Basic Data of Plasma Physics‘TECHNOLOGY PRESS BOOKS IN SCIENCE AND ENGINEERING Moxecuiat Sctenee sum Mocecotax Exoneeeaine ‘By Arthur Bon Hippel Nowe am Eurcrnox Devens Baied by Louts D Smullin and Hermann A Haus ‘Tap, Prrstcar Cuzmsray of Sreesseatine ‘Baned by John F lore Lacruaes ox Ouossaty Dirrexeenan Ravariont By Whteld Hurewee Nores ox Avator Dictrat Convenstow Tecusraves aned by Aled K Saad Anuossnene Exztonarions ‘By Henry G Hooghton Cexante Fansicarzon Process ByW D Kisgery Cunesyrs, Fietos, ano Paaricces ‘By Francs Heer ‘Te Turon 4xp Trenwique oF Sur Drsicn By George © Manning Srznoroat, Ware Foxton’ Byy A Stratton, PM Merse,L J Chu, J DC Lede, and F J Corbato Pancreurs or Execrne Urtuire Exemtezame Wr A Powel Deeteeene Marenuazs axo Aesuicxrions Siy Arthur vos Hippel Purncur Meteonovocy ‘By Joba C Johnson ‘Tur Marvivanes or Cincurt Auatyie ‘By E'A Gulema Macwerre Cincures ayo Taavsronstens ‘By Merabers ofthe Electra! Engteronng Stu, MT. Arputo Execrnowtes ‘Second Ein by Truman § Gray Execraie Cnevirs ‘By Mewebers of the Bletreal Engineering Sta Mexnoos of Orzxanions Resraney By Philp MT Morse and George E’ Kimball, ‘x. Inoex oF Nowoonssrs "Compiied and Batted by Douglas P Adams tation, Tntenpotatiox, amo SuoovinNe oF Srariovany Tote Seates tion, 8 Mit Impex Fosse or Noni Aursica By W Shimer and kt R Shrock Waveurnorn Tans Measured and Compiled under the Durecnon of GR Harnvon ‘Tapucs of Estcrate Dirove Moweers Compiled by LG Wesson ‘Avacrass of tue Fors Bax Lineace "By Jako A'Hrooes and George L- Nelson Nowiaeean Peanvene in Ravoost Titory By Norbert Wiener Cincarr Terre o7 Livean Notsy Netwones ‘By Hermaan A Haus and Richard B Adler Marnpasrieat Paocnsuaive: ano Extetatcat Newonns By Jack Denese Nores ow Onenarions Reseanci: Nrebld by te Gpeatoe Reeth Center, MOT Bane Dara ox Pianta Puraes ‘By Sanborn © BrowsCHECKED Basic Data of Plasma Physics Published jointly by The Technology Press of The Massachusetts Institute of Technology and John Wiley & Sons, Inc., New York Chapman and Hall, Limted, LondonCopyright © 1959 by ‘The Massachusetts Institute of Technology AUl Rights Reserved hes Book or any part thereof must not € reproduced in any forms without the ritten. permission of the publisherPREFACE A graduate course in gas discharges has been offered at M.L T. for many years, and it has been the author's custom to provide each student with his own lecture notes for study and reference. These class notes have been rewritten every few years and have been supplemented by pictures and other data included in a Research Laboratory of Electronics technical report on Basic Data of Electrical Discharges. The R.L.E. report has been re-~ vised four times since it was originally issued. The present volume, a combination of our most recent class notes and the current Basic Data technical report, has been prepared specifically for an M.1. T. course in plasma dynamics given during the summer of 1959, No attempt has been made to make this volume a complete text on gas discharge physics. Emphasis is placed on those parts that interest our particular laboratory, to the exclusion of a great deal of im- portant fundamental work with which we have had very little ex- perience. We gather from many requests that much of this material will be useful elsewhere, and since we have found no similar col- lection, it has seemed worthwhile to produce these notes and data in book form. My greatest debt is to Professor W. P. Allis of M.1LT., who alternates with me in teaching ‘the’ gas discharge course for which these notes were originally prepdred and who helped me put together the first Basic Data technical report (Research Laboratory of Electronics Report No. 283). Iam also deeply indebted to the graduate students who have criticized these notes in their many forms and who continue to be the inspiration that makes this kind of labor worthwhile. Cambridge, Massachusetts Sanborn C, Brown June 12, 1959CONTENTS Preface Chapter 1 Elastic-Collision Cross Sections 1, Probability of Elastic Collision Between Electrons and Gas Atoms 2. Probability of Elastic Collision for Ions with Gas Atoms Chapter 2 Charge- Transfer Cross Sections Chapter 3 Diffusion and Mobility i. Diffusion 2, Electron Mobility 3. Tonic Mobility 4. Average Energy of Electrons 5. Ambipolar Diffusion 6, Transition Diffusion 7. Ambipolar Diffusion with Variable Ion Mobility Chapter 4 Inelastic Collisions of Electrons 1. Currents at Low Fields 2. Probability of Excitation 3. Probability of Ionization 4. The First Ionization Coefficient Chapter 5 Diffusion-Controlled Breakdown 1. High-Frequency Breakdown 2. Effects of a Superimposed Magnetic Field 3. Cyclotron Resonance Method for Determining Collision Cross Sections Chapter 6 Electron Attachment 1. Attachment Coefficients 2. Attachment to Impurities 3. Diffusion and Attachment Combined Chapter 7 Breakdown Controlled by Electron Attachment Chapter 8 Recombination 1, Ion-Jon Recombination 2. Electron-lon Recombination 3. Experimental Determinations of Recombination Chapter 9 Secondary Electron Emission 1, Metal Surfaces 2. Insulators Chapter 10 Breakdown Controlled by Secondary Electron Emission 1. Secondary Electron Resonance Breakdown 2. Secondary Electron Resonance Breakdown in Magnetic Fields we be Be - 31 36 47 47 50 61 79 86 Oo 95 99 101 103 122 142 142 155 160 164 165 180 180 185 188 188 192 197 202 202 205 209 209 al4Chapter 11 The Second Townsend Goefficient Ghapter 12 D-C Breakdown 1. Space-Charge Pifects 2. The Streamer (y ~ o - B process) 3. Townsend Discharge (a ~ y process) 4, Space-Charge-Controlled Townsend Discharge (a- y-¢ process) Chapter 13. The Corona Discharge 1. ‘The Geiger- Miller Counter 2. Current and Voltage Characteristics 3. The Negative Gorona 4. The Absence of Positive Corona Chapter 14 Glow Discharges 1. General Features of the Glow Discharge 2. Crookes Dark Space and the Cathode Fall of Potential 3. The Negative Glow 4. The Positive Column 5. The Positive Column in a Longitudinal Magnetic Field 6 The Anode Fall Chapter 15 Steady-State Microwave Discharges 1, Comparison of Steady-State and Breakdown Fields 2. Plasma Resonance Chapter 16 Are Discharges 1. Glow-to-Are Transition 2. Are Glasmfication 3. Low-Preasure Arcs A. High-Pressure Ares 5, Metal Arcs Author Index Subject Index 222, 247 248 249 254 256 258 259 266 270 272 215 275 279 286 286 293 297 302 304 308 310 310 au 311 318 321 a7 331Chapter 1 ELASTIG-COLLISION CROSS SECTIONS The fundamental phenomenon that distinguishes the study of gas discharges from all others is the interaction of electrons with the atoms of a gas. In defining quantities relating to collisions between electrons and atoms, it is sufficiently accurate to picture the atoms as rigid spheres with definite boundaries and a collision as an event in which an electron suffers a change in the magnitude or direction of its original velocity. The simplest type of colli- sion is an elastic collision, defined as an event in which the kine- tic energy is conserved. 1. Probability of Elastic Collision Between Electrons and Gas Atoms In 1903 Lenard [1] carried out a series of measurements to determine the attenuation of a beam of monoenergetic electrons by same of the common gases. His apparatus is shown in Fig. 1.1. FARADAY CAGE PHOTO ELECTRIC SOURCE Fig. 1.1. Lenard's apparatus for measuring the probability of elastic collision between electrons and gas atoms. The electron beam passed through a screen into a field- free space and was collected in a Faraday cage. If the electron current that passes into the field-free space is I, and the current leaving is I, the difference in current will arise Pecause electrons are scattered 12 elastic-collision cross sections out of the beam owing to collisions with the gas atoms. Lenard called the number of collisions that occur when an electron travels a given distance at a standard pressure the "absorbing power " His results, given in Fig, 1.2, show that the absorbing power decreases as the velocity increases. Unfortunately, the nomen- clature im this field is poor. True absorption (attachment or recombination) 18 a very rare event, the electrons are for the most part scattered out of the beam, Therefore, it 1s more common to call what Lenard termed absarbing power a "probabil ity of collision" P_. The probabshity of collision P_ can be defined T T + HroRoceN a = ARGON . AR 2 2* 4 z & 20-4 2 aS Fars Fig. 1.2. Lenard! s measurements of "absorbing power." as the average number of collisions that occur when an electron travels a digtance of lem ata pressure of mm at 0'C It may be determined in principle from experiment by measuring the change an current when an electron beam passes through various distances of gas at different preseures If the imual current 18 Ip, itis found that the final current I 28 a function of the distanve through the gas x, the pressure p, and the intial velocity of the electrons x, Ifthe distance alone 1s varied, T= Ip exp [-K, (viel, where the constant k, 18 a fanction of both pasdy If the pressure alone is varied, 1= 49 exp [-k,(e, vip], where k, 28 a function of both x andv, Combining these'two expressions, ‘we may write T= 19 exp [-PpP tobe] an ‘This defines the probabihty of collision P_, which 8 found an general to be a function of velocity Here, py = 273 p/T 18 the "reduced" pressure in millimeters of mercuty, Pg expresses aelastic-collision cross sections 3 concentration, N/V = 3.54x 102%, molecules per em, We can see from Eq. 1.1 that pgP, has the units of e-l, hence, the di- mensions of P, are f-1p-T or ¢29-3p-1, or physically, an area per unit volume per unit pressure. For this reason the quantity P, is sometimes called the effective collision cross section Q.. The effective cross section for a single atom q is found by” dividing P_ by the number of atoms per cm3 at 0°C and 1-mm pressure, Numerically, the relation between q and P_ may be written in units of cem?: q= 0.283 x 1o-l Py. Cross sections are sometimes given in units of Tag? = 0.88A2, The relationship described by Eq. 1.1 was determined experi- mentally, but may also be derived by means of simple kinetic theory considerations. Let us assume that an electron beam of density n electrons per cm3 traveling with a velocity v and of cross section A passes through the gas a distance dx. Let N be the number of atoms per cm3. The number of electrons colliding with gas atoms per unit time may then be written dn/dt = -(NqA dx/A dx)nv, (1. 2) the term NgA dx being the probability of collision in the volume element A dx, and nv being the current density of incoming electrons. We may simplify to the form dn/n = -Nqv dt. Writing v dt = dx and Nq = PoP we obtain n= Np) exp (-ppP x). (1.3) which is the same as Eq, 1.1. It is also convenient to write n= ng exp (-pPoP vt) = ny exp (-v introducing thereby an average collision frequency vor PoP .Y (1. 4) Another quantity which is often used is the average distance that an electron travels before colliding with a gas atom. This is called the mean free path and may be given by the relation 9 =1/poP,. Amean free time 1 is defined as l/r =v/? = 5.93 x 107ul /2p oP sec~! where u = mv@/Ze is the energy in elec- tron volts. The difficulty with the simple apparatus used by Lenard was that electrons which suffered energy changes on collision with the gas atoms might not be deflected from the beam but would still be detected in spite of having suffered collisions. To eliminate this difficulty, a magnetic field may be used to remove electrons whose velocity only has been changed. Such an apparatus, design- ed by Ramsauer [2], is shown schematically in Fig.1.3. A4 elastic-collision cross sections photoelectric source emits electrons that are bent in a uniform magnetic field to give a collimated monoenergetic beam of elec trons at a source sht The measured collisions take place in a field-free box, and the residual clectrons are measured ma collector. ‘The quantity measured in thts type of electron-beam experiment determines a "total" collision probabilty, since elec PrOlceLEcrR: ‘Seusee Fig 1,3 Ramsauer's apparatus for measuring the probabity of elastic collision between electrons and gas atoms trons are Jost to the beam if they suffer any angular deflection greater than the angular aperture of the detector ‘The expersmental determinations of the probabslty of elastre collision are summarized in Figs 1 4tol 26 Above energies of 2 few volts, the collision probabihty decreases as the electron velocity mcreases At the higher velocities of electrons in mona- tomic elements, P, 18 inversely proportional to the 1omzation potential and directly proportional to the gas polarizabihty These Télationa would'be expected, since’bofh the magmitude anu instor- tion of the potential field of the external electrons of the atoms control the scattering of the electrons The extremely low values of Pe for slow electrons are commonly known as the Ramsauer effect Since the potential field of the external electrons of the atoms 1s the determining factor in the collision probability, it 28 not surprieing to find great similarity between curves for atoms and molecules with similar external electron arrangements A theoretical explanation of the Ram- sauer effect was arrived at by Allis and Moree [3] by considering the diffraction of the electron wave by the potential field of the atom The remarkable agreement between their theory andelastic-collision cross sections 5 60 50 40 p ° 30 o'123456 78 9 0 /VOLTS Fig. 1.4. Probability of collision in Hy and He. R. B. Brode, Revs. Modern Phys. 5, 257 (1933). A. V. Phelps, O. T. Fundingsland, andS. C. Brown, Phys. Rev. 84, 559 (1951). L. J. Varnerin, Jr., Phys. Rev. 84, 563 (1951). L. Gould and S. C. Brown, Phys. Rev. 95, 897 (1954), VOLTS Fig. 1.5. Probability of collision in atomic hydrogen. A. A. Kruithof and L. S. Ornstein, Physica 2, 611 (1935). 2010'5 po | Pa 16 ~ He 2 = Siz Co 8 7 1 20 30 40 50 60xi0' VELOCITY (CM/SEC) Fig. 1.6. Gollision cross section for electrons in deuterium and hydrogen.o Fig 17 elastic-collisson cross sections 2000 os 1600 = = oh B00 600 EEN SS 200} mss = ia ovesas6ra9 0 SA0r8 Probability of collision in the alkali metals RB Brode, Revs Modern Phys 5 257 (1933) oo Fig 18 300, 280} 260} 2a0| 220} ore sas 6789 0 AOLTS Probabihty of collision in Hg Zn and Cd RB Brode Revs Modern Phys _$ 257 (1933) Ho Marg enau and FP Adler, Phys Rev 79 970(1950)elastic-collision cross sections VVOLTS Fig. 1.9. Probability of collision in thallium. R, B. Brode, Phys, Rev. 37, 570 (1931). o'1234 56 789 0 / VOLTS Fig. 1.10. Probability of collision in Ne, A, Kr, and Xe. R. B. Brode, Revs. Modern Phys. 5, 257 (1933).elastic-collision cross sectrot 130 @PREEEEE HO 100 90 80 70 60 50 othe 30) ALS 20a I 10 + o 1234 5676 9 10 AOS Fig 1 11 Probabiltty of collision nO, N,, and CO R B Brode, Revs Modern Phys § 257 (1933) 90 PEP | ow SS 80| 70 | 60! | s 50 lH A 40 2 zo 20! 10! LIT PIrr rrr o1234567865 0 af VOLTS: Fig 112 Probability of collssion in CO, ard N,O R B Brode, Reve Modern Phys 5, 257 11933)elastic-collision cross sections SVOUS Fig. 1.13. Probability of collision in NH,, H,0, and HCl. E, Briche, Ann, Physik 1, 93(1929); 83, 1065 (1927). 160 150 1 7 40 130 % I 120 oa HO i ets 109 i 30 80 7 CH, | 60 50 40 30 20 10 «a o123456789 1 SVOLTS Fig. 1.14. Probability of collision in CHy, CoH, and C3H,- R. B. Brode, Revs, Modern Phys. 5, 257 (1933).10 elastic-collision cross sections eat cs I vers Fig. 1,15, Probabslsty of collision an HCN and CH). F. Schmieder, 2, Elektrochem, 36, 700 (1930). : [Ns a SS Pe i Fig. 1,16. Probabihty of collision in CCl,. W. Holst and J. Holtemark, Kgl. Norske Vadenskab. Selskabs 4, 89° (1931).elastic-collision cross sections li Fig. 1.17. Probability of collision in C,He and CoH, W. Holst and J. Holtsmark, Kgl. Norske Videnskab, Selskabs 4, 89 (1931). Fig. 1.18. Probability of collision in CHy, C,H, C,H» and CAHy 9: E. Briiche, Ann. Physik 4, 387 (1930).12 elastic-collision cross sections 18 w " re Bo 8 so} al 7 Yr a) * > STS Fig 1.19, Probabity of collusion in CHCL,, CHCl), and CH,CI. W. Holst, J. Holtsmark, Kgl. Norske Videnskab Selskabs 4, 89 (1931). v4 c 100 }- nom * } . HE“ bs orig = oT sae Voos Fig.1.20, Probabihty of collision in CH,OH, CHF, and CHNH,. F, Schmeder, ochem. 36, 700 (1930).elastic-collision cross sections 13 Fig. 1.21. Probability of collision inn -~- C C,H, OH, CH,OH, and HO. F, Schmieder, Z. Elektrochem. 36, 700 (1930). 3H, OH, /VOTS Fig. 1.22. Probability of collision in (CH,),CH and (CH,) 3h. F. Schmieder, Z. Elektrochem. 36, 700 (1930).14, elastie-collision cross sections ar 1 as Fig. 1.23, Probability of collision n G)H,OH and (CH,},0. F, Schmmeder, Elektrochem. 