US2588008A - Germanium crystal rectifiers and method of producing the crystal element thereof - Google Patents
Germanium crystal rectifiers and method of producing the crystal element thereof Download PDFInfo
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- US2588008A US2588008A US764580A US76458047A US2588008A US 2588008 A US2588008 A US 2588008A US 764580 A US764580 A US 764580A US 76458047 A US76458047 A US 76458047A US 2588008 A US2588008 A US 2588008A
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims description 57
- 229910052732 germanium Inorganic materials 0.000 title claims description 46
- 239000013078 crystal Substances 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 15
- 238000005530 etching Methods 0.000 claims description 12
- 238000003776 cleavage reaction Methods 0.000 claims description 9
- 230000007017 scission Effects 0.000 claims description 9
- 238000007493 shaping process Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 11
- 229940119177 germanium dioxide Drugs 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- -1 germanium dioxide compound Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000003486 chemical etching Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 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
-
- 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
- H01L21/18—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 elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
Definitions
- This invention relates to crystal rectifiers or detectors of the type suitable for use as rectifiers or mixers in circuits carrying electrical oscillations, for example in radio receivers.
- Such rectifiers or detectors comprise as one contact element a semiconducting crystalline mass associated in use with a contact element which is usually a metal point.
- the invention relates also to the manufacture of crystal rectifier elements of the type specified.
- germanium is no more stable or uniform than commercial silicon; on the other hand we have found that if the germanium is highly pure and preferably is subjected to a chemical etching treatment its rectifying action may be improved and is then often better than that of most of the commercial silicon we have examined.
- a crystal rectifier element comprises a body of germanium having unremoved impurities in an amount not exceeding 0.10 per cent and having an etched crystallographic cleavage contact surface.
- unremoved impurities is used hereinafter and in the appended claims to mean those impurities occurring in the ores from which the germanium is derived and in the reaction agents utilized to derive the high-purity germanium and which remain in the germanium after the purification process has been completed.
- a method of producing a crystal rectifier element in accordance with the invention comprises etching a contact surface on a body of germanium of high purity.
- the effectiveness of the nonlinear or rectifying action of a crystal is to be measured by the value of the back-to-forward resistance ratio; that is to say, the ratio of the higher resistance in one direction of flow of current through a contact of which the crystal forms part to the lower resistance in the opposite direction of flow of current through the contact; the higher the value of this ratio the better is the rectifying action of the crystal.
- the crystal body per se comprises one element in contact with the point of a tungsten wire 0.2 mm. in diameter having a pointed contact end which is formed by shearing the wire along a cleavage plane inclined to the axis of the wire at an angle of about 45 degrees.
- the sheared point is electrolytically etched and polished, the pressure between the'point and the crystal is about 10 grams weight, the voltage applied to measure the resistance is 1.5 volts direct, and the average is taken of a number of readings, for example six, with the metal point in contact with a different part of the contact surface of the crystal for each reading.
- the contact surface of a semiconducting crystal element is the surface of the element which is adapted to abut against the other element of the contact, e. g. against a pointed metallic wire contact.
- the improvement sought in accordance with the invention is to be regarded statistically as applied to the production of a number of crystal contacts regarded as a whole. It is, as far as we are aware, impossible to predict with certainty the effect of the etching treatment on any individual element and some elements may in fact exhibit no improvement or may even be worse after the treatment than before. But with any batch of appreciable size the majority usually are improved.
- the chemical etching reagent may be either acid or alkaline; thus we have obtained improvements using individually hydrofluoric acid, nitric acid, sodium hydroxide, or ammonia. But we have found it generally preferable to use a reagent consisting of or comprising hydrofluoric acid, and we have obtained the best results with a mixture in the proportions by volume of 1 part of distilled water, 1 part of 50 per cent. hydrofluoric acid, and 1 to 2 parts of concentrated nitric acid.
- the crystalline element may be simply dipped into the' reagent for a length of time which will depend on the nature of the reagent and possibly also on the sample of germanium being used; the optimum time is best determined by experiment for each particular case. For guidance it may be said that, for the reagents mentioned, vwe have obtained improvements with dipping for the following lengths of time:
- the etching treatment in accordance with the invention usually also improves polished contact surfaces.
