US3508915A - Method of fabrication of germanium-silicon alloy - Google Patents

Method of fabrication of germanium-silicon alloy Download PDF

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Publication number
US3508915A
US3508915A US500487A US3508915DA US3508915A US 3508915 A US3508915 A US 3508915A US 500487 A US500487 A US 500487A US 3508915D A US3508915D A US 3508915DA US 3508915 A US3508915 A US 3508915A
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United States
Prior art keywords
germanium
alloy
silicon
mixture
thermal conductivity
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Expired - Lifetime
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US500487A
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English (en)
Inventor
Pierre Paoli
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Commissariat à l'Énergie Atomique et Aux Énergies Alternatives
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Commissariat a lEnergie Atomique CEA
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C30B29/48—AIIBVI compounds wherein A is Zn, Cd or Hg, and B is S, Se or Te
    • C30B29/50—Cadmium sulfide
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys
    • 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
    • H10N10/8556—Thermoelectric active materials comprising inorganic compositions comprising compounds containing germanium or silicon
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S420/00—Alloys or metallic compositions
    • Y10S420/903—Semiconductive

Definitions

  • the method consists of mixing germanium and silicon and thereafter melting the mixture by application of high frequency energy from a source which is displaced relative to the mixture of germanium and silicon at a rate sufiicient to obtain good homogenization of the mixture.
  • the doping material may be added to the germanium and silicon prior to mixing or during the melting step.
  • This output also depends on the proportion of dope incorporated with the alloy which determines the electrical resistivity and the Seebeck coefficient.
  • this time-consuming method of preparation results in the volatilization of the dope and does not make it possible to retain a sufficiently high proportion of dope in the final alloy.
  • the invention is directed to a method of preparation of a germanium-silicon alloy which is more rapid than existing processes and which makes it possible to attain sufficient proportions of dope without difficulty.
  • the method according to the invention consists in mixing fragments of germanium and silicon in the desired proportions, in melting said mixture at high frequency as a result of the relative displacement of an induction coil and of said germanium-silicon mixture and in cooling the mixture which is obtained, the melting process being performed at a frequency and at a rate of displacement which are sufficiently high to obtain good homogenization of the mixture.
  • the relative displacement of the induction coil and of the mixture is carried out by means of a movement of translation of the induction coil over the mixture which remains stationary or alternatively by means of a movement of displacement of the mixture itself whilst the induction coil remains motionless.
  • the relative displacement must be sufficiently rapid to ensure that the mixture of the different constituents is correct.
  • the effect of the rate of displacement necessarily depends on the power of the generator and on the coupling which is formed.
  • the rate of displacement must be at least equal to 15 millimeters per minute: depending on the power of the generator, speeds of up to 165 millimeters per minute can be attained but will preferably be of the order of millimeters per minute under normal operating conditions.
  • the relative displacement is carried out in both direc tions and homogenization is improved by effecting a number of successive passes.
  • the number of passes thus effected in back and forth motion has an influence on the homogeneity of the alloy which is formed; when the number of back-and-forth passes exceeds 40, the influence is less marked, so that the operation usually consists in effecting 30 to 40 passes in back-and-forth motion.
  • the requisite proportions of dope can be readily introduced, such proportions being usually within the range of 50 to 500 ppm. in the case of antimony and indium.
  • the dope is introduced either in the initial mixture or between two successive passes.
  • the method makes it possible to obtain germaniumsilicon alloys which have a particularly low thermal conductivity while permitting of relatively rapid processing; thus, in one hour and thirty minutes, it has been possible to obtain ingots having a thermal conductivity K which is less than 30 mW.//cm. This result can be considered very satisfactory.
  • the germanium-silicon alloy shows a germanium-silicon alloy having the same composition in which the high germanium-content phase (reference 6 in the figure) is well dispersed, and the thermal conductivity of which is equal to 25 mw./ cm. Moreover, in this case, the compositions of the two phases have become more similar, in that the phase (6) which is rich in germanium contains 50% by weight of this metal and the phase (8) which is low in germanium contains 45% by weight of germanium.
  • EXAMPLE 3 10 g. of germanium and 10 g. of silicon were melted at an average speed of displacement of the induction coil of the order of millimeters per minute in 26 passes back and forth; there was obtained an ingot of 17.6 g. of germanium-silicon alloy containing 48% by weight of germanium having the same dimensions as in Example 1.
  • the thermal conductivity as measured at 300 C. was 20 mW.//cm. and the time of preparation was approximately 185 minutes.
  • the method of preparing a doped germanium-silicon alloy comprising mixing germanium and silicon, melting said mixture by application of energy having a frequency at least equal to 4 mHz. from a high frequency energy source which is displaced relative to said mixture at a rate of displacement at least equal to 15 millimeters per minute to obtain good homogenization of the mixture, and adding a doping material to said germanium and silicon at a point prior to the completion ofthe melting step.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US500487A 1964-10-27 1965-10-15 Method of fabrication of germanium-silicon alloy Expired - Lifetime US3508915A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR992829A FR1420509A (fr) 1964-10-27 1964-10-27 Procédé de fabrication d'alliage germanium-silicium

