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EP0757370A1 - Tube à décharge électrique ou lampe à décharge et cathode à réserve comprenant du scandate - Google Patents

Tube à décharge électrique ou lampe à décharge et cathode à réserve comprenant du scandate Download PDF

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Publication number
EP0757370A1
EP0757370A1 EP96202114A EP96202114A EP0757370A1 EP 0757370 A1 EP0757370 A1 EP 0757370A1 EP 96202114 A EP96202114 A EP 96202114A EP 96202114 A EP96202114 A EP 96202114A EP 0757370 A1 EP0757370 A1 EP 0757370A1
Authority
EP
European Patent Office
Prior art keywords
layer
cathode
scandium
alloy
tungsten
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96202114A
Other languages
German (de)
English (en)
Other versions
EP0757370B1 (fr
Inventor
Georg Dr. Gärtner
Peter Dr. Geittner
Ernst Klein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Philips Intellectual Property and Standards GmbH
Koninklijke Philips NV
Original Assignee
Philips Corporate Intellectual Property GmbH
Philips Patentverwaltung GmbH
Koninklijke Philips Electronics NV
Philips Electronics NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Philips Corporate Intellectual Property GmbH, Philips Patentverwaltung GmbH, Koninklijke Philips Electronics NV, Philips Electronics NV filed Critical Philips Corporate Intellectual Property GmbH
Publication of EP0757370A1 publication Critical patent/EP0757370A1/fr
Application granted granted Critical
Publication of EP0757370B1 publication Critical patent/EP0757370B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02Main electrodes
    • H01J1/13Solid thermionic cathodes
    • H01J1/20Cathodes heated indirectly by an electric current; Cathodes heated by electron or ion bombardment
    • H01J1/28Dispenser-type cathodes, e.g. L-cathode

