Thin Solid Films 520 (2012) 4219–4236

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Thin Solid Films

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Critical Review

Atmospheric plasmas for thin film deposition: A critical review

Delphine Merche, Nicolas Vandencasteele, François Reniers ⁎
Université Libre de Bruxelles, Faculty of Sciences, Analytical and Interfacial Chemistry Department, Avenue F. D. Roosevelt 50, B-1050 Brussels, Belgium

a r t i c l e i n f o a b s t r a c t

Available online 21 January 2012 An overview of the possibilities of atmospheric plasma for the deposition of inorganic and organic coatings is
presented. Some particularities of the atmospheric discharges and their consequences on the synthesis of
Keywords: films are presented and discussed.
Atmospheric plasma © 2012 Published by Elsevier B.V.
Deposition
APECVD
Organic coatings
Inorganic coatings
Hybrid coatings
Plasma-polymerization

Contents

1. Introduction and historical background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4219

2. Atmospheric pressure plasma for the deposition of coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4221
3. Basic facts about atmospheric plasmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4223
4. The pressure–distance constraint in atmospheric plasma . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4226
5. Coatings deposited by atmospheric plasmas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4226
6. Synthesis of hybrid coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4227
7. Co-deposition: organic sulfonated membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4227
8. Polymerization using atmospheric pressure plasmas: general mechanisms and experimental parameters. . . . . . . . . . . . . . . . . . . 4228
9. Effect of the power on coatings properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4229
10. Effect of the nature of the plasma gas and of the nature of the substrate material on the chemical structure of an organic coating . . . . . . . 4229
11. Post-discharge or “in discharge” plasma polymerization? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4230
12. Pulsed plasmas at atmospheric pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4230
13. Effect of the injection mode on the resulting chemistry of a coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4231
14. Comparison: coatings under vacuum/liquid/plasma. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4232
15. Deposition rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4233
16. Nucleation in the gas phase or at the gas substrate interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4234
17. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4234
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4234
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4234

1. Introduction and historical background
Plasmas, a word proposed by Langmuir [1], are often called the 4th
state of matter and represent 97% of the universe. A commonly accept-
ed definition is that a plasma is a partially or fully ionized gas. Although
at the beginning, plasmas were considered as a topic of fundamental re-
search for physicists; very quickly, the energy available in a plasma dis-
charge was thought to be useful for applications. In parallel, the
deposition of coatings has always been a technological and
⁎ Corresponding author.
E-mail address: freniers@ulb.ac.be (F. Reniers).
fundamental challenge for academia and industry. More specifically,
in order to modify the surface properties of a material, scientists have
developed many technologies to deposit the appropriate coatings on
essentially every substrate. The challenges are numerous: control of
the chemistry and structure of the layer, adhesion of the layer on a sub-
strate, deposition rate, geometric concerns, minimizing the energy
injected…. It was therefore normal that sooner or later, the energy
available in a plasma discharge was used to help depositing a coating.
In the first part of this introduction, we will briefly describe some
other major existing deposition techniques. We will then introduce
atmospheric plasmas, and basic concerns about plasmas in general,
while stressing the particularities of atmospheric plasmas.

0040-6090/$ – see front matter © 2012 Published by Elsevier B.V.

doi:10.1016/j.tsf.2012.01.026
4220 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
Fig. 1. « Historical » Siemens ozone process using the dielectric barrier discharge (DBD) tech-
nology, in 1857, extracted from Kogelschatz (above) [43]. Schema and picture of the Siemens
ozone process using DBD technology for water treatment (below) (from Kogelschatz) [43].
The core part of this paper will present a list of typical coatings
that can be deposited at atmospheric pressure, followed by some par-
ticular applications. Then, some specificities of atmospheric plasma
deposition will be presented and discussed.
Although the history of the deposition of thin films goes back to
the mid-20th century, where physical (PVD) and chemical vapor
(CVD) deposition techniques were developed, Michael Faraday was
using PVD to deposit coatings as far back as 1838 [2].
PVD is a variety of vacuum deposition technologies involving a
physical process to deposit thin coatings by the condensation of a va-
porized form (transportable vapor) of a solid precursor. There are dif-
ferent variants of PVD, including cathodic arc deposition, electron
beam, thermal evaporation deposition (where the material to be de-
posited, often a metal, is heated to a high vapor pressure by electrical-
ly resistive heating in “low” vacuum), pulsed laser deposition, and
sputter deposition, this latter using a glow discharge plasma.
Glow discharge DC sputtering technique has been used to deposit
conductive (mostly metals and alloys) films on substrates, from the
ion bombardment of a metal target. By heating the substrate, and
carefully controlling the deposition conditions (mostly the deposition
rate), one could obtain dense films, sometimes crystalline and epitax-
ially grown [3–6]. The radio frequency (RF) sputtering technique was
used to deposit films from a sputtered non-conductive target.
Variations of these techniques were realized by introducing a re-
active gas in the previously inert atmosphere (reactive sputtering).
Fig. 2. Number of hits in “ISI web of knowledge” for the words “atmospheric plasma”
and “deposition or coatings”, as recorded in December 2011.
Fig. 3. General setup of an industrial in-line atmospheric plasma deposition system.
In such conditions, one could deposit carbides [7–11], nitrides
[11–14] and oxides [14–19]. Typical operating conditions for the de-
position of hard coatings (such as CrN) are a vacuum ranging from
10 2 to 10 − 1 Pa in a background of inert gas (such as Ar), in the pres-
ence of nitrogen. Typical cathode voltages are in the range of 1 to 4 kV.
Being non-equilibrium deposition conditions, metastable phase
thin films can be deposited by such techniques.
These PVD deposition techniques had, however, some major draw-
backs; namely, a low deposition rate, in the range of 1 nm/s, the require-
ment of a clean low pressure background vacuum, combined with a
relatively “high” working pressure from 1 Pa up to 100 Pa necessary to
sustain a stable and intense glow discharge, and the use of high quality
sputtering targets. Subsequent annealing time was also a major issue.
In order to circumvent the low deposition rate problem, (reactive)
magnetron sputtering technique has been developed. By the addition
of magnets to the cathode, the trapping of the electrons just above it
was greatly increased, leading to a much higher ionization yield. As a
consequence, the sputtering rate of the target is much higher, and the
discharge voltage lower (~500 V) [20].
Using magnetron sputtering, typical deposition rates for metals of
10–100 nm/s and more can be achieved. Moreover, magnetron sput-
tering operates at lower pressure than the conventional diode
discharge (typically 10 − 2 Pa), which leads to higher purity final coat-
ings. By adding a reactive gas to the discharge, one can also deposit
complex compounds such as oxides and mixed compounds starting
from a simple metal target [21,22]. The use of two cathodes can lead
to co-deposition [23]. A great amount of research has been done in
(reactive) magnetron sputtering and this technique has now left the
laboratory scale for big industrial plants. One of the major drawbacks
of the magnetron sputtering technique is the possible poisoning of the
cathode when operating in the reactive mode. The poisoning of the
cathode occurs when the cathode surface is chemically modified by
the reactive gas present in the plasma. This can lead to changes of the
film stoichiometry, and decrease of the deposition rate.
DC, RF, and magnetron sputtering operate in low pressure condi-
tions, making their industrial scaling a technological challenge when
large substrates have to be coated. As this paper is not dedicated to
these techniques, we refer to the literature for more information
[24–27]. However, coatings obtained using these techniques can be
Fig. 4. Classification of plasmas in terms of density and energy for different Debye
lengths (λD) [55].
 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
Fig. 5. Evolution of the temperature of the electrons (Te) and the heavy particles (Tg) as
a function of the total pressure in the plasma.
of superior quality, showing excellent crystallinity and purity. The re-
active magnetron technique is widely used in industry these days.
In chemical vapor deposition, the gaseous precursor (or vapor of a liq-
uid carried by gas) reacts with another molecule in the gas phase, most
often at high temperature, or with the heated substrate to create the mol-
ecule of interest that will deposit to form the coating. Typical examples
are carbon nanotubes [28], ZnO [29–31], diamond [32–34], TiO2[35,36],
and SnO2[37,38]. Chemical vapor deposition is an easy to operate tech-
nique that does not require complicated setup. However, thermal con-
straints are often a disadvantage (energy cost to heat the gas phase,
difficulty to deposit onto low melting point polymers…). For example,
in a study by Chakraborty [39] on the growth of diamond nanoparticles
by CVD, the substrate is heated to 1100 K. For the deposition of SnO2
films, substrates are heated to several hundred K [37,38]. ZnO and SnO2
are transparent conductors, they can be used in solar cell and as transpar-
ent electrodes in displays which explains their growing popularity these
last few years. For more information we refer to the literature [40,41].
In PECVD (Plasma Enhanced Chemical Vapor Deposition), like in
CVD process, the precursor is introduced to the reaction chamber in
the gaseous state. The assistance of the plasma reactive media for
the dissociation of the precursor allows the process to proceed at
much lower temperatures compared to CVD, in which the gas and
surface reactions occur by thermal activation. Most of the PECVD pro-
cesses (organic or inorganic) are conducted at low pressure in order
to stabilize the discharge plasma by increasing the mean free path
of the plasma species. But recently, there has been increasing interest
to operate these technologies under atmospheric pressure. This paper
will focus specifically on “atmospheric pressure plasma enhanced (or
assisted) chemical vapor deposition”.
Fig. 6. Schematic illustrations of a discharge current as a function of the duration of the
discharge.
4221
Fig. 7. A few example schemes for dielectric barrier discharge set up [43].
2. Atmospheric pressure plasma for the deposition of coatings
The purpose of this paper is not to give an extensive list of every
coating that can be deposited using atmospheric plasma. We will
only present selected examples where the effect of the plasma pa-
rameters (pressure, gas, frequency…) have been studied. Similarly,
our goal is also certainly not to give a full description of the atmo-
spheric plasma technology, as it has already been reported elsewhere.
For instance, Tendero et al. [42] presented a full review about atmo-
spheric plasmas and their applications in 2006, Kogelschatz [43] fo-
cused on presenting the dielectric barrier discharges (DBDs) and
their applications in a review paper. Bogaerts, in 2002 [44], published
a nice review about gas discharges and their applications, describing
the different low and high pressure plasma systems. Napartovitch
presented an overview of atmospheric-pressure discharges produc-
ing non-thermal plasmas [45]. In 2010, Bárdos [46] presented a re-
view of the cold atmospheric plasma sources, processes, and
applications and, in 2011, Pappas published a paper entitled “Status
and potential of atmospheric plasma processing of materials” [47]. Al-
though, all of these reviews present the deposition process as one of
the applications, none of them focus specifically on this item, and
on the particularities of atmospheric plasma on the resulting coating,
which will be the topic of this review.
Although the use of atmospheric plasmas discharges has expand-
ed enormously since the late 1990s, atmospheric plasmas have been
known for a long time already. Indeed the "Siemens ozone process"
(for the generation of ozone from air or oxygen) was developed in
1857 [48]. A schematic picture of the instrument is presented in Fig. 1.
Although the topic of this review is to discuss the recent develop-
ments in atmospheric plasma deposition of coatings, the use of atmo-
spheric pressure discharges to deposit materials is not new. The first
experiments were reported in 1796 [49] followed by many others in
the late 19th century [50]. But recent advancements in technology,
characterization of the film [51,52] and the plasma [53], as well as im-
provement of the electrical generators [54] have opened new hori-
zons for these techniques, thus renewing the interest of the
scientific community. Therefore, in recent years, researchers have
been able to transfer the knowledge developed for film deposition
at low pressure to atmospheric pressure systems. There is an obvious
pragmatic interest in the wish to develop atmospheric plasma as a
coating technology, or as a technology to assist coating. Similar to
vacuum plasma techniques, they allow avoidance of the use of
Fig. 8. Schematic of an atmospheric RF discharge used for the deposition of SiO2 (from
Babayan) [60].
4222 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236

