US3632442A - Photocathodes - Google Patents

Photocathodes Download PDF

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US3632442A
US3632442A US722864A US3632442DA US3632442A US 3632442 A US3632442 A US 3632442A US 722864 A US722864 A US 722864A US 3632442D A US3632442D A US 3632442DA US 3632442 A US3632442 A US 3632442A
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alkali metal
cesium
oxygen
maximum
layer
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US722864A
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Andrew Alfred Turnbull
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US Philips Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • H01J9/12—Manufacture of electrodes or electrode systems of photo-emissive cathodes; of secondary-emission electrodes
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S148/00—Metal treatment
    • Y10S148/065—Gp III-V generic compounds-processing

Definitions

  • FIG. 1 A first figure.
  • the invention relates to a method of manufacturing an electric discharge tube comprising a photocathode, the active constituent of which is formed by a strongly P-conductive AIll-BV compound or mixed crystals of such compounds which are activated by means of an alkali metal.
  • the invention furthermore relates to an electric discharge tube comprising a photocathode manufactured by said method.
  • AIII-BV a compound which is a substantially equiatomic intermetallic compound of one of the elements Alll of the third column of the Periodical System, boron, aluminum, gallium, indium, and an element BV of the fifth column of the Periodical System, nitrogen, phosphorus, arsenic, antimony. With mixed crystals the quantity of AIII atoms is approximately equal to that of the EV atoms.
  • Photocathodes of the above compositions are described by Scheer and Van Laar in Solid State Communications, US. Pat. No. 3,387,161, 1965 and in Dutch Patent application 64-13961.
  • the activating layer consists substantially of a monoatomic layer of cesium, as the case may be with oxygen.
  • the invention has for its object to provide a cathode and a method in which the requirements relative to vacuum are less extreme and a decline of sensitivity does not occur so soon.
  • an electric discharge tube having a photocathode whose active constituent is formed by a strongly P-conductive AIII-BV compound or mixed crystals of such compounds which are activated by means of an alkali metal such a quantity of alkali metal is admitted, in accordance with the invention, to the surface of the semiconductor that after having reached a maximum the photosensitivity drops to a value lying between 50 and percent of the maximum, after which such a quantity of oxygen is admitted that the photosensitivity again reaches a maximum, which treatments with the alkali metal and the oxygen are repeated once or several times.
  • the advantageous effect of the method according to the invention is probably due to the fact that more alkali metal is admitted than the quantity corresponding to a monolayer so that the impurity affects the larger quantity of alkali metal to a lesser extent, while the larger quantity of alkali metal supplied to the cathode provides at the same time a larger quantity of alkali metal for the interior of the discharge tube. Since the alkali metals have fairly high vapor pressures, transport phenomena of the alkali metals may readily occur in such discharge tubes, but in the presence of a larger quantity on the cathode than that of a monolayer, they are less likely to give rise to modifications of the photocathode structure.
  • one or two monolayers of the alkali metal will be applied during each treatment, and preferably not more than five treatments are carried out, the thickness of the layer being about 50 to 100 A.
  • the treatment is carried out in oxygen at a pressure of 5X10 Torr so that in the case of cesium as the alkali metal the composition of the layer corresponds approximately to the formula Cs 0.
  • the influence of impurities on the cathode surface is also reduced by the method according to the invention, it may be advisable according to the invention in the event of strong contamination, for example, due to a long stay in air, to sinter the semiconductor surface in alkali metal vapor at a temperature of a few hundred degrees for a few minutes. In the case of cesium this temperature is 300 C.
  • FIG. I shows a contaminated semiconductor surface with an activating layer
  • FIGS. 2 to 4 shows discharge tubes comprising a photocathode according to the invention.
  • reference numeral 1 designates part of a gallium-arsenide crystal having a dopant of 4X10 zinc atoms per cc.
  • the surface of the crystal is slightly contaminated by a layer 2 mainly of oxygen, shown on an exaggerated scale.
  • the activating layer 3 consists of cesium oxygen of 50 A. thick having a work function of 1.3 ev., which is slightly lower than the energy gap of 1.4 ev. of the gallium-arsenide crystal.
  • the photocathode formed by the crystal and the activating layer are worked as follows.
  • the crystal 1 having an upper surface obtained by splitting and having (110) orientation is slightly contaminated by this treatment by the layer 2.
  • the crystal 1 with the impurity 2 is exposed to cesium vapor until the photoemission for white light attains a maximum as deter mined in the manner disclosed in US Pat. No. 3,387,161, which issued June 4, 1968.
  • the cesium supply is continued until the photoemission drops to about 15 percent of the maximum.
  • Subsequently oxygen is admitted at a pressure of 10 Torr until the photoemission again attains a maximum.
  • This treatment with cesium and oxygen is repeated once or several times, but not more than five times in total; then photosensitivities are obtained which are percent or more of that of the known photocathodes with monolayers, whereas they have a higher stability.
  • the cathode is heated prior to the alternating cesium and oxygen treatments in cesium vapor at 300 C. so that the impurity disappears approximately completely.
  • FIG. 2 illustrating a photocell with a bulb 7, a gallium-arsenide layer is deposited from the vapor phase on a molybdenum plate 8, which layer is treated in the same manner as the crystal 1 of FIG. I.
  • the anode is designated by 10.
  • FIG. 3 shows a photoelectron multiplier tube in which the vapor-deposited cathode layer 12 of gallium-arsenide is applied to the flat window 11. Also this cathode is treated in the manner described with reference to FIG. 1.
  • the multiplier electrode 13 and the anode 14 form the further electrodes of the tube.
  • a gallium-arsenide layer 16 is applied to the flat window 15 of the iconoscope, which layer is also activated by an alternating treatment with cesium and oxygen. Of the further electrodes of the tube only the filament cathode 17 is shown.
  • a method of manufacturing an electric discharge tube having a photocathode whose active constituent is formed by a strongly P-conductive AIII-BV compound or mixed crystals of such compounds which are activated by means of an alkali metal comprising the steps of depositing a strongly P-conductive AIIl-BV compound or mixed crystals of such compounds onto the surface of the photocathode substrate, then depositing a quantity of alkali metal onto the surface of the P-conductive AIII-BV compound or mixed crystals until after having attained a maximum the photosensitivity drops to a value lying between 50 and 10 percent of that of the maximum, thereafter adding to the cesium a quantity of oxygen until the photosensitivity again reaches the maximum, and repeating the deposition of the alkali metal until the sensitivity reaches a maximum and adding the oxygen at least once.
  • a method as claimed in claim 1 wherein the addition of oxygen is carried out at a pressure of about 5X10 Torr.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Common Detailed Techniques For Electron Tubes Or Discharge Tubes (AREA)
  • Image-Pickup Tubes, Image-Amplification Tubes, And Storage Tubes (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Hybrid Cells (AREA)

