CN1013159B - Cathode for electron tube - Google Patents

Cathode for electron tube

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Publication number
CN1013159B
CN1013159B CN88106323A CN88106323A CN1013159B CN 1013159 B CN1013159 B CN 1013159B CN 88106323 A CN88106323 A CN 88106323A CN 88106323 A CN88106323 A CN 88106323A CN 1013159 B CN1013159 B CN 1013159B
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China
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material layer
electron emission
family
substrate
cathode
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Expired
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CN88106323A
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Chinese (zh)
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CN1031776A (en
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田口贞憲
山本惠彦
渡部勇人
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Hitachi Ltd
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Hitachi Ltd
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Publication of CN1031776A publication Critical patent/CN1031776A/en
Publication of CN1013159B publication Critical patent/CN1013159B/en
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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
    • H01J1/14—Solid thermionic cathodes characterised by the material
    • H01J1/142—Solid thermionic cathodes characterised by the material with alkaline-earth metal oxides, or such oxides used in conjunction with reducing agents, as an emissive material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2201/00—Electrodes common to discharge tubes
    • H01J2201/19—Thermionic cathodes

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  • Solid Thermionic Cathode (AREA)

Abstract

The present invention discloses a kind of cathode for electron tube, it is made of substrate and electron emission material layer formed thereon, this material layer is that the oxide by the alkaline-earth metal that comprises Ba constitutes, wherein, mix the binary metal oxide powder, this powder contains a kind of element of selecting at least from comprise Sc, Y element, and other metallic element or Si.The emitting performance of this negative electrode is greatly improved.

