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Debate – Discussion

Comment on ‘‘Ion-Assisted Processes of

Polymerization in Low-Pressure Plasmas’’

Riccardo d’Agostino,* Fabio Palumbo

1. Introduction always involves plasma physics, in of microscopic plasma-surface inter-

particular the role of (positive) ions. action processes (etching, deposition,
In the present issue of Plasma Pro- The article by Whittle et al. was and modification) in low pressure
cesses and Polymers (PPaP) appears originally inspired by the featured discharges, deserves to be continued
an interesting article by J. D. Whittle, review paper entitled ‘‘Mechanisms even though it is currently not receiv-
D. A. Steele, and R. D. Short, entitled of Plasma Polymerization—Reviewed ing much attention in the literature.
‘‘Reconciling the Physical and Chemi- from a Chemical Point of View’’ Mechanisms of etching and deposition
cal Environments of Plasma: A Com- by J. Friedrich,[7] which primarily were developed in detail in 1980s and
mentary on ‘‘Mechanisms of Plasma explores plasma polymerization from 1990s through contributions by many
Polymerization—Reviewed from a a chemist’s point of view. In contra- groups:[13–18] in 1979, Coburn and
Chemical Point of View’’. Although distinction, Whittle et al. propose Winters[15] demonstrated (albeit
our views regarding the role of positive positive ions as building blocks in rather indirectly) the synergetic role
ions often differ from those expressed the deposition of plasma polymers; of positive ions and neutral radicals in
in that article, we believe it has let us at this early stage stress the enhancing etch rates by orders of
important merits, namely to focus opposition between that latter view- magnitude. Their work, carried out in
the attention of plasma scientists point and one which considers posi- the early 1980s, incited other workers
toward the ‘‘real’’ microscopic tive ions primarily as promoters and to reassess the role of positive ions
mechanisms of plasma polymeriza- initiators of the polymerization pro- near the plasma edge in low-pressure
tion, as opposed to general ‘‘overall’’ cess, which itself is based mainly on plasma processes.[16] However, since
macroscopic kinetics approaches,[1–4] neutral species (radicals).[10–13] that time, all plasma scientists have
which have stimulated discussions Whittle et al. further argue in terms come to accept the important role of
among several leading experts[5–9] of a ‘‘physical’’ role of electrical poten- ions in etching and deposition pro-
with varying opinions. Another merit tial distributions in the discharge as cesses, not because ions directly ablate
is its indirect reminder that any low- driving forces that propel high mole- a surface or produce a coating (because
pressure plasma process, i.e., etching, cular weight ions, produced by ‘‘che- their arrival rates at substrates would
deposition or surface modification, mical’’ condensation reactions in the be too small), but for initiating or
plasma’s gas phase, toward the grow- activating microscopic processes at
R. d’Agostino ing film’s surface. However, the the surfaces where etching or deposi-
Dipartimento di Chimica, Università degli authors ignore important physical tion occur. The following attempts to
Studi di Bari, Aldo Moro, Via Orabona 4, effects of these heavy (or smaller) ions present a simplified picture:
70126 Bari, Italy when they impact upon the surface,
E-mail: and their possible consequences on (1) In a low-pressure reactor, positive
R. d’Agostino, F. Palumbo
the deposition mechanism. From this ions start to accelerate at the
Consiglio Nazionale delle Ricerche,
latter point of view, the positions plasma edge (inside the sheath);
Istituto di Metodologie Inorganiche e dei
Plasmi, Via Orabona 4, 70126 Bari, Italy
expressed by Whittle et al. and by when they strike the substrate
R. d’Agostino Friedrich are not far apart. surface, they produce damage, for
Plasma Solutions, Spinoff of the We believe that a discussion of the example lattice disruptions, bond
University of Bari, Via Orabona 4, 70126 microscopic mechanism of plasma breakage, creation of free radical
Bari, Italy polymerization, one particular aspect sites. All these damaged sites

