US2181494A - Light-sensitive electric device - Google Patents

Light-sensitive electric device Download PDF

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Publication number
US2181494A
US2181494A US87231A US8723136A US2181494A US 2181494 A US2181494 A US 2181494A US 87231 A US87231 A US 87231A US 8723136 A US8723136 A US 8723136A US 2181494 A US2181494 A US 2181494A
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US
United States
Prior art keywords
thallium
cell
sulphide
thallous
cells
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Expired - Lifetime
Application number
US87231A
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English (en)
Inventor
Foster C Nix
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AT&T Corp
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Bell Telephone Laboratories Inc
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Publication date
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Priority to US87231A priority Critical patent/US2181494A/en
Priority to FR823551D priority patent/FR823551A/fr
Priority to GB17706/37A priority patent/GB479825A/en
Application granted granted Critical
Publication of US2181494A publication Critical patent/US2181494A/en
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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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/16—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 cuprous oxide or cuprous iodide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • This invention is based upon the discovery that contiguous layers of thallium and thallium properly treated with sulphur provide a photo- E. M. F. cell having improved characteristics as compared with those of other known photo- E. M. F. cells.
  • the thallium is treated with sulphur to produce thallous sulphide and this isthe form of cell to which the following description primarily relates.
  • a metal base may be provided for the thallium and a transparent conducting film for the thallous sulphide. The thallous sulphide is then exposed to light through the transparent film and contacts made to the cell through the transparent film and the metal base.
  • This cell has been found to give a current response from a tungsten filament lamp or similar light source having a maximum spectral response in the red or infrared which response is many times that. obtained from any other known photo-E. M. F. cell. This cell also has other advantages which will be discussed more fully below.
  • One method of preparing such cells is by evaporating a layer of thallium upon a metallic base member, which may be, for example, nickel, removing the surface oxidation from the thallium layer by any suitable means such as by heating it in vacuum, exposing the pure thallium surface to a glow discharge inhydrogen sulphide (H28) to form a film of thallous sulphide on the thallium surface, cooling to room temperature, and then applying to the thallous sulphide surface a thin, semi-transparent auxiliary electrode of sputtered metal such as platinum.
  • thin discs of pure thallium may be used instead of evaporating the thin layer of thallium on a metal backing.
  • the sulphurization process maybe carried out by vaporizing pure flowers of sulphur instead of subjecting the thallium to a glow discharge in His gas.
  • Fig. 1 is a schematic diagram of a photo-E. M. F. cell of the type to which this invention is directed; 5
  • Fig. 2 is'a perspective view of one of these cells in a suitable protecting cover
  • Fig. 3 is an exploded view of the cell of Fig. 2;
  • Fig. 4 is a side view, partly in cross-section, of the cell shown in Fig. 2; 10
  • Fig. 5 is a side view, partly in cross-section of a cell having a different casing from that of the cell shown in Figs. 2 to 4; and Figs. 6 to 9, inclusive, show characteristic curves of photo-E. M. F. cells of the kind de- 15 scribed above and illustrated in Figs. 1 to 5.
  • any suitable rigid, conducting metal such as, for example, nickel or copper which serves as a conducting mechanical support for a layer ll of thallium which is partially sulphurized to form a thin film l2 of thallous sul- 25 phide upon which is sputtered a semi-transparent conducting film l3 of a suitable metallic material such as platinum.
  • the only members necessary to produce the electromotiveiorce are the thallium layer ll 30 and the thallous sulphide film l2 as the other two members are merely for the purpose of making electrical contact to the cell. It was observed in a large number of cells that a photo- E. M. F. effect was obtained by simply making contact with a platinum-pointed needle at points on the illuminated thallous sulphide surface before the sputtering of the platinum auxiliary electrode 13 upon this surface. These observations clearly show that the presence of the sputtered film is not essential to the observed photo- E. M. F. effect.
  • Fig. 1 indicates the direction of flow of'the photoelectrons.
  • An impedance such as, for example, that represented diagrammatically 50 by the load Il may be placed in the external circuit to control the current in that circuit.
  • the thallium layer may be a disc punched out of a thin sheet or it may be a thin film evaporated upon the metal base member lll.
  • the thallium in disc form rather than to evaporate a thin layer of thallium upon a base member.
  • Thallium which in its commercial form is usually in sticks or pellets, must be purified before it is suitable for use in-these processes.
