US2060905A - Asymmetrical conductor - Google Patents
Asymmetrical conductor Download PDFInfo
- Publication number
- US2060905A US2060905A US13888A US1388835A US2060905A US 2060905 A US2060905 A US 2060905A US 13888 A US13888 A US 13888A US 1388835 A US1388835 A US 1388835A US 2060905 A US2060905 A US 2060905A
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- US
- United States
- Prior art keywords
- chlorine
- copper
- atmosphere
- oxide
- oxidizing
- 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
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- 239000004020 conductor Substances 0.000 title description 3
- 239000000460 chlorine Substances 0.000 description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 29
- 229910052801 chlorine Inorganic materials 0.000 description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 229910052802 copper Inorganic materials 0.000 description 27
- 239000010949 copper Substances 0.000 description 27
- 230000001590 oxidative effect Effects 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 11
- 229940112669 cuprous oxide Drugs 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- -1 specifically Inorganic materials 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 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
- H01L21/16—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising cuprous oxide or cuprous iodide
- H01L21/161—Preparation of the foundation plate, preliminary treatment oxidation of the foundation plate, reduction treatment
- H01L21/164—Oxidation and subsequent heat treatment of the foundation plate
-
- 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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- 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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
Definitions
- This invention relates to the manufacture of devices that oder a greater resistance to current flow in one direction therethrough than in the reverse direction, and, more particularly, to such 5 devices of the copper-cuprous oxide type.
- An object of this invention is to improve the method of manufacture of copper-cuprous oxide rectifier-s.
- Another object is to increase the rectification ratio of copper-cuprous oxide rectiflers.
- a feature of this invention comprises providing in the oxidizing atmosphere in which the rectifier disc or unit is formed a small amount of a halogen, specifically, chlorine.
- the oxidizing atmosphere in which the copper blank is heated to form a layer of cuprous oxide thereon contains a small amount of chlorine ⁇
- the chlorine may be contained in the oxygen or in a mixture of oxygen and nitrogen supplied to the furnace; or may be added to the oxidizing atmosphere during the heat treatment of the copper blank by being liberated from a suitable chlorine compound, for instance, cupric or cuprous chloride.
- Figs. l, 2 and 3 show cross-sections of furnaces in which asymmetrical conductors may be manufactured in accordance with this invention.
- Fig. 4 shows a cross-sectional view of a coppercuprous oxide rectifier manufactured in accordance with the invention.
- copper-cuprous oxide rectiers may be manufactured by placing copper blanks in an oxidizing atmosphere at about 1000 C., leaving them therein for a predetermined length of time, for example, six to eight minutes,
- the atmosphere in which the copper blank is oxidized is caused to contain a small amount of a halogen, specically, chlorine.
- a pair of copper blanks Ill, I0, annular in shape, are supported on and in a trapezoidal cut II in a supporting rod I2, carried at its end portions I3 by suitable ledges Il on the walls I5 of a furnace I6, which may be an electric furnace.
- the chamber I1 is maintained, preferably, at a temperature of about 1000 C. while a gas containing oxygen is introduced therein through inlet or port I8.
- An outlet is provided at I9, whereby there is a continuous flow of the oxidizing agent through the 5 chamber and over the blanks to be oxidized.
- the gas introduced into the furnace contains a small quantity of a halogen, specifically, chlorine. Chlorine in amounts ranging from .015 to .1% by volume has 10 been added with good results.
- the chlorine may be present in the oxidizing. atmosphere throughout the period during which the blanks are being oxidized, or only during the latter part thereof.
- copper blanks 15 have been oxidized in atmospheres in which .05% chlorine was present during the last two minutes of'the oxidizing period; or in which .02 to .05% chlorine was present during the last four minutes 4of the oxidizing period; or in which .015% 20 chlorine was present during the entire oxidizing period, for example, eight minutes.
