EP1385190A1 - Cathode à oxyde pour canon à électrons avec un substrat métallique présentant un dopage différentiel - Google Patents

Cathode à oxyde pour canon à électrons avec un substrat métallique présentant un dopage différentiel Download PDF

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Publication number
EP1385190A1
EP1385190A1 EP02291859A EP02291859A EP1385190A1 EP 1385190 A1 EP1385190 A1 EP 1385190A1 EP 02291859 A EP02291859 A EP 02291859A EP 02291859 A EP02291859 A EP 02291859A EP 1385190 A1 EP1385190 A1 EP 1385190A1
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EP
European Patent Office
Prior art keywords
weight concentration
inferior
cathode
layer
substrate
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.)
Withdrawn
Application number
EP02291859A
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German (de)
English (en)
Inventor
Jean-Michel Roquais
D.J. Wierschke
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Thomson Licensing SAS
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Thomson Licensing SAS
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Publication date
Application filed by Thomson Licensing SAS filed Critical Thomson Licensing SAS
Priority to EP02291859A priority Critical patent/EP1385190A1/fr
Priority to EP03771116A priority patent/EP1535298B1/fr
Priority to DE60305931T priority patent/DE60305931T2/de
Priority to PCT/EP2003/050323 priority patent/WO2004012217A1/fr
Priority to CNB038172151A priority patent/CN100437874C/zh
Priority to US10/522,115 priority patent/US7208864B2/en
Priority to PL03374774A priority patent/PL374774A1/xx
Priority to AU2003262530A priority patent/AU2003262530A1/en
Priority to JP2004523813A priority patent/JP2005534153A/ja
Priority to MXPA05001022A priority patent/MXPA05001022A/es
Publication of EP1385190A1 publication Critical patent/EP1385190A1/fr
Withdrawn legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details 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
    • H01J1/02—Main electrodes
    • H01J1/13—Solid thermionic cathodes
    • H01J1/20—Cathodes heated indirectly by an electric current; Cathodes heated by electron or ion bombardment
    • H01J1/26—Supports for the emissive material

