Debate – Discussion
Comment on ‘‘Ion-Assisted Processes of
Polymerization in Low-Pressure Plasmas’’
Riccardo d’Agostino,* Fabio Palumbo
1. Introduction
In the present issue of Plasma Pro-
cesses and Polymers (PPaP) appears
an interesting article by J. D. Whittle,
D. A. Steele, and R. D. Short, entitled
‘‘Reconciling the Physical and Chemi-
cal Environments of Plasma: A Com-
mentary on ‘‘Mechanisms of Plasma
Polymerization—Reviewed from a
Chemical Point of View’’. Although
our views regarding the role of positive
ions often differ from those expressed
in that article, we believe it has
important merits, namely to focus
the attention of plasma scientists
toward the ‘‘real’’ microscopic
mechanisms of plasma polymeriza-
tion, as opposed to general ‘‘overall’’
macroscopic kinetics approaches,[1–4]
which have stimulated discussions
among several leading experts[5–9]
with varying opinions. Another merit
is its indirect reminder that any low-
pressure plasma process, i.e., etching,
deposition or surface modification,
R. d’Agostino
Dipartimento di Chimica, Università degli
Studi di Bari, Aldo Moro, Via Orabona 4,
70126 Bari, Italy
E-mail: r.dagostino@chimica.uniba.it
R. d’Agostino, F. Palumbo
Consiglio Nazionale delle Ricerche,
Istituto di Metodologie Inorganiche e dei
Plasmi, Via Orabona 4, 70126 Bari, Italy
R. d’Agostino
Plasma Solutions, Spinoff of the
University of Bari, Via Orabona 4, 70126
Bari, Italy
Plasma Process. Polym. 2012, 9, 844–849
844 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
always involves plasma physics, in
particular the role of (positive) ions.
The article by Whittle et al. was
originally inspired by the featured
review paper entitled ‘‘Mechanisms
of Plasma Polymerization—Reviewed
from a Chemical Point of View’’
by J. Friedrich,[7] which primarily
explores plasma polymerization from
a chemist’s point of view. In contra-
distinction, Whittle et al. propose
positive ions as building blocks in
the deposition of plasma polymers;
let us at this early stage stress the
opposition between that latter view-
point and one which considers posi-
tive ions primarily as promoters and
initiators of the polymerization pro-
cess, which itself is based mainly on
neutral species (radicals).[10–13]
Whittle et al. further argue in terms
of a ‘‘physical’’ role of electrical poten-
tial distributions in the discharge as
driving forces that propel high mole-
cular weight ions, produced by ‘‘che-
mical’’ condensation reactions in the
plasma’s gas phase, toward the grow-
ing film’s surface. However, the
authors ignore important physical
effects of these heavy (or smaller) ions
when they impact upon the surface,
and their possible consequences on
the deposition mechanism. From this
latter point of view, the positions
expressed by Whittle et al. and by
Friedrich are not far apart.
We believe that a discussion of the
microscopic mechanism of plasma
polymerization, one particular aspect
wileyonlinelibrary.com
of microscopic plasma-surface inter-
action processes (etching, deposition,
and modification) in low pressure
discharges, deserves to be continued
even though it is currently not receiv-
ing much attention in the literature.
Mechanisms of etching and deposition
were developed in detail in 1980s and
1990s through contributions by many
groups:[13–18] in 1979, Coburn and
Winters[15] demonstrated (albeit
rather indirectly) the synergetic role
of positive ions and neutral radicals in
enhancing etch rates by orders of
magnitude. Their work, carried out in
the early 1980s, incited other workers
to reassess the role of positive ions
near the plasma edge in low-pressure
plasma processes.[16] However, since
that time, all plasma scientists have
come to accept the important role of
ions in etching and deposition pro-
cesses, not because ions directly ablate
a surface or produce a coating (because
their arrival rates at substrates would
be too small), but for initiating or
activating microscopic processes at
the surfaces where etching or deposi-
tion occur. The following attempts to
present a simplified picture:
(1) In a low-pressure reactor, positive
ions start to accelerate at the
plasma edge (inside the sheath);
when they strike the substrate
surface, they produce damage, for
example lattice disruptions, bond
breakage, creation of free radical
sites. All these damaged sites
DOI: 10.1002/ppap.201200072
Comment on Ion-Assisted Plasma Polymerization
increase the surface free energy,
resulting from momentum trans-
fer provided by ion collisions. This,
in turn, creates surface sites that
readily form bonds with physi-
cally adsorbed atoms or radicals
on the surface.
