On the Influence of Electron Energy on Iodine-Doped

Polyaniline Formation by Plasma Polymerization

M. G. OLAYO,1,2 J. MORALES,3 G. J. CRUZ,1 R. OLAYO,3 E. ORDOÑEZ,1 S. R. BAROCIO4

1
Departamento de Sı́ntesis y Caracterización, ININ, AP 18-1027, Col. Escandón, 11801 Distrito Federal, Mexico

2
Posgrado en Materiales, FQ-UAEM, Colón y Tollocan, 50000 Toluca, Mexico

3
Departamento de Fı́sica, UAM-I, AP 55-534, Iztapalapa, 09340 Distrito Federal, Mexico

4
Departamento de Fı́sica, ININ, AP 18-1027, Col. Escandón, 11801 Distrito Federal, Mexico

Received 30 June 2000; revised 8 September 2000; accepted 12 October 2000

ABSTRACT: The influences that both electron energy and density of a plasma bear on
thin film formation are examined in the case of iodine-doped polyaniline polymeriza-
tion. The plasma was produced by means of 13.5-MHz radiofrequency– generated glow
discharges in low-pressure (ca. 10⫺2 mbar) air between electrodes. Four representative
inner regions of the reactor were selected according to the electron incidence. Given the
uneven energy distribution found on the inside of this kind of reactors, variations in the
polymer structure formed in the presence of iodine were found and studied by elemental
analysis, thermogravimetry, infrared spectroscopy, and X-ray diffraction. The results
indicate that the electric conductivity of polyaniline by plasma is a function of the iodine
content and that such content is a function of the combined conditions of both reactor
and plasma. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 175–183, 2001
Keywords: plasma; polymerization; polyaniline; electron energy; Langmuir probe

