US3170856A - Method and device for producing hyperpure gallium - Google Patents

Method and device for producing hyperpure gallium Download PDF

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Publication number
US3170856A
US3170856A US141381A US14138161A US3170856A US 3170856 A US3170856 A US 3170856A US 141381 A US141381 A US 141381A US 14138161 A US14138161 A US 14138161A US 3170856 A US3170856 A US 3170856A
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United States
Prior art keywords
gallium
electrolyte
cathode
hyperpure
nipple
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Expired - Lifetime
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US141381A
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English (en)
Inventor
Leibenzeder Siegfried
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Siemens Schuckertwerke AG
Siemens AG
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Siemens AG
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Priority to US370749A priority Critical patent/US3170861A/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells

Definitions

  • dram-s9 My invention relates to a method and apparatus for the production of hyperpure gallium, such as required for the production of electronic semiconductors from gallium compounds, for example, GaP, GaAs, GaSb, or as required for use as doping or contact substance for semiconductor bodies. Hyperpure gallium is also used, for example, in high-temperature thermometers and as a metallic heat-exchange liquid in cooling systems.
  • I employ as electrolyte for electrolytic precipi tation, the solution of a gallium complex of the type Ga(GaX in a non-aqueous organicsolvent, wherein X denotes a halogen element, which as used herein is understood to be chlorine, bromine and iodine.
  • non-aqueous organic solvent particularly suitable as the non-aqueous organic solvent are benzene, toluene and xylene, and as gallium complexes are Ga(GaCl Ga(GaBr.,) and Ga(GaI
  • the purifying effect obtained by virtue of the invention is not mainly predicated upon a refining action as known from the electrolysis of aqueous solutions or molten salt, but is rather predominantly based upon the insolubility of many metal halides in the organic solvents to be employed. This results in a considerable advantage over the just-mentioned known methods, namely the fact that the131-fying action does not depend upon the separation potential so'that relatively high cell voltages can be used trolyte results in the precipitationof gallium.
  • gallium bromide complex An example of the technique is given by the production of gallium bromide complex.
  • Commercially available gallium metal is heated in a flow of nitrogen laden with Table 2 Concentration of the foreign elements of the anodic Ga in p.p.m. (10- (percent) the foreign elements of the oath odicallyprecipitated Gain p.p.m. (10- percent) Element Not detectable.
  • the purifying effect can Because of the insolubility of many metal- 7 Concentration of Table 3 Concentration'of the foreign elements of Element the'twice cathodically precipitated Ga in p.p.m. (IO-t Percent) Pb- Not detectable. Fe. ,Do.
  • the drawing shows a schematic and sectional view of an electrolysis device for performing the above-described method.
  • the anode is formed by molten gallium located at 1 on the bottom of the electrolytic cell. Current is supplied to the anode by a platinum wire 2 which is immersed at its lower end into the molten gallium.
  • the cathode is denoted by 3 and a collector funnel by 4.
  • the funnel 4 is connected with a receiving vessel 5 through a capillary 6.
  • the electrolyte 7 covers the anode 1 and forms part of a thermosiphon system which serves to maintain the electrolyte in circulation.
  • This system comprises the two legs 8 and 9 which are interconnected by transverse portion 13. Leg 9 is surrounded by a cooler 19.
  • Leg 8 has its lower end widened to form an inverted funnel portion at 11 above the cathode 3 and in upwardly spaced relation to the funnel 4.
  • a reflux condenser 712 Connected to the circulation system of the electrolyte is a reflux condenser 712.
  • the suction nipple of the reflux condenser 12 is denoted by 14.
  • the nipple 14 is closed by a protective cover 15 during operation of the device.
  • a stopcock is provided at 16.
  • the cell vessel is further provided at 17 with a conical ground nipple through which the anode current-supply lead enters into the vessel.
  • the nipple 17 also serves to supply the vessel with electrolyte.
  • purified gallium 19 is sealed by a stoppered ground nippie 18.
  • Conically ground junctions at 21 connect the lower portion of the electrolytic cell with the upper portion that contains the above-described entire electrolytecirculating system.
  • the quantity of cathode gallium required for starting the process is supplied through the receiving vessel 5 so that the capillary 6 and the receiving funnel 4 are filled with gallium.
  • the anode gallium l is supplied through the central nipple 17 in a quantity adequate to bring the level of the anode gallium to a height of at most a few millimeters below the lower end of the tube 9.
  • the electrolyte is filled into the vessel through the same nipple 17. Since the electrolyte must not be subjected to moisture, the filling must be done in a sealed container through a siphon or pump with the aid of a dry inert gas, for example, nitrogen.
  • the electrolyte for example, is composed of 50% by weight of Ga(GaBr and 50% benzene.
  • nipple 17 With nipple 17 open, the electrolyte is inducted through V the suction nipple 14 up to the stopcock 16. Thereafter, the stopcock 16 is closed, the suction line removed from nipple 14, and the protective cap 15 placed over nipple 14. Simultaneously, the condensers and 12 are put into operation, the anode current supply lead 2 is inserted, thus closing the opening of the nipple i7, and the cathode 3 is inserted through nipple 20. A voltage of from about to about v. is applied to the cell between cathode and anode. This results in the flow of an average current value of about 0.4 amp. Precipitation of about 1 g./hour of hyper-pure gallium takes place with a current yield of about 100%. I
  • the device operates practically automatically, continuously and free of maintenance over a long period of time.
  • the platinum wire of the cathode The receiving vessel 5 for the involves the thermosiphon principle.
  • the precipitation is preferably carried out with a high cathode current density which preferably should not be below 200 amperes/decimeter This is aided by the fact that the cathode surface is very small in comparison with the anode surface.
  • the gallium becomes precipitated as a fine pulverulent metal.
  • This powder is suitable, for example, for the production of gallium containing semiconducting sinter materials, which have been recently employed for thermoelectric purposes.
  • the circulatory system prevents the occurrence of a solid bottom body of Ga(GaX on top of the anode gallium. Such a body would considerably increase the ohmic resistance of the cell and, for the same cell voltage, would result in a reduction of the current density.
  • the method of producing hyperpure gallium for electronic purposes by electrolytic precipitation which comprises using a solution of a gallium complex of the type Ga(GaX wherein X is a halogen, in a non-aqueous organic solvent.
  • the method of producing hyperpure gallium for electronic purposes by electrolytic precipitation which comprises using a solution of a gallium complex of the type Ga(GaXr) wherein X is a halogen, in a non-aqueous aromatic organic solvent selected from the group consisting of benzene, toluene and xylene.
  • the method of producing hyperpure gallium for electronic purposes by electrolytic precipitation which comprises using a solution of a gallium complex of the type Ga(GaX wherein X is a halogen, in a non-aqueous aromatic organic solvent selected from the group consisting of: benzene, toluene and xylene, and adjusting the current density above 200 amperes/square decimeter to precipitate gallium at the cathode in liquid form.
  • the method of producing hyperpure gallium for electronic purposes by electrolytic precipitation which comprises using a solution of a gallium complex of the type Ga(GaBr in a non-aqueous aromatic organic solvent selected from the group consisting of benzene, toluene and xylene, and adjusting the current density below 200 amperes/square decimeter to precipitate gallium at the cathode in pulverulent form.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
US141381A 1960-09-30 1961-09-28 Method and device for producing hyperpure gallium Expired - Lifetime US3170856A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US370749A US3170861A (en) 1961-09-28 1964-05-06 Apparatus for producing hyperpure gallium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DES70729A DE1141461B (de) 1960-09-30 1960-09-30 Verfahren und Vorrichtung zum elektrolytischen Herstellen von hochreinem Gallium
DES85697A DE1183249B (de) 1960-09-30 1963-06-15 Verfahren und Vorrichtung zum elektrolytischen Herstellen von hochreinem Gallium