Fig. 9. Comparison of current (red)–voltage (blue) curves for a pure He DBD discharge, and He discharge with 2% and 10% O2 with both electrodes covered with a dielectric, and for a
100% O2 discharge with one electrode not covered with a dielectric [74].

organic solvents (often not environmentally friendly), and they have
a relatively good energetic yield (at least for the cold atmospheric
plasma, where only the electrons are energetic). Moreover, contrary
to vacuum plasmas, atmospheric plasmas avoid the use of expensive
pumping systems, the building of complex transfer chambers from
air to vacuum and vice versa, with a high pressure gap. The plasma
parameters, such as current, power, gas flow and composition, and
voltage, are relatively easy to control. They can therefore easily be
implemented on an industrial line, provided the reaction mechanisms
are well understood.
This domain of research is indeed strongly growing, as a review
of the literature shows in Fig. 2. This graph shows the number of
hits in the ISI web of knowledge for the combined words in topics
“atmospheric plasma” and “deposition” or “coatings”. The trend is
clear.
Interestingly, one should add that more than 500 patents have
been deposited on this very specific subject (based on an “espacenet”
search, with the items “atmospheric plasma” and “coating”), indicat-
ing that there is a huge demand from the industrial world. We stress
that for both of these analyses (papers published and patents), we
 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236 4223

Table 1 equilibrium. Indeed, a decrease in the electron mean free path with
Bond energies of various species commonly encountered [75]. a corresponding increase in pressure will result in an increase of the
Bond or gas molecule Bond or dissociation energy (eV) number of collisions (including elastic collisions). This will, in turn,
lead to a heating of the gas, as represented in Fig. 5.
C\C 3.65
C_C 6.35 An arc plasma is a typical example of an LTE plasma. In order to
C\H 4.3 avoid reaching this state, a common approach is to reduce the num-
C\O 3.74 ber of collisions by limiting the time of the discharge (i.e. limiting
C_O 7.78
the time during which the electrons are accelerated by the electric
C\F 5.35
H2 4.5 field in a single direction), as shown in Fig. 6.
N2 9.8 The technical tricks to avoid arcs are well known in the atmo-
O2 5.1 spheric plasma community today. They consist in applying pulses to
the electrodes (pulsed voltage, AC or DC), by alternating the polarities
of the electrodes with a high frequency generator, and/or by placing
at least one dielectric material between the electrodes. The effect of
the dielectric is to provoke an accumulation of electrons at one elec-
restricted the search to the above mentioned words, neglecting all
trode, decreasing the apparent voltage difference between the elec-
other related expressions.
trodes, which, in turn, decreases the electric field responsible for the
This paper will discuss the current state of the art, and emphasize
acceleration of the electrons and the subsequent collisions. Such
the particularities and the challenges present in the plasma deposi-
plasmas are called dielectric barrier discharges (DBD) and they are
tion of materials using cold atmospheric plasma. Indeed, one of the
used nowadays in most applications for plasma deposition. A sche-
advantages of cold atmospheric plasmas is that they can be applied
matic of a DBD is presented in Fig. 7.
to any kind of substrate: from steel or glass, to highly temperature
Other atmospheric plasma technologies developed for the deposi-
sensitive materials such as plastics, or even textiles [55].
tion of coatings are capacitive radiofrequency discharges [60] or mi-
If atmospheric plasmas can be used for plasma polymerization
crowave plasmas [61]. A schematic of a capacitive RF discharge is
(or plasma synthesis of coatings), they can also be used to help
presented in Fig. 8. More general information about plasma can be
the adherence of the coating on the substrate through plasma acti-
found in these text books [59,62–64].
vation [56–58]. The substrate can be a metal, a polymer or an inor-
Kurosawa et al. [65–67] have developed micro-discharges for
ganic substrate, such as glass or silicon, or even textiles. In an in-line
micro-plasma polymerization, which are obtained by a very high fre-
system, they can even be combined, as represented in Fig. 3.
quency (438 MHz) micro-plasma jet machine at atmospheric pres-
sure (in a thin quartz capillary, 1.5 mm in diameter). They used the
3. Basic facts about atmospheric plasmas micro-discharges for the local synthesis of very thin plasma
polymerized-PS coatings for bio-sensors and chemical-sensors (with-
Since a plasma is defined as a partly or totally ionized gas, an out masks) applications. The automation of the micro-plasma jet ma-
atmospheric plasma refers to such media developed at ambient chine allows patterns to be drawn (line art painting).
pressure. In some cases, the word atmospheric is replaced by By using plasma gases (i.e., noble gases like He and Ar, or N2, or
“high pressure” plasma, which, to our opinion may be confusing air), it is possible to obtain glow and filamentary (streamers) dis-
as some plasmas used in physics are really at high pressure (hun- charges at atmospheric pressure. Despite its name, the glow dis-
dreds of bars). Other terms used are “atmospheric glow discharge”, charge will never be perfectly homogeneous, such as a low pressure
or “atmospheric plasma jet”. glow discharge, except for the case of pure helium. For this reason,
The literature often refers to the temperature of the plasma. This helium is usually preferred for fundamental laboratory studies. More-
term is ambiguous, as plasmas are composed of neutrals, ions, and over, it obviously does not react to make secondary products, contrar-
electrons, each of them having a different temperature. A more rig- y to less noble gases such as nitrogen. The homogeneity of the He
orous separation would deal with the plasma at local thermal equi- discharge is due to the existence of its high energy metastables
librium – LTE (where all species are, on average, at the same (19.82 eV for 2 3S and 20.62 eV for 2 1S) [68,69]. The helium 2 3S
temperature), and with the plasma at non local thermal equilibrium – state has a lifetime of 7900 s [70].
non-LTE (where the temperatures of the “heavy” particles, neutrals
and ions, is much lower than the temperature of the electrons). The
electron density in LTE plasma is high, in the range of 1021–1026 m − 3,
whereas the electron density in non-LTE plasma is lower than
1019 m − 3. In this electrified gas phase, the species that are the most
influenced by the electric field are the electrons, as they are charged
and have a mass considerably lower than those of neutrals and ions
(often referred to as the “heavy” particles). Consequently, the vector
for the energy transfer in the plasma is the electrons. Electrons can
cause inelastic and elastic collisions with the heavy particles. The inelas-
tic collisions will create the plasma reactive species and are responsible
for the plasma chemistry, whereas the elastic collisions will be respon-
sible for heating the heavy particles. Because of the difference in elec-
tron density, there are much fewer elastic collisions in non-LTE
plasma, which inhibits the heating of the gas.
The different plasma types are usually classified as in Fig. 4.
The discussion about temperature and plasma classification pre-
sented above are, of course, valid for all plasmas, low or high pressure,
cold or hot. Fig. 10. Typical breakdown voltage curves for different gases between two parallel
However, a particularity that must be stressed is that, under nor- plate electrodes. p = pressure and d = electrode separation.
mal conditions, at atmospheric pressure plasma should be at thermal Data taken from [76].
4224 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236

Table 2
List of thin film deposited by atmospheric plasma.