- each blank I0 Upon subsequent cooling by quenching, or cooling to an intermediate temperature and quench.- ing, and removal of cupric oxide in accordance 25 with known practice, each blank I0 presents a cross-section such as shown by Fig. 4, wherein the mother copper 20 has an integral layer of cuprous Y oxide 2I.
- the blanks I0 may be initially provided with a film of copper chloride, and, thereafter, oxidized at about 1000 C. in an atmosphere containing oxygen or oxygen and nitrogen, only.
- the chloride compound decompos'es '35 to provide the free element chlorine.
- a dish or other receptacle 22 containing cuprous or cupric chloride 23 may be placed in the furnace, as shown by Fig. 2, during the oxidation process, as a source of chlorine, the oxidizing 40 atmosphere being supplied through the port I8.
- the method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere containing about .015 to .1% chlorine by volume.
- the method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank' in an oxidizing atmosphere, said atmosphere for a portion of the time containing .02 to .05% chlorine by volume.
- an electrically conductive device comprising a body of copper having a layer of cuprous oxide thereon, which comprises placing the copper body and a source of chlorine in an oxidizing atmosphere at an oxidizing temperature ⁇ to form an oxide on the copper body, said chlorine source adding about .015 to .1% chlorine by volume to said atmosphere, and thereafter cooling said body.
- an electrically conductive device comprising a copper body having a layer of cuprous oxide thereon, which comprises placing the copper body and a chloride in an oxidizing atmosphere at an oxidizing and chlorine-liberating temperature to form a layer of oxide on the body, said chloride adding about .015 to .1% chlorine by volume to said atmosphere.
- a conductive device comprising a copper body having a layer of oxide that has been formed thereon by heating the copper body in an oxidizing atmosphere containing about .015 to .1% chlorine by volume.
- the method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere for about six to eight minutes, said atmosphere containing about .05% chlorine by volume for the last two minutes.
- the method of manufacture of an electrically conductive device comprises a copper body having a layer of cuprous oxide thereon, that comprises coating the copper body with copper chloride, placing it in an oxidizing atmosphere at a temperature to decompose the chloride to add chlorine to the atmosphere to about .015 to .1% by volume, forming an oxide on said body,
- an electrically conductive device comprising a copper body having a layer of cuprous oxide thereon, that comprises placing the copper body and a body of copper chloride in an oxidizing atmosphere at a temperature to decompose the chloride to add chlorine in the atmosphere to about .015 to .1% by volume. forming an oxide on said body, and thereafter cooling said body.
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Thermal Sciences (AREA)
- Conductive Materials (AREA)
Description
Patented Nov. 1'47, 1936 PATENT OFFICE ASYMltIETRICAL CONDUCTOR George 0. Smith, Bloomfield. N. J., assignor to Bell Telephone Laboratories, Incorporated, New York, N. Y., a corporation of New York Application March 30,1935, Serial No. 13,888
14 Claims. (Cl. 175-366) This invention relates to the manufacture of devices that oder a greater resistance to current flow in one direction therethrough than in the reverse direction, and, more particularly, to such 5 devices of the copper-cuprous oxide type.
An object of this invention is to improve the method of manufacture of copper-cuprous oxide rectifier-s.
Another object is to increase the rectification ratio of copper-cuprous oxide rectiflers.
A feature of this invention comprises providing in the oxidizing atmosphere in which the rectifier disc or unit is formed a small amount of a halogen, specifically, chlorine.
In accordance with this invention, the oxidizing atmosphere in which the copper blank is heated to form a layer of cuprous oxide thereon contains a small amount of chlorine` The chlorine may be contained in the oxygen or in a mixture of oxygen and nitrogen supplied to the furnace; or may be added to the oxidizing atmosphere during the heat treatment of the copper blank by being liberated from a suitable chlorine compound, for instance, cupric or cuprous chloride.
A more complete understanding of this invention will be obtained from the detailed description which follows, read with reference to the appended drawing, wherein:
Figs. l, 2 and 3 show cross-sections of furnaces in which asymmetrical conductors may be manufactured in accordance with this invention; and
Fig. 4 shows a cross-sectional view of a coppercuprous oxide rectifier manufactured in accordance with the invention.