Definitions

  • the present invention concerns the oxide cathodes that are commonly used, as an electron source, in electron guns for cathode ray-tubes.
  • the electrons are emitted from the cathode thanks to a thermoionic effect.
  • Cathode ray-tubes are mainly used as display device for computers or television.
  • a conventional oxide cathode comprises
  • the conventional oxide cathode shown on figure 1 comprises more precisely a cup-liked shape nickel alloy monolayer substrate 1, a tube-liked shape sleeve 2 made of an alloy containing at least Ni and Cr, onto which the metallic substrate 1 is welded.
  • a cathodo-emissive layer 3 of double or triple carbonates i.e. a mixture of (Ba, Sr) CO 3 or (Ba, Sr, Ca) CO 3 is deposited onto the substrate 1.
  • a double layer of nickel alloys is also commonly used as a metallic substrate (see for example US n° 3,919,751, G.T.E Sylvania Inc.).
  • This double layer is commonly referred to as a bimetal.
  • a cathode using a bimetal for a metallic substrate 1 is shown in figure 2.
  • the double layer comprises a top layer 11 of nickel or an alloy of nickel containing 1 to 5 % tungsten or alternatively 1 to 5 % molybdenum (in weight percent) bonded to a bottom layer 12 of alloy of nickel and chromium (typically an alloy called "nichrome", containing 20 % Cr, the remainder being essentially Ni).
  • the double layer substrate 1 comprising nickel top layer 11 and nickel-chromium bottom layer 12 can be formed into a cup which is welded onto a nickel-chromium sleeve 2, as described on figure 2.
  • this cathode is also called a "two-piece cathode", as the other conventional cathode described on figure 1.
  • a usual cathodo-emissive layer 3 is made of triple carbonates, i.e. a mixture of (Ba, Sr, Ca) CO 3 , that is deposited onto the top layer 11. The deposited layer is heated to its operating temperature by thermal radiation of a heater 4 inserted into the sleeve 2 as in figure 1.
  • a bimetal strip which comprises a top layer 11 and a bottom layer 12 as previously described in reference to figure 2, is formed into a tube which is closed at one end, with the nickel-based top layer 11 appearing as the outside face of the tube.
  • the creation of the metallic baryum is maintained through the cathode life by reduction of BaO into Ba caused by the chemical reaction of BaO with all elements contained in the nickel having a reducing power with respect to BaO.
  • the chemical reduction occurs at the operating temperature of the cathode (typically 700 °C - 850 °C) or at any step of the fabrication of the cathode ray tube where the cathode is heated, for instance the activation step designed to bring a cathode to its optimum emission capabilities.
  • the reducing elements contained in the substrate 1 thermally diffuse to the interface between the substrate 1 and the cathodo-emissive layer 3 where they react with BaO to liberate metallic Ba and form reaction compounds.
  • Examples of chemical reactions between reducing elements and BaO are given below for Mg, Al, Si and W :
  • Metallic barium at the operating temperature of the cathode, constantly evaporates from the cathodo-emissive layer 3. To maintain good emission properties, this loss of barium must be compensated by the creation of metallic barium through chemical reactions as described above.
  • the flux of reducing elements that react with BaO must not go below the minimum level necessary to create the amount of metallic barium needed for good emission properties to be sustained.
  • the reducing elements come to the interface between the double-layer substrate 1 and the cathodo-emissive layer 3 by diffusion from the top layer 11 of the substrate.
  • the reducing elements contained in the bottom layer 12 migrate from the bottom layer 12 into the top layer 11, as these reducing elements can also diffuse further to the interface between the top layer 11 and the cathodo-emissive layer 3 to play a positive role for cathode life, they act in fact as an additional reserve of reducing elements.
  • the increase of silicon concentration in the top layer 11, measured by the ICP method (Inductively Coupled Plasma) as a function of operation time of such various cathodes is displayed.
  • the initial concentration of silicon is the concentration on the metal of the top layer 11, as set at the elaboration of this metal.
  • the enrichment of the top layer in silicon with time is attributed to the diffusion of the silicon from the bottom layer 12 to the top layer 11.
  • the average concentration of silicon in the nichrome bottom layer is 0.18 %.
  • the difference between this value of concentration in the bottom layer and the value in the nickel top layer is the driving force for the diffusion of Si from the bottom to the top layer.
  • Mg or Zr as a fast activator acting at the beginning of cathode life combined with Si or Al as a long-term activator to extend cathode life when the fast activator is no longer acting.
  • Two main factors are known to limit the flux of reducing elements to the interface between the top layer 11 and the cathodo-emissive layer 3. Firstly, as the reducing elements are consumed in the reaction with BaO, their concentration in the top layer 11 tends to decrease with life, and accordingly, their flux to this interface decreases. Complete exhaustion of the reducing elements can even occur if their initial concentration in the top layer 11 is low.
  • this blocking layer starts to be created at the annealing steps performed on the substrate 1 prior to deposition of the cathodo-emissive layer 3.
  • the reducing elements are oxidized by minute amounts of oxygen resulting in the creation of MgO, SiO 2 or Al 2 O 3 .
  • the oxygen comes from the decomposition of the water vapor added in the atmosphere of the furnace used for annealing, usually composed of excess hydrogen. Then, this blocking layer is further built up during cathode operations.
  • the interfacial compounds that mainly build-up during life are the W-based compounds and the Si-based compounds.
  • the thickness E of the substrate has to be taken into account for the design of the cathodes for cathode ray tubes, such as display tubes for computers or television.
  • the electron-beam turn-on time is directly linked to the time needed for the cathode to reach its operating temperature. This time increases with the cathode weight so it is of importance to have the substrate 1 with the lowest possible weight.
  • the lowest thickness commonly used for cathode metallic substrate 1 is about 70-100 ⁇ m, but such a low thickness forbids the use of low concentrations of reducing elements in this substrate, because firstly, at least 1 % of W and/or Mo in weight in the nickel used for the substrate is necessary to maintain a good mechanical strength of the substrate and secondly, the concentration of the active reducing elements like Mg or Si cannot be set at low levels around 0.01 % in weight because the reserve of reducing elements would be too low. If the thickness of the substrate is increased in a range of 150 to 200 ⁇ m, far lower concentration of W and/or Mo can be used for the substrate based on nickel, but the turn-on-time is degraded in comparison with a substrate thickness of 70 ⁇ m.
  • top face 111 is the surface on which the cathodo-emissive layer 3 is deposited and bottom face 122 as the surface of the substrate which is opposite to top face 111, as shown on figure 3.
  • Bottom face 122 faces the heater 4 and several electrical metallic connectors of the electron gun which are not represented.
  • the deposition of the metallic vapors of reducing elements coming from the cathode onto these electrical connectors create electrical leakages or shortcuts between electrodes of the gun detrimental to the good operation of the electron gun in the cathode-ray tube.