Coating Technology Precursor(s) used Remark Reference

SiO2 DBD HMDSO/N2 + N2O From pure SiO2 to SiOxCyHz depending Massines [70]
on HMDSO/N2O ratio.
SiO2 DBD HMDSO/Ar or Ar + air Faster in Ar, but carbon contaminated. Morent [86]
Slower with Ar + air, but SiO2.
SiO2 DBD HMDSO/N2 + Air (+O2) or controlled N2 Evidence of the oxygen role in the open Zhu [98]
atmosphere air reactor.
SiO2 DBD HMDSO or BTSE/Ar or Ar + O2 Evidence of the covalent bond between Batan [84]
the surface and the SiOx coating.
SiO2 RF capacitive torch HMDSO, TMDSO, HMDSN, TMCTS, TEOS/ Glass coatings on plastics without carbon Moravej [85]
He + 2% O2 contamination.
SiO2 Atmospheric pressure TEOS/He + O2 Substrate temperature from 388 K to Babayan [60]
plasma jet 623 K. Comparable properties (FTIRa,
capacitance) to those of thermally grown
SiO2 films at 1173 K.
SiO2 Atmospheric microplasma HMDSO/Ar At low flow rate (b 0.1 sccm), no carbon Raballand [99]
jet contamination. At higher flow rate, 21% C
contamination. O2 not necessary to
obtain inorganic films.
TiO2 DBD TiCl4/N2O Deposition under a wide range of Zhang [91]
working pressure (200 Pa to atmospheric
pressure). Higher photocatalytic activity
for films deposited under atmospheric
pressure.
TiO2 Single and multi plasma jet Titanium (IV) diisopropoxide bis(2,2,6,6- Influence of the substrate (quartz, Si, Ni) Kment [90]
tetramethyl-3,5-heptanedionate [Ti(O-i- on the physical properties of the layers.
Pr)2(thd)2]/He + N2 + OESb.
SnOx DBD Monobutyltin trichloride C4H9SnCl3 SnOx deposited from MBTC are soluble in Korotkov [100]
(MBCT) or Tetrabutyltin C16H36Sn (TBT)/ water, contrary to those deposited from
air TBT precursors. Amorphous coatings
with small concentrations of SnO2, SnO,
and Sn crystalline phases.
CeOx RF plasma jet Cerium acetate (CH3COOH)3Ce in H2O CeOx films contaminated by carbon. Soukup [101]
spray
SiNx RF capacitive torch SiH4/N2/He Substrate temperature ranging from Moravej [85]
373 K to 773 K.
Fluoroalkyl silanes RF capacitive torch C8F17C2H2Si(OC2H5)3 (l)/He + N2 Precursor dissolved in isooctane and Barankin [102]
spun onto the substrate before the
atmospheric plasma exposition.
DLC (Diamond-like carbon) RF capacitive torch Acetylene/H2/He Deposition rates ~ 0.10 μm/min at Ladwig [97]
substrate temperatures ~ 473 K. Solid 13 C
NMRc study.
DLC DBD Methane or acetylene/H2 Coatings are close to those ones obtained Bugaev [96]
by PECVD at low pressure (b 10 Torr).
Carbon nanotubes Atmospheric pressure Acetylene/He Vertical growth of CNT on metal nuclei Lee et Overzet et
plasma jet (Fe, Ni). al. [95]
CxHy(Oz) DBD Ethylene, Ethylene oxide, Propylene/Ar Appearance and chemical structure Goossens [103]
or He different if deposited in Ar or He.
CxHy DBD Acetylene Morphology and deposition rates versus Jiang [104]
discharge mode (diffuse-filamentary-
corona).
PS (Polystyrene) DBD and RF capacitive Styrene/Ar or He Films of better quality with the DBD. Merche [105]
torch Influence of the carrier gas on the
chemical structure.
PEG (Polyethylene glycol) RF capacitive torch Tetraethylene glycol dimethyl ether Low power necessary to maintain the Nisol [106]
(tetraglyme) vapor or aerosol/Ar ether (C\O\C) functionalities for
biocompatibility (if vapor precursor).
PEG (Polyethylene glycol) Tetraethylene glycol dimethyl ether Control of the monomer fragmentation Da Ponte [107]
(tetraglyme) aerosol/He by controlling the plasma power and the
gas feed.
PMMA (polymethyl methacrylate) DBD MMA/He Study of the deposition rate. De Geyter [93]
PAA (polyacrylic acid) DBD AA (acrylic acid)/He IR/UV–vis spectrometry. Topala [94]
DBD (+EHDA — AA (acrylic acid) New spray method. Tatoulian [108]
electrohydro dynamic
atomization)
PTFE-like DBD and HF torch CxFyAz (with A : heteroatom) + He or Ar CF2 fingerprint in XPSd + 110° contact Reniers [109]
angle.
PTFE-like DBD C3F6/He or C3F8/He + H2 For C3F6/He mixtures, the ratio F/C ~ 1.5, Fanelli [110]
whereas for C3F8/He + H2, the ratio
ranged from 0.6 to 1.5 depending of the
H2 gas feed. Variation of the cross-linking
and the polymerization rates with the
hydrogen feed.
PTFE-like DBD CF4, C2F6, C2H2F4, C3F8, C3HF7 and c-C4F8/ Correlation between the plasma Vinogradov [111]
Ar + N2 or air diagnostic (OESb, OASe) and the films
properties.
 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236 4225

Table 2 (continued)
Coating Technology Precursor(s) used Remark Reference

PVDC-like DBD C4Cl6 or C2H2Cl4 Ratio Cl/C ~ 1. C\Cl and C\Cl2 bonds Hubert [112]
observed by XPSd.
Poly-pyrrole DBD C4H5N/He Coatings were significantly different Heyse [113]
from those deposited in vacuum plasmas.
Sulfonated-PS DBD C8H8 + CF3SO3H/Ar or He Good preservation of the sulfonic acid Merche [114]
groups grafted inside the entire
membrane.
a
Fourier Transform Infrared Spectroscopy.
b
Optical Emission spectroscopy.
c
Nuclear Magnetic Resonance.
d
X-ray photoelectron spectroscopy.
e
Optical absorption spectroscopy.

The metastable states of helium can be reached by collision with
energetic electrons:
− þ −
He þ e →He þ 2e
−  −
He þ e →He þ e
 þ −
2He →He2 þ e
 
He þ 2He→He2 þ He:
Where the He* is the 2 3S1 state, with a potential energy of
19.82 eV and the He2* molecular metastable has an energy of 18–
19 eV. These high energy states cannot return to the ground state
by direct photoemission, they usually do so by transfer of energy by
collision.
For other applications, argon is an alternative of choice, as it also
possesses high-energy metastable states (11.5 eV for ( 3P2) and
11.7 eV for ( 3P0) [71,72]). Argon metastables have a shorter lifetime
than helium, but the availability of argon makes it much more inter-
esting for industrial applications, although it is more difficult to ob-
tain a homogeneous discharge with Ar.
The existence of neutral metastable states is of huge importance
for the homogeneity of the discharge. Indeed, these atoms, being
formed in a microchannel in the discharge, are not sensitive to the
electric field and they can travel freely in the plasma. They can
later decay by a collision generating a new electron that will in
turn induce ionization. This homogenization effect is of enormous
importance for the deposition of coatings, as it insures a good distri-
bution of the energy within the entire discharge. The effect is not
observed in air and with corona discharges for instance. A good ho-
mogeneity of the discharge will help to obtain, in turn, a homoge-
neous coating. Moreover the existence of metastables, and the
presence of other excited species of the plasma gas will induce a
major difference between the deposition mechanisms of coatings
at atmospheric pressure and those at low pressure: the metastables
and the other excited species can collide with precursor molecules,
ð1Þ to initiate the nucleation and growth mechanisms, such as electrons
are doing at low pressure.
ð2Þ The following equations show the typical Penning effect of a meta-
stable (M*) on a diatomic molecule (A2):
ð3Þ
 þ −
M þ A2 →M þ A2 þ e ð5Þ
ð4Þ
 þ −
M þ A2 →M þ A þ A þ e : ð6Þ
To illustrate the change in homogeneity of a discharge with the
gas composition and the electrode nature, Fig. 9 shows the evolution
of the current–voltage curves for a DBD with 2 dielectrics and filled
with pure He and contaminated with up to 10% oxygen. The last
curve shows results of a 100% O2 discharge with only one electrode
covered with a dielectric. One can clearly see the changes in the ho-
mogeneity of the discharge both in the images and in the current
vs. time curves. A filamentary discharge yields multiple and very
short current pulses (one for each streamer), while a homogeneous
glow discharge has only one large current peak per half period of
voltage, like for pure He. The other discharges are filamentary (even
if they look homogeneous by eye). The oxygen discharge is a fully fil-
amentary discharge.
The proportion of impurities plays an important role because it
controls the density of metastables species at the time of discharge ig-
nition. Oxygen (like N2) disturbs the discharge by quenching the He
metastables which stabilize the discharge [73]. The presence of two
dielectrics (instead of one in the case of pure oxygen) also contributes
to render the discharge more homogeneous.
Most chemical bonds can be broken by these metastable neutral
atoms. One should also mention that O2 and N2 also present metasta-
ble states, but they are of lower energy and/or lower lifetime. Table 1

