US2766508A - Blocking layer for titanium oxide rectifier - Google Patents
Blocking layer for titanium oxide rectifier Download PDFInfo
- 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
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 31
- 230000000903 blocking effect Effects 0.000 title description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 25
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- 238000002048 anodisation reaction Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000011282 treatment Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 241000282461 Canis lupus Species 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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 H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
Description
Oct. 16, 1956 E. LE LOUP 2,766,508
BLOCKING LAYER FOR TITANIUM OXIDE RECTIFIER Filed May 22, 1952 Ih'vehtor: Theodore E. Le Loup, y" p? 4. 7%
His Attorney.
BLOCKING LAYERFOR TITANIUM OXIDE RECTIFIER Theodore E. Le Loup, Schenectady, N. Y., assignor to General Electric Company, a corporation of New York Application May 22, 1952, Serial No. 289,248
8 Claims. (Cl. 29-253) Thisinve'ntion relates toa titanium dioxideal ternating current rectifier; more particularly, it refers to a titanium dioxide rectifier having a blocking layer applied-by electrolytic anodization.
In the copending application of Le Loup and Marinace, SerialNo. 289,247, filed May 22, 1952, which is assigned to the same assignee as the present invention, a titanium dioxide rectifier is described together with a method for producing such a rectifier. In accordance with this copending application, 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.
It is an object of this invention to provide a titanium dioxide rectifier having a titanium dioxide blocking layer which confers improved rectification characteristics upon the rectifier.
It is another object of this invention to provide a method whereby a uniform blocking layer'may be incorporated in a titanium dioxide rectifier.
Briefly stated, in accordance with one embodiment'of this invention, 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.
The drawing is a sectional view illustrating one embodiment of my invention. 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. Y
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.
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 high melting States Patent ,Ece
2. point of titanium enables this treatment to be carried out at an extremely'high temperature. However, above 800 C. the rate of oxidation becomes a-little difiicult to controldue to the fact that it takes place rather rapidly. Below 600 C. the rate of oxidation is quite slow necessitating prolonged treatment. I prefer to carry out the oxidation between 600 C. and 800 C., within which range the. time of treatment varies from about two to five hours. However, it must be emphasized that there is nothing critical about the temperature and time of treatment. If the treatment temperaure is above 800 C., for example 1200" C., the time of treatment may be of the order of a few minutes. If the treatment temperature is below 600 C., for example 300 C., the time of treatment is many hours or. even ays.
Air and steam are both satisfactory oxidizing atmos. pheres but of? the two steam is preferable. Itis necessary that the layer 11 contain some reduced titanium dispersed therethrough. Consequently if the layer 11 is provided by an air oxidation treatment, there must also be a heat treatment in a. reducing atmosphere, such as hydrogen, to providethe free titanium necessary for rectificationaction. This may be provided by a heat treatment at the same temperature as the oxidation treatment in an atmosphere of hydrogen.
If. the oxygen containing atmosphere is provided by steam,,reducing action is provided by the hydrogen produced-in the decomposition of the water vapormolecule. For each atom of oxidizing oxygen, two atoms of reducing hydrogen are produced. Thus the steam treatment producesa layer 11. having-minute particles of titanium dispersed therethrough. The layer 11 should preferably have-a thickness of the'orderof 0.0005".
While 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.
After the reduction step the layer 11' is subjectedto an electrolytic anodization in order to provide a block-v ing layer. of oxide. It is well known that an oxide layer applied by electrolytic anodization is self-insulating. Thus, after the oxide layer on a particular portion of the layer 11 hasbeen built up to a particular thickness, 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.
. After the anodization step has been completed, the counterelectrode 13 is applied by any method which will insure the close union of the layers 12 and 13. The
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.
It has been previously mentioned that 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
platinum. A possible explanation for this behavior lies in the fact that 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. used herein, 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. When the plates are anodized after a partial oxidation, there is 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.
Of the satisfactory counterelectrodes previously enumerated, I prefer to use bismuth as this element has a low melting point which makes it easy to handle and a thin layer of bismuth allows the plate 10 to are through at a weak spot without destroying the rectifying properties of the device. 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.
While the present invention has been described with reference to particular embodiments thereof, it will be understood that numerous modifications may be made by those skilled in the art without actually departing from the invention. Therefore, I aim in the appended claims to cover all such equivalent variations as come within the true spirit and scope of the foregoing disclosure.
