US2766509A - Titanium dioxide rectifier - Google Patents

Titanium dioxide rectifier Download PDF

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Publication number
US2766509A
US2766509A US289247A US28924752A US2766509A US 2766509 A US2766509 A US 2766509A US 289247 A US289247 A US 289247A US 28924752 A US28924752 A US 28924752A US 2766509 A US2766509 A US 2766509A
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United States
Prior art keywords
layer
hours
titanium dioxide
titanium
rectifier
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Expired - Lifetime
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US289247A
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English (en)
Inventor
Loup Theodore E Le
John C Marinace
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General Electric Co
Original Assignee
General Electric Co
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Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Priority to US289248A priority Critical patent/US2766508A/en
Priority to US289247A priority patent/US2766509A/en
Priority to GB13888/53A priority patent/GB736251A/en
Priority to GB13887/53A priority patent/GB733267A/en
Priority to BE520122D priority patent/BE520122A/xx
Priority to FR1083556D priority patent/FR1083556A/fr
Application granted granted Critical
Publication of US2766509A publication Critical patent/US2766509A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • H01L21/34—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 not provided for in groups H01L21/18, H10D48/04 and H10D48/07, with or without impurities, e.g. doping materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B7/00—Machines or devices designed for grinding plane surfaces on work, including polishing plane glass surfaces; Accessories therefor
    • B24B7/10—Single-purpose machines or devices
    • B24B7/16—Single-purpose machines or devices for grinding end-faces, e.g. of gauges, rollers, nuts, piston rings
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
    • H10D62/875—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being semiconductor metal oxide, e.g. InGaZnO
    • 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
    • Y10T29/00—Metal working
    • Y10T29/43—Electric condenser making

