The choice of cathode ionization gauge

received P E in final form 8 August Research 1975 Council. Rutherford

material

in a hot cathode

Gear.

The Science

Laboratory,

Chilton.

Oxfordshire,

England

A paper in our Education in Schools and Colleges.

Series:

The Theory

and Practice

of Vacuum

Science

and Technology

The paper outlines the problems encountered in using a hot cathode ionization gauge with particular reference to the tungsten cathode. The theory of thermionic emission from metals semiconductors is mentioned as is activation and poisoning of surfaces. Low temperature cathodes are discussed with emphasis on the monolayer cathodes, oxide cathodes and the refractory compound cathodes.

and

1. Introduction

These

In a solid of macroscopic dimensions the fraction of atoms of the total at the surface is of the order of 10e8 and the contribution of these atoms to the normal bulk properties of the solid is negligible. However, the properties of the surface can become extremely important under certain circumstances. It is through the surface that charge must flow in thermionic emission and it is on the surface that chemical reactions with the gaseous environment occurs. One of the most important technical applications of the properties of surfaces is the emission of electrons from the surface of metals. This effect, known as thermionic emission is very important for all devices requiring electron guns e.g. thermionic valves, TV tubes, electron microscopes etc. and thermionic ionization gauges. However the use of hot cathodes in ionization gauges introduces problems in the measurement of low pressures. These problems are due to: (a) Chemical interaction of the residual gases at the hot cathode resulting in changes in gas composition. (b) Emission of positive ions and neutrals from the cathode. (c) Thermal effects resulting from heating of electrodes and gauge walls by radiation from the hot cathode. Many different types of ionization gauges (see for example Leek or Redhead et a12) and various cathode materials have been developed to try and reduce the effects of the above problems.
2. Principles of thermionic emission

owx potentlot

electrons

con escape borrler

Metal \

Vacuum

Dlstrl

butlon

at T=b

\ NlEl-

Figure 1. The potential diagram of a metal-vacuum interface, with

Fermi..Diract energy distributions. At T = 0 all electrons lie below the Fermi level and there can be no thermal emission.At T > 0 the distribution is modified so that some electronshave enough energy to escapeover the potential barrier and thermal emissioncan occur. The current drawn from the metal can be calculated from the Richardson-Dushman equation.

I, = AT(l

At the surface of any material is a potential barrier which prevents electrons escaping unless they acquire sufficient energy to overcome the barrier. The electron energies in a pure metal have a Fermi-Dirac distribution (Figure 1) which is strongly dependent on temperature. At absolute zero all electrons lie below the Fermi level EF and the height of the potential barrier above this level is known as the work function 4. As the temperature is raised so the distribution is modified, as shown, until some of the electrons have acquired enough kinetic energy to escape over the barrier into the vacuum, and thermal emission occurs. Vacuum/volume 26/number 1.
Pergamon Press LtdJPrinted in Great

-2 ( > where 1, is the emission current A is the Richardson constant = (4rmek2/h3) $ is the work function (usually expressed in electron volts) k is Boltzmanns constant T is temperature (absolute) I is a reflection coefficient to take into account reflection of electrons approaching the metal surface. Taking logs of equation (1) gives:

- r)exp

In $

= In A(1 - r) - $T

A plot of In IO/T2 against 1/T givesa strait&t liqe frc$ $iir# {he constant A and the work function 4 can be determined. Eigurei shows such a plot for tungsten.3
Britain

P 15 Gear:The

choice

of cathode

material

in a hot cathode

ionization

gauge and levels. semiconductor can only be achieved if the Fermi level between the donor and conduction with energies emitted. The

lies

approximately midway

Only electrons in the conduction band than x the electron affinity can be thermally drawn is given by
IO = AT2 exp - y

greater current

This is the Richardson-Dushman equation with the metallic work function + replaced by (x + U). Hence (x + U) is often called the semiconductor work function. 3. Activation and poisoning of surfaces
The work function of a metal such as tungsten can be lowered by surface adsorption of alkali or alkaline earth atoms. The lowest value of the work function is obtained when there is a