  • the impurities "which are essentially oxide coatings, were removed by melting in vacuum and allowing the molten metal to flow through several constrictions about 0.03 inch in diameter, thus effectively straining out much of the oxide from, the thallium and leaving it in a clean condition.
  • the thallium in this form was melted in a reducing flame and allowed to flow into smooth fiat bars, about 5 of an inch thick. These bars were then rolled out into sheets about 0.021 inch thick from which the discs used in making the cells were punched. Care must be taken in rolling out the thallium sheets to avoid developing a flaky surface.
  • thallium had a bright, metallic luster it was ready for sulphurization.
  • One method employed for sulphurizing the thallium was to expose it to a glow discharge in an atmosphere of hydrogen sulphide gas (HzS) at a temperature of about 260 C. This temperature is not critical as sensitive cells have been made when the temperature was as low as C. and as high as 280 C. These temperatures are both below and above the allotropic transformation point of thallium which is about 230 G. However, up to the present time a temperature of 260-140 C. has produced the most sensitive cells.
  • HzS hydrogen sulphide gas
  • This temperature may be maintained by any suitable means, such as, for example, a cylindrical coil or furnace around the containing tube,
  • the glow discharge took'place between two perforated aluminum plates about A; inch apart and located about 4 inch from the disc and parallel thereto. The distance between the plates and the distance of the plates from the disc was chosen so as to bring the disc just within the region of the glow discharge so that a heavy concentration of sulphur atoms will be produced near the thallium.
  • the H25 gas was allowed to flow through the tube continuously at a rate which would maintain a gas pressure of about 1.3 millimeters of mercury.
  • the voltage impressed on the perforated aluminum plates was about 390 volts. This gave a discharge current of 29 milliamperes for the given pressure and size of plates. The time of exposure to the discharge for best results was about three minutes.
  • a second method of sulphurizing the thallium consists in vaporizing flowers of sulphur (preferably degassed) to produce sulphur vapor and allowing the sulphur vapor to pass into the process tube wherein the thallium disc or layer is mounted.
  • the sulphur may be boiled in vacuum and vaporized to remove all impurities.
  • the side tube in which the purified sulphur was placed was joined to the process tube at a point intermediate the ends thereof.
  • the process tube was evacuated and then the thallium disc or layer was heated to a temperature of 260:10 C. and this temperature maintained throughout the sulphurization process.
  • the sulphur was then heated to a high enough temperature to cause it to boil and the sulphur vapor thus allowed to flow into the proc-' ess tube and sulphurize the thallium, producing a film of thallous sulphide.
  • Some typical cells which have been made by one or the other of the processes stated above have been tested to' determine chemically the composition of the thin film produced by the sulphurization. In all cases the film was found to comprise TlzS (thallous sulphide). Possibly some additional sulphur may i be present in the film, either as free sulphur or in the combined state as thallic sulphide ('IlS).
  • the evacuated system After sulphurization the evacuated system is allowed to cool to room temperature at which time the unit is removed and receives a thin auxiliary electrode of sputtered platinum. Gold is also a suitable substance for this auxiliary electrode.
  • the semi-transparent conducting auxiliary electrode l3 serves as the front electrode, and the metallic supporting disc I constitutes the back electrode.
  • the completed cells may then be placed in an evacuated glass vessel in order to protect them from changes in atmospheric conditions. The cells have proven to be quite stable over an observation period of several months.
  • Vacuum is not necessary to the successful operation of the completed photo-E. M. F. cell herein described, but some container or casing is, necessary in order to protect the cell from changes in atmospheric conditions such, as, for example, an excess of water vapor in the air.
  • a casing may be evacuated if desired Two typical casings will be described below.
  • Figs. 2, 3 and 4 show by way ofexample a thallous sulphide photo-E. M. F. cell in a typical molded container.
  • assembled cell Fig.3 is an exploded view of the cell and Fig. 4 shows the cell in cross-section.
  • the complete assembly comprises a cell 'unit member I5, a front cover l6 and a back cover I! together with means such as the screws 18 for connecting the parts together.
  • a casing of molded ceramic material I! on which may be placed a brass cover plate 20 having an opening 2
  • the brass plate 20 is fastened to the ceramic material l9 by any suitable means such as the screws 22 and nuts 23.
  • the plate 20 may be slightly concave so that it forces the elements of the cell unit in close contact'relation with each other.