- the following figures are given by way of example to indicate the improvement obtainable by the treatment in accordance with the invention.
- the etching reagent used was a mixture of, by volume, 1 part of 50 per cent. hydrofluoric acid, 1 part of concentrated nitric acid, and 1 part of distilled water. A natural cleavage surface was treated in each case, and the time of dipping was 10 seconds for each crystal.
- the germanium used should be of a high degree of purity, and preferably is of a spectroscopic purity of not less than 99.95 per cent. We have, however, obtained satisfactory results with a lower purity of about 99.90 per cent, but germanium whose purity was believed to be as low as 99.24 per cent. gave much poorer results.
- a suitable method for purifying the germanium to the requisite extent is to distill the tetrachloride of the metal from a hydrochloric acid solution in which there is maintained some excess of chlorine or chloride ion.
- the distilled tetrachloride is received in distilled water where it is hydrolysed and a hydrated germanium dioxide compound is precipitated.
- the dioxide compound is separated, and then it may be dissolved in hydrochloric acid to reform the tetrachloride and the process repeated several times if necessary until germanium dioxide of a predetermined purity is obtained.
- the purified germanium dioxide then is reduced in a current of pure dry hydrogen and the resulting germanium powder fused in a vacuum or in an inert atmosphere and cooled to form the solid crystalline metal, which is subsequently broken into fragments and otherwise shaped if necessary to provide individual contact elements.
- rectifier elements made with germanium are usually negative; 1. e. such that electrons flow from the crystal to the metal point, assuming a metal point to be used, whereas contacts made with commercial silicon are usually positive, i. e. such that electrons flow from the metal to the crystal.
- crystals of germanium that give positive contacts have been found. It is likely on theoretical grounds that the difference of sign with different germanium crystals is associated with differences in the content of some very minute trace of impurity, possibly oxygen.
- Such positive contact crystals are of comparatively rare occurrence and it will be understood that they are to be regarded as anomalies.
- germanium elements manufactured in accordance with the invention often have one notable advantage over most silicon crystals; with both typesthe aforesaid back-to-forward resistance ratio decreases rapidly with time if the current passed through the contact exceeds some limit, but, whereas with elements of commercial silicon the limit is usually 10-24 ma., with germanium elements in accordance with the invention it is often many times greater. This may be expressed more appropriately by stating that the germanium elements usually can withstand materially greater voltage across the contact in the high resistance direction (i. e., tending to send current in the direction in which the contact has the higher resistance) than can elements made with ordinary commercial silicon.
- a crystal rectifier element comprising a body of germanium having unremoved impurities in an amount not exceeding 0.10 per cent, and having an etched crystallographic cleavage contact surface.
- An electrical translating device comprising a body of germanium of high purity having an etchedcrystallographic cleavage contact surface and a pointed metallic contact held against said contact surface whereby the device may serve as a circuit component presenting a nonlinear impedance to the passage of electric current therethrough.
- the method of producing a crystal rectifier comprising shaping a body of germanium of high purity to form a'crystallographic cleavage contact surface on said body and subsequently etching said contact surface.
- the method of producing a crystal rectifier element comprising, forming a contact surface on a body of germanium of high purity and etching said surface with a mixture having the approximate proportions by volume of one part of water, one part to two parts of concentrated nitric caid, and hydrofluoric acid equivalent to that obtained by including in said mixture one part of 50 per cent. hydrofluoric acid.
- the method of producing a crystal rectifier element comprising, forming a contact surface on a body of germanium of high purity, heating at least said contact surface of said body of germanium in air to a temperature of 600 to 700 degrees centigrade for approximately half an hour, and subsequently etching said surface.
- the method of producing a crystal rectifier element comprising, reducing a germanium dioxide compound with dry hydrogen gas to form metallic germanium powder, fusing said germanium powder in the absence of chemically active gases, cooling the fused germanium to form an uncomminuted mass of germanium of high purity, and shaping at least a part of said uncomminuted mass into a crystalline body of convenient size having a surface suitable for application of a metallic contact thereto.