36, 700 (1930). pa 2 Vworrs Fig. 1.24, Probability of collision an (GH,),0, {CH,),NH, and (CH,),CH). F. Schmieder, Z Elektrochem, 36, 700 (1930)+elastic-~collision cross sections VOIS Fig. 1.25, Probability of collision in butane and isobutane. F, Schmieder, Z, Elektrochem, 36, 700 (1930), 60) t Sos Fig. 1.26, Probability of collision in n- pentane and tetramethyl methane. F. Schmieder, Z. Elektrochem. 36, 700 (1930). is16 elastic-collision cross sections expersment, shown in Fig 1 27, leaves little doubt as to the necessity of applying wave mechanice to the scattering phenomena Elastie-colliason cross sections have been calculated for a number of different gases since the original theoretical work of Allis and Morse, and all have substantiated their approach [4] (Fig 1 28) © 5 vous VOLTS Fig 127 Comparison of theory (solid lines) and experi- ment (dashed lines) for P_ for slow electrons anatomic gases © A eratzcal examination of the low-energy studies of the collision Probabihties shows a chaotic state of experimental disagreement an this regson among measurements by various workers (Fig 1 29) This reaults from the great difficulty of making very low energy determinations by measuring a direct current with a probe In mmcrowave discharge phenomena the collision probability forelastic-collision cross sections 17 low-energy electrons is important, and the measurements are not difficult. These new techniques have been used for determin- ing P,. When electrons are acted on by an electric field, oscillating with a radian frequency w, E= Ep exp (jut) in the presence of a \ He 100, 40, 8 7 | . | ‘a LL 30) 4 20) | —) °0 T 2 3 4 5 6 % 7 2 3 % 5 % VOLTS: SVOUTS Fig. 1.28. Comparison of theory (solid lines) and experi- ment (dashed lines) for P, for slow electrons in molecular gases. gas in which collisions are assumed to act as a continuous viscous- damping force, Newton's second law of motion may be written m(dv/dt) + kv= -eEy exp (jot). (1-5) For an assumption that the damping constant k is independent of18 elastie-collision cross sections velocity, the electron drift velocity determined from this equation of motion can be written ve [-eE, exp (0t}] /Qum +k}, 6) ‘The current density 16 (ne? eg exp Got} (om +H). ‘Since the complex conductity 6, = J/E, and tg =o, + Jy, we may write for the real component of the conductivity ne? k/ms , a7 PO cfm)? +1 ana for the amagsnary component of the conductivity 1 (c/o? +1 From theee equations we see that [o_/e,| = k/ms, . a8) seecimoe recite eel Fig. 1.29, Low-energy collision probabilities in hydrogen, BRODER. B. Brode, Phys. Rev. 25, 636 (1925) RUSCH. M. Rusch, Physi 26-798 (1925), BRUCHE: E, Briiche, Ann. Physik 82, 912 (1927). RAMSAUER AND KOLLATH G, Ramaauer and R. Kollath, Ann. Physik 4, 92 (2929). PHELPS ET AL." A.V Phelps, O. T. Fundingsland, and 5. C. Brown, Phys. Rev. 84, 559 (1951). VARNERIN: L.'J, Varnerin, Jz.. Phys. Rev. 84, 563(1951). BEKEFIAND DROWN. G. Bekeli ai SC Brown, Phy Rev. 112, 159 (1958).elastic~collision cross sections 19 50) = / z ARGON / = 40] f 4 > # zg é #30) ff 4 20| ee 4 g Norwano mois 3 Zé Bo , p< | 2727 __-RAMSAUER 8 KOLLATH 9, 6 iG 15a SVOrTS Fig. 1.29b. Low-energy collision probabilities in argon. ILLINOIS: ©. L, Coates and L, Goldstein, Tech. Rep. No. 8, E. E. Research Lab., Univ. of Ill, (1955). M.1.T.: A. V. Phelps, O. T. Fundingsland, and S. C. Brown, Phys. Rev. 84, 559 (1951). NORMAND: C. E, Normand, Phys. Rev. 35, 1217 (1930). RAMSAUER AND KOLLATH: C. Ramsauer and R. Kollath, Ann. Physik 12, 529 (1932). RUSCH: M, Rusch, Physik Z. 26, 748 (1925). To determine the physical significance of the damping constant k, let us write Newton's second law in the form -eEy exp (jot) = d(mv)/dat + vomv(1 ~ cos®@). 2.9) Thus the total rate of change of momentum in the electric- field direction is equal to the rate of change of momentum due to the field plus the rate of change of momentum in the field direction produced by collisions. Consequently, it is convenient to intro- duce a frequency of collision for momentum transfer, defined as “= yl - cos ®). (4.10) Although this is introduced here for a single electron, the same relation holds for a beam of electrons with velocity v. provided the average value of the scattering angle is used. We find, there- fore, that Io fo, = Veni G@.1) and that Pat Ven! Pov (1,12) Thus, in principle, the probability of collision can be determined by measuring the complex electric current in a discharge, the20 elastic-collision cross sections gas pressure and the frequency of the applied fields Actually. the collssion frequency 19 not an general a constant independent of energy and these sample relations between P__ and e, are not straightforward To obtain a more exact solufion, Newton s laws are expressed in terms of distribution functions, and reasonable assumptions must be made to allow a determanation of Pm Although to be able to interpret properly the results of the micro~ wave determinations, reference must be made to the more rigor~ ous treatments of the varsation of collision probabilty wath electro energy [5], te following treatment auffices to present the physical situation Assume that the probabrhty of collision varses as some power of the velocity hn pe vig = APgY and PL = av! a1) where a 1s a constant and h the power to which the velocity must be raised, ss a collision probabihty parameter A relation may be derived between h and the experimental parameters of pressure pp radian frequency of the microwave measuring field ©, the effective temperature of the electrons kT, and the elec- tromc mass which can take the form. y ot? 2) tany/e ai) ‘The physical meaning of ¥ 16 that xt measures the number of collisions that an average electrou makes per radian of the elec- NUMBER OF COLLISIONS PER CYCLE (7) COLLISION PROBABILITY PARAMETER hl Fig 1 30° Solution of Eqs 1 11 andi 1422 elastie-collision cross sections continuous-wave tunable magnetron and a standing-wave detector that as sensitive only for a period of a few mucroseconds dering the afterglow. The transient standing-wave detector consists of a calibrated waveguide-beyond-cutoff attenuator followed by a superheterodyne receiver whose local oscillator frequency 28 con- trolled by a delayed sweep from a single- sweep oscilloscope The output of the receiver 18 observed on the single-sweep oscillo- scope, and the standing-wave ratio is determined by adjusting the cahbrated attenuator to maintain constant amplitude at the output ofthe recenver, ‘The delay crremt for the single- sweep ascilla- scope and the modulator for the pulsed magnetron are syncho- mazed by a trigger generator operating at 60 cps. The output of the continuous-wave magnetron 16 momatored with a cavity wave- meter and a bolometer. The power incadent on the cavity 18 controlled by a calibrated varsable attenuator. It has been known for some time that, when two raciowaves traverse a common region of an ionized medium and one of the waves 45 of sufficient strength, an interaction between the two waves can be observed. In particular, there 1s a measurable transfer of modulation from the stronger wave to the carrier of the weaker wave. The absorbed waves increase the mean energy of the electrons, and thus increased mean energy leads to a change m the collision frequency of the electrons, As the absorp- thon of an electromagnetic wave 1s determined by the collision frequency of the electrons in the 1omzed region, the absorption of the weaker 18 modsfied by the presence of the absorbed dis- rupting wave. In ionospheric work this phenomenon 1s known as the Luxemburg effect, Several determinations of the probability of collision of electrons in gases have been made by using thie cross-modulation effect in the microwave region. [6] Another way to determine frequencies of collision by mucto- waves relies on the action of a magnetic field on an somzed plasma, Ifthe applied magnetic field causes the electrons to move in cyclotron orbits under the action of the applied rf eld, the effacrenty of the transfer of energy from the applied field to the electrons wall be modified by the collisione of the electrons wath the gas atoms, One can relate the broadening of this cy¢lo- tron resonance curve to the collision frequency and, hence, determune the frequencies of collisions of electrons in the gas.[7] Another microwave method also utilizes the properties of a plasma ina d-c magnetic field [8] The effect can be understood qualitatively by considering the motion of the plasma electrons an crogsed a-c electric and d-c magnetic fields. In the absence of collisions, the phase of the electron current with respect t@ the electric field 1s determined solely by the magnetic field, For values of the magnetic field that are lower than the cyclotron value, the current for # given radian frequency lags belund the electric field, for higher values, at leads, Introducing collisionselastic-collision cross sections 23 GAS DISCHARGE TUBE DIRECTIONAL COUPLER CRYSTAL, KLYSTRON CRYSTAL. MULTIPLIER FREQUENCY P\ orRection at METER COUPLER Fagguenicy SUPPLY Fig. 1.32, Block diagram of the microwave interferometer apparatus for measuring high-density plasmas. serves to shift the position of no phase difference, just as the addition of damping to any oscillator shifts its natural frequency. The point at which the plasma is purely resistive is determined experimentally when the resonant frequency of a microwave cavity containing the magnetized plasma is the same as its reso- nant frequency with no plasma present. In practice, this position is located by adjusting the strength of the magnetic field until the cavity frequency shifts vanish. The quantity Pin Can be deter- mined from this value of the magnetic field. Finally, the free transmission of a microwave signal through a discharge provides a method for studying electron loss processes. [9] Horns can be used to transmit the microwave signal in the millimeter region through a plasma many wavelengths long, The plasma forms an arm of an interferometer bridge circuit, and measurements are made of the changes of the path through the transmission system as a function of time in a decaying discharge, A block diagram of the apparatus is shown in Fig. 1.32. This method is particularly useful in a high-density plasma, The inter- ferometer pattern goes through maxima and minima corresponding to the electron density in the decaying plasma. In the absence of collisions the fringes are about the same size. In the presence of collisions the electron motion is attenuated because the smaller amplitude signal transmitted through the plasma increases the amplitude of the observed fringes, The rate at which the amplitude of the transmitted signal increases can be related to the collision frequency. The behavior of the function of time is recorded by an oscilloscope trace, which can be recorded photographically. Such a trace is illustrated in Fig. 1.33. Experimental determinations of the collision probabilities of various gases by the microwave technique may be compared with those of the d-c beam method only when the relation between the momentum-transfer-collision cross sections and the total-collision24 elastic-collision cross sections cross sections 1s known In comparing these we must know the angular dependence of the scattered electrons undergomg collision The total clastic-collision cross sections 1s Q.. The probabi- ‘ty 21 elastic collision that an electron 1s scattered into a solid angle @@ = sin © dd dg 16 p(8) sm8 a9 ds. We then introduce the term differential cross section for p (8) sin @ d9 ag, which as the elastic scattering into the solid angle d%, Defining 1(8 ) = (8 JQ_, we have the differential cross section as (9) sin ad ag, and age §f §P 10) ame anes, ws LS, When we worry about the momentum transfer in collision, the fraction of energy lost per impact by 2n electron scattered through an angle 8 is 2(1 - cos © }m/M, where m and M are the masses of the electron and atom, respectively. ‘The mean fractional-energy loss for collision 28 rae emmy § f {1 - coe 0)p(0} ain 0 d0 ae, Jo Jo and the momentum-transfer-collision cross section 12 defined as "Can nF f S 18) (1- cos @) sin @d9 dp (1.16) 0 40 where the mean fractional energy loss per collstion 18 (2m/M) (Qyq/Qe)- Fig. 1.33, Oscilloscope trace of a decaying plasma in a mcrowave interferometer.elastic-collision cross sections 25 ELECTROMETER CO.LECTOR COLLISION VOLUVE Fig. 1.34. Apparatus for measuring the angular dependence of electron scattering in gases, The Qm values may be compared with the values of Q, only after the scattering as a function of angle and velocity has been measured, Using an apparatus illustrated schematically in Fig, 1.34, Ramseauer and Kollath [10] measured the angular depen- dence of the scattered beam for the noble gases, with the results shown in Figs. 1.35 to 1.45. For these gases, the beam deter- os Os o4 SCATTERED INTENSITY a2 al—- ° OG 65° 90° 135° 1g0° ANGLE OF SCATTERING Fig. 1.35, Angular distribution of 10-volt electrons scattered in helium, C, Ramsauer and R, Kollath, Ann. Physik 12, 527 (1932).26 elastic-collision cross sections g SCATTERED WNTENSITY ons ca ca a TF Tsar Antue OF SeArTERNG Fig. 1.36, Angular distribution of 10-volt electrons scattered in neon. C, Rameauer and R, Kollath, Ann, Physik 12, 527 (1932). os} av Bev g | — aay besy SCATTERED NTENSITY 2 ry 1 ‘eo" ANGLE OF SCATTERING Fig. 1,37, Angular distribution of electrons scattered C, Ramsauer and R, Kollath, Ann. Physik 12, 527 (1932). as"elastic-collision cross sections 27 2. ol SCATTERED INTENSITY aol, 3 3 6 a5 20° 138 180° ANGLE OF SCATTERING Fig. 1.38. Angular distribution of electrons scattered in neon, Cc. Ramsauer and R, Kollath, Ann, Physik 12, 527 (1932). 4 3 2 8 45° go? 135° igoe ANGLE OF SCATTERING SCATTERED INTENSITY Fig. 1.39. Angular distribution of 4-volt electrons scattered in hydrogen, C, Ramsauer and R, Kollath, Ann. Physik 12, 527 (1932).28 elastic-collision cross sections r iA PREP q q aE “ i (ik ‘ i Fig. 1 40, Angular distribution of electrons scattered an mercury H. 8, W. Massey and EH, S, Burhop, Electronic ‘and Jone Impact Phenomena, Clarendon Press, Oxford (1952), p 98. NSE me (G SEE. ( Fig 1 41 Angular distribution of electrons scattered an argon HS W Massey and E H S Burhop, Electrome and Iome Impact Phenomena, Clarendon Press, — re Pelastic-collision cross sections 29 ce Zn Hg By Bev Be ev sy 53 ZERO s2 zev S$ re ZERO ce aev Pe 38v ZERO 25 BV 82 aev ZER as ay gs ZERO} 33 a 0 30° 90° 150" 0 30° 90° 150" ANGLE OF SCATTERING {9} {b) {ey Fig. 1.42. Angular distribution of electrons scattered elastically in Cd, Zn, and Hg. H. S. W. Massey and E. H. S. Burhop, Electronic and Ionic Impact Phenomena, Clarendon Press, Oxford (1952), p. 93.” 1 He \ ae ssov | 4x50 By. ~~ 7eov SS Zeno \ xo ze x20. ZERO os Swan NS : ay Ns -330¥ \Y80_asoy ZERO ZERO “sw-- ZERO Te BS 205v eT 89 soov ZERO 2ERO Ke ZERO e3y. sav a E 2 g 5 é é 3 é = 2 (ov ZERO 2eRO |S ZERO = 15QV Sey t Sev Jo 3 8 Xe hope 5 \ \, x20 ‘x10 2 NS a20v \ # os ZERO. Sot é Sao 3X gov § 1%, —- ZERO 2 V7 # x 200v 5 ZERO e 3 8OV s ZERO — 8 av oO 60° Teo" 180° O° 60" 120° 180° o* 60° 120° ANGLE OF SCATTERING Fig. 1.43. Observed angular distributions of electrons scattered elastically by the rare gases and by mercury. H. S. W. Massey and E, H. S. Burhop, Electronic and Ionic Impact Phenomena, Clarendon Press, Oxford (1952), p. 91.30 elastic-collision crose sections Ua Wy vag coe EN ae Sed cee e Fig, 1.44, Observed angular distribution of electrons scattered elastically by the rare gases and by mercury, H. S. W. Massey and E. H. S Burhop, Electrome and ‘Jomc Impact Phenomena, Clarendon Press, Oxford (1952), Pe 92. rory FRO} ie = i \eeny” Awa | ves Jags, |B stove) meen orl . - g A 2 — 3 DS yew [4 o as = ca vat [ANOLE OF SCATTERING Fig. 1.45, Angular distr:bution of electrons scattered an carbon diomde, C, Rameauer and R. Kollath, Ann, Physik 12, 527 (1932).elastic-collision cross sections 31 minations of Q, may be corrected to Qn by using the measured scattering intensity and integrating over all the scattering angles from 0 to 7. A comparison of the momentum-transfer cross sec- tions with the total-collision cross sections is shown in Fig. 1,46. The low energy range of electrons in helium is the only case in which the momentum-transfer cross section is greater than the total, Physically this means that for this case the electron is more likely to be scattered backward than forward, For most gases the differences between P, and P, is less than 10 per cent. 2 0 Q6 10m IN UNITS 1a, PSS 0} 0 10 20 30 40 50 60 Oo 10 20 30 40 50 60 Oo 10 20 30 40 50 60 ELECTRON ENERGY (ELECTRON VOLTS) Fig. 1.46, Comparison of momentum transfer with total collision cross sections. 