US2735048A - Chs cjhj - Google Patents
Chs cjhj Download PDFInfo
- Publication number
- US2735048A US2735048A US2735048DA US2735048A US 2735048 A US2735048 A US 2735048A US 2735048D A US2735048D A US 2735048DA US 2735048 A US2735048 A US 2735048A
- Authority
- US
- United States
- Prior art keywords
- selenium
- layer
- baking
- ammonium hydroxide
- counterelectrode
- 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
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 229910052711 selenium Inorganic materials 0.000 claims description 21
- 239000011669 selenium Substances 0.000 claims description 21
- 230000000903 blocking effect Effects 0.000 claims description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 238000005323 electroforming Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- ZLRANBHTTCVNCE-UHFFFAOYSA-N 2-phenyl-3-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CN=C1C1=CC=CC=C1 ZLRANBHTTCVNCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical class CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000006023 eutectic alloy Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/06—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising selenium or tellurium in uncombined form other than as impurities in semiconductor bodies of other materials
- H01L21/10—Preliminary treatment of the selenium or tellurium, its application to the foundation plate, or the subsequent treatment of the combination
- H01L21/108—Provision of discrete insulating layers, i.e. non-genetic barrier layers
Definitions
- This invention relates to power transmission and more particularly to blocking layer devices such as selenium rectifier and light-sensitive cells, and to methods of making such devices.
- the selenium layer is heat-treated to change it from the amorphous state to its conducting crystalline form; (3) an artificial barrier layer, such race of the counterelectrode and the selenium layer, due to a barrier at that point. not known with any degree of many artificial These are generally formed by treating the annealed have been employed with varying degrees of success in improving the rectification ratio of rectifier cells.
- the present invention has special utility in the manuratio in the end product. After the baking step the unit is electroformed in the usual manner.
- Another object of the invention is to provide a method of making a blocking layer device with improved rectification characteristics.
- Still another object of the invention is to provide a blocking layer device having improved electrical characteristics.
- 2,735,048 Patented Feb. 14, 1956 preferred, such as low boiling point alcohols, low boiling point ketones, etc.
- solvents are methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, and ethyl methyl ketones.
- Water may be used as a solvent with a sacrifice in the uniformity of the applied coating because of low wetting ability.
- the selenium coated plates may be clipped in the solution, spraying permits a better control of the concentration per unit area.
- the actual amount of the rectification ratio is improved with any increase in concentration.
- too great a concentration will result in an impractical low forward conductivity even though the resulting rectification ratio in itself will be high.
- concentrations on a volume basis of about one part of the hydroxide in 50 to 1000 parts of solvent provides a wide variety of concentrations from which a suitable choice selected method of application.
- N is the nitrogen atom
- OH is the hydroxyl radiwhere cal
- each R 15 a radical or group having three carbon atoms or less, for example, tetraethanol ammonium hydroxide whose formula is is intended to cover not only the case where each R is the same, but also where the radicals are mixed, for example, dimethyl diethyl ammonium hydroxide CH2.
- each R is a radical having three carbon atoms or less.
- suitable counterelectrode is placed on the treated selenium surface;
- the counterelectrode may be formed by spraying onto the treated selenium surface a low melt ing metal or alloy.
- a low melt ing metal or alloy there are many known alloys usable as counterelectrodes and the process herein is not confined to the use of any particular counterelectrode material. Examples of commonly used alloys which were used in the practice of the method herein are: 70% tin- 30% cadmium; 20% tin-80% cadmium; and the 130 eutectic alloy of tin, bismuth, and cadmium.
- the composite unit is heated by any suitable means such as baking in an oven.
- the heating temperature is preferably below the melting point of the electrodes, and the temperature and the length of heating time may be varied depending upon the final cell characteristics desired.
