(Read Feb. 16,1940). Introduction.

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1 Conductivity Oxide By Eizaburo rmionic Emission Cathode. NISHIBORI Hazime of KAWAMURA. (Read Feb. 16,1940). Introduction. It had been believed, in regard to mechanism of rmionic of oxide cathode. that metal atoms on surface of oxide layer play an important part in rmionic that metal atoms in oxide itself promote only transfer of electrons in oxide layer. R. H. Fowler(1), however, discussing this rmionic of semi-conductors from stpoint of modern electron ory of solids, concluded with that rmionic from semi-conductor, such as BaO, is of conducting electrons are rmally excited of sufficient energy; show that re exists an intimate relation between conductivity rmionic. It may be true, also, that knowledge about conductivity, as explained above, will throw a light in understing complicated phenomena of oxide cathode. We report, experiment taken at laboratory of Tokyo-Shibaura Electric Co., on simultaneous measurments on conductivity rmionic of an oxide cathode. Many investigators(2), however, have reported previously on experiment of conductivity of oxide cathode, but ir results do not coincide some of m were merely data on non-activated cathode. We desired to measure thode arid, m in normal operating condition of oxide that is, at well activated state as much as possible. Procedures We constructed a diode bulb ca- of experiment. is, later, to be thoroughly (1) R. H. Fowler : Proc. Roy. Soc. A 137 (1932), 503. (2) A. L. Reimann & R. H. Murgoci : Phil. Mag. 9 (1931), 44. W. Albricht: Physica 11 (1931), 146. Lubke & Krokzeck: Wiss. Veroff. a.d. Siem. Konz. 9 (1930), 252. W. Meyer & A. Schmidt Z. S. f. Techn. Phys. 13 (1932), 137. J. A. Becker : Trans. Am. Electrochem. Soc. 59 (1931), 302. eva-

2 1940] Conductivity cuated anode in diameter earth carbonate of Ni wound in measurement rmionic Emission. 379 of this diode is a cylindrical mesh made of Nickel 4 mm 10 mm in length. cathode consists of alkali sprayed on a nickel core, contain a helical wire layer of carbonate is used as a " Sonde " in of resistance. (Fig. 1.) cathode core is 1 mm. in diameter 2.5 cm. in length of extend of 1.0 cm. is coated. bulb containing evacuated by se elements was a 3-stage oil diffusion pump, baked at some 400 C. All metal parts were heated to about 1000 C by an induction furnace, carbonate was decomposed to oxide. At final stage after a barium getter was flashed, bulb was sealed off. For measurements of conductivity, anode current Ip was drawn Fig. 1. from cathode by applying 3 volts to anode, potential drop E produced by this current between core nickel wire was measured by a potentiometer. E/Ip, thus obtained, may be considered as inner resistance of oxide layer. saturated current was measured appling 100 volts to anode. alkali earth metal oxide employed for cathode material in this experiment was BaO, SrO, ir mixture. Results obtained from Experiments. A. Each of family of Ip-E curves is linear as shown in Fig. 2. Generally it will be seen that increasing anode current curves is bend toward current axis. Our experiments performed in region where curves are linear. It is also shown that rs is a potential diffefence of about 0.1 volt where current is zero. This is probably because. of rmionic power due to temperature difference between core Ni wire. B. change of resistance due to activation: cathode can be activated by overheating cathode drawing out space current from it. In this process free alkali earth metal atoms will be liberated electrolytically from oxide are dispersed in oxide layer.

3 380 E. NISHIBORI H. KAWAMURA. During such a process of activation conductivity form similar increase of se two quantities indicates between m. rmionic [Vol. 22 as shown in Fig. 3. similarity existence of an intimate relation Fig. 2. Fig. 3. C. temperature coefficient of of conductivity:-we measured current conductivity varying temperature of cathode front 1200 K to 700 K. obtained curves of log Is or log verses I/T, as shown in Fig. 4, are straight lines. Thus, we are able to ascertain rmioaie work function temperature coefficient of conductivity from slopes of se curves. According to W. Heinz S. Wagner(3), rmionie work function varies as much as 0.5. e.v. with activation. Wher varies simultaneously with or not, is a very interesting problem concerning mechanism of rmionic. To investigate this relation we measured simultaneously conductivity of range cathode before after activation. For activation we vaporized Ba or Sr atoms from a Tantalum wire coated with Bao or SrO is placed closely to cathode. U pper eurves infig. 4 are those taken after activation. From se curves we see that both conductivity increase as stated in B) temperature coefficients are also decreasing (3) W. Heinze & S. Wagner: Z. S. Phys. 110 (1938), 164.

4 1940] Conductivity rmionic Emission. 381 at same tune. results obtained on SrO mixed Oxide (such as BaO SrO) are tabulated in Table 1. From se we sec that difference between * is remaining fairly constant in spite of se mselves changing in as wide a range as 0.4 e.v. Discussions. From results obtained we known that: 1. resistance of oxide is ohmic in considerable wide srange. 2. Both conductivity rmionie 3. Although Fig. 4. increase simultaneously change in wide during activation. range, ir difference V is almost constant. In order to clarify above results, we considered alkali earth oxide consists cathode as a semiconductor. Its conduction electrons are rmally excited gained suffcient energy can be emitted. conductivity of oxide is due to neutral atoms of alkali earth metal is excessively dispersed in oxide. se neutral atoms may be similar to Fcentre as found in alkali-halide. valency electrons of se neutral atoms have relatively high energy may easily be excited to

5 382 E. NISHIBORI Table H. KAWAMURA. 1 Upper figures are those of before activation, conduction level. If E is energy required sity of neutral atoms, baud is given by following conductivity mean free path by, we have As depending [Vol. 22 for this density formula is proportional to of conducting elections. lowers are of after it. excitation of electrons ; in n0 is den- conduction product of density Denoting mean free path does not suffer a notable change with temperature. factor on Temperature in is only. Hence we have, where On or h, rmionic electrons are conduction electrons are shot through potential barrier V (Fig. 5). refore current i can be given lay n times. Substituting (1) in this equation, we get

6 1940] Conductivity rmionic Emission. 383 where Combining (2) (5) we get a relation between conductivity current Values of we obtained are different by about 0.4 e.v. even in same oxide for different degree of activation. This is due to Fig. 5. second term of right h side in equation (4)( ). In this equation if. density of alkali earth metal atoms changes by factor 104, will change about 0.4 e.v. consequently will also suffer same change as can be seen from (6). On or h, V= - is energy difference between conduction b out-side of oxide, it is, refore, related to conditions of surface. For example, it may be lowered by absorption of barium atoms or or electro-positive atoms. But in our experiments on same cathode variation of V with activation could not begobserved. It may be very small even if it were present. refore we can say that conditions of surface do not change by activation process.

7 384 Shoji KOJIMA. [Vol. 22 of our conclusion, laboratory we wish to thank In for his kind support also too Messrs.. Y. Ashizaki assistance, also we are greatly Y. Ota. T. indebted (Received.April Mr. S. Hamada, to our work. Vice president Our thanks are Ishibashi for to discussion ir labourious given by Mr. 23, 1940).

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