It is known that copper-cuprous oxide rectiers may be manufactured by placing copper blanks in an oxidizing atmosphere at about 1000 C., leaving them therein for a predetermined length of time, for example, six to eight minutes,
and thereafter, cooling them in a suitable quenching medium or allowing them to cool slowly in an atmosphere maintained at about 500-600 C. until the latter temperature is reached, and thereafter, cooling them in a suitable quenching medium.
In accordance with this invention, the atmosphere in which the copper blank is oxidized is caused to contain a small amount of a halogen, specically, chlorine.
As indicated by Fig. 1, a pair of copper blanks Ill, I0, annular in shape, are supported on and in a trapezoidal cut II in a supporting rod I2, carried at its end portions I3 by suitable ledges Il on the walls I5 of a furnace I6, which may be an electric furnace. The chamber I1 is maintained, preferably, at a temperature of about 1000 C. while a gas containing oxygen is introduced therein through inlet or port I8. An outlet is provided at I9, whereby there is a continuous flow of the oxidizing agent through the 5 chamber and over the blanks to be oxidized. In accordance with this invention, the gas introduced into the furnace contains a small quantity of a halogen, specifically, chlorine. Chlorine in amounts ranging from .015 to .1% by volume has 10 been added with good results.
The chlorine may be present in the oxidizing. atmosphere throughout the period during which the blanks are being oxidized, or only during the latter part thereof. For example, copper blanks 15 have been oxidized in atmospheres in which .05% chlorine was present during the last two minutes of'the oxidizing period; or in which .02 to .05% chlorine was present during the last four minutes 4of the oxidizing period; or in which .015% 20 chlorine was present during the entire oxidizing period, for example, eight minutes.
Upon subsequent cooling by quenching, or cooling to an intermediate temperature and quench.- ing, and removal of cupric oxide in accordance 25 with known practice, each blank I0 presents a cross-section such as shown by Fig. 4, wherein the mother copper 20 has an integral layer of cuprous Y oxide 2I.
Instead of introducing the chlorine with the 30 oxidizing agent, the blanks I0 may be initially provided with a film of copper chloride, and, thereafter, oxidized at about 1000 C. in an atmosphere containing oxygen or oxygen and nitrogen, only. The chloride compound decompos'es '35 to provide the free element chlorine. Alternatively, a dish or other receptacle 22 containing cuprous or cupric chloride 23 may be placed in the furnace, as shown by Fig. 2, during the oxidation process, as a source of chlorine, the oxidizing 40 atmosphere being supplied through the port I8.
I f the chlorine is introduced with the oxygen or the oxygen-nitrogen mixture, a -more uniform distribution is ensured by providing, as shown in Fig. 3, a continuation 24 of the entrance port I8, 45 with a plurality of outlet pipes 25 and a baille plate or member 26 disposed over and in spaced relation to the outlet openings.
Copper-cuprous oxide rectifier units manufactured in accordance with this 'invention have 50 It will be understood that this invention has been disclosed with reference to preferred forms thereof, and that it is to be considered as limited in scope by the appended claims, only.
What is claimed is:
1. The method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere containing about .015 to .1% chlorine by volume.
2. The method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere containing approximately .02% chlorine by volume.
3. The method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere at about 1000 C., said atmosphere containing about .015 to .1% chlorine by volume.
4. The method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere, said atmosphere for a portion of the time containing about .015 to .1% chlorine'by volume.
5. The method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank' in an oxidizing atmosphere, said atmosphere for a portion of the time containing .02 to .05% chlorine by volume.
6. The method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere, said atmosphere for the entire time containing about .015% chlorine b y volume.
'7. The method of manufacture of an electrically conductive device comprising a body of copper having a layer of cuprous oxide thereon, which comprises placing the copper body and a source of chlorine in an oxidizing atmosphere at an oxidizing temperature` to form an oxide on the copper body, said chlorine source adding about .015 to .1% chlorine by volume to said atmosphere, and thereafter cooling said body.