Abstract

A method of manufacturing a photocathode for an electron tube whose active constituent is formed by a strongly P-conductive AIII-BV compound or mixed crystals of such compounds in which cesium is deposited on the surface of the cathode until after having reached a maximum the photosensitivity drops to a value lying between 10 percent and 50 percent that of the maximum. Thereafter, the surface of the cesium is exposed to oxygen to form Cs20 and these steps are repeated until an activating layer about 50-100 A. in thickness is formed.

Description

United States Patent 1,994,904 3/1935 Wilson 1 17/224 X 2,070,691 2/1937 Spencer... 1 17/224 X 2,190,695 2/1940 Bruining.. 1 17/219 X 2,228,945 l/ 1941 Bruining 1 17/224 X 2,698,397 12/1954 befcount 117/224 X 2,702,259 2/1958 Sommer 1 17/107 X 2,739,084 3/1956 Sommer 117/219 X 2,880,344 3/1959 Stovdenheimer 1 17/107 X Primary Examiner-Alfred L. Leavitt Assistant ExaminerAlan Grimaldi Att0rneyFrank R. Trifari [72] Inventor Andrew Alfred Turnbull London, England [21] Appl. No. 722,864 [22] Filed Apr. 22, 1968 [45] Patented Jan. 4, 1972 [73] Assignee U.S. Philips Corporation New York, N.Y. 32 Priority Apr. 21, 1967 [33] Great Britain [31] 18,486/67 [54] PHOTOCATHODES 4 Claims, 4 Drawing Figs.
[52] US. Cl 117/219, 117/107,117/224, 313/94, 313/346 R [51] Int. Cl B44d l/l8, B0 1 j 39/00 [50] Field ofSearch 117/224, 107, 202, 219; 313/94, 346
[56] References Clted UNITED STATES PATENTS 3,387,161 6/1968 Van Laaret a1. 313/94 PATENTED JAN 4m 316132.442
FIG.2.
FIG/I.
INVENTOR ANDRE A- TURNBILL BY A M 2- PHOTOCATHODES Method of manufacturing an electric discharge tube comprising a photocathode and electric discharge tube manufactured by said method.
The invention relates to a method of manufacturing an electric discharge tube comprising a photocathode, the active constituent of which is formed by a strongly P-conductive AIll-BV compound or mixed crystals of such compounds which are activated by means of an alkali metal. The invention furthermore relates to an electric discharge tube comprising a photocathode manufactured by said method.
It is customary to denote by AIII-BV a compound which is a substantially equiatomic intermetallic compound of one of the elements Alll of the third column of the Periodical System, boron, aluminum, gallium, indium, and an element BV of the fifth column of the Periodical System, nitrogen, phosphorus, arsenic, antimony. With mixed crystals the quantity of AIII atoms is approximately equal to that of the EV atoms.
Photocathodes of the above compositions are described by Scheer and Van Laar in Solid State Communications, US. Pat. No. 3,387,161, 1965 and in Dutch Patent application 64-13961.
With the known photocathodes the activating layer consists substantially of a monoatomic layer of cesium, as the case may be with oxygen.
It has been found, however, that such cathodes are very sensitive to small quantities of impurities on the surface of the semiconductor. Therefore, the requirements with respect to the vacuum are very severe. On the other hand such photocathodes exhibit, after a comparatively short period of photoemission, a drastic drop of sensitivity.
The invention has for its object to provide a cathode and a method in which the requirements relative to vacuum are less extreme and a decline of sensitivity does not occur so soon.
In a method of manufacturing an electric discharge tube having a photocathode whose active constituent is formed by a strongly P-conductive AIII-BV compound or mixed crystals of such compounds which are activated by means of an alkali metal, such a quantity of alkali metal is admitted, in accordance with the invention, to the surface of the semiconductor that after having reached a maximum the photosensitivity drops to a value lying between 50 and percent of the maximum, after which such a quantity of oxygen is admitted that the photosensitivity again reaches a maximum, which treatments with the alkali metal and the oxygen are repeated once or several times.
It has been found that the photocathodes thus manufactured are less sensitive to impurities and that even semiconductor crystals having been in contact with air are activated to a satisfactory sensitivity. The drop of sensitivity does not occur as soon as in the known photocathodes.
The advantageous effect of the method according to the invention is probably due to the fact that more alkali metal is admitted than the quantity corresponding to a monolayer so that the impurity affects the larger quantity of alkali metal to a lesser extent, while the larger quantity of alkali metal supplied to the cathode provides at the same time a larger quantity of alkali metal for the interior of the discharge tube. Since the alkali metals have fairly high vapor pressures, transport phenomena of the alkali metals may readily occur in such discharge tubes, but in the presence of a larger quantity on the cathode than that of a monolayer, they are less likely to give rise to modifications of the photocathode structure.
