US3322516A - Method of coating p-type germanium with antimony, lead or alloys thereof by electrodeposition and product thereof - Google Patents

Method of coating p-type germanium with antimony, lead or alloys thereof by electrodeposition and product thereof Download PDF

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Publication number
US3322516A
US3322516A US349182A US34918264A US3322516A US 3322516 A US3322516 A US 3322516A US 349182 A US349182 A US 349182A US 34918264 A US34918264 A US 34918264A US 3322516 A US3322516 A US 3322516A
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United States
Prior art keywords
antimony
lead
type germanium
layer
alloys
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.)
Expired - Lifetime
Application number
US349182A
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English (en)
Inventor
Minjer Clara Henderina De
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US Philips Corp
North American Philips Co Inc
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US Philips Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/34—Electroplating: Baths therefor from solutions of lead
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
    • H01L21/2885—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition using an external electrical current, i.e. electro-deposition
    • H10P14/47—
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/923—Physical dimension
    • Y10S428/924—Composite
    • Y10S428/926—Thickness of individual layer specified
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12528—Semiconductor component
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12681—Ga-, In-, Tl- or Group VA metal-base component
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12701—Pb-base component

Definitions

  • the invention relates to a method of coating p-type germanium with a layer consisting of antimony, lead or alloys thereof by electrodeposition and to the products obtained by this method.
  • the invention provides a method by which a complete coating of p-type germanium with the above metals is possible.
  • a thin layer of antimony is deposited, also electrolytically, in a thickness of approximately 0.1-1 at that cathode potential at which the saturation current of antimony is reached but at which no gas development occurs.
  • a bath consisting of an aqueous solution which contains per liter 15-19 g. of potassium antimonyl tartrate, 15-52 g. of citric acid and 375-195 g. of sodium citrate, at room temperature and at a cathode potential of approximately --850 to 1000 mv. with respect to a standard hydrogen electrode.
  • a layer of antimony is to be deposited on p-type germanium, this may be carried out by means of any known electrolyte after the flash of black antimony is deposited.
  • the electrolyte used for providing the flash of black antimony may be chosen for the purpose, in which case the cathode potential must be increased by approximately 200 to 3'50 rnv. after the flash is deposited. For depositing thicker layers of antimony, however, this flash-bath is less suitable.
  • Strips of germanium having the dimensions 20 x 2 x 0.25 mm. which were of the p-type by doping by means of indium in a quantity of 3.5 atoms per cm. with a resistivity of approximately 1 ohm cm. were sawed out of a single crystal in the [UH-orientation, lapped with Carborundum powder and then pickled for 14 seconds in a mixture of 5 ml. of HNO (d. 1.4), 10 ml. of HF 50%, and 5 ml. of ethanol.
  • a thin layer of indium was deposited electrolytically on one of the sides of the strips and a copper wire was connected with silver paste.
  • the side of the strip to which the copper wire was connected, and the copper wire itself, were coated with a layer of nitrocellulose lacquer.
  • a platinum strip was used as the anode.
  • the potential was adjusted via a Haber-Luggin capillary and a saturated calomel electrode by means of a potentiostat.
  • the electrolysis was carried out at 20 C.
  • the potential was connected at -600 mv. (with respect to a standard hydrogen electrode), then rapidly brought to 850 mv., maintained at this value for one minute, then connected back to -600 mv. and maintained at this value for one minute also. This is shown in the E-i diagram of the drawing.
  • the strips were removed from the bath, rinsed, and then a part was coated electrolytically with lead and the remainder with an alloy of lead and antimony.
  • the lead bath had the following composition per liter of solution in water.
  • the alloying bath contained per liter of solution 3 g. of antimony as antimony fiuoborate or as Sb O and 72 g. of tartaric acid in addition to the above substances.
  • the anodes consisted of lead.
  • the cathodic current density was 4 a./dm.
  • the bath temperature was maintained at 20 C.
  • the alloy deposit contained approximately 3% of Sb.
  • a method of providing a coating selected from the group consisting of antimony, lead and mutual alloys thereof on p-type germanium comprising first electrolytically depositing on the surface of said p-type germanrum a layer of a thickness of about 0.11,u of black antimony, said electrodeposition being carried out at a cathode potential at which the saturation current of antimony is reached but at which no gas is evolved, and then electrolytically depositing on said layer of black antimony an outer layer of a metal selected from the group consisting of lead, gray antimony and mutual alloys of said metal.
  • a method of claim 2 characterized in that the pH of the solution is adjusted at a value above 6.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US349182A 1963-03-05 1964-03-03 Method of coating p-type germanium with antimony, lead or alloys thereof by electrodeposition and product thereof Expired - Lifetime US3322516A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL289818 1963-03-05

Publications (1)

Publication Number Publication Date
US3322516A true US3322516A (en) 1967-05-30

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US349182A Expired - Lifetime US3322516A (en) 1963-03-05 1964-03-03 Method of coating p-type germanium with antimony, lead or alloys thereof by electrodeposition and product thereof

Country Status (5)

Country Link
US (1) US3322516A (enExample)
DE (1) DE1273954B (enExample)
FR (1) FR1383653A (enExample)
GB (1) GB1064274A (enExample)
NL (1) NL289818A (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4216071A (en) * 1977-03-04 1980-08-05 Energietechnik GmbH Studiengesellschaft fur Energie-Umwandlung- , -Fortleitung und -Anwendung Electrodeposition cell
US4311769A (en) * 1979-02-21 1982-01-19 Andreev Oleg M Mercury contact
CN101235526B (zh) * 2007-11-01 2010-08-18 华侨大学 电镀低锑铅合金的镀液及其配制方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2603693A (en) * 1950-10-10 1952-07-15 Bell Telephone Labor Inc Semiconductor signal translating device
CA608181A (en) * 1960-11-08 F. Smart Clarence Antimony plating bath

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2753299A (en) * 1953-04-23 1956-07-03 Bell Telephone Labor Inc Electroplating with antimony
US2817629A (en) * 1953-10-23 1957-12-24 Gen Motors Corp Antimony plating bath

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA608181A (en) * 1960-11-08 F. Smart Clarence Antimony plating bath
US2603693A (en) * 1950-10-10 1952-07-15 Bell Telephone Labor Inc Semiconductor signal translating device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4216071A (en) * 1977-03-04 1980-08-05 Energietechnik GmbH Studiengesellschaft fur Energie-Umwandlung- , -Fortleitung und -Anwendung Electrodeposition cell
US4311769A (en) * 1979-02-21 1982-01-19 Andreev Oleg M Mercury contact
CN101235526B (zh) * 2007-11-01 2010-08-18 华侨大学 电镀低锑铅合金的镀液及其配制方法

Also Published As

Publication number Publication date
DE1273954B (de) 1968-07-25
FR1383653A (fr) 1964-12-24
NL289818A (enExample)
GB1064274A (en) 1967-04-05

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