Description

Cathode for electron tube
The present invention relates to the used negative electrode of electron tube for TV Braun (Braun) pipe one class.Or rather, the present invention relates to be suitable for prolonging the electron emission material layer in oxide coated cathode life-span.
Such as TV with Braun pipe or this electron-like pipe of camera tube negative electrode commonly used, i.e. oxide coated cathode, its structure is shown in No. 15430/83 Japanese Patent Application Publication specification.This structure is shown in the profile shown in Figure 2.More particularly, negative electrode commonly used has following structure: substrate 21, and it is by basis nickel (Ni) and a spot of reduction elements such as silicon (Si), magnesium (Mg) or zirconium (Zr) formation; Electron emission material layer 22, it places on the end face on emitting electrons surface of substrate 21, is made of the oxide powder of barium (Ba) or other alkaline-earth metal such as calcium (Ca) or strontium (Sr); The heater 23 that also has the emission of thermic electronics.Explanation in passing, label 24 is represented sleeve pipe.With alkaline earth metal carbonate (Ba, Sr, Ca) CO 3Powder and slurry are sprayed in the substrate 21 together, are heated by 23 pairs of these coatings of heater in steps of exhausting then, thereby make carbonate change into the alkaline earth metallic oxide powder end, can be made into electron emission material layer 22.In consequential activation step, alkaline-earth metal oxide layer 22, particularly barium monoxide (BaO) migrate to substrate 21 surfaces through thermal diffusion, with silicon, magnesium or the zirconium reaction in the substrate 21, generate barium, thereby layer 22 is characteristic like the semiconductor, just may emitting electrons.This reaction is represented with following reaction equation:
From above-mentioned reaction equation as can be seen, SrO 2, MgO or ZrO 2This class product, perhaps further reaction product such as the BaSiO of this class product and BaO 3, BaMgO 2Or BaZrO 3This class intermediate layer is formed between electron emission material layer 22 and the substrate 21.This intermediate layer is a high impedance layer, and it suppresses flowing of electric current, perhaps hinders the diffusion of this class reduction elements of Si, Mg or Zr, and is not too abundant thereby Ba generates, and hot-electron emission property also just descends.The intermediate layer thickness of Xing Chenging directly is proportional to the operating time like this, sharply descends so hot-electron emission property thickens with intermediate layer thickness.
That is to say that the shortcoming of above-mentioned common technology is: be formed at the intermediate layer thickness between substrate 21 and the emitting electrons material 22, pass and sharply thicken with the operating time, thus the very fast decline of the hot-electron emission property of cathode for electron tube.
The purpose of this invention is to provide a kind of highly reliable cathode for electron tube, wherein, prevent the rapid decline of hot-electron emission property by the formation speed that reduces the intermediate layer, thereby can keep good hot-electron emission property long-term and stably.
According to the present invention, be by adding the binary metal oxide powder in covering suprabasil emitting electrons material layer, realize this purpose.The above-mentioned material layer is that the oxide by the alkaline-earth metal that comprises Ba constitutes: above-mentioned powder contains at least a element of choosing from that gang that comprises Sc, Y and rare earth element, and the dosage that other metallic element or SiO work as the binary metal oxide that is added accounts for 0.5～30% of electron emission material layer total weight, and above-mentioned other element is when being the element of selecting from the gang of periodic table of elements IV a to Y III family, more remarkable effect of the present invention.
Introduce the characteristic of the cathode for electron tube of making according to the present invention below.
(1) electron emission material layer is formed in the substrate; Described material layer is by constituting as the oxide that comprises the Ba alkaline-earth metal of basis with as a kind of binary metal oxide of supplementary element; Described binary metal oxide comprises first metallic element and second metallic element at least; Described first metallic element is to choose from the family of elements that comprises Sc, Y and lanthanide series rare-earth elements; Described second metallic element is from comprising IV a, V a in the periodic table of elements, VI a, VII a and VIII family, and choose in the family of elements formed of Si; Described substrate is made of basis Ni and a small amount of reduction elements.
(2) the supplementary element content of emitting electrons material layer can be in 0.5～30%(weight) between adjust.
(3), be a kind ofly from the lanthanide series that comprises lanthanum (La), praseodymium (Pr), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb) and dysprosium (Dy), to choose at least as the lanthanide series rare-earth elements of first metallic element.
(4) select Zr to be used as second metallic element as the metal of IV a family, select Ta to be used as second metallic element as V a family metal, select Mo or W to be used as second metallic element as VI a family metal, select Re to be used as second metallic element, and select Ir to be used as second metallic element as VIII family metal as VII a family metal.
(5) supplementary element of electronic emission material has a kind of binary metal oxide at least, and it can be chosen from following oxide: Sc 2W 3O 12, Sc 2Mo 3O 12, Y 2W 3O 12, Y 2Mo 3O 12, Sc 2Zr 3O 2, Y 2Zr 3O 9, Sc 2Ta 2O 8, Y 2Ta 2O 8, Sc 2Re 3O 12, Y 2Re 3O 12, Sc 2IrO 5, Y 2IrO 5, Sc 2SiO 5, Y 2SiO 5And Ln 2M 3O 12, wherein, Ln represents at least a lanthanide series rare-earth elements, and a kind of element of selecting in that gang that M representative is made up of W and Mo at least.
As being included in minor constituent with Ni, can adopt well-known element such as Si, Mg and Zr as the reduction elements in the substrate of basis.Needless to say, except that Ba, also be included in wherein as the Ca or the Sr of alkaline-earth metal.