Definitions

  • the invention relates to an electric discharge tube, in particular a vacuum electron tube, or a discharge lamp, in particular a low-pressure gas discharge lamp, with at least one scan data storage cathode, which consists of a cathode body and a cover layer with an emitting surface, the cathode body being a matrix of at least one high-melting metal and / or a refractory alloy and a barium compound in contact with the matrix material to supply barium to the emitting surface by chemical reaction with the matrix material. It also relates to such a Scandat supply cathode.
  • Electron tubes in particular vacuum electron tubes, are primarily used as picture tubes in televisions, as monitor tubes, as X-ray tubes, as high-frequency and microwave tubes for various applications in the construction of equipment and systems in every sector, in medical technology, in diagnostic and measuring equipment in workshops and also in gaming equipment .
  • TV and monitor tubes are subject to ever increasing demands in terms of greater brightness, increased resolution, constant image quality and better long-term operation.
  • higher electron emission current densities in the tubes are necessary, which can only be achieved with improved electron sources, ie cathodes.
  • standard oxide cathodes with an emission current density of 2 A / cm 2 met long-term operation, currently 10 A / cm 2 are required and far higher emission current densities are required for the new high-performance tubes.
  • a cathode with a lower work function ⁇ can deliver a higher emission current density at the same operating temperature T.
  • a cathode with a lower work function ⁇ allows operation at lower temperatures with the same current density.
  • a lower operating temperature has a positive effect on the service life of the cathode and the discharge tube.
  • Scandat supply cathodes are currently the cathodes with the highest electron emission.
  • the two most important types of Scandat supply cathodes are the “Mixed Matrix Scandat Cathode” and the “Top Layer Scandat Cathode”.
  • the "Mixed Matrix Scandat Cathode” consists of a porous cathode body made of tungsten and scandium oxide, which is impregnated with 4 BaO.CaO.Al 2 O 3 .
  • Top Layer Scandat Cathodes consist of a porous tungsten body, which is impregnated with 4 BaO.CaO.Al 2 O 3 and is covered with a thin cover layer made of tungsten and scandium oxide or Sc 2 W 3 O 12 .
  • EP 0 317 002 proposed to use scandium-containing metal compounds or alloys which are a compound of scandium with one or more of the metals rhenium, ruthenium, hafnium, nickel, cobalt, palladium, zirconium or tungsten Use scandium segregation in the surface of the cathode.
  • the long-term behavior of the cathodes according to EP 0 317 002 is improved, but the reproducibility of the results leaves something to be desired.
  • EP 0 549 034 discloses a cathode with a matrix body impregnated with an alkaline earth metal compound, on the surface of which a cover layer is applied, which contains high-melting metal such as, in particular, tungsten and scandium.
  • a cover layer contains at least two layers of different composition, with a purely metallic layer being applied to the impregnated matrix body, which contains scandium and a high-melting metal such as contains in particular tungsten and / or rhenium, and that a metallic layer made of a high-melting metal such as in particular tungsten is applied as the final layer.
  • cathodes are preferably produced by a process in which initially purely metallic layers of scandium and / or rhenium are produced by means of a plasma-activated CVD process in particular, preferably by means of a plasma generated by direct current glow discharge, and then by means of a metallic tungsten layer as the last layer CVD process is applied.
  • a plasma-activated CVD process in particular, preferably by means of a plasma generated by direct current glow discharge, and then by means of a metallic tungsten layer as the last layer CVD process is applied.
  • the emission current density of this type of cathode is low.
  • the object of the invention is therefore to create an electrical discharge tube or discharge lamp which delivers reproducibly high emission current densities over a long period of time.
  • an electrical discharge tube or discharge lamp with at least one scandate supply cathode which consists of a cathode body and a cover layer with an emitting surface, the cathode body comprising a matrix of at least one high-melting metal and / or a high-melting alloy and a barium compound in contact with the matrix material for supplying barium to the emitting surface by chemical reaction with the matrix material and the top layer one or more times a layer composite of optionally a lower layer of tungsten and / or a tungsten alloy, an intermediate layer of rhenium and / or a rhenium alloy and a top layer of scandium oxide, a mixture of scandium oxide with rare earth oxides, a scandate and / or a scandium alloy.
  • Such a discharge tube or discharge lamp has a long service life because it shows good resistance to ion bombardment with doses up to a few 10 19 ions / cm 2 .
  • it can be used as a high-resolution computer monitor (CMT), in high-definition television sets with a screen aspect ratio of 16: 9 and as a high-performance X-ray tube, because at 965 ° C, measured as the radiation temperature of the molybdenum cap of the cathode holder, it has a saturation emission current density i 0 of ⁇ 25 A / cm 2 reached.
  • CMT computer monitor