- the method of producing a crystal rectifier element comprising, reducing a germanium dioxide compound with dry hydrogen gas to form metallic germanium powder, fusing said germanium powder in the absence of chemically active gases, cooling the fused germanium to form an uncomminuted mass of germanium of high purity, shaping at least a part of said uncomminuted mass into a crystalline body of convenient size having a contact surface, and etching said contact surface.
- the method of producing a crystal rectifier element comprising, distilling germanium tetrachloride from hydrochloric acid solution, receiving the distilled tetrachloride into aqueous solution to effect hydrolysis and precipitate a germanium dioxide compound, reducing said dioxide compound with dry hydrogen gas to form metallic germanium powder, fusing said germanium powder in the absence of chemically active gases, cooling the fused germanium to form an uncomminuted mass of germanium of high purity, and shaping at least a part of said uncomminuted mass into a crystalline body of convenient size having a surface suitable for application of a metallic contact thereto.
- the method of producing a crystal rectifier element comprising, distilling germanium tetrachloride from hydrochloric acid solution, receiving the distilled tetrachloride into aqueous solution to effect hydrolysis and precipitate a germanium dioxide compound, reducing said dioxide compound with dry hydrogen gas to form metallic germanium powder, fusing said germanium powder in the absence of chemically active gases, cooling the fused germanium to form an uncomminuted mass of germanium of high purity, shaping at least a part of said uncomminuted mass into a crystalline body of convenient size having a contact surface, and etching said contact surface.
- the method of producing a crystal rectifier element comprising: distilling germanium tetrachloride from hydrochloric acid solution; receiving the distilled tetrachloride into aqueous solution to effect hydrolysis and precipitate a germanium dioxide compound; dissolving said precipitated dioxide compound in hyrochloric acid to reform germanium tetrachloride and repeating said operations of distilling and hydrolysis, the cycle of dissolving, distilling, and hydrolysis being carried out until a precipitate of germanium dioxide compound of a predetermined purity is obtained; reducing said last-mentioned dioxide compound with dry hydrogen gas to form metallic germanium powder; fusing said germanium powder in the absence of chemically active gases; cooling the fused germanium to form an uncomminuted. mass of germanium of a predetermined high purity; shaping at least a part of said uncomminuted'mass into a crystalline body of convenient size having a contact surface; and etching said contact surface.
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- Condensed Matter Physics & Semiconductors (AREA)
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- Crystals, And After-Treatments Of Crystals (AREA)
Description
Patented Mar. 4, 1952 GERMANIUM CRYSTAL RECTIFIERS AND METHOD vOF PRODUCING THE CRYSTAL ELEMENT THEREOF Douglas E. Jones and John W. Ryde, Wembley, England, assignors to Hazeltine Research, Inc., Chicago, 111., a corporation of Illinois No Drawing. Application July 29, 1947, Serial No. 764,580. In Great Britain July 16, 1941 Section 1, Public Law 690, August 8, 1946 Patent expires July 16, 1961 Claims. 1
This invention relates to crystal rectifiers or detectors of the type suitable for use as rectifiers or mixers in circuits carrying electrical oscillations, for example in radio receivers. Such rectifiers or detectors comprise as one contact element a semiconducting crystalline mass associated in use with a contact element which is usually a metal point. The invention relates also to the manufacture of crystal rectifier elements of the type specified.
One crystalline material often used as a semiconductor of this type is silicon. Experiments with the closely allied element germanium have been reported, but the only statement comparing germanium with other materials that we have found is that of E. Merritt (Proceedings of the National Academy of Science, vol. II (1925) p. 743) Merritt states that the rectifying action of germanium is less marked than with many other materials, but the contacts are quite stable and the behavior at different points on the surface is more uniform than in the case of most crystal rectifiers.
Our experiments do not confirm these statements generally. In our experience germanium is no more stable or uniform than commercial silicon; on the other hand we have found that if the germanium is highly pure and preferably is subjected to a chemical etching treatment its rectifying action may be improved and is then often better than that of most of the commercial silicon we have examined.
Accordingly, it is an object of the present invention to provide a new and improved germanium crystal rectifier.
It is a further object of the invention to provide a germanium crystal rectifier having substantially improved sensitivity, or ratio of forward-to-backward conductance, and one characterized by the ability safely to conduct in its forward direction much higher values of current than heretofore readily attainable.