In the present invention, the binary metal oxide powder that contains Sc or Y adds in the electron emission material layer, by the reducing metal of being contained in the substrate, slows down the formation in intermediate layer.Fig. 1 referring to expression cathode for electron tube of the present invention.This negative electrode has structure as described below, wherein electron emission material layer 12 is made of the oxide 15 and the binary metal oxide powder 16 of the alkaline-earth metal that comprises Ba, contain Sc or Y in this binary metal oxide powder, and be blended in this alkaline earth oxide 15, this electron emission material layer 12 is formed on the surface of substrate 11.Now with Sc 2W 3O 12As the example of the binary metal oxide 16 that contains Sc or Y, describe and slow down the effect that the intermediate layer forms.Carry out in the first step of activation starting heater 13, the reduction elements in the substrate 11 is spread, is arrived the interface of electron emission material layer 12 as Si, Mg or Zr, with generation Ba.This will be described as the example of reduction elements with Si.The generation of barium is to be caused by the represented reaction of above-mentioned reaction equation (1).The generation of Ba, Ba diffusion and the barium in electron emission material layer is discharged from layer 12, is constantly carrying out.Be diffused in that part of Ba and the Sc that is added in the electron emission material layer 12 2W 3O 12Reaction between this oxide 16 generates Sc(and is seen in diagram), this reaction is represented by following reaction equation (4):
The a part of Sc that is generated by the described reaction of formula (4) reacts with BaO, but most of Sc then with the SiO that is formed at the interface 2Reaction, thus make SiO 2Be reduced into Si, this process is represented by following reaction equation (5):
The Si that reduction generates be with electron emission material layer in BaO react, rather than and substrate 11 and electron emission material layer 12 between the interface in BaO react, thereby generation Ba.At the negative electrode duration of work, formula (1), (4) and (5) described reaction are being carried out always.Therefore, the high impedance intermediate layer that BaSiO or analog constitute is difficult to form on the interface between substrate 11 and the electron emission material layer 12, and this high impedance material is in electron emission material layer 12 diffusions.Therefore, can't see the rapid decline of hot-electron emission property fully.So can realize prolonging the purpose in cathode for electron tube life-span.If insert the oxide powder 16 in the electron emission material layer, for example Sc 2W 3O 12Dosage less, then do not reach the effect that reaches of attempt, and even the dosage of oxide powder 16 is very big, the growing amount of Ba also is limited, and is quite high although the impedance of emitting electrons material layer 12 becomes.The practical dose that effectively prolongs the additional oxide 16 of cathode life is 0.5～30%(weight).Explanation in passing, label 14 is represented sleeve pipe among Fig. 1.
Fig. 1 is the profile of explanation embodiments of the invention.
Fig. 2 is the profile of explanation cathode for electron tube commonly used.
Fig. 3 adds Sc according to the present invention 2W 3O 12The time viewed emission current time dependent performance diagram.
Fig. 4 adds Y according to the present invention 2W 3O 12The time viewed emission current time dependent performance diagram.
Fig. 5 is Sc among the present invention 2W 3O 12The performance diagram of the relation between addition and the emission current.
Fig. 6 to 17 adds Sc respectively according to the present invention 2Zr 3O 9, Y 2Zr 3O 9, Sc 2Ta 2O 8, Sc 2Mo 3O 12, Y 2Mo 3O 12, Sc 2Re 3O 12, Y 2Re 3O 12, Sc 2IrO 5, Y 2IrO 5, Sc 2SiO 5And Y 2SiO 5The time, the time dependent performance diagram of viewed emission current.
Figure 18 is the intermixture dosage that adds among the present invention and the performance diagram of the relation between the emission current, and this mixture is Sc 2W 3O 12And Y 2W 3O 12Composite by mole ratio 1/1.
Example 1
Narrate one embodiment of the present of invention referring now to Fig. 1.
Negative electrode has structure as described below.Substrate 11, it is made of basis Ni and a small amount of reduction elements Si; Electron emission material layer 12 is formed on the surface of substrate 11, by as basis, comprise the oxide 15 ((Ba, Sr, Ca) O) of the alkaline-earth metal of Ba and account for 0.5～0.3% Sc as supplementary element, weight 2W 2O 12Or Y 2W 3O 12This class binary metal oxide powder 16 constitutes.At first introduce the formation of electron emission material layer 12 in substrate 11.With Sc 2O 3Powder or Y 2O 3Powder and WO 3Powder mixes by weight 1/3, in the open in the environment, under 1100 ℃ temperature, is heated 3 hours then, just can prepare Sc 2W 3O 12Or Y 2W 2O 12This class binary metal oxide powder.In this binary metal oxide powder 16, the triplex carbonate that contains Ba, Sr or Ca (when carbonate changes into oxide fully, account for weight 0.5～30%) that adds scheduled volume, make the mixture suspended matter, with spray gun this suspended matter is sprayed on the upper surface of substrate 11 again, coating layer thickness is about 75 microns.Like this, just can make two utmost point electron tubes.
In making two utmost point electron tubes, by carbonate decomposition being become the activation step of oxide, restore partial oxide, just can this coating form electron emission material layer 12.Fig. 3 and 4 illustrates the time dependent curve of emission current, and this two curve is respectively with Sc 2W 3O 12And Y 2W 3O 12With 0.5～30%(weight) to add electron emission material layer viewed.In these two figure, it is the relative value of the 100% cathode emission electric current that calculates that ordinate is represented with the initial transmissions electric current, and abscissa is represented cathode heating time (unit: thousand hours).Add Sc 2W 3O 12And Y 2W 3O 12The time, the variation of emission current (decline) is that the increase with addition reduces, and weight accounts for 8%(to Sc 2W 3O 12) or 15%(to Y 2W 2O 12) time, it is minimum that its variation reaches.If addition increases again, then the variation of electric current also increases.Its reason is: because binary metal oxide (Sc 2W 3O 12Or Y 2W 2O 12) decompose, the Ba major part that forms on the interface between substrate 11 and the emitting electrons material layer 12 is consumed.
Little this fact of the variation of emission current (decline) shows that emission current not too descends, and therefore cathode life of the present invention is longer than negative electrode commonly used.
When with the interface between X-ray diffractometer detection substrate 11 and the electron emission material layer 12, can find that topographic feature is formed in the BaSiO in the negative electrode commonly used that does not contain binary oxide 3This intermediate layer is difficult to be formed, and the thickness in intermediate layer is corresponding to the variation of emission current.Find that in addition the Si that adds substrate has been diffused in 12 li of electron emission material layers.
Fig. 5 illustrates Sc 2W 3O 12Relation curve between addition (weight %) and the negative electrode initial transmissions current relative value, this curve be to same embodiment shown in Figure 3 heat 4,000 hours viewed.