  • a scandate supply cathode which consists of a cathode body and a cover layer with an emitting surface, the cathode body comprising a matrix of at least one high-melting metal and / or a high-melting alloy and a barium compound in contact with the matrix material for delivery from barium to the emitting surface by chemical reaction with the matrix material and the top layer one or more times a layer composite of optionally a lower layer of tungsten and / or a tungsten alloy, an intermediate layer of rhenium and / or a rhenium alloy and an upper layer of scandium oxide, a mixture of scandium oxide Contains rare earth metal oxides, a scandate and / or a scandium alloy.
  • the scandate supply cathode according to the invention has little tungsten loss and the scandium supply into the emitting surface is not passivated during operation.
  • the layer structure prevents oxygen diffusion to the tungsten.
  • a scandate supply cathode according to the invention in which the cathode body has a scandium compound or a scandium alloy for subsequent delivery of scandium to the emitting surface, has a particularly long service life.
  • the layer composite consist of ultrafine particles.
  • Scandate supply cathodes with a cover layer made of ultrafine particles have a surface structure and surface modulation from particles in the diameter range from 1 to 100 nm, i.e. they have relatively small radii of curvature in dense particle and tip distribution on the macroscopic surface.
  • the layer composite in the top layer of the scandate supply cathode according to the invention is produced by a laser ablation deposition process.
  • the laser ablation deposition process has short reaction times.
  • the grain size distribution of the ultrafine particles is easy to control, in contrast to known evaporation processes.
  • the lower layer, intermediate layer and upper layer each have a layer thickness of 5 to 150 nm. Scandat supply cathodes with such layers have excellent emitter properties.
  • the cover layer of the scandate supply cathodes according to the invention has a layer thickness of 50 to 1000 nm, preferably 400 to 600 nm. This achieves a cathode life of 10,000 hours.
  • An electrical discharge tube or discharge lamp consists of four functional groups: electron beam generation, beam focusing, beam deflection and the fluorescent screen.
  • the electron beam generation system of the discharge tubes or discharge lamps according to the invention contains an arrangement of one or more supply cathodes.
  • the electron gun can be one or more point cathodes or a system of one or more wire cathodes, flat ribbon cathodes or surface cathodes. Wire cathodes, surface cathodes and ribbon cathodes do not have to emit over their entire surface. They can also contain the emitting supply cathode arrangement only in individual surface segments.
  • a supply cathode according to the invention consists of a cathode body and a cover layer.
  • the cathode body comprises a matrix of at least one high-melting metal and / or a high-melting alloy and a barium compound in contact with the matrix material for supplying barium to the emitting surface by chemical reaction with the matrix material.
  • Storage cathodes of a known type such as L-cathodes, M-cathodes and I-cathodes and mixed-matrix cathodes, are suitable as cathode bodies for the invention.
  • I-cathodes and mixed-matrix cathodes are particularly suitable as cathode bodies.
  • the cover layer of the cathodes according to the invention contains one or more layers of a composite of optionally a lower layer of tungsten and / or a tungsten alloy, an intermediate layer of rhenium and / or rhenium alloy and an upper layer of scandium oxide, a mixture of scandium oxide with rare earth metal oxides, a scandate and / or a scandium alloy.
  • the total thickness of the cover layer is dimensioned so that the cathode has an adequate service life.
  • the service life of supply cathodes is limited by erosion due to sputtering reactions on the cathode surface. Ions are involved in the sputtering reaction, which are formed by the electron beam from the residual gases in the vacuum of the discharge tube or discharge lamp.
  • the total layer thickness of the cover layer is estimated from this erosion rate. In general, the total thickness of the top layer will be 600 to 1000 nm.
  • the individual layers of the layer composite ie the lower layer with tungsten, the intermediate layer made of rhenium and the upper layer with scandium oxide or a scandium alloy should preferably be very thin.
  • the mass-equivalent layer thickness of the scandium layer should preferably be in the nanometer range between 5 and 20 nm, that of the tungsten- and rhenium-containing layer between 20 and 200 nm.
  • the mass-equivalent layer thicknesses are determined from the theoretical densities and applied basis weights of the cover layer substances.
  • the cover layer has a slightly dissolved, radially and laterally structured surface. If the particles of the lower layer, the intermediate layer and the upper layer are deposited one after the other, their nanostructures interlock and a material combination is created in the cover layer which has excellent emitter properties.
  • the lowermost tungsten-containing layer can also be formed by the tungsten-containing matrix of the cathode body.
  • Scandium oxide Sc 2 O 3 or scandium oxide which is mixed with the oxides of other rare earth metals such as europium, samarium and cerium, and scandates, for example alkaline earth metal scandates, can be used as material for the scandium-containing upper layer.
  • alloys containing scandium and / or intermetallic compounds such as Re 24 Sc 5 , Re 2 Sc, Ru 2 Sc, Co 2 Sc, Pd 2 Sc and Ni 2 Sc can be used.
  • these compounds, compound mixtures or alloys should not contain tungsten.
  • Metallic rhenium is used as the material for the rhenium-containing intermediate layer.
