US2121603A - Method of producing selenium rectifiers - Google Patents

Method of producing selenium rectifiers Download PDF

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Publication number
US2121603A
US2121603A US136900A US13690037A US2121603A US 2121603 A US2121603 A US 2121603A US 136900 A US136900 A US 136900A US 13690037 A US13690037 A US 13690037A US 2121603 A US2121603 A US 2121603A
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selenium
rectifier
layer
reducing
rectifiers
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Expired - Lifetime
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US136900A
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Lotz Albert
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CBS Corp
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Westinghouse Electric and Manufacturing Co
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    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/06—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising selenium or tellurium in uncombined form other than as impurities in semiconductor bodies of other materials
    • H01L21/10—Preliminary treatment of the selenium or tellurium, its application to the foundation plate, or the subsequent treatment of the combination
    • H01L21/105—Treatment of the surface of the selenium or tellurium layer after having been made conductive

Definitions

  • 'Ihe invention relates to rectiers, and especially to the selenium, dry-plate type of rectifiers.
  • An object of the invention is to reduce the value of back current in selenium rectii'lers.
  • Selenium has been utilized as the effective layer in dry plate rectiiiers because it can withstand a comparatively high blocking potential, for example, 2O volts per cell.
  • One of the diiiiculties, however, with the selenium type of rectifier has been the fact that there is a very considerable so-called back currentihat flows in the blockingdirection with this high potential. This back current is a maximum immediately after the rectifier is produced and decreases in time to smaller values with the aging of the rectifier in use.
  • the magnitude of. the back current is ⁇ undesirably too large in value, even after the rectifiers have been in use for some time.
  • the invention provides means for reducing the value of this back current by preferably pretreating the selenium layer of the rectifier with a reducing agent before assembling the rectifier.
  • This treatment may consist of a vaporization of the reducing means in a vacuum or by wet treatment of the selenium.
  • reducing agents organic materials are preferably used. Certain inorganic materials, such as, for example, stannic salts, sulphur dioxide, and hydroxylamine (NH2.OH) may be utilized. Of. the organic materials, those which are preferably effective are generally known as photographic developers, such, i'or example, as pyrogallol, hydroquinine and 40 others.
  • Suitable materials are phenol and phenol derivatives as well as resorcin; hydrazin and its derivatives', for example, methol hydrazin or phenol hydrazon; certain unsaturated compounds, for example, oleic acids and several unsaturated carbonates; nitrogen or sulphur containing organic compounds, for example, quinoline, aniline and its derivativesdimethol aniline, methol aniline and thiophen.
  • a layer of ductile metal on the selenium layer of the rectifier.
  • This metal can be sprayed on, for example, in a liquid condition, or by vaporization in a vacuum.
  • the metal most desirable is cadmium.
  • the drawing illustrates the selenium effective 10 layer of the rectifier with the preferred cadmium layer thereon, as well as listing the materials that have been found suitable for reducing agents.
  • the treatment of the selenium layer with one or more of the reducing agents or their 15 compounds or derivatives, as above specified somewhat decreases the forward directional or transmission current, yet this decrease is not of vital importance.
  • the magnitude of 20 the back current is reduced to usually small values, for example, 20 milliamperes at 20 volts blocking potential and not infrequently a resistance relationship of 1 to 800and better istattained.