Pigure2. Richardson plot for tungsten, from which the work function and the Richardson constant can be determined. From equation (1) the temperature T for a given emission current la is approximately proportional to 4 so that a low value of 4 is needed for a low temperature cathode. The above is a simplified equation which fails to take into account a number of difIiculties namely, (a) The temperature dependence of 4. (b) Effect of electric fields at the surface on the work function. (c) Non uniformity of the work function. Simple theory also suggests that the work function might be expected to vary between different crystal planes. The atoms in lattice planes with low crystal indices are tightly arranged and gives a higher work function than the less closely packed planes. Differences of up to 10% from the mean work function for polycrystalline materials have been measured between different crystal planes. Thermionic emission from an n-type semiconductor layer deposited on a metal substrate is the basis of an important type of cathode-the oxide cathode. The potential diagram is shown in Figure 3. Electron equilibrium between the metal
Semi-conductor Vacuum

monolayer of adsorbed atoms. The reason for such a change can be shown by considering the potential energy of an atom as a function of its distance from the metallic surface (Figure 4). The curve ABC is the attraction due to Van der Waals forces with D, the energy required to dissociate the adsorbed atom from the metal

/
/R / / / /

Figure 4. Potential energy as a function of distance from a metal

surface.ABC correspondsto an atom, PQR to an ion.

Conduction

bond

P-r X

Fermi

level

Donor SL

impurity L z

level A

surface. If the atom is ionized the electron is taken into the metal yielding a gain in energy equal to the work function 4 of the metal. Hence the potential energy curve for the ion starts (I - 4) above the atomic curve at point P, (where I is the ionization energy). On approaching the metal the ion is under the influence of an image force, i.e. the attraction potential is a coulomb attraction proportional to the reciprocal of the distance from the metal. As the potential curve for the atom is of the Van der Waals type it varies with a higher power of the distance. Hence the potential curve for the ion intersects the atomic curve and if Q is lower than B, the atom is adsorbed as a positive ion rather than as an atom. The condition for ionic adsorption is Di-I+~>D, where D, is the binding energy of the ion.

Figure 3. The potential diagram of an n-type semiconductor-vacuum

interface.

P E Gear:

The

choice

of cathode

material

in a hot cathode

ionization

gauge

Atoms with a low ionization energy (such as alkali and alkaline earth atoms) will be adsorbed as ions on a metal with a relatively high work function like tungsten. If atoms are electropositive i.e. they are adsorbed as positive ions on the metal surface, then a negative surface charge is built up and a double layer exists. Thus electrons emitted from the interior of the metal into vacuum see an extra potential energy drop resulting from the double layer equal to A$ = 4nNe2d where n is the distance between positive and negative charges and N is the number of ions adsorbed per unit area. It is therefore easier for the electrons to escape than without the double layer and the effective work function of the metal is lowered by A# (Figure 5a). This process is known as activation. A reduction in the work function results in a particular thermionic emission level being obtained at a lower operating temperature with a consequent reduction in gas-cathode surface reactions. This activation process will be looked at further when considering low temperature monolayer emitters.

