WO1998051417A1 - Procede et appareil permettant de fabriquer des cathodes a revetement d'oxyde thermo-ionique - Google Patents

Procede et appareil permettant de fabriquer des cathodes a revetement d'oxyde thermo-ionique Download PDF

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Publication number
WO1998051417A1
WO1998051417A1 PCT/US1998/010045 US9810045W WO9851417A1 WO 1998051417 A1 WO1998051417 A1 WO 1998051417A1 US 9810045 W US9810045 W US 9810045W WO 9851417 A1 WO9851417 A1 WO 9851417A1
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WIPO (PCT)
Prior art keywords
ions
substrate
cathode
oxide
barium
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Application number
PCT/US1998/010045
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English (en)
Inventor
George Caryotakis
Glenn Scheitrum
Ian Brown
Othon R. Monteiro
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The Board Of Trustees Of The Leland Stanford Junior University
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Publication date
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Publication of WO1998051417A1 publication Critical patent/WO1998051417A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21K—TECHNIQUES FOR HANDLING PARTICLES OR IONISING RADIATION NOT OTHERWISE PROVIDED FOR; IRRADIATION DEVICES; GAMMA RAY OR X-RAY MICROSCOPES
    • G21K1/00—Arrangements for handling particles or ionising radiation, e.g. focusing or moderating
    • G21K1/08—Deviation, concentration or focusing of the beam by electric or magnetic means
    • 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
    • H01J9/04—Manufacture of electrodes or electrode systems of thermionic cathodes
    • H01J9/042—Manufacture, activation of the emissive part
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/30—Electron or ion beam tubes for processing objects
    • H01J2237/31—Processing objects on a macro-scale
    • H01J2237/3142—Ion plating