INTRODUCTION direct formation of the polymer from the vapor

Polyaniline (PAn), a polymer whose electric prop-
erties are often similar to those of semiconduc-
tors, can present some structural variants accord-
ing to the degree in which its molecules are
oxidized, resulting in a diversified electric conduc-
tivity.1– 6 The latter has proved to be a function of
the environmental humidity, especially when
some anionic groups or metallic elements are
added to the structure.7–10 Polyaniline has been
synthesized by several techniques, one of which is
carried out by means of plasmas, allowing the
Correspondence to: M. G. Olayo (E-mail: gog@nuclear.
inin.mx)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 39, 175–183 (2001)
© 2000 John Wiley & Sons, Inc.
phase onto surfaces where thin films of the poly-
mer are developed.11–18
The energy levels of the plasma particles play
an important role in the structure and morphol-
ogy of the polymer during the synthesis by
plasma. Two kinds of techniques for plasma gen-
eration are usually applied: (1) the resistive tech-
nique, in which the gas is ionized by an electric
field created between two charged electrodes and
(2) the inductive technique, in which the ionizing
electric field is produced by an external time-
varying magnetic flux created by a coil that is
wound around the reactor. Each technique leads
to different reaction rates, provided that each one
is characterized by different regions in the reactor
vessel as to the kinetic energy of the impinging
particles. By as much as the electric properties of
175
176 OLAYO ET AL.
PAn depend on its degree of oxidation, which in
turn is a function of the particle energy, the re-
sulting polymer conductivity can vary by several
orders of magnitude.
Free radicals and ions mixed up with monomer
molecules and with the developing chains of the
polymer in formation can be found within the
plasma volume. Yet, the particles that trigger the
radical and ion cascade are free electrons collid-
ing against neutral particles. Electrons possess a
greater mobility than the rest of the particles,
given their comparatively small mass and conse-
quent higher speed. So, by measuring the kinetic
energy of the free electrons, the capacity of the
whole system to react and produce the polymers
can be assessed.
Although the study of polymerization by
plasma is on the increase, the relationship be-
tween the incident electron energy and the struc-
ture of the impinged material, dealt with here,
remains barely reported in the literature. In the
first place, it should be noted that the particle
incidence within the reactor behaves very much
like the scheme shown in Figure 1. The ionized
particles collide with the electrodes at right an-
gles to their surfaces, whereas their angles of
incidence on the reactor walls are multiple. The
effect of this phenomenon is discussed in the
present work, studying the structure, thermal
stability, and electric properties found in PAn and
iodine-doped PAn (PAn/I) synthesis by radiofre-
quency (RF)-induced plasma, within a reactor op-
erated resistively. The results are complemented
with the analysis of the main plasma parameters
by means of Langmuir probes, to gain a better
understanding of the role of the plasma in the
final structure in the polymers.
Figure 1. Reactor scheme exhibiting the location of
the electrodes. The measurement points are located in
terms of the inner vessel horizontal length, L ⫽ 50 mm.
EXPERIMENTAL
The experiments were carried out on a 1500-cm3
cylindrical glass reactor vessel endowed with two
63.6-cm2 stainless steel electrodes (Fig. 1), one of
which was kept grounded as a reference potential.
Vaporized aniline (J. T. Baker Chemical, Phillips-
burg, NJ) was admitted into the reactor through
one of the accesses. Vapor of iodine (Aldrich, Mil-
waukee, WI) entered by another port. For the
synthesis of PAn/I, they were mixed together in-
side the reactor simultaneously with the polymer-
ization. The reactions were promoted by the col-
lisions of the monomer molecules with the elec-
trons, ions, and the other particles in the plasma.
Aniline and iodine flowed into the reactor from
their respective flasks, pumped indirectly by the
vacuum system, that is, by using the pressure
gradient between reactor and containers. In this
way, no carrier gas or other additional chemical
elements were present.
The reactor was connected to a vacuum system
and the electrodes were connected to a 13.5-MHz
