US2408116A - Selenium coated elements and method of making them - Google Patents

Selenium coated elements and method of making them Download PDF

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Publication number
US2408116A
US2408116A US402103A US40210341A US2408116A US 2408116 A US2408116 A US 2408116A US 402103 A US402103 A US 402103A US 40210341 A US40210341 A US 40210341A US 2408116 A US2408116 A US 2408116A
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US
United States
Prior art keywords
selenium
metal
nickel
coated
solution
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
US402103A
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English (en)
Inventor
Hippel Arthur Von
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.)
Federal Telephone and Radio Corp
Original Assignee
Federal Telephone and Radio Corp
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
Priority to BE481454D priority Critical patent/BE481454A/xx
Priority to FR962190D priority patent/FR962190A/fr
Application filed by Federal Telephone and Radio Corp filed Critical Federal Telephone and Radio Corp
Priority to US402103A priority patent/US2408116A/en
Priority to GB16824/42A priority patent/GB569473A/en
Application granted granted Critical
Publication of US2408116A publication Critical patent/US2408116A/en
Priority to CH283551D priority patent/CH283551A/de
Priority to DEF4300A priority patent/DE973445C/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D48/00—Individual devices not covered by groups H10D1/00 - H10D44/00
    • H10D48/01—Manufacture or treatment
    • H10D48/04—Manufacture or treatment of devices having bodies comprising selenium or tellurium in uncombined form
    • H10D48/043—Preliminary treatment of the selenium or tellurium, its application to foundation plates or the subsequent treatment of the combination
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D48/00—Individual devices not covered by groups H10D1/00 - H10D44/00
    • H10D48/01—Manufacture or treatment
    • H10D48/04—Manufacture or treatment of devices having bodies comprising selenium or tellurium in uncombined form
    • H10D48/042—Preparation of foundation plates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D48/00—Individual devices not covered by groups H10D1/00 - H10D44/00
    • H10D48/01—Manufacture or treatment
    • H10D48/04—Manufacture or treatment of devices having bodies comprising selenium or tellurium in uncombined form
    • H10D48/043—Preliminary treatment of the selenium or tellurium, its application to foundation plates or the subsequent treatment of the combination
    • H10D48/0431—Application of the selenium or tellurium to the foundation plate