in a decrease in emission at a particular operating temperature. This can occur whenever oxidizing gases such as 01, HZ0 or CO2 are present. 4. Pure metal cathodes For a clean metal to be useful as a cathode it must give the required emission and have long life, i.e. it should not evaporate too rapidly at the operating temperature. Table 1 gives the emission characteristics of various pure metals.4 As can be seen only tungsten, tantalum and rhenium give useful emission levels. These metals have an advantage that due to their high operating temperature contaminating electronegative gases which would increase the work function and reduce emission levels are rapidly evaporated. Tantalum and rhenium have disadvantages that will be discussed later, and it is tungsten that is in genera1used in ionization gauges operating in mediumhigh vacuum range. However a tungsten cathode is run at temperatures between 2250-2500 K to give adequate emission levels and at these temperatures chemically active gases react at the filament to produce other gases. Hence use of a tungsten cathode can cause considerable changes in the gas composition of an ultra high vacuum system. 4.1. Reaction of oxygen with tungsten. Oxygen molecules incident on a hot tungsten cathode can be adsorbed for a sufficient time to enable dissociation to take place. The degree of dissociation has been calculated to be 99 % at a temperature of 2000 K.5 The chemically active atomic oxygen produced at the cathode surface then reacts with carbon impurities in the cathode to produce CO and CO1. The production of CO occurs at the surface of the cathode and the replacement of surface carbon, by diffusion from the bulk, results in a continuous generation of CO. If the cathode is run at temperatures in excessof 2000 K, in oxygen pressures greater than 10S6 then the diffusion process is rapid enough to produce depletion of the carbon impurities with subsequent reduction in CO* production.6 If the time of the reaction is long enough (10-60 h depending on the cathode) then the carbon impurities are eliminated. If carbon free tungsten cathodes are used no CO or COZ formation occurs. However atomic oxygen can evaporate from the cathode and combine with the carbon impurities on

Monolayer Vacuum
(01

Metal Monolayer (b) Vacuum

Figure5. Potential diagrams of metal surfaces,4 is the work function of a clean surface, 9, is the work function when the surface is contaminated with an electropositive layer and 4. the work function when contaminated with an electronegativelayer. The opposite effect known as poisoning occurs when atoms are adsorbed as negative ions (electronegative contamination). In this case the work function is increased (Figure 5b) resulting

Table 1. The emissioncharacteristics various pure metals; only tungsten, tantalum and of rhenium give useful emmission levels
Mctnl Melting
OK

point

Richardson
constant A

Work

function eV

Usable emission A cm

Acm

-2 T -2

-2

w Ta RI.2 PlO Pt

3640 3270 3440 2890 2050 1730 1120

80 60 700 55 170 60 60

4.54 4.10 4.7 4.15 5.40 4.1 2.11

4 x 10-l 6 x IO-' 2.6 x IO-' -3 5 x IO 2 x IO -8

5 x 1o-g I x lo-

Ni
Ba

P E Gear:The choice of cathode material in a hot cathode ionization gauge the gauge walls to give CO. The atomic oxygen also interacts with the tungsten at the surface of the cathode forming gaseous tungsten oxides, the amounts desorbed depending on cathode temperature. The principal products of oxidation are WOz and W03, the trioxide being most important at low temperatures and the dioxide the dominant product at high temperatures. At temperatures in excess of 2600 K, WO is produced. These chemical processes result in the removal of oxygen from the system, therefore an ion gauge acts as a pump for oxygen. An analysis of the oxygen pumping effect by tungsten has been carried out using a quasiequilibrium treatment of gassolid reactions. The general shape of the predicted curves (the fraction of incident oxygen molecules that are pumped against filament temperature), is very similar to those obtained from an experimental study of the oxygen-tungsten interaction5 (The same analysis provides a semiquantitative explanation of experimental data on the rate of impurity emission from hot tungsten.) 4.2. Reaction of hydrogen with tungsten. Hydrogen is dissociated by a hot tungsten cathode at temperatures above 1000 K, the probability of dissociation being dependent on cathode temperature. The atomic hydrogen evolved is readily adsorbed on most surfaceswithin the ion gauge and hence an anomalously high pumping speed for hydrogen is obtained. The contaminant gasesformed from the interaction of atomic hydrogen with the chamber walls and electrodes are CO, CH4 and H20. The carbon is present in the gauge or in the cathode and the oxygen in the gauge walls. Table 2 shows the relative ion current cient of the electrons at the grid. These reflected electrons oscillate about the grid structure and are indistinguishable from primaries coming directly from the cathode. They contribute directly to the gauge collector current increasing the sensitivity by a factor (I -II y -1-yz t- . . .), where y is the reflection coefficient. Similar experiments have shown that Bayard-Alpert gauges with low temperature cathodes have a more stable sensitivity in hydrogen. A monolayer coverage of hydrogen increases the work function of tungsten by 0.35 eV resulting in a decrease in the emission current. 4.3. Reaction of other gases with tungsten. Reactions with the cathode is not restricted to oxygen and hydrogen but takes place readily with gases containing either of these elements. The following reactions with water vapour can occur with a hot tungsten cathode. H,O+W+C 7 + I WOJ CO H