2, Probability of Elastic Collision for Ions with Gas Atoms The probability of elastic collision between positive ions of one type passing through gases of another type has been studied by various workers, [11-14] Typical results are shown in Figs. 1.47 to 1.52. The collision probability in a given gas increases with the mass of the ion and decreases to a constant value with the increasing kinetic energy of the ion, For a given ion, the collision probability increases with increasing atomic mass of the vehicular gas. Ramsauer and Beeck [11] used their measurements to deter- mine ionic radii and found order-of- magnitude agreement with the calculations for gas kinetic theory. Thompson [12] has also measured some of these same cross sections and finds their abso- lute magnitude to be functions of the apparatus. One must conclude that there are few good measurements of these cross sections. The collision probability of ions traveling in their own gas is subject to the phenomenon of charge transfer. Since a charge- transfer collision does not follow our definition of an elastic colli- sion, this will be dealt with in the next chapter.32 elastic-collision cross sections "80 - 60 heuiu 0 120 2 ® 100 80 Kt 60 40 20 [——— = ao ° v 2 3 4 5 Fig. 1,47. Probabilty of collision for posstive rons of La, Ky and Ge in helium. ©, Ramsauer and O. Beeck, Ann Physik 87, 1 (1928), 200 NEON wo I rcs” 190 “tS too + 2 80 60 a = ol [ 7 z 3 4 5 6 SOS Fig. 1.48, Probabuity of collision for positive sons of Li, K, and Gs in neon G, Ramsauer and 0, Beeck, Ann. Physik 87, 1 (1928).elastic-collision cross sections 33 400 a) 200) ae [ 180 oh \\ ° 120 . ) +t ho” ! £0 | = 7 ° AVOTS Fig. 1.49. Probability of collision for positive ions of Li, Na, K, Rb, and Cs in argon. GC. Ramsauer and O. Beeck, Ann. Physik 87, 1 (1928). 160, 40; 7 i i } 5 OLTS Fig. 1.50. Elastic scattering of low-velocity hydrogen ions in hydrogen, J. H. Simons, C. M. Fontana, E. E. Muschlitz, Jr., and S. R. Jackson, J. Chem Phys. 11, 307 and 316 (1943).4 elastic-collision cross sections oo , = ‘TOTAL $ |__| 3 — = a jes waste ae 0 enencr uss Fig, 1.51, Scattering cross sections of Hin Hy. E, E, Muschhtz, Jz., T. L, Basley, and J. Simons, J, Chem, Phys. 24, 1202 (1956). H, 220} Tr Potassium 200} 120) ‘eo! 140 120 10: 60] 49) 0 2 3 4 3 SRS Fig. 1.52, Probabuty of collision for positive sons of Kin Ky, 03, and Nj. G, Ramsauer and 0, Beeck, Ann. Physik 87, 1 (1928).» as Rev. 95, 897 (1954). and A. J. Penico, Rocket Interscience Pub- Serson arc L. Golésteix, 102, 388 (1956); 162, 933 (1956). Rev, 10G, iG37 (1955); Margenac, end S. C. Brown, Pi Rev. 108, Preys. 29, 1749 (1958). . Rev. 104, 372 (1956). . Ramseter exe R. Kolieth, Ann. Peysik 12, 529 (1932). . Ramsate> exc O. Beeck, + Pays. 87, 1 (1928). I. S. Trompsoz, Pays. Rev. 35, 1196 (1930). EL Meschiitz, Ir., and LI, 307 anc 316 (1943). J. EH. Simors, C. 38 Fontana, S. RB. Tackson; I, Chem. Pry » tT. L. Beiley, and IJ. H. Simors, , 1202 (1956). 24Chapte> 2 GHARGE-TRANSFER CROSS SECTIONS, As was mentioned at the close of Chapte~ 1, the passage cf ros through their own gas 1s subject to the phenarezon of the transfe~ of charge between the 10n avd the neutval gas atom This is a type of inelastic collisio: whose probability can p-edorninate ore> o.be> arterachions Change transfe~ results in the fovmanea of very low aons and atoms having ar ene~gy practically ecual to the mtal en- ergy of the tons An ion that has traveled a single change-trancte~ fee path becomes a neut-al atom bat retains its veloc t) The atom, which has gnen up its elect-on to the 10n and has become ar. aon, begins to duuft im the field wth zero imal veloc (\) This new aon travels the next free path ennl the next charge tvansfe~ takes place and the collision to be a gradual piercmeson where the ates aparorch each other woth a velocity which as vex) small compa-ed wth that of the atomic electrous Classically We may rep-ese-t this by com sidering the arphiude of vibrat.oa set up whes a dista-bive force as apphed to an oscillator of natural freqaeict » Ths dista be ance will vary with time according to serne farction of the force To determine the effect on the ovcillatoy We expard the fazcho™ ana Fourier astegral [tas only the compone-ts of this expa~sie~ that have frequencies between «and s+ ¢ which wll proe.ce any aporeciable forced oscillations In o-de~ fo~ the cemmponen cf the force to be st-ong the time of collasion + stould rot be Jarge compared with a natural period of the oscillatoy Tak “g > as the orde> of afk, where a is the vange of irtevactio~ between, the atoms and \ their relatye velocity the coné.ties for mac mun excitations (av/ij f To Cransfer ths ciassicaf picture to the quantum theors we need only to -eptace 1 by AE/h We then have the chance that the transitios occe~-ang pe pact [1] well be maximal if fa AEM) = 1 en where ea < Yas the energy of mneidest 2035 19 volts and Was the 207 30charge-transfer cross sections 37 Measurements of the charge-transfer-collision cross sections are consistent with this picture. The cross section for an ion traveling through its own gas is greatest when its kinetic energy is the least, as illustrated in Figs, 2,1 to 2.3. For ions passing + 160 29) aha oJ 25 35 40 LE Fig. 2,1, Charge-transfer cross sections of at in A and Het in He as a function of energy. J.B.Hasted, Proc. Roy. Soc. (London) A205, 421 (1951). 150 00 Prom 50 SVs Fig. 2.2, Probability of collisions of Het ions in He. W.H.Cramer and J.H.Simone, J. Chem, Phys. 26, 1272 (1957). through a different vehicular gas, the cross section passes through a maximum, this maximum shifting to higher velocities as the dif- ference in the ionization potentials increases. This is illustrated in Figs. 2.4 and 2.5.38 charge-transfer cross sections 00 3409 x00 — 200, o 30 SOS a0 Fig 23 Charge-transfer cross sections of ons and atoms of mercury B M Palyukh and 1, A Sena, J_Exp Theoret Phys (US'S R ) 20, 481 (1950) wing say _ heres O,MUNTS wef 2 38. 8 aq 4 00” 1900 O65 0 350 ENeRey (oLTD) 30.600 Fig 24 Charge-transfer cross section of Ht in H, HOS W Mai ey and E HS Burhop Electrome and Tonte Impact Phenomena , Clarendon Press Gxtord (F952), p 526charge-transfer cross sections 39 50, 40) Pxon"h NeyHe: ° 5 10 15 20 25 30 SVOTS Fig. 2.5. Normal charge-transfer cross sections. J.B.Hasted, Proc. Roy. Soc. (London) A205, 421 (1951). Although many of the charge-transfer cross sections appear to behave in a normal fashion, there are some anomalous cases such as, ot in A and N* in Aand o* in He, given in Fig. 2.6, as well g ote Fig. 2.6, Abnormal charge-transfer cross sections with metastable 1ons present. J.B.Hasted, Proc. Roy. Soc. (London) A205, 421 (1951).40 charge-transfer cross sections as Otin N5, shown an Fig, 2.7. In these cases 1 seems likely that other melastic collisions contribute to the measured cross section. For the molecular case, there are a large mimber of possibilities snvolving vibrational and rotational etates a8 well as electronic { ! co Fig. 2.7. Charge-transfer cross section of 0+ in Nz as a function of energy Dotted line 1s extrapolated, JB, Hasted, Proc, Roy. Soc. (London) A205, 421 (1951). metastable states of the oxygen ton, the mtrogen ion, and the oxy- gen atom, Some of these may well have low values of AE, a fact that would account for the observed maximum cross section at very low energies. For the case of the oxygen ton 1n argon, the posorbility of the presence of atomic metastable 1ons in the beam seems quite likely in the type of source used by Hasted [2] an these expermenta, When the difference in velocities between the 10n and the atom transfer cross sec- of the same gas becomes large, the charg trons asymptotically approach constant value that depends upon ‘the ron:zation potential u,. Sena [3] has worked out an approxi- mate theory for this, whith gives for a value of this miting cross section Py = Lasx 10/07. 23 Holstein [4] has worked oat a general theory applicable to any charge-transfer collision between an atomic 1on and atom for whach the wave functions are known, He shows that the charge-transfer-~ collision region may be considered as a aphere of radius +. aur~ Founding the atom. Insider, the probability of charge-trdnster is 1/2, and outside r, it 18 zero, As an son approaches an atom, it will be deflected toward the atom as a result of the dipole moment it induces ma the atom. ifcharge-transfer cross sections 41 the distance of closest approach is greater than r_, the only de- flection of the ion results from scattering. If the ton enters the charge-transfer sphere, half the time it emerges as a neutral atom and the other half remains an ion. The momentum-transfer- collision cross section resulting from the charge transfer is Q = mb (2. 4) where b. is the critical impact parameter for charge-transfer and is relatedto r. by 2 (bit = 14 (e JE), (2.5) Here E is the initial kinetic energy of relative motion between ion and atom, and , is the potential energy at r, resulting from the polarization attraction: oF e a/2r4 (2. 6) c where a is the polarizability of the gas atom. A substantial number of measurements have been made of the probability of charge-transfer collisions, and these are illustrated in Figs. 2,8 - 2.17. In principle, these measurements are carried 20) a CROSS SECTICN(UNTS OF © 8) 3 senor tent] 3a &£§ Ir rithe reactions (H, Al” , Pies 28. Hee Ale). ih De, Ht bit), and (Hare: H’ + Al*)as a function of the amprct energy of the colliding ton. A. Dalgarno, Proc. Phys, Soc. (London) eT 1OL0 (1984),42 Fig. 2.9, Gharge-transfer cro: 9, cou’) charge-transfer cross sections ™s o a i ba | ie : fot ata ° —1 _) ec [aesct enenev or couse cnunieD 1% ol] ections for the reactions (H, S124, Ht, 5:4) and (H, Be“*, Ht, Bet), D R Bates and B,L Moisetwitsch, Proc, Phys Soc. (London) 67A, 805 (1954). lca 2 '6 ict Ne 1 7 ohne 4| ol 10203045 0 Sors Fig. 2,10, Charge-transfer cross sections of C2 in argon, neon, and helium, J.B. Hasted and R.A.Smuth, Proc, Roy. Soc. (London) A235, 354 (1956).charge-transfer cross sections 43 25x10" 20 Q, (cM?) J VOLTS Fig. 2.11, Charge-transfer cross sections of N4 in argon, LOWER CURVES neon, and helium. J.B.Hasted and R.A.Smith, Proc, Roy. Soc. (London) A235, 354 (1956). UPPER CURVE 30 x to""® 10 ' 20 et arin Ne a2* in He 5 |}-——110 I 0 0 20 30.40 50 rs) ¥VOLTS Fig. 2.12, Charge-transfer cross sections of A2* in argon, neon, and helium. J.B.Hasted and R.A.Smith, Proc. Roy. Soc. (London) A235, 354 (1956).44 charge-transfer cross sections ‘ . ota & La Onna 6 c ions a © Fig. 2,13, Charge-transfer cross sections of 0*, cot, and Nj 1m argon, J.B Haeted, Proc. Roy. Soc. (London) A212, 235 (1952). oo 7 ote “9 —— ome = Nevin oma 5 % Si Fig. 2.14, Charge-transfer cross sections of H* in argon, Dt an argon, krypton, and xenon J.B.Hasted, Proc. Roy. Soc. (London) A212, 235 (1952).charge-transfer cross sections 45 40 20 R (cM) oO 20 40 60 J VOLTS Fig. 2.15. Charge-transfer cross sections of ot in krypton, and Br* and C* in xenon. J.B.Hasted, Proc. Roy. Soc. (London) A214 235 (1952). 0, ) : 40) oO 20 40 0 Fig. 2.16, Charge-transfer cross section of Nt in krypton. J.B.Hasted, Proc. Roy. Soc. (London) A212, 235 (1952 OF IHD {ARBITRARY UNITS~ IGM!) Hy INA 40; & = fo pe 20 40 60 J VOLTS Fig. 2.17, Charge-transfer cross sections of 0* in water and ot, and Ht in argon.46 charge-transfer cross sections out by placing in a collision chamber, through which a beam of tons 1s traveling, an electrode maintamned at a potential of a few volte negative relative to the walls of the chamber. It 1s assumed that the low-energy sone produced in the gas arise from charge-transfer and that sons elastically scattered by the gas molecules are cai tered only through small angles and without much loss of energy, so that they vall not in general be collected. A diagram of such an arrangement for the experimental determination of the charge-trans- fer phenomenon 3s shown in Fig. 2,18. i o..e5T08 Ta =] Fig, 2.18, Apparatus for measuring charge-transfer cross sections. REFERENCES 1. HS, Wo Massey and E, H. 8, Burhop, Blectrome and Iome Impact Phenomena, Clarendon Press, Oxford (1952), p 518 2. 3, B. Hasted, Proc. Roy. Soc. (London) A205, 421 (21951). 3, L, Sena, J, Exp, Theoret. Phys, (U S.5.R_) 9, 1320 (1939) 4. T. Holatesn, J. Phys, Chem. 56, 832 (952).Chapter 3 DIFFUSION AND MOBILITY 1, Diffusion Let us consider particles in free space diffusing in a gas of simi- lar particles. To start with, we assume that a uniform flow has been established so that the particles are ina steady state. For simplicity we consider flow in one dimension along which a density gradient dn/dx has been established. We found by considering Newton's second law that we could write for the change in momen- tum due to elastic collisions between electrons and gas atoms d(nmv,) dt Som a{av,) . i dt Vm * The diffusion velocity v,. is acquired by the particle due to random collision with the gas with which it is assumed to be in energy equi- librium. Hence, Vy is independent of co-ordinates, and we may therefore write: a{nv,) ay (nv) ee (3.1) at x dé x dx xm When we average over v, , substitute the particle current q =nv, and make the substitution vee v@/3 » we obtain: 2 v dn T,7 ~Goave & m When generalized to three dimensions, this equation may be writ- ten as 2 Pe Vn =-DVn (3. 2) v - (sy dave m The proportionality constant between the total particle flow and the concentration gradient defines the diffusion coefficient 2 s . 3.3 D2 W/V) Le (3.3) AF48 @xffusion and mobality In terms of the mean free path for momentum transfer defined as 2, = 1/p,P.,, » this coafficient 18 often written as D= (vin /Mayer we had Considered the problem more correctly, using the velo- city distribution function, we would have obtained a more general expression for Eq. 3.2 of the form F = - VDn. If we consider the motion of electrons an a gas before steady flow has been established, we can calculate the tume variation in concen- tration in any element of space from the continuity equation 3f there 19 no source of electrons by the relation aafa +V- B= 0, This leads directly to the diffusion equation anfor = Dn (0.4) Let us now consider the case in which the particle concentration varies with time, For example, we can imagme that a particle concentration ng(x,y, 2) 15 initially set up in a container and allowed to diffuse out exponentially so that the particle density at any time 15, given by abe, yezt) = ngbss yz) exp (t/t). (35) The quantity + here becomes a decay constant, The diffusion equation then becomes DVn = -n/r = = (/Dr) Da, If we restrict our calculations to the case of a constant diffusion coefficient, we obtain vn = -(/Dr) a. G.6) ‘The solution of this equation 16 a standard characteristic-value problem whose solution depends upon the geometry of the container an which the diffusion takes place, The solution takes the form, for example, for rectangular geometry nlx) = En cos e/A\) 3.7) where AX = Dry. The quantity A defines the characteristic dif fasion length and {8 very useful in describing the shape of the par~ ticle container when diffusion problems are under discussion ‘As an allustration of the solution in a particular caso, Let us take the example of infinite parallel plates, imposing the boundary con ditions that n=O at x= !L/2, where L 1s the plate separation. We then have the condition con (L/2Ay)=0 where (L/2 Ay) = (2-1) Hf?diffusion and mobility 49 This leads to an infinite number of /\'s given by A, = (E/T 2k - 1). If one considers the solutions to consist of single values of A for kK any integer, only k = 1 is physically possible, since for values of k higher than this, the solution predicts the existence of places within the space where there is a negative number of particles. However, if one considers the solution to be made up of combinations of higher modes in such a way that the sum leads to a concentration that is positive, by proper choice of n, these higher modes offer physical solutions. Corresponding to each /\,, there is a decay time +, , where the subscript indicates the order of mode in one direction, with the lowest mode in the remaining two directions. The average n can be made up of many terms: Ave 7 Ay exp (-t/7)) + A, exp (-t/7 5) + Ay exp (-t/7) Fore, For the case of infinite parallel plates, the ratio between the time constant for higher diffusion modes to the time constant of the funda- mental mode are: % TIT, = 25. tlt 2° Thus, for this one-dimensional case, if combinations of higher modes exist, these higher modes decay much faster than the fundamental. In an experimental observation of diffusion in