Definitions

  • the present invention relates to an improved alternating current rectifying device and method for producing such a device; more particularly; the invention relates to a rectifying device employing titanium dioxide as the rectifying medium.
  • Plate rectifiers of the copper oxide and selenium type have been known for many years. Other substances which are good semi-conductors have been known but in general their use for rectification purposes has not measured up in quality to plate rectifiers utilizing copper oxide or selenium;
  • a rectifier comprises a base electrode composed of titanium which has a layer of titanium dioxide in which titanium metal is incorporated, overlying at least a portion of the titanium surface, and a metal electrode of high work function or one having a higher work func tion than the titanium dioxide overlying the layer of titanium dioxide.
  • Fig. 1 is a sectional view showing the layers of a rectifier produced in accordance with this invention.
  • Fig. 2 is a sectional view of an alternative embodiment of the invention.
  • a base electrode 10 composed of titanium metal, is subjected to a treatment which produces a partially-reduced oxide layer 11 over all, or a portion of, its surface.
  • a ⁇ counterelectrode layer 12 composed of a metal or alloy having a higher work function than layer 11.
  • the base electrode is made thick enough to provide structural rigidity for the rectifier.
  • layers 11 and 12 is greatly exaggerated in the drawing in order to achieve clarity of illustration. In actual practice these layers may be less than a thousandth of an inch in thickness.
  • the layer 11 may have a thickness of about 0.0005".
  • Fig. 2 the base electrode 10, partially reduced oxide layer 11, and counterelectrode 12 are the same as in Fig. 1.
  • Fig. 2 includes a blocking layer 11a which is applied to the partially reduced oxide layer 11.
  • the layer 11a may be composed of a semiconducting oxide such as an oxide of germanium, silicon, or titanium. These oxides may be applied by vapor deposition in a vacuum.
  • the layer 1111 may also be produced by further oxidation of the surface portion of the partially reduced oxide layer 11 as by heating the layer 11 in the presence of free oxygen.
  • the titanium plate forming the base electrode 10 is provided with a clean surface. This may be accomplished by an abrasive process or by immersing the plate in an acid cleaning solution. A solution of 80% nitric acid and 20% hydrofluoric acid is satisfactory for this purpose. After the base electrode 10 has been provided with a clean surface, it is subjected The thickness of the.
  • Titanium has a very high melting point and consequently the oxidation step may be carried out at a high temperature in order to promote rapid oxidation. I prefer temperatures in excess of 600 C. for this purpose and preferably within the range of 600 C. [to 800 C. However, there is nothing critical about this temperature range. Lower temperatures may be used but the time of treatment to produce a satisfactory oxide layer must be increased. Temperatures above 800 C.
  • the rate of oxidation is fairly rapid, and it is difficult .to maintain close control over the thickness of the oxide layer.
  • the time of .treatment may run to many, many hours.
  • oxidation in air for a period of 2' to 4 hours is suflicient.
  • the layer 11 of titanium dioxide must be partially reduced. This reduction may be carried out by maintaining the temperature at the same level that was used for oxidation but changing the atmosphere to a reducing atmosphere, preferably provided by hydrogen. Continuing the heat treatment for four to eight hours in a hydrogen atmosphere is normally sufiicient to bring about :the partial reduction of the oxide layer 11.
  • Air oxidation is satisfactory for the purposes of this invention but we prefer to have the oxidation take place in an atmosphere of steam.
  • Treatment in a steam atmosphere at a temperature of about 650 C. for about 4 hours is suflicient to produce a partially reduced oxide layer having a thickness of approximately 0.005", which is satisfactory for our purposes.
  • the layer is applied by heat treatment in an atmosphere of air followed by heat treatment in an atmosphere of hydrogen.
  • the layer is applied by heat treatment in an atmosphere of steam. Both treatments produce a layer 11 which has a certain amount of reduced titanium metal in it. In .the case of the steam treatment, this is brought about by the fact that the breakdown of the water vapor molecule to provide the oxygen for oxidation results in the production of a hydrogen molecule which has a reducing effect. Rectification requires that the layer 11 contain some titanium in the reduced state.
  • the counterelectrode 12 is composed of a metal having a work function greater than that of layer 11 such as bismuth, nickel, or platinum. Metals having a Work function lower than that of layer 11, such as cadmium, zinc, tin, aluminum, and magnesium, are not satisfactory counterelectrodes as the resulting rectifier would have inferior rectification properties.
  • the partially reduced oxide layer is an n type semiconductor and, as previously explained, the free titanium associated with the layer 11 contributes the electron conduction.
  • the counterelectrodes of bismuth, nickel, or platinum all having missing electrons in their d shells which contribute holes for p type conduction. Counterelectrodes of materials having these characteristics are satisfactory for our purpose. Accordingly, the term metals of high Work function is intended to include metals which have missing electrons in their d shells and which have p type conduction.
  • the counterelectrode 12 may be applied by any method which insures a union between the layers 11 (or 11a) and 12. Application from the molten state will accom- Patented Oct. 16, 1956 plish this it carefully performed and vapor deposition is also satisfactory. Bismuth lends itself readily to vapor deposition and for this reason we prefer to utilize this metal as a counterelectrode.
  • the method of preparing a titanium dioxide rectifier which comprises oxidizing at least one surface of a titanium plate by heating it in air for from four hours at 600 C. to two hours at 800 C., reducing the resulting oxide surface by heating said plate in a hydrogen atmosphere for from eight hours at 600 C. to four hours at 800 C. and coating said reduced surface layer with a counterelectrode metal of work function greater than that of said reduced surface layer, said counterelectrode metal being selected from the group consisting of bismuth, p1atinum and nickel.
  • the method of preparing a titanium dioxide rectifier which comprises partially oxidizing at least one surface of a titanium plate in a steam atmosphere for about four hours at about 600 C. and coating the partially oxidized surface with a counterelectrode metal of work function greater than that of said partially oxidized surface, said counterelectrode metal being selected from the group consisting of bismuth, platinum and nickel.
  • the method of preparing a titanium dioxide rectifier which comprises oxidizing a surface of a titanium plate by heating said plate in air for from four hours at 600 C. to two hours at 800 C., reducing the surface of the resulting oxide layer by heating said plate in a hydrogen atmosphere for a period of from four to eight hours at a temperature of about 600 C. and coating the reduced surface of said oxide layer with a counterelectrode metal having a work function greater than that of said reduced surface, said counterelectrode metal being selected from the group consisting of bismuth, platinum and nickel.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Inert Electrodes (AREA)
US289247A 1952-05-22 1952-05-22 Titanium dioxide rectifier Expired - Lifetime US2766509A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US289248A US2766508A (en) 1952-05-22 1952-05-22 Blocking layer for titanium oxide rectifier
US289247A US2766509A (en) 1952-05-22 1952-05-22 Titanium dioxide rectifier
GB13888/53A GB736251A (en) 1952-05-22 1953-05-18 Improvements in and relating to titanium oxide rectifiers
GB13887/53A GB733267A (en) 1952-05-22 1953-05-18 Improvements in and relating to titanium dioxide rectifiers
BE520122D BE520122A (enrdf_load_stackoverflow) 1952-05-22 1953-05-21
FR1083556D FR1083556A (fr) 1952-05-22 1953-05-22 Nouveau redresseur à bioxyde de titane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US289248A US2766508A (en) 1952-05-22 1952-05-22 Blocking layer for titanium oxide rectifier
US289247A US2766509A (en) 1952-05-22 1952-05-22 Titanium dioxide rectifier

Publications (1)

Publication Number Publication Date
US2766509A true US2766509A (en) 1956-10-16

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US289247A Expired - Lifetime US2766509A (en) 1952-05-22 1952-05-22 Titanium dioxide rectifier
US289248A Expired - Lifetime US2766508A (en) 1952-05-22 1952-05-22 Blocking layer for titanium oxide rectifier