for contaminant gases as a function of tungsten cathode temperature.8 As can be seen the most commonly evolved gas is carbon monoxide. Many complex actions take place with hydrogen and it has been shown that the pumping effect is due to a complex function of both cathode and grid temperatures.g Under normal operation the cathode dissolves hydrogen, while the grid adsorbs hydrogen. Experimental data has shown that there is a variation in the sensitivity of Bayard-Alpert gauges of the order of 10% when operated in hydrogen.O This has been interpreted as being due to the adsorption of the atomic hydrogen on the grid, causing a change in the reflectidh coeffi-

The atomic hydrogen and tungsten oxide recombine at the glass walls of the gauge to form tungsten and water vapour. Water vapour therefore acts as a mechanism for transporting tungsten from the cathode to glass walls with a consequent reduction in the life of the tungsten cathode. Methane and other hydrocarbons are found in most vacuum systems due to back-streaming of diffusion pump oils and flashing of getters and these can dissociate on the cathode to form carbon monoxide. A small degree of dissociation of nitrogen can occur but the effect is very small. Similarly there is negligible dissociation of carbon dioxide, although it does react to form metal oxides and CO. In the casesof both nitrogen and carbon dioxide there is a change in the work function of tungsten in the presence of a monolayer coverage. In the presence of COz the work function is increased by 0.55 eV giving a decrease in emission. While in the presence of Nz the work function is decreased by 0.5 eV giving an increase in the emission current. 4.4. Emission of positive ions and neutrals from tungsten. The emission of positive ions and neutrals from heated surfaces is a common occurrence and can affect the performance of hot cathode ionization gauges.

Table2. The relativeion current (1+/I +(H~) for contaminant gases a function A) as of tungsten cathode temperature, the most commonly evolved gas is carbon monoxide
Filament Temperature OK 300 1010 1550 la40
1975 H202 co H20 CH4

9.
0.26

x
0.56

x
0.33

%
0.02

0.25 0.44 0.78 0.66

0.65 0.82 3.1 11.3

0.28 0.44 0.95 0.65

0.01 0.04 0.46 2.5

P E Gear: The choice of cathode material in a hot cathode ionization gauge When metals are heated close to their melting point signiticant ion emission can occur. Impurity ions are also emitted usually at lower temperatures. The current of positive ions emitted at a temperature T is given by

where C, is the specific heat at constant pressure of an ion in the condensed state.
r is the ion reflection coefficient