It is a further object of the invention to provide a new and improved method of producing crystal rectifier elements of the germanium type.
In accordance with the invention, a crystal rectifier element comprises a body of germanium having unremoved impurities in an amount not exceeding 0.10 per cent and having an etched crystallographic cleavage contact surface.
The term unremoved impurities is used hereinafter and in the appended claims to mean those impurities occurring in the ores from which the germanium is derived and in the reaction agents utilized to derive the high-purity germanium and which remain in the germanium after the purification process has been completed.
Also, a method of producing a crystal rectifier element in accordance with the invention comprises etching a contact surface on a body of germanium of high purity.
For a better understanding of the present invention, together with other and further objects thereof, reference is had to the following description, and its scope will be pointed out in the appended claims.
The effectiveness of the nonlinear or rectifying action of a crystal is to be measured by the value of the back-to-forward resistance ratio; that is to say, the ratio of the higher resistance in one direction of flow of current through a contact of which the crystal forms part to the lower resistance in the opposite direction of flow of current through the contact; the higher the value of this ratio the better is the rectifying action of the crystal.
It will be understood that where hereinafter any quantitative statement is made concerning the value of the back-to-forward resistance ratio, the crystal body per se comprises one element in contact with the point of a tungsten wire 0.2 mm. in diameter having a pointed contact end which is formed by shearing the wire along a cleavage plane inclined to the axis of the wire at an angle of about 45 degrees. The sheared point is electrolytically etched and polished, the pressure between the'point and the crystal is about 10 grams weight, the voltage applied to measure the resistance is 1.5 volts direct, and the average is taken of a number of readings, for example six, with the metal point in contact with a different part of the contact surface of the crystal for each reading. The contact surface of a semiconducting crystal element is the surface of the element which is adapted to abut against the other element of the contact, e. g. against a pointed metallic wire contact.
Referring again to the germanium body of the crystal it may be remarked that the improvement sought in accordance with the invention is to be regarded statistically as applied to the production of a number of crystal contacts regarded as a whole. It is, as far as we are aware, impossible to predict with certainty the effect of the etching treatment on any individual element and some elements may in fact exhibit no improvement or may even be worse after the treatment than before. But with any batch of appreciable size the majority usually are improved.
The chemical etching reagent may be either acid or alkaline; thus we have obtained improvements using individually hydrofluoric acid, nitric acid, sodium hydroxide, or ammonia. But we have found it generally preferable to use a reagent consisting of or comprising hydrofluoric acid, and we have obtained the best results with a mixture in the proportions by volume of 1 part of distilled water, 1 part of 50 per cent. hydrofluoric acid, and 1 to 2 parts of concentrated nitric acid.
The crystalline element, or at least the contact surface thereof, may be simply dipped into the' reagent for a length of time which will depend on the nature of the reagent and possibly also on the sample of germanium being used; the optimum time is best determined by experiment for each particular case. For guidance it may be said that, for the reagents mentioned, vwe have obtained improvements with dipping for the following lengths of time:
40 seconds with 50 per cent. hydrofluoric acid.
30 seconds with concentrated nitric acid.
seconds with a mixture of 1 part of distilled water, 1 part of 50 per cent. hydrofluoric acid, and 1 part of concentrated nitric acid.
60 seconds with per cent. aqueous sodium hydroxide solution.
120 seconds with .88 liquid ammonia.
We have found it generally preferable to use a natural cleavage surface of the germanium as the contact surface to be treated, but the etching treatment in accordance with the invention usually also improves polished contact surfaces.
The following figures are given by way of example to indicate the improvement obtainable by the treatment in accordance with the invention. The etching reagent used was a mixture of, by volume, 1 part of 50 per cent. hydrofluoric acid, 1 part of concentrated nitric acid, and 1 part of distilled water. A natural cleavage surface was treated in each case, and the time of dipping was 10 seconds for each crystal.
In some cases we have obtained improved results by heating the germanium in air to a temperature of about 600-700 degrees centigrade for about half an hour before submitting it to the etching treatment.
