US2766508A - Blocking layer for titanium oxide rectifier - Google Patents

Blocking layer for titanium oxide rectifier Download PDF

Info

Publication number
US2766508A
US2766508A US289248A US28924852A US2766508A US 2766508 A US2766508 A US 2766508A US 289248 A US289248 A US 289248A US 28924852 A US28924852 A US 28924852A US 2766508 A US2766508 A US 2766508A
Authority
US
United States
Prior art keywords
layer
titanium
rectifier
plate
partially oxidized
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
US289248A
Other languages
English (en)
Inventor
Loup Theodore E Le
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.)
General Electric Co
Original Assignee
General Electric Co
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
Application filed by General Electric Co filed Critical General Electric Co
Priority to US289247A priority Critical patent/US2766509A/en
Priority to US289248A priority patent/US2766508A/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 US2766508A publication Critical patent/US2766508A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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

  • Thisinve'ntion relates to a titanium dioxideal ternating current rectifier; more particularly, it refers to a titanium dioxide rectifier having a blocking layer applied-by electrolytic anodization.
  • a titanium dioxide rectifier is described together with a method for producing such a rectifier.
  • a titanium rectifier is produced by heat treating a titanium plate in an atmosphere containing oxygen to produce an oxide layer, further treating the titanium plate to partially reduce the oxide layer, and applying over the partially reduced oxide layer a counterelectrode composed of a metal having a high work function.
  • a titanium plate is subjected to a heat treatment' in an oxidizing, or partially oxidizing, atmosphere to produce an oxide layer over at least a portion of the titanium plate surface.
  • the partially oxidized layer is then subjected to an electrolytic anodization treat ment to provide a thin uniform blocking layer of oxide to which an overlying layer of counterelectrode metal having a high work function is then applied.
  • a base electrode 10 is composed of a titanium plate thick enough to impart rigidity to the device. Overlying all or a part of the titanium plate 10 is a'partially oxidized layer 11. Theexposed surface of the layer 11 is subjected to an electrolytic anodization treatment which results in the formation of a thin layer 12 of oxide. Overlyingall or a portion of the layer 12 is a counterelectrode layer 13 composed of a metal having a high work function.
  • the thickness of the layers 11, 12 and 13 is greatly exaggerated for purposes of clarity of illustration.
  • the layers 11 and 12 are normally less than a thousandth of an inch in thickness and the layer 13 may be of the order of a thousandth of an inch.
  • the base electrode 10 may be much thinner than it is shown in the illustration.
  • the titanium plate 10 In preparing a titanium dioxide rectifier in accordance with my invention, the titanium plate 10 must have a clean surface. This may be obtained by subjecting a plate to an abrasive process or by treatment in an acid solution. A satisfactory acid solution in which the plate may be immersed consists of 80% nitric acid and hydrofluoric acid.
  • the plate is then subjected to a heat treatment in an atmosphere containing oxygen.
  • the oxygen containing atmosphere is provided by steam
  • reducing action is provided by the hydrogen produced-in the decomposition of the water vapormolecule.
  • two atoms of reducing hydrogen are produced.
  • the steam treatment produces a layer 11. having-minute particles of titanium dispersed therethrough.
  • the layer 11 should preferably have-a thickness of the'orderof 0.0005".
  • the base electrode 10 is shown with the layer 11 coveringa portion of one surface thereof, in practice the layer. 11 covers the entire surface of the titanium base 10 since it is most easily manufactured with this construction.
  • the layer 11' is subjectedto an electrolytic anodization in order to provide a block-v ing layer. of oxide.
  • an oxide layer applied by electrolytic anodization is self-insulating.
  • no more current will flow through this portion and further oxidation, if any, will takeplace only on portions of the surface having a thinner oxide layer. This action re sul'tsin. an. oxide layer of uniform thickness over the entire surface.
  • Anodizing solutions are well known in the electrolytic art. Solutions of sodium hydroxide, potassium hydroxide, chromic: acid, ammonium hydroxide, and sul-. furic acid are all satisfactory for purposes of. applying an oxide blocking layer to the partially oxidized layer 11. I have obtained best results from the use of a sodium hydroxide solution of about 10 to 17 percent concentration.