Description

June 21, 1938. A, LOTZ 2,121,603
METHOD oF PRODUCING SELENIUM RECTIFIERS Filed April 14, y1937' 460o/warn WiTNEssEs; l INVENTOR Patented June 2l, 1938 UNITED "STATES PATENT OFFICE METHOD F PRODUCING SELENIUM RECTIFIERS Application April 14,
1937, Serial N0. 136.900
In Germany May 30, 193'6 2 Claims.
'Ihe invention relates to rectiers, and especially to the selenium, dry-plate type of rectifiers.
An object of the invention is to reduce the value of back current in selenium rectii'lers.
Other objects and advantages of the invention will be apparent from the following description, taken in conjunction. with the accompanying drawing in which the singlei figure is a crosssection through a selenium rectier plate and its contact layer.
Selenium has been utilized as the effective layer in dry plate rectiiiers because it can withstand a comparatively high blocking potential, for example, 2O volts per cell. One of the diiiiculties, however, with the selenium type of rectifier has been the fact that there is a very considerable so-called back currentihat flows in the blockingdirection with this high potential. This back current is a maximum immediately after the rectifier is produced and decreases in time to smaller values with the aging of the rectifier in use. The magnitude of. the back current, however, when high blocking potential is applied is` undesirably too large in value, even after the rectifiers have been in use for some time. y
The invention provides means for reducing the value of this back current by preferably pretreating the selenium layer of the rectifier with a reducing agent before assembling the rectifier. This treatment may consist of a vaporization of the reducing means in a vacuum or by wet treatment of the selenium. As reducing agents, organic materials are preferably used. Certain inorganic materials, such as, for example, stannic salts, sulphur dioxide, and hydroxylamine (NH2.OH) may be utilized. Of. the organic materials, those which are preferably effective are generally known as photographic developers, such, i'or example, as pyrogallol, hydroquinine and 40 others. Other suitable materials are phenol and phenol derivatives as well as resorcin; hydrazin and its derivatives', for example, methol hydrazin or phenol hydrazon; certain unsaturated compounds, for example, oleic acids and several unsaturated carbonates; nitrogen or sulphur containing organic compounds, for example, quinoline, aniline and its derivativesdimethol aniline, methol aniline and thiophen.
After the selenium has been treated with the reducing agent, it is preferred to place a layer of ductile metal on the selenium layer of the rectifier. This metal can be sprayed on, for example, in a liquid condition, or by vaporization in a vacuum. The metal most desirable is cadmium.
The drawing illustrates the selenium effective 10 layer of the rectifier with the preferred cadmium layer thereon, as well as listing the materials that have been found suitable for reducing agents. Although the treatment of the selenium layer with one or more of the reducing agents or their 15 compounds or derivatives, as above specified, somewhat decreases the forward directional or transmission current, yet this decrease is not of vital importance. In each case it is possible to attain a condition such that the magnitude of 20 the back current is reduced to usually small values, for example, 20 milliamperes at 20 volts blocking potential and not infrequently a resistance relationship of 1 to 800and better istattained.
The above described treatment of selenium rectifier plates with reducing materials may be applied if necessary to plates of the type in which the selenium layer has already been covered with a metal coating.
I claim as my invention:
1. The method of reducing the value of. the back current in a selenium rectifier which comprises treating the selenium with an organic reducing agent.
2. The method of reducing the value of the back current in a selenium rectifier which com- -prises treating the selenium with any one or more of the following reducing agents:v pyrogallol,
hydroquinine, phenol, resorcin, hydrazin, oleic 40 acids, unsaturated carbonates, quinoline, aniline, thiophen, stannic salts, sulphur dioxide, and hydroxylamine.
ALBERT LOTZ.
US136900A 1936-05-30 1937-04-14 Method of producing selenium rectifiers Expired - Lifetime US2121603A (en)