  • a contact lead 24 may be connected to the screw 22 by nuts 23 and 25 to form a front contact lead.
  • the screws 22 also act as spacers in the assembly of the complete cell.
  • the rear contact is made by a screw 26 whichmakes electrical contact, through the ceramic material IS, with the base -member Ill;
  • the contact lead 21 may be connected to the screw 26 by any suitable means, such as by nuts 28 and 29..
  • a thin coating 30 of a wax-like substance may be provided for the transparent metallic layer l3. This coating 30 is placed in the aperture 2
  • the front cover I6 for the cell unit may com prise a casing 3
  • is adapted to completely enclose the cell unit IS with the exception of the ends of the screws 22 and is provided with threaded holes 33 to receive the screws H3.
  • the back cover-member l1 comprises a casingwhich is preferably of the same material as that of the front casing 3
  • the contact lead 21 is adapted to be connected to the screw 36 and the contact lead Fig. 2 shows the completely the inner surface of the back cover I! press the cell unit l5 close to the glass 32.
  • Fig. 5 shows a thallous sulphide cell having a metal container.
  • This container comprises a metal cylinder 40, of suitable material such as brass, having a shoulder 4
  • a brass ring 42 rests on this shoulder and is fastened to the cylinder 40 by any suitable means such as solder.
  • disc 32 which is sealed into the cylinder by any suitable means such as by Picien, a commercial form of sealing wax.
  • a hard rubber ring 43 having holes or indentations 44 to fit around the heads of the screws 22 and hold the unit IS in place in the cylinder 40, is placed against the The leads 24 and 21 extend through the wax for contact purposes.
  • a hole 46 may be drilled in the cylinder 40 before the cell is assembled so that when the wax is poured in there is a pas.- sage for the escape of air. This hole is sealed after the wax is poured by any convenient means such as solder. In the metal case cell, the coating 30 of Ozokerite or other wax may not be necessary.
  • Fig. 6 shows the characteristic short-circuit current versus per cent il1umina-- -tion of a-cell at -180 C'., the unfiltered light standard being taken as 100% and filters being used to produce the other intensities incident upon the cell.
  • Fig. 7 shows. the open circuit voltage versus per cent illumination of a typical one of these cells. This characteristic departs from the linear form at higher percentages of illumination but the curvature is not serious, Many cells have been made in which this characteristic is also linear.
  • the curves shown in Fig. 6 and Fig. '7 are typical of results obtained on a large number of cells.
  • the short-circuit current yield from cells of 4 Against the ring 42 is placed the glass energy emission in the region of red and infrared such as, for example, an incandescent tungsten lamp.
  • This short-circuit yield of 5000 microamperes per lumen may be compared with a yield from cuprous oxide front and back wall cells of 150 and 15 microamperes per lumen respectively, and a yield from selenium photo- E. M. F. cells of about 450 microamperes per lumen.
  • Curve I of Fig. 8 shows a typical equi-energy spectral response curve of a thallous sulphide photo-E. M. F. cell.
  • Curve 2 of this figure shows a typical transmission curve of thallous sulphite film on glass. This latter curve is included in order to show the relationship between optical a direct comparison to be made between this characteristic of the two cells.
  • the thallous sulphide photo- E. M. F. cell possesses vastly superior properties at high frequencies to the selenium photo-E. M. F. cell or for that matter to any other known photo-E. M. F. cell.
  • the cells have internal resistances of from 20 to 1500 ohms but this resistance appears to be substantially independent of the intensity of illumination. The cells cannot therefore be considered as photoconducting.
  • a photo-E. M. F. cell comprising a metal base a thallium member adjacent to and in contact with said metal base, and a film of thallous sulphide on the face of said thallium member remote from the base.
  • a photo-E. M. F. cell comprising a metal base, a thallium layer deposited on said base so as to be integral therewith, and a film of thallous sulphide on said thallium layer.
  • a photo-E. M. F. cell comprising a metal base, a thallium layer on said base, a film of thallous sulphide on said thallium layer, and a semi-transparent electrically conducting layer of a noble metal on said thallous sulphide.
  • a photo-E. M. F. cell comprising a base of conducting metal, a thallium layer on said base, a film of thallous sulphide on said thallium layer, and a thin film of a noble metal on said thallous sulphide.
  • the method of preparing a thallous sulphide photo-E. M. F. cell comprising the steps of sulphurizing a layer of thallium until the surface of the thallium attains a dark gray color, and applying a. thin light-conducting layer of a noble metal to said sulphurized layer.