Definitions

  • This invention relates to processes of treatin metal surfaces and products thereof, and it comprises processes wherein metal surfaces are subject to the action of selenidingagents to form a film including a form of selenium, presumably a metal selenium compound on the surface; it further comprises processes wherein such coated surfaces are thereafter further coated with selenium, and it further comprises the products of such processes.
  • selenium metal is customarily applied by spreading the molten selenium on the metal surface or otherwise producing a smooth coating on one surface.
  • Selenimn has a very high tension and it is difilcult to wet the metal surface with the molten selenium. As a consequence the selenium layer is not uniformly spread on the disc and does not adhere firmly thereto.
  • the problem involves at least two factors. The first is that of so changing surface tension relationships between molten selenium and the metal to be coated that the selenium will spread evenly over the metal.
  • My invention is based upon the discovery that In the single figure of the drawing is shown. by way of example, a disc, partly broken away, which may be considered as a selenium rectifier disc or a photo-sensitive element made in accordance with my invention. The dimensions of the disc are exaggerated in order to more clearly illustrate the component parts.
  • This comprises a metal disc I coated with a film 2 of a metal selenium compound of the metal. On the upper surface of the disc is shown a selenium layer 3.
  • my invention in part can be looked upon as the formation of a metal-selenium film on the metal prior to the application of metallic selenium thereto with the metal "selenide acting as a bonding agent for bonding the metal to the overlying selenium coating.
  • This film also improves the surface tension relationship so that ent ways.
  • One of the most convenient is that of selenium metal adheres much more strongly to dipping the metal, or otherwise treating its surface, with aqueous solutions of selenious acid or a. selenate, to which in some cases nitric acid has been added.
  • one suitable solution (for convenience called bath 1) consists of an aqueous nitric acid solution containing, in each liter, about 252 grams of nitric acid and about 105 grams of selenious acid expressed as $802. Such a solution is approximately 4 normal in nitric acid.
  • the metal surface on which a film of the selenide is to be formed is dipped or otherwise contacted with such a solution. The time of dipping is not important, from two to ten minutes is adequate. In such a solution the metal of the surface undergoing treatment reacts with selenium ions to form a metal-selenium compound.
  • the nickel for example, a strip or disc thereof
  • the surface of the nickel is attacked by the acid in the solution and nickel ions are formed.
  • a certain amount of nitrous oxide (NO) is also liberated and the nitrous oxide reduces selenious acid present to liberate divalent selenium ions.
  • NO nitrous oxide
  • These negative ions react with the positive nickel ions to form nickel selenide, NiSe.
  • the reactions actually occurring may be somewhat more complicated than this simple explanation would indicate.
  • the nickel selenium compound is deposited on the surfaces of the nickel strip or disc exposed to the solution. Then the treated metal is withdrawn from the aqueous solution. washed and dried. It can thereafter be coated with molten selenium and the selenium layer thus provided on the metal is uniform throughout and adheres firmly to the base metal.
  • the temperature during the selenidin8" operation is not critical although I find it advantageous to use moderately elevated temperatures of about 50 C. to 60 C. when using the nitric acid-selenious acid solution just described. With the solution at 57 C. treatment must continue for a minimum time of about 10 minutes to produce the desired result. If the treatment is continued too long, a pitting of the base metal results.
  • magnesiumaluminum alloys such as that known as Dow- Metal
  • aqueous solutions containing selenious acid can be dipped in aqueous solutions containing selenious acid, thereafter washed and dried, and finally coated with metallic selenium in any convenient way.
  • This alloy a selenium compound having a gray color is formed but the actual chemical composition of such compound is not clearly understood.
  • Dow-Metal is destroyed by acids so for this metal the nitric acid is omitted. In tests it was found that a 60% S802 solution produced a satisfactory film with a two minute treatment at 21 C. and a 10% S802 solution produced a satisfactory coating in three minutes at 21 C.
  • Tests alsoindicate that the same beneficial effects can be obtained with other metals, for example, the results of treating zinc with three types of solution to give satisfactory films are I Tempera- Bath Metal Time mm 140 Minutes C. mseori-"i norm HNOQ Zn 1 21 %%8e0
  • the metal Before seleniding the surface of the metal it is advantageous to first thoroughly clean it to free it of any solid particles, grease, rust, and the like. While this canbe accomplished in any way, I find it advantageous to first wipe the metal with a cloth to free it of any solid particles, dust, etc., then degrease the metal with any suitable solvent for oils and fats, such as trichlorethylene, ethylene dichloride, and the like, then subject the metal to an -electro-cleaning operation in ways known to the art. Finally the thus treated metal can be washed in hot and cold water and pickled in hydrochloric acid solutions, for example, to remove any rust and oxidation products.
  • any suitable solvent for oils and fats such as trichlorethylene, ethylene dichloride, and the like
  • the process of coating metal surfaces with selenium which comprises the steps of treating the surface with an aqueous solution containing nitric and selenious acid to form a metal selenium compound on the surface and thereafter coating the treated surface with selenium.
  • a selenium-coated metal plate having a selenium compound of the metal formed by sub- Jecting the surface of metal to an aqueous solu- ,tion of selenious acid underlying the selenium coating.

Landscapes

  • Chemical Treatment Of Metals (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Chemically Coating (AREA)
  • Photovoltaic Devices (AREA)
US402103A 1941-07-12 1941-07-12 Selenium coated elements and method of making them Expired - Lifetime US2408116A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE481454D BE481454A (en, 2012) 1941-07-12
FR962190D FR962190A (en, 2012) 1941-07-12
US402103A US2408116A (en) 1941-07-12 1941-07-12 Selenium coated elements and method of making them
GB16824/42A GB569473A (en) 1941-07-12 1942-11-26 Selenium coated elements and method of making them
CH283551D CH283551A (de) 1941-07-12 1948-02-24 Verfahren zum Anbringen eines Selenüberzuges auf einer Metalloberfläche.
DEF4300A DE973445C (de) 1941-07-12 1950-10-01 Verfahren zur Herstellung von mit Selen bedeckten Platten aus Metall fuer Gleichrichter, Fotoelemente u. dgl.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US402103A US2408116A (en) 1941-07-12 1941-07-12 Selenium coated elements and method of making them

Publications (1)

Publication Number Publication Date
US2408116A true US2408116A (en) 1946-09-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
US402103A Expired - Lifetime US2408116A (en) 1941-07-12 1941-07-12 Selenium coated elements and method of making them

Country Status (6)