By the method according to the invention one or two monolayers of the alkali metal will be applied during each treatment, and preferably not more than five treatments are carried out, the thickness of the layer being about 50 to 100 A. According to the invention the treatment is carried out in oxygen at a pressure of 5X10 Torr so that in the case of cesium as the alkali metal the composition of the layer corresponds approximately to the formula Cs 0.
Although the influence of impurities on the cathode surface is also reduced by the method according to the invention, it may be advisable according to the invention in the event of strong contamination, for example, due to a long stay in air, to sinter the semiconductor surface in alkali metal vapor at a temperature of a few hundred degrees for a few minutes. In the case of cesium this temperature is 300 C.
The invention will be described more fully with reference to the drawing, in which FIG. I shows a contaminated semiconductor surface with an activating layer, and
FIGS. 2 to 4 shows discharge tubes comprising a photocathode according to the invention.
Referring to FIG. 1, reference numeral 1 designates part of a gallium-arsenide crystal having a dopant of 4X10 zinc atoms per cc. The surface of the crystal is slightly contaminated by a layer 2 mainly of oxygen, shown on an exaggerated scale. The activating layer 3 consists of cesium oxygen of 50 A. thick having a work function of 1.3 ev., which is slightly lower than the energy gap of 1.4 ev. of the gallium-arsenide crystal.
The photocathode formed by the crystal and the activating layer are worked as follows. The crystal 1 having an upper surface obtained by splitting and having (110) orientation is slightly contaminated by this treatment by the layer 2. The crystal 1 with the impurity 2 is exposed to cesium vapor until the photoemission for white light attains a maximum as deter mined in the manner disclosed in US Pat. No. 3,387,161, which issued June 4, 1968. Then the cesium supply is continued until the photoemission drops to about 15 percent of the maximum. Subsequently oxygen is admitted at a pressure of 10 Torr until the photoemission again attains a maximum. This treatment with cesium and oxygen is repeated once or several times, but not more than five times in total; then photosensitivities are obtained which are percent or more of that of the known photocathodes with monolayers, whereas they have a higher stability.
Suppose the impurity layer 2 is more serious than that which guarantees a satisfactory result, the cathode is heated prior to the alternating cesium and oxygen treatments in cesium vapor at 300 C. so that the impurity disappears approximately completely.
As is shown in FIG. 2, illustrating a photocell with a bulb 7, a gallium-arsenide layer is deposited from the vapor phase on a molybdenum plate 8, which layer is treated in the same manner as the crystal 1 of FIG. I. The anode is designated by 10.
FIG. 3 shows a photoelectron multiplier tube in which the vapor-deposited cathode layer 12 of gallium-arsenide is applied to the flat window 11. Also this cathode is treated in the manner described with reference to FIG. 1. The multiplier electrode 13 and the anode 14 form the further electrodes of the tube.
As is shown in FIG. 4, a gallium-arsenide layer 16 is applied to the flat window 15 of the iconoscope, which layer is also activated by an alternating treatment with cesium and oxygen. Of the further electrodes of the tube only the filament cathode 17 is shown.
What is claimed:
1. A method of manufacturing an electric discharge tube having a photocathode whose active constituent is formed by a strongly P-conductive AIII-BV compound or mixed crystals of such compounds which are activated by means of an alkali metal, comprising the steps of depositing a strongly P-conductive AIIl-BV compound or mixed crystals of such compounds onto the surface of the photocathode substrate, then depositing a quantity of alkali metal onto the surface of the P-conductive AIII-BV compound or mixed crystals until after having attained a maximum the photosensitivity drops to a value lying between 50 and 10 percent of that of the maximum, thereafter adding to the cesium a quantity of oxygen until the photosensitivity again reaches the maximum, and repeating the deposition of the alkali metal until the sensitivity reaches a maximum and adding the oxygen at least once.
2. A method as claimed in claim I wherein in each treatment with the alkali metal one to two monolayers are deposited from the vapor phase.
3. A method as claimed in claim 1 wherein the addition of oxygen is carried out at a pressure of about 5X10 Torr.
4. A method as claimed in claim 1, wherein prior to the deposition of alkali metal on the semiconductor surface, the
surface is heated in alkali metal vapor at about 300 C. S