++ is the work function for positive ions and M is the ion mass. This equation is identical in form to the Richardson-Dushman equation for thermionic electron emission except for a factor of 2 and the specific heat term. As with thermionic emission of electrons the emitted ions have a Maxwellian velocity distribution. Impurities leaving a hot cathode come off as both neutral particles and ions as predicted by the Langmuir-Saha equation. This equation gives the ratio of positive ions to neutral atoms evaporated per unit time as 2 = A+ exp[(s-kTy,)e] The problem with alkali metal impurities in tungsten can usually be overcome by using a heat treatment or by using a low temperature emitter. Ions can also be emitted as a result of surface ionization of gas atoms and molecules which impinge on a hot cathode. A modified form of the Langmuir-Saha equation can be used to find the probability of an incident atom leaving the surface as a positive ion. It is assumed that the adsorbed atoms and molecules come to thermal equilibrium with the surface. The probability will be high for atoms and molecules with low ionization potentials incident on a surface of high work function. 4.5. Thermal effects using a tungsten cathode. The increase in the bulb temperature of an ion gauge due to radiation from a hot tungsten cathode results in: (a) Increased helium permeation through the glass envelope. (b) Increase in the rate of evolution of water from the glass. These can affect the gas composition and total pressure below lo-* torr. Table 3 shows the partial pressuresobserved when a Bayard-Alpert gauge (B.A.G.) is operated at equilibrium bulb temperature (-50C) and corresponding pressure when the bulb is cooled with an air blast. The total pressure in the system is changed by a factor of 2. Also the relative gas composition has been radically changed. This thermal effect can be reduced by operating the filament at a lower temperature, containing the gauge in a large diameter bulb or inserting the gauge nude into the vacuum system. 4.6. Other pure metal cathodes. Although possessing a lower work function and containing less carbon impurities than tungsten, tantalum is completely unsuitable as a cathode material. This is due to its adsorption properties for hydrogen. Tantalum will adsorb many hundreds of times its own volume
7

,o.:

I I300

I 1500

I I700 Filament

/ 1300

I Zloil

I 2300 OK

I 2500

10

temperature.

Figure 6. Positiveion current vstemperature at different pressures.

where A+ is a constant involving the statistical weights of ions and atoms +- is the electron work function and V, is the ionization potential of the atom. It has been shown that tungsten (which contains impurities of the alkali metals Na, K, Rb and Cs) emits alkali metal ions in pulses at temperatures above 1300 K. These pulses contain approximately lo6 ions and the pulse rate varies from 102lo4 s-l. The cause of this ion pulsing has been shown to be due to the uncovering of impurity pockets of defects and grain boundaries in the crystal structure. 13 In the presenceof chemically active gases 02, COZ and HZ0 the pulse rate increases, while the presence of N2, CO and A, which do not react with tungsten, have little effect. Although the positive ions cannot normally reach the collector because of the grid potential, the Langmuir-Saha equation predicts that the emission of positive ions is accompanied by a large flux of neutrals. These can reach all parts of the gauge including the grid. By the process of electron induced desorption a fraction of these neutrals are ionized. These ions are then able to reach the collector giving an anomalous ion current not related to gas pressure. Thy ion current from a heated cathode varies as shown in Figure 6. As can be seen, at low pressures (<10m6 tort-) the ion current increases as the filament temperature is reduced from about 2200 K to 1700 K, which results in an increase in the anomalous ion current to the collector. These temperatures correspond to an electron emission of 10 mA and 10 pA. It is therefore possible for the sensitivity of an ion gauge to increase (due to increase in anomalous collector current) if the filament current is reduced while the gauge is operating in a chemically active gas, with resultant errors in. pressure measurement. An example of this affect has been reported.14

P E Gesr: The

choice

of

cathode material in

a hot

cathode ionization gauge

when (-50C) a Bayard-Alperl and corresponding gauge (BAG) pressure is operwhen the