Definitions

  • This invention relates generally to electron-emitting cathodes and methods for making such cathodes. More specifically, it relates to a plasma deposition technique for depositing barium oxide, strontium oxide, and calcium oxide onto a substrate to produce an electron-emitting cathode.
  • Electron-emitting cathodes are widely used in high-power and high-voltage vacuum tube electronics, and in display devices such as flat-panel displays and CRTs.
  • Oxide cathodes in particular, have been used as electron emitters in vacuum tubes since 1903. This type of cathode is still used in some electron guns but it has been replaced by dispenser cathodes in most applications due to low production yield.
  • the basic cost of an oxide cathode is much less than an equivalent dispenser cathode but the variability in performance and poor production yield make the overall cost too high.
  • Oxide cathode performance is highly variable from cathode to cathode. Nevertheless, the oxide cathode has significant advantages over the dispenser cathode. Because the oxide cathode has a lower work function than the dispenser cathode, an oxide cathode operates at a lower temperature than the dispenser cathode and can have a much higher maximum pulsed current density.
  • a conventional oxide cathode is produced by coating the surface of a nickel base material with a thin layer of barium and strontium carbonates. Sometimes calcium carbonate is added to control barium evaporation. The carbonates are conventionally deposited by painting or spraying using a hydrocarbon-based binder. The coating is usually less than 0.002 inches thick. The carbonate-coated cathode is then placed in a vacuum and heated. Heating first evaporates the binder materials at temperatures up to 500 C. At 800 C to 900 C the carbonates break down releasing carbon monoxide and carbon dioxide. Finally, at temperatures up to 1000 C, the surface of the oxide coating is reduced to produce free barium. At this point, the cathode has been activated and will emit electrons when an electric field is present at the cathode surface. The normal operating temperature for a conventional oxide cathode is 800 C to 1000 C, depending on the emission current density required.
  • the wide range of emission characteristics makes it necessary to operate the cathodes at a relatively high temperature such that all cathodes produce the minimum amount of emission.
  • An increased operating temperature increases the evaporation rate of barium from the cathode, thereby reducing the operating lifetime.
  • Contamination by binder materials also plays a role in reducing emission and thus requiring higher operating temperatures .
  • U.S. Pat. no. 4,764,394 to Conrad discloses a method of implanting ions from a plasma source by applying a pulsed voltage between a target and the walls of a vacuum chamber containing the plasma. Conrad does not discuss the deposition of metal oxides which can be used as thermionic cathodes .
  • U.S. Pat. no. 5,039,547 to Jung discloses a method for coating thermionic oxide cathode materials using plasma spraying. Particles of the oxide or carbonate material are inserted into a plasma spray gun simultaneous to injecting a carrier gas such as nitrogen or argon. A plasma formed of the carrier gas between two electrodes heats the material to a high temperature. The plasma and heated particles are directed toward a substrate to be coated with the thermionic emissive material .
  • the method of Jung is characterized in that the material to be deposited is inserted into the apparatus in an oxidized state.
  • U.S. Pat. no. 5,013,578 to Brown et al discloses a method and apparatus for coating a surface using a metal vapor vacuum arc plasma gun.
  • the surface receives a bias voltage synchronized with the pulses of plasma from the plasma gun.
  • the bias voltage enhances the adhesion of the metal atoms to the surface.
  • Brown et al . do not disclose or suggest the use of the plasma gun for depositing thermionic cathode materials or oxide materials .
  • the method begins with producing a beam of ions containing barium ions, strontium ions or calcium ions.
  • the ions are directed toward a substrate surface to receive the oxide thermionic coating.
  • the substrate surface is exposed to oxygen gas.
  • the ions incident upon the surface adhere to the surface and are oxidized by the oxygen gas, producing oxides of barium, strontium, or calcium on the substrate surface.
  • the ions are produced by a metal vapor vacuum arc plasma source.
  • the ion beam is pulsed. Adhesion between the deposited ions and the substrate surface is promoted by providing a negative bias voltage to the substrate during deposition to accelerate the ions toward the substrate.
  • the bias voltage is high (about 2 kV) at the beginning of the deposition process and reduced after adhesion to the substrate is assured.
  • the bias voltage pulses are synchronized with the ion beam pulses .
  • the oxygen gas preferably has a pressure in the range of about 1 x 10 ⁇ 5 to 1 x 10 ⁇ 2 Torr.
  • the oxygen gas should be relatively pure.
  • the partial pressure of all gases other than oxygen totals to less than about 10 ⁇ 7 Torr.
  • the present invention includes oxide thermionic cathodes made according to the method of the present invention.