  • the subject of the invention is an oxide cathode for an electron gun comprising
  • the present invention brings simultaneously the following advantages ;
  • Si and Al together as the so-called second reducing agent, it is preferred to have either Si alone, either Al alone to avoid adhesion problems of the cathodo-emissive layer on the substrate.
  • Such weight concentration may be measured by any known analytical methods, preferably by ICP (Inductively Coupled Plasma) spectrometry.
  • ICP Inductively Coupled Plasma
  • This bottom part of the substrate where the Cr weight concentration is superior or equal to 12 % constitutes a bottom layer which gives advantageously the substrate enough mechanical strength, allowing the very low concentration of W on the top face or from this face up to said top depth into the substrate.
  • the said substrat comprises two superimposed bonded metallic layers : a top layer and a bottom layer.
  • Such two superimposed bonded metallic layers forms a so-called bimetal.
  • the invention brings advantageously an optimized usage of a bimetal as a cathode metallic substrate. Taking the opportunity that a given doping element can be added in the two layers constituting the bimetal, for instance a nickel based top layer and a nichrome based bottom layer, at two different concentrations, it is proposed in the present invention to dope the two layers differently as far as the first reducing agent Mg and the second reducing agent Si and/or Al are concerned.
  • the low Mg doping level according to the invention in the top layer preferably high enough so as to have enough Mg at top face initially to ensure good cathode emission properties in the early life, while having almost no Mg in the bottom layer to limit Mg evaporation towards electrical connectors facing bottom face and resulting metallic film causing electrical leakages between electrodes of the electron gun.
  • the low Si and/or Al doping level according to the invention in the top layer so as to limit the initial formation of detrimental interfacial compounds and of a blocking layer between the top face and the cathodo-emissive layer
  • the high Si and/or Al doping level according to the invention in the bottom layer so as to get a high reserve of Si ensuring long-term cathode life despite the moderate Si and Mg concentrations in the top layer.
  • This difference in doping of the two layers of the bimetal used as a substrate for the cathode according to the invention can be summarized as being a "differential doping", offering the advantages described above.
  • This double layer substrate has :
  • the said bottom layer is made of nichrome.
  • nichrome Such a Ni-Cr alloy is well-known for electron gun parts ; Cr weight concentration lies generally in the range 12% to 40% ; the minimum thickness of such a bottom layer would be around 15 ⁇ m.
  • a nichrome bottom layer ensures the stiffness of the substrate and brings good thermo-mechanical behavior to the cathode, it is possible to have a "no tungsten" top layer.
  • Said alkaline earth oxides are preferably selected from the group consisting of BaO, SrO and CaO or BaO, SrO.
  • the mixture of alkaline earth metal oxides can be doped with other oxides such as Sc 2 O 3 , or Y 2 O 3 .
  • Said plurality of reducing agents may further include elements which are selected from the group consisting of Cr and Zr. Any other element with enough reducing power for reducing the alkaline earth metal oxides can also be used.
  • Such a cathode according to the invention may be a "one-piece” cathode or a "two-piece” cathode.
  • the subject of the invention is also an electron gun having, as electron source, a cathode according to the invention.
  • the subject of the invention is also a cathode-ray tube including at least such an electron gun.
  • this bimetal comprises two superimposed bonded layers, a top layer 11 with a top face 111 in contact with the cathodo-emissive layer 3, and a bottom layer having its external bottom face 122 facing the heater 4 inside the sleeve 2.
  • the top layer is mainly composed of nickel; its thickness is about 60 ⁇ m.
  • the bottom layer is mainly composed of a nickel alloy having 20% of chromium, called nichrome ; its thickness is about 30 ⁇ m.
  • the substrate 1 according to the invention is made of 70 -100 ⁇ m thick bimetal ; although W concentration in the Ni-based top layer is inferior or equal to 0.008%, it was proven that mechanical behavior is satisfactory.
  • the conventional substrates which use a single layer un-allied nickel e-g without W or Mo added
  • table 1 gives the range of concentration for W, Mg and Si of the top layer 11 (or on the top face 111 for a monolayer cathode), the range of concentration for Mg and Si of the bottom layer 12 (or on the bottom face 122 for a monolayer cathode), the range of the substrate thickness, and comments. From top to bottom, table 1 shows these ranges for conventional substrates (4 first lines) and for bimetal substrates according to the invention.
  • the doping of substrate by Si is now given to illustrate the principle of differential doping on which the invention is based.
  • the doping with Si of the conventional single layer substrate to be used in conventional two-piece cathode is shown.
  • the doping of the conventional bimetal is shown.
  • the top layer is doped with silicon in a preferred range
  • the nichrome layer is not doped with silicon, which means that its concentration is inferior to silicon concentration in the top layer, and inferior or equal to 0.02 %. Lowest Si concentration that can be detected using conventional analysis method is around 0.003%.
  • the differential doping of the bimetal base substrate is illustrated according to the invention. Both the top layer and the bottom layer are doped with silicon.
  • the preferred range of concentration of Si in the top layer has a maximum that is inferior to the minimum of the range of Si concentrations in the bottom layer
  • all possible combinations of Si doping levels in top layer and bottom layer can be referred to as "differential doping”.
  • This differential doping with the same ranges can be also proposed with Al as a reducing element instead of Si.
  • Figures 7 and 8 show the typical performance in life-test of cathodes using bimetal of the invention compared to cathodes using conventional bimetal, both type of cathodes being operated at the same temperature in cathode ray tubes.
  • the operating conditions for the cathodes are typical of TV receiver operation.
  • the bimetals that have been used for these life-tests have the following characteristics :
  • Figure 7 shows the relative change of the cut-off voltage, which depends on the change in distance between cathode and first electrode linked to thermal behavior of the system. Relative change of the cut-off voltage is very similar for cathodes of the invention ( ⁇ ) and conventional cathodes (%). This proves that the mechanical behavior of the cathode according to the invention is as satisfactory as the one from conventional cathodes.
  • the bimetal with differential doping of this invention within the concentration ranges shown in table 1 can be used in two-piece cathode or in one-piece cathodes as well.
  • the cathode design is as described on figure 2 and in the case of a one-piece cathode, the cathode design is as described on figure 3.
  • a monolayer substrate with progressive differential doping can be used without departing from the invention.
  • the cathode design would therefore be as described on figure 1.