Fig. 11. Commonly used monomers for the deposition of SiO2 coatings. With TMCTS = tetramethylcyclotetrasiloxane, HMDSO = hexamethyldisiloxane, HMDSN = hexamethyl-
disilazane, TEOS = tetraethoxysilane, and TMDSO = tetramethyldisiloxane.
4226 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
Fig. 12. (a) Secondary Electron Microscopy (SEM) image of a well-aligned Multiwall Carbon nanotubes (MWCNT) forest on an Fe film with the Atmospheric Pressure Plasma Jet
(APPJ) off (inset, high resolution SEM image), and (b) SEM image of a well-aligned MWCNT forest on an Fe film with the APPJ on (inset, high resolution SEM image) [95].
gives the bond energy (or dissociation energy) for a few bonds or
gases.
4. The pressure–distance constraint in atmospheric plasma
One of the major drawbacks of atmospheric plasma is the very
strong dependence of the voltage that one should apply to the elec-
trodes with the pressure and the distance, as shown in Fig. 10.
This is expressed by the Paschen law:
Bpd
V breakdown ¼ ð7Þ
C þ lnðp  dÞ
With:
d inter-electrode spacing
p pressure
B and C constants depending of the nature of the gas and the elec-
trode material.
Eq. (7) and Fig. 10 show that the breakdown voltage strongly de-
pends on the nature of the plasma gas, and on the inter-electrode
spacing, the pressure being fixed when operating at atmospheric
pressure. This limits the geometry that can be used in plasma reac-
tors, as the inter-electrode spacing must remain small, typically in
the range of a few mm, in order to avoid elevated breakdown volt-
ages. It also reveals that the use of air is generally not recommended
if one wants to reduce energy consumption, as its breakdown voltage
Fig. 13. Schematic of the DBD system used for the deposition of plasma polymerized
sulfonated polystyrene [114].
is considerably higher than that of noble gases, for example. This is
another reason why many studies dealing with atmospheric plasmas
are realized with a noble gas, whether for surface activation or PECVD
of inorganic or organic coatings (plasma-polymerization). These lim-
itations have also contributed to the development of post-discharge
deposition processes, where the substrate can be placed further
away, and does not have to be inserted in the tiny inter-electrode gap.
5. Coatings deposited by atmospheric plasmas
Table 2 presents a non-exhaustive list of coatings that were depos-
ited using atmospheric plasma technology. The choice of these coat-
ings is mostly dictated by the industrial applications. The first
column identifies the coating obtained, and the second describes
the technology used (mostly DBD). The third column lists the most
important results of the paper.
For inorganic coatings, silicon oxide coatings are certainly the
most studied. Indeed, silica — like coatings are of great industrial in-
terest, as silicon oxide layers have many valuable chemical, thermal,
and optical properties such as being a good permeation barrier to
gas diffusion (when dense enough) and good wettability (when cov-
ered by silanol groups). They can also be used in the fabrication of
photovoltaic solar cells, as layers resisting corrosion, and in precision
engineering (aeronautical and automotive). These coatings can be de-
posited by magnetron sputtering [77–79], chemical vapor deposition
[80–82], and now by atmospheric plasma [70,83–86]. In all these
techniques, a precursor monomer is used and reacts with oxygen in
the gas phase. The most frequently used monomers are presented in
Fig. 11.
All these precursors are characterized by their symmetrical chem-
ical structure which results in a low enthalpy of vaporization (be-
cause of the weak intermolecular interactions) and by the fact that
they all contain silicon already bonded to oxygen, except for
Fig. 14. Yasuda's mechanism for plasma polymerization at low pressure [120].
 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
Fig. 15. Schematic comparison between conventional polymers and plasma polymers
[125].
HMDSN. For all these precursors, like for low pressure deposition and
for CVD, oxygen must be added in the reacting plasma phase to reach
the stoichiometric SiO2 composition and to efficiently remove the
remaining carbonaceous contaminants.
Amongst them, HMDSO and TEOS are the most popular nowadays.
In atmospheric plasma, the main parameters to be controlled are the
relative ratios among the monomer flux, the oxygen flux, and the
electron density.
Titanium oxide is also a coating bringing more and more interest,
as the anatase and rutile phases are widely used for photocatalysts,
chemical sensors, solar cells, dielectric materials, etc. More generally,
TiO2 coatings can exhibit self-cleaning properties, present an antibac-
terial effect, and are superhydrophilic. They can already be easily pre-
pared by CVD or by magnetron sputtering and a few studies report
their preparation by cold plasmas [87,88].
Nie et al. [89] managed to synthesize nanocrystalline anatase TiO2
using TiCl4 and O2 as precursors by atmospheric cold plasmas in a
DBD without extra heating or thermal treatment. Only one phase, an-
atase (with a nanocrystal size about 10–15 nm), was observed by the
means of X-Ray Diffraction (XRD), High Resolution Transmission
Electron Microscopy (HRTEM), and SAED (Selected Area Electron Dif-
fraction) measurements.
Fig. 16. CAP-model for plasma-polymerization [124].
4227
TiO2 was also deposited using an atmospheric plasma torch [90],
and by a DBD discharge [91].
Matsumoto [92] deposited silicon nitride coatings by dielectric
barrier discharge starting from silane, nitrogen, and hydrogen. They
present optical applications (as for the fabrication photovoltaic fuel
cells), and excellent barrier properties; they are also used for the fab-
rication of electronic components.
For organic coatings, acrylates are similarly very popular. Coatings
issued from acrylates can be used in a large domain of applications, as
resistant layers to electron beams, membranes for gas separation, hu-
midity sensors, optical components, etc. [93,94], and they are often
the starting point for the post-deposition of other materials, due to
their good adhesion properties.
More exotic coatings like nanotube forests [95] as shown in
Fig. 12, or diamond-like carbon (DLC) are nowadays also deposited
by atmospheric plasma [96,97]. The DLC coatings (doped or not)
deposited on a variety of industrial components (on metals, glasses,
ceramics, plastics) provide protection due to their high hardness,
and can be used as electrical passivation layers.
6. Synthesis of hybrid coatings
The possibility to work at atmospheric pressure makes it easier
also to combine two precursors in different phases (liquid or gas +
solid). Atmospheric plasmas can also be used easily to synthesize hy-
brid multifunctional inorganic coatings. For instance, Bardon et al.
[115] dispersed solid AlCeO3 nanoparticles in a hexamethyldisiloxane
solution (HMDSO), and then sprayed this mixture in an aerosol form
into the gas flow of a DBD system. The cerium-based nanoparticles
inserted in an organosilicon plasma coating were deposited on steel
for anticorrosion purposes.
7. Co-deposition: organic sulfonated membranes
As already mentioned, atmospheric plasma systems allow simul-
taneously deposition of more than one molecule, allowing the forma-
tion of hybrid, multifunctional compounds. Other techniques such
as reactive magnetron sputtering [116] or magnetron sputtering
with multiple targets also allow to do so [23], but they are usually
restricted to inorganic materials and metals, and organic polymers
are prohibited.
As an example, we recently synthesized sulfonated polystyrene at
atmospheric pressure in one step starting from styrene and trifluoro-
methane sulfonic acid monomers using a DBD plasma chamber. This
could be a major advance in the synthesis of complex, multifunctional
membranes that are currently made by conventional organic chem-
istry, requiring time consuming multiple steps, organic non-eco-
4228 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
Fig. 17. (Left) pp-sulfonated polystyrene synthesized by DBD with He as plasma gas; (right) with Argon as plasma gas.
friendly solvents, and delicate operations. The plasma polymerized-
sulfonated PS can be used as proton exchange membranes for min-
iaturized PEMFC (Polymer Electrolyte Membrane Fuel Cell) using
hydrogen or methanol. XPS results have shown that the sulfonated
groups (ionizable groups) content is tunable by varying the tempera-
ture of the acid monomer (so the acid-to-styrene ratio) or by increas-
ing the voltage (leading to more radical sites available for the grafting
of sulfonated groups). The simultaneous injection of the both precur-
sors allows an homogeneous distribution of the sulfonated groups in-
side the whole membrane thickness, as observed by dynamic
Secondary Ion Mass Spectrometry (dynamic SIMS) which is necessary
for its good conductivity. The schematic of the system used in this case
is presented in Fig. 13.
Atmospheric plasma systems can also be successfully used for the
deposition of hybrid coatings by introducing vapor of a hybrid organ-
ic–inorganic monomer (as vinyltriethoxysilane) and an organic
monomer (such as hexene). These synthesized coatings present ex-
cellent barrier properties due the synergistic effect of the organic
and inorganic network [117]. Hody et al. [118] used a similar DBD sys-
tem for the synthesis of functionalized hybrid coatings carrying car-
boxylic groups (able to create covalent bonds with various chemical
groups) from the simultaneous injection of vinyltrimethoxysilane
and maleic anhydride.
8. Polymerization using atmospheric pressure plasmas: general
mechanisms and experimental parameters
Generally, the precursors that can be used for atmospheric pres-
sure plasma polymerization are identical to those used for low
Fig. 18. AFM 3D image obtained in tapping mode on a modified SiO2 sample deposited
in He DBD. From [118].
pressure processes. However, at low pressure, the monomer is often
injected alone in the plasma (especially for highly volatile mono-
mers), whereas at atmospheric pressure, the use of a plasma gas is
most often required. Note that the presence of a plasma gas is neces-
sary for plasma polymerization at low pressure, when the monomer
is introduced in the afterglow region.
The polymerization process is induced by the formation of an acti-
vated species, usually in the radical form, in the gas phase. This radical
is typically generated by a collision with a high-energy particle (elec-
trons, ions, or metastables) or can be generated by irradiation using
UV light. A bond in the precursor is broken, generating active radicals
that can polymerize.
The plasma polymerization process that takes place at atmospheric
pressure is usually considered as being almost similar to the one pro-
posed by Yasuda [119] for low pressure plasmas (Fig. 14).
Other mechanisms for plasma polymerization have been pro-
posed, for instance by Tibbitt [121], Kobayashi [122] and Stille [123].
A critical review of the mechanisms for plasma polymerization was
recently presented by Friedrich [50].
A major difference with the processes operating at low pressure is
the “plasma” excitation step. At low pressure, the excitation mecha-
nism leading to the activated monomer (Mi• or Mk• ) is mostly due to
collisions between the monomer (Mi) with an electron inducing the
breaking of a chemical bond leading to two radicals:
− • • −
Mi þ e →Mj þ Mk þ e : ð8Þ
Fig. 19. AFM 3D image recorded in tapping mode on a modified SiO2 sample deposited
in Ar DBD. From [118].
 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236 4229

Table 3 increase of the radical recombination rate) in the region of “soft con-
Comparison between the “in-discharge” and “post-discharge” plasma deposition. ditions”, and decreases after reaching a maximum, as described by
In discharge Post discharge the CAP model (competition ablation-polymerization) proposed by
Yasuda (see Fig. 16) [120].
(Very) High deposition rates, depends (Relatively) Lower deposition rates,
on current and precursor flow. depends also on distance between
substrate and plasma, and the precursor 10. Effect of the nature of the plasma gas and of the nature of the
flow. substrate material on the chemical structure of an organic coating
Strong effect of inter-electrode No effect of inter-electrode distance.
distance.
Higher reactivity: higher fragmentation Lower reactivity, lower fragmentation of In an atmospheric plasma, the choice of the nature of the main
of precursor. precursor. plasma gas can have large consequences on the chemistry and the
Coating and substrate exposed to high Coating and substrate less exposed to structure of the resulting coating. To illustrate this, three examples
energy species from plasma high energy species from plasma are presented.
(electron, ions, molecules, UV). (mostly UV and neutrals).
The influence of the nature of the plasma gas on the chemical
Easy to rapidly treat large two- Ideal for small samples or three
dimension samples in-line. dimensional coatings. structure of polystyrene coatings synthesized in a DBD under atmo-
Good control of the atmosphere Poorer control of the atmosphere for spheric pressure was studied in [105]. Plasma-synthesized poly-
for deposition. deposition, especially in open air styrene exhibits a higher degree of unsaturation, branching, and
environment.
cross-linking, and a lower density of aromatics when using argon as
Poisoning of the electrodes. No effect on the electrodes.
plasma gas, than when using helium. This effect was reinforced
when the substrate was metallic (because this asymmetry generates
a much more filamentary discharge). The relative change in the de-
Although this mechanism is also present at high pressure; one has gree of unsaturation, branching, and cross-linking were studied by
to also take into account reactions involving high-energy metastable Fourier-transform infrared spectrometry (FTIR) and time-of-flight
atoms (or molecules) from the plasma gas: secondary ion mass spectrometry (ToF-SIMS). These two techniques
were proposed by Luo [126], Chen [127], and Oran [128].
 þ −
M þ A2 →M þ A þ A þ e : ð9Þ More generally, the texture of the coating and its roughness will
also depend on the nature of the plasma gas at high pressures [105].
Because plasma-polymerized coatings are often formed by ran- Fig. 17 shows surface images of pp-sulfonated polystyrene realized
dom radical recombination, it is generally accepted that their in helium or in argon. While the left image reveals a homogeneous
structure is different from that of conventional polymers [124]. and smooth coating, the right one reveals a structured layer. This is
Plasma-polymers are more disordered. They are not characterized induced by the change in the nature of the discharge. The helium-
by repeating units and they can exhibit a higher degree of cross- based plasma is indeed more homogeneous than the argon one,
linking and branching. A comparative schematic often seen in the which is mostly filamentary (glow discharge with many streamers).
literature is shown in Fig. 15. The streamers are volumes in the plasma where the density of elec-
This assertion is somewhat simplistic, as it depends strongly on trons is higher, therefore where the reactivity is increased, with
the operating conditions. The chemical structure and morphology more radicals and ions created. These streamers are direct conse-
of plasma-polymerized coatings depend on the internal (as (non)- quences of the presence and consumption of metastables in a high
homogeneity of the discharge, distribution of the various species in pressure plasma, as shown in Fig. 9, and will have dramatic conse-
the plasma, energy of the species…), and the external (reactor geom- quences on the bulk structure of the deposited coating and its surface.
etry, discharge power or applied voltage, frequency, total pressure, The key effects are summarized below:
partial pressure of the monomer, flow rates…) plasma parameters.
Since the external parameters influence the internal parameters, the – because of the higher reactivity, the fragmentation of the precur-
properties of the coatings can be tailored by controlling the external sor will be higher, leading to a higher degree of branching and
parameters. Some of these parameters are presented below. cross-linking, more unsaturation, and to a decrease of the density
of aromatics (in the case of the presence of aromatic groups).
9. Effect of the power on coatings properties – because of local higher reactivity, the deposition rate will be
higher under the streamers leading to coatings of non-uniform
The chemical regularity of the plasma-polymerized coatings de- thickness. Moreover, the deposition rate of pp-sulfonated PS is
creases with an increase in the effective power as described by slightly higher in the presence of Ar than with He (260–280 nm/
Yasuda (for identical flow rates) [124]. Yasuda's factor is given in min in the presence of He as carrier gas, vs. 360–580 nm/min
the following equation.