Claims (3)

  1. 2. A method as claimed in claim 1 wherein in each treatment with the alkali metal one to two monolayers are deposited from the vapor phase.
  2. 3. A method as claimed in claim 1 wherein the addition of oxygen is carried out at a pressure of about 5 X 10 6 Torr.
  3. 4. A method as claimed in claim 1, wherein prior to the deposition of alkali metal on the semiconductor surface, the surface is heated in alkali metal vapor at about 300* C.
US722864A 1967-04-21 1968-04-22 Photocathodes Expired - Lifetime US3632442A (en)

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SE (1) SE333415B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3811002A (en) * 1971-08-17 1974-05-14 Philips Corp Method of manufacturing an electric discharge tube having an electron emitting electrode comprising a cesium-containing layer on a support
US3958143A (en) * 1973-01-15 1976-05-18 Varian Associates Long-wavelength photoemission cathode
US3992233A (en) * 1975-03-10 1976-11-16 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Surface treatment of III-V compound crystals
US4242373A (en) * 1976-02-20 1980-12-30 Hitachi, Ltd. Method for vapor depositing a cerium oxide film
US4816183A (en) * 1986-08-21 1989-03-28 The Board Of Trustees Of The Leland Stanford Junior University Composite photosensitive material
US4907051A (en) * 1987-05-22 1990-03-06 Sharp Kabushiki Kaisha Photocathode
WO1999060598A1 (en) * 1998-05-18 1999-11-25 The Regents Of The University Of California Low work function, stable compound clusters and generation process
US20040140432A1 (en) * 2002-10-10 2004-07-22 Applied Materials, Inc. Generating electrons with an activated photocathode
US20060055321A1 (en) * 2002-10-10 2006-03-16 Applied Materials, Inc. Hetero-junction electron emitter with group III nitride and activated alkali halide
US20090322222A1 (en) * 2008-01-25 2009-12-31 Mulhollan Gregory A Robust activation method for negative electron affinity photocathodes