  • the method of preparing a thallous sulphide cell comprising the steps of evaporating a film of thallium upon a metallic member, exposing the thallium surface to a glow discharge in H2S gas to form a film of thallous sulphide on said thallium surface, cooling to room temperature, and applying to said thallous sulphide surface a. thin semi-transparent electrode of a noble metal.
  • 7. The method of preparing a thallous sulphide cell comprising the steps of sulphurizing a thallium disc by exposure to sulphur vapor in a temperature of approximately 260 C. to form a film of thallous sulphide on said, thallium surface, cooling to room temperature, and applying to said thallous sulphide surface. a thin semi-transparent electrode of a noble metal.
  • the method of preparing a thalloussulphide cell comprising the step of sulphurizing a thallium member by exposure to sulphur vapor at a temperature within the range from 250 C. to 270 C. to form a film of thallous sulphide on said thallium.
  • the method of preparing a thallous su1- :phide cell comprising the steps of sulphurizinga thallium member by exrmsure to sulphur vapor at a temperature within the range from 250 C. to 270 C. to form a film of thallous sulphide on said thallium surface, and then cooling to room temperature.
  • the method of preparing a thallous sulphide cell comprising the steps of sulphurizing a thallium member by exposure to sulphur vapor at a temperature within the range from 250 C. to 270 C. to form a film of thallous sulphide on said thallium surface, cooling to room temperature, and sputtering on said thallous sulphide surface a thin semi-transparent electrode of a noble metal.
  • a photo-E. M. F. cell comprising a metal base, a thallium member adjacent to and in contact with said metal base, and a film of a material comprising thallium and sulphur on the face of said thallium member remote from the base.
  • A. photo-E. M. F. cell comprising a metal base, a thallium member adjacent to and in contact with said metal base, and a film of a sulphide of thallium on the face of said thallium member remote from the base.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Electromagnetism (AREA)
  • Manufacturing & Machinery (AREA)
  • Hybrid Cells (AREA)
  • Photovoltaic Devices (AREA)
US87231A 1936-06-25 1936-06-25 Light-sensitive electric device Expired - Lifetime US2181494A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US87231A US2181494A (en) 1936-06-25 1936-06-25 Light-sensitive electric device
FR823551D FR823551A (fr) 1936-06-25 1937-06-24 Ferfectionnement aux cellules photo-voltaïques
GB17706/37A GB479825A (en) 1936-06-25 1937-06-25 Photo-voltaic cells

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2773158A (en) * 1953-01-27 1956-12-04 Electrol Lab & Sales Co Housing structure for photocell or the like and method of making the same
US2875308A (en) * 1953-04-25 1959-02-24 Soc Nouvelle Outil Rbv Radio Photoresistive cells
US2931847A (en) * 1945-07-18 1960-04-05 Robert K Dahlstrom Photoelectric cell mounting
US3178621A (en) * 1962-05-01 1965-04-13 Mannes N Glickman Sealed housing for electronic elements
US4785338A (en) * 1979-08-09 1988-11-15 Canon Kabushiki Kaisha Semi-conductor I.C. element
WO2020160359A1 (fr) * 2019-01-31 2020-08-06 Alta Devices, Inc. Dispositif énergétique à utiliser dans des dispositifs électroniques

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2931847A (en) * 1945-07-18 1960-04-05 Robert K Dahlstrom Photoelectric cell mounting
US2773158A (en) * 1953-01-27 1956-12-04 Electrol Lab & Sales Co Housing structure for photocell or the like and method of making the same
US2875308A (en) * 1953-04-25 1959-02-24 Soc Nouvelle Outil Rbv Radio Photoresistive cells
US3178621A (en) * 1962-05-01 1965-04-13 Mannes N Glickman Sealed housing for electronic elements
US4785338A (en) * 1979-08-09 1988-11-15 Canon Kabushiki Kaisha Semi-conductor I.C. element
WO2020160359A1 (fr) * 2019-01-31 2020-08-06 Alta Devices, Inc. Dispositif énergétique à utiliser dans des dispositifs électroniques
US11356052B2 (en) 2019-01-31 2022-06-07 Utica Leaseco, Llc Energy device for use in electronic devices

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Publication number Publication date
FR823551A (fr) 1938-01-22
GB479825A (en) 1938-02-11

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