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US289248A Expired - Lifetime US2766508A (en) 1952-05-22 1952-05-22 Blocking layer for titanium oxide rectifier

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US (2) US2766509A (enrdf_load_stackoverflow)
BE (1) BE520122A (enrdf_load_stackoverflow)
FR (1) FR1083556A (enrdf_load_stackoverflow)
GB (2) GB736251A (enrdf_load_stackoverflow)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2826725A (en) * 1953-11-10 1958-03-11 Sarkes Tarzian P-n junction rectifier
US2940941A (en) * 1953-05-26 1960-06-14 R daltqn
US2942134A (en) * 1955-03-16 1960-06-21 Bendix Aviat Corp Gap bridging material
US2978618A (en) * 1959-04-13 1961-04-04 Thomas E Myers Semiconductor devices and method of making the same
US3139754A (en) * 1961-06-15 1964-07-07 Sylvania Electric Prod Electronic vacuum gauge
US3310685A (en) * 1963-05-03 1967-03-21 Gtc Kk Narrow band emitter devices
US3384879A (en) * 1964-03-13 1968-05-21 Bbc Brown Boveri & Cie Diode-matrix device for data storing and translating purposes
US3391309A (en) * 1963-07-15 1968-07-02 Melpar Inc Solid state cathode
US3502953A (en) * 1968-01-03 1970-03-24 Corning Glass Works Solid state current controlled diode with a negative resistance characteristic
US4361951A (en) * 1981-04-22 1982-12-07 Ford Motor Company Method of fabricating a titanium dioxide rectifier
US4385966A (en) * 1980-10-07 1983-05-31 Bell Telephone Laboratories, Incorporated Fabrication of thin film resistors and capacitors

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL246765A (enrdf_load_stackoverflow) * 1958-12-23
US3264707A (en) * 1963-12-30 1966-08-09 Rca Corp Method of fabricating semiconductor devices
US3337429A (en) * 1964-05-28 1967-08-22 Union Carbide Corp Solid electrolytic capacitor and process therefor
US4394672A (en) * 1981-04-22 1983-07-19 Ford Motor Company Titanium dioxide rectifier

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB483088A (en) * 1936-10-13 1938-04-12 Franz Rother Improvements in and relating to barrier plane rectifying cells and photo-electric cells
US2721966A (en) * 1950-06-22 1955-10-25 Westinghouse Brake & Signal Manufacture of dry surface contact rectifiers

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL34153C (enrdf_load_stackoverflow) * 1930-03-08 1934-10-23 Philips Nv
US1955564A (en) * 1931-10-14 1934-04-17 Gen Electric Electric current rectifier
US2291592A (en) * 1940-08-10 1942-07-28 Union Switch & Signal Co Electrical rectifier
BE497748A (enrdf_load_stackoverflow) * 1949-08-26
US2692212A (en) * 1950-02-09 1954-10-19 Westinghouse Brake & Signal Manufacture of dry surface contact rectifiers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB483088A (en) * 1936-10-13 1938-04-12 Franz Rother Improvements in and relating to barrier plane rectifying cells and photo-electric cells
US2721966A (en) * 1950-06-22 1955-10-25 Westinghouse Brake & Signal Manufacture of dry surface contact rectifiers

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2940941A (en) * 1953-05-26 1960-06-14 R daltqn
US2826725A (en) * 1953-11-10 1958-03-11 Sarkes Tarzian P-n junction rectifier
US2942134A (en) * 1955-03-16 1960-06-21 Bendix Aviat Corp Gap bridging material
US2978618A (en) * 1959-04-13 1961-04-04 Thomas E Myers Semiconductor devices and method of making the same
US3139754A (en) * 1961-06-15 1964-07-07 Sylvania Electric Prod Electronic vacuum gauge
US3310685A (en) * 1963-05-03 1967-03-21 Gtc Kk Narrow band emitter devices
US3391309A (en) * 1963-07-15 1968-07-02 Melpar Inc Solid state cathode
US3384879A (en) * 1964-03-13 1968-05-21 Bbc Brown Boveri & Cie Diode-matrix device for data storing and translating purposes
US3502953A (en) * 1968-01-03 1970-03-24 Corning Glass Works Solid state current controlled diode with a negative resistance characteristic
US4385966A (en) * 1980-10-07 1983-05-31 Bell Telephone Laboratories, Incorporated Fabrication of thin film resistors and capacitors
US4361951A (en) * 1981-04-22 1982-12-07 Ford Motor Company Method of fabricating a titanium dioxide rectifier

Also Published As

Publication number Publication date
US2766508A (en) 1956-10-16
GB736251A (en) 1955-09-07
GB733267A (en) 1955-07-06
BE520122A (enrdf_load_stackoverflow) 1955-05-27
FR1083556A (fr) 1955-01-11

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