8. The method of manufacture of an electrically conductive device comprising a copper body having a layer of cuprous oxide thereon, which comprises placing the copper body and a chloride in an oxidizing atmosphere at an oxidizing and chlorine-liberating temperature to form a layer of oxide on the body, said chloride adding about .015 to .1% chlorine by volume to said atmosphere.
9. A conductive device comprising a copper body having a layer of oxide that has been formed thereon by heating the copper body in an oxidizing atmosphere containing about .015 to .1% chlorine by volume.
10. The method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere for six to eight minutes, said atmosphere containing about .015% chlorine by volume.
11. The method of manufacture of a copper- .cuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere for six to eight minutes, said atmosphere containing about .02 to .05% chlorine by volume for the last five minutes.
12. The method of manufacture of a coppercuprous oxide rectifier that comprises heating a copper blank in an oxidizing atmosphere for about six to eight minutes, said atmosphere containing about .05% chlorine by volume for the last two minutes.
13. The method of manufacture of an electrically conductive device comprises a copper body having a layer of cuprous oxide thereon, that comprises coating the copper body with copper chloride, placing it in an oxidizing atmosphere at a temperature to decompose the chloride to add chlorine to the atmosphere to about .015 to .1% by volume, forming an oxide on said body,
and thereafter-cooling said body.
14. The method of manufacture of an electrically conductive device comprising a copper body having a layer of cuprous oxide thereon, that comprises placing the copper body and a body of copper chloride in an oxidizing atmosphere at a temperature to decompose the chloride to add chlorine in the atmosphere to about .015 to .1% by volume. forming an oxide on said body, and thereafter cooling said body.
GEORGE O. SMITH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13888A US2060905A (en) | 1935-03-30 | 1935-03-30 | Asymmetrical conductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13888A US2060905A (en) | 1935-03-30 | 1935-03-30 | Asymmetrical conductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2060905A true US2060905A (en) | 1936-11-17 |
Family
ID=21762324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13888A Expired - Lifetime US2060905A (en) | 1935-03-30 | 1935-03-30 | Asymmetrical conductor |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2060905A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2484252A (en) * | 1944-11-07 | 1949-10-11 | Bell Telephone Labor Inc | Asymmetrical conductor |
| US2692212A (en) * | 1950-02-09 | 1954-10-19 | Westinghouse Brake & Signal | Manufacture of dry surface contact rectifiers |
| US2721966A (en) * | 1950-06-22 | 1955-10-25 | Westinghouse Brake & Signal | Manufacture of dry surface contact rectifiers |
| US2739276A (en) * | 1951-02-23 | 1956-03-20 | Gen Electric | Copper oxide rectifier and method of making the same |
| US2793968A (en) * | 1954-05-28 | 1957-05-28 | Gen Electric | Method of making copper oxide rectifier cells |
| US2812273A (en) * | 1955-06-09 | 1957-11-05 | Theodore S Shilliday | Method of making titanium-dioxide rectifiers |
-
1935
- 1935-03-30 US US13888A patent/US2060905A/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2484252A (en) * | 1944-11-07 | 1949-10-11 | Bell Telephone Labor Inc | Asymmetrical conductor |
| US2692212A (en) * | 1950-02-09 | 1954-10-19 | Westinghouse Brake & Signal | Manufacture of dry surface contact rectifiers |
| US2721966A (en) * | 1950-06-22 | 1955-10-25 | Westinghouse Brake & Signal | Manufacture of dry surface contact rectifiers |
| US2739276A (en) * | 1951-02-23 | 1956-03-20 | Gen Electric | Copper oxide rectifier and method of making the same |
| US2793968A (en) * | 1954-05-28 | 1957-05-28 | Gen Electric | Method of making copper oxide rectifier cells |
| US2812273A (en) * | 1955-06-09 | 1957-11-05 | Theodore S Shilliday | Method of making titanium-dioxide rectifiers |
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