(2) The atoms or radicals diffusing to
the surface are first adsorbed;
then, when they reach an active
site, they form a chemical bond.
These are the first steps toward
forming a volatile etch product (in
ablation) or a polymer-like chain
(in deposition). Therefore, etching
and deposition have essentially
the same microscopic mechanism,
the only difference being the fate
of the formed compound: in the
former case, etching, it is a volatile
molecule, which desorbs from the
surface; in the latter case it is a
part of a polymer-like chain. So, in
general terms:
(1) S + I+ S*
Rgas Rads
Rads + S* polymer
Etching products
where S and R stand for ‘‘Surface
sites’’ and ‘‘Radical’’, respectively.
2. The Sheath
In low-pressure plasmas, electrons are
the species with the highest mobility;
in a matter of a few nanoseconds
they charge all exposed solid surfaces
negatively—reactor walls, electrodes,
immersed items at floating potential.
This results in a potential drop with
respect to the (positive) glow, a
reduced electron density in the
sheath and, consequently, an accelera-
tion of positive ions toward the solids’
walls. It is important to recall that
in MHz-driven glow discharges, i.e.,
at frequencies higher than the Ion
Plasma Process. Polym. 2012, 9, 844–849
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Transit Frequency, values of potentials
that drive the ions are averaged over
a voltage cycle. Furthermore, the
(average) potential drop depends on
the electrical connection (grounded
or powered), as well as on power,
pressure, and area of the electrode(s).
In all cases, the ion energies are
governed by the potential drops, and
they can range from a few eV to several
hundreds of eV, while their energy
inside plasma bulk is only a fraction of
an eV to a few eV, at most. Evidently,
therefore, the effective energy of
positive ions that strike the substrate
is related to the potential drop, but
it will also be strongly affected by
the numbers of collisions inside the
sheath, to be examined in the next
section. It is now also accepted that
the reactor’s architecture and certain
external parameters strongly affect
the potential drop: the areas, A, of
electrodes ‘‘1’’ and ‘‘2’’ are related to
their respective electrical potentials
as:[19]
V1 =V2 ¼ ðA2 =A1 Þn ;
where n is typically <4. Generally,
parallel-plate reactors are asym-
metric: grounded electrodes usually
being larger than powered ‘‘cath-
odes’’, the voltage drop at grounded
surfaces is smaller than at the
powered electrode. This effect can
be enhanced at low pressures,
p
50 mTorr, because by reducing p
the plasma volume will spill out
beyond the geometric volume of the
inter-electrode gap space. Basically,
the plasma often ‘‘brushes’’ the walls
(normally grounded), in such a way
that these should be taken into
account in the overall effective sur-
face area of grounded surfaces and
in considerations of the electrodes’
asymmetry. As a rule of thumb, the
voltage drop at the grounded elec-
trode (and substrates placed on it)
generally ranges between a few volts
and some tens of volts, while sub-
strates on the powered electrode can
experience several tens to some
hundreds of volts.
Positive ions are the only ones that
can reach the substrates, because
negative ions are driven back by the
potential drop in the sheath. The ions’
energy at the substrates can be very
high compared with that in the plasma
bulk; the value of their flux, Øþ, is:[20]
þ ¼ np ½ðkTe =mÞ=ð1 þ 2C0 Þ1=2;
where np is their density in the bulk
plasma, k the Boltzmann’s constant,
Te the electron temperature, m the
ion mass, and C0 is a dimensionless
(collision) number.