  • the base electrode 10 is made the anode in such a solution.
  • the current density is a function of time (at constant voltage) and the back voltage of the cell is dependent on the final current density.
  • the anodization is preferably accomplished by gradually increasing the potential to about 40 volts while keeping the current at about 5 ma./cm. Under continued application of 40 volts, the current decreases to a range of 5-20 ma. on a plate 1" x
  • the anodization may be carried out with the solution at room temperature.
  • the counterelectrode 13 is applied by any method which will insure the close union of the layers 12 and 13.
  • I method of effecting a close union between the layers 12 and 13 is dependent to some extent upon the nature of the counterelectrode metal used. Certain metals may be applied in a molten state while others are best applied by vapor deposition. In general, vapor deposition is a preferred method of applying the layer 13.
  • the counterelectrode 13 is composed of a metal having a high work function.
  • Bismuth, nickel, and platinum fulfill these requirements whereas cadmium, zinc, tin, aluminum, and magnesium when used as counterelectrodes, produce a rectifier which is considerably inferior to a rectifier having a counterelectrode composed of bismuth, nickel, or
  • the partially oxidized titanium is an 11 type semi-conductor with the free titanium contributing the electron conduction.
  • the counterelectrodes of bismuth, nickel, or platinum all have missing electrons in their d shells which contribute holes for a p conduction.
  • the other metals mentioned do not have missing electrons in their d shells.
  • the term high work function includes metals having missing electrons in their at shells which contribute holes for p type conduction.
  • the deposition of the counterelectrode on the n type titanium establishes a p-n junction.
  • a thin insulating layer or a layer with fewer n or p carriers between the n type region and the p type region. This layer reduces the leakage and raises the reverse voltage of the rectifiers.
  • a rectifier made in accordance with my invention has superior high temperature stability and compares favorably with other rectifiers from the standpoint of current loading and voltage rating.
  • the method of preparing a titanium dioxide rectifier which comprises forming a partially oxidized layer on a surface of a titanium plate by heating said plate in an atmosphere containing oxygen, forming a layer of oxide on said partially oxidized surface by electrolytic anodization and applying to said oxide layer a counterelectrode metal having a high work function.
  • the method of preparing a titanium dioxide rectifier which comprises forming a partially oxidized layer on a surface of a titanium plate by heating said plate to a temperature in excess of 600 C. in an atmosphere of steam for four hours, forming an oxidized layer on said partially oxidized layer by electrolytic anodization and applying to said oxidized layer a counterelectrode metal having a high work function.
  • the method of preparing a titanium dioxide rectifier which comprises forming a partially oxidized layer on a surface of a titanium plate by heating said plate in an atmosphere containing oxygen, forming an oxidized layer on said partially oxidized layer by electrolytic anodization in an aqueous sodium hydroxide bath and applying to said oxidized layer a counterelectrode metal having a high work function.
  • the method of preparing a titanium dioxide rectifier which comprises forming a partially oxidized layer on a titanium plate by heating said plate in an atmosphere containing oxygen, forming an oxidized layer on said partially oxidized layer by electrolytic anodization in a chromic acid solution and applying to said oxidized layer a counterelectrode metal having a high work function.
  • the method of preparing a titanium dioxide rectifier which comprises forming a partially oxidized layer on the surface of a titanium plate by heating said plate in an atmosphere containing oxygen, forming an oxidized layer on said partially oxidized layer by electrolytic anodization in an ammonium hydroxide solution and applying to said oxidized layer a counterelectrode metal having a high work function.
  • the method of preparing a titanium dioxide rectifier which comprises forming a partially oxidized layer on a surface of a titanium plate by heating said plate to a temperature between 600 C. and 700 C. in an atmosphere of steam for about four hours, forming an oxidized layer on said partially oxidized layer by electrolytic anodization in sodium hydroxide solution and applying to said oxidized layer a counterelectrode composed of bismuth.

