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Feb- 6, 1940- B. A. DIGGORY ET AL ' 2,138,940 H20 Mpon

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Feb- 6, 1940- B. A. DIGGORY ET AL ' 2,138,940 H20 Mpon Feb- 6, 1940- B. A. DIGGORY ET AL ' 2,138,940 ELECTRON DISCHARGE DEVICE Filed Dec. 2, 1937 H20 mpon . B. A. D/GGORV INVENTORS- 61K. TEAL _ A 7' TORNE V ‘ Patented Feb._ 6, 1940 ' 2,188,940; 1 UNITED STATES PATENT Fries v _ t I ' 2,188,940. ‘ ' . ELECTRON DISCHARGE DEVICE Benjamin A. mil-‘my, Plain?eld, N. 3., macer ; idon K. Teal, NewxYork», N. Y., assignors to f Bell‘ Telephone Laboratories, Incorporated, I . New York, N.v Y., a corporation of New York _ Application December 2,1937, Serial No. 177,660 11 Claims. (01'. 250M275), This invention relates to methods of oxidizing ' tures which is particularly‘ suitable for use in the ' ' metallic elements and to electrode vstructures, preparation‘of electrode structures and photo and ‘more speci?cally to- electrode structures in sensitive targets‘ such as, for example, those used special ‘types of electron discharge devices and in television electronic cameras and electron v to methods of oxidizing the electrodes inysuch vmultipliers. '‘ '. ' i _ ‘ '5 devices.v j _ . '1 X .' In the method according to this invention as In certain electron discharge devices such as, hereinafter described in detail by way of exam for example, photoelectric tubeselectroni'c cam; ple, ozone [(03) is generated ‘by any suitable‘ ‘ era tubes for television, an‘de'lectron multipliers, , means such as, for example, by means of a spark U electrodes having photosensitive surfaces are pro, coil and the gas allowed to flow through‘ water 0 vided. _. In the preparation 'of these surfaces a vapor to moisten it. ‘The moist ozone‘ is then metal face'of the electrode is oxidized and then, passed into theelectronic camera tube or elec in many teases, treated with a metal, such as sil tron multiplier to oxidize the-metal electrode or ver. followed by photosensitization with an alkali electrodes therein, the tube being heated to ‘a temperature of about 50° C. to prevent the water metal._ , I‘ . _ , 3 , ;_ . In the preparation ‘of some'types of standard from condensingtherein'. 'After oxidation of the photoelectric tubes, the oxidation of the cathode ~ \ metallic electrode, the vtube structure-is baked is accomplished by the passage of, an electric out and‘ evacuated at about 250° C. Photosensi m discharge throughan atmosphere of- oxygen'be tizaticn of the oxide ?lm follows this-vbake-out. 0 T" tween the cathode and anode of the tube. This Theinvention will be more‘ readily understood oxidation method is successful in this‘ instance from the following description taken‘ in connec- _ because ‘the ‘electrode being sensitized is fairly tion with the accompanying drawing" forming a ' . symmetrically'disposed relative to the-anode, part thereof in which: , " electrical contactcan be made to, it, it"is me Fig. 1v shows an ‘electronic camera such as is “5 chanically strong, and it is made of 'si1ver,:a used in television transmission in which the 25 material’ which is‘ readily oxidized‘ by electric method of thisinvention may ‘be applied; ‘ _ discharge. Such conditions, however, cannot be' . Fig, 2 is'an; enlarged cross-sectional view of simultaneously ful?lled in all photoelectric and the mosaic screen or target of the tube shown secondary emission. devices; Asymmetries' in the ‘ in Fig.1; I _ '. 30 electrode structure of aydevice are re?ected in ~' ‘- Fig. 3 shows apparatus for preparing the ozone 30 asymmetries in the electric‘?elds and, where the ‘used in the method of this invention; and‘v ‘ , oxidation is accomplished by means of ‘charged Fig. 4 shows an electron multiplier tube in particles, ‘nonuniformity of oxidation of they which the method‘of this'inv‘entioncan be used. _ electrodes may follow._ ‘In a device in which. the Referring ‘more particularly to the drawing, 3'? electrode is insulated and to which an electrical Fig. vv1 shows an electronic camera tube used as 35' connection cannot bemade, 'it is impossible vto ' a pick-up device in t'elevisiontransmission com, pass a continuous current to it as is done‘ in the prising'an‘evacuated container l 0' enclosing an‘ . discharge method described. above. If the elec electron "gun assembly ll for producing a mov trode to be oxidized‘ is a‘ thin metal film on glass, ing beam ofelectrons and. for accelerating this» W a continuous discharge passed directly to it usu beam toward'a screen S at the end of the tube 40 ‘ ally tears-it o? the glass.‘ Also, it is sometimes‘. remote from the electron gum-and means (not desirable use metals other than silverfas' a shown) for’ causing the beam to scan the various base of a photoelectric or secondary emitting elemental- areas of the screens in turn.