Whittle et al. refer to a plasma at
1 mTorr,[21] where they measured an
ion flux of 3  1018 m2  s1; they
state:
‘‘For the same plasma, this gives
a thermal flux of neutrals of
1.7  1021 molecules  m2  s1. There-
fore in terms of relative arrival rates,
the ratio of neutrals to ions is 560–
nearly twenty times greater than the
calculation on the basis of plasma
density. Data taken across a range of
pressures in argon plasma indicate that
this observation is repeated up to at
least 100 mT (at which point the sheath
becomes collisional), with the ratio of
measured neutral and ion flux around
10–20 times higher than values calcu-
lated on the basis of the plasma density
and under the assumption that the
fluxes are thermal’’
From that statement one would
deduce that:
(1) the ratio of the flux of neutrals to
ions is higher than that calculated
on the basis of thermal fluxes;
(2) even at 1 mTorr the flux of neu-
trals is about 600 times higher
than that of ions; at 100 mTorr,
a common pressure for plasma
polymerization experiments, the
sheath is already collisional.
3. Effects of Pressure
The most important effects of pres-
sure, p, in plasma systems have gen-
www.plasma-polymers.org 845

erally been well understood for some reactor has magnetic confinement
time: and can operate even below
1 mTorr.[23,24] Further, the ion
(1) p affects the energy delivered to energy is at a maximum; as a
molecules, according to the para- consequence, their physical effect
meter W/p; in rearranging structure of the
(2) p influences the collision frequency; depositing material can be impor-
(3) it induces expansion/contraction tant. Sputtering can be the domi-
of the plasma volume; nant process when the absorbed
(4) it determines the probability of power is raised. However, at low
many-body (bi- and tri-molecular) power, identifying ions as build-
reactions, e.g., recombination; ing blocks in polymerization reac-
(5) p governs the residence time. tions might not be unreason-
able—the view expressed by
Whittle et al. We can refer to this
Limiting one’s attention to how p regime as one of ionic processes.
may affect physical/chemical contri- (b) 70 < p < 350 mTorr, where the
butions to plasma polymerization [ions]/[neutrals] ratio decreases
mechanisms, one can readily envisage by orders of magnitude; here, in
that by raising p the ion density will fact, the degree of ionization
decrease and the energy that ions gain is generally considered to be
in the sheath will be greatly reduced. ca. 107–105. Under these condi-
Varying ion bombardment by chan- tions the flux of ions can definitely
ging p is qualitatively illustrated not be responsible for ablation of a
in Figure 1:[22] ion-induced damage solid, nor for deposition of thin
greatly increases by reducing p; films, no matter how high the
one may note three regimes (the value of sticking probability may
pressure limits are only approximate): be. However, positive ions can
markedly affect the rates of etch-
(a) p < 70 mTorr, is characterized by a ing/deposition processes, because
high [ions]/[neutrals] ratio. The they can activate the substrate, as
collision frequency is quite low, discussed in point (1) of the first
and the flux of ions can be section. This is the regime of ion-
appreciable compared with that assisted processes.
of neutrals (as also shown by (c) p > 350 mTorr, where [ions]/[neu-
Whittle et al.), particularly if the trals] ratios are very low and
Ion-induced damage(au)
ionic
processes
ion assisted
processes
pure chemical
processes
70 350 Pressure (mtorr)
Figure 1. Generalized view of ion-induced surface damage as a function of pressure in
plasma processing operations (deposition, etching, surface modification).
Plasma Process. Polym. 2012, 9, 844–849
846 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
R. d’Agostino, F. Palumbo
where the number of ion/neutral
collisions in the sheath becomes
so large as to nullify possible
surface activation by ions. This
is the purely chemical process
regime of deposition or etching.