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  • Solid Thermionic Cathode (AREA)
  • Electrodes For Cathode-Ray Tubes (AREA)
EP02291859A 2002-07-24 2002-07-24 Cathode à oxyde pour canon à électrons avec un substrat métallique présentant un dopage différentiel Withdrawn EP1385190A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
EP02291859A EP1385190A1 (fr) 2002-07-24 2002-07-24 Cathode à oxyde pour canon à électrons avec un substrat métallique présentant un dopage différentiel
EP03771116A EP1535298B1 (fr) 2002-07-24 2003-07-21 Cathode a base d'oxyde destinee a un canon electronique revetu d'un substrat metallique a dopage differentiel
DE60305931T DE60305931T2 (de) 2002-07-24 2003-07-21 Oxidkathode für eine elektronenkanone mit einem unterschiedlich dotierten metallischem substrat
PCT/EP2003/050323 WO2004012217A1 (fr) 2002-07-24 2003-07-21 Cathode a base d'oxyde destinee a un canon electronique revetu d'un substrat metallique a dopage differentiel
CNB038172151A CN100437874C (zh) 2002-07-24 2003-07-21 用于具有差分掺杂的金属基板的电子枪的氧化物阴极
US10/522,115 US7208864B2 (en) 2002-07-24 2003-07-21 Oxide cathode for electron gun with a differentially doped metallic substrate
PL03374774A PL374774A1 (en) 2002-07-24 2003-07-21 Oxide cathode for electron gun with a differentially doped metallic substrate
AU2003262530A AU2003262530A1 (en) 2002-07-24 2003-07-21 Oxide cathode for electron gun with a differentially doped metallic substrate.
JP2004523813A JP2005534153A (ja) 2002-07-24 2003-07-21 差分ドープされた金属支持体を有する電子銃のための酸化物陰極
MXPA05001022A MXPA05001022A (es) 2002-07-24 2003-07-21 Catodo de oxido para canon de electrones con un sustrato metalico adicionado diferencialmente.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP02291859A EP1385190A1 (fr) 2002-07-24 2002-07-24 Cathode à oxyde pour canon à électrons avec un substrat métallique présentant un dopage différentiel