As indicated, the germanium used should be of a high degree of purity, and preferably is of a spectroscopic purity of not less than 99.95 per cent. We have, however, obtained satisfactory results with a lower purity of about 99.90 per cent, but germanium whose purity was believed to be as low as 99.24 per cent. gave much poorer results.
We have found that a suitable method for purifying the germanium to the requisite extent is to distill the tetrachloride of the metal from a hydrochloric acid solution in which there is maintained some excess of chlorine or chloride ion. The distilled tetrachloride is received in distilled water where it is hydrolysed and a hydrated germanium dioxide compound is precipitated. The dioxide compound is separated, and then it may be dissolved in hydrochloric acid to reform the tetrachloride and the process repeated several times if necessary until germanium dioxide of a predetermined purity is obtained. The purified germanium dioxide then is reduced in a current of pure dry hydrogen and the resulting germanium powder fused in a vacuum or in an inert atmosphere and cooled to form the solid crystalline metal, which is subsequently broken into fragments and otherwise shaped if necessary to provide individual contact elements.
It may be noted that rectifier elements made with germanium are usually negative; 1. e. such that electrons flow from the crystal to the metal point, assuming a metal point to be used, whereas contacts made with commercial silicon are usually positive, i. e. such that electrons flow from the metal to the crystal. However, crystals of germanium that give positive contacts have been found. It is likely on theoretical grounds that the difference of sign with different germanium crystals is associated with differences in the content of some very minute trace of impurity, possibly oxygen. Such positive contact crystals are of comparatively rare occurrence and it will be understood that they are to be regarded as anomalies.
Finally it may be observed that germanium elements manufactured in accordance with the invention often have one notable advantage over most silicon crystals; with both typesthe aforesaid back-to-forward resistance ratio decreases rapidly with time if the current passed through the contact exceeds some limit, but, whereas with elements of commercial silicon the limit is usually 10-24 ma., with germanium elements in accordance with the invention it is often many times greater. This may be expressed more appropriately by stating that the germanium elements usually can withstand materially greater voltage across the contact in the high resistance direction (i. e., tending to send current in the direction in which the contact has the higher resistance) than can elements made with ordinary commercial silicon.
While there have been described what are at present considered to be the preferred embodiments of this invention, it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the invention, and it is, therefore, aimed to cover all such changes and modifications as fall within the true spirit and scope of the invention.
What is claimed is:
1. A crystal rectifier element comprising a body of germanium having unremoved impurities in an amount not exceeding 0.10 per cent, and having an etched crystallographic cleavage contact surface.
2. An electrical translating device comprising a body of germanium of high purity having an etchedcrystallographic cleavage contact surface and a pointed metallic contact held against said contact surface whereby the device may serve as a circuit component presenting a nonlinear impedance to the passage of electric current therethrough.
3. The method of producing a crystal rectifier comprising shaping a body of germanium of high purity to form a'crystallographic cleavage contact surface on said body and subsequently etching said contact surface.
4. The method of producing a crystal rectifier element comprising, forming a contact surface on a body of germanium of high purity and etching said surface with a mixture having the approximate proportions by volume of one part of water, one part to two parts of concentrated nitric caid, and hydrofluoric acid equivalent to that obtained by including in said mixture one part of 50 per cent. hydrofluoric acid.
5. The method of producing a crystal rectifier element comprising, forming a contact surface on a body of germanium of high purity, heating at least said contact surface of said body of germanium in air to a temperature of 600 to 700 degrees centigrade for approximately half an hour, and subsequently etching said surface.
6. The method of producing a crystal rectifier element comprising, reducing a germanium dioxide compound with dry hydrogen gas to form metallic germanium powder, fusing said germanium powder in the absence of chemically active gases, cooling the fused germanium to form an uncomminuted mass of germanium of high purity, and shaping at least a part of said uncomminuted mass into a crystalline body of convenient size having a surface suitable for application of a metallic contact thereto.
7. The method of producing a crystal rectifier element comprising, reducing a germanium dioxide compound with dry hydrogen gas to form metallic germanium powder, fusing said germanium powder in the absence of chemically active gases, cooling the fused germanium to form an uncomminuted mass of germanium of high purity, shaping at least a part of said uncomminuted mass into a crystalline body of convenient size having a contact surface, and etching said contact surface.