As binary metal oxide, the listed oxide of table 1 is with above-mentioned Sc 2W 3O 12Or Y 2W 3O 12Same mode is added as supplementary element, detects to the characteristic of emission current with the relation between the time of heater heats negative electrode.Fact proved that listed each binary metal oxide can both reach the effect that prolongs cathode life equivalently.
The binary metal oxide list that is added
(1) total score minor Ln 2M 3O 12, wherein, Ln represents a kind of lanthanide series rare-earth elements at least, and this element is selected from the lanthanide series that comprises La, Pr, Nd, Sm, Eu, Gd, Tb and Dy, and M represents W and/or M.
(2) Sc 2W 3O 12And Y 2W 3O 12Mixture
(3) Sc 2Zr 3O 9(Zr is IV a family, second metallic element in this example)
(4) Y 2Zr 3O 9(Zr is IV a family, second metallic element in this example)
(5) Sc 2Ta 2O 8(Te is V a family, second metallic element in this example)
(6) Y 2Ta 3O 8(Ta is V a family, second metallic element in this example)
(7) Sc 2Mo 3O 12(Mo is VI a family, second metallic element in this example)
(8) Y 2Mo 3O 12(Mo is VI a family, second metallic element in this example)
(9) Sc 2Re 3O 12(Re is VII a family, second metallic element in this example)
(10) Y 2Re 3O 12(Re is VII a family, second metallic element in this example)
(11) Sc 2IrO 5(Ir is VIII a family, second metallic element in this example)
(12) Y 2IrO 5(Ir is VIII a family, second metallic element in this example)
(13) Sc 2SiO 2(Si is second metallic element in this example)
(14) Y 2SiO 2(Si is second metallic element in this example)
Example 2
Referring now to Fig. 6 to 17 second embodiment of the present invention described.
Negative electrode has following structure.Substrate 11, it is made of basis Ni and a small amount of reduction elements Si; Electron emission material layer 12 is formed on the surface of substrate 11; By as basis, comprise Ba alkaline earth oxide ((Ba, Br, Ca) O) 15 and as supplementary element, weight account for 0.5～30%, the powder 16 chosen from these binary metal oxides of (3)～(14) constitutes.At first introduce the formation of electron emission material layer 12 on substrate 11.With regard to binary metal oxide (3) and (4), the mole ratio with 1/3 is with powder Sc 2O 3Or Y 2O 3With ZrO 2Mix; With regard to binary metal oxide (5) and (6), the mole ratio with 1/1 is with powder Sc 2O 3Or Y 2O 3With powder Ta 2O 3Mix.Also have, with regard to (7) and (8), the mole ratio with 1/3 is with powder Sc 2O 3Or Y 2O 3With MoO 3Mix, by that analogy, with regard to (9) and (10), (11) and (12) and (13) and (14), all with 1/3 identical this mole ratio, with Sc 2O 3Or Y 2O 3Powder respectively with ReO 3, IrO 2And SiO 2Mix.To all heating 3 hours under 1100 ℃ of temperature in the environment in the open of each mixture, thereby make binary metal oxide powder 16.
Binary metal oxide powder 16 added with scheduled volume (account for when carbonate changes into oxide fully weight 0.5～30%) contain in the triplex carbonate of Ba, Sr or Ca, thereby make the mixture suspended matter.With spray gun this suspended matter is sprayed on the upper surface of substrate 11, coating layer thickness is about 75 microns.So just can make two utmost point electron tubes.
In making two utmost point electron tubes,, with the partial oxide reduction, just can produce electron emission material layer 12 again from this coating by carbonate decomposition being become the activation step of oxide.
Fig. 6 to 7 illustrates the time dependent curve of emission current, these curves be will the table 1(3) to (14) listed binary metal oxide 0.5～30%(weight) and add respectively fashionable observed.In these figure, it is the relative value of the 100% cathode emission electric current that calculates that ordinate is represented with the initial transmissions electric current, and abscissa is represented cathode heating time (thousand hours).As can be seen, under each situation, all reach predetermined effect.
Example 3
Referring now to Figure 18, another embodiment of the present invention is described.
Negative electrode has following structure.Substrate 11, it is made of basis Ni and a small amount of reduction elements Si; Emitting electrons material layer 12 is formed on the surface of substrate 11; By as basis, comprise the oxide 15 ((Ba, Br, Ca) O) of the alkaline-earth metal of Ba and account for 0.5～30% Sc as supplementary element, weight 2W 3O 12With Y 2W 3O 12Mixture (mole ratio is 1/1) 16 constitutes.At first introduce the formation of electron emission material layer 12 on substrate 11.With Sc 2O 3And Y 2O 3Powder and WO 3Powder mixes by 1/3 mole ratio, under 1100 ℃ of temperature it is heated 3 hours in the environment in the open then, just can prepare Sc 2W 3O 12And Y 2W 3O 12Such binary metal oxide powder 16.This binary metal oxide powder 16 predetermined amounts (account for when carbonate changes into oxide fully weight 0.5～30%) are added contain in the triplex carbonate of Ba, Sr or Ca, make the mixture suspended matter.With spray gun this suspended matter is sprayed on the upper surface of substrate 11, coating layer thickness is about 75 microns.So just can make two utmost point electron tubes.
When making this two utmost points electron tube,, with the partial oxide reduction, just can form electron emission material layer 12 again by carbonate decomposition being become the activation step of oxide.Figure 18 illustrates the emission current time history plot, and it is with Sc 2W 3O 12And Y 2W 3O 12Mole ratio by 1/1 is mixed, observed arriving when weight accounts for 0.5～30% mixture adding electron emission material layer.In the drawings, it is the relative value of the 100% cathode emission electric current that calculates that ordinate is represented with the initial transmissions electric current, and abscissa is represented cathode heating time (thousand hours).Also can find in the present embodiment, can obtain similar desired effects.
As can be seen from the above description, according to the present invention, the BaSiO directly related with the thermionic emission characteristic 3Or the high impedance intermediate layer of analog formation, on the interface between substrate 11 and the electron emission material layer 12, not forming, this high impedance material is to be diffused in the electron emission material layer.Therefore, flowing of electric current is not too influenced, and Ba constantly generates in the interface, so the thermionic emission characteristic can keep for a long time.So can being made into, negative electrode of the present invention do not have the caused electronics emission of conventional manufacture method sharply to change.The cathode for electron tube of making according to the present invention can be described as the long-life type negative electrode.