Landscapes

  • 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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Inert Electrodes (AREA)
US289248A 1952-05-22 1952-05-22 Blocking layer for titanium oxide rectifier Expired - Lifetime US2766508A (en)

Priority Applications (6)

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

Publications (1)

Publication Number Publication Date
US2766508A true US2766508A (en) 1956-10-16

Family

ID=26965538

Family Applications (2)

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

Family Applications After (1)

Application Number Title Priority Date Filing Date
US289247A Expired - Lifetime US2766509A (en) 1952-05-22 1952-05-22 Titanium dioxide rectifier

Country Status (4)

Country Link
US (2) US2766508A (is")
BE (1) BE520122A (is")
FR (1) FR1083556A (is")
GB (2) GB733267A (is")

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Families Citing this family (13)

* 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
NL246765A (is") * 1958-12-23
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
DE1266353B (de) * 1964-03-13 1968-04-18 Bbc Brown Boveri & Cie Matrixfoermige Anordnung von Oxydschichtdioden zur Verwendung als manipulierbarer Festwertspeicher oder Informationsumsetzer
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
US4394672A (en) * 1981-04-22 1983-07-19 Ford Motor Company Titanium dioxide rectifier
US4361951A (en) * 1981-04-22 1982-12-07 Ford Motor Company Method of fabricating a titanium dioxide rectifier

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1968571A (en) * 1931-10-14 1934-07-31 Gen Electric Electric current rectifier
US1985118A (en) * 1930-03-08 1934-12-18 Philips Nv Dry rectifier
US2291592A (en) * 1940-08-10 1942-07-28 Union Switch & Signal Co Electrical rectifier
US2692212A (en) * 1950-02-09 1954-10-19 Westinghouse Brake & Signal Manufacture of dry surface contact rectifiers
US2695380A (en) * 1949-08-26 1954-11-23 Int Standard Electric Corp Electric current rectifier

Family Cites Families (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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1985118A (en) * 1930-03-08 1934-12-18 Philips Nv Dry rectifier
US1968571A (en) * 1931-10-14 1934-07-31 Gen Electric Electric current rectifier
US2291592A (en) * 1940-08-10 1942-07-28 Union Switch & Signal Co Electrical rectifier
US2695380A (en) * 1949-08-26 1954-11-23 Int Standard Electric Corp Electric current rectifier
US2692212A (en) * 1950-02-09 1954-10-19 Westinghouse Brake & Signal Manufacture of dry surface contact rectifiers

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
GB733267A (en) 1955-07-06
GB736251A (en) 1955-09-07
US2766509A (en) 1956-10-16
BE520122A (is") 1955-05-27
FR1083556A (fr) 1955-01-11

Similar Documents

Publication Publication Date Title
US2766508A (en) Blocking layer for titanium oxide rectifier
US2189576A (en) Dry plate rectifier and method of producing same
US3864217A (en) Method of fabricating a semiconductor device
GB1479563A (en) Methods of anodizing articles
US3939047A (en) Method for fabricating electrode structure for a semiconductor device having a shallow junction
US2221596A (en) Method of manufacturing dry rectifiers
US3351825A (en) Semiconductor device having an anodized protective film thereon and method of manufacturing same
US2349622A (en) Manufacture of rectifiers of the blocking layer type
US3201667A (en) Titanium dioxide capacitor and method for making same
US2163393A (en) Selenium rectifier having light metal carrier electrodes
US1925307A (en) Electric condenser
US3285836A (en) Method for anodizing
US3010885A (en) Method for electrolytically etching and thereafter anodically oxidizing an essentially monocrystalline semiconductor body having a p-n junction
US3393091A (en) Method of producing semiconductor assemblies
US3254390A (en) Electrolyte solution of
US3848260A (en) Electrode structure for a semiconductor device having a shallow junction and method for fabricating same
US2266922A (en) Manufacture of alternating current rectifiers
US2610386A (en) Semiconductive cell
US3882000A (en) Formation of composite oxides on III-V semiconductors
US2244771A (en) Composite conductor and contact between conductors
US2383311A (en) Contact for copper oxide rectifiers
US3588627A (en) Leadless solid electrolyte tantalum capacitor
US3299326A (en) Solid electrolytic capacitor with porous sintered electrode of thermally pretreated anodizable metal particles
US3284252A (en) Method of manufacturing semiconductor systems comprising cadmium chalcogenide semiconductors
US2215890A (en) Electrical rectifier