To the best of our knowledge,
plasma polymerization is mostly car-
ried out at p > 70 mTorr. In order to
lend weight to this statement, we have
screened all related articles published
in Plasma Processes and Polymers (a
time interval that extends over almost
9 years) and have subdivided the data
by pressure ranges, see bar-graph in
Figure 2. We observe that among 77
papers dealing to varying extents
with plasma polymerization, roughly
two thirds describe processes at
p > 70 mTorr. Articles on powder
synthesis were not considered, nor
work at atmospheric pressure, nor a
few papers that do not clearly mention
the value of p under investigation.
It therefore would appear that the
experimental conditions utilized by
Whittle et al., in which ions could make
a massive contribution to the rate
of polymerization, are uncommon
indeed. This definitely can be consid-
ered as a merit of the paper, because it
contributes toward filling a gap in
the plasma polymerization literature.
However, certain arguments raised
there cannot be justified when dis-
cussing general aspects of the plasma
polymerization mechanism.
4. Ion-Assisted
Polymerization Processes
Most plasma polymerization work
is performed in the range of
70 < p < 350 mTorr, i.e., under condi-
tions of ion-assisted chemistry, as
suggested by Figure 2. Lower p-values
are generally avoided because deposi-
tion can be impractically slow, and
because the discharge volumes
expand—with glows that contact
DOI: 10.1002/ppap.201200072
Comment on Ion-Assisted Plasma Polymerization
35
Number of papers 30
25
20
15
10
5 similar reactor with a triode config-
0
P<70
Figure 2. Number of papers relating to plasma polymerization published in Plasma
Processes and Polymers; the total number, 77, has been subdivided according to the
operating pressure ranges used.
the vessel walls and render it difficult
to define the discharge region and the
exact electrical conditions that prevail.
When intermediate p-values are uti-
lized, ion-assisted polymerization pro-
cesses can become very important. The
first reports, at least to our knowledge,
were those of Vinogradov et al.[25] and
of Smolinsky and Vasile.[26] Shortly
thereafter, d’Agostino et al.[27,28] devel-
oped a model based on reaction
scheme (1), to which they gave the
name Activated Growth Model (AGM)
of polymerization. In that case the rate
of polymerization, rpol, was expressed
as:
 
rpol ¼ K Rg f ðIþ Þ; (2)
where f(Iþ) is a function of the energy
and flux of ions striking the surface.
Equation (2) predicts a rise in the rate
of polymerization with increased sub-
strate bias, provided that the radical
density, Rg, does not vary much with
experimental conditions. An impor-
tant confirmation of the AGM was
published by Fracassi et al.[14] They
utilized a diode RF reactor, equipped
with two extra electrodes on the sides
of the reactor. These were Quartz-
Crystal Microbalances, QCM, one
grounded and the other biased to
150 volts. It is important to note
that this bias of the small QCM
electrode was verified not to influence
the overall electrical conditions (e.g.,
Plasma Process. Polym. 2012, 9, 844–849
ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
70<P<350 P>350
range (mtorr)
power input) and the density of active
species. The experiments were run
with several feed gases (O2, CF4,
and C2F4) and gas mixtures, some of
which led to etching reactions
because they produced mainly F-
atoms or O-atoms, while others pro-
ducing mainly CFx-radicals led to
polymerizing reactions. Both rates,
of etching and polymerization
reactions, clearly increased in the
presence of bias, in agreement with
the AGM.
d’Agostino et al. developed a triode
reactor with a very small third elec-
trode in an aside position—smaller
than the reactor’s main cathode.[13]
This had the advantage of permitting
a negative substrate bias without
increasing the total input power and
without changing the density of active
species—monitored by emission spec-
troscopy in most cases. They measured
polymerization rates from a variety of
fluorinated feed gases and observed
the rate to increase with rising bias,
in most cases passing through a
maximum. Indeed, the expression for
polymerization rate must take into
account the fact that positive ion
bombardment triggers deposition,
but can also assist etching and even-
tually even sputtering,[29] as follows:
rpol ¼ Kp ½CFx f ðIþ Þ  Ke ½FgðIþ Þ
(3)
 Ks hðIþ Þ;
where Kp, Ke, and Ks represent the rate
constants of the ion-assisted polymer-
ization, etching, and sputtering pro-
cesses, respectively. Similarly, Favia
et al.[30] demonstrated that an AGM
mechanism can be useful in inter-
preting results obtained in plasma
deposition of tetramethylsilane: in a
uration they found the deposition
rate to reach a maximum when bias
voltage was increased independently
from other experimental parameters.