Table 3. The partial pressures observed

ated at equilibrium bulb temperature bulb is cooled with an air blast
Gas

Partial at 5OC x IO
x 3 x

Pressure (torr) -10

Partial with bulb

IO

Pressure cooled
14,6 65.5 14.6

H2
Hc co

I.1
1.3

36 42.6 9.9

2 x 9 x 2 x

-I I

IO -10 lo-11

IO-II 1o-l

cty
3.5 CH4) Ii lo-l

11.5

7.5

x lo-l2

5.3

Total

prcssurc

3 x

10 -10

I.4

IO

-10

of hydrogen when heated in a hydrogen atmosphere and cooled to room temperatureI (as can happen to an ion gauge filament). On reheating about 30% of the hydrogen remains within the structure of the material causing it to become very brittle due to crystal formation. A further effect of the hydrogen is to increase the resistance of the cathode by as much as 100% which would cause severe problems for any emission control circuit. Rhenium has a number of advantages over tungsten as a cathode material. It is more resistant to water cycling and does not form stable nitrides and carbides. Hence oxygen interaction with carbon impurities produces lesscarbon monoxide. It does not become brittle at high temperatures and because of its hexagonal close-packed crystalline structure is an ideal base material for lanthanum hexaboride coatings. The high work function is a disadvantage as the evaporation rate is about 150 times higher than tungsten for the same emission level. The lifetime of a rhenium cathode is still long enough however to be useful in ionization gauges. Iridium and rhodium have high work functions, low melting points and high vapour pressuresat relatively low temperatures. This makes them unsuitable as cathode materials. However they are extremely resistant to oxidation and are used as base materials in both thoriated and oxide coated cathodes. Most of the problems outlined above in respect of pure metal cathodes can be reduced by lowering the operating temperature of the cathode. This has led to a search for suitable cathode materials with low work functions to replace the conventional tungsten cathode. The cathode materials that have been investigated can be grouped into three main sections. (a) Monolayer emitters. (c) Oxide cathodes. (d) Refractory compounds. 5. Monolayer emitters In the previous discussion on cathode materials only clean metal surfaces have been considered. It was stated in section 3, that in the process known as activation a small amount of foreign material adsorbed onto a metal surface can cause a large reduction in the work function of the surface. This
8

process is made use of in producing cathodes collectively known as monolayer emitters. Table 4 gives values for the work functions of tungsten contaminated with a monolayer of various electropositive materials. A reduction in the work function means that a cathode can be run at a much lower temperature for a given emission current. In general the operating temperature for a given emission is reduced by approximately the same ratio as the reduction in work function. Table4. Values
a monolayer Adsorbed Carsium

for the work functions of various electropositive

of tungsten materials

contaminated

with

material

Work

function
1.5 1.4 1.6

eV

Oxygen-Qesiutn
Barium OxygenThorium Barium

1.3 2.7 3.1 4.54

Zi 1:conium
Clean tungsten

For a monolayer cathode to be suitable, the evaporation rate of the contaminant at the operating temperature must be low and some means for its replenishment must be found. A monolayer gives the maximum possible emission and is at the same
time inherently stable, and so any excess contaminant must be

quickly removed. Fortunately, the binding energy of the monolayer atoms to the substrate is usually greater than the binding energy of any subsequent layer deposited on the monolayer. So providing the rate of supply of atoms is sufficient to maintain the monolayer and any contaminants are evaporated there will be very little reduction in emission. The types of monolayer emitters are limited due to the problem of replenishment of the monolayer. The most common types are thoriated tungsten and the barium dispenser cathodes.