  • Thermionic cathode coatings made according to the present invention are characterized in part by a high density compared to oxide cathode coatings made according to prior art methods .
  • the present invention also includes an apparatus for forming an oxide thermionic coating on a substrate.
  • the apparatus has a vacuum chamber containing the substrate and a partial pressure of oxygen gas and an ion beam forming device.
  • the ion beam forming device is directed toward the substrate.
  • the ion beam forming device is capable of forming an ion beam having barium, strontium and/or calcium ions.
  • the ion beam forming device is a metal vapor vacuum arc plasma gun.
  • the cathode comprising barium, strontium or calcium it is preferable for the cathode comprising barium, strontium or calcium to have a coating of a material which has a melting temperature higher than the melting temperature of the cathode material (barium, strontium, or calcium) and is relatively resistant to oxidation.
  • the coating is on the sides of the cathode.
  • the coating material can be nickel, for example.
  • the ion beam forming device is an ion gun.
  • the apparatus can also have a bias power supply for supplying a negative bias to the substrate during deposition.
  • the apparatus can also have a bend region and a curved magnetic field producing means.
  • the bend region and curved magnetic field so produced acts as a macroparticle filter to prevent debris particles from reaching the substrate.
  • Fig. 1 is a side view of an apparatus for forming an oxide thermionic coating on a substrate surface according to the present invention.
  • Fig. 2 is a side view of a vacuum arc cathode having a protective coating on the sides of the cathode.
  • Fig. 3 is a side view of an oxide cathode having a substrate with a patterned substrate which can be made by the method of the present invention.
  • Fig. 4 is a side view of an oxide cathode having a reducing agent reservoir.
  • Fig. 1 shows an apparatus for producing a cathode according to the present invention.
  • the apparatus has a metal vapor vacuum arc plasma gun 19.
  • the plasma gun has a cathode 20, and an anode 22 with a hole 24.
  • a power supply 26 applies a voltage between the cathode and anode.
  • a trigger electrode 28 is located next to the cathode.
  • the cathode is made of a material which is to be oxidized and coated onto a surface 37 of a substrate 36. For example, if barium oxide is to be coated on the substrate, the cathode is made of pure barium.
  • the cathode is made of an alloy of barium, strontium, and calcium. In the present specification, the cathode is assumed to be made of barium and strontium, but it is understood that calcium can also be included.
  • the plasma gun 19 has multiple cathodes 20, with each cathode made of a separate material.
  • a plasma gun having separate barium and strontium cathodes can be used to deposit a mixture of barium oxide and strontium oxide.
  • separate plasma guns 19 can be used for each material.
  • two plasma guns, one for barium and one for strontium can be used if a mixture of barium oxide and strontium oxide is desired on the substrate surf ce. The use of such multiple source plasma guns in other contexts is known in the art .
  • the substrate is preferably made of nickel containing traces of reducing agents such as zirconium or tungsten. During operation of an oxide cathode, the reducing agents slowly react with barium oxide to produce a continuous supply of barium metal.
  • Nickel substrates containing reducing agents are commonly used with oxide cathodes and are known in the art.
  • the substrate surface 37 can be smooth or rough, depending on the desired characteristics of the thermionic oxide cathode to be formed.
  • a high voltage trigger pulse is applied to the trigger electrode 28.
  • the resulting trigger discharge initiates a high power discharge between the cathode 20 and anode 22, which is powered by the power supply 26.
  • the high power discharge produces a plasma in a plasma region 29.
  • the plasma is made of barium vaporized from the cathode 20.
  • Barium and strontium ions 31 from the plasma escape through the hole 24 traveling at high speed.
  • the trigger discharge and high power discharge are pulsed and so the plasma gun produces pulses of barium and strontium ions 31 from the hole 24.
  • the ions 31 so produced are typically doubly ionized.
  • the construction and use of metal vapor vacuum arc plasma guns in other contexts is known in the art. Reference can be made to U.S. Pat. nos. 5,013,578, 4,785,220, and 4,714,860 to Brown et al . concerning metal vapor vacuum arc plasma guns.
  • the vacuum arc plasma gun 19 is a specific example of an ion beam forming means which is preferably used in the present invention. Vacuum arc plasma guns are preferred for their high ion flux and therefore fast coating speed. Other ion beam forming devices such as ion guns can also be used with the present invention. Also, extraction grids can be used with the ion gun.
  • Magnet coils 32 produce a curved magnetic field 34.
  • the substrate 36 to be coated with oxide cathode material barium and strontium oxides
  • the bend region contains a vacuum.