Plasma Process. Polym. 2012, 9, 844–849

844 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201200072
Comment on Ion-Assisted Plasma Polymerization

increase the surface free energy, Transit Frequency, values of potentials Positive ions are the only ones that
resulting from momentum trans- that drive the ions are averaged over can reach the substrates, because
fer provided by ion collisions. This, a voltage cycle. Furthermore, the negative ions are driven back by the
in turn, creates surface sites that (average) potential drop depends on potential drop in the sheath. The ions’
readily form bonds with physi- the electrical connection (grounded energy at the substrates can be very
cally adsorbed atoms or radicals or powered), as well as on power, high compared with that in the plasma
on the surface. pressure, and area of the electrode(s). bulk; the value of their flux, Øþ, is:[20]
(2) The atoms or radicals diffusing to In all cases, the ion energies are
þ ¼ np ½ðkTe =mÞ=ð1 þ 2C0 Þ1=2;
the surface are first adsorbed; governed by the potential drops, and
then, when they reach an active they can range from a few eV to several where np is their density in the bulk
site, they form a chemical bond. hundreds of eV, while their energy plasma, k the Boltzmann’s constant,
These are the first steps toward inside plasma bulk is only a fraction of Te the electron temperature, m the
forming a volatile etch product (in an eV to a few eV, at most. Evidently, ion mass, and C0 is a dimensionless
ablation) or a polymer-like chain therefore, the effective energy of (collision) number.
(in deposition). Therefore, etching positive ions that strike the substrate Whittle et al. refer to a plasma at
and deposition have essentially is related to the potential drop, but 1 mTorr,[21] where they measured an
the same microscopic mechanism, it will also be strongly affected by ion flux of 3  1018 m2  s1; they
the only difference being the fate the numbers of collisions inside the state:
of the formed compound: in the sheath, to be examined in the next ‘‘For the same plasma, this gives
former case, etching, it is a volatile section. It is now also accepted that a thermal flux of neutrals of
molecule, which desorbs from the the reactor’s architecture and certain 1.7  1021 molecules  m2  s1. There-
surface; in the latter case it is a external parameters strongly affect fore in terms of relative arrival rates,
part of a polymer-like chain. So, in the potential drop: the areas, A, of the ratio of neutrals to ions is 560–
general terms: electrodes ‘‘1’’ and ‘‘2’’ are related to nearly twenty times greater than the
their respective electrical potentials calculation on the basis of plasma
(1) S + I+ S* as:[19] density. Data taken across a range of
pressures in argon plasma indicate that
Rgas Rads V1 =V2 ¼ ðA2 =A1 Þn ; this observation is repeated up to at
where n is typically <4. Generally, least 100 mT (at which point the sheath
Rads + S* polymer
parallel-plate reactors are asym- becomes collisional), with the ratio of
Etching products measured neutral and ion flux around
metric: grounded electrodes usually
being larger than powered ‘‘cath- 10–20 times higher than values calcu-
where S and R stand for ‘‘Surface
odes’’, the voltage drop at grounded lated on the basis of the plasma density
sites’’ and ‘‘Radical’’, respectively.
surfaces is smaller than at the and under the assumption that the
powered electrode. This effect can fluxes are thermal’’
be enhanced at low pressures, From that statement one would
p  50 mTorr, because by reducing p deduce that:
the plasma volume will spill out
2. The Sheath beyond the geometric volume of the (1) the ratio of the flux of neutrals to
inter-electrode gap space. Basically, ions is higher than that calculated
In low-pressure plasmas, electrons are the plasma often ‘‘brushes’’ the walls on the basis of thermal fluxes;
the species with the highest mobility; (normally grounded), in such a way (2) even at 1 mTorr the flux of neu-
in a matter of a few nanoseconds that these should be taken into trals is about 600 times higher
they charge all exposed solid surfaces account in the overall effective sur- than that of ions; at 100 mTorr,
negatively—reactor walls, electrodes, face area of grounded surfaces and a common pressure for plasma
immersed items at floating potential. in considerations of the electrodes’ polymerization experiments, the
This results in a potential drop with asymmetry. As a rule of thumb, the sheath is already collisional.
respect to the (positive) glow, a voltage drop at the grounded elec-
reduced electron density in the trode (and substrates placed on it)
sheath and, consequently, an accelera- generally ranges between a few volts
tion of positive ions toward the solids’ and some tens of volts, while sub- 3. Effects of Pressure
walls. It is important to recall that strates on the powered electrode can
in MHz-driven glow discharges, i.e., experience several tens to some The most important effects of pres-
at frequencies higher than the Ion hundreds of volts. sure, p, in plasma systems have gen-