this case, all higher modes will disappear much faster than the fundamental, and one is left with only the lowest mode. For a cubical cavity, the ratio of time constants is found to be tT lta5 3.67; t/73 6, 33; TIT ge 9, In this case, the effect of the higher modes may be very pronounced. For an infinite-parallel-plate geometry, the solution for the low- est diffusion mode becomes: 2 2 n = ny cos (mX/L) and (l/A)” = (n/L) (3.8) One other example of a useful geometrical boundary condition is the case of a cylinder with flat ends. The solution is of the form = 3. n ny cos ax Jy (br) (3.9) where at ap? = (1/Dr).50 diffusion and mobility Putting in the boundary conditions that n = 0 at the walls of the cylin- der of radius r and height h, a= (n/h), b= (2 405/z) and 2 2 2 QUAY = (L/Dr) = (n/ty® + (2,405 /2)°. (3,10) ‘When the diffusion takes place in free space, the rate at which an initial particle number ng decays with time from a point source is given by 342 B® ng exp (-r7/4D1) / (458) Qa Electron Mobility We found from our discussion of Eq 1.5 that we could write Newton's second law as m(dy/dt) + (mv, wv = -eEgexp (ut) and the velocity where E= Ey exp (ut). The proportionality constant between the average drift velocity and the electric field defines a mobality con- stant » such that efm te, | » (12) If we are interested in the case of a d-c electric field where w = 0, or a case at high pressure where the collision frequency 18 much Jazger than the radian frequency of the ogcallating electric field, we obtain fer the mobility B= elm. 61D We have already seen that the probability of elastic collssion for electrons differs greatly from gas to gas and 18 1 general a strong fonction of the electron energy. Thus, without a mathematical des- eription of the electron energy distribution and without taking ante account the Rameauer cross sections, a quantitative solution of thie mobility equation cannot be obtained Two simple cases ext however, 1n which v;q, 18 very nearly constant, these cases are helium and hydrogen above 3 or 4 volts, Referring to the curves of Fig. 1.4, we may deduce for the collision frequency in helium that ve = 2,3 109p, and sn hydrogen v= 4.8% 109p Since the draft velocity 3a given by v= #E, we find for helium that v(em/sec) = 1.6% 10? E/p (volts/em-mn Hg), and for hydrogen vier sec) = 3.7.x 10° E/p (volta/em-mn Hg). Drift velocities for a number ofdiffusion and mobility 51 gases as a function of E/p were measured by R. A. Nielsen, and N. E, Bradley and R. A. Nielsen [1]. The gases studied included H, and He as well as Nz, Ne, and A. One finds that the simple cal- culation, assuming Vp, Constant for H, and He, provides a fairly good check of the validity of this simple mobility equation, as shown in Figs, 3.1 and 3.2. VELOCITY (CM/SEC) Oo 05 10 16 20 25 30 35 49 48 50 Esp (VOLTS/CMxMM Hg) Fig. 3.1. Drift velocity of electrons in helium as a function of E/p, TxIO VELOCITY(GM/SEC) ow HYDROGEN ° 2 4 6 8 Oo 2 4 16 1@ 20 E/p(VOLTS/GM x MM He) Fig. 3.2. Drift velocity of electrons in hydrogen as a function of E/p. Anything but a qualitative theory of electron mobility must, of course, involve the proper use of the energy distribution function for the electrons moving through the gas. A number of such theories have been worked out in detail which agree well with the dependence of the velocity with E/p [2]. Measurement of Electron Mobility A large fraction of the data available on elect ron mobilities comes from the studies of Bradbury and Nielsen [1], who used an electron- shutter method. The principle of the method can be described with52 diffusion and mobility reference to Fig 3.3 Photoelectrons emitted from plate P are accelerated upwards by the electric field maintained between P and A In passing through the tube, which contains the gas under consideration, the electrons pass through two sets of grids G and G' Alternate wires of these grids are connected to an a-e poten- tual of such a magnitude that only those electrons which arrive at the grids when the electric field passes through zero are tran: mitted The electron bunch that 1s thus allowed to pass ito the uniform field region between the grids drifts across the space The second grid is driven in phase with the firet grid s0 that oaly af the electron transit time 18 equal to one or more full hal! cycles of the grid frequency will current be collected at A Thus by know- rng the distance between the grids and the frequency at which cur- rent is observed, the drift velocity of the electrons may be determine Measuring the electron collection following a burst of ronization 1n an aonization chamber 19 also a fairly common method of determining electron mobilities [3] A typical experimental arrangement of tins sort 1s illustrated schematically in Fig 34 As shown, the volume between two parallel plates 1s ionized by the Compton electrons gen- erated by a square wave of X rays striking a gold film Direct 0n- ization of the gas by X rays and pulsed beams of a-partictes have alae been used Because of the electric field between the plates, the electrons move toward the eollector electrode The time of measure ment 1s sufficiently short so that during the measurement the positive fons move only negligibly and the current depends only on the motion of the electrons Rehable theories have been worked out for the res ponse of parallel-plate chambers to square pulses of 1omzation, 60 that by analyzing the shape of the current pulses the electron drift velocities may be calculated The best experimental work that has been ao far published consists of the studies of Hornbeck [4] A diagram of hus apparatus 16 shown am Fig 35 Light from a spark source falla on plate G refeasing a very short burst of photoelectrons, which move under the action of an electric field to plate A Wath the sudden creation of the electrons by the external ght pulse the current risea abruptly from zero and remams constant, white tne padket of diectrona crosses trom catnote toanode The current drops discontinuously to zero at one electron transit tune, except for diffuaion effects and the fimte tune duration of the light pulse The published data for electron drift velocities an various gases as shown in Figs 3 6 to 319diffusion and mobility 53 ht Fig. 3.3. Electron shutter for measuring electron mobility. We GOLD BACKED WINDOW | 4 Fig. 3.4. Iomzation chamber for measuring electron mobihty. TRAVELING: {jmeriscore SPARK EXPERIMENTAL LIGHT SOURCE ERIE MAGNET 2. Fig. 3.5. Hornbeck's apparatus for measuring electron mobility.54 diffusion and mobility tant — mei i. me i ' > LF ae Oo 3s es Bas wetaO evstvourercurun na) Fig. 3.6, Drift velocity of electrons in helium as a fanction of E/p. R.A.Nielsen, Phys. Rev. 50, 950 (1936) J.A.Hornbeek, Phys, Rev. 83, 374 (1951). sou ota 08 8S ee events emranse) Fig. 3.7% Drift veloesty of electrons in neon as a fanetion of E/p. R.A, Nielsen, Phys. Rev_ 50, 950 (2936)diffusion and mobility 55 24x10 20! VELOCITY (CM/SEC) & Oo 6 05 10 18 20 RE BOOB Esp(VOLTS /CM/MM Hg) Fig. 3.8. Drift velocity of electrons in argon as a function of E/p. R.A.Nielsen, Phys. Rev. 50, 950 (1936), L, Colli and U, Facchini, Rev. Sci, Instr, 23, 39 (1952). J.M. Kirshner and D.S, Toffolo, J, Appl. Phys, 23,594 {1952). ARGON+ QI% NITROGEN ‘Of of O3 O04 OS oO6 OF o8 a8 to Wt re E /p(VOLTS/OM/MM Hg} Fig. 3.9, Electron drift velocities in argon and argon-nitrogen mixtures. L. Colli and U. Facchini, Rev. Sci. Instr. 23,39 (1952). J.M. Kirshner and D.S.Toffolo, J. Appl. Phys. 23, 594 (1952),58 diffusion and mobility VELocrre (eM etc) * s o za(VOLTS C/U He) Fig 3 14 Drift velocity of electrons in arr af @ fonction of E/p RA Nielsen and N E Bradbury, Phys Rev 51, 69 (1937) es po ae Fig 315 Drift velocsty of electrons in the halogens RH Healey and 3 W Reed, The Behavior of Slow Electrons sn Gases, Amalgamated Wireless, Ltd , Sydney (1941), p53diffusion and mobility 59 axto® | . | | NITROUS OXIDI VELOCITY (CM/SEC) ° 8 16 24 32 40 E/P(VOLTS/CM/ MM Ho) Fig. 3.16. Drift velocity of electrons in nitrous oxide as a function of E/p. R.A. Nielsen and N.E.Bradbury, Phys. Rev. 51, 69(1937). 12108 g S T 2 2 > e : | s g AMMONIA Fy ° 4 ‘0 2 4 € = 10 1 6 16 is 20 E pp (VOLTS/CM/¥M Ha) Fig. 3.17 Drift velocity of electrons in ammonia as a function of E/p. R.A. Nielsen and N. 5. Bradbury, Phys. Rev. 51, 69(1937)diffusion and mobility wane : 8 ™ Ve i 2 lew a PTT I a e 3 cs em vourscran may Fig, 3.18. Drift velocity of electrons in CgHy 9, Nig. 20, and HCI. R.H, Healey and J.W.Reed, The Behavior of Slow Elec- trons in Gases, Amalgamated Wireless, Ltd., Syéney (1941), p 86 Let WE er Fig. 3.19 Draft velocity of electrons 1m N30, C02, NO, and CO, R,H. Healey and J. W. Reed, The Behavior of Slow Elec- trons in Gases, Amalgamated Wireless, Lid., Sydney (1941), p. 85.diffusion and mobility 61 tonic Mobility When én ion finds itself in an electric field, the force on it is expressed by the definition of the field, F = Ee. In a vacuum, the ion is accelerated an amount a = Ee/M, where M is the mass of the ion. In the presence of a gas, the collisions between the ion and the gas atoms slow down the motion of the ion. On the average, the ion moves with a constant drift velocity so long as the velocity gained from the field is small compzred to the random velocity due to the thermal motion of the ions themselves. This drift motion due to the electric field is called the mobility of the ion, and the mobility can be defined as in Eq, 3.13: BF e/My {3.14) A very elementary expression for the mobility of ions passing through a gas, in terms of the random and drift velocities, may be derived in the following manner, The distance that an ion moves in time t between collisions is the sum of v_t, the average random velocity times the time, and a term involving the accelera- tec motion due to the field. If we write s,, for the drift distance and s, for the distance covered by the ion in its random motion, + ~ +2 s +s, = vttat /2. r d r Thus we find sg = at”/2 = est? /2M. The average drift velocity vg is teken as the drift distance divided by the average time be- tween collisions, Since the rendom motion is the controlling effect and the average time between collisions is T= Z Ivy we write for the average drift velocity vg = sft = (e £/2Mv JE . The proportionality constant eA/2Mv, =p. This derivation assumes that the collisions are perfectly elastic and that the mass of the ions is the seme as the mass of the atoms of the gas through which they move, but neglects any effect of charge transfer. It also neglects the fact that after collision an ion may have an ini- tial velocity in the direction of the electric field. Langevin [5] derived 2 more exact expression for the mobility by considering the changes in momentum at impact and introducing an average of the persistence of the velocity in the direction of the field. He also removed the restriction of equal masses by introducing into his expression the mass of the ion M; and the mass of the gas atoms M, and obtained 8 M,/M yr B= (0.75 e £/M,y,;) (Lt MA ¢ (3.15) Since the kinetic energy of the gas atoms and ions are equal, this may also be written as62 aiffusron and mobility : a2 BF (0,75 edim,y,,) (1 +M IM) . ‘The numerical factor of 0.75 arises from the particular process of averaging which Langevin employed. It 1s seen that the equa- tion predicts the variation of mobility coefficient as being propor- tional to (14 My/M,)//2, ‘This 18 shown in Fig. 3,20. The ex- perimental data were obtained for various sons traveling through [et owe (oumccrenten Sa eel “TS ‘i See Fig. 3.20 Mobshty an nitrogen of various sons as a function of mass at L atmosphere pressure, J.H.Mitchell and KE W.Ridler, Proc. Roy Soc (London) A146, 912 (1934), mtrogen, It should be noticed that nitrogen rons passing through nitrogen gas 1s an exception to the agreement between theory and experiment illustrated in Fig. 3 20, This 26 a result of the phe- nomenon of charge transfer Another goad illustration of the effects of charge transfer 18 shown in Fig. 3.21 Considerable confusion existed concerning this case of helsum ions in helium until it was shown that the value at 14 cm /sec/volt/em was cor- rectly attributed, bath theoretreally and experimentally, to charge-transfer mobility, and that the value around 21 cm/sec/ volt/em was due to the helum molecule ion [6] _ Unfortunately, Eq, 3,15 19 not accurate m predicting the actual magnitude of the mobility, and Langevin introduced another relation that fits ‘the experimental observations of the mobility coefficient to a much more satisfactory degree. He assumed that a gas atom, though t might have no permanent dipole moment, could be polar= azed by an 10n Where the two approach each other. Thus there would be a possibility of exchange of momentum between ron anddiffusion and mobility 63 p= 760mm Hg © PEARGE & HOSELITZ X TYNDALL & POWELL (1930) 0 TYNDALL & POWELL (1931) A VALUE FROM Dg ++ MASSEY & MOHR{THEORETICAL) He (cm/sec /yatt/om ) Kt 30 40 50 60 MASS NUMBER Fig. 3.21. Mobility of various positive ions in helium, atom caused by the induced dipole even though no actual collision occurred. Determining the electric moment produced in the atom by the ion in terms of the polarizability and suitably averaging over the velocities, he arrived at an equation that considered the interactions as a combination of polarization attraction and hard- sphere repulsion. The mobility is given by 1/2 M sth) + 8 (3. 16) [NK-1)} 1/2 M,; where 4 1/2 R= (Se. y . ae Here o is the sum of the radii of the ions and gas atoms, a is the polarizability, K is the dielectric coefficient, and g{\) is a function of } which is given in Fig. 3.22 as calculated by Hassé [7]. When the mobility is controlled by the polarization force, p is proportional to 1/p, The proportionality constant is only a func- tion of the gas parameters. This leads to the prediction that at low values of E/p, the drift velocity should be proportional to E/p. This qualtity, E/p, is the experimental parameter that measures the energy gained per mean free path. At high values of E/p, where the drift velocity is larger than the random velocity, the energy gained between collisions is pro- portional to the kinetic energy of the ion, and hence, the drift velo- city is proportional to the square root of E/p. The fact that the66 diffusion and mobility Frost [9] has shown that 1 EB, 2 = reate 3.17] b= nol Gu (G.17) Values of jay and a are given in Table 3.1. Table 3.1 Values of jg and a im Eq. 3.17 Jon and Ga: Ho a Het He 9200 0.040 Net Ne 3500 0,040 at A 1460 0, 0264 Since the equations for mobtlity mvolve the thermal velocity of the gas atoms, one would expect the mobility to vary inversely as the square root of the absolute temperature as an Eq. 3.16 As E/p 1s increased, the ions gain more energy from the field until at sufficiently high E/p, the mobility should be independent of the gas temperature, The atormc ione in Figs, 3,25, 3,26, and 3.27 illustrate these temperature effects. Fig. 3.25. Helium ion mobility as a function of temperature L.M, Chania and M.A. Bionds, Phys, Rev 106, 473 (1957). Fig. 3,26 Neon ron mobilities as a function of temperature, L.M.Chanin and M. A.Biondi, Phys. Rev. 106, 473 (1957).diffusion and mobility 67 MODILITY (CM E/VOLT - SEC) Fig. 3.27. Argon ion mobilities as a function of temperature. L.M.Chanin and M.A. Biondi, Phys. Rev.106, 473 (1957), The mobility of ions through gas mixtures depends in a straight- forward manner on the relative concentrations of the mixed gases: t.4,4,1h..., {3. 18) B Ba Be ¢ where ,, ) He °** are the mobilities in the pure gases a, b, cc++ attheir partial pressures p., Py: Pe ttt> assuming the v, of each species has the same velocity dependence. David and Munso [10] showed that the mobility of alkali ions in He-Xe mixtures gave mobility values which were linearly proportional to the relative concentrations in the binary gas mixture, Some of their results are given in Fig. 3.28. They further showed that clustered lithium o7 03 to 0.6 ea a ut Gs* 3 g 5 08 Ss 02 os 8 aw o o 5 9 go4 8 3 Ss s 2 oO! 04 S03 = 0235 a0 60 80 100 o 20 40 60 80 100 PERCENTAGE XENON PERGENTAGE XENON Fig. 3.28. Mobility of alkali ions in He-~Xe mixtures.6B diffusion and mobility rons formed an rmxtures of noble gases and water vapor did not follow ths simple peture. These results appear in Fig, 3.25, More recent data on recsprocal mobilities are shown in Figs. 3.30 and 3.31. |» 1 TA oo iy BD So sae PeRcENTICE Ware Fig. 3.29. Mobility of lithium ions an the noble gases an the presence of water vapor. Fig. 3.30. Reerprocal mothties reduced to 160 ma Hg and 0 C of 0” nO, and COz, Nz, Hy. E,W. McDaniel and H,R Crane, Rev. Sct, Instr. 