Conductive Polyaniline on Paper as a Flexible Electronic

Material With Controlled Physical Properties Through Vapor

Phase Polymerization

Krishna Deb,1 Arun Bera,1 Kartick Lal Bhowmik,1,2 Biswajit Saha 1

1
Department of Physics, National Institute of Technology Agartala, Jirania 799046, India
2
Department of Chemistry, Bir Bikram Memorial College, Agartala 799004, India

Tuning of hole transport and optical properties were
accomplished in polyaniline incorporated flexible paper
during vapor phase polymerization process. Vapor phase
polymerization of aniline using FeCl3 as polymerizing agent
was done in a reaction chamber, where the concentration
of FeCl3 on paper played the key role in tuning its proper-
ties. The energy band gap and electrical conductivity of
the polyaniline incorporated paper have been tuned effec-
tively during the polymerization process. The band gap
changes from 2.45 eV to 2.65 eV, when the electrical sheet
resistance varied from 1.0 3105 X/ⵧ to 4.33 3107 X/ⵧ in
response to the different FeCl3 concentration. The electri-
cal sheet resistance can be tuned within a range of two
order of its value. Polymer-based electronic materials with
outstanding electrical conductivity due to their delocalized
molecular orbitals are of great interest in the recent devel-
opment of materials chemistry and physics. Paper being a
flexible substrate and incorporated with a hole transporting
medium like polyaniline in its emeraldine base form will
find its significant role in designing flexible electronic devi-
ces. POLYM. ENG. SCI., 00:000–000, 2018. VC 2018 Society of Plas-
tics Engineers
INTRODUCTION
The conductive polymers are appearing in the central focus
of solid state physics because of their outstanding charge trans-
port properties. Exploration and stimulation of the charge trans-
port properties by employing the due recipe of chemistry and
physics offers an interesting and wide field of research in poly-
mer science and its applications. Conductive polymers like poly-
aniline containing conjugating p-electrons offer the opportunity
of preparing engineered macromolecules [1–4] with excellent
properties. Polymer-based electronic devices [5–7] are therefore
drawing great attention in the recent context. Moreover, finding
a good hole transport layer is one of the most significant chal-
lenges in enhancing the electronic device performances and
selecting high-performance electrode. Ultrathin and flexible
energy storage devices are of significant scientific interest
because of the increasing demands for modern electronics such
as soft electronic equipment, roll-up displays, and stretchable
integrated circuits.
The excellent combination of electrical and optical proper-
ties in a number of conductive polymers such as polyacetylene
[8–11], polypyrrole [12, 13], polyaniline [14, 15], poly(p phe-
nylene-vinylene) (PPV) [16], poly(3,4-ethylene dioxythio-
phene) (PEDOT) [17–19], are attracting the researchers
attention. Polyaniline is one of the promising conductive poly-
mers, which has been chosen in this work to prepare and tune
its optical and electrical properties. Particular attentions are
being paid in understanding the conductive mechanism of such
polymers. As a result, more effective ways are emerging in
bringing control over the functionality of polymer materials
[20, 21]. Preparation of polyaniline can be achieved in various
process such as electrochemical polymerization [22, 23], solu-
tion polymerization [24, 25], interfacial polymerization [26,
27], seeding polymerization [28], emulsion polymerization
[29], vapor phase self-assembling polymerization [30, 31],
photoinduced polymerization [32, 33], plasma polymerization
[34, 35], and sonochemical synthesis process [36, 37]. Among
all of the aforementioned processes the vapor phase polymeri-
zation of aniline offers number advantages like uniform film
preparation over large area, low process temperature (608C)
and very simple reactor chamber. Most significantly it offers
an effective way to bring control over the synthesis process by
regulating the concentration of oxidizing agent over the surface
of the substrate itself. This technique has been employed in
this work to observe the effect of concentration of polymeriz-
ing agent on the optical and electrical properties of polyaniline.
Generally, polyaniline is prepared by oxidation of aniline in
solution using different appropriate chemical oxidizers [15, 38,
39]. FeCl3 has been chosen as polymerizing agent of aniline
into polyaniline. Second, flexible butter paper has been chosen
as substrate to deposit polyaniline in this work to observe the
effect of concentration of polymerizing agent in tuning its opti-
cal and electrical properties. As a result, a remarkable effect
has been observed in the energy band gap and electrical con-
ductivity of the polyaniline incorporated paper with variation
of FeCl3 concentration. More the concentration of oxidizing
agent more is the density of polaron and bipolaron leading to
higher electrical conductivity. Such polymer-based electronic
materials loaded on paper, which are environmentally safe and
nontoxic can reduce the electronic hazards. Thus, this work
will find its significance in advancement of science toward
paper-based electronic materials and would attract the
researchers because of its flexibility and cost effectiveness and
better functionality.