RF oscillator and amplifier, to create an initial
low-pressure air plasma on the order of 10⫺2
mbar. After that, the pressure in the reactor at
the time of the polymerization was set between 8
and 4 ⫻ 10⫺2 mbar, with power in the range of
10 –14 W. The experimental setup and the oper-
ational parameters with which the syntheses
were performed were very similar to those previ-
ously reported.12 The most relevant aspect of the
present experiment, however, was the measure-
ment of the electron energy along the reactor,
which was accomplished by means of electric
probes whose circuits were independent from
those of the plasma generation.
RESULTS AND DISCUSSION
Once the polymers were grown in the form of a
thin film (reaction time of 180 min), they were
removed and classified according to the reactor
region from which they originated. Four energy
regions of the reactor, that is, the electrode sur-
faces and the walls, were identified and subdi-
vided as: grounded, central, and RF zones, shown
in Figure 1. In general it was found that the
polymer films extracted from the electrodes were
more rigid than those developed on the walls.
Characteristics of the Plasma
The characteristics of the plasma were measured
on seven locations within the reactor by means of
 INFLUENCE OF ELECTRON ENERGY ON PAn FORMATION
an electric Langmuir probe introduced through
one of the diagnostic portholes. The measurement
points were distributed, as shown in Figure 1,
just outside the volume between the electrodes, to
allow the free displacement of the probe along the
vessel. The data were collected just before the
chemical reactions, to avoid the interference of
the polymer on the probe surface. The electron
kinetic energy, density, and plasma potential
were calculated in accordance with the method
proposed by Ball.19
Figure 2 presents the average distribution of
the measured plasma electric potential as a func-
tion of the probe position within the vessel. For
values on the horizontal axis, scaled with respect
to the chamber’s inner length (L ⫽ 50 mm), refer
to those in Figure 1. The origin is located at the
center of the vessel. The plasma potential was
displaced from negative values to have almost
positive values. In this way, next to the grounded
electrode, the potential measured ⫺1.6 V and, as
the probe moved away from it, the potential in-
creased up to 230.7 V as it approached the RF
electrode; however, as the probe moved even
closer to the RF electrode, the potential decayed
at 142.3 V as a result of the electron shielding
effect.
The plasma potential determines the accelera-
tion to which the charged particles are subjected.
In turn, the chemical reactions are influenced by
both the acceleration and the energy of the
charged particles. The number of collisions
among these particles and the neutrals increases
the ion population, promoting changes in the
plasma polymerization mechanics.
Figure 2. Plasma potential as a function of the probe
position inside the vessel. L ⫽ 50 mm.
177
Figure 3. Electron density as a function of the probe
position inside the vessel. L ⫽ 50 mm.
In the absence of oscillations, the theoretical
plasma potential curve, from one electrode to an-
other, should have a rather monotonically de-
creasing profile, from ⫺L to ⫹L, in which the
Debye shielding of the electrodes plays an impor-
tant role in the profile shape. However, under the
alternating field, the profile shape is largely dom-
inated by the electron population, as the consid-
erable inertia of the ions renders their population
practically stagnant.
The electron density ne can be considered as
the result of two major competitive processes: (1)
ionization by collision and (2) loss by diffusion.
Thus, the equation of continuity under the equi-
librium condition ⭸ne/⭸t ⫽ 0 yields a typically
senoidal one-dimensional solution, adjusted by
the boundary conditions and similar potential
profiles, given the Poisson’s equation. In the RF
half of the reactor (Fig. 2), the probe measured a
senoidal potential profile with a maximum lo-
cated at about ⫺0.6L. The lowest value is 140 V
and the maximum value is about 240 V, a differ-
ence of approximately 100 V. In the grounded half
of the reactor the potential varies from 140 V to
about 0 V, a variation that is 40% greater than
that in the RF half of the reactor.
The electron density, also as a function of the
probe position, is displayed in Figure 3. Close to
the grounded electrode the density is 7.63 ⫻ 107