- the temperature and time of heating or baking is not critical, the most practical ranges extend from about 50 C. to about 150 C., and from about ten minutes to about six hours. The lower the temperature, the more time is required to achieve a particular end characteristic. Tests show that for a selected temperature the end characteristic will vary with the heating time. In a test of a series of cells made according to the method herein and where the melting point of the counter- 3 electrode was 103, a baking temperature of 95 was selected, and the following results were tabulated after the cells were electroformed.
- the composite unit is electroformed by any suitable method, such as applying unidirectional current to the cell in the reverse direction until the desired rectification ratio is attained.
- baking as used throughout the specification and claims is intended to cover all forms of heating.
- a method of forming a barrier layer in a selenium blocking layer cell which comprises surface treating a crystalline selenium layer with a quaternary ammonium hydroxide, applying a counterelectrode to the treated selenium surface, baking the composite .cell before any electroforming, and electroforrning the cell, and quaternary ammonium hydroxide having the general formula N+-OH- R R 1 where each R is a group having less than four carbon atoms.
- the method of producing blocking layer devices which comprises providing a supporting base with a layer of crystalline selenium, applying a quaternary ammonium hydroxide to the surface of the selenium, applying a counterelectrode to the treated selenium surface, and baking the composite product, said quaternary ammonium hydroxide having the general formula n R +-0H- where each R is a group having less than four carbon atoms.
- a method of making blocking layer devices having a crystalline selenium layer ona base which comprises the steps of applying to the crystalline selenium surface a solution of a quaternary ammonium hydroxide in a solvent, applying a counterelectrode to the treated selenium surface, baking the composite product before any electroforming, and electroforming the device said quaternary ammonium hydroxide having the general formula N ⁇ '0K' B B r where each R is a group having less than four carbon atoms.
- a barrier layer in a selenium device which comprises surface treating baking the composite product, said quaternary ammonium the general formula where each R is a atoms.
- a method for forming a barrier layer in a selenium blocking layer device which comprises surface treating group having less than four carbon where each R is a group having less than four carbon atoms.
- a method of making blocking layer devices layer on a base which comprises hydroxide in a solvent, applying a counterelectrode to the treated selenium surface, and baking the composite product, the concentration range of the tetraethanol amwhere each R is 21 atoms.
- a blocking layer device comprising a conductive base, a layer of crystalline group having less than four carbon R R where each R is a group having less than four carbon atoms.
- a blocking layer device comprising a conductive base, a layer of crystalline selenium unit before any electroforming.
- a blocking layer device comprising a conductive base, a layer of crystalline
Description
2,735,048 POWER TRANSMISSION DEVICE Monroe D. Levy, University City, Mo., assignor to Vickers Incorporated, Detroit, Mich., a corporation of Michigan No Drawing. Application March 15, 1951, Serial No. 215,867
14 Claims. (Cl. 317-234) This invention relates to power transmission and more particularly to blocking layer devices such as selenium rectifier and light-sensitive cells, and to methods of making such devices.
num, etc.; (2) the selenium layer is heat-treated to change it from the amorphous state to its conducting crystalline form; (3) an artificial barrier layer, such race of the counterelectrode and the selenium layer, due to a barrier at that point. not known with any degree of many artificial These are generally formed by treating the annealed have been employed with varying degrees of success in improving the rectification ratio of rectifier cells.
The present invention has special utility in the manuratio in the end product. After the baking step the unit is electroformed in the usual manner.
It is therefore an object of the invention to provide a nited States Patent method of forming an artificial barrier layer in a blocking layer device.
Another object of the invention is to provide a method of making a blocking layer device with improved rectification characteristics.
Still another object of the invention is to provide a blocking layer device having improved electrical characteristics.
Further objects and advantages of the present invention will be apparent from the following description.
2,735,048 Patented Feb. 14, 1956 preferred, such as low boiling point alcohols, low boiling point ketones, etc. Examples of such solvents are methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, and ethyl methyl ketones. Water may be used as a solvent with a sacrifice in the uniformity of the applied coating because of low wetting ability.