W
E¼ ð10Þ
F⋅M

with:

W discharge power (J/s)

F monomer flow rate (μl/min)
M molecular weight of monomer (kg/mol).

The factor introduced by Yasuda corresponds to the energy sup-

plied per unit of monomer. For low ratios (low discharge power and
high flow rates), the structure of the coatings is closer to the conven-
tional polymer than for high ratios, where the films are more disor-
dered (more fragmentation). In the same way, the deposition rate Fig. 20. Cross-sectional schematic of an APPLD system [Dow Corning Plasma Solutions,
increases with this ratio (more activated radicals leading to an Ireland] [108].
4230 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
Fig. 21. Synthesis of plasma polymerized polyethylene glycol by injection of (left) liquid tetraglyme droplets into the post-discharge of an atmospheric RF argon plasma and (right)
tetraglyme vapor in the post-discharge.
with Ar at a voltage of 1 kV). Jiang [104] showed similarly that the
polymerization rate was higher along the streamers in a DBD than
outside the filaments. He compared by SEM three types of micro-
scopic structures of films corresponding to three different DBD
discharges modes (a diffuse glow discharge, a “corona-like”, and
a filamentary discharge). The self-organized pattern obtained
under the discharge filaments can be of interest in many applica-
tions such as electronic devices fabrication, bionic materiel
growth, etc.
– because of the higher electron density and the presence of
streamers at the growing film surface, local electron and ion bom-
bardment may occur inducing surface damage such as pitting.
Hody et al. [118] also highlighted the importance of the carrier gas
nature (He or Ar) for coatings synthesized from maleic anhydride and
vinyltrimethoxysilane. Coatings deposited in continuous Ar plasmas
show a highly rough surface, contrary to those deposited in He. The
roughness can be attributed to the inhomogeneous discharge ob-
served in Ar. They observed particles on top of the film for deposits
in the presence of He. Moreover the degree of carboxylic functionali-
zation is higher in the presence of Ar instead of He. Fig. 18 is an AFM
image of a sample deposited in He, and Fig. 19 an image of a sample
deposited under the same conditions in Ar.
Similarly, Goossens et al. [103] observed that polyethylene films
deposited in a He DBD are different in polymer structure, from
those deposited in an Ar DBD. The ones deposited with He yield a
low density, sticky, and opaque polymer that can be dissolved in chlo-
roform, whereas Ar gives a clear and more solid polymer, with good
adhesion to all substrates, and not soluble in chloroform.
11. Post-discharge or “in discharge” plasma polymerization?
The number of bonds broken by the high energy particles, and the
number of radicals originating from the precursor, will depend on the
ratio between the precursor flow and the injected power (cf. Yasuda's
factor, defined above in Eq. (10)). Nevertheless, some geometrical as-
pects, and some non-obvious effects must be taken into account also
for the polymerization process.
For example, the precursor can be injected either in the discharge
or in the post-discharge of the plasma. That will result in drastically
different reactivities: the plasma region contains electrons and ions
(which are influenced by the electrical field), metastables and UV,
whereas the post-discharge region is mostly neutral, containing as re-
active species mostly neutral metastable and UV photons. The geom-
etry will also induce a difference in the polymerization process and
mechanisms. Indeed, as the “in discharge” process is more reactive,
it could create more damages to the precursor than the post-
discharge deposition process. This is especially true in organic poly-
merization, where keeping the appropriate functionality brought by
the precursor is of importance. This effect is already known from
low pressure processes. The low pressure polymerization of polyeth-
ylene glycol, a biocompatible material, showed that coatings deposit-
ed in the post or pre-discharge are of better quality than a coating
deposited in the discharge, because the polyether character responsi-
ble for the biocompatibility property is not destroyed in the post-
discharge [129]. As already shown, deposition inside the discharge
may alter the quality of the final coating, as well as the substrate, be-
cause of the presence of streamers in the plasma. The progressive poi-
soning of the electrodes must also be taken into account when
injecting the precursor into the discharge. For online industrial
coaters, that could be an issue.
Table 3 presents a comparison between “in-discharge” and “post-
discharge” atmospheric plasma deposition.
12. Pulsed plasmas at atmospheric pressure
Although most of the studies reported used continuous-wave (ex-
ample: sinusoidal wave) plasma generators (high frequency from 1 to
400 kHz for the DBDs and 13.56 or 27 MHz for RF capacitive dis-
charges), the voltage can also be applied in the form of discrete pulses
(of a few milli- to microseconds).
Asymmetrical pulsed RF plasma constitutes a very promising tech-
nique to enhance the controllability of plasma-polymerized film
chemistry due to better control of the energy dissipation in the plas-
ma, which leads to chemically better-defined plasma-polymer films.
Because the pulsed discharge can operate at much higher peak volt-
ages and current for the same average power, the instantaneous pre-
cursor activation (during the light phase of the cycle — ton) can be
enhanced. The reaction continues during the “off” period, as de-
scribed by Yasuda [119]. The radical (co)-polymerization is favored
when the plasma is off during the dark phase (toff). By playing on
the duty cycle (relationship between the plasma ON and the OFF
times), one can control the retention of the precursor functional
groups.
A few examples of the use of pulsed-plasma for the plasma-
deposition at atmospheric pressure are described below.
Denis et al. [130] used pulsed plasmas at atmospheric pressure for
the polymerization of allylamine and cyclopropylpamine. The primar-
ily amine-based films show potential applications in the modification
of filtration membranes, treatment of carbon nanotubes, biomedical
applications, etc.
According to Boscher et al. [131], the use of appropriate pulsed-
plasma conditions in a DBD enables morphological control and
 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236 4231

Fig. 22. XPS C1s peak of (left): APPLD plasma polymerized PEG coatings as a function of the plasma power; (right) PEG coatings synthesized from tetraglyme injected as a vapor in
the post-discharge of the plasma [106].

improves electrochemical properties (such as polarization resistance,
passivation, etc.) of HMDSO synthesized on aluminum foils (in a ni-
trogen atmosphere) for corrosion protection. They showed that a
higher degree of cross-linking with equivalent deposition rates can
be obtained, and the pulsing of the electric signal prevents the forma-
tion of pinholes and heterogeneities in the coatings.
Topala [132] obtained hydrophobic polystyrene in a He discharge
(DBD) by optimizing discharge current parameters (pulses, pulse
shape, duty-cycle, gap length, He gas flow…). He noticed that the
electric parameters of the plasma such as the voltage pulse shape (si-
nusoidal or ramp wave) and the rise time have a strong influence on
the discharge current maximum, and this more than the other param-
eters, such as the distance between the electrodes or the He flow rate
carrying the styrene monomer.
The coatings of Hody et al. [118] deposited from maleic anhydride
and vinyltrimethoxisilane by pulsed Ar plasma are less rough than
films deposited in a continuous mode. The sample roughness is prob-
ably smoothened during the “off period”.
13. Effect of the injection mode on the resulting chemistry of a
coating
One of the big advantages of the use of atmospheric plasma is the
ability to inject liquids directly into the discharge, or into the post-
discharge. This process is called atmospheric pressure plasma liquid
deposition (APPLD). The “in discharge” process was developed by
Badyal and Dow Corning and is presented in Fig. 20 [133].
APPLD has the advantage that large surfaces can be treated quick-
ly, using a simple method of injection (spraying droplets of the liquid
directly in the plasma), in the absence of oxygen (in a He atmo-
sphere), which allows complex organic chemistry. The fact that the
precursor is injected in the liquid form results in less degradation,
4232 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236

Fig. 23. SEM micrograph of the cross-section of BTSE films deposited on Al by (A) wet deposition, (B) vacuum plasma, and (C) atmospheric plasma.
From [83].

as the precursor is protected inside the liquid droplet from plasma
degradation. In the Dow Corning process, the surface is also pre-
activated by the plasma before exposure to the precursor, which in-
sures better adhesion of the deposited layer.
A comparison of the precursor injected as a liquid or as a vapor has
been carried out by Nisol [106], who synthesized biocompatible PEG
coatings from tetra(ethylene glycol) dimethylether also known as
tetraglyme. The precursor was injected as shown in Fig. 21.
FTIR, XPS and ToF-SIMS results show that the APPLD process (left)
maintains the polyether character (the C\O component in the C1s
peak of the coating is the signature for the polyether character),
whereas the vapor phase process is strongly dependent on the plasma
power, as represented in Fig. 22.
APPLD systems have also been used to deposit polyacrylic acid
films [134]; silicon-based films [135], and pure SiO2 could be deposit-
ed from organosilicon in a He\O2 plasma using a nebulizer system
[136]. Nebulizers were also used to “spray” colloid solutions of
metal nanoparticles in order to decorate various surfaces [137].
14. Comparison: coatings under vacuum/liquid/plasma
As the use of an atmospheric technology is more recent than the
well-established use of vacuum techniques, an immediate question
deals with the comparison between the quality of the coatings
obtained by different techniques. This is obviously difficult to do, as
many parameters, in each technique can influence the final quality
of the deposited layer. Sawada et al. [138] compared SiO2 films depos-
ited from TEOS and HMDSO at atmospheric pressure to those pre-
pared using low pressure plasma. They came to the conclusion that
the films deposited by both methods (as characterized by FTIR and
XPS) were very similar. Similarly, in a joint research proposal, three
groups investigated the comparison between films deposited from
BTSE (bis-1,2-(triethoxysilyl) ethane) by three different techniques
(wet deposition, vacuum plasma deposition, and atmospheric
deposition).
Fig. 23 shows typical FEG-SEM pictures of these 3 coatings.
From Fig. 23, it can be seen that the three techniques provide
dense layers, with similar thicknesses (depending on the plasma pa-
rameters). The composition of the coatings, however, are slightly dif-
ferent, the one deposited by atmospheric plasma being more oxidized
than the two others, as shown in Table 4. This was interpreted by the
fact that the atmospheric plasma was operating using a torch running
with argon, in an open air environment, which results in a higher ox-
idation of the precursor during the condensation reaction. The adhe-
sion of such layers deposited (on aluminum) by atmospheric plasma
proved to be excellent, due to the formation of a strong interfacial
bond evidenced by ToF-SIMS (see Fig. 24).
When comparing sulfonated polystyrene synthesized at low or
high pressure, better retention of sulfonated groups is obtained
under atmospheric pressure than at low pressure (where the XPS S
2p peak is often split [139,140]). This suggests milder plasma condi-
tions at high pressure. This can be explained by a lower mean free
path of the species. If their collision frequency is higher, their energy
can become too low to fragment the sulfonated groups [114]. In this
specific case, in order to preserve the chemical structure in low-
pressure plasma conditions, it is preferable to operate in the post-

Table 4
Comparison of the atomic composition of BTSE films using various deposition method
[83].