P E Gear: The choice of cathode material in a hot cathode ionization gauge 5.1. Thoriated tungsten. A monolayer of thorium on tungsten results in a decrease in the work function from 4.54 eV for the pure metal to 2.7 eV for the contaminated metal, with a corresponding reduction in the operating temperature to approximately 1400 K. Thoriated tungsten in the form of a wire contains approximately 0.5-l y0 thorium oxide, Th02, uniformly dispersed throughout the tungsten. To prevent poisoning by residual oxidizing gases such as 02, H20 and CO,, the cathode is carburized by heating in a hydrogen or hydrogen-nitrogen mixture containing an organic vapour such as xylene at a temperature of 2200 K. The hydrocarbon is then dissociated at the hot cathode to produce free carbon which diffuses into the tungsten.and combines with it to give tungsten carbide, W2C. The degree of carburization is limited by the fact that the mechanical strength of the cathode decreases rapidly with increasing carbon penetration. In practice the thickness of the carburized layer is about 10% of the wire radius. The presence of the carbon in the surface inhibits the adsorption of the oxidizing vapours and they are removed by the formation of co. Heating to the operating temperature activates the cathode by causing the Thor to diffuse through the W2C layer where it is reduced to give free thorium. 2W,C + ThOz --+4W + 2C0 + Th The thorium then diffuses to the surface and migrates over it to form a monolayer. This type of cathode has a very long life and can provide a saturated emission of 4 A cm- with a life in excessof 10,000 h. A much improved electron emission from thoriated tungsten has been obtained by depositing a layer of grain orientated tungsten over the cathode surface. The effect of this is to increase the Richardson constant by factor of 4 while keeping the work function almost constant. Thoriated tungsten cathodes have been used by many workers, and commercial ionization gauges are available using this type of cathode. A cathode of thoriated iridium is not as susceptible to poisoning as thoriated tungsten at high oxygen pressure. This makes it very suitable for high pressure operation (--lOmZ torr) in the ionization gauge of Schulz and Phelps.* Conventional ionization gauges using thoriated iridium cathodes are available, and several have been used successfully in the authors laboratory. 5.2. Barium dispenser cathodes. A major group of monolayer emitter cathodes is the barium dispenser cathodes, where the emitting surface is a monolayer of barium on a substrate of tungsten. There are various forms of this cathode of which the most important are the 'L' cathode and the impregnated tungsten cathode. These cathodes are used extensively in high power microwave valves such as klystrons and magnetrons where high current densities are required. There are no reports of tungsten based dispenser cathodes being used in ionization gauges because of the large evaporation rate. The barium would be adsorbed onto the electrodes of any gauge and give rise to large residual currents. An ionization gauge was developed using a platinum based barium dispenser cathode but high residual currents were found.ig 6. Oxide cathodes Thermionic emission from an II type semiconductor layer deposited on a metal substrate is the basis of the oxide cathode. There are three main groups, alkali earth oxide coatings (barium, strontium, calcium), rare earth oxides and thorium oxide coatings. Cathodes of the first group are very susceptible to poisoning by oxidizing gases, 02, HZ0 and CO and as such are not suitable for use in ionization gauges. They are used extensively in gas discharge devices such as thyratrons. Of the second group only yttrium oxide has been used as a cathode in ionization gauges.* This cathode consisted of a platinum-rhodium substrate with a yttrium oxide coating and was used in an ionization gauge operating in the high pressure range up to 1 torr. The thoria coated cathodes offer several advantages over the alkali earth and rare earth oxide cathodes. (a) Electrical resistance is lower for same temperature. (b) Does not form interface compounds. (c) Easier to activate. (d) Less easily poisoned. These cathodes are prepared by depositing a layer of thoria on a base metal of tungsten or iridium by cataphoresis. The coating is then activated by operation in a vacuum at about 2000 K. The thoria coated iridium is more commonly used because iridium is very resistant to oxidation and hence the cathode is not subject to burn out if exposed to an increase in pressure while hot. Also stable emission is obtained in pressure as high as 10m2 torr. The operating temperature is also much lower than for the tungsten-based cathode. Because of these advantages many ionization gauges are commercially available with thoria coated iridium cathodes. 7. Refractory compounds Of the refractory compounds such as the carbides, nitrides and borides, lanthanum hexaboride is the most important. It has a work function of 2.8 eV and gives adequate emission at a temperature of 1400 K to be of use in ionization gauges. The cathodes are prepared by coating a refractory metal with lanthanum hexaboride powder. At high temperatures however the small boron atoms which form a three-dimensional framework around the relatively large lanthanum atom tends to diffuse into the underlying metal substrate, forming interstitial metal-boron alloys. This leads to a collapse of the boron framework around the lanthanum atom which in turn allows the lanthanum to evaporate rapidly thus shortening cathode life. In addition the base metal becomes embrittled. Carburization of the surface of the base metal before coating with the lanthanium hexaboride can be used to reduce this diffusion. This process fills interstitial spaces in the base metal with carbon atoms thus preventing boron atoms diffusing into the bulk. The diffusion of boron is least with rhenium as the base material due to its close packed hexagonal structure. Investigations of the poisoning characteristics shows there is a reasonable resistance to poisoning and an adequate cathode life if the temperature is kept below 1400 K. If a LaBs cathode becomes poisoned it can be reactivated by increasing the temperature for a short time. The time required to reactivate increases as the 9