Publications (1)

Publication Number Publication Date
EP1385190A1 true EP1385190A1 (fr) 2004-01-28

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ID=29797335

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EP02291859A Withdrawn EP1385190A1 (fr) 2002-07-24 2002-07-24 Cathode à oxyde pour canon à électrons avec un substrat métallique présentant un dopage différentiel

Country Status (8)

Country Link
EP (1) EP1385190A1 (fr)
JP (1) JP2005534153A (fr)
CN (1) CN100437874C (fr)
AU (1) AU2003262530A1 (fr)
DE (1) DE60305931T2 (fr)
MX (1) MXPA05001022A (fr)
PL (1) PL374774A1 (fr)
WO (1) WO2004012217A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3535757A (en) * 1968-03-22 1970-10-27 Rca Corp Method for making cathode assembly for electron tube
US3911312A (en) * 1973-06-06 1975-10-07 Philips Corp Oxide cathode for an electric discharge tube
US4215180A (en) * 1978-04-24 1980-07-29 Hitachi, Ltd. Oxide-coated cathodes for electron tubes
EP1152447A1 (fr) * 2000-04-26 2001-11-07 Thomson Licensing S.A. Tube à rayons cathodique et alliage

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100366073B1 (ko) * 1995-10-30 2003-03-06 삼성에스디아이 주식회사 전자관용음극

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3535757A (en) * 1968-03-22 1970-10-27 Rca Corp Method for making cathode assembly for electron tube
US3911312A (en) * 1973-06-06 1975-10-07 Philips Corp Oxide cathode for an electric discharge tube
US4215180A (en) * 1978-04-24 1980-07-29 Hitachi, Ltd. Oxide-coated cathodes for electron tubes
EP1152447A1 (fr) * 2000-04-26 2001-11-07 Thomson Licensing S.A. Tube à rayons cathodique et alliage

Also Published As

Publication number Publication date
CN100437874C (zh) 2008-11-26
WO2004012217A1 (fr) 2004-02-05
DE60305931T2 (de) 2007-06-21
PL374774A1 (en) 2005-10-31
DE60305931D1 (de) 2006-07-20
JP2005534153A (ja) 2005-11-10
MXPA05001022A (es) 2005-05-16
CN1669104A (zh) 2005-09-14
AU2003262530A1 (en) 2004-02-16

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