28, 684 (1957),diffusion and mobility 69 3 e ke tveur-scesemty 2 a = | oy an a PERCENT Og OBA od ST a 00 Fig. 3,31. Reciprocal mobilities reduced to 760 mm Hg and 0°C of 0” in O2 and the noble gases. E.W.McDaniel and H.R. Crane, Rev. Sci. Instr. 28, 684 (1957). Under some conditions, ions do not move singly but tend to form clusters. Small admixtures of polar molecules such as water va- por show this effect, illustrated in Fig, 3,32, It can be seen from this figure that the clustering effect becomes less marked as E/p |] 35 = 0. 008-0 43% #1,0: & . / | 5 8 13% M_0: ff g 3 é z 2g 20 Es (VOLTS/GN/MHg) Fig. 3.32. Mobility of Lit ions in argon in the presence of water vapor, to show effect of clustering. H. S. W. Massey and E.H.S.Burhop, Electronic and Ionic Impact Phenomena, 1952, p. 414. Clarendon Press, Oxford,70 diffusion and mobility 18 reduced, 0 that at the lumit of E/p = 0 the mobiltty of the elu: tered 10n 1s independent of the percentage of water vapor | This suggests that the chance of attaching the firat water molecule 1s quite low, but once one such molecule 18 attached the chance of attaching others 1s so much increased that the final cluster builds up very rapidly, Presumably, the first attachment can take place only ina three-body collision. Onee this occurs, the structure 18 50 complex that the excess energy acquired in attaching a second molecule 13 redistributed among the many internal degrees of free dom and may be dissipated gradually in the following collisions. ‘Thus at 15 observed [11] that the fraction of ions clustered for a given E/p mcreases with the pressure of the main gas. The rea- son for the observed increase in mobility of the clustered group vnth E/p 1s not clear, but must be due in some way to that in- creased mean energy of the rons which corresponds to a tempera- ture increase, Experimental Methods of Measuring Tonie Mobility One of the useful methods of measuring mobility of tone was worked out by Townsend [12] The apparatus 1s shown schemati= cally in Fag, 3.33. A magnetic field 1s applied to the apparatus FILAMENT Ce Fig. 3.33. Apparatus for measuring one mobility.diffusion and mobility 7 at right angles to the plane of the paper. The experimental pro- cedure is to change the value of the magnetic field, keeping the electric field E and the pressure in the apparatus constant. The magnetic field is first adjusted for a value of +B such that the cur- rent to the collector C4 as measured by the electrometer equals the sum of the current measured by the other two collecting elec- trodes, C,=C,+C 2. The value of the magnetic field is then re- versed and 2 value -B adjusted so that Cy = C,+C,. The center of the beam is then displaced the width of cy by the sum of the two fields. If the sur of the fields is denoted by B, the beam is de- flected a distance of 2/2 centimeters where a is the width of C2. If one assumes that the curvature of the bear is small, the angle of deflection of the beam is related to the fields and the drift velo- city of the ions as follows: wane - 2 = Bev ne 2a" Ee Thus, by measuring B and E and knowing the deflection, one may determine the mobility constant. Another method for measuring mobilities was introduced by Tyndall and Powell [13]. A schematic diagram of their apparatus is shown in Fig. 3.34. The grids A, B, C, and D are coupled to a high-frequency oscillator. The arrangement is such that either TO ELECTROMETER Fig, 3.34, Tyndall and Powell's apparatus for measuring ion mobilities.crs diffusron and mobility the oscillator frequency (they used 2 4 10" eps) or the distance between the sets of grids could be varied. By varying either af these, a series of maxima was obtained in the current measured by the electrometer. ‘These maxima represent the 1on¢ that reach the detector during the time of transit under the action of an elec tric field E, corresponding to one opening of the grids AB and the neat opening of AB and CD ‘The best experimental determinations of tons of a gas moving through the same gas under the action of an electric field are those. of Hornbeck [4], His apparatus is illustrated in Fig. 3.5. The experiment was arranged to cause the release of a 0 Isp sec pulse of photoelectrons {com the cathode of the tube and to observe the current transient that follows, Ionization and excitation of the gas, molecules occurred by electron umpact during the light pulse. Be- cause the electron drift velocity an the field 28 high compared wath the positive-ion draft velocity, an ioitial transient occurs which 1s attributable to the initial photoclectrons followed by a smaller cur- Fent lasting the order of 10 microseconds The slower component originates primarily from the motion of positive ons tn the fiel@ The experment provides a direct, time-of-flight method for meas uring the drift velocity of positive rons in a gas as a function of Efp up to very high E/p Results of these experiments are shown an Fig. 3.24 and Fags, 335 to 3.38 'A summary of farther measurements of ton mobility 1s given in Figs, 3.39 to 3.50 sagt i 1 [ te i | 7 5 | ! \ oe g. 4 see t fo on xe _ = ' I 0 ~ Lia ot 1 it O46 Go wows B00 #0050 1060 F600 ErptveATS eH Ha) Fig 3.35 Drift velocity of atemic rons in krypton and xeno7. RN. Varney, Phys. Rev. 88 362 (1952),diffusion and mobility ax af ] oot | Lo P im] was os LOGITY(GM/SEC) ve o7 aL Cot Baan 20 30 40 50 70 90 150 200 300 600 1000 E/p(VOLTS/CM/MM Hg) Fig. 3.36a. Drift velocity of ions in nitrogen. Low (E/p) Ng, high (E/p) Nb . R.N. Varney, Phys. Rev. 89, 708 (1953). “| 20 + NITROGEN 5 2 77°K $19 & }s00°K, a) z + 5 a50°K 97 - § | 5s —- 4 30. 40 50 60 7060 100 150 200 E/p (VOLTS/GM x MM Hg) Fig. 3, 36b. Drift velocities of ions in No at various temperatures, Ny ions at low E/p, nt ions at high E/p. F.R.Kovar, £.C. Beatty, and R.N. Varney, Phys. Rev. 107, 1490 (1957).4 diffusion and mobility 6110 10 os 06 os os { VELociTY (ewrsee) oe ! SWAT id 180 359 — Soo fy (VOLTS CMP 4M Hg) Fig, 3 37 Drift velocity of rons an oxygen, R.N.Vazney, Phys. Rev. 89, 708 (1953), 10 08 VELocITY (om/SEC) 06 80 89100 200 300 400 600 6001000 Erp (VOLTS/CM/MM 4g) Fig, 3.38 Drift velocity of 1ons an carbon monoxide, Low (E/p) and high (E/p) COt, antermed- sate (E/p) may be CO% R.N. Varney, Phys. Rev, 89, 708 (1953).diffusion and mobility 75 Hole? VOLT -SEC) ‘0 2. 4 6 @ i 2 @ 6 1 E/p(VOLTS/GM/MM Hg) Fig. 3.39, Mobility of He* and Het, in helium. M,A.Biondi and L.M.Chanin, Phys. Rev. 94,910 (1954). Bo(GM2/VOLT- SEG) E/p(VOLTS/CM/MM Hg) Fig. 3.40, Mobility of Net and Ned in neon, M.A. Biondi and L.M.Chanin, Phys. Rev. 94, 910 (1954). Bo(GM?/VOLT- SEC) E/p(VOLTS/CM/MM Hg) Fig. 3.41. Mobility of At and A$ in argon. M.A.Biondi and L.M.Chanin, Phys. F 94, 910 (1954).6 diffusion and mobility melouS/vour see) ° 5 if 3 3 Evp(VOLTS/0M174M HG) Fig 3 42 Mobthty of Krt and Kr} in krypton M A Biondi and L M Chanin, Phys Rev 94, 910 (1954) of § os a 3 [—— we z T oe woe cinevoutscuran nny Fig 343 Mobily of Xe and Xe} in xenon M A Biond: and L M Chamn Phys Rev 94 910 (1954) ee Wop rvien®y your sec) Eve enemy Fig 3 44 Mobilty of mercury tons an helium at 300° K LM Chanin and M A Baonds, Phys Rev 107, 1219 (1957)diffusion and mobility 77 am 4 aT a fo} S 3 n 2 | MOBILITY (CM®/VOLT - SEG) & —|— 4 | 0 2 4 6 8 10 12 4 16 8 20 Ep (VOLTS/CMxMM Hg) Fig. 3.45. Mobility of mercury ions in neon at 300° K. LL.M. Chanin and M.A.Biondi, Phys. Rev.107, 1219 (1957). JTTTTTT MOBILITY (CM°/ VOLT- SEC) ol ——_ J) 0 20 30 40 50 60 70 Efp(VOLTS/CM NM Hg} Fig. 3.46. Mobility of mercury ions in argon at 300° K. LL. M.Chanin and M.A. Biondi, Phys. Rev. 107, 1219 (1957). 40 - 30 } = oh OM*/voLT-SEC) so 3 ag 25 ep wouseunning) Fig. 3.47. Mobility of 0°, 05 ,03 im oxygen. D.S. Burch and R. Geballe, Phys. Rev. 106, 183 (1957).18 diffusion and mobility 1609] HvoROGeN 888 MopUTY (cMt/VOLr SEC) aq] 24 2 ‘64 KeeTON ‘2 EHOW ro) p 7 ess os BS Uns OF 1ON Fig 3 48 Mobuhty of alkali rons in Hy, Kr, and Xe at 1 atmosphere pressure C F Powell and L Brada, Proc, Roy Sec _{London) A138, 117 (1932) P 4 a —— gs \ z ren 3 ‘aan o 100 780 200 Mass OF 18 Fig. 3.49 Mobility as a function of son mass in He, Ne, and A L.M.Chanin and M A Biondi, Phys.Rev 107 1219 (1957)diffusion and mobility 79 25 Notne | ————| 2 3 A il cetne | MOBILITY AT NORMAL DENSITY (CM/SEC/VOLT/CM) i) 160 B00 300400 500) 600 TEMPERATURE (°K) Fig. 3.50. Variation of mobility of ions with temperature. A.M. Tyndall and A.F,Pearce, Proc. Roy. Soc. (London) A149, 426 (1935). A.F.Pearce, Proc. Roy. Soc. (London) A155, 490 (1936). 4. Average Energy of Electrons The ratio of the diffusion coefficient to the mobility is an im- portant quantity because it is a measure of the average particle energy. We have seen that the diffusion coefficient D = v“/3v_, and the mobility coefficient p= e/mv,,. The ratio of these two gives us = 2 (gm) - 2a, (3.19) The quantity u,y, is the average energy of electrons, and the numerical constant depends on how the averaging is carried out. The value of 2/3 is correct for a Maxwellian distribution of velocities, If we write the particle flow equation for the electrons discussed in the section on diffusion, with the added mobility flow due to an80 diffusion and mobility applied electric fheld, we obtain Fe ->D th-nsE (3 20) For assumptions that the electric field 1s applied an the 2 direce tuon and that a steady-state condition prevails, an/at = 0, the con thausty equation grves an vo-- Bek an Townsend [14] designed an experiment to determne p/D for which he was able to solve this differentyal equation for the geo metrical conditions of his apparatus He used the same apparatus as he had for measuring the tonic mobility shown an Fig 3.33 In the absence of any magnetic field, the beam collected at CCC nll be spread out by the diffusion of the electrons while they are moving under the action of the electric field E This beam diffs sion may be correlated with the experimental observations by solving the differential equation in terms of wE/D and R, where R= Co/{C, + C, + C,) and the C's correspond to the currents draun by these plates Showa in Fig 333 The solution is shown graphi- cally [15] 1n Fig 3 Stasaplotof Rvs Z, where Z~ pE/40 3D, the numerical factor being introduced s0 that the abscissa may ‘xepresent the quantities an the usual units Thus, knowing the value of the applied electric field E and the gas pressure p, the average energy 18 determined as a function of E/p The results of this type of measurements are shown in Figs 3 52 to 3 58 LT} Fig. 351 Solution to Eq (3 21)diffusion and mobility 81 180) Om Oe os to Emp (VOLTS/CM MM Hg) Fig. 3.52. Ratio of electron to gas temperature in A and Ne. R.H.Healey and J. W. Reed, The Behavior of Slow Electrons in Gases, Amalgamated Wireless, Ltd., Sydney (1941), p. 78. oo 2 po > ENERGY{ELECTRON VOLTS) A t 10 20 30~~«40~=C« 70 Esp (WOLTS/CMM High 8 Fig. 3.53, Average electron energy in hydrogen. L.J.Varnerin, Jr., and S$.C.Brown, Phys.Rev. 79, 946 (1950). J.S, Townsend and V.A.Bailey, Phil. Mag. 42, 873 (1921).62 diffusion and mobality 69, B 49] 20! eT 4 OS ee vp (VOLTS soMbnn Hg) Fig 3 54 Ratio of electron to gas temperatures an deatersum and hydrogen BIH Hall, AustralanJ Phys 8 468 (1955) ter cy é e888 crevasse) Fig. 3 55 Ratio of electron to gas temperature 2n Brp, Clzs and ROH Healey and J W Reed, The Behavior of Slow Electrons 1 Gases, Amalgamated Wireless, Ltd Sydney (941), p 52Te/Tq diffusion and mobility 83 70 rT T TT) et — +H a AZ TT 60 Ne | | 55 | +t | | 50 cH | 74 45 Pt | | || “8 NITROGEN | r 30 OXYGEN: tT i 25 AIR } jt 20 15) 10 —j | [ 4 ; Li | o1 02 03 0405 07 10 20 304050 70 10 20 30 4050 70 100 E/p {VOLTS/CM/MM Hg) Fig. 3.56. Ratio of electron to gas temperature. Air: No: Op: R.W.Crompton, L.G.H.Huxley, and D.J.Sutton, Proc. Roy. Soc. {London} A218, 507 (1953). R.W. Crompton and D.J.Sutton, Proc. Roy. Soc. (London) A215, 467 (1952). R.H. Healey and J. W. Reed, The Behavior of Slow Electrons in Gases, Amalgamated Wireless, Ltd., Sydney (1941) p. 79.diffusion and mobility a4 15 7 3 0 cotvxzerourwuns) Fig. 3.57. Ratio of electron to gas temperature in CO2, NO, N,0, and CO. RH Healey and J W Reed, The Behavior of Slow Elec- trons in Gages, Amalganiated Wireless, Lid , Sydney (1941) p. 80 ropa 5 7 fe ie | 5 srnwreenooang Fig. 3.58, Ratio of electron to gas temperature in NH3, CH, gs HzO, and HCL R,H, Healey and J. W. Reed, The Behavzos_of Slow Elec- Amalgamated Wireless, Lid. ,Syaney trons an Gi (1941) p. Bt.diffusion and mobility 85 Another method of determining the average electron energy is by measuring a microwave gas discharge breakdown modified by an applied d-c field [16]. A gas will break down when the losses of electrons to the walls of a container are replaced by ionization in the body of the gas. When an a-c field alone is applied, elec- trons are lost by diffusion, When a small d-c sweeping field is applied, electrons are lost both by diffusion and mobility, thus changing the breakdown condition. In this case the flow of elec- trons is given by re ~D Vn - npE yg, - (3. 22) When the electrons lost are replaced by new ones resulting from ionization, vi Fe yn. (3. 23) If the applied d-c field is too small to affect appreciably the fre- quency of ionization vy, , and E. is directed along the z axis, the density at breakdown is the solution of v, = -# an _ i vn D Enc oz Dt: (3. 24) This equation may be solved for the case of a cylinder of axial height L and axial co-ordinate z, and radius R and radial co-ordinate r, by separation of variables to yield 2.4r, st zp DC n= constant J, ( R ) [ sin z z] exp ( D2 z). (3,25) This solution is subject to the breakdown conditions: i 1 a= —y (3. 26) D Ape where Ape defines a modified diffusion length E 1 1 we DC \2 eop +t (kh Se)’, 3.27 Ape Az (3) ( ) and /\ is the characteristic diffusion length previously defined for cylindrical geometry. The only difference between the break- down condition in the a-c - d-c case and the pure a-c case is the substitution of a modified diffusion length Age for the character- istic diffusion length A. 2 22 In the pure a-c case we may write v,/(DE,c y= MlEacG A”, and one finds this to be a function of ‘ac/P: With the a-c field alone, this curve is obtained experimentally, The d-c field86 @iffusion and mobility imereases the tate of loss of electrons, and hence, the cavity will appear to have a lasge value of 1/.\ whon the dee fneld 1 present, as shown by Eq 3.27, Since the (1/EA)* vs. E/p curve 1s inde- pendent of A, the new diffusion length 1/Apq may be determined by finding the E/p value at which breakdown occurs with the d-e field present, Thus, having found 1/A, — experimentally and Knowing the geometrical 1/A , we can edlculate D/p from Eq 3.27. ‘The experimental determinations of the average electron energy ug), by Tounsend and Bailey by the Townsend method, and by Varnesin and Brown by the microwave method, are given an Fig. 3.53 ‘An indirect determination of the electron energy mn helum has been made [17] by making use of the energy distribution function theory, The energy distribution function is derived, checked for example by its abihty to predict gas discharge breakdown correctly, and then used to determine the average energy of the electrons The results of such a process are shown in Fig. 3.59. aa vevosacuny —— Fig. 3.59, Average energy of electrons in helium. F.H.Reder andS.C. Brown, Phys Rey 95, 885 (1954) Ambipolay Diffusion So far m our chscussion of diffusion, we have assumed that the tons have diffused freely with no interaction between 1078 of dif~ ferent sign. When the density 18 high, this 18 not the case If we consider the case of an arbitrary denssty distribution 1m space at t= 0, we could represent this as in Fag. 3,600 At some Tater tine the distribution would change and one maght expect that since the electrons diffusing freely move faster than the positive ions, the distribution allustrated in Fig. 3. 60% might re- fult, However, af this occure, an electric fielé te set up which Would retard the electrons and enhance the positive-1on motion Thus on fact 18 found to be the case The flow of both the positivediffusion and mobility 87 (a) (b) Fig. 3.60. Charged particle distribution leading to a space charge field. ions and the electrons is equal; that is, Te r . If we consider first the case of the positive particles, x D, =. ¥. eT TP, Vey teem = My where E, is the space charge field. In terms of the velocity, ot Stu e “4° 7 hy BLY Bye By writing a similar equation for negative particles, D v 2 ¥ E vier m= BL . i we eliminate E, between these equations and set ny=n =n, Vn, =Va_ = Vn and v_*= v4 = v, we obtain the result Dp tDe, ¢ —. 3. ate (3. 