  • Tungsten or a tungsten alloy containing osmium, iridium, ruthenium, tantalum and / or molybdenum is selected as the material for the underlayer.
  • the production process for the supply cathode according to the invention is a two-step process. It begins with the production of the cathode body, to which the emitting cover layer is then applied in a second step.
  • cathode bodies Conventional I-cathodes or mixed-matrix cathodes are preferred as cathode bodies.
  • I cathodes are impregnated supply cathodes. They consist of a porous tungsten matrix produced by powder metallurgy from tungsten powder. This porous matrix is impregnated with a mixture of BaO, CaO and Al 2 O 3 . For this purpose, a mixture of BaCO 3 , CaCO 3 and Al 2 O 3 is melted and the porous matrix is filled with the mixture by melt infiltration. The surface of the body is then cleaned by ultrasound and water from externally adhering oxide mixture.
  • Mixed matrix cathodes contain scandium in a common matrix of tungsten and scandium oxide.
  • the matrix is produced by sintering a powder mixture of tungsten and scandium oxide, the sintering process being carried out in such a way that a porous body is formed.
  • This porous sintered body is then impregnated with the same method as for the I cathodes with a mixture of BaO, CaO and Al 2 O 3 .
  • the cleaning and activation procedures are also the same.
  • the top layer can be produced using conventional coating processes. These methods include CVD, PCVD, and sputtering. However, it is preferred in the context of the present invention that the individual layers of the cover layer are produced from ultrafine particles in a laser ablation deposition process.
  • the cathode body is brought into the deposition chamber of a laser ablation deposition system. It is favorable to use an excimer laser as the laser, which unlike CO 2 lasers also ablates tungsten without any problems. If necessary, the tungsten-containing layer is deposited first, the rhenium-containing layer second, and the scandium-containing layer third. It's cheap multi-targets to use, which contain all three components on a target arrangement.
  • the emission properties of the finished scandate supply cathode are favorably influenced if the gas atmosphere in the ablation process consists of high-purity argon or argon / hydrogen.
  • the substrates (cathode bodies) for the cover layer are heated during the ablation deposition process.
  • the conditions for the laser ablation deposition process are set so that the grain size of the ultrafine particles is in a medium to high range.
  • the emitting surface of the cathode is activated in a further process step.
  • An I-cathode body is produced in the form of a porous pill by sintering tungsten powder at 1500 ° C. in a hydrogen atmosphere to a cylindrical body 1.8 mm in diameter and 0.5 mm in height and with 7% by weight barium calcium aluminate powder having the composition 4 BaO- CaO-Al 2 O 3 is impregnated.
  • the pill is inserted into a molybdenum bowl and placed in the ablation chamber of a laser ablation deposition apparatus.
  • a cylindrical multitarget is used as the target, which contains Sc 2 O 3 , rhenium and tungsten side by side.
  • the laser is a UV excimer laser with a wavelength of 248 nm and an average power of 100 W, which produces a cold ablation on the rotating target.
  • a mixture of high-purity argon and hydrogen is used as the carrier gas.
  • the total pressure in the ablation chamber was 1 mbar.
  • the multitarget is translated and the three partial areas of the target are scanned continuously in the order of tungsten, rhenium, and scandium oxide. To fix the coating, the tungsten pills are heated to 800 ° C. during the coating process.
  • the ablation deposition process is continued until a mass-equivalent total layer thickness of 600 nm is reached.
  • the pill with the cover layer according to the invention is welded onto a cathode shaft which contains a heating coil.
  • This indirectly heated cathode is assembled with other components, such as radiation cylinders and ceramic insulation, to form a cathode unit. Three of these units are then installed in a color television tube.
  • the measured emission current density of the cathode was 120 A / cm 2 at a cathode temperature of 950 ° C.
  • An I-cathode body is produced in the form of a porous pill by sintering tungsten powder at 1500 ° C. in a hydrogen atmosphere to a cylindrical body 1.8 mm in diameter and 0.5 mm in height and with 7% by weight barium calcium aluminate powder having the composition 4 BaO- CaO-Al 2 O 3 is impregnated.
  • the pill is inserted into a molybdenum bowl and placed in the ablation chamber of a laser ablation deposition apparatus.
  • a cylindrical multitarget containing Sc 2 O 3 and rhenium side by side is used as the target.
  • the laser is a UV excimer laser with a wavelength of 248 nm and an average power of 100 W, which produces a cold ablation on the rotating target.
  • a mixture of high-purity argon and hydrogen is used as the carrier gas.
  • the total pressure in the ablation chamber was 1 mbar.
  • a Re layer with a mass-equivalent layer thickness of 120 nm and a scandium oxide layer with a mass-equivalent layer thickness of 20 nm are deposited in each case. This sequence of layers is repeated five times.
  • the tungsten pills are heated to 800 ° C. during the coating process.
  • the pill with the cover layer according to the invention is welded onto a cathode shaft which contains a heating coil.
  • This indirectly heated cathode is assembled with other components, such as radiation cylinders and ceramic insulation, to form a cathode unit. Three of these units are then installed in a color television tube.
  • the measured emission current density of the cathode was 25 A / cm 2 at a cathode temperature of 980 ° C.