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1994904A (en) * 1933-04-22 1935-03-19 Westinghouse Electric & Mfg Co Automatic heat control
US2070691A (en) * 1928-07-02 1937-02-16 Raytheon Mfg Co Electron discharge device
US2190695A (en) * 1937-04-02 1940-02-20 Rca Corp Secondary electron emitter and method of making it
US2228945A (en) * 1937-03-30 1941-01-14 Rca Corp Electric discharge tube
US2698397A (en) * 1948-07-01 1954-12-28 Sylvania Electric Prod Electron discharge device
US2702259A (en) * 1951-08-09 1955-02-15 Emi Ltd Manufacture of electrodes which are sensitized so as to be emitters of photoelectrons or secondary electrons
US2739084A (en) * 1951-04-28 1956-03-20 Emi Ltd Secondary electron emitting coatings and method for producing same
US2880344A (en) * 1951-03-02 1959-03-31 Rca Corp Photosurface
US3387161A (en) * 1964-12-02 1968-06-04 Philips Corp Photocathode for electron tubes

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2070691A (en) * 1928-07-02 1937-02-16 Raytheon Mfg Co Electron discharge device
US1994904A (en) * 1933-04-22 1935-03-19 Westinghouse Electric & Mfg Co Automatic heat control
US2228945A (en) * 1937-03-30 1941-01-14 Rca Corp Electric discharge tube
US2190695A (en) * 1937-04-02 1940-02-20 Rca Corp Secondary electron emitter and method of making it
US2698397A (en) * 1948-07-01 1954-12-28 Sylvania Electric Prod Electron discharge device
US2880344A (en) * 1951-03-02 1959-03-31 Rca Corp Photosurface
US2739084A (en) * 1951-04-28 1956-03-20 Emi Ltd Secondary electron emitting coatings and method for producing same
US2702259A (en) * 1951-08-09 1955-02-15 Emi Ltd Manufacture of electrodes which are sensitized so as to be emitters of photoelectrons or secondary electrons
US3387161A (en) * 1964-12-02 1968-06-04 Philips Corp Photocathode for electron tubes

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3811002A (en) * 1971-08-17 1974-05-14 Philips Corp Method of manufacturing an electric discharge tube having an electron emitting electrode comprising a cesium-containing layer on a support
US3958143A (en) * 1973-01-15 1976-05-18 Varian Associates Long-wavelength photoemission cathode
US3992233A (en) * 1975-03-10 1976-11-16 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland Surface treatment of III-V compound crystals
US4242373A (en) * 1976-02-20 1980-12-30 Hitachi, Ltd. Method for vapor depositing a cerium oxide film
US4816183A (en) * 1986-08-21 1989-03-28 The Board Of Trustees Of The Leland Stanford Junior University Composite photosensitive material
US4907051A (en) * 1987-05-22 1990-03-06 Sharp Kabushiki Kaisha Photocathode
WO1999060598A1 (en) * 1998-05-18 1999-11-25 The Regents Of The University Of California Low work function, stable compound clusters and generation process
US20040140432A1 (en) * 2002-10-10 2004-07-22 Applied Materials, Inc. Generating electrons with an activated photocathode
US20060055321A1 (en) * 2002-10-10 2006-03-16 Applied Materials, Inc. Hetero-junction electron emitter with group III nitride and activated alkali halide
US7015467B2 (en) 2002-10-10 2006-03-21 Applied Materials, Inc. Generating electrons with an activated photocathode
US7446474B2 (en) 2002-10-10 2008-11-04 Applied Materials, Inc. Hetero-junction electron emitter with Group III nitride and activated alkali halide
US20090322222A1 (en) * 2008-01-25 2009-12-31 Mulhollan Gregory A Robust activation method for negative electron affinity photocathodes
US8017176B2 (en) * 2008-01-25 2011-09-13 Mulhollan Gregory A Robust activation method for negative electron affinity photocathodes

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NL6805301A (en) 1968-10-22
BE713951A (en) 1968-10-21
CH474147A (en) 1969-06-15
DE1764170A1 (en) 1971-05-27
FR1569963A (en) 1969-06-06
SE333415B (en) 1971-03-15
GB1200899A (en) 1970-08-05
DE1764170B2 (en) 1975-10-23

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