28) vz -{ The quantity in the parentheses is a diffusion coefficient for the two signs of particles interacting on each other so that they both diffuse together. This quantity is called the ambipolar-diffusion coefficient and is thus defined as Dp, t+D pe poet. (3.29) a H, + BL88 diffusion and mobility ‘The ambipolar-diffusion equation 16 an Bs owe. Ie we again assume an exponential decay of the electron density, we find the same characteristic value solution as we did in the case of free diffusion, From this solution we have D, = A‘/t, which shows that D, may be determined by measurig’the rate of decay of the chazge density 1n a container of known dimensions, The only experimental determinations of D, which have s0 faz been made have used an ultra-high-frequency*techmique for deter- maning the electron concentration 1 a resonant cavity [18]. The presence of free electrons 2 a resonant cavity has the effect of shifting the resonant frequency. Even when the electrons make collisions wath gas atoms, as long as the pressure 18 not 00 high, the amaginary component of the electron conductivity © 3a auf- ficient to give a measurable relation between the cavity trequency staft and the electron density. Mathematically tha may be ex- pressed ag (3.30) where X16 the wavelength of the applied field and ¢ 1s the velo- city of hght The change in the resonant wavelength AX may be expressed as an = Ka, ean where K 1s the geometrical coefficient that takes account of the distribution of electron density and field configuration sn the reso- nant cavity and W 1s the average electron density within the cavity Details of the experimental procedure are outlined in the paper by Bondi and Brown [6] ‘The usual procedure in recognszing a diffusion loss mechanism as to plot the electron density as a function of time on a semiloga- “ritame tae, with toe tate Sah Ua Vengo, storage exponential decay of density, diffusion 28 assumed to be the con- trolling phenomenon. A decay curve of thie sort 1s illustrated in Fig. 3 61, ‘The slope of such a decay curve gives an experimental value for the diffusion coefficient Since the microwave method as not suffierently sensitive to measure electron dennities below that characterized by ambipolar diffasion, all such measurements savolve D,. If higher modes of the diffusion decay are present, the result- ang data will fall on a curve that 15 the sum of exponentials, Hence, the fact that electron loss does not follow a simple exponential law does not rule out diffusion as a loss mechanism. This 19 stustrated an Fig. 3.62, Here an asymmetric discharge 18 produced in adiffusion and mobility 89 HELIUM B3ss ry 8 PRESSURE «80mm 0 TH 4.28m sec & Dap = 586 ©" Zee —mm Hg g § ELECTRON DENSITY (x107%) /ee in wis ‘TIME (rn sec} Fig. 3. 61, Experimental observation of electron density decay in a microwave resonant cavity. LIGHT DISTRIBUTION nf? ELEGTRONS/CM UGHT DISTRIBUTION 2 ra 1 a L Lo 1 05 i 1S 2 25 1x 2 OP xEEe SEG/mm Hg xem Fig. 3.62. Experimental observations of high-mode diffusion. resonant cavity. Changing the coupling of the input power of the pulsed discharge, brings into prominence the effect of the higher modes, and speeds up the initial decay of electron density. When only the fundamental mode of diffusion remains, the characteristic diffusion coefficient for this fundamental mode is the only one left, and the curves are parallel.90 diffusion and mobility When the electrons and 10ns are an thermal equihbrium wath the gas at a given temperature, the following relation can be written: 2 De v/3¥. * w/3py PL Dipg = constant. (3.32) This relation 1s found to be experumentally verified, as illustrated in Fig. 3.63 from Biond: and Brown's [6] paper, They further e 1 300% a Asean 4 3 I RCSF (om Ho) Fig. 3 63 Variation with pressure of the ambipolar- diffusion coefficient for hehum. checked to see that the diffusion length /\ was the proper varzable by takang measurements wath contamers of different sizes and shapes and measuring the mean decay time of the discharge, The results affirm the diffusion length as the correct variable, :Mlus~ trated by Fig, 3.64. g 8 8 000(88 -nmta) pA (mmigrend Fig. 3,64 Effect of the variation of the diffusion con- tamer sie and shape upon the measured values of D.diffusion and mobility 91 If thermal equilibrium is present, D D 22s: iw, By BL 3° ave and since B, << > > Dip, + Dip _ 2D pb = op (3.33) a BB Bt BR +7 . If we assume that the ionic mobility is constant, the collision frequency is independent of velocity. Therefore, the collision cross section for positive ions in helium varies with the recipro- cal of the positive-ion velocity, which agrees with the experimen- tal measurements of Ramsauer and Beeck [I 9]. We know that Di= vi /3p9Py and P= l/v,. Under the condition that p is held constant during the experiment, the gas density varies in- versely with the oe temperature. Since Py = pl273/T), it fol- lows that D, This was experimentally demonstrated by Biondi and Brown [6] as shown in Fig. 3.65. p +85 mmig A =0.56 cm Te x10 (°K Fig. 3.65. Variation of the ambipolar-diffusion coefficient with energy. 6. Transition Diffusion Having shown the effects of free-electron diffusion and ambipolar diffusion, it is worth while to discuss briefly the transition between these two cases. If we produce a discharge that is controlled by ambipolar diffusion in its fundamental mode in plane-parallel] plate geometry, we expect a cosinusoidal electron spatial distribution. In the low-power steady-state microwave discharges, however,” diffusion and mobility 2 1+ a? eg leg, abe a? — os (45) z 14a agg. Thus we can sce that the effect of space charge 1s to increase the effective size of the volume occupied by the plasma. The variation of the diffusion coefficxent will change the cosinu- soidal spatial distribution that would obtain sf the diffusion coeffi- crent Were constant The situation can best be deseribed with reference to Fig 3 67 X — meas Trans 7 * noncose cxnren oF wa, esonnse Fig 3 67 Exfect of the variation of diffusion coefficrent ‘The rate of production of 1onization stays approximately constant across the discharge, and thus the total current to the walls re- mains essentially unchanged However, as we move from the den- ter of a discharge whose effective diffusion coefficient 1s increas ang with radius, more current will flow because of the higher dif- fusion coefficient than for the case of pure ambipolar &fiamon Since the effective diffusion coefficient increases all the way to the walls, and since the current reaching the walls 18 limited, Va. has to decrease below the ambipolar value near the walls If the gradient of n decreases, the spatial distribution of the density departs from a cosinusoidal distribution for ambipolar diffue.ca, to a bell-shaped distribution for a transition case Aths and Rose [20] have carried out a theoretical study of the transition from free to ambipolar diffusion The current equations determining the process were examined, and approxunate solutions were obtained by means of 2 large electronic computing machine These theoretical calculations can be compared directly withdiffusion and mobility 95 experiment. A microwave discharge having been set up in a reso- nant cavity, probe measurements were taken of the electron density as a function of position. The agreement between theory and experi- ment is evident in Fig. 3.68. ——— ALLIS & ROSE MACHINE SOLUTION xxx EXPERIMENTAL BY PROBES ° ° ° a a @ NORMALIZED DENSITY n/ng ° 0 0 a2 of 06 08 10 NORMALIZED DISTANCE x/x Fig. 3.68. Comparison of theory and experimental measurements of electron density as a function of position. 7. Ambipolar Diffusion with Variable Ion Mobility The ambipolar-diffusion coefficient was derived on the assump~ tion that the positive-ion mobility is a constant independent of energy. In certain ranges of energy this is not a valid assump- tion, as discussed on p. 65. Frost [21] has calculated this effect. Starting with the relation Di+D, Vn Be aa) (3. 46) - + and assuming 1_?> Hy and D_ >> DL Ya 2 we (3.47) Es -(3) y * Save on We rewrite Eq. 3.20 for positive ions in the form P= - (ju, .+D,) Va (3. 48) re Vn= pb, En . (3. 49) - BU #yMave Using the continuity equation for a going discharge,96 diffusion and mobility an Bevrevn where v, 18 the frequency of tomzation This leads to the diffu tion length (D,//\2) - v,, which we may partrcularize for a long cylindrical discharge as A= R/2 405 Frost solved the flow equation for a long cylindrical tube for the variation of an effective ambipolar diffusion coefficient D,,, using the variation of mobility given in Eq 317 His resulte are shown an Figs 3 69and3 70 InFig 3 69 19 plotted the ratio of D,,/D, 20 to — RS i o8| 50 & 4 ™ ° ‘oor 008 01 02 05 10 20 80 20, /pR Fig 3.69 Effective ambipolar diffusion coefficient for a long cylindrical tube aaa 2 NM 320406 98 to HR Fig 370 Variation of charged particle dennty for a long cylindrical tubediffusion and mobility 97 where D,, is the coefficient given by Eq. 3,29 as a function of au, /pR (a is given in Table 3.1). Figure 3,70 shows the varia- tion of density with radius for a constant and variable Be GENERAL REFERENCE E. H. Kennard, Kinetic Theory of Gases, McGraw-Hill Book Co., New York, 184 ff. (1938). REFERENCES R. A. Nielsen, Phys. Rev. 50, 950 (1936). N. E. Bradbury and R. A. Nielsen, Phys. Rev. 49, 388 (1936). D. Barbiere, Phys. Rev. 84, 653 (1951). P. M. Davidson, Proc. Phys. Soc. (London) B67, 159, 279 (1954), W. J. Graham and A. J. Ruhlig, Phys. Rev. 94, 25 (1954). J. M. Kirshner and D. S. Toffolo, J. Appl. Phys. 23, 594 (1952), L. Colli and V. Facchini, Rev. Sci. Instr. 23,39 (1952). J. A. Hornbeck, Phys. Rev. 83, 374 (1951). P, Langevin, Ann. chim. et phys. 5, 245 (1905). A. M. Tyndall and G. F. Powell, Proc. Roy. Soc. (London) Al34, 125 (1931). A. M. Tyndall and C, F. Powell, Proc. Roy. Soc. (London) A129, 162 (1930). H. S. W. Massey and C. B. O. Mohr, Proc. Roy. Soc. (London) Al44, 188 (1934). A. F. Pearce, Proc. Roy. Soc. (London) A155, 490 (1936). K. Hoselitz, Proc, Roy. Soc. (London) A177, 200 (1941). M. A. Biondi andS. C. Brown, Phys. Rev. 75, 1700 (1949). A. V. Phelps and S. C. Brown, Phys. Rev. 86, 102 (1952). J. A. Hornbeck, Phys. Rev. 84, 615 (1951). H. R. Hassé, Phil, Mag. 1, 39 (1926). J. A, Hornbeck and G. H. Wannier, Phys. Rev. 82, 458 (1951). L. S. Frost, Phys. Rey, 105, 354 (1957). H. G. David and R. J. Munson, Proc. Roy. Soc. (London) Al77, 192 (1941).8 a 42 13 14 15 16 v 18 19 20 21 diffusion and mobility R J Munson and A M Tyndall, Proc Roy Soc_(London! ALT2, 28 (1939) JS Townsend andH T Tizard, Proc Roy Soc (London) ABB, 336 (1913) TT A M Tyndalland © F Powell, Proc Rey Soc (London) A136, 145 (1932) JS Townsend, Electricity in Gase: Oxford (1915), p_ 166 Clarendon Pre: JS Townsend and ¥ A Bailey, Phul Mag 42, 873 (1921) LJ Varnerin, Jr , andS C Brown, Phys Rey 79, 946 (1950 I A Srait Physrea 3, 543 (1936) F H RederandS CG Brown Phys Rev 95 885 (1954) S C BrownandD J Rose 3 Appl Phys 23 711, 719%, 1028 (1952) © Ramsauer andO Beeck, Ann Physik 87 1 (1928) WP AlbsandD J Rose, Phys Rev _93 84 (1954) LS Frost, Phys Rev 105, 354 (1957)Chapter 4 INELASTIC COLLISIONS OF ELECTRONS §as of pressu light falls on one electrod density Jo re Pp as shown in Fig, 4,1, Ultraviolet e, liberating photoelectrons of current amperes per square centimeter. Let us determine the TO ELECTROMETER QUARTZ WINDOW ACCELERATING POTENTIAL Fig. 4.1, Diagram of chamber showing plane- parallel zinc electrodes, ‘urrent passing between the electrodes as a function of the uni- orm field E applied between the electrodes and the gas pres- ure. We assume that the photoelectric yield is unaffected by he gas, The electrons are emitted with an average velocity of emission » but in a short distance they are moving with a constant velo- ity v= pE. The electric field is assumed to be unaffected by 1e few electrons present in the tube, Near electrode A there ill bea diffusion of electrons back to the electrode resulting ‘om the retarding effect of the gas impacts and the high random elocity of the electrons, Most of the electrons that diffuse back- ards will be captured by electrode A and will therefore be lost the current, Near the cathode, the random electron speed is ¥,, and one ‘n compute from kinetic theory that the current produced by ectrons per square centimeter per second due to diffusion is 99100 inelastic collisions of electrons %o where 3, 28 the current of electrons per square centumeter per second which return to the source electrode by diffusion in spite of the presence of the electric freld ‘The number of electrons per cc which are uniformly distributed am the gas is n, and the current density received at the top elec- trode 15 J = newE. ‘The total current density recerved at the top electrode becomes 4B 2 0 REE wT (4.1) ‘The quantity jo 15 the vacuum photoelectric current density Hence, the evaluation of 3 and the comparison of J/3p with ex- perimental results depend eritically on the value of the amtial electron energy assumed. If the drift velocity 1 much larger than the random speed, that is, af ¥, << uF, we can see that alg = 1 and we have a “saturation current. We mentioned on page él, that pp ~ (E/p)7}/2 approximately, and soa curve of J/Jq as a function of voltage between the electrodes should mitially. vise roughly as NE/p , gradually approaching a saturation value an WE becomes much larger than ¥, . Curves of this sort [1] are ahown an Fig, 4.2. The value of ¥, 26 for electrons near the HYDROGEN one! os ots oe Eze vourscisx mung) Fig. 4.2. Current-ratio curves plotted against E/p for hydrogen for the two photoelectric energy die- tributions in hydrogeninelastic collisions of electrons 101 cathode, where the electron velocity corresponds to the velocity of electron emission from the electrode and not upon their velo- city of thermal agitation. For cases in which the velocity of electron emission v. can be determined from the energy of the incident ultraviolet light and the work function of the surface, Eq. 4.1 can be used to de- termine the mobility from measurements of the current and voltage. 2. Probability of Excitation The probability of inelastic collision is defined as the number of atoms that are excited or ionized per electron per centimeter path length at a pressure of 1mm and at 0°C. The probability of excitation, given the symbol Pye can be meas- ured by the classical Frank and Hertz experiment. Electrons are accelerated through a uniform field to a grid with a plate directly behind the grid. A retarding potential applied between the grid and the plate enables one to measure the number of electrons that have made inelastic collisions. By varying the accelerating poten- tial, the dependence of the number of inelastic collisions on velo- city may be estimated. Although the usual form of tube used ina standard Frank and Hertz experiment is not well suited for accu- rate determinations of excitation probabilities in most gases, Maier-Leibnitz [2] used a similar type of apparatus to measure inelastic-collision probabilities. Maier-Leibnitz's apparatus is shown in Fig. 4.3. Electrons were emitted from a hot tungsten filament K, passed through slit S into a field free space between A and B, which contained the gas to be studied. Most of the outer cylinder B was a wire Fig. 4,3. Maier-Leibnitz's apparatus for measuring probabilities of excitation. gauze surrounded by the collecting cylinder C. A retarding po- tential, U, between B and C, alloweda determination to be made of the energy distribution of the electrons reaching B. The current collected by C was measured as a function of the accelerat- ing potential V between K and A. The ratio of U to V was kept constant so that, apart from the effect of electrons reflected from C, the collected current remained constant, independentloz imelastre collisions of electrons of V unfess an inelastic collision occurred. When V became great enough to excite one of the levels of the gas, the number of electrons reaching C showeda sharp drop From a study of this decrease in current, Marer-Leibnitz determaned the absolute yreld for the corresponding excitation, A summary of these meas- urements 1s given in Fig. 4.4, E s ° = o----- SONGS 2 a i ne g i ° 8 ° "PROBABILITY" OF INELASTIG COLLISION e i @ 6 ww 20 2 24 26 2 yours Fig. 4.4 Probability of excitation and ionization an He, Hy, Ne, and A 'M.J. Druyvesteyn and F M Penning, Reve Mod. Phys 12, 87 (1940) The probability of excitation measured spectroscopically does not usually give the necessary gas-discharge information When P,, 15 measured optically by determsning the intensity of spectral lines, one usually observes only the P,, of