Publications (1)

Publication Number Publication Date
US3508915A true US3508915A (en) 1970-04-28

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US500487A Expired - Lifetime US3508915A (en) 1964-10-27 1965-10-15 Method of fabrication of germanium-silicon alloy

Country Status (9)

Country Link
US (1) US3508915A (fr)
BE (1) BE670718A (fr)
CH (1) CH448542A (fr)
DE (1) DE1483201B1 (fr)
ES (1) ES318922A1 (fr)
FR (1) FR1420509A (fr)
GB (1) GB1111678A (fr)
LU (1) LU49680A1 (fr)
NL (1) NL6513861A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898080A (en) * 1968-05-14 1975-08-05 Atomic Energy Authority Uk Germanium-silicon Thermoelectric elements
EP0061388A3 (en) * 1981-03-16 1983-08-24 Fairchild Camera & Instrument Corporation Binary germanium-silicon interconnect and electrode structure for integrated circuits
US4857270A (en) * 1987-05-19 1989-08-15 Komatsu Electronic Metals Co., Ltd. Process for manufacturing silicon-germanium alloys

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739088A (en) * 1951-11-16 1956-03-20 Bell Telephone Labor Inc Process for controlling solute segregation by zone-melting
US2858275A (en) * 1954-12-23 1958-10-28 Siemens Ag Mixed-crystal semiconductor devices
US2997410A (en) * 1954-05-03 1961-08-22 Rca Corp Single crystalline alloys
US3279954A (en) * 1961-06-09 1966-10-18 Rca Corp Thermoelectric device having silicongermanium alloy thermoelement

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2739088A (en) * 1951-11-16 1956-03-20 Bell Telephone Labor Inc Process for controlling solute segregation by zone-melting
US2997410A (en) * 1954-05-03 1961-08-22 Rca Corp Single crystalline alloys
US2858275A (en) * 1954-12-23 1958-10-28 Siemens Ag Mixed-crystal semiconductor devices
US3279954A (en) * 1961-06-09 1966-10-18 Rca Corp Thermoelectric device having silicongermanium alloy thermoelement

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3898080A (en) * 1968-05-14 1975-08-05 Atomic Energy Authority Uk Germanium-silicon Thermoelectric elements
EP0061388A3 (en) * 1981-03-16 1983-08-24 Fairchild Camera & Instrument Corporation Binary germanium-silicon interconnect and electrode structure for integrated circuits
US4857270A (en) * 1987-05-19 1989-08-15 Komatsu Electronic Metals Co., Ltd. Process for manufacturing silicon-germanium alloys

Also Published As

Publication number Publication date
LU49680A1 (fr) 1965-12-22
FR1420509A (fr) 1965-12-10
CH448542A (fr) 1967-12-15
BE670718A (fr) 1966-01-31
ES318922A1 (es) 1967-01-01
NL6513861A (fr) 1966-04-28
DE1483201B1 (de) 1969-09-04
GB1111678A (en) 1968-05-01

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