P E Gear: The choice of cathode material in a hot cathode ionization gauge number and severity of poisonings increases varying from a few seconds for a new cathode to several minutes towards the end of its life. Ionization gauges using LaB6 have been constructed using both rhenium and tantalum as the base material.
8. Conclusions

Ionization gauges constructed with low temperature electron emitters are preferable to gauges constructed with tungsten cathodes. With relatively low operating temperatures of 1200-1500 K not only are gas-surface interactions reduced to a minimum but the gauges give a much more stable reading. For use in an uhv gauge a cathode should have a very low evaporation rate and a low operating temperature. Figure 7 shows the maximum emission density available from various

cathodes as a function of temperature.2 LaB6 has a high evaporation rate at temperatures above 1400 K and is not suitable for uhv use except where the emission density is kept below 10e4 A cmm2. Cathodes of Th02 on tungsten or iridium have reasonable emission efficiencies, low evaporation rates and are relatively unaffected by chemically active gases. ThOz on iridium has the advantage that it can be exposed to air when hot without damage. These factors make this cathode very popular, and many ionization gauges using Th02 on iridium cathodes are commercially available.

Acknowledgement

The author wishes to acknowledge the assistance given by the Rutherford Laboratory in the preparation of this article.

References

Filament

temperature.

OK

Figure 7. Maximum electronemissiondensityasa function of cathode

temperature for different cathode materials.

J H Leek, Pressure Measuremen/ in Vacuum SyssIems,Chapman and Hall Ltd, London (1964). 2 P A Redhead, J P Hobson and E V Kornelsen, The Physical Busis of Ultrahigh Vacuum, Chapman and Hall Ltd. London (I 967). 3 G Herrmann and S Wagener, The Oxide Coaled Cathode, Chapman and Hall (1951). 4 R 0 Jenkins, Vacuum, 19, 1969, 353. 5 J H Singleton,J C/iernPhys, 45, 1966, 2819. 6 J A Becker,E JBeckerand R G Brandes,J Appl Phys, 32, 1960,411. A E Dabin and R E Stickney,J Vat Sci Technol, 9, 1972, 1032. s T W Hickmott, J Appl Phyi, 31, 1960, 128. 9 L A Petermann and F A Baker, Br J Applphys, 16, 1965,487. I0 J G Werner and J H Lock, Vacuum, 19, 1969, 317. I D E Abey, J Appl Phys, 40, 1969, 284. I* S Datz. R E Minturn and E H Tavlor. J Aool Phvs. 31. 1960.880. I3 fi F Winters, D R Denison, D G Bil1sand.EE Donaldson, j Appl Phys, 34, 1963, 1810. I4 J W Ackley, C F Lothrop and W R Wheeler,9th An Vat Symp Am Vat Sot, Los Angeles(I 962). Is P A Redhead, Trans A. VS. Vat Symp, 7, 1960, 108. I6 M Pirani, Hecrrochem, 11, 1905, 555: * I Weissman.J Aool Phvs. 36. 1965.406. I8 G J Schulzand k V Phelps,Reu&i Instrum, 28, 1957, 1051. I9 R W Lawson, Br J Appl Phys, 18, 1967, 1763. 2oJ S Cleaves,J Sci Instrum, 44, 1967, 969. 2LJ D Buckingham, Er J Appl Phys, 16, 1965, 1821.

10