Correspondence to: Biswajit Saha; e-mail: biswajit.physics@gmail.com

Grant sponsor: University Grants Commission (UGC), Government of India; EXPERIMENTAL DETAILS
Grant number: F.5–324/2015–16/MRP/NERO/1093. Materials Used
DOI 10.1002/pen.24845
Published online in Wiley Online Library (wileyonlinelibrary.com). The synthesis of polyaniline was performed through vapor
C 2018 Society of Plastics Engineers
V phase polymerization process. In this approach the chemicals of

POLYMER ENGINEERING AND SCIENCE—2018

high purity were used in the reaction process. FeCl3 (Merck)
was used as polymerizing agent and aniline (Merck) was used
to produce its vapor. The polymerization was carried out on but-
ter paper to obtain polyaniline.
Synthesis Process
The synthesis process of conductive polyaniline on paper is
discussed in detail in this section. To obtain extremely pure ani-
line, double distillation process was followed, and the distilled
aniline was stored in a refrigerator. In polymerization process
we have approached for the oxidation of aniline in acidic media.
FeCl3 has been chosen as polymerizing agent. The standard oxi-
dation/reduction potential of FeCl3 (0.77) is suitable for this pro-
cess. 50 ml of aniline was taken in a beaker and heated at
temperature 608C to produce aniline vapor. The synthesis pro-
cess was carried out in a reaction chamber as shown in Fig. 1.
The temperature of the vapor inside the reactor chamber was
recorded by the thermometer kept inside. In another beaker,
50 mL of 0.2 molar solution of FeCl3 was prepared in methanol.
Butter paper cut into strips of size (2 cm 3 5 cm) have been
used for preparing polyaniline on those. The butter paper strips
were dipped gently into the FeCl3 solution and taken out in
ambient condition. Thus, the FeCl3 soaked butter paper have
been produced and kept in ambient condition allowing the sol-
vent to evaporate out. Then the FeCl3 soaked butter papers have
been placed inside the reactor for polymerization process to
occur. During the process the FeCl3 soaked butter paper comes
FIG. 1. Photographic view of reaction chamber used for vapor phase poly-
merization of aniline on paper. [Color figure can be viewed at wileyonlineli-
brary.com]
2 POLYMER ENGINEERING AND SCIENCE—2018
in contact with the aniline monomer in vapor form and radical
cations are formed as described in Fig. 2. The radical cations
then form polymer chain through chemical interaction. The reac-
tion was allowed to occur for 20 min and during the process the
butter paper gradually found to become green colored indicating
the formation of polyaniline. The polyaniline loaded butter
papers were then removed from the reactor and washed care-
fully in methanol to remove the unreacted chemicals if any, and
bi-product of ferrous chloride. Finally, the prepared polyaniline
loaded butter paper was dried at 508C for 10 min. The entire
process was followed to prepare such polyaniline incorporated
paper with various concentrations (0.2, 0.3, 0.4, and 0.5 M) of
FeCl3 in order to bring a control over the physical properties of
such conductive polymer incorporated paper.
Characterizations
The polyaniline coated papers with different concentrations
have been characterized with different techniques to study their
physical properties to explore their outstanding optical and elec-
trical properties. The crystallinity was examined through X-ray
diffraction (XRD, Bruker, D-8 Advance) measurements, and
scanning electron microscopic measurement was employed for
studying the morphology of the prepared samples. The FESEM
measurements were done using Zeiss FESEM. Optical properties
were studied through UV–vis-NIR spectrophotometric (Shi-
madzu UV-3101PC) measurements. The electrical properties
have been studied through current voltage measurements using
Keithley instrument (model 2400).
RESULTS AND DISCUSSIONS
Structural Properties
Crystalline phase of materials are always of scientific worth
because of their excellent physical properties. Occurrence of
crystalline phase in polymer material attracts due attention and
in this study the crystallinity was investigated for all polyaniline
loaded papers prepared with different concentrations of oxidiz-
ing agent. The X-ray diffraction pattern as obtained for different
samples of polyaniline loaded paper are shown in Fig. 3. From
the X-ray diffraction pattern of the polyaniline loaded paper it
was observed that all the samples prepared with different FeCl3
concentrations are crystalline with the occurrence of peaks at 2h
515:4 and 2h522:4 corresponding to Miller planes (011) and
(020). Polyaniline in its emeraldine salt form can occur in crys-
talline form. The interplanar distances (d) corresponding to these
diffraction peaks are 0.28 and 0.20 nm.
The X-ray diffraction results can be extended to obtain the
crystallite size (T) of the samples from the highest intense peak
using the Scherrer relation [40]
bk
T5 (1)
bCosh
where b is the shape factor for the average crystallite (0.9), b
is the full width at half maxima of the crystalline peak in radi-
ans. The crystallite size has been found to be 37.46A . Using
the relation shown in Eq. 2, given by Klug and Alexander [41],
the inter-chain separation (R) can be obtained. Corresponding to
the highest intense crystalline peak this has been calculated
as 2.5A
DOI 10.1002/pen
 FIG. 2. Formation of radical cation and molecular structure of polyaniline. [Color figure can be viewed at wileyon-
linelibrary.com]
5k
R5
8 sin h
Thus, the crystalline structure of polymer as obtained on paper
can be realized with better electrical properties. The ordered
crystalline form of polyaniline will assist the charge transport
through the long-range propagation of polarons. Interchain and
interdomain electrical conductivity are influenced by crystallin-
ity, as the increase in crystallinity allows for an increase in
charge hopping sites. The pictorial view of the polyaniline
loaded papers was examined from FESEM images. A typical
FESEM image is shown in Fig. 4, which shows continuous and
uniform loading of polyaniline on paper. The flexibility of the
polyaniline loaded paper with p-type carrier transport will pro-
vide an additional advantage in designing flexible electronic
devices. Figure 5 demonstrates the flexibility of the polyaniline
loaded paper.
Optical Properties
Optