K beträgt bei maximal zulässigem Gehalt an Natrium 20 mV, an Kalium 27 mV bzw. an Thallium 0,41 mV. Der spezifische Widerstand dieser Produkte A. B und C mit maximalen Akzeptormengen nach der Erfindung beträgt 0,33, 0,37 bzw. 1,3 mü · cm. Diese Werte zusammen mit je einem Beispiel der erfindungsgemäßen Halbleitermaterialien für jedes Akzeptorelement gehen aus folgender Tabelle und dem Diagramm hervor, in welchem der spezifische Widerstand ο in mü · cm gegen den Peltierkoeffizient (oder die Thermokraft) π in mV aufgetragen worden ist. Darüber hinaus enthält die Tabelle auch noch Angaben über die Effektivität oder den Wirkungsgrad Als Schenkel für Thermoelemente geeignetes Halbleitermaterial aus p-leitendem Bleitellurid It was found that the lead telluride doped in this way is a very suitable semiconductor material with a high efficiency in heat pumps due to its high thermal power and low thermal conductivity. The Peltier coefficient for doped material at 300 ° K is 20 mV for the maximum permissible sodium content, 27 mV for potassium and 0.41 mV for thallium. The resistivity of these products A. B and C with maximum amounts of acceptor according to the invention is 0.33, 0.37 and 1.3 m · cm, respectively. These values, together with an example of the semiconductor materials according to the invention for each acceptor element, can be seen from the following table and the diagram in which the specific resistance ο in mu · cm is plotted against the Peltier coefficient (or the thermal force) π in mV. In addition, the table also contains information on the effectiveness or the degree of efficiency . Semiconductor material made of p-conductive lead telluride suitable for use as a limb for thermocouples

Anmelder:Applicant:

Minnesota Mining and Manufacturing Company,Minnesota Mining and Manufacturing Company, St. Paul, Minn. (V. St. A.)St. Paul, Minn. (V. St. A.)

Vertreter:Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Puls undDr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Pechmann,Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Bad luck man, Patentanwälte,Patent attorneys,

8000 München 90, Schweigerstr. 28000 Munich 90, Schweigerstr. 2

Als Erfinder benannt:Named as inventor: Robert Washburn Fritts,Robert Washburn Fritts, Elm Grove, Wis., Sebastian Karrer, Md.Elm Grove, Wis., Sebastian Karrer, Md.

(V. St. A.)(V. St. A.)

Beanspruchte Priorität: V. St. v. Amerika vom 15. Dezember 1954 (475 544),Claimed priority: V. St. v. America December 15, 1954 (475 544),

vom 1. Juni 1955 (512436)dated June 1, 1955 (512436)

der Beispiele für die drei erfindungsgemäßen Akzeptorelemente. the examples of the three acceptor elements according to the invention.

PeltierPeltier Wärmewarmth ElektrischerElectric Leistungpower koeffizientcoefficient leitwertconductance Widerstandresistance TXTX KK titi 2K2K °C° C mVmV W/cm-''CW / cm - '' C rail · cm rail cm 48,348.3 D 62,5 D 62.5 0,0300.030 1,351.35 41,341.3 E 62E 62 0,0300.030 1,551.55 21,821.8 F 42F 42 0,0300.030 1,351.35

D = 61,7% Pb + 38,3% Te + 0,007% Na. E = 61,7% Pb + 38,3% Te + 0,012% K. F = 61,7% Pb + 38,3% Te + 0,18 % Tl.D = 61.7% Pb + 38.3% Te + 0.007% Na. E = 61.7% Pb + 38.3% Te + 0.012% K. F = 61.7% Pb + 38.3% Te + 0.18% Tl.

809 617/452809 617/452

Claims (1)

Patentanspruch:Claim: Als Schenkel für Thermoelemente geeignetes Halbleitermaterial aus p-leitendem Bleitellurid, bestehend aus 59 bis 61,8% Blei, Rest 41 bis 38,2% Tellur und bis 0,001% Verunreinigungen, dem als Akzeptor 0,007 bis 0,14% Natrium, 0,012 bis 0,23% Kalium oder 0,18 bis 0,6U/0 Thallium zulegiert sind, wobei der Gehalt an dem Akzeptor in Gewichtsprozent des Bleitellurids ausgedrückt ist.Semiconductor material suitable as a leg for thermocouples made of p-conductive lead telluride, consisting of 59 to 61.8% lead, the remainder 41 to 38.2% tellurium and up to 0.001% impurities, the acceptor 0.007 to 0.14% sodium, 0.012 to 0 , 23% potassium or 0.18 to 0.6 U / 0 thallium are added, the content of the acceptor being expressed in percent by weight of the lead telluride. In Betracht gezogene Druckschriften:
Deutsche Patentschriften Nr. 822 397, 823 299, 170,. 829 171, 872 210, 906 813.Considered publications:
German Patent Nos. 822 397, 823 299, 170 ,. 829 171, 872 210, 906 813. Hierzu 1 Blatt Zeichnungen1 sheet of drawings KM 617/452 9.6JO Bundesdruckerei BerlinKM 617/452 9.6JO Bundesdruckerei Berlin
DEM29059A 1954-12-15 1955-12-14 Semiconductor material made of p-conductive lead telluride, suitable as a limb for thermocouples Pending DE1278111B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47554454A 1954-12-15 1954-12-15
US512436A US2896005A (en) 1954-12-15 1955-06-01 Thermoelectric heat pump

Publications (1)

Publication Number Publication Date
DE1278111B true DE1278111B (en) 1968-09-19

Family

ID=27044828

Family Applications (2)

Application Number Title Priority Date Filing Date
DEM27647A Pending DE1106968B (en) 1954-12-15 1955-07-12 Tellurium and selenium or selenium and sulfur-containing lead-based alloys are suitable as legs of thermocouples
DEM29059A Pending DE1278111B (en) 1954-12-15 1955-12-14 Semiconductor material made of p-conductive lead telluride, suitable as a limb for thermocouples

Family Applications Before (1)

Application Number Title Priority Date Filing Date
DEM27647A Pending DE1106968B (en) 1954-12-15 1955-07-12 Tellurium and selenium or selenium and sulfur-containing lead-based alloys are suitable as legs of thermocouples

Country Status (7)

Country Link
US (1) US2896005A (en)
BE (2) BE543675A (en)
CH (2) CH386504A (en)
DE (2) DE1106968B (en)
FR (1) FR1143255A (en)
GB (2) GB814594A (en)
NL (1) NL202808A (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3157801A (en) * 1960-03-07 1964-11-17 Itt Cooling means for thermostats
DE1295195B (en) * 1961-12-26 1969-05-14 Minnesota Mining & Mfg Thermoelectric semiconductor material
DE1283978B (en) * 1965-12-08 1968-11-28 Telefunken Patent Electronic solid-state component with electrical resistance controllable by charge carrier injection
US3527622A (en) * 1966-10-13 1970-09-08 Minnesota Mining & Mfg Thermoelectric composition and leg formed of lead,sulfur,and tellurium
US3460996A (en) * 1968-04-02 1969-08-12 Rca Corp Thermoelectric lead telluride base compositions and devices utilizing them
US4019113A (en) * 1974-11-20 1977-04-19 James Keith Hartman Energy conversion device
US20050056799A1 (en) * 2003-09-11 2005-03-17 Malone Steven J. Valves having a thermostatic actuator controlled by a peltier device
KR101663183B1 (en) * 2010-08-26 2016-10-06 삼성전자주식회사 Thermoelectric materials, and thermoelectric module and thermoelectric device comprising same
CN111799360B (en) * 2020-07-03 2022-08-05 中国科学院合肥物质科学研究院 A kind of n-type PbTe-based thermoelectric material and preparation method thereof
CN114538544B (en) * 2022-03-21 2023-08-18 中国科学院沈阳应用生态研究所 Method for treating selenium-containing wastewater by taking scrap iron as iron source sulfur induced stabilization

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE822397C (en) * 1949-02-19 1951-11-26 Siemens Schuckertwerke A G Arrangement for electrothermal cold generation using the Peltier effect
DE823299C (en) * 1949-02-19 1951-12-03 Siemens Schuckertwerke A G Process for the production of thermocouples for electrothermal cold generation
DE829171C (en) * 1950-06-15 1952-01-24 Siemens Schuckertwerke A G Electrothermal cold generation
DE829170C (en) * 1950-08-17 1952-01-24 Siemens Schuckertwerke A G Device for electrothermal cold generation
DE872210C (en) * 1949-03-25 1953-03-30 Siemens Ag Arrangement for heat delivery by means of thermocouples, in particular for electrothermal cold generation
DE906813C (en) * 1951-11-03 1954-03-18 Siemens Ag Thermocouple, especially for electrothermal generation of cold

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2602095A (en) * 1950-06-03 1952-07-01 Gen Electric Thermoelectric device
US2811571A (en) * 1954-12-15 1957-10-29 Baso Inc Thermoelectric generators
US2811440A (en) * 1954-12-15 1957-10-29 Baso Inc Electrically conductive compositions and method of manufacture thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE822397C (en) * 1949-02-19 1951-11-26 Siemens Schuckertwerke A G Arrangement for electrothermal cold generation using the Peltier effect
DE823299C (en) * 1949-02-19 1951-12-03 Siemens Schuckertwerke A G Process for the production of thermocouples for electrothermal cold generation
DE872210C (en) * 1949-03-25 1953-03-30 Siemens Ag Arrangement for heat delivery by means of thermocouples, in particular for electrothermal cold generation
DE829171C (en) * 1950-06-15 1952-01-24 Siemens Schuckertwerke A G Electrothermal cold generation
DE829170C (en) * 1950-08-17 1952-01-24 Siemens Schuckertwerke A G Device for electrothermal cold generation
DE906813C (en) * 1951-11-03 1954-03-18 Siemens Ag Thermocouple, especially for electrothermal generation of cold

Also Published As

Publication number Publication date
NL202808A (en)
GB827724A (en) 1960-02-10
DE1106968B (en) 1961-05-18
US2896005A (en) 1959-07-21
BE543676A (en) 1955-12-30
FR1143255A (en) 1957-09-27
GB814594A (en) 1959-06-10
BE543675A (en)
CH389701A (en) 1965-03-31
CH386504A (en) 1965-01-15

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