‘ matrix and difficulty may‘then ‘be experienced As an example of a satisfactory electron ‘gun. 1' 4-1 in oxidizing the metal by passing ‘adischarge assembly, reference may be madev to Patent ‘1&5 current to it in an oxygen‘ atmosphere. For'ex- ' 2,173,923 to. G. K. Teal, issued September 26,‘ ' ample, copper cannot be; oxidized, at least not > 1939, which/shows and describesan electron gun‘ f more than.- very super?cially, by an electric dis‘ comprising a cathode and two accelerating an ~ charge. ' v ' " . odes for iocussing. a beam of electrons upon ‘a so It is an object of this invention to ‘provide target, one ‘of these anodes being'a conducting cu, ' , novellelectron'discharge structures utilizing elec coating on the inside wall of the tube A simi-' trodes which behave differently in. the presence lar. coating is shown in Fig. l of this application of an oxidizing atmosphere. ' ' . and is designated by‘ the reference numeral l2. vIt is aiurther object of this invention to pro Either electrostatic or, electromagneticv means. ' “ vide anovel method ofuoxidizing metal vstruc ,(not shown) can .be. used for deflecting) the 55 2,188,940 . beam so that it scans ‘every elemental area in ing the latter to about 50° '0. Failure ‘to do this , turn of the screen S. Both of these means are 1 results in a 'non-uniform?lm of silver oxide; * well known to the art. The excess ozone delivered from the‘,electronic._fv"l. vReference will. now be made to Fig. '2 for a camera‘tube through tube M is preventedfront,v more detailed description of the mosaic screen entering the outside atmosphere by decomp'osi- , structure S. This screen structure has as a tio-n brought about by passage of the excess gases ' base a glass member 20 in the form of a very through a glass tube heated to about 550‘? C. ' (not thin center portion 2| and ya thicker edge por shown).‘ ' . " ’, :1 l r tion 22. On the face of the glass member remote The degree of oxidation of the silver ?lm mayv 10 from the electron beam is evaporated a thin be followed by determining its resistance as a ’ _ coating 23 of a suitable electrical conducting function of time. When the‘resistance reaches a j . - ' material, such as aluminum. On the surface of limiting value it is assumed that oxidation of the, ' the center portion 21 nearer the electron beam silver is approximately complete. Measurements . is coated a discontinuous layer 24 of photosen made on the approximate ratio of silver to oxygen 15 sitized metallic globules which isfprepared by in silver ?lms oxidized with moist ozone, in-Y sputtering the center portionwith a layer of dicated approximate agreement with the formula I metallic material such as silver, which is heated AgzOL‘ This indicates thatthe chief reaction I, to make it discontinuous. The discontinuous occurring‘ maybe represented by the equation J" globules are oxidized and caesium is'introduced 20 and the tube is‘ baked to make the surface 24 20v. -" photo-emissive. ' p Moisture :is necessary to catalyze the reaction; The preparation. of the glass member'ZEl for without it, the oxidation proceeds with extreme, use in the screen S will now be described. A slowness. ' piece of glass, preferably about .005 inch thick . vAfter oxidation of the silver ?lm, the electronic \ ‘ 25 is etched by total immersion in a suitable etching camera‘ tube is then baked out and'evacuate'd at vsolution, such as hydro?uoric acid, the edges of about 250° C. This vtemperature is su?icicnt to - the glass being ‘protected by a coating of a suit decompose the silver oxide‘ completely if ‘main able substance which is not affected by‘ the hy 'tained for a sufficient length, of time to fully l . i dro?uoric acid, such as, for example, beeswax, establish equilibrium. conditions. I However, the 30 so that the ?lmlof glass produced by the etching approach to these conditions is rather slow and : process has a. border of glass of the thickness of the amount of decomposition, is made negligible - I the original‘ glass plate by which it may be sup by limiting the time‘ of baking. If thaozone ported. For amore complete description of the method of oxidation asv described abov'ejis used, method of preparing these glass screen members, the metal portions of the tube ‘should be made of 35 reference maybe made to the above-mentioned materials not attacked readily by ozone. Alumi- ' ‘Teal patent wherein the process is described in num metal, platinum, and chromium-plated nickel ~have been found, to be‘ fairly satisfactory‘ detail. ‘ . - , ‘ v a _ After the glass blank has been prepared so in-this respect. 1 I ' ‘ > that the center portion is as thin as desired and ,At the conclusion" of the: ‘oxidation process, there is approximately a quarter of an inch of excess gas is removed by evacuation and a known raised border alljaround the center portion, silver amount of caesium is emitted in the bulb by is sputtered on the center portion of one face of ?ashing a “caesium” pill.‘ The‘ pill is ?ashedin , " the blank for about 20 to 30 minutes.
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