US2766509A - Titanium dioxide rectifier - Google Patents
Titanium dioxide rectifier Download PDFInfo
- 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
- Authority
- US
- United States
- Prior art keywords
- layer
- hours
- titanium dioxide
- titanium
- rectifier
- 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 28
- 239000004408 titanium dioxide Substances 0.000 title claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 230000001603 reducing effect Effects 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 230000006870 function Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000011282 treatment Methods 0.000 description 8
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 241000282461 Canis lupus Species 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 230000000903 blocking effect 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
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting 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
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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
- 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.
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)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Inert Electrodes (AREA)
Description
Oct 1956 T, E. LE LOUP ET AL 2,766,509
TITANIUM DIOXIDE RECTIFIER Filed May 22, 1952 Inv entor's:
Theodor e E. Le Loup,
John C. Mari mace,
by 4. TheirA-tt-orney.
United States Patent 70 TITANIUM DIOXIDE RECTIFIER Theodore Le Loup and John 'C. Marinace, Schenectady, N. Y., assignors to General Electric Company, a corporation of New York Application May 22,- 1952, Serial No. 289,247
3 Claims. (Cl. 29-2523) 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;
It is an object of this invention to provide a titanium dioxide alternating current rectifier of the plate type which has a high degree of temperature stability and in other respects compares favorably with rectifiers utilizing copper oxide and selenium.
Briefly stated, in accordance with one embodiment of this invention, 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.
In the drawing 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. In Fig. 1, 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. Overlying the layer 11 is 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. For example, the layer 11 may have a thickness of about 0.0005".
In Fig. 2, the base electrode 10, partially reduced oxide layer 11, and counterelectrode 12 are the same as in Fig. 1. However, 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.
In fabricating the rectifier, 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.
to a heat treatment in an atmosphere containing oxygen in order to produce the thin layer 11 of titanium dioxide. While the layer 11- is shown as covering only a portion of one surface of the base electrode 10, it is frequently easier in actual practice to cover the entire surface of the electrode 10 with the oxide layer. 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. may also be used but in this event the rate of oxidation is fairly rapid, and it is difficult .to maintain close control over the thickness of the oxide layer. At temperatures above 800 C. treatment for just a few minutes is sufficient to provide an oxide layer of the necessary thickness while at temperatures below 600 C. the time of .treatment may run to many, many hours. Within the range 600 C. to 800 C. 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.
Two methods of treatment with reference to the layer 11 have been described. On the one hand, the layer is applied by heat treatment in an atmosphere of air followed by heat treatment in an atmosphere of hydrogen. On the other hand, 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.
Rectifiers made in accordance with our teaching possess excellent stability under high temperature conditions and in other respects, such as current loading and voltage rating, are on a par with selenium rectifiers.
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, we aim in the appended claims to cover all such equivalent variations as come within the true spirit and scope of the foregoing disclosure.
What we 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 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.
2. 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.
3. 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.
References Cited in the file of this patent UNITED STATES PATENTS 2,721,966 Jenkins et a1 Oct. 25, 1955 FOREIGN PATENTS 483,088 Great Britain Apr. 12, 1938 OTHER REFERENCES Electronic Engineering, October 1946, pp. 313-315.
Claims (1)
1. 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, PLATINUM AND NICKEL.
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 |
---|---|
US2766509A true US2766509A (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 Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US289248A Expired - Lifetime US2766508A (en) | 1952-05-22 | 1952-05-22 | Blocking layer for titanium oxide rectifier |
Country Status (4)
Country | Link |
---|---|
US (2) | US2766508A (en) |
BE (1) | BE520122A (en) |
FR (1) | FR1083556A (en) |
GB (2) | GB733267A (en) |
Cited By (11)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL246765A (en) * | 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)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL34153C (en) * | 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 (en) * | 1949-08-26 | |||
US2692212A (en) * | 1950-02-09 | 1954-10-19 | Westinghouse Brake & Signal | Manufacture of dry surface contact rectifiers |
-
1952
- 1952-05-22 US US289248A patent/US2766508A/en not_active Expired - Lifetime
- 1952-05-22 US US289247A patent/US2766509A/en not_active Expired - Lifetime
-
1953
- 1953-05-18 GB GB13887/53A patent/GB733267A/en not_active Expired
- 1953-05-18 GB GB13888/53A patent/GB736251A/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 (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 |
Cited By (11)
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 |
---|---|
BE520122A (en) | 1955-05-27 |
GB736251A (en) | 1955-09-07 |
FR1083556A (en) | 1955-01-11 |
GB733267A (en) | 1955-07-06 |
US2766508A (en) | 1956-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2766509A (en) | Titanium dioxide rectifier | |
US2682101A (en) | Oxidation protected tungsten and molybdenum bodies and method of producing same | |
US2973466A (en) | Semiconductor contact | |
US2805370A (en) | Alloyed connections to semiconductors | |
US2279187A (en) | Alternating electric current rectifier of the selenium type | |
US2995475A (en) | Fabrication of semiconductor devices | |
US2349622A (en) | Manufacture of rectifiers of the blocking layer type | |
US2334554A (en) | Method of producing blocking layer devices | |
US3201667A (en) | Titanium dioxide capacitor and method for making same | |
US3447958A (en) | Surface treatment for semiconductor devices | |
US2699522A (en) | Titanium dioxide rectifier | |
US2124306A (en) | Electrical device | |
US2610386A (en) | Semiconductive cell | |
US2163393A (en) | Selenium rectifier having light metal carrier electrodes | |
US2823149A (en) | Process of forming barrier layers in crystalline bodies | |
US2887633A (en) | Titanium-dioxide rectifiers | |
US2692212A (en) | Manufacture of dry surface contact rectifiers | |
US2826725A (en) | P-n junction rectifier | |
US1936792A (en) | Method of making copper oxide rectifiers for high voltage application | |
US2162362A (en) | Asymmetrical conductor | |
US2554237A (en) | Rectifier | |
US2981646A (en) | Process of forming barrier layers | |
US2465228A (en) | Liquid treatment of contact surfaces for copper oxide rectifiers | |
US2749596A (en) | Method of making titanium dioxide rectifiers | |
US1968571A (en) | Electric current rectifier |