8. The method of producing a crystal rectifier element comprising, distilling germanium tetrachloride from hydrochloric acid solution, receiving the distilled tetrachloride into aqueous solution to effect hydrolysis and precipitate a germanium dioxide compound, reducing said dioxide compound with dry hydrogen gas to form metallic germanium powder, fusing said germanium powder in the absence of chemically active gases, cooling the fused germanium to form an uncomminuted mass of germanium of high purity, and shaping at least a part of said uncomminuted mass into a crystalline body of convenient size having a surface suitable for application of a metallic contact thereto.
9. The method of producing a crystal rectifier element comprising, distilling germanium tetrachloride from hydrochloric acid solution, receiving the distilled tetrachloride into aqueous solution to effect hydrolysis and precipitate a germanium dioxide compound, reducing said dioxide compound with dry hydrogen gas to form metallic germanium powder, fusing said germanium powder in the absence of chemically active gases, cooling the fused germanium to form an uncomminuted mass of germanium of high purity, shaping at least a part of said uncomminuted mass into a crystalline body of convenient size having a contact surface, and etching said contact surface.
10. The method of producing a crystal rectifier element comprising: distilling germanium tetrachloride from hydrochloric acid solution; receiving the distilled tetrachloride into aqueous solution to effect hydrolysis and precipitate a germanium dioxide compound; dissolving said precipitated dioxide compound in hyrochloric acid to reform germanium tetrachloride and repeating said operations of distilling and hydrolysis, the cycle of dissolving, distilling, and hydrolysis being carried out until a precipitate of germanium dioxide compound of a predetermined purity is obtained; reducing said last-mentioned dioxide compound with dry hydrogen gas to form metallic germanium powder; fusing said germanium powder in the absence of chemically active gases; cooling the fused germanium to form an uncomminuted. mass of germanium of a predetermined high purity; shaping at least a part of said uncomminuted'mass into a crystalline body of convenient size having a contact surface; and etching said contact surface.
DOUGLAS E. JONES. JOHN W. RYDE.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,708,571 Hartmann et a1 Apr. 9, 1929 2,266,922 Thompson et al Dec. 23, 1941 2,402,661 Ohl June 25, 1946 2,402,839 Ohl June 25, 1946 OTHER REFERENCES Merritt, Proc. Natl Acad. of Science, vol. II. 1925.
Claims (2)
- 2. AN ELECTRICAL TRANSLATING DEVICE COMPRISING A BODY OF GERMANIUM OF HIGH PURITY HAVING AN ETCHED CRYSTALLOGRAPHIC CLEAVAGE CONTACT SURFACE AND A POINTED METALLIC CONTACT HELD AGAINST SAID CONTACT SURFACE WHEREBY THE DEVICE MAY SERVE AS A CIRCUIT COMPONENT PRESENTING A NONLINEAR IMPEDANCE TO THE PASSAGE OF ELECTRIC CURRENT THERETHROUGH.