cm⫺3. Then, it successively declines and increases
as one moves to the middle of the vessel, where
the density reaches 2.8 ⫻ 108 cm⫺3. Further on, it
drops, only to rise again up to 5.15 ⫻ 107 cm⫺3 at
the RF electrode. Such behavior indicates that the
178 OLAYO ET AL.
density concentrates in the central region and in
the electrode vicinities on both sides of the reac-
tor. The results also indicate that the electron
density presents three partially overlapping dis-
tributions. The profile suggests senoidal distribu-
tions with a central half period from ⫺0.4 to 0.4L.
Given the time-averaging reading of the probe,
the lateral distributions may be related to the
accumulation of electrons near an electrode,
which reverts every time that the RF electrode
changes its polarity.
The average electronic temperature in the ves-
sel, as a function of the position between the
electrodes, is shown in Figure 4. The electron
kinetic energy presents little variation in the mid-
dle portion of the reactor (12–14 eV), in spite of
the plasma potential fluctuation, although a sig-
nificant increase in the electron temperature, up
to 26 eV, is measured as the RF electrode is ap-
proached. On the other hand, although accurate
measurement at the points beyond the ground
electrodes was prevented by the loss of resolution
in the probe, the observed tendency of the elec-
tron temperature was to decline rather rapidly
toward the grounded end.
The electrons are the dominant particles in-
volved in the molecular ionization of the chemical
species in a plasma. The elastic and inelastic col-
lisions of the molecules propagate excitation,
fragmentation, and ionization, sustaining the
polymer development. From this point of view,
the electron kinetic energy is a promoter of the
chemical reactions involving the monomers and
the consecutive segments like dimers, trimers,
Figure 4. Electron temperature as a function of the
probe position inside the reactor. L ⫽ 50 mm.
and so forth. That is why the nonuniform elec-
tronic energy obtained in the reactor produces
different polymer structures along its length,
whose differences change the final properties of
the material.
Bearing in mind the time-averaging effect of
the probe readings, in the neighborhood of the RF
electrode, the electrons acquire acceleration and
energy as a result of the Debye shielding, which
acts as an electric sheath, producing a particular
energy profile. It is difficult to measure the
plasma parameters in this space because the
charges do not freely move as they do in the rest
of the plasma. However, it is possible to assume
that, in the proximity of the RF electrode, the
kinetic energy profile reaches its peak when the
electrons are accelerated at a close range. The
influence of the Debye shielding on the experi-
mental conditions imposed on the plasma poly-
merization synthesis mentioned here is around
0.4L, that is, 40%. The RF electrode region pre-
sents the highest electron energy and, therefore,
the probability is higher there than in the rest of
the reactor, that the collisions of the electrons
with the neutral monomers produce excited par-
ticles prone to react to form polymers.
As seen in Figure 4, the electron temperature
Te exhibits a plateau, from ⫺0.6 to 0.6L, between
the electrodes. Again, given the time-averaging
operation of the probes, this result is consistent
with the classical electron velocity distribution
function: in the case of nonalternating fields, the
temperature Te ⬀ ⌽/ln(ne/n0), where ⌽ is the elec-
tric potential and n0 is the electron density in its
absence. By comparing Figures 2 and 3, the cen-
tral plateau in Figure 4 seems to result from the
opposing concavities of ⌽ and 1/ln(ne/n0) in the
region. Toward the RF region, ⌽ is not far from its
peak value, whereas ne ⬃ n0, leading to high Te
values. On the grounded side, by contrast, the
condition ⌽ 3 0 decreases the temperature.
Provided that the electron energy is varied but
high throughout the vessel, polymers with greatly
diversified structures can be developed, as the
average energy is able to break down the bonds
among the elements.20 Such diversification
makes it necessary to rely on multiple analyses,
to determine the influence of the plasma param-
eters on the polymer structures found in the dif-
ferent regions of the reactor.
IR Analysis
Figure 5 presents the IR spectra of PAn/I. The
most interesting aspects of the IR spectra are the
 INFLUENCE OF ELECTRON ENERGY ON PAn FORMATION 179