a few levels and not the total P,, since many transitions emat radiation that 1s strong~ ly absorbed in the gas. Although some measurements of excita- thon probability are in sharp disagreement with the majority of determinations, the experiments indicate in general that P, r18¢5 to a maximum at or very near the eritical potential and then de- Greases with mereasing energy Some observers have published results indicating further maxima at higher energy, but theinelastic collisions of electrons 103 existence of these further maxima is in doubt. Indirect determin- ations of the probability of excitation have been made in the course of theoretical calculations of ionization coefficients and breakdown [3]. Such determinations are both complicated and roundabout, but in the absence of direct measurements appear to give satisfactory answers, 3. Probability of Ionization The probability of ionization P; has attracted the attention of many Workers, although many of the earlier measurements can be considered to be of qualitative value only. Maier-Leibnitz used his apparatus of Fig. 4.3 to measure P., and his results are shown in Fig. 4.4. The best of the earlier work was done on mer- cury by Nottingham [4], who used an apparatus schematically indi- cated in Fig, 4.5. Electrons emitted from the filament F were Fig. 4.5. Nottingham's apparatus for measuring probabilities of ionization. accelerated through the slit S, into the velocity analyzer A. Be- tween the slits S, and S, the electrons were accelerated and passed through the ionization chamber I, which contained the gas to be studied, The electrons were collected in E, The ion col- lector was a wire § ata negative potential surrounded by grids G, and G2, which shielded the space through which the electron beam passed from the effects of the ion-collector field. The ion- ization current measured resulted from the ions which drifted through the outer grid 6). The results of Nottingham's measure- ments are shown in Fig. 4.6. Hagstrum [5] has used a method combining the measurement of kinetic energy by retardation following mass analysis in a spectro- meter to determine ionization probabilities. His apparatus is shown schematically in Fig. 4.7. Electrons emitted from the fila- ment A are accelerated to the desired energy through slits in elec- trodes B and C into the ionization chamber bounded by electrodes106 inelastic colliaions of electrons ELECTRON BEAM RETARDATION ‘CHAMBER MAGNETIC ANALYZER TO PUMP. Fig 4.7. Schematic view of Hagetrum!e mass spectrometer.inelastic collisions of electrons 107 Results of Hagstrum's measurements are given in Fig. 4,8. A method for measuring ionization probabilities that eliminates the difficulties arising from uncertainties in the energy of the bom- barding electrons has recently been devised [6]. A sketch of the ion source is shown in Fig. 4.9. Electrons leaving the filament zg no* O35 2 2 > Lost & 5 a = = e 2 a c = 5 3 & | 8 9 0 " 12 13 4 ELEGTRON ENERGY (VOLTS) Fig. 4.8, Probability of ionization for electrons in NO and o>. H.D.Hagstrum, Revs. Mod, Phys, 23, 185 (1951). Fig. 4.9. Fox's method of measuring probabilities of ionization.110 anelastic collisions of electrons 1200 7 c aro " r 10 / < 3 : es a d =A ae te [ELECTRON ENERGY ELECTRON VOLTS) Fig. 4,12 Ionization cross section for argon R E,Fox, Research Report 60-94439-4-R2, Weating- house Electric Corporation, Aug 15, (1956) 36 | i 2s] von cuRnent a apnea Fig, 4.12b Probabulsty of tonization in argon. R.E Fox, W M.Hickam, T.Kyeldaas, and D J Grove, Phys. Rev. 84, 859 (2951)inelastic collisions of electrons ill ELECTRON ENERGY (VOLTS) Fig. 4.12c. Probability of ionization in argon. W.Bleakney, Phys. Rev. 36, 1303 (1930). 14.10 14.20 1430 1440 ELECTRON ENERGY (VOLTS) 14.00 Fig. 4.13a. Relative ionization probability for ioniza- tion to the 1/2 state in krypton. R.E. Fox, W.M.Hickam, and T.Kjeldaas, Phys. Rev. 89, 555 (1953).uz inelastic collisions of electrons ware TON ow cuRRENT a 0 HS GO 6S 60 65 ELECTRON ENERCY (WERTS) Fig, 4,13b. Relative ionization probabihty for 1omza~ tron to the “P47, state in krypton. RE, Fox, W M.Hickam, and T Kyeldaas, Phys. Rev, 89, 555 (1953). 169; 190] xeKon iy g 8 SR a Lo ye us 20 @5 BO 185 Oo 48 ELECTRON ENERGY (VOLTS) Fig, 4.14 Relative tonization probability for omza- tion by electron impact m xenon R.E. Fox, W.M.Hickam, and T. Kyeldaa: Rev. 89, 555 (1953). Phys.inelastic collisions of electrons 113 5 * 3 zn 2p, € : | 3 g 'p, = ‘ E 54 1 2 = 5 | | = | | 5 3 32 ! 2 30 94 96 102 16 NO 4 ue 22 126 BO 134 ELECTRON ACCELERATING VOLTAGE Fig. 4.15. Probability of ionization in zinc. W.M.Hickam, Scientific Report 1819, Westinghouse Research Laboratory, March 31, 1954. ION GURRENT (ARBITRARY UNITS) 85 90 95 100 105 HO 5 120 125 130 135 140 ELECTRON ACCELERATING VOLTAGE Fig. 4.16, Probability of ionization in cadmium. W.M.Hickam, Scientific Report 1819, Westinghouse Research Laboratory, March 31, 1954.2 a c | 4 hae] | L-4 tL | pe rd at ol a 705 5 00 To ELEGTRON ENERGY (VOLTS) Fig. 4, 1%.Probabrlty of ronization in mercury. W,Bleakney, Phys. Rev. 35, 139 (1930), T T T | 7d 10M GRRENT (ARERR UTED eae ee oases ne Lathe ACEELERETING OLTASE Fig. 4.17 Probability of 1omzation in mercury W.M, Hickam, Scientific Report 1819, Westinghouse Research Laboratory, March 31, 1954,inelastic collisions of electrons 115 ob CROSS SECTION (UNITS OF ok) ° a 100 200 ‘300 400) 500 ELECTRON ENERGY (EV) Fig. 4.18. Ionization cross sections of hydrogen on electron impact. 25x10" + No 20 a’ sf -187! 15 4 _ f © = & cf 10 | A? = 16 94} if 5 i P x? 52215 58 0 5 6 7 8 19 20 2) 22 23 24 ELECTRON ENERGY(ELECTRON VOLTS) Fig. 4.19. Ionization cross section for nitrogen. R.E. Fox, Research Report 60-94439-4-R2, Westing- house Electric Corporation, Aug. 15, 1956.116 anelastic collisions of electrons sox10% cot ertuser/ 2» Z : J 7 fea 3. 1653 s 39) Lo fs* shiaor i a a a ELECTRON ENERGY {ELECTRON VOLTS) Fig. 4,20 Yonization cross section for carbon monoxide, RE. Fox, Research Report 60-94439-4-R2, Westing- house Bleetrie Corporation, Aug 15, 1956 8; (CoH co NO te SQN | Uy % 0-300: «450 600 750 ENERGY OF ELECTRONS (VOLTS) Fig. 4.20 Probability of tonization in Ny, 2, CO, NO, and CoH2. J.T.Tate, P,T Smith, Phys.Rev. 39, 270 (1932)~ vvassoions of electrons ON CURRENT (ARBITRARY UNITS) ELECTRON ENERGY (VOLTS) Fig. 4.22. Probability of ionization in acetylene. J.T. Tate, P.T.Smith, and A.L, Vaughan, Phys. Rev. 48, 525 (1935). NOT KIO ION CURRENT (ARBITRARY UNITS) Ne 1 o 100 200 ‘300 400 500 ELECTRON ENERGY (VOLTS) Fig. 4,23. Probability of ionization in nitric oxide, NO. J.T. Tate, P.T.Smith, and A.L. Vaughan, Phys. Rev. 48, 525 (1935).1 ON CURRENT (ARBITRARY UNITS) l B ION CURRENT (ARBITRARY UNITS) anelastic collisions of electrons [ane — li | cN* oe aH 5 ae Tato ELECTRON ENERGY (VOLTS) Fig. 4.24 Probability of 1ontzation in cyanogen, CN). J.T Tate, PT Smith, and A L Vaughan, Phys Rev, 48, 525 (1935), 4 2 q a ue 120 BO 140 50 160 170 180 130 ELECTRON ENERGY(VOLTS) Fig. 4.25 Probability of omzation an water WG Price and T M Sugden, Trans. Faraday Soc_44, 108 (1948)inelastic collisions of electrons 119 T Th 4, w TON CURRENT (ARBITRARY UNITS) — —_— 0; 90 wo no 120 130 140 150 ELECTRON ENERGY {VOLTS} Fig. 4.26. Probability of ionization in hydrogen sulfide. W.C.Price and T.M.Sugden, Trans, Faraday Soc. 44, 108 (1948). 5 nee eed a a us nD ION CURRENT (ARBITRARY UNITS) %4 6 18 20 22 24 26 ELECTRON ENERGY (VOLTS) Fig. 4.27. Probability of ionization for cH from methane. C.A.McDowell and J. W. Warren, Discussions Faraday Soc. No. 10, 53 (1951).1zz inelastic collisions of electrons loo — TH TT 19) KRYPTON NITROGEN ARGON T TT T— ACETYy, ene ION GURRENT (ARBITRARY UNITS) oto 2 3 @ & 6 IT ELECTRON ENERGY (VOLTS) Fig. 4 31 Jomzation probability for ethylene, acetylene, water, methane, carbon dioxide, krypton, nitrogen, and argon, F P.Lossing, A W Tickner, and W A Bryce, J_ Chem Phys 19, 1254 (1951) 4, The Furst lonization Coefficient Ts carrying out an experiment wath the apparatus sIlustrated an Fig. 4.32, one finds that as the potential between anode and cathode 16 increased a saturation value 1s reached, correspond= ang to the case of collection of all the smtually produced photoelec- trons. As the electric field 18 increased still more, a point 1sinelastic collisions of electrons 123 Fig. 4.32. Diagram of apparatus for measuring the first ionization coefficients. reached where the current again increases. This rise is very rapid. The rapid rise corresponds to the production of ioniza- tion by collision of the initial photoelectrons with the gas atoms. The theory for this was first described by Townsend [7]. A very large amount of experimental work has been done on the study of the phenomenon of ionization by electron collision with gas atoms and molecules. The type of data one obtains [8] is shown in Fig. 4.33. The logarithm of the current when plotted as a function of the electrode plate separation is found to be a straight line for a given field strength and pressure, The physi- cal interpretation of the phenomena is as follows: If an electron creates a new electrons in a path 1 centimeter long in the field direction, the increase of electrons dn produced by n electrons ina distance dx will be dn = an dx (4.2) n= My exp (ax) where n, is the initial electron concentration. This corresponds to the observed current determination i = igexp (ax). The quan- tity a is called the first Townsend coefficient. Alpha itself is not a unique function of E/p, buta/pis. Data of a/p as a func- tion of E/p have been measured for many gases and useful sum- mary plots are given in Figs. 4, 34 to 4,47. The historical authority of Townsend has emphasized the im- portance of a perhaps beyond its physical usefulness. A ratherLea inelastic collisions of electrons ° r r Espa 365, 107] 4 0 ot 220 a mio 7 & 330 07 4 é 20 0 315 3 et Em 4 10" Saas 60 no" v 2 $ em Fog 433 Typical data for determining the st sonization coefficientinelastic collisions of electrons 125 10° a/p (1ON PAIRS/CMx MM Hg) 2 4 0 2 4 We 2 4 0 2 E/p (VOLTS/CM xMM Hg) Fig. 4. 34a. First Townsend ionization coefficients in noble gases. A.von Engel, Handbuch der Physik, Springer Verlag, Berlin (1956) Vol. 21, p. 504.126 inelastic collisions of electrons 29 x aa pL 2 20} : i ve Zi 3 I a zu 3 Ee 4 hn LN0 9 Bed BOS GH BOT HOT TAU TROT OT oo estVO1T8 06 awea) Fig, 4.346 First Townsend omzation coeffiexent an Xe, Kr, and A, ‘A. von Engel, Handbuch der Physik, Springer Verlag, Berhn (1958), Vol. 21, p. 504, I x 3. = i, L g " : oe we oe EvetvOLTs CM AAI Fig. 4, 34e. First Townsend sonization coefficient in argon Avon Engel, Handbuch der Phy Berlin (1956), Vol. 2: Soon Springer Veriag,inelastic collisions of electrons 127 or et eS = | T = | | = t = 2 4 9 ua © = | a oor T s t o cool | tf 20 40 60 80 100 120 Evp (VOLTS/GM/MM Hg) Fig. 4.35. Townsend's first ionization coefficients in nitrogen, M.A.Harrison, Phys. Rev. 105, 366 (1957). 02 oF 007] 005 7 003 4 02 — ool 0 007] a/ptlON PAIRS /CM/MM Hg) 0 005) ° oy 9002) 20 40 60 80 p/E (MM Hg/ VOLT/CM) x10> Fig. 4.36. First Townsend ionization coefficient for oxygen. D.S.Burch and R.Geballe, Technical Report 4, De- partment of Physics, University of Washington, Aug. 24, 1956.128 inelastic collisions of electrons fe Ne 2 Be g 2 Me z 4 & 5 800% 60 0B EyptvouTS/om sng) Fig, 4.37 First Townsend tonization coefficients of az, Nz and Hy A von Engel, Handbuch der Physik, Springer Verlag, Berlin (1956), Vol @l, p 504 Biota fete ag 3 oao 868, a6 wo 0os Ge —Cor Broweseene voor > Fig. 4.38 First Townsend tonization coefficients in Dy & Hy. ‘D.J.Rose (unpublished)sucaastic collisions of electrons 129 20 oO 500 1000 1500 E/p Fig. 4,39. First Townsend coefficient for mercury. E.Badareu and G.G, Bratescu, Bull, soc. roumaine phys. 45, 9 (1944). 32x10 28 24 z = =z 20 = g 2 6 € é = 12 ajo og! 8 to 12 4 16 18 20 22 E/p (VOLTS/GM/MM Hg) Fig. 4.40. First Townsend coefficient in CO). D.R. Young, Technical Report No. 22, Laboratory for Insulation Research, M.1.T., August 1949.130 inelastic collisions of electrons ne. i : g i 01 Tae ey ese pase eporeets cumin Fig. 4.41 First Townsend romzation coefficient for H20, C,H,0H. A.von Engel, Handbuch der Physik, Springer Verlag, Berlin (1956), Vol. 21, p 504. 5 ero umsrouuny hs i o a Fig. 4.42, First Townsend ionization coefficient 1n HCl and COz ‘A.von Engel, Handbuch der Physik, Springer Verlag, Berlin (1956), Vol. 2l, p. 504.inelastic collisions of electrons 131 toxto-? Se 8 S x= = = x = Oo S oO & ra 34 g a 2 3 2 J 7 | 10 m5 120 125 130 E/p(VOLTS/CM x MM Hg) Fig. 4.43, First Townsend ionization coefficients in SF. A.von Engel, Handbuch der Physik, Springer Verlag, Berlin (1956), Vol. 21, p. 504. 5— Se 2 z 2 2 CF sor = v g @ Cte Fe (* FREON 12) Z 05 Zz 2 £ . 4____ ° > 50 100 150, 200 250 E/p (VOLTS/CM xMM Hg) Fig. 4.44 First Townsend ionization coefficients in CC12F, and CF,CF,. A.von Engel, Handbuch der Physik, Springer Verlag, Berlin (1956), Vol. 21, p. 504,132 amelastic collisions of electrons Boo! | = L cots, z 2H z g 2 z 10?) & | GHGs ctl, ° GgHip ain! CHC! 3 "9 700 200 300 E70 (VOLTS /GMx MM Ha) Fig 4.45 Farst ionization coefficients mn air, CoH,Cl, CoH», CpHgBr, SF, CHC1y, and CCly A von Engel, Handbuch der Physik, Springer Verlag, ‘Beri (1956) Vor 2h p S08 *— «2/9008 Pas /oMsnneHe ‘O05 Va —Gu BOE 0 ore og VOM Fig. 4.46 Firet Townaend ionization coefficient for ethyl alcohol L Frommhold, Z_ Physik 144, 396 (1956).inelastic collisions of electrons 133 (ION PAIRS/GM/MM Hg) a P o 500 1000 1500, 2000 2500 3000 E/p(VOLTS/CM/MM Ha) Fig. 4.47, First Townsend coefficients for benzene, toluene, and cyclohexane. M.Valeriu-Petrescu, Bull. soc. roumaine phys. 44, 3 (1943). more significant coefficient is the ionization produced by an elec- tron falling through a potential difference of 1 volt (rather than traveling 1 centimeter). In this case the current may be written as i= i, exp[n(V - V,)] (4. 3) 0 0 where V, is a constant correction factor that is necessary be- cause the energy distribution becomes steady only after the elec- trons have traveled a certain distance from the cathode. The values for V, as a function of E/p for the noble gases are given in Fig. 4.48. The ionization coefficient 4 is related to a by nee (4.4) One of the advantages of the use of 4 is that itis a function of E/p itself. Experimental determinations of n asa function of E/p for a number of pure gases are shown in Figs. 4.49 to 4.51. The studies of Fig. 4.50 show the effect of mixing pure gases in special cases. For mixtures of neon and argon, very large changes in the values of 4 are observed. This results from the interaction of the metastable neon atoms and the normal argon. The neon metastable level lies at 16. 6 volts, while the argon ion- ization potential is 15.7 volts. A collision between these two re~- sults in the ionization of the argon and the return of the neon to its ground state, The increase in ionization due to this cause is obvious from the very large values of q at low E/p. This phenom- enon is called the "Penning Effect."134 imelastic collisions of electrons ty a i & 4 |__——“} Ke % vo 3 700 evowvotrsremssney Fig. 4 48 Vin s= 19 exp [hlV - VQ] M J.Druyvesteyn and F M Penning, Reva Mod Phys. 12, 87 (1940) ~ t 002} — = AG ASAN jon i= Att a y * coos! Ne! con Fite 0002) coool Hy +o fy. | PE Fig. 4.49 fom the EvetVOLTS/CM/¥ItAHo) izations per volt per mm Hg at 0° C for rare gases and air. ‘M.J,Druyvesteyn and F M Penning, Revs Mod 1 87 (2940)inelastic collisions of electrons 135 7 (ION PAIRS/ VOLT ) o Qo QO a re la ART YP ty7 te Pee eT 05 10 20 50 10 20 50 100 200 500 E/P(VOLTS/CM/MM Hg) Fig. 4.50. Ionizations per volt per mm Hg at 0°C for neon-argon mixtures, The numbers on each curve give the ratio of the argon pressure to the total pressure of the mixture. A.A. Kruithof and F.M.Penning, Physica 4, 450 (1937). 0.0003 0.0002136 inelastic collisions of electrons 08 zations vain) ws Fig 4,51a Variations of » with p/E for high pressure Hy C.C. Leiby, Jr. 5.B. Thesis, Department of Physics, M.LT y May 1954, egernes 2 gant Fig. 4,51b Iomzations per volt per mm Hg at 0°C an hydrogen. D,J. Rose (unpublished)inelastic collisions of electrons 137 The first ionization coefficients may be written in terms of an "jonization" collision frequency. Since a is the number of elec- trons produced on collision of the primary electron traveling 1 centimeter, one can also write a= vil¥ where vy, is the fre- quency of ionization on collision and ¥ is the average drift velo- city of the electron in the field. The average drift velocity ¥ = LE, and one may write ve ay a= —= and yne—,. (4. 