  • the curved magnetic field 34 guides the barium and strontium ions 31 from the hole 24 to the substrate 36. Large debris particles are not bent by the magnetic field and so do not reach the substrate 36.
  • the bend region acts as a macroparticle filter, allowing only ions to reach the substrate. Large particles hitting the substrate can cause damage to the oxide coating being formed or damage to the substrate itself.
  • the substrate 36 is located within a vacuum chamber 38 containing a partial pressure of oxygen at low pressure.
  • the vacuum chamber is evacuated with a vacuum pump 40.
  • the oxygen is of high purity and is provided by an oxygen source 42 through a valve 44.
  • the valve 44 may be a precision leak valve. The valve provides an accurate pressure of oxygen inside the vacuum chamber 38.
  • a bias power supply 46 applies a pulsed bias voltage between the substrate 36 and anode 22.
  • the substrate 36 is negative with respect to the anode 24.
  • the bias voltage is synchronized with the ion pulses from the plasma gun 19.
  • the negative bias on the substrate accelerates the positively charged barium and strontium ions 31 towards the substrate, causing some to be implanted into the substrate 36. Some ions will also adhere to the substrate surface 37.
  • the bias voltage also helps the ions adhere to the substrate.
  • Barium ions 31 from the plasma gun are incident upon the substrate and adhere to the substrate.
  • Each pulse from the plasma gun 19 deposits about 0.1 to 1 nanometers of barium.
  • the deposited barium is oxidized by contact with the oxygen present in the vacuum chamber 38.
  • the repetition rate of the plasma gun 19 and the pressure of oxygen in the vacuum chamber 38 are selected so that each layer of barium is completely oxidized before the following pulse of barium ions from the plasma gun 19.
  • the oxygen pressure should be in excess of what is needed for complete oxidation.
  • the oxygen pressure will generally be higher for faster deposition rates.
  • the oxygen pressure can be in the range of about 1 x 10 ⁇ 7 to 1 x 10 _1 Torr, but is preferably in the range of about 1 x 10 "5 to 1 x 10 -2 Torr.
  • the plasma gun is pulsed at a rate of about 1 Hz, deposits 0.1 nanometers of barium per pulse, and the oxygen pressure is between 1 x 10 ⁇ 6 Torr and 1 x 10 -5 Torr. With these parameters, each barium layer is completely oxidized before the following barium layer is deposited.
  • a finished coating suitable for use for a thermionic cathode is about 10-20 microns thick.
  • the oxygen inside the vacuum chamber should be as pure as possible.
  • the oxygen used should have a purity of at least 99%.
  • Residual gases other than oxygen should have a total combined pressure of less than about 1 x 10 -7 Torr.
  • Water vapor is particularly important to remove. Water vapor chemically reacts with barium oxide and so damages the barium oxide coating as it is formed. Water vapor also damages strontium oxide and calcium oxide. Also, hydrocarbons should be removed as completely as possible. Contaminants in the vacuum chamber can poison the oxide coating, increasing its work function and thereby reducing its ability to provide an electron beam.
  • the bias voltage is important for helping the barium ions adhere to the substrate surface 37.
  • the bias voltage should be relatively high. In a preferred embodiment, a bias voltage of about 2 kilovolts is used. This relatively high bias voltage helps the first few layers of barium adhere strongly to the substrate surface. After about 10 nanometers of barium is deposited, the bias voltage is reduced to about 200 to 400 volts. This lower bias voltage is sufficient to cause successive barium layers to adhere to deposited oxide layers and the deposited oxide coating so produced has a high density. Since the barium ions are typically doubly ionized, they have a kinetic energy in electron-Volts which is about twice the value of the bias voltage.
  • barium ions deposited when the bias voltage is 2 kV will strike the substrate surface with a kinetic energy of about 4 keV. Therefore, the bias voltage may not be necessary if the ion beam forming device can produce barium ions having a kinetic energy of about 4keV and about 400-800 eV.
  • the substrate surface can be smooth.
  • Use of a smooth substrate surface results in a final barium oxide coating having a smooth surface. This is beneficial for some applications because an oxide cathode with a smooth surface produces an electron beam with better beam quality. More specifically, an electron beam generated from a smooth surfaced oxide cathode is more uniform and the electron trajectories are more closely parallel.
  • oxide coatings made according to the present invention are characterized in that they have a high density, often in excess of 90 % of the maximum density for the oxide cathode material.
  • Oxide coatings made using binder materials according to prior art methods typically have densities in the range of about 40-50 %. The present invention, therefore, provides cathodes with surprising and unexpected increases in very desirable properties compared with known cathodes .
  • the cathode becomes very hot and can melt the barium, strontium, and/or calcium cathode.
  • the cathode material is typically very reactive and forms an insulating oxide layer when exposed to the atmosphere.