EDS (energy-dispersion spectroscopy) by means of a

Figure 5. IR spectra of PAn/I in the four energy re-
gions.
evidence of the substitutions in the aniline rings
of the polymers located in the peaks at 696, 754,
and 830 cm⫺1 belonging to the meta, ortho, and
para disubstitutions. This means that the aniline
rings survive to the energy of the discharges, thus
allowing the formation of the polymers. Further
interesting evidence is the peaks at 1173, 1315,
and 2935 cm⫺1, generated by the aliphatic COC,
CAC, and COH bonds that can be the result of
the breaking of the aniline rings. This evidence
suggests that there are also some rings that break
because of the high-energy electronic flux that
generates segments of branching and probably
crosslinking in the final polymers. In the most
energetic zone, that is, the surface of the elec-
trodes, the presence of the aniline rings dimin-
ishes, as seen in Figure 5.
Elemental Analysis
Elemental analysis data on polymer films, from the
four energy regions of the reactor, were taken by
Phillips XL 30 scanning electronic microscope. No
significant differences of PAn were found in the
polymers from the four regions, although PAn/I did
show changes in the polymers formed in those re-
gions.
Results from the elemental analysis of PAn/I
are listed in Table I. Polymers formed in the cen-
tral zone present an iodine content that is 16 –
25% higher than that in the other three zones,
behavior that is attributed to two factors: the
density and the electron energy. The electron den-
sity attains the highest values in the central zone,
as discussed in the previous section. Such behav-
ior might well be extended to the other negative
particles, that is, the iodine ions, as iodine atoms
ionize by capturing an electron from the plasma
environment. The particle energy appears to be
the other plausible explanation for this differ-
ence, as the continuous impact on the electrodes,
which are both perpendicular and accelerated
(Fig. 1), releases some iodine atoms bonded to the
polymer chains or trapped between the polymer
layers. The particle trajectory impinging on the
vessel walls in the zone between the electrodes is
oblique and less accelerated (Fig. 1), so that many
of the iodine atoms remain bonded or trapped by
the chains growing on the surfaces.
In the electrode regions it is not easy to under-
stand, based only on the electronic data, which
parameters influence the particle trajectories,
given the complex combination of the density and
energy of the particles. The other dominant factor
on the surface of the electrodes could be the for-
mation of reticular polymers because of the local
higher particle acceleration. In such conditions, it
is more difficult for the iodine atoms to react or be
trapped by the chains that grow on those sur-
faces.
According to the elemental analysis reported in
Table I, there exists approximately one iodine