5) pE ye? When an ultra-high-frequency field is applied toa gas, the elec- tron loss is controlled by diffusion. As we have seen before, we can discuss this in terms of the characteristic diffusion length “AN where v,/D = ViAZ, By analogy with the first Townsend coefficient for d-c ionization where the electron loss is controlled by mobility, we may define a coefficient for high-frequency dis- charges where the loss is by diffusion: i 1 $=-—y = (4, 6) DE? A2.2 Measurements of this ionization coefficient are shown as a func- tion of E/p in the papers by Herlin and Brown [9] and MacDonald and Brown [10], anda typical example is reproduced in Fig, 4.52. 17 \LO.1588 om. Ls 2.54em. 10" 0 (a0 (000 E/ lemmmnHe) Fig. 4.52a. The a-c ionization coefficient for helium.138 inelastic collisions of electrons PARMLEL MATE cary #10318 om SL s0s7 em AL so0e3s em | Fig. 4.52b The a-c 1onization coefficient for hydrogen at high gas pressure. The ratio of the two 1enization coefficrents may be written as a ,2 ae (4.7) which we have seen ma previous chapter to be a measure of the avesage electron energy. Thus in principle one could determine the d-c coefficient q from the a-c coeffrerent | af we knew the average energy as a function of E/p. This can be done correctly only for those cases where xt can be shown that the electron ener- gy distribution functions are essentsally the same For the case of the ultra-high-frequency breakdown in hydrogen in which a small d-c field could be superimpored on the a-c field, 1 was thus determined from { by Varnemin and Brown [11] and was shown in Fig. 4,53 to be in good agreement with the results of ve n measurements of Ayers and Hale It is sometimes convenient to express the Townsend coefficient an terms of empirical equations that fit the observed data in cer- tain regions of E/p. The most commonly used of these empirical equations 15 due to von Engel aud Steenbeck and takes the forma alp = A exp [-BAE/e)] (4.8)inelastic collisions of electrons 139 10° 7 (ONIZATIONS/ VOLT) to* : 10 20°30 50 10-200 E,/p (VOLTS/CM x MMHg) Fig. 4.53. Ionization coefficient for hydrogen. The values of A and B in cgs units and the range of E/p over which these values are satisfactory are given in Table 4.1. A theoretical description of the first Townsend coefficient can be set up formally in a simple way, but lack of knowledge of the electron energy distribution precludes a general solution for all gases. However, for some gases suitable approximations may be made to give agreement between theory and experiment. A frequency of ionization per electron may be defined such that vi = vi £; = vpP,. If we represent the energy distribution function as. f(u), we may write ow P t P,vé(u) du , (4.9) i where u, is the ionization potential, P, is a function of energy, and v= (2e/300 m)! (21/2 . Since we have seen that a= vite > we find co a ze 1/2 1 > = 350m) = § Pet? ‘f(u) du. a140 inelastic collisions of electrons Table 4 1, Constants A ard Bin Eq. 4 @ A B Range of vahaity |, Efe Gao son pairs v v emxmm Ny | emxmmite | cmemmég | mv Hy 3 130 150. 600 154 % we aa Yoo. 600 ass °, - - - wa co, | 20 466 300-1000 137 ar 8 365 oo 800 - HO] 13 290 50-1000 we wer {as 380 209-1000 - He 3 saa | 2 i500 | 245 Ne ‘ 100 00. 400 as A 4 180 200 600 37 xe a 240 Looe000 “ xe 6 350 200 800 we tg 20 370 200-600 toa From A von Engel , Handbuch der Pyni, Springer Verlag, Berka (986), Vol Hep Sot Table 4.1 Constants A and Bin Eq 48 A.von Engel, Handbuch der Physik, Springer Verlag, Berlin (1986), Vol. 21, p. 504. Emeleus, Lunt, and Meek [12] made a study of various distri- bution fanetions, making various assumptions as to the form of P,, Using a Maxwellian distrabution, they wrote 3/2 3/2 ze m 12 fo) du = 20 Soo) Geer eu exp (- 3ga EE) oH Wrsting the electron temperature in terms of the average elec- tron energy €0/300= 3kT,/2, we haveinelastic collisions of electrons 141 8 © | 1.23x10° | .-3/2 3u > = (a) , Pu exp (- al ) du. i (4.10) Comparing the most recent experimental measurements in hydrogen, Blevin and Haydon [13] have obtained excellent agree- ment between this theory and experiment, They showed further that the most critical parameter not well determined was the average electron energy u. A 5% error in this quantity pro- duces a 50% error in a/p when E/p = 30, and a 15% error when E/p = 100. REFERENCES . 1. WN. E. Bradbury, Phys. Rev. 40, 980 (1932). J. K. Theobald, J. Appl. Phys. 24, 123 (1953). 2. H. Maier-Leibnitz, Z. Physik 95, 489 (1935). 3. I. Abdelnabi and H. S. W. Massey, Proc. Phys. Soc. (London) 466, 288 (1953). F. H. Reder and S. C. Brown, Phys. Rev. 95, 885 (1954). 4. W. B. Nottingham, Phys. Rev. 55, 203 (1939}. 5. H. D. Hagstrum, Revs. Mod. Phys. 23, 185 (1951). 6. R. E. Fox, W. M. Hickam, T. Kjeldaas, Jr., and D. J. Grove, Phys. Rev. 84, 859 (1951). 7. J.S. Townsend, Phil, Mag. 1, 198 (1910). 8. F.H. Sanders, Phys. Rev. 41, 667 (1932). 9. M. A, Herlin andS. C. Brown, Phys. Rev. 74, 291 (1948). 10. A. D. MacDonald and S. C. Brown, Phys. Rev. 75, 411 (1949). ll. L. J. Varnerin and S. C, Brown, Phys. Rev. 79, 946 (1950). 12. K. G. Emeleus, R. W. Lunt, and C. A. Meek, Proc. Roy. Soc. (London) A156, 394 (1936). 13. H. A. Blevin and S, C, Haydon, Australian J. Phys. 10, 590 (1957).Chapter 5 DIFFUSION-CONTROLLED BREAKDOWN, 1, High: Frequency Breakdown [1,2,3] lia high-frequency gas-diecharge breakdown, the primary romzation caused by the electron motion 16 the only production phenomenon that controls the breakdown, and for this reason xt 18 the simplest type to consider. If one calculates the maxamum Janetze energy an the oscillatory motion of an electron at the mini- mum field mtensities for breakdown experimentally determined, ‘one finds that ths energy corresponds to about 10°? volt. Its, therefore, obvious that the energy of oscillation 1s insufficient to account for breakdown, It xs well known that a free electron in a vacuum under the action of an alternating freld oscillates wath zt velocity 90° out of phase with the field, and thus takes no power, on the average, from the applied field, ‘The electron can gam energy from the field only by suffering coll:exone with the gas atoms, and 1t does s0 by having ate ordered oscillatory motion changed to random motion on collision, The electron gains random energy on cach collision until it 1 able to make an snelastic coll:eion wath a gas atom. The fact that the average electron can continue to gain energy in the field, despite the fact that 1t may move esther with or against the field, can be seen by showing that the energy ab- sorbed 18 proportional to the square of the electric field and, hence, independent of its sign, The rate of gain of energy of the electron from the electric field E (rms) 1a P= eEv. The average draft velocity expressed in terms of the a-c mobility previously cscussed 18 2_eF ‘m P= ee me (TF 6.1) ‘This equahon may be written in terms of an effective field EB, ez, 2 a 8.2) where E, 18 the effective field that would produce the same energy transfer as a steady field. ‘The gas-discharge breakdown occurs when the gain in electron 142diffusion-controlled breakdown 143 density caused by ionization of the gas becomes equal to the loss of electrons by diffusion, recombination, or attachment, When the loss is by diffusion, the problem becomes simple, Referring to our previous discussion of diffusion where the current density I'=-VDn, we have at breakdown on ot = vn- V- r=0, where »; is the frequency of ionization. By writing the diffusion equation as 2 ¥3 2 Vv Dn+ 3) Dn=0, it follows from our previous work that we may write v3/D =i] Is”. The experimental method of determining breakdown at micro- wave frequencies can best be described with reference to the block diagram of Fig. 5,1. A continuous-wave tunable magnetron in the 10-cm wavelength region supplies power to a coaxial line leading to the measuring equipment. A cavity wavemeter, used for fre- SPECTRUM ANALYZER (USED AS. DETECTOR) CRYSTAL AND METER *WAVEMETER ‘CALIBRATED ATTENUATOR (_) THERMSTOR DIRECTIONAL COUPLER SLOTTED SECTION POWER RESONANT DIVIDER CAVITY MATCHED LOAD Fig. 5.1. Block diagram of an experimental method of deter- mining breakdown at microwave frequencies. quency measurement, receives a small signal from a probe in the line. The power incident on the cavity is varied by a power divid- er. A directional coupler provides a known fraction of the incident power to a thermistor element, whose resistance, measured bya sensitive bridge, indicates power incident on the cavity. mode and is coupled to the coaxial trans- mission line by a coupling loop. A second coupling loop provides144 4: ffusion-controlled breakdown a transmutted signal to an attenuator, crystal, and meter, The electric field is calculated by standard microwave methods, It 1 customary in resonant-cavity systems to specify the losses in the careuit by means of a Q-factor, which 1s defined as Q= 2n(energy stored) /energy dissipated per cycle, In the absence of a discharge, the Q of the cavity 1s calculated from standing-wave measurements. ‘The power absorbed in the cavity 1s determined by the measured incident power and the standing-wave ratio at resonance. The absorbed power is related to the stored energy through the Q, and the electric field is determined from the known field configuration and the stored energy. at 1 L 1 Phion om 9) Fig. 5.2, High-frequency gas-discharge breakdown an pure hebum, Breakdown experiments at frequencies lower than the mcro- wave region are well sllustrated by the work ef Thomson. [4] The electric field necessary to produce breakdown 18 determined by ‘the physical dhmensons of the apparatus and the peak voltage applied to the tube. The frequency of the applied field was mea- sured by the Lecher wire system. Typrcal of the behavior of the diffusion- controlled breakdown ‘eld at hagh frequency [5] wath changes 1n gas pressure are the results shown in Fige. 5-2 to 5.5. Data shown an Fig 5,3 and Fig, 5.6 were taken in heluum contaimng small admixtures of mercury vapor.[6] Thie muxture, which for convemence we call Heg gas, had the theoretical advantage of acting as an atom with- cout excitation levels, Helum has a metastable level at 19.8 Volts, and transitions from ths level to the ground state by radi- ation are forbidden, Since the metastable etates have mean hvesdiffusion-controlled breakdown 145 10,00; ; 1000! 1 E 2 | = = tod Sac _] ” L0475em a L=2.54em | ' Si t 10 100 1000 pimm-Hg) Fig. 5.3. High-frequency gas-discharge breakdown in Heg gas. £(VOLTS/CM) ou a it f1 itt 10 100 1000 p(MM-Hg) 2| pol Wor \ Fig. 5.4, High-frequency gas-discharge breakdown in neon,Fata diffuss:on-controlled breakdown TT 1 ToTTYq TTT] 1 55a, Hugh- frequency breakdown voltag. of pAfor hydrogen. C= 10.6 em, A. OX f pion mesh ° as a function 05 em, 300 cm, A= 0,2 cm, AX= 10.6 cm, 1.028 em, SZ Ty TTT Lr 0189 em 20475 em e234 om J i 100 ‘01 Fig. 5.5b. High-frequency g To 10 100 Pum OF Ha) discharge breakdown an hydrogen at 3000 Mc/aec.ifusion-controlled breakdown e ab st OKC = TTT TTT iy TUTTI CT Tint g oF TTT i rr my TPT TTY 8 Fig. 5.6. Experimental breakdown electric fields compared with 2 simplified theory. oi the order of thousands oi microseconds, practicaliy every helium atom that reaches an energy of 19.8 volts will collide with @ mercury atom and lose its energy by ionizing the mercury. Therefore, each inelestic collision will produce an ionization, and the effective ionization potential will be u; = 19.8 volts. Although an accurate description of the breakdown measure~ ments can be given theoretically only by taking into account the electron energy distribution [7], a physical picture of the mechan- isms involved can be seen qualitatively in the following way. Let us consider first a ges at high pressure 2 >>w2), Here the power that goes into the electron from the electric field is dissi- pated in elastic collisions between the electrons and the gas mole- cules, For this case, 2m ~- Energy/collision = s45 =e > . {5. 3) mv From this we mzy calculate the electric field to be 1/2 _ fm 2m — =06.9. gi le 4 E= Te 3) - v= 0. 94p{a) (5.4)148, da f{usion-controlled breakdown for the case of Heg gas in which nearly all the loss goes into non= ronizing collision, Taking the average energy equal to one third of the somzation potential, E= 2. 4p, 2t ean be seen that the hngh- pressure breakdown measurements of Fig. 5.6 tend to approach thas line at hagh pressures. In the low-pressure region, the electrons make many oscilla- tions per collision, and the breakdown field may be determaned by equating the number of collisions to ionize to the number of colli sions to diffuse out of the tube, Since we are discussing Heg gas, where all the inelastic collisions are ronizing ones, let us consid- er that all the mput power goes anto 1omzahion We may write 2 2 », P cE m z | (5.5) ve ee le Pe! We have just seen that the breakdown condition 1s ¥, = D/A, and svbstituting the value of the diffusion coefficient D= £4/3 we find v= {v/3A® Uwe muluply numerator and denominator of this ekpression by the velocity, we obtain an expression an terme of the previous expression for », in which o® >> v2, to obtain (6) 3a" Me RS If we solve dus expression for the electz1c field, writing o in terms of } and 20 = mvZ/e, we get are f2 a, =ah V3, - (5.7) For the case of helsum, we find that the collision frequency 15 = constant independent of energy aver almost the entire energy range and equal to vq = 2,37 x10%p For Heg, the rorszation potential 1s 19,8 volis, and we assume a very low pressure where all the mput power goes snto 1omzation, Galeulating the electric Seld under these approxamations leads to a relation E= 1284/pAR, which agrees fairly well with che low-pressure measurements 1m Heg as shown in Fig. 5.6. 1a pas contained im a vessel 1s placed in an alternating electric field for a certain value of the electric field, the gax will break down into an electrical discharge. This breakdown field may be expressed as Ey = Blu Aeds Pe where Eis the electric eld intensity, u; 25 the 2omzahondiffusion-controlled breaksown 149 potential, A is a parameter describing the vessel, \ is the wave- length of the exciting field, and pis the pressure. The field Eis measured in volts per cm, and u; is measured in volts. The term Ahas the units of length, and its appearance in explicit calcula- tions also involves various known dimensionless ratios to describe the shape of the vessel. It is customary to measure pressure in millimeters of mercury, and the mean free path, which is inverse- ly proportional to pressure, is measured in centimeters, A rela- tion between pressure and mean free path is obtained by introducing the quantity P,,, which is the number of collisions per unit length at l mm Hg pressure. Thus, p may be regarded as having the units of reciprocal length, even though this is not its true dimen- sion, In treating the breakdown problem dimensionally, there are five variables with but two fundamental dimensions, volts, and centi- meters. This leads to three independent dimensionless variables between which there is a functional relation [8]. It is often con- venient in physical problems to introduce variables that are not dimensionless but are nevertheless proper variables for dimen- sional analysis because the completely dimensionless variables contain one or more physically invariant quantities that need not be carried along in a practical discussion, There are a number of sets of such proper variables in a gas discharge problem which may be transformed into one another, and their relative conven- ience depends on the purpose for which they are to be used [ 9]. One very useful set of proper variables is EA, pa, par. The advantage of these variables lies in the fact that p, A, andh are the experimentally independent parameters that determine the dependent variable E, the observed breakdown field, Another set of proper variables which we shall use is obtained by dividing the first variable by the second and so obtaining EA, E/p, pr. This set has the particular advantage, in a discussion of break- down phenomena, that we may define an ionization coefficient & =1/E2,2 which is a function of E/p and pr. For the cases of a d-c field, or when the pressure is high so that in an a-c field the electrons make many collisions per oscil- lation, the wavelength variation does not enter as a significant variable. Breakdown can then be described by the other two variables such as EA and pA. This is called "Paschen's Law." This is illustrated [10] in Figs. 5.7 and 5,8. Certain basic assumptions are made in the calculations of breakdown as a balance between the ionization rate and the loss of electrons by diffusion, We examine here the limits that these