Claims (2)

1, a kind of cathode for electron tube, constitute by substrate and electron emission material layer formed thereon, described substrate contains basis Ni and a small amount of reduction elements, described electron emission material layer is characterized in that by constituting as the oxide of the alkaline-earth metal that comprises Ba of basis with as the binary metal oxide of supplementary element
The content of the described supplementary element in the described electron emission material layer is 0.5～30% (weight),
Described binary metal oxide comprises a kind of first metallic element and a kind of second metallic element at least, described first metallic element is selected from the element that comprises Sc, Y, IV a, V a, VI a, VII a and the VIII family of described second metallic element from comprise the periodic table of elements, and choose in the family of elements of Si, wherein from IV a family element, select Zr, from V a family element, select Ta, from VI a family element, select MO or W, from VII a family element, select Re, and from VIII family element, select I r.
2, cathode for electron tube according to claim 1 is characterized in that, the supplementary element of electron emission material layer has a kind of binary metal oxide at least, and it is from comprising Sc 2W 3O 12, Sc 2Mo 3O 2, Y 2W 3O 12, Y 2Mo 3O 12, Sc 2Zr 3O 2, Y 2Zr 3O 9, Sc 2Ta 2O 8, Y 2Ta 2O 8, Sc 2Re 3O 12, Y 2Re 3O 12, Sc 2IrO 5, Y 2IrO 5, Sc 2SiO 5, Y 2SiO 5Binary metal oxide in select.
CN88106323A 1987-09-01 1988-08-31 Cathode for electron tube Expired CN1013159B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP21642787A JPS6460938A (en) 1987-09-01 1987-09-01 Cathode for electron tube
JP216427/87 1987-09-01