Table I. Elemental Composition of PAn/I in Weight and Atom Percentages

RF Electrode RF Central Grounded

Element Wt % At % Wt % At % Wt % At % Wt % At %

C 68.52 85.08 66.29 84.13 63.29 84.03 68.04 85.67

N 10.88 11.29 11.17 11.86 10.19 11.52 9.71 10.59
O 1.87 1.21 1.51 1.29 1.48 1.1 1.03 1.09
I 18.73 2.42 21.03 2.72 25.04 3.35 20.95 2.65
Total 100 100 100 100 100 100 100 100
180 OLAYO ET AL.
atom for each five benzene rings in the grounded,
RF, and RF electrode regions, whereas in the
central region, one iodine is found for each four
rings. As iodine becomes preferably ionized by
acquiring one electron, the iodine ions become
attracted to the regions with higher positive po-
tential. Thus, iodine should concentrate in the RF
region at ⫺0.75L, where the potential peak is
found (see Fig. 2). However, the grounded and RF
regions show very similar iodine percentages in
their respective polymers, suggesting that VP in
both regions is not nearly as important as is the
density of electrons.
Thermal Analysis
The thermal decomposition of PAn and PAn/I is
described in Figure 6. The PAn thermograms
show little difference among the four energy re-
gions. Mass losses of around 3%, resulting from
humidity, are detected within the 50 –200 °C in-
terval. Then, a relatively fast decomposition
starts from 200 °C until, at 450 °C, a 60 – 65%
mass remains in all four regions. The plots
present a change in slope in the 450 – 600 °C in-
terval, indicating a slower loss rhythm, which
accelerates up to 850 °C when about 80% mass is
lost.
PAn/I decomposition exhibits notable regional
variations from the beginning to the end of the
temperature domain. Starting from the humidity
losses in the 30 –100 °C interval, the electrode
region released 2% more mass than did the other
samples. At 150 °C, the decomposition curves be-
Figure 6. PAn and PAn/I thermograms according to
the energy regions.
gin to diverge and, between 200 and 450 °C, io-
dine is being lost, in combination with the ther-
mal degradation of all the polymers. The RF and
central regions evolve in a very similar manner:
at 350 °C they have lost 45% of their mass and,
from this temperature on, they decompose at a
rather constant rate. The RF electrode region
shows a slower decay, in which its mass loss at
350 °C is 35% without major later fluctuations.
Decomposition is faster in the case of the ground
region, with 65% mass lost at 350 °C and a slower
pace up to 750 °C. At 800 °C, it becomes approx-
imately a 10% residual mass.
The PAn/I RF electrode region thermogram de-
picts a slow decomposition, similar to that of PAn,
possibly resulting from the fact that the high en-
ergy available in the region allows the formation
of strong bonds that hinder iodine release.
The thermograms indicate that every energy
region liberates a particular amount of iodine.
The plasma parameters clearly reflect the influ-
ence of the plasma on the iodine within the struc-
ture of the growing polymers. The grounded re-
gion, with the lowest energy, releases more iodine
than does any other region, in spite of not having
the highest iodine content according to elemental
analysis, but as a result of its small plasma po-
tential (Fig. 2). Thus, as the influence of the ionic
current in the region becomes greater, it is prob-
able that the ion energy prevents the iodine from
penetrating deep into the polymer structure, pro-
vided that iodine captures electrons to become
ionized.
The high plasma potential in the RF and cen-
tral regions (Fig. 2) indicates no dramatic differ-
ences in their respective polymer structures, as
expected. Therefore, the thermograms of both re-
gions display similar conducts all along the tem-
perature domain.
The results from the differential scanning cal-
orimetry (DSC) of PAn and PAn/I are seen in
Figure 7. All polymers absorb energy between 30
and 100 °C, which is associated with the loss of
humidity. No major variations are found in the
case of PAn at higher temperatures. The PAn/I
curves indicate another important absorption
that corresponds to the iodine release between
214 and 440 °C.
Again, the energy regions clearly influence this
absorption. The maximum iodine release takes
place in the grounded region with a 223.1 WC/g
energy absorption in the 214 – 418 °C interval and
a peak at 334.5 °C. The absorption energy in this
region turns out to be 23– 43% higher than that in
 INFLUENCE OF ELECTRON ENERGY ON PAn FORMATION 181