Although the selenium coated plates may be clipped in the solution, spraying permits a better control of the concentration per unit area. The actual amount of the rectification ratio is improved with any increase in concentration. However, too great a concentration will result in an impractical low forward conductivity even though the resulting rectification ratio in itself will be high.
hydroxide concentrate in the solvents.
In general, concentrations on a volume basis of about one part of the hydroxide in 50 to 1000 parts of solvent provides a wide variety of concentrations from which a suitable choice selected method of application.
With the fast drying solvent the sprayed solution dries RN*-0H N is the nitrogen atom, OH is the hydroxyl radiwhere cal, and each R 15 a radical or group having three carbon atoms or less, for example, tetraethanol ammonium hydroxide whose formula is is intended to cover not only the case where each R is the same, but also where the radicals are mixed, for example, dimethyl diethyl ammonium hydroxide CH2. (31K:
Gs CzHi It is apparent that each R is a radical having three carbon atoms or less.
After the hydroxide application is dry, 2. suitable counterelectrode is placed on the treated selenium surface; For instance, the counterelectrode may be formed by spraying onto the treated selenium surface a low melt ing metal or alloy. There are many known alloys usable as counterelectrodes and the process herein is not confined to the use of any particular counterelectrode material. Examples of commonly used alloys which were used in the practice of the method herein are: 70% tin- 30% cadmium; 20% tin-80% cadmium; and the 130 eutectic alloy of tin, bismuth, and cadmium.
After the counterelectrode is applied the composite unit is heated by any suitable means such as baking in an oven. The heating temperature is preferably below the melting point of the electrodes, and the temperature and the length of heating time may be varied depending upon the final cell characteristics desired.
Although the temperature and time of heating or baking is not critical, the most practical ranges extend from about 50 C. to about 150 C., and from about ten minutes to about six hours. The lower the temperature, the more time is required to achieve a particular end characteristic. Tests show that for a selected temperature the end characteristic will vary with the heating time. In a test of a series of cells made according to the method herein and where the melting point of the counter- 3 electrode was 103, a baking temperature of 95 was selected, and the following results were tabulated after the cells were electroformed.
The following tables show examples of cell groups treated by spraying the crystalline layers with tetraethanol ammonium hydroxide in intermediate concentrations by volume of one part hydroxide in 250, 500, and 750 parts methyl alcohol, respectively.
Concentration 1 part in 750 lmkinflf Av. Voltage B t a g ec No. of Cells O" Ratio minutes Inverse Forward SAME CELLS AFTER 1 WEEK SHELF AGING Concentration 1 part in too Biggie o! Av. Voltage R t mg on No. of Cells 0 O Ratio minutes Inverse Forward Concentration 1 part m :50
Time of Av. Voltage Y Baking Rect. l\0. of Cells 0" Ratio minutes Inverse Forward SAME CELLS AFTER 1 WEEK SHELF AGING The above charts indicate that higher concentrations decrease the reverse conductivity and that cell stability is enhanced by a longer heating time. The charts also indicate that with a longer baking time, shelf aging after electroformation tends to further improve the rectification ratio. It is preferable to stabilize the plates by aging them after electroformation, regardless of the baking time employed.
Improvements of at least 24% in the rectification ratio of the end product have been obtained by the addition of the baking step. After the baking step, the composite unit is electroformed by any suitable method, such as applying unidirectional current to the cell in the reverse direction until the desired rectification ratio is attained.
The term baking as used throughout the specification and claims is intended to cover all forms of heating.
While the form of embodiment of the invention as herein disclosed constitutes a preferred form, it is to be understood that other forms might be adopted, all coming within the scope of the claims which follow.
What is claimed is as follows:
1. A method of forming a barrier layer in a selenium blocking layer cell which comprises surface treating a crystalline selenium layer with a quaternary ammonium hydroxide, applying a counterelectrode to the treated selenium surface, baking the composite .cell before any electroforming, and electroforrning the cell, and quaternary ammonium hydroxide having the general formula N+-OH- R R 1 where each R is a group having less than four carbon atoms.