What I claim as new and desire to secure by Letters Patent of the United States is:
l. 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.
2. 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 Accordingly, as
type
in a steam atmosphere, 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.
3. 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.
4. 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.
5. The method of claim 4 wherein the concentration of the sodium hydroxide solution is between 10% and 17% and the anodization is carried out at room temperature.
6. 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.
7. 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.
8. 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.
References Cited in the file of this patent UNITED STATES PATENTS 1,968,571 Rupp '-s- July 31, 1934 1,985,118 Van Geel et al Dec. 18, 1934 2,291,592 Dowling July 28, 1942 2,692,212 Jenkins et al Oct. 19, 1954 2,695,380 Mayer et al. Nov. 23, 1954
Claims (1)
1. 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.
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 (en) | 1952-05-22 | 1953-05-21 | |
FR1083556D FR1083556A (en) | 1952-05-22 | 1953-05-22 | New titanium dioxide straightener |
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 |
---|---|
US2766508A true US2766508A (en) | 1956-10-16 |
Family
ID=26965538
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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 |
Family Applications Before (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) | US2766509A (en) |
BE (1) | BE520122A (en) |
FR (1) | FR1083556A (en) |
GB (2) | GB736251A (en) |
Cited By (2)
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)
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 (en) * | 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 (en) * | 1964-03-13 | 1968-04-18 | Bbc Brown Boveri & Cie | Matrix-shaped arrangement of oxide layer diodes for use as manipulable read-only memory or information converter |
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 |
US4394672A (en) * | 1981-04-22 | 1983-07-19 | Ford Motor Company | Titanium dioxide rectifier |
Citations (5)
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)
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 |
-
1952
- 1952-05-22 US US289247A patent/US2766509A/en not_active Expired - Lifetime
- 1952-05-22 US US289248A patent/US2766508A/en not_active Expired - Lifetime
-
1953
- 1953-05-18 GB GB13888/53A patent/GB736251A/en not_active Expired
- 1953-05-18 GB GB13887/53A patent/GB733267A/en not_active Expired
- 1953-05-21 BE BE520122D patent/BE520122A/xx unknown
- 1953-05-22 FR FR1083556D patent/FR1083556A/en not_active Expired
Patent Citations (5)
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)
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 |
---|---|
BE520122A (en) | 1955-05-27 |
GB736251A (en) | 1955-09-07 |
FR1083556A (en) | 1955-01-11 |
US2766509A (en) | 1956-10-16 |
GB733267A (en) | 1955-07-06 |
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 | |
US2822606A (en) | Titanium oxide rectifier and method for manufacturing same | |
GB1479563A (en) | Methods of anodizing articles | |
US3939047A (en) | Method for fabricating electrode structure for a semiconductor device having a shallow junction | |
US2711496A (en) | Lead peroxide rectifiers and method of making the same | |
US2221596A (en) | Method of manufacturing dry rectifiers | |
US2349622A (en) | Manufacture of rectifiers of the blocking layer type | |
US3201667A (en) | Titanium dioxide capacitor and method for making same | |
US2334554A (en) | Method of producing blocking layer devices | |
US2163393A (en) | Selenium rectifier having light metal carrier electrodes | |
US3848260A (en) | Electrode structure for a semiconductor device having a shallow junction and method for fabricating same | |
US1925307A (en) | Electric condenser | |
US3010885A (en) | Method for electrolytically etching and thereafter anodically oxidizing an essentially monocrystalline semiconductor body having a p-n junction | |
US3285836A (en) | Method for anodizing | |
US3393091A (en) | Method of producing semiconductor assemblies | |
US3254390A (en) | Electrolyte solution of | |
US2610386A (en) | Semiconductive cell | |
US3882000A (en) | Formation of composite oxides on III-V semiconductors | |
US3079536A (en) | Film-forming metal capacitors | |
US2244771A (en) | Composite conductor and contact between conductors | |
US3299326A (en) | Solid electrolytic capacitor with porous sintered electrode of thermally pretreated anodizable metal particles | |
US2215890A (en) | Electrical rectifier | |
US3321389A (en) | Method of anodically etching aluminum foils at elevated temperatures in an electrolyte including chloride and sulfate ions |