Plasma Process. Polym. 2012, 9, 844–849

ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 845
R. d’Agostino, F. Palumbo

erally been well understood for some reactor has magnetic confinement where the number of ion/neutral
time: and can operate even below collisions in the sheath becomes
1 mTorr.[23,24] Further, the ion so large as to nullify possible
(1) p affects the energy delivered to energy is at a maximum; as a surface activation by ions. This
molecules, according to the para- consequence, their physical effect is the purely chemical process
meter W/p; in rearranging structure of the regime of deposition or etching.
(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 To the best of our knowledge,
(4) it determines the probability of power is raised. However, at low plasma polymerization is mostly car-
many-body (bi- and tri-molecular) power, identifying ions as build- ried out at p > 70 mTorr. In order to
reactions, e.g., recombination; ing blocks in polymerization reac- lend weight to this statement, we have
(5) p governs the residence time. tions might not be unreason- screened all related articles published
able—the view expressed by in Plasma Processes and Polymers (a
Whittle et al. We can refer to this time interval that extends over almost
Limiting one’s attention to how p regime as one of ionic processes. 9 years) and have subdivided the data
may affect physical/chemical contri- (b) 70 < p < 350 mTorr, where the by pressure ranges, see bar-graph in
butions to plasma polymerization [ions]/[neutrals] ratio decreases Figure 2. We observe that among 77
mechanisms, one can readily envisage by orders of magnitude; here, in papers dealing to varying extents
that by raising p the ion density will fact, the degree of ionization with plasma polymerization, roughly
decrease and the energy that ions gain is generally considered to be two thirds describe processes at
in the sheath will be greatly reduced. ca. 107–105. Under these condi- p > 70 mTorr. Articles on powder
Varying ion bombardment by chan- tions the flux of ions can definitely synthesis were not considered, nor
ging p is qualitatively illustrated not be responsible for ablation of a work at atmospheric pressure, nor a
in Figure 1:[22] ion-induced damage solid, nor for deposition of thin few papers that do not clearly mention
greatly increases by reducing p; films, no matter how high the the value of p under investigation.
one may note three regimes (the value of sticking probability may It therefore would appear that the
pressure limits are only approximate): be. However, positive ions can experimental conditions utilized by
markedly affect the rates of etch- Whittle et al., in which ions could make
(a) p < 70 mTorr, is characterized by a ing/deposition processes, because a massive contribution to the rate
high [ions]/[neutrals] ratio. The they can activate the substrate, as of polymerization, are uncommon
collision frequency is quite low, discussed in point (1) of the first indeed. This definitely can be consid-
and the flux of ions can be section. This is the regime of ion- ered as a merit of the paper, because it
appreciable compared with that assisted processes. contributes toward filling a gap in
of neutrals (as also shown by (c) p > 350 mTorr, where [ions]/[neu- the plasma polymerization literature.
Whittle et al.), particularly if the trals] ratios are very low and However, certain arguments raised
there cannot be justified when dis-
cussing general aspects of the plasma
polymerization mechanism.
Ion-induced damage(au)

4. Ion-Assisted
ion assisted
pure chemical 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-
70 350 Pressure (mtorr)
tion can be impractically slow, and
Figure 1. Generalized view of ion-induced surface damage as a function of pressure in because the discharge volumes
plasma processing operations (deposition, etching, surface modification). expand—with glows that contact

Plasma Process. Polym. 2012, 9, 844–849

846 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201200072
Comment on Ion-Assisted Plasma Polymerization