Figure 8. X-ray diffraction of PAn in the four energy

Figure 7. DSC of PAn and PAn/I according to the regions.
energy regions.

ity in this kind of polymers.22,23 It is possible that

the other regions. The iodine release in the cen- the energy of the plasma particles that conform
tral region corresponds to a 171.3 WC/g energy the polymer does not allow the formation of crys-
occurring between 273 and 473 °C, with a peak at talline structures that are usual in other forms of
337 °C. In the RF and RF electrode regions, the synthesis.
recorded energies are 137.9 and 128 WC/g, with The diffractograms of PAn/I can be seen in
peaks at 314 and 322 °C, respectively. It should be Figure 9. The spectrum is amorphous in the case
remarked that all these results are in good agree- of the RF electrode region, although in the diffrac-
ment with the thermogravimetric analysis. tograms of the central, RF, and ground regions,
two small diffraction peaks appear around 21.3
X-ray Diffraction and 24.6°, respectively. Such peaks have been
reported as the most intense in the diffraction of
Polymers are generally amorphous materials, al- PAn and PAn/I.22,23 The calculated crystallinity
though some of them possess localized crystallin-
ity. Figure 8 exhibits the X-ray spectra of PAn,
taken by means of a Siemens D5000 system. The
diffractograms of the ground and RF regions dis-
play an amorphous spectrum, although the one
from the central region presents a shoulder be-
tween 11.9 and 13.5°, which may coincide with
the location of one of the characteristic diffraction
peaks of PAn. The crystallinity was calculated on
the basis of general considerations. The difference
between the completely amorphous spectrum and
the spectrum that gives signs of crystallinity was
calculated,21 yielding a 3% value for the central
region. Another shoulder, between 11.5 and
14.27°, was present in the RF electrode spectrum,
coinciding with one from the diffraction planes of
PAn, leading to the conclusion that there is about
3.5% crystallinity in the film.
In spite of the fact that PAn is a polymer capa-
ble of developing crystallinity, its amorphous part Figure 9. X-ray diffraction of PAn/I in the four en-
has covered the characteristic peaks of crystallin- ergy regions.
182 OLAYO ET AL.
Table II. Electric Conductivity of PAn/I in the Reactor Regions
RF Electrode
Electric conductivity
(S/cm) 2.596 ⫻ 10⫺9 8.987 ⫻ 10⫺8
yielded 4.9% in the RF region, 6.1% in the central
region, and 5.5% in the ground region.
By collating the results of X-ray diffraction one
can assess how the combination of iodine and
plasma particle energy contribute to the forma-
tion of more crystalline films. In the electrode
region, where the highest electron energy is
found, crystalline arrays are not favored. In the
other regions, the energy is lower and iodine can
give rise to small crystalline aggregates mani-
fested as two of the most intense and character-
istic peaks of PAn.
Electric Conductivity
The electric conductivity of PAn/I, once averaged
in each region inside the reactor, is shown in
Table II. The conductivity of PAn is not listed
here, given its extremely low values. In PAn/I, the
region with minor electric conductivity (2.5
⫻ 10⫺9 S/cm) is the RF electrode region. The zone
with the highest conductivity was the grounded
region, with 1.5 ⫻ 10⫺7 S/cm, a difference of ap-
proximately two orders of magnitude. The RF re-
gion yielded a 9.8 ⫻ 10⫺8 S/cm conductivity and
the central zone, a 7.4 ⫻ 10⫺9 S/cm value.
Because the polymers were synthesized in the
same thermodynamic, geometric, and electric
conditions, the difference in their electric conduc-
tivities can be directly associated with differences
in the polymer structure as a result of the various
local plasma conditions. In the region with the
hypothetically highest electronic energy, that is,
the RF electrode surface, the conductivity has the
lowest value. The crosslinking promoted in the
polymer chains by the high electron energy may
prevent the right order in the structure, neces-
sary to transport the electric charges. Iodine at-
oms also play an important role in the conductiv-
ity, yet, on the electrode surface, the percentage of
iodine becomes minimal. Thus, both components
seem to coalesce to make the conductivity de-
crease to its lowest value on the electrode surface.
Regions
RF Zone Central Grounded
7.389 ⫻ 10⫺9 1.56 ⫻ 10⫺7
On the other hand, the RF and grounded re-
gions present the highest conductivity. Although
both regions show considerable differences in the
electron energy, the population of electrons has a
similar distribution in both regions, with a lower
intensity than that at the center of the reactor.
The weight percentage of iodine in the structure
is approximately the same: 21.03% in the RF and
20.95% in the grounded region. So, it is possible
that the presence of such similar content in both
regions is more than adequate to transport the
electron flux. Higher and lower iodine percent-
ages produce a decrease in the conductivity, as
can be seen in the central and electrode surfaces,
respectively.
The ionization of a neutral atom of iodine can
occur as a result of an impact with any particle in
the plasma. The first ionization energy of iodine is
10.4 eV. Consequently, if the collision of an iodine
atom with an electron produces an iodine ion,
then the energy of the electron should be greater
than 10.4 eV. The region in the reactor with elec-
tronic energy lower than 10.4 eV is the grounded
zone. Therefore, in this zone, the iodine atoms
may be trapped among the polymer chains with-
out being chemically bonded with them. This ef-
fect can be detected on the DSC thermograms,
where the grounded zone easily releases the io-
dine content.
CONCLUSIONS
The effects of the reactions with plasma particles
at different energies on the polymers studied in
this work are unmistakable. The variation of en-
ergies in the electron incidence, both on the react-
ing molecules of the polymer being formed and on
the superficial structure of the polymer already
formed, creates a diversity of elemental composi-
tions. Given that iodine is present in multiple
concentrations in each energy region of the reac-
tor, it follows that the greatest difference in the
 INFLUENCE OF ELECTRON ENERGY ON PAn FORMATION
polymer composition is found when iodine inter-
venes in the reactions. The central region is the
richest in iodine, about 16 –25% higher than the
iodine content in the other regions. The thermal
conduct of the polymer is consistent with the po-
tential and the temperature of the plasma in each
energy region. Thermal analysis reveals striking
differences between the doped polymers and
those without doping, mainly in the range 214 –
440 °C, where much of the iodine escapes from the
doped polymer, particularly in the ground region.
X-ray diffraction confirms that iodine combined
with the particle energy contributes to the devel-
opment of crystallinity in the polymers, formed in
the regions where the particle trajectories, do not
permit direct incidence. Provided that iodine,
when ionized, becomes sensitive to the electric
fields generated by the plasma discharge, dope-
less PAn does not respond with the same sensi-
tivity to the fields as does PAn/I, possibly because
reaction mechanisms of PAn are not greatly ionic.
The authors gratefully acknowledge L. Carapia and J.
de la Torre from ININ Electronic Microscopy Labora-
tory for their assistance in the SEM analysis; T. Falcon
from ININ X-ray Diffraction Laboratory for her partic-
ipation in the X-ray analysis of samples; C. Rodriguez
from ININ Chemistry Department for collaborating in
the analysis of DSC; and Conacyt and Dynasol Elas-
tómeros S.A. for the partial support for this work.
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