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2443878A (en) * 1943-02-22 1948-06-22 Hartford Nat Bank & Trust Co Method of manufacturing selenium cells
US2446238A (en) * 1944-11-11 1948-08-03 Fansteel Metallurgical Corp Selenium rectifier plate
US2446239A (en) * 1944-11-11 1948-08-03 Fansteel Metallurgical Corp Selenium rectifier disk
US2446237A (en) * 1944-11-11 1948-08-03 Fansteel Metallurgical Corp Selenium rectifier
US2446465A (en) * 1944-11-11 1948-08-03 Selenium rectifier
US2446466A (en) * 1944-11-11 1948-08-03 Fansteel Metallurgical Corp Blocking layer rectifier
US2471898A (en) * 1947-04-10 1949-05-31 Vickers Inc Reclamation of selenium rectifier cells
US2488369A (en) * 1943-12-15 1949-11-15 Westinghouse Electric Corp Selenium rectifier
US2493241A (en) * 1944-11-11 1950-01-03 Fansteel Metallurgical Corp Dry plate selenium rectifier
US2510361A (en) * 1944-04-06 1950-06-06 Hartford Nat Bank & Trust Co Method of producing selenium rectifiers
US2524270A (en) * 1945-09-27 1950-10-03 Sylvania Electric Prod Selenium rectifier
DE963538C (en) * 1953-03-30 1957-05-09 Licentia Gmbh Method of manufacturing selenium rectifiers
DE966879C (en) * 1953-02-21 1957-09-12 Standard Elektrik Ag Process for cleaning and / or removal of semiconductor material, in particular germanium and silicon substances
US2828453A (en) * 1955-06-15 1958-03-25 Westinghouse Brake & Signal Selenium rectifiers
DE1031428B (en) * 1955-06-07 1958-06-04 Siemens Ag Process for the production of selenium rectifiers and arrangement for the implementation of this process
DE971458C (en) * 1951-11-05 1959-01-29 Licentia Gmbh Process for the production of asymmetrically conductive systems accommodated in cup-shaped recesses
US2875103A (en) * 1956-06-07 1959-02-24 Westinghouse Brake And Sigual Method of manufacturing selenium rectifiers
US2880497A (en) * 1955-12-13 1959-04-07 Harry H Hall Method of making pressure measuring gage means
US2888620A (en) * 1956-04-30 1959-05-26 Westinghouse Air Brake Co High resistance semiconductor cells
US3077386A (en) * 1958-01-02 1963-02-12 Xerox Corp Process for treating selenium

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2443878A (en) * 1943-02-22 1948-06-22 Hartford Nat Bank & Trust Co Method of manufacturing selenium cells
US2488369A (en) * 1943-12-15 1949-11-15 Westinghouse Electric Corp Selenium rectifier
US2510361A (en) * 1944-04-06 1950-06-06 Hartford Nat Bank & Trust Co Method of producing selenium rectifiers
US2446238A (en) * 1944-11-11 1948-08-03 Fansteel Metallurgical Corp Selenium rectifier plate
US2446239A (en) * 1944-11-11 1948-08-03 Fansteel Metallurgical Corp Selenium rectifier disk
US2446237A (en) * 1944-11-11 1948-08-03 Fansteel Metallurgical Corp Selenium rectifier
US2446465A (en) * 1944-11-11 1948-08-03 Selenium rectifier
US2446466A (en) * 1944-11-11 1948-08-03 Fansteel Metallurgical Corp Blocking layer rectifier
US2493241A (en) * 1944-11-11 1950-01-03 Fansteel Metallurgical Corp Dry plate selenium rectifier
US2524270A (en) * 1945-09-27 1950-10-03 Sylvania Electric Prod Selenium rectifier
US2471898A (en) * 1947-04-10 1949-05-31 Vickers Inc Reclamation of selenium rectifier cells
DE971458C (en) * 1951-11-05 1959-01-29 Licentia Gmbh Process for the production of asymmetrically conductive systems accommodated in cup-shaped recesses
DE966879C (en) * 1953-02-21 1957-09-12 Standard Elektrik Ag Process for cleaning and / or removal of semiconductor material, in particular germanium and silicon substances
DE963538C (en) * 1953-03-30 1957-05-09 Licentia Gmbh Method of manufacturing selenium rectifiers
DE1031428B (en) * 1955-06-07 1958-06-04 Siemens Ag Process for the production of selenium rectifiers and arrangement for the implementation of this process
US2828453A (en) * 1955-06-15 1958-03-25 Westinghouse Brake & Signal Selenium rectifiers
US2880497A (en) * 1955-12-13 1959-04-07 Harry H Hall Method of making pressure measuring gage means
US2888620A (en) * 1956-04-30 1959-05-26 Westinghouse Air Brake Co High resistance semiconductor cells
US2875103A (en) * 1956-06-07 1959-02-24 Westinghouse Brake And Sigual Method of manufacturing selenium rectifiers
US3077386A (en) * 1958-01-02 1963-02-12 Xerox Corp Process for treating selenium

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