35 where Kp, Ke, and Ks represent the rate

Number of papers 30 constants of the ion-assisted polymer-
ization, etching, and sputtering pro-
cesses, respectively. Similarly, Favia
20 et al.[30] demonstrated that an AGM
mechanism can be useful in inter-
preting results obtained in plasma
10 deposition of tetramethylsilane: in a
5 similar reactor with a triode config-
uration they found the deposition
rate to reach a maximum when bias
P<70 70<P<350 P>350
range (mtorr) voltage was increased independently
from other experimental parameters.
Figure 2. Number of papers relating to plasma polymerization published in Plasma Energetic ions contributed to the
Processes and Polymers; the total number, 77, has been subdivided according to the
operating pressure ranges used.
formation of active sites, enhancing
the growth of plasma polymer; how-
ever, raising the bias even further had
the vessel walls and render it difficult power input) and the density of active the effect of reducing the deposition
to define the discharge region and the species. The experiments were run rate on account of competing etching
exact electrical conditions that prevail. with several feed gases (O2, CF4, and sputtering processes.
When intermediate p-values are uti- and C2F4) and gas mixtures, some of
lized, ion-assisted polymerization pro- which led to etching reactions
cesses can become very important. The because they produced mainly F-
first reports, at least to our knowledge, atoms or O-atoms, while others pro- 5. Modulated (Pulsed)
were those of Vinogradov et al.[25] and ducing mainly CFx-radicals led to Discharges
of Smolinsky and Vasile.[26] Shortly polymerizing reactions. Both rates,
thereafter, d’Agostino et al.[27,28] devel- of etching and polymerization The case of pulsed plasma, whereby
oped a model based on reaction reactions, clearly increased in the CW power is chopped, deserves sepa-
scheme (1), to which they gave the presence of bias, in agreement with rate comment. Plasma polymerization
name Activated Growth Model (AGM) the AGM. in such cases can lead to extremely
of polymerization. In that case the rate d’Agostino et al. developed a triode high monomer structure retention.[31–36]
of polymerization, rpol, was expressed reactor with a very small third elec- It has even been demonstrated that
as: trode in an aside position—smaller plasma polymerization can take place
  than the reactor’s main cathode.[13] during the ‘‘Off’’ time-interval (for
rpol ¼ K Rg f ðIþ Þ; (2) This had the advantage of permitting certain precursors, even at higher
a negative substrate bias without deposition rate), under conditions of
where f(Iþ) is a function of the energy increasing the total input power and negligible (if not zero-) ion- and
and flux of ions striking the surface. without changing the density of active electron bombardment. As a conse-
Equation (2) predicts a rise in the rate species—monitored by emission spec- quence, the coating can grow almost
of polymerization with increased sub- troscopy in most cases. They measured ‘‘undisturbed’’ under these mild con-
strate bias, provided that the radical polymerization rates from a variety of ditions, compared with continuous
density, Rg, does not vary much with fluorinated feed gases and observed plasma ignition at the same nominal
experimental conditions. An impor- the rate to increase with rising bias, power: in the latter case, impinging
tant confirmation of the AGM was in most cases passing through a ions re-arrange surface atoms, gener-
published by Fracassi et al.[14] They maximum. Indeed, the expression for ally leading to a more cross-linked, less
utilized a diode RF reactor, equipped polymerization rate must take into ‘‘conventional’’ structure. However,
with two extra electrodes on the sides account the fact that positive ion during the ‘‘On’’ time-interval the
of the reactor. These were Quartz- bombardment triggers deposition, contribution of ions can be important
Crystal Microbalances, QCM, one but can also assist etching and even- in creating active sites, where chemi-
grounded and the other biased to tually even sputtering,[29] as follows: sorption of radicals can also promote
150 volts. It is important to note growth of the coating.[32]
that this bias of the small QCM J. D. Whittle et al. commented that,
rpol ¼ Kp ½CFx f ðIþ Þ  Ke ½FgðIþ Þ
electrode was verified not to influence (3) as demonstrated in some papers,[37,38]
 Ks hðIþ Þ;
the overall electrical conditions (e.g., positive and negative ions can survive

Plasma Process. Polym. 2012, 9, 844–849

ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 847
R. d’Agostino, F. Palumbo

for several milliseconds during the although this topic is too often over- [12] K. Masek, L. Laska, R. d’Agostino,
‘‘Off’’ period of pulsed plasma in looked, we nevertheless wish to stress F. Cramarossa, Contrib. Plasma Phys.
1987, 27, 15.
acrylic acid vapor. The notion that our viewpoint that ions mainly serve
[13] R. d’Agostino, F. Cramarossa, F. Illuzzi,
stable macromolecular ions can form as ‘‘activators’’ rather than as ‘‘build- J. Appl. Phys. 1987, 61, 2754.
inside the plasma and participate in ing blocks’’ in plasma polymerization [14] F. Fracassi, E. Occhiello, J. W. Coburn,
the deposition process appears reason- reactions. J. Appl. Phys. 1987, 62, 3980.
able, but we do not believe that such [15] J. W. Coburn, H. F. Winters, J. Appl.
ions can play an important role during Phys. 1979, 59, 3189.
[16] H. F. Winters, J. W. Coburn, T. J.
the ‘‘Off’’ time interval, for the follow- Chuang, J. Vac. Sci. Technol., B 1983,
ing reasons: beside the low value of Acknowledgements: We are indebted to 1, 469.
ion density we already pointed out, Prof. Michael R. Wertheimer for the valu- [17] G. S. Oehrlein, in Reactive Ion Etching:
able discussions during the preparation of Handbook of Plasma Processing Tech-
at the start of the ‘‘Off’’ period the
this manuscript. Mariagrazia Troia is nology, S. M. Rossnagel, Ed., Park
plasma sheath collapses, hence also thanked for her assistance in sifting Ridge, NJ Noyes 1990, p. 196.
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ions toward the growing coating’s literature. Ibbotson, J. Vac. Sci. Technol., B 1983,
surface. This means that during that 1, 23.
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and Plasma Etching, Brian Chapman,
toward nearby solid surfaces primarily
John Wiley & Sons 1980.
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Plasma Process. Polym. 2012, 9, 844–849

848 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/ppap.201200072
Comment on Ion-Assisted Plasma Polymerization

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ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 849