Energetic ions contributed to the
formation of active sites, enhancing
the growth of plasma polymer; how-
ever, raising the bias even further had
the effect of reducing the deposition
rate on account of competing etching
and sputtering processes.
5. Modulated (Pulsed)
Discharges
The case of pulsed plasma, whereby
CW power is chopped, deserves sepa-
rate comment. Plasma polymerization
in such cases can lead to extremely
high monomer structure retention.[31–36]
It has even been demonstrated that
plasma polymerization can take place
during the ‘‘Off’’ time-interval (for
certain precursors, even at higher
deposition rate), under conditions of
negligible (if not zero-) ion- and
electron bombardment. As a conse-
quence, the coating can grow almost
‘‘undisturbed’’ under these mild con-
ditions, compared with continuous
plasma ignition at the same nominal
power: in the latter case, impinging
ions re-arrange surface atoms, gener-
ally leading to a more cross-linked, less
‘‘conventional’’ structure. However,
during the ‘‘On’’ time-interval the
contribution of ions can be important
in creating active sites, where chemi-
sorption of radicals can also promote
growth of the coating.[32]
J. D. Whittle et al. commented that,
as demonstrated in some papers,[37,38]
positive and negative ions can survive
www.plasma-polymers.org 847

for several milliseconds during the
‘‘Off’’ period of pulsed plasma in
acrylic acid vapor. The notion that
stable macromolecular ions can form
inside the plasma and participate in
the deposition process appears reason-
able, but we do not believe that such
ions can play an important role during
the ‘‘Off’’ time interval, for the follow-
ing reasons: beside the low value of
ion density we already pointed out,
at the start of the ‘‘Off’’ period the
plasma sheath collapses, hence also
the driving force that propels positive
ions toward the growing coating’s
surface. This means that during that
‘‘Off’’ time any residual ions migrate
toward nearby solid surfaces primarily
by diffusion, and that their ‘‘physical’’
effects on film growth are no different
from those of neutral precursor spe-
cies. Furthermore, if heavy ions are
stable enough to survive for several
milliseconds, they are likely to be as
reactive as radicals. However, we fully
agree with the assertion of Whittle
et al. that in a pulsed plasma
stable heavy negative ions might
contribute to film formation, whereas
in CW plasma the presence of a sheath
potential tends to repel negative ions
from all solid surfaces.
6. Conclusion
In conclusion, we underline that the
present short contribution is not
intended to present any revolutionary
‘‘new’’ ideas about plasma process
mechanisms; instead, its objectives
have been (a) to highlight and con-
solidate certain documented facts
about physical effects of ions in
plasma polymerization; (b) to incite
workers in this field to seek new
experimental approaches designed
to advance understanding of these
issues. Finally, we salute Whittle
et al.’s initiative to draw attention to
potentially important roles of ions in
plasma polymerization mechanisms:
Plasma Process. Polym. 2012, 9, 844–849
848 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
although this topic is too often over-
looked, we nevertheless wish to stress
our viewpoint that ions mainly serve
as ‘‘activators’’ rather than as ‘‘build-
ing blocks’’ in plasma polymerization
reactions.
Acknowledgements: We are indebted to
Prof. Michael R. Wertheimer for the valu-
able discussions during the preparation of
this manuscript. Mariagrazia Troia is
thanked for her assistance in sifting
through the vast plasma polymerization
literature.
Received: May 15, 2012; Revised: June 12,
2012; Accepted: June 19, 2012; DOI:
10.1002/ppap.201200072
Keywords: activated growth model; ion-
assisted deposition; ion bombardment;
plasma polymerization
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