Binding energy (eV) Atomic concentration (%)

Si2p C1S O1s Si2p C1S O1s

Wet deposition 102.3 284.4 532.3 27.5 26.7 45.8

Fig. 24. Evidence of the formation of an Al\O\Si bond at the interface between an
Vacuum plasma 102.7 284.4 532.3 28 24.3 47.6
atmospheric-plasma-deposited SiOx layer and an aluminum substrate.
Atmospheric plasma 103.2 284.4 532.8 34.7 6.7 58.6
From [84].
 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
Fig. 25. High deposition speed DBD system [70].
discharge (to avoid fragmentation due to electrons) [140,141], while,
due to the milder conditions in atmospheric plasma, the deposition
can take place inside the discharge, leading to much higher deposi-
tion rates [140–143].
Fei et al. [144], while comparing MoSi2 coatings deposited by
atmospheric and vacuum plasma spray processes, observed that
the density and the homogeneity, as well as the contamination, the
Vickers Hardness, and the resistance to thermal oxidation were
much better for coatings deposited using vacuum plasma than for
those deposited under atmospheric pressure.
15. Deposition rates
One of the interests in the development of atmospheric plasma
technologies is the possibility to install them on industrial coaters.
In that respect, the deposition rate is a crucial parameter. Although
one should always take these numbers with great care (it depends
on the parameters, on the desired purity, and structure of the layers,
etc.), we give here some indications extracted from recent studies.
In 2005, Massines [70] obtained deposition rates of 12 nm/min,
using a DBD system reproduced in Fig. 25. However, these values
were obtained inside the DBD; when going to the post-discharge,
Fig. 26. Profile of the deposition rate (r) and percent of SiO2 (g) in case of N2–N2O–
HMDSO coatings deposition under standard conditions as a function of position along
the direction of the gas flow (the gas entrance is at position 0), and the residence time.
Reprinted from: F. Massines et al. [70].
4233
Fig. 27. SiO2 deposition rate as a function of the precursor type, and the precursor par-
tial pressure (reprinted from Moravej et al. [85] (the plasma gas is Helium, with 2% ox-
ygen added, injected in a RF capacitive torch operating a 13.56 MHz, with a volumetric
plasma power of 20 W cm− 3).
the deposition rate dropped drastically due to a decrease of the con-
centration of activated precursors as shown in Fig. 26.
De Geyter et al. [145] reported in 2009 deposition rates of 180
to 288 nm/min for HMDSO deposition by DBD. They used very low
plasma power (5 to 12 W), but the films still contain carbon-based
groups.
Morent [86] studying the deposition of SiOx films from HMDSO,
came to the same conclusion as many groups: deposition of a coating
is fast (6 nm/s) using a pure noble gas (He, Ar), but this layer is
SiOxCyHz. When an oxygen-containing source is added, the deposi-
tion rate decreases (2 nm/s), but pure SiO2 coatings are obtained.
In the post-discharge, a linear log–log relationship between the
precursor pressure and the deposition rate is observed, as reported
by Moravej (Fig. 27) [85]. Indeed, in the post-discharge, less energetic
species are able to break bonds and to activate the nucleation and
growth process. Therefore, the growth process will mostly take
place at the gas substrate interface.
A parameter which is rarely used in atmospheric plasma deposi-
tion of coatings is the plasma gas temperature. Sawada [138] already
pointed out a positive effect (increase in the deposition rate when in-
creasing the gas temperature) and we could evidence it for the depo-
sition of SiO2 starting from HMDSO by DBD. In our experimental
conditions, going from room temperature to 200 °C led to doubling
the deposition rate, reaching 100 nm/s rates for ultra-pure and
dense SiO2. According to Sawada, this is because the gas-phase reac-
tion of monomer decomposition is enhanced by atomic oxygen, and
the reaction rates in the gas phase increase as the gas-phase temper-
ature increases. A side effect of the temperature is to favor the
Fig. 28. Domains of plasma polymerization reactions of styrene obtained at atmospheric
pressure. Adapted from [146].
4234 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
Fig. 29. Thickness profiles of plasma-polymerized PS films deposited by DBD as a func-
tion of different discharge power. Adapted from [146].
elimination of volatile carbonaceous residues from the precursor,
leading to purer SiO2 coatings.
De Geyter [93] studied the effect of plasma DBD parameters on the
deposition rate and the structure of PMMA coatings. They show that
the deposition rate is, to a large extent, increasing with the monomer
concentration injected in the chamber. The deposition rate is constant
with time, which is a characteristic of many well-controlled plasma
techniques. They also show that the deposition rate starts to increase
with the plasma power, reaches a maximum, and decreases at high
plasma power. Simultaneously, the plasma power changes the distri-
bution of chemical functions in the film. Average deposition rates
range from 1 to 2 nm/s.
Asandulesa et al. [146] studied the influence of the flow rate and
the discharge power on the polymerization rate of plasma polymer-
ized PS coatings synthesized in a DBD (in the presence of He).
They identified different domains of plasma-polymerization and
showed that the polymerization rate increases with the ratio W/FM
in the energy deficient region (soft conditions) and decreases (after
a critical point) in the monomer deficient region, as shown in
Fig. 28. The increase of the thickness (constant deposition time) for
pp-PS coatings with the power is presented in Fig. 29.
More generally, for the synthesis of organic coatings, the deposi-
tion rate will also strongly depend on the chemical structure of the
precursor. Precursors easy to polymerize and containing one or two
Fig. 30. Uncontrolled atmospheric plasma deposition of TiO2 starting from titanium
isopropoxide and leading to a porous layer [147].
double bonds will have very high deposition rates, while, for example,
fully saturated precursors will have very small deposition rates.
16. Nucleation in the gas phase or at the gas substrate interface
As described above, one of the challenges in the deposition of
coatings by plasma technology is to obtain dense, homogeneous,
and uniform films. The same rationale as the one operating at low
pressure applies here: to obtain such coatings, the nucleation and
growth processes must take place mostly at the gas/substrate inter-
face, and not in the gas phase. A case leading to the formation of pow-
ders and/or to a non-dense coating is presented in Fig. 30.
At high pressure conditions, characterized by a very small mean
free path of the particles, many collisions can take place, leading
sometimes to nucleation and growth in the gas phase, rather than
at the substrate surface. The condensation in the gas phase leads, in
turn, to the formation of powder instead of a dense coating.
In order to avoid that, one should avoid having too high of a con-
centration of precursor (or monomer) molecules activated simulta-
neously. Therefore, careful control of the monomer injection flow is
required. This will limit, to some extent, the linear dependence of
the deposition rate on the monomer flow.
17. Conclusions
Atmospheric plasma deposition of coatings, a relatively “new”
technology, is gaining more and more interest. Nowadays, one can
deposit organic, inorganic and hybrid coatings on various substrates,
with different geometries, quite easily. In some cases, very high depo-
sition rates can be reached, which are of the order of magnitude suit-
able for industrial applications. However, the quality of the coating is
strongly dependent on experimental parameters such as the geome-
try used (in discharge or post-discharge), the nature of the plasma
