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N ST J Braithwaite 2000 Plasma Sources Sci. Technol. 9 517
N ST J Braithwaite 2000 Plasma Sources Sci. Technol. 9 517
ef−ast + A → eslower
−
+ A∗ and the electron is very likely to have a collision
− −
(cf equation (4) which has a factor of four to account for the
→ eslower +A +e .
+
size of the projectile atom). From equation (6), the frequency
(iii) Superelastic: a third class also needs to be anticipated— of encounters can be estimated for projectiles, electrons in
here there is more kinetic energy after the collision. this case, with a mean speed v̄
Momentum is conserved and internal energy in the
v = v̄ng σ. (11)
particles entering into a collision is transferred into
kinetic energy, e.g. The scaling of mean free path and frequency of collisions with
∗
Aslow + Bslow → Af aster + Bf aster . pressure, through ng , and energy, through v̄, are consistent
with intuition.
Detailed analysis of binary collisions reveals some useful In practice cross sections are not actually independent
general points. of energy, even for elastic collisions. High-energy electrons
• Lighter particles (m) cannot lose much energy elastically speed past so quickly that the chances of interacting with the
to heavier particles (M)—at best a fraction 2m/M, outer shell electrons on an atom are reduced. Also, at very low
nevertheless, substantial changes in momentum occur energy, quantum mechanics may prevail, taking an electron
(cf tennis). around an atom with a marked inability to interact over
• A moving particle on striking elastically a stationary a narrow range of energy—the so-called Ramsauer effect.
one of equal mass head-on can transfer all of its kinetic Figure 2 illustrates these features for argon, showing also
energy (cf billiards). inelastic cross sections. The simple hard sphere cross section
• Lighter particles can lose virtually all their kinetic energy is about 3 × 10−20 m2 .
through inelastic collisions with heavier objects (cf
sandblasting).
3. Characterizing plasmas
• Equal mass particles can lose no more than half their
kinetic energy inelastically on collision (cf ion impact 3.1. Similarities and differences
ionization).
• Binary collisions in which at least one particle is charged All plasmas have a number of features in common. For
may be dominated by long-range Coulomb forces. instance, they are composed of equal amounts of positive
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N St J Braithwaite
Table 4 gives some data on thermionic emission for Escape from the material is still subject to a statistical
various materials. The work function is sensitive to factor. Table 5 shows ionization energy data for a range
crystal orientation and purity. Richardson’s theory of gases; comparison with work function data in table 4
predicts a value for the constant A that is larger than shows that the threshold condition above is usually met
generally observed. even without taking account of the kinetic energy of
Photons are effective removers of electrons provided that incident ions. Neutralization of 10 or 100 eV ions
in practice seems to release secondary electrons with
hν > eφ almost equal effectiveness. Typical values are given
in table 6, in which γi records the effectiveness of
the excess energy being in the kinetic energy of emitted electron release being the average number of electrons
electrons. Data in table 4 indicate that ultraviolet (UV) per incident ion. High energy electron impact (100s of
radiation will give rise to photoemission whereas visible eV) is also effective in releasing electrons.
radiation (<3 eV) will not (λ (in µm)= 1.2/E (in eV)). (iii) Electric fields of around 108 V m−1 are enough to pull
Very energetic photons (e.g. x-rays) release inner shell electrons directly out of solids in measurable quantities.
electrons from the atoms and the spectrum of emitted This kind of field is most easily achieved around sharp
electrons gives a signature characteristic of the material features.
(cf the analytical technique ‘XPS’).
(ii) An important source of energy for electron emission
from surfaces at plasma boundaries is in the internal 4.2. Surface production of positive ions
energy of particles such as ions and excited states Bombardment by a stream of high-energy particles can lead
(especially the metastable ones). In the case of positive to the formation of positive ions on or near surfaces in
ions, recombination on a surface releases to that surface quantities useful for analytical purposes (cf SIMS). Hot
an amount of energy equivalent to that invested in the surfaces (2000 K) of high work function materials will ionize
ion’s production, namely eVi , the ionization energy. If low ionization energy atoms, some ions of the hot surface
the total ion energy exceeds twice the work function material would also be produced. At lower temperatures
of the surface 21 Mv 2 + eVi 2eφ then in addition (1200 K) metal ions can be derived thermionically from
to neutralization a secondary electron may be released. salts coated on filaments. None of these mechanisms is
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Introduction to gas discharges
Table 4. Thermionic emission data. The theoretical value of A is 4.3. Volume ionization (simultaneous electron and ion
1.2 × 106 . production)
Electrons
Material φ (eV) A (A m−2 K−2 ) (m−2 s−1 ) at 2000 K
Table 5 lists the energies necessary to remove an electron
from a range of gas atoms.
