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Fluorocarbons are the most common feedstock gases used in etching
plasmas. However, perfluorinated gases (PFCs) have been found to be
detrimental to the environment and global climate, as most of the
compounds are strong greenhouse gases and ozone depleters. PFCs are
consumed only partially in the etching processes and the waste gases
are emitted into the atmosphere. They have an extremely high global
warming potential (up to four orders of magnitude higher than CO2)
and atmospheric lifetimes that are practically infinite on the
timescale of human life (see table below).

The global warming potential (GWP) depends upon infrared absorption and
time horizon (hold up time) in the atmosphere. It is defined as the
cumulative radiative forcing, or heating, integrated over a period of
time from the emission of a unit mass of gas relative to some reference
gas. Carbon dioxide (CO2) was chosen as this reference gas.
The Kyoto protocol on gas emissions requires the phasing out of the use
of CF4 C2F6 C3F8
and C4F8 as feedstock gases by 2010. Emission
reduction strategies have to combine both optimisation of plasma
equipment efficiency and search for the new plasma compounds. CF3I
, C2F4 and 1-C4F8 have been
proposed as new plasma reactants (Samukawa et al 1999). The first two
are of particular interest from the point of view of controlling the
composition of the CF2 and CF3 radicals in the
plasma (Mason et al 2003).
There is very little information, however, about how CFx
radicals interact with low energy electrons. Recent studies have shown
that the concentration of these radicals has a significant effect on
the behaviour of fluorocarbon plasmas (Chabert et al 2003) and that
these radicals also occur in significant concentrations in other
plasmas (Chabert et al 2001). CF3I and C2F4
have received special attention as new feedstock gases also because
they both have low global warming potential and short lifetimes (see
table). CFx radicals are highly reactive and experimental
studies on highly reactive radicals are extremely difficult. Ab initio
calculations are therefore crucial in providing data upon which the
necessary models can be based (Winstead and McKoy 2000).
| Species |
GWP100 |
GWP20 |
Lifetime |
| CO2 a |
1 |
1 |
50 - 200 |
| CF4 a |
6500 |
4400 |
50000 |
| C2F6 |
9200 |
6200 |
10000 |
| c-C4F8 d |
8700 |
- |
3200 |
| CF3I |
0.25 |
< 5 b |
< 0.006 b |
| C2F4 c |
0.07 |
0.021 |
0.005 |
GWP, calculated over 100 and 20 years time horizon, and atmospheric
lifetime (years) for the molecular species used in plasma etching of
silicon surfaces.
a From Gillenwater at. Al. (2002)
b From Solomon et al
c From Acerboni et al (2001)
d From IPCC (1996)
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