Publications (2)

Publication Number Publication Date
CN1031776A CN1031776A (en) 1989-03-15
CN1013159B true CN1013159B (en) 1991-07-10

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100200661B1 (en) * 1994-10-12 1999-06-15 손욱 Cathode for electron tube
CN1056465C (en) * 1994-10-25 2000-09-13 电子工业部第十二研究所自动工程研究所 Laser-evaporated thin-film scandium series cathode and its preparation method
KR100338036B1 (en) * 1994-12-28 2002-11-30 삼성에스디아이 주식회사 Cathode as oxide and manufacturing method thereof
KR100297687B1 (en) * 1998-09-24 2001-08-07 김순택 Cathode used in an electron gun
JP2001006521A (en) * 1999-06-22 2001-01-12 Nec Kansai Ltd Cathode body structure and color picture tube
US6882093B2 (en) * 2001-08-01 2005-04-19 Matsushita Electric Industrial Co., Ltd. Long-life electron tube device, electron tube cathode, and manufacturing method for the electron tube device
WO2018016375A1 (en) 2016-07-20 2018-01-25 昭和電工株式会社 Gas supply apparatus and gas supply method

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KR890005806A (en) 1989-05-17
CN1031776A (en) 1989-03-15
JPS6460938A (en) 1989-03-08

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