W 4.5 6.0 × 105 8.2 × 1019
BaO 3.4 2.5 × 104 1.7 × 1021 (i) Hot gas will ionize itself (effectively through kinetic
ThO2 2.9 1.6 × 102 2.0 × 1020 energy of the random motion of particles). Since 1 eV
Al2 O3 3.8 1.4 × 104 9.5 × 1019 is equivalent to a kinetic temperature of 11 000 K, one
Cu 4.4 6.5 × 105 1.4 × 1020 would not expect much thermal ionization below a few
Si 4.9 — —
thousand kelvin. This is the regime of high-pressure arcs
and thermal equilibrium,
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Introduction to gas discharges
A + e− → A− + hν
AB∗ + e− → A− + B
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Introduction to gas discharges
so
and the current density is given locally by φ (ne − ni )e
≈ .
j = nevd = neµE. L 2 ε0
Since in the plasma ne ∼ ni the potential changes only over
The structure of higher frequency discharges differs relatively large distances.
somewhat. Near the electrodes displacement current lessens As electrons and ions leave the quasi-neutral plasma,
the requirement for the physical action of the negative glow passing into the boundary sheath, a positive space charge
in maintaining the continuity of current at the negative must develop and the potential must fall, according to the
electrode. argument above. So, entering from the plasma
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N St J Braithwaite
for as heat, arriving at surfaces with the particle fluxes leaving where δ is the fraction of energy transferred in an elastic
the plasma collision (maximum 2m/M for electron gas collisions) and
ν is the frequency of collisions. This suggests that
Pin = ns cs (Te )Aeff [εc (Te ) + εs (Te ) + 2Te ].
(Te − Tg ) M eE
The energy contributions to the right-hand side are as follows. ≈ λ. (25)
Te m kTe
The first accounts for the average cost per electron for
producing one electron–ion pair (ionization energy plus So at low pressure, when mean free paths are relatively long,
an extra amount to account for losses in non-ionizing the electrons remain much hotter than the gas; conversely, at
collisions—the extra being less as Te increases). The second high pressures, thermal equilibrium can be approached.
relates to energy taken specifically by ions, accelerated in A crude estimate of the electric field in a self-sustaining
space charge boundary layers, and delivered to surfaces as plasma can be obtained by supposing that electrons travel
ions (and or fast neutrals). Axially this may be comparable their entire free path in the direction of the field and lose all
with the discharge voltage; radially it is dependent on the the energy gained in an optimum collision with the (cold) gas
boundary physics. The third term accounts for the drain on
the electron thermal energy. m kTe
Eλ ≈
So, rearranging, M e
Pin (which suggests a scaling of temperature with E/p, though
ns = . (23)
cs (Te )Aeff [εc (Te ) + εs (Te ) + 2Te ] this is not always the case in practice). This gives several
volts per centimetre at 1 Torr in argon. A better model would
This relationship suggests that the density of a discharge take proper account of the collision dynamics.
plasma can be expected to increase with input power and that
More complex scenarios occur in molecular gases and
the power can be used more effectively to obtain a denser
elsewhere when inelastic collisions play a significant part in
plasma if the electron temperature is higher (ionization is
the local energy balance.
more efficient so the term εc (Te ) is smaller) and, or, the
potential across boundary sheaths is lower (the term εs (Te )
is smaller). 6.6. Discharge structure II (Schottky—medium
pressure, 1-dimensional)
6.4. Steady state discharges (zero-dimensional model) Here the basic structure perpendicular to the direction of
II: temperature (assumed Maxwellian) current flow is quantified in a regime where electric fields and
At low to medium pressure, in simple discharge media, diffusion jointly determine the particle fluxes. The scenario
volume production balances surface loss. The particle is this. To ensure that volume-production equals wall-loss
balance therefore requires that an electric field must develop to drive ions out while slowing
the loss of electrons, that would otherwise be excessive. This
Kiz (Te )ng ne Veff = ns cs (Te )Aeff electric field acts in conjunction with the diffusion of particles
down gradients of density. One dimensional equations for the
where Kiz ng is effectively the ionization rate, νi discussed in ion and electron fluxes arising from the combined effects of
section 4 and ns cs (Te ) is the particle flux at the boundaries. diffusion and electric field driven drift are:
The term cs (Te ), is not strongly dependent on Te . So
∂ni
Kiz (Te ) 1 i = −Di + n i µi E (26)
= (24) ∂x
cs (Te ) ng L
∂ne
where geometric terms (including ne /ns , which is the ratio of e = −De − n e µe E (27)
∂x
average electron density to that at the boundary) are combined
to give L, the effective characteristic size of the system. This where Di , De are diffusion coefficients, for which values can
expression effectively sets Te for any given pressure (ng ) and be estimated.
geometry (L).
The rate constant for ionization, Kiz , is generally a strong 6.6.1. Ambipolar diffusion. In the plasma the charged
function of Te covering five orders of magnitude for argon particle densities are the same. The drag between energetic
over the range 1–10 eV; see figure 8. thermal electrons and the positive ions gives rise to an
effective diffusive loss of particles with positive and negative
6.5. Steady state discharges (zero-dimensional model) charges both leaving the volume at the same rate (ambipolar
III: electric field diffusion). The net diffusive flux is associated with a gradient
in the species density (ne = ni = n) and a hybrid diffusion
In a steady state dc discharge the electrons gain energy by coefficient that can be obtained by equating the fluxes and
moving through the electric field in the bulk of the plasma. eliminating the electric field from equations (27) and (28)
Energy is lost locally at the same rate to the background gas,
predominantly by elastic collisions. So, ∂n
= −Da
∂x
e2 E 2 3
eEvd = = δ k(Te − Tg )
mν 2 where Da is the ambipolar diffusion coefficient.
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