Publications (1)

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US3170856A true US3170856A (en) 1965-02-23

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Application Number Title Priority Date Filing Date
US141381A Expired - Lifetime US3170856A (en) 1960-09-30 1961-09-28 Method and device for producing hyperpure gallium
US375211A Expired - Lifetime US3325380A (en) 1960-09-30 1964-06-15 Method and apparatus for electrolytically producing highly pure gallium

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Application Number Title Priority Date Filing Date
US375211A Expired - Lifetime US3325380A (en) 1960-09-30 1964-06-15 Method and apparatus for electrolytically producing highly pure gallium

Country Status (7)

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US (2) US3170856A (fr)
AT (1) AT249389B (fr)
CH (2) CH409415A (fr)
DE (2) DE1141461B (fr)
FR (2) FR1306202A (fr)
GB (2) GB913325A (fr)
NL (1) NL6403726A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897317A (en) * 1974-06-24 1975-07-29 Texas Instruments Inc Process for making hyperpure gallium

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2440238A (en) * 1942-12-09 1948-04-27 Harold R Alley Means for producing mercury electrolytically from acid solutions
US2928731A (en) * 1955-09-06 1960-03-15 Siemens Ag Continuous process for purifying gallium
US2952589A (en) * 1956-04-09 1960-09-13 Karl Ziegler Purification of aluminum
US2985568A (en) * 1954-11-26 1961-05-23 Ziegler Electrolytic process for the production of metal alkyls
US2998374A (en) * 1959-02-09 1961-08-29 Goodyear Tire & Rubber Container linings
US3007858A (en) * 1959-05-06 1961-11-07 Nalco Chemical Co Preparation of organo metallic compounds

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3170857A (en) * 1963-03-28 1965-02-23 Siemens Ag Method for producing gallium, particularly for semiconductor purposes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2440238A (en) * 1942-12-09 1948-04-27 Harold R Alley Means for producing mercury electrolytically from acid solutions
US2985568A (en) * 1954-11-26 1961-05-23 Ziegler Electrolytic process for the production of metal alkyls
US2928731A (en) * 1955-09-06 1960-03-15 Siemens Ag Continuous process for purifying gallium
US2952589A (en) * 1956-04-09 1960-09-13 Karl Ziegler Purification of aluminum
US2998374A (en) * 1959-02-09 1961-08-29 Goodyear Tire & Rubber Container linings
US3007858A (en) * 1959-05-06 1961-11-07 Nalco Chemical Co Preparation of organo metallic compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897317A (en) * 1974-06-24 1975-07-29 Texas Instruments Inc Process for making hyperpure gallium

Also Published As

Publication number Publication date
FR1306202A (fr) 1962-10-13
DE1141461B (de) 1962-12-20
AT249389B (de) 1966-09-26
CH409415A (de) 1966-03-15
NL6403726A (nl) 1964-12-16
CH478246A (de) 1969-09-15
FR86816E (fr) 1966-04-22
GB913325A (en) 1962-12-19
GB1013997A (en) 1965-12-22
DE1183249B (de) 1964-12-10
US3325380A (en) 1967-06-13

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