2. The method of producing blocking layer devices which comprises providing a supporting base with a layer of crystalline selenium, applying a quaternary ammonium hydroxide to the surface of the selenium, applying a counterelectrode to the treated selenium surface, and baking the composite product, said quaternary ammonium hydroxide having the general formula n R +-0H- where each R is a group having less than four carbon atoms. i
3. A method of making blocking layer devices having a crystalline selenium layer ona base which comprises the steps of applying to the crystalline selenium surface a solution of a quaternary ammonium hydroxide in a solvent, applying a counterelectrode to the treated selenium surface, baking the composite product before any electroforming, and electroforming the device said quaternary ammonium hydroxide having the general formula N\'0K' B B r where each R is a group having less than four carbon atoms.
of solvent, said quaternary the general formula \NQOH where each R is a group having less than four carbon atoms.
for forming a barrier layer in a selenium device which comprises surface treating baking the composite product, said quaternary ammonium the general formula where each R is a atoms.
6. A method for forming a barrier layer in a selenium blocking layer device which comprises surface treating group having less than four carbon where each R is a group having less than four carbon atoms.
7. A method of making blocking layer devices layer on a base which comprises hydroxide in a solvent, applying a counterelectrode to the treated selenium surface, and baking the composite product, the concentration range of the tetraethanol amwhere each R is 21 atoms.
12. A blocking layer device comprising a conductive base, a layer of crystalline group having less than four carbon R R where each R is a group having less than four carbon atoms.
13. A blocking layer device comprising a conductive base, a layer of crystalline selenium unit before any electroforming.
14. A blocking layer device comprising a conductive base, a layer of crystalline
Claims (1)
11. A BLOCKING LAYER DEVICE COMPRISING A CRYSTALLINE SELENIUM LAYER, A COUNTERELECTRODE ON SAID LAYER, AND A BARRIER LAYER BETWEEN THE ELECTRODE AND THE SELENIUM LAYER, SAID BARRIER BEING THE PRODUCT BY THE INTERPOSITION OF A QUATERNARY AMMONIUM HYDROXIDE BETWEEN THE ELECTRODE AND THE SELENIUM SURFACE AND BAKING THE COMPOSITE UNIT BEFORE ANY ELECTROFORMING, SAID QUATERNARY AMMONIUM HYDROXIDE HAVING THE GENERAL FORMULA
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21586751A | 1951-03-15 | 1951-03-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2735048A true US2735048A (en) | 1956-02-14 |
Family
ID=22804729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2735048D Expired - Lifetime US2735048A (en) | 1951-03-15 | Chs cjhj |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2735048A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2255358A (en) * | 1940-09-16 | 1941-09-09 | Battelle Memorial Institute | Process for the preparation of selenium for electrical uses |
| US2362545A (en) * | 1942-01-29 | 1944-11-14 | Bell Telephone Labor Inc | Selenium rectifier and method of making it |
| US2395259A (en) * | 1942-10-24 | 1946-02-19 | Bell Telephone Labor Inc | Method of making dry rectifiers |
| US2471898A (en) * | 1947-04-10 | 1949-05-31 | Vickers Inc | Reclamation of selenium rectifier cells |
| US2507782A (en) * | 1946-02-23 | 1950-05-16 | Radio Receptor Company Inc | Rectifiers |
-
0
- US US2735048D patent/US2735048A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2255358A (en) * | 1940-09-16 | 1941-09-09 | Battelle Memorial Institute | Process for the preparation of selenium for electrical uses |
| US2362545A (en) * | 1942-01-29 | 1944-11-14 | Bell Telephone Labor Inc | Selenium rectifier and method of making it |
| US2395259A (en) * | 1942-10-24 | 1946-02-19 | Bell Telephone Labor Inc | Method of making dry rectifiers |
| US2507782A (en) * | 1946-02-23 | 1950-05-16 | Radio Receptor Company Inc | Rectifiers |
| US2471898A (en) * | 1947-04-10 | 1949-05-31 | Vickers Inc | Reclamation of selenium rectifier cells |
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