Landscapes

  • Solid Thermionic Cathode (AREA)
  • Discharge Lamp (AREA)
EP96202114A 1995-07-31 1996-07-25 Tube à décharge électrique ou lampe à décharge et cathode à réserve comprenant du scandate Expired - Lifetime EP0757370B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19527723 1995-07-31
DE19527723A DE19527723A1 (de) 1995-07-31 1995-07-31 Elektrische Entladungsröhre oder Entladungslampe und Scandat-Vorratskathode

Publications (2)

Publication Number Publication Date
EP0757370A1 true EP0757370A1 (fr) 1997-02-05
EP0757370B1 EP0757370B1 (fr) 2000-07-05

Family

ID=7768092

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96202114A Expired - Lifetime EP0757370B1 (fr) 1995-07-31 1996-07-25 Tube à décharge électrique ou lampe à décharge et cathode à réserve comprenant du scandate

Country Status (4)

Country Link
US (1) US6348756B1 (fr)
EP (1) EP0757370B1 (fr)
JP (1) JP3957344B2 (fr)
DE (2) DE19527723A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013018027A1 (fr) 2011-08-03 2013-02-07 Koninklijke Philips Electronics N.V. Cible pour une cathode à diffusion riche en barium et en scandate

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19828729B4 (de) * 1998-06-29 2010-07-15 Philips Intellectual Property & Standards Gmbh Scandat-Vorratskathode mit Barium-Calcium-Aluminat-Schichtabfolge und korrespondierende elektrische Entladungsröhre
DE19961672B4 (de) * 1999-12-21 2009-04-09 Philips Intellectual Property & Standards Gmbh Scandat-Vorratskathode
DE50112861D1 (de) * 2000-09-19 2007-09-27 Philips Intellectual Property Oxidkathode
EP2293316B1 (fr) 2003-02-14 2012-04-04 Mapper Lithography IP B.V. Cathode à réserve
US20100060136A1 (en) * 2004-12-09 2010-03-11 Koninklijke Philips Electronics, N.V. Cathode for electron emission
JP2008524794A (ja) * 2004-12-21 2008-07-10 コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ スカンデート含浸型カソード
JP2009508320A (ja) * 2005-09-14 2009-02-26 リッテルフューズ,インコーポレイティド ガス入りサージアレスタ、活性化化合物、点火ストライプ及びその方法
JP2008204837A (ja) * 2007-02-21 2008-09-04 Sumitomo Electric Ind Ltd 冷陰極蛍光ランプ用電極

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0052047A1 (fr) * 1980-11-07 1982-05-19 Thomson-Csf Cathode thermo-électronique
GB2170950A (en) * 1985-02-08 1986-08-13 Hitachi Ltd Impregnated cathode
EP0317002A1 (fr) * 1987-11-16 1989-05-24 Koninklijke Philips Electronics N.V. Cathode à scandate
US5218263A (en) * 1990-09-06 1993-06-08 Ceradyne, Inc. High thermal efficiency dispenser-cathode and method of manufacture therefor
EP0549034A1 (fr) * 1991-12-21 1993-06-30 Philips Patentverwaltung GmbH Cathode et son procédé de fabrication
EP0641007A2 (fr) * 1993-08-31 1995-03-01 Samsung Display Devices Co., Ltd. Structure de cathode à réserve du type à chauffage direct

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GB2050045A (en) * 1979-05-29 1980-12-31 Emi Varian Ltd Thermionic cathode
NL8403032A (nl) * 1984-10-05 1986-05-01 Philips Nv Werkwijze voor het vervaardigen van een scandaatnaleveringskathode, naleveringskathode vervaardigd met deze werkwijze.
US4904896A (en) * 1984-11-27 1990-02-27 Rca Licensing Corporation Vacuum electron tube having an oxide cathode comprising chromium reducing agent
EP0248417B1 (fr) * 1986-06-06 1992-11-11 Kabushiki Kaisha Toshiba Cathode imprégnée
JPS63224127A (ja) * 1987-03-11 1988-09-19 Hitachi Ltd 含浸形陰極
US4823044A (en) * 1988-02-10 1989-04-18 Ceradyne, Inc. Dispenser cathode and method of manufacture therefor
US5138224A (en) * 1990-12-04 1992-08-11 North American Philips Corporation Fluorescent low pressure discharge lamp having sintered electrodes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0052047A1 (fr) * 1980-11-07 1982-05-19 Thomson-Csf Cathode thermo-électronique
GB2170950A (en) * 1985-02-08 1986-08-13 Hitachi Ltd Impregnated cathode
EP0317002A1 (fr) * 1987-11-16 1989-05-24 Koninklijke Philips Electronics N.V. Cathode à scandate
US5218263A (en) * 1990-09-06 1993-06-08 Ceradyne, Inc. High thermal efficiency dispenser-cathode and method of manufacture therefor
EP0549034A1 (fr) * 1991-12-21 1993-06-30 Philips Patentverwaltung GmbH Cathode et son procédé de fabrication
EP0641007A2 (fr) * 1993-08-31 1995-03-01 Samsung Display Devices Co., Ltd. Structure de cathode à réserve du type à chauffage direct

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013018027A1 (fr) 2011-08-03 2013-02-07 Koninklijke Philips Electronics N.V. Cible pour une cathode à diffusion riche en barium et en scandate

Also Published As

Publication number Publication date
JPH09106751A (ja) 1997-04-22
DE59605538D1 (de) 2000-08-10
US6348756B1 (en) 2002-02-19
EP0757370B1 (fr) 2000-07-05
DE19527723A1 (de) 1997-02-06
JP3957344B2 (ja) 2007-08-15

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