gas (He or Ar), the state of the precursor (liquid or gas) and much
work still has to be done in order to understand the complex mecha-
nisms that take place at atmospheric pressure. Understanding these
phenomena will certainly help, in the future, to develop technologies
as robust as the standard PVD techniques, but with different goals. For
example, we are convinced that very high purity coatings can, at this
moment, only be obtained with vacuum-based technologies. In this
review, we have tried to illustrate a few examples of the current
state of the art, trying to underline the major routes that are currently
investigated in this complex research area.
Acknowledgments
Although this paper is a review, some of the results presented here
were recently generated in our research group thanks to various
funding agencies. The authors would like to thank the Belgian Federal
Government "IAP -PSI (physical chemistry of plasma surface interac-
tions) – P6-08 network", the FOMOS program (Belgian technology
pole), the FRIA, the MIRAGE project (Marshall Plan, Walloon Region),
and the ULB post-doctoral program.
References
[1] I. Langmuir, Proc. Natl. Acad. Sci. U.S.A. 14/8 (1928) 627.
[2] M. Faraday, The Bakerian Lecture: Experimental Relations of Gold (and Other
Metals) to Light, The Royal Society, London, 1857.
[3] F. Reniers, P. Delcambe, L. Binst, M. Jardinieroffergeld, F. Bouillon, Thin Solid
Films 170 (1) (1989) 41.
[4] F. Reniers, P. Kons, P. Delcambe, L. Binst, M. Jardinieroffergeld, F. Bouillon,
Microsc. Microanal. Microstruct. 1 (3) (1990) 189.
[5] M.P. Delplancke, F. Reniers, A. Asskali, M. Jardinieroffergeld, F. Bouillon, J. Vac.
Sci. Technol. A Vac. Surf. Films 11/4 (1993) 1510.
[6] F. Reniers, M.P. Delplancke, A. Asskali, V. Rooryck, O. VanSinay, Appl. Surf. Sci. 92
(1996) 35.
[7] S. Kacim, L. Binst, F. Reniers, F. Bouillon, Thin Solid Films 287 (1–2) (1996) 25.
 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
[8] M. Detroye, F. Reniers, C. BuessHerman, J. Vereecken, Appl. Surf. Sci. 120 (1–2)
(1997) 85.
[9] M. Cekada, M. Macek, D.K. Merl, P. Panjan, Thin Solid Films 433 (1–2) (2003)
174.
[10] Q. Liu, T. Liu, Q.F. Fang, F.J. Liang, J.X. Wang, Thin Solid Films 503 (1–2) (2006)
79.
[11] J.F. Pierson, D. Wiederkehr, A. Billard, Thin Solid Films 478 (1–2) (2005) 196.
[12] F. Reniers, M. Detroye, P. Kons, S. Kacim, M. maoujoud, M. Soussi el Begrani, E.
Silbeberg, T. Vandevelde, C. Herman-Buess, Synthesis of Thin Films of Cr, Mo,
W Carbides and Nitrides, Chapman and Hall, New York, 1996.
[13] M. Maoujoud, L. Binst, P. Delcambe, M. Offergeldjardinier, F. Bouillon, Surf. Coat.
Technol. 52 (2) (1992) 179.
[14] S. Wd, Vacuum 51 (4) (1998) 641.
[15] T. Yang, X. Qin, H.-h. Wang, Q. Jia, R. Yu, B. Wang, J. Wang, K. Ibrahim, X. Jiang, Q.
He, Thin Solid Films 518/19 (2010) 5542.
[16] C.-W. Hsu, T.-C. Cheng, W.-H. Huang, J.-S. Wu, C.-C. Cheng, K.-W. Cheng, S.-C.
Huang, Thin Solid Films 518 (8) (2010) 1953.
[17] K. Pedersen, J. Bottiger, M. Sridharan, M. Sillassen, P. Eklund, Thin Solid Films
518 (15) (2010) 4294.
[18] M.A. Signore, A. Rizzo, L. Tapfer, E. Piscopiello, L. Capodieci, A. Cappello, Thin
Solid Films 518 (8) (2010) 1943.
[19] C.N. Yeh, Y.M. Chen, C.A. Chen, Y.S. Huang, D.S. Tsai, K.K. Tiong, Thin Solid Films
518 (15) (2010) 4121.
[20] B. Window, N. Savvides, J. Vac. Sci. Technol. A 4/196 (1986) 7.
[21] D. Depla, J. Haemers, R. De Gryse, Thin Solid Films 515 (2) (2006) 468.
[22] R. Snyders, R. Gouttebaron, J.P. Dauchot, M. Hecq, Surf. Coat. Technol. 200 (1–4)
(2005) 448.
[23] C.S. Sandu, R. Sanjinés, M. Benkahoul, F. Medjani, F. Lévy, Surf. Coat. Technol. 201
(7) (2006) 4083.
[24] K. Wasa, S. Hayakawa, Handbook of Sputter Deposition Technology Principles,
Technology and Applications, Elsevier, Amsterdam, 1992.
[25] P.M. Martin, Handbook of Deposition Technologies for Films and Coatings, 3rd
ed., Elsevier, Amsterdam, 2010.
[26] P.J. Kelly, R.D. Arnell, Vacuum 56 (3) (2000) 159.
[27] R.D. Arnell, P.J. Kelly, Surf. Coat. Technol. 112 (1–3) (1999) 170.
[28] J. Kong, A.M. Cassell, H.J. Dai, Chem. Phys. Lett. 292 (4–6) (1998) 567.
[29] J.J. Wu, S.C. Liu, Adv. Mater. 14 (3) (2002) 215.
[30] C.R. Gorla, N.W. Emanetoglu, S. Liang, W.E. Mayo, Y. Lu, M. Wraback, H. Shen, J.
Appl. Phys. 85 (5) (1999) 2595.
[31] K. Minegishi, Y. Koiwai, Y. Kikuchi, K. Yano, M. Kasuga, A. Shimizu, Jpn. J. Appl.
Phys. Part 2 Lett. 36/11A (1997) L1453.
[32] K. Okano, S. Koizumi, S.R.P. Silva, G.A.J. Amaratunga, Nature 381 (6578) (1996)
140.
[33] W.A. Yarbrough, R. Messier, Science 247 (4943) (1990) 688.
[34] S. Yugo, T. Kanai, T. Kimura, T. Muto, Appl. Phys. Lett. 58 (10) (1991) 1036.
[35] O. Carp, C.L. Huisman, A. Reller, Prog. Solid State Chem. 32 (1–2) (2004) 33.
[36] X. Chen, S.S. Mao, Chem. Rev. 107 (7) (2007) 2891.
[37] R. Karshoglu, M. Uysal, H. Akbulut, J. Cryst. Growth 327 (1) (2011) 22.
[38] I. Volintiru, A. de Graaf, J. van Deelen, P. Poodt, Thin Solid Films 519 (19) (2011)
6258.
[39] R. Chakraborty, S.C. Sharma, Phys. B Condens. Matter 406 (22) (2011) 4170.
[40] D.M. Dobkin, M.K. Zuraw, Principles of Chemical Vapor Deposition, Springer,
Berlin, 2003.
[41] H.O. Pierson, Second Edition: Principles, Technology and Applications (Materials
Science and Process Technology), 2nd ed., William Andrew, 1999.
[42] C. Tendero, C. Tixier, P. Tristant, J. Desmaison, P. Leprince, Spectrochim. Acta Part
B At. Spectrosc. 61 (1) (2006) 2.
[43] U. Kogelschatz, Plasma Chem. Plasma Process. 23 (1) (2003) 1.
[44] A. Bogaerts, E. Neyts, R. Gijbels, J. van der Mullen, Spectrochim. Acta Part B At.
Spectrosc. 57 (4) (2002) 609.
[45] N.P. Napartovich, Plasma Polym. 6 (1) (2001) 1.
[46] L. Bardos, H. Barankova, Thin Solid Films 518 (23) (2010) 6705.
[47] D. Pappas, J. Vac. Sci. Technol. A Vac. Surf. Films 29/2 (2011) 020801.
[48] W. Siemens, Poggendorff's Ann. Phys. Chem. 102 (1857) 66.
[49] Bondt, Deimann, P.v. Trostwijk, Lauwerenburg, J. Fourcroy, Ann. Chem. 21
(1796) 58.
[50] J. Friedrich, Plasma Processes Polym. 8 (9) (2011) 783.
[51] A. Benninghoven, Angew. Chem. (International Edition in English) 33/10 (1994)
1023.
[52] N. Vandencasteele, F. Reniers, J. Electron. Spectrosc. Relat. Phenom. 178–179/C
(2010) 394.
[53] Handbook of Advanced Plasma Processing Techniques, Springer, Berlin, 2000.
[54] C. Tendero, C. Tixier, P. Tristant, J. Desmaison, P. Leprince, Spectrochim. Acta Part
B At. Spectrosc. 61 (1) (2006) 2.
[55] R. Morent, N. De Geyter, J. Verschuren, K. De Clerck, P. Kiekens, C. Leys, Surf.
Coat. Technol. 202 (14) (2008) 3427.
[56] G. Borcia, C.A. Anderson, N.M.D. Brown, Plasma Sources Sci. Technol. 14/259
(2005).
[57] B. Johansson, A. Larsson, A. Ocklind, A. Ohrlund, J. Appl. Polym. Sci. 86 (2002)
2618.
[58] M.J. Shenton, G.C. Stevens, J. Phys. D: Appl. Phys. 34 (18) (2001) 2761.
[59] H.V. Boenig, Fundamentals of Plasma Chemistry and Technology, Technomic
Publishing Company, Lancaster, 1988.
[60] S.E. Babayan, J.Y. Jeong, V.J. Tu, J. Park, G.S. Selwyn, R.F. Hicks, Plasma Sources Sci.
Technol. 7 (1998) 286.
[61] H. Barankova, L. Bardos, D. Soderstrom, J. Vac. Sci. Technol. A 24 (2006).
4235
[62] B. Chapman, Glow Discharge Processes Sputtering and Plasma Etching, John
Wiley & Sons, New York, 1980.
[63] A. Grill, Cold Plasma in Materials Fabrication From Fundamentals to Applica-
tions, Institute of Electrical and Electronics Engineers, Inc., New York, 1994.
[64] M.A. Lieberman, A.J. Lichtenberg, Principles of Plasma Discharges and Materials
Processing, Wiley, Hoboken, 2005.
[65] H. Aizawa, T. Makisako, S.M. Reddy, K. Terashima, S. Kurosawa, M. Yoshimoto, J.
Photopolym. Sci. Technol. 20 (2) (2007) 215.
[66] S. Kurosawa, H. Harigae, H. Aizawa, J.W. Park, H. Suzuki, K. Terashima, J. Photo-
polym. Sci. Technol. 18/2 (2005) 273.
[67] S. Kurosawa, H. Harigae, H. Aizawa, H. Suzuki, K. Terashima, J. Photopolym. Sci.
Technol. 19 (2) (2006) 253.
[68] F. Massines, R. Messaoudi, C. Mayoux, Plasma Polym. 3/1 (1998).