Country Link
US (1) US2408116A (en, 2012)
BE (1) BE481454A (en, 2012)
CH (1) CH283551A (en, 2012)
DE (1) DE973445C (en, 2012)
FR (1) FR962190A (en, 2012)
GB (1) GB569473A (en, 2012)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2522474A (en) * 1942-07-02 1950-09-12 Battelle Memorial Institute Treatment of zinc surfaces
US2527232A (en) * 1948-11-04 1950-10-24 Wright G Scroxton Bluing metals
US2575388A (en) * 1947-01-06 1951-11-20 Vickers Inc Electrical rectifiers
US2649409A (en) * 1943-07-30 1953-08-18 Standard Telephones Cables Ltd Electrodeposition of selenium
DE926987C (de) * 1952-06-10 1955-04-28 Falkenthal Verfahren zur Herstellung von duennen, zusammenhaengenden, homogenen, hexagonalen Selenschichten auf glatter, lichtdurch-laessiger Unterlage, z. B. auf Glas oder Quarzglas
US2822299A (en) * 1955-11-28 1958-02-04 Philips Corp Method of making a cadmium-telluride semi-conductive device
DE971697C (de) * 1948-10-01 1959-03-12 Siemens Ag Verfahren zur Herstellung von Selengleichrichtern
US2937594A (en) * 1955-05-03 1960-05-24 Harris Intertype Corp Lithographic printing
US2997409A (en) * 1959-11-04 1961-08-22 Santa Barbara Res Ct Method of production of lead selenide photodetector cells
US3130137A (en) * 1959-10-14 1964-04-21 Nippon Electric Co Manufacture of selenium rectifier cell
US3178312A (en) * 1959-01-02 1965-04-13 Santa Barbara Res Ct Solutions and methods for depositing lead selenide
DE1207508B (de) * 1957-08-01 1965-12-23 Siemens Ag Halbleiterbauelement mit sperrfreien Kontakt-elektroden und Verfahren zum Herstellen
DE1229192B (de) * 1956-10-11 1966-11-24 Standard Elektrik Lorenz Ag Verfahren zur Herstellung von Selengleichrichtern
US5089349A (en) * 1989-06-05 1992-02-18 Calgon Corporation Compositions and method for applying coatings to metallic surfaces

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1133471B (de) * 1961-08-30 1962-07-19 Licentia Gmbh Verfahren zur Herstellung von Selentrockengleichrichtern
DE1141028B (de) * 1961-09-05 1962-12-13 Licentia Gmbh Verfahren zur Herstellung von Selengleichrichtern
DE1185727B (de) * 1962-03-15 1965-01-21 Licentia Gmbh Verfahren zur Herstellung von Selengleichrichtern

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT117386B (de) * 1927-12-06 1930-04-25 Sueddeutsche Telefon App Kabel Elektrischer Wechselstromgleichrichter.
AT131780B (de) * 1930-08-07 1933-02-10 Erwin Falkenthal Lichtelektrische Zelle und Verfahren zur Herstellung derselben.
DE922896C (de) * 1938-08-16 1955-01-27 Siemens Ag Verfahren zur Herstellung eines Selengleichrichters

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2522474A (en) * 1942-07-02 1950-09-12 Battelle Memorial Institute Treatment of zinc surfaces
US2649409A (en) * 1943-07-30 1953-08-18 Standard Telephones Cables Ltd Electrodeposition of selenium
US2575388A (en) * 1947-01-06 1951-11-20 Vickers Inc Electrical rectifiers
DE971697C (de) * 1948-10-01 1959-03-12 Siemens Ag Verfahren zur Herstellung von Selengleichrichtern
US2527232A (en) * 1948-11-04 1950-10-24 Wright G Scroxton Bluing metals
DE926987C (de) * 1952-06-10 1955-04-28 Falkenthal Verfahren zur Herstellung von duennen, zusammenhaengenden, homogenen, hexagonalen Selenschichten auf glatter, lichtdurch-laessiger Unterlage, z. B. auf Glas oder Quarzglas
US2937594A (en) * 1955-05-03 1960-05-24 Harris Intertype Corp Lithographic printing
US2822299A (en) * 1955-11-28 1958-02-04 Philips Corp Method of making a cadmium-telluride semi-conductive device
DE1229192B (de) * 1956-10-11 1966-11-24 Standard Elektrik Lorenz Ag Verfahren zur Herstellung von Selengleichrichtern
DE1207508B (de) * 1957-08-01 1965-12-23 Siemens Ag Halbleiterbauelement mit sperrfreien Kontakt-elektroden und Verfahren zum Herstellen
US3178312A (en) * 1959-01-02 1965-04-13 Santa Barbara Res Ct Solutions and methods for depositing lead selenide
US3130137A (en) * 1959-10-14 1964-04-21 Nippon Electric Co Manufacture of selenium rectifier cell
US2997409A (en) * 1959-11-04 1961-08-22 Santa Barbara Res Ct Method of production of lead selenide photodetector cells
US5089349A (en) * 1989-06-05 1992-02-18 Calgon Corporation Compositions and method for applying coatings to metallic surfaces

Also Published As

Publication number Publication date
CH283551A (de) 1952-06-15
BE481454A (en, 2012)
DE973445C (de) 1960-02-18
GB569473A (en) 1945-05-25
FR962190A (en, 2012) 1950-06-02

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