  • Fig. 2 shows a vacuum arc cathode according to the present invention which prevents problems associated with the cathode being exposed to high temperatures and the ambient atmosphere.
  • the cathode 20 has a coating 50 made of a material with a melting temperature higher than the melting temperature of the cathode material and resistant to oxidation.
  • the coating 50 is made of nickel.
  • the nickel coating is about 0.2 to 0.5 millimeters thick.
  • the coating holds the cathode material if the cathode melts during plasma gun operation.
  • the plasma gun 19 can operate with a molten cathode 20.
  • the coating also prevents oxidation of the sides of the cathode.
  • the nickel coating 50 is not eroded by the high power plasma discharge in the vacuum arc plasma gun 19.
  • the present plasma deposition technique eliminates the problems with the conventional methods for oxide cathode production.
  • the plasma deposition process is easily controlled and very repeatable .
  • the oxide is deposited directly and no carbonates or binders are required.
  • the accelerated ions adhere strongly to the nickel surface providing superior adhesion.
  • FIG. 3 A particular embodiment of an oxide cathode made according to the present invention is shown in Fig. 3.
  • the substrate surface 37 is not smooth.
  • the surface 37 has patterned or etched pits in regions. This results in a deposited oxide coating 52 having a nonuniform thickness which in turn results in a reduction of the electrical resistance of the coating.
  • the electrical resistance is measured between the substrate surface 37 and a top surface 53 of the coating 52. It is sometimes desirable to have a low resistance coating because a high resistance limits the flow of electrons from the oxide cathode surface 53.
  • a reduced resistance of the coating 52 allows the coating to be thicker while still maintaining an acceptably low coating resistance. This is beneficial because a thicker oxide coating 52 has a longer lifetime.
  • reservoirs of metallic barium 55 can be deposited in the recessed pits of the substrate surface 37.
  • the barium 55 is deposited on the substrate surface before the oxide coating 52.
  • the barium reservoirs 55 increase the lifetime of the oxide cathode .
  • the substrate 36 has a well defined thickness 58 and a reservoir 60 of reducing agent material is diffusion bonded to a back surface of the substrate 36.
  • the reservoir can comprise a slab of tungsten/ zirconium alloy, for example.
  • the reducing agents from the reservoir 60 diffuse through the substrate 36 and react with the oxide coating 52.
  • the thickness of the substrate 58 is selected such that the diffusion rate of reducing agents through the substrate 36 matches the evaporation rate of barium from the coating surface 53. This results in the oxide cathode having a relatively long operating lifetime.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Cathode thermo-ionique et procédé de fabrication de ladite cathode qui consiste à déposer un revêtement d'oxyde thermo-ionique sur une surface de substrat. Le revêtement comporte de l'oxyde de baryum, de l'oxyde de strontium ou de l'oxyde de calcium ou une combinaison desdits oxydes. Un faisceau ionique ayant des ions de barium, de strontium, ou de calcium est dirigé vers la surface (37) du substrat. Les ions (31) possèdent une énergie cinétique suffisante pour provoquer leur adhérence sur le substrat. La surface de substrat est exposée à de l'oxygène pur. Dans un mode de réalisation particulier, l'oxygène présente une pression d'environ 5 x 10-6 torr. L'oxygène réagit avec les ions déposés, formant ainsi le revêtement d'oxyde thermo-ionique. De préférence, le faisceau ionique est généré par un pistolet (19) à plasma à arc sous vide à vapeurs métalliques. De préférence également, les ions sont accélérés vers la surface de substrat à l'aide d'une tension de polarisation d'accélération appliquée sur le substrat par un dispositif d'alimentation (46) en puissance polarisée destiné à aider les ions à adhérer à la surface du substrat.
PCT/US1998/010045 1997-05-16 1998-05-15 Procede et appareil permettant de fabriquer des cathodes a revetement d'oxyde thermo-ionique WO1998051417A1 (fr)

Applications Claiming Priority (2)

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US4673197P 1997-05-16 1997-05-16
US60/046,731 1997-05-16

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WO1998051417A1 true WO1998051417A1 (fr) 1998-11-19

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1863947B1 (fr) * 2005-03-24 2011-10-05 Oerlikon Trading AG, Trübbach Couche de materiau solide
CN111392762A (zh) * 2020-04-09 2020-07-10 沈阳师范大学 一种基于金属离子注入的氧化铜纳米线阵列场发射阴极材料的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3678325A (en) * 1969-03-14 1972-07-18 Matsushita Electric Ind Co Ltd High-field emission cathodes and methods for preparing the cathodes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3678325A (en) * 1969-03-14 1972-07-18 Matsushita Electric Ind Co Ltd High-field emission cathodes and methods for preparing the cathodes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1863947B1 (fr) * 2005-03-24 2011-10-05 Oerlikon Trading AG, Trübbach Couche de materiau solide
CN111392762A (zh) * 2020-04-09 2020-07-10 沈阳师范大学 一种基于金属离子注入的氧化铜纳米线阵列场发射阴极材料的制备方法

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