[69] A.A. Radzig, B.M. Smirnov, Reference Data on Atoms, Molecules and Ions, 1985.
[70] F. Massines, N. Gherardi, A. Fornelli, S. Martin, Surf. Coat. Technol. 200 (5–6)
(2005) 1855.
[71] A. Ricard, Plasmas réactifs, Société Française du Vide, Paris, 1995.
[72] N. Gomathi, A. Sureshkumar, N. Sudarsan, Curr. Sci. 94/11 (2008).
[73] F. Massines, G. Gouda, J. Phys. D: Appl. Phys. 31 (1998).
[74] E. Michel, E. Silberberg, F. Reniers, 16th International Symposium on Plasma
Chemistry, 2003.
[75] CRC Handbook of Chemistry and Physics, 70th ed., CRC Press, Boca Raton, 1990.
[76] J.D. Cobine, Gaseous Conductors: Theory and Engineering Applications, Dover
Publications, Mineola, 1958.
[77] H. Bartzsch, D. Gloss, B. Bocher, P. Frach, K. Goedicke, Surf. Coat. Technol. 174
(2003) 774.
[78] S.H. Jeong, J.K. Kim, B.S. Kim, S.H. Shim, B.T. Lee, Vacuum 76 (4) (2004) 507.
[79] Y. Pihosh, H. Biederman, D. Slavinska, J. Kousal, A. Choukourov, M. Trchova, A.
Mackova, A. Boldyryeva, Vacuum 81 (1) (2006) 38.
[80] D. Barreca, A. Gasparotto, C. Maccato, E. Tondello, G. Rossetto, Thin Solid Films
516 (21) (2008) 7393.
[81] A. Barranco, J. Cotrino, F. Yubero, J.P. Espinos, J. Benitez, C. Clerc, A.R. Gonzalez-
Elipe, Thin Solid Films 401 (1–2) (2001) 150.
[82] S.C. Deshmukh, E.S. Aydil, J. Vac. Sci. Technol. B 14/2 (1996) 738.
[83] A. Batan, F. Brusciotti, I. De Graeve, J. Vereecken, M. Wenkin, M. Piens, J.J.
Pireaux, F. Reniers, H. Terryn, Prog. Org. Coat. 69 (2) (2010) 126.
[84] A. Batan, N. Mine, B. Douhard, F. Brusciotti, I. De Graeve, J. Vereecken, M.
Wenkin, M. Piens, H. Terryn, J.J. Pireaux, F. Reniers, Chem. Phys. Lett. 493
(1–3) (2010) 107.
[85] M. Moravej, R.F. Hicks, Chem. Vap. Deposition 11 (11–12) (2005) 469.
[86] R. Morent, N. De Geyter, S. Van Vlierberghe, P. Dubruel, C. Leys, L. Gengembre, E.
Schacht, E. Payen, Prog. Org. Coat. 64 (2–3) (2009) 304.
[87] J.A. Ayllón, A. Figueras, S. Garelik, L. Spirkova, J. Durand, L. Cot, J. Mater. Sci. Lett.
18 (16) (1999) 1319.
[88] H. Bai, C. Chen, C. Lin, W. Den, C. Chang, Ind. Eng. Chem. Res. 43 (22) (2004)
7200.
[89] L.-H. Nie, C. Shi, Y. Xu, Q.-H. Wu, A.-M. Zhu, Plasma Processes Polym. 4 (5)
(2007) 574.
[90] S. Kment, P. Kluson, H. Zabova, A. Churpita, M. Chichina, M. Cada, I. Gregora, J.
Krysa, Z. Hubicka, Surf. Coat. Technol. 204 (5) (2009) 667.
[91] X.W. Zhang, G.R. Han, Thin Solid Films 516 (18) (2008) 6140.
[92] M. Matsumotoa, Appl. Surf. Sci. 254 (19) (2008) 6208.
[93] N. De Geyter, R. Morent, S. Van Vlierberghe, P. Dubruel, C. Leys, L. Gengembre, E.
Schacht, E. Payen, Prog. Org. Coat. 64 (2–3) (2009) 230.
[94] I. Topala, N. Dumitrascu, G. Popa, Nucl. Instrum. Methods Phys. Res., Sect. B
267/2 (2009) 442.
[95] K.H. Lee, H.-S. Jang, G.-Y. Eom, B.-J. Lee, D. Burk, L. Overzet, G.S. Lee, Mater. Lett.
62 (23) (2008) 3849.
[96] S.P. Bugaev, A.D. Korotaev, K.V. Oskomov, N.S. Sochugov, Surf. Coat. Technol. 96
(1) (1997) 123.
[97] A.M. Ladwig, R.D. Koch, E.G. Wenski, R.F. Hicks, Diamond Relat. Mater. 18 (9)
(2009) 1129.
[98] X. Zhu, F. Arefi-Khonsari, C. Petit-Etienne, M. Tatoulian, Plasma Processes Polym.
5 (2005) 407.
[99] V. Raballand, J. Benedikt, A. von Keudell, Appl. Phys. Lett. 92 (9) (2008) 1.
[100] R.Y. Korotkov, R. Gupta, P. Ricou, R. Smith, G. Silverman, Thin Solid Films 516
(15) (2008) 4720.
[101] L. Soukup, Z. Hubička, A. Churpita, M. Cada, P. Pokorny, J. Zemek, K. Jurek, L.
Jastrabik, Surf. Coat. Technol. 169–170 (2003) 571.
[102] M.D. Barankin, T.S. Williams, E. Gonzalez Ii, R.F. Hicks, Thin Solid Films 519 (4)
(2010) 1307.
[103] O. Goossens, E. Dekempeneer, D. Vangeneugden, R. Van de Leest, C. Leys, Surf.
Coat. Technol. 142–144 (2001) 474.
[104] N. Jiang, S.F. Qian, L. Wang, H.X. Zhang, Thin Solid Films 390 (1–2) (2001) 119.
[105] D. Merche, C. Poleunis, P. Bertrand, M. Sferrazza, F. Reniers, IEEE Trans. Plasma
Sci. 37 (6) (2009) 951.
[106] B. Nisol, C. Poleunis, P. Bertrand, F. Reniers, Plasma Processes Polym. 7 (8)
(2010) 715.
[107] G. Da Ponte, E. Sardella, F. Fanelli, A. Van Hoeck, R. d'Agostino, S. Paulussen, P.
Favia, Surf. Coat. Technol. 205 (Suppl. 2/0) (2011) S525.
[108] M. Tatoulian, F. Arefi-Khonsari, J.-P. Borra, Plasma Processes Polym. 4 (2007)
360.
[109] F. Reniers, N. Vandencasteele, O. Bury, Belgium Patent 2011.
[110] F. Fanelli, F. Fracassi, R. d'Agostino, Plasma Processes Polym. 4/S1 (2007) S430.
[111] I.P. Vinogradov, A. Dinkelmann, A. Lunk, Surf. Coat. Technol. 174–175/0 (2003)
509.
4236 D. Merche et al. / Thin Solid Films 520 (2012) 4219–4236
[112] J. Hubert, Master, CHANI, ULB, Brussels, 2010.
[113] P. Heyse, R. Dams, S. Paulussen, K. Houthoofd, K. Janssen, P.A. Jacobs, B.F. Sels,
Plasma Processes Polym. 4 (2) (2007) 145.
[114] D. Merche, J. Hubert, C. Poleunis, S. Yunus, P. Bertrand, P. De Keyzer, F. Reniers,
Plasma Processes Polym. 7 (9–10) (2010) 836.
[115] J. Bardon, J. Bour, D. Del Frari, C. Arnoult, D. Ruch, Plasma Processes Polym. 6
(2009) S655.
[116] A. Daniel, C. Le Pen, C. Archambeau, F. Reniers, Appl. Surf. Sci. 256 (3) (2009)
S82.
[117] S. Paulussen, R. Rego, O. Goosssens, D. Vangeneugden, K. Rose, Surf. Coat.
Technol. 200 (2005) 672.
[118] H. Hody, P. Choquet, M. Moreno-Couranjou, R. Maurau, J.-J. Pireaux, Plasma
Processes Polym. 7 (5) (2010) 403.
[119] H. Yasuda, Plasma Polymerization, Academic Press, Waltham, 1985.
[120] H. Yasuda, T. Yasuda, J. Polym. Sci. Part A: Polym. Chem 38 (1999) 943.
[121] J.M. Tibbitt, M. Shen, A.T. Bell, J. Macromol. Sci. A 10 (1976) 1623.
[122] H. Kobayashi, A.T. Bell, M. Shen, J. Appl. Polym. Sci. 17 (3) (1973) 885.
[123] J.K. Stille, R.L. Sung, J.V. Kooi, J. Org. Chem. 30 (9) (1965) 3116.
[124] H. Biederman, Y. Osada, Plasma Polymerization Processes, Elsevier, Amsterdam,
1992.
[125] P.W. Kramer, Y.S. Yeh, H. Yasuda, J. Membr. Sci. 46 (1) (1989) 1.
[126] H.L. Luo, J. Sheng, Y.Z. Wan, Appl. Surf. Sci. 253 (12) (2007) 5203.
[127] M. Chen, T.C. Yang, Z.G. Ma, J. Polym. Sci. Part A: Polym. Chem. 3 (6/8) (1998) 1265.
[128] U. Oran, S. Swaraj, J.F. Friedrich, W.E.S. Unger, Surf. Coat. Technol. 200 (1–4)
(2005) 463.
[129] B. Nisol, PhD, Chemistry, ULB, Brussels, 2011.
[130] L. Denis, P. Marsal, Y. Olivier, T. Godfroid, R. Lazzaroni, M. Hecq, J. Cornil, R.
Snyders, Plasma Processes Polym. 7 (2) (2010) 172.
[131] N.D. Boscher, P. Choquet, D. Duday, S. Verdier, Plasma Processes Polym. 7 (2)
(2010) 163.
[132] I. Topala, M. Asandulesa, D. Spridon, N. Dumitrascu, IEEE Trans. Plasma Sci. 37
(6) (2009) 946.
[133] M. Tatoulian, F. Arefi-Khonsari, J.-P. Borra, Plasma Processes Polym. 4 (4) (2007)
360.
[134] L.J. Ward, W.C.E. Schofield, J.P.S. Badyal, A.J. Goodwin, P.J. Merlin, Chem. Mater.
15 (7) (2003) 1466.
[135] L.J. Ward, W.C.E. Schofield, J.P.S. Badyal, A.J. Goodwin, P.J. Merlin, Langmuir 19
(6) (2003) 2110.
[136] B. Twomey, D.P. Dowling, G. Byrne, W.G. Graham, L.F. Schaper, D.D. Croce, A.
Hynes, L. O'Neill, IEEE Trans. Plasma Sci. 37 (6) (2009) 961.
[137] N. Claessens, F. Demoisson, T. Dufour, A. Mansour, A. Felten, J. Guillot, J.-J.
Pireaux, F. Reniers, Nanotechnology 21 (2010) 385603.
[138] Y. Sawada, S. Ogawa, M. Kogoma, J. Phys. D: Appl. Phys. 28 (8) (1995) 1661.
[139] F. Finsterwalder, G. Hambitzer, J. Membr. Sci. 181 (1) (2001) 105.
[140] H. Mahdjoub, S. Roualdes, P. Sistat, N. Pradeilles, J. Durand, G. Pourcelly, Fuel
Cells 5 (12) (2005) 277.
[141] Z. Jiang, Z. Jiang, X. Yu, Y. Meng, Plasma Processes Polym. 7 (5) (2010) 382.
[142] A. Ennajdaoui, PhD, GREMI, Université d'Orléans, Orléans, 2010.
[143] I. Topala, S. Roualdes, H. Mahdjoub, N. Dumitrascu, G. Popa, J. Durand, XXVIIth
ICPIG, Eindhoven, 2005.
[144] X. Fei, Y. Niu, H. Ji, L. Huang, X. Zheng, Ceram. Int. 37 (3) (2011) 813.
[145] N. De Geyter, R. Morent, T. Jacobs, F. Axisa, L. Gengembre, C. Leys, J. Vanfleteren,
E. Payen, Plasma Processes Polym. 6 (2009) S406.
[146] M. Asandulesa, I. Topala, V. Pohoata, N. Dumitrascu, J. Appl. Phys. 108 (9) (2010)
093310.
[147] S. Collette, Master, Chemistry, ULB, Brussels, 2011.