- 3. THE METHOD OF PRODUCING A CRYSTAL RECTIFIER COMPRISING SHAPING A BODY OF GERMANIUM OF HIGH PURITY TO FORM A CRYSTALLOGRAPHIC CLEAVAGE CONTACT SURFACE ON SAID BODY AND SUBSEQUENTLY ETCHING SAID CONTACT SURFACE.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB899741A GB592659A (en) | 1941-07-16 | Improvements in crystal contacts of which one element is germanium |
Publications (1)
Publication Number | Publication Date |
---|---|
US2588008A true US2588008A (en) | 1952-03-04 |
Family
ID=9863366
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US764580A Expired - Lifetime US2588008A (en) | 1941-07-16 | 1947-07-29 | Germanium crystal rectifiers and method of producing the crystal element thereof |
Country Status (4)
Country | Link |
---|---|
US (1) | US2588008A (en) |
BE (1) | BE471989A (en) |
CH (1) | CH261491A (en) |
FR (1) | FR944003A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2698780A (en) * | 1953-02-03 | 1955-01-04 | Bell Telephone Labor Inc | Method of treating germanium for translating devices |
US2744000A (en) * | 1953-02-21 | 1956-05-01 | Int Standard Electric Corp | Method of cleaning and/or etching semiconducting material, in particular germanium and silicon |
US2786750A (en) * | 1952-01-21 | 1957-03-26 | Sekitan Sogo Kenkyujo Zh | Process of recovering germanium-containing material from coal |
US2809103A (en) * | 1953-11-10 | 1957-10-08 | Sylvania Electric Prod | Fabrication of semiconductor elements |
US2827369A (en) * | 1953-12-23 | 1958-03-18 | Metallurg De Hoboken Soc Gen | Method of separating germanium from primary materials containing germanium and other, less volatile, elements |
US2885364A (en) * | 1955-05-31 | 1959-05-05 | Columbia Broadcasting Syst Inc | Method of treating semiconducting materials for electrical devices |
US3102786A (en) * | 1961-06-14 | 1963-09-03 | American Metal Climax Inc | Purification of germanium tetrachloride |
US3266961A (en) * | 1961-02-03 | 1966-08-16 | Siemens Ag | Method of etching si and ge semiconductor bodies |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1157709B (en) * | 1953-12-10 | 1963-11-21 | Siemens Ag | Method for producing a semiconductor component with tip contact electrodes on a polished and then roughened surface of the monocrystalline semiconductor body |
CH413119A (en) * | 1964-09-22 | 1966-05-15 | Bbc Brown Boveri & Cie | Process for manufacturing semiconductor devices |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1708571A (en) * | 1925-02-21 | 1929-04-09 | Carborundum Co | Rectifying element |
US2266922A (en) * | 1938-12-28 | 1941-12-23 | Union Switch & Signal Co | Manufacture of alternating current rectifiers |
US2402661A (en) * | 1941-03-01 | 1946-06-25 | Bell Telephone Labor Inc | Alternating current rectifier |
US2402839A (en) * | 1941-03-27 | 1946-06-25 | Bell Telephone Labor Inc | Electrical translating device utilizing silicon |
-
0
- BE BE471989D patent/BE471989A/xx unknown
-
1947
- 1947-03-10 CH CH261491D patent/CH261491A/en unknown
- 1947-03-27 FR FR944003D patent/FR944003A/en not_active Expired
- 1947-07-29 US US764580A patent/US2588008A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1708571A (en) * | 1925-02-21 | 1929-04-09 | Carborundum Co | Rectifying element |
US2266922A (en) * | 1938-12-28 | 1941-12-23 | Union Switch & Signal Co | Manufacture of alternating current rectifiers |
US2402661A (en) * | 1941-03-01 | 1946-06-25 | Bell Telephone Labor Inc | Alternating current rectifier |
US2402839A (en) * | 1941-03-27 | 1946-06-25 | Bell Telephone Labor Inc | Electrical translating device utilizing silicon |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2786750A (en) * | 1952-01-21 | 1957-03-26 | Sekitan Sogo Kenkyujo Zh | Process of recovering germanium-containing material from coal |
US2698780A (en) * | 1953-02-03 | 1955-01-04 | Bell Telephone Labor Inc | Method of treating germanium for translating devices |
US2744000A (en) * | 1953-02-21 | 1956-05-01 | Int Standard Electric Corp | Method of cleaning and/or etching semiconducting material, in particular germanium and silicon |
US2809103A (en) * | 1953-11-10 | 1957-10-08 | Sylvania Electric Prod | Fabrication of semiconductor elements |
US2827369A (en) * | 1953-12-23 | 1958-03-18 | Metallurg De Hoboken Soc Gen | Method of separating germanium from primary materials containing germanium and other, less volatile, elements |
US2885364A (en) * | 1955-05-31 | 1959-05-05 | Columbia Broadcasting Syst Inc | Method of treating semiconducting materials for electrical devices |
US3266961A (en) * | 1961-02-03 | 1966-08-16 | Siemens Ag | Method of etching si and ge semiconductor bodies |
US3102786A (en) * | 1961-06-14 | 1963-09-03 | American Metal Climax Inc | Purification of germanium tetrachloride |
Also Published As
Publication number | Publication date |
---|---|
BE471989A (en) | |
FR944003A (en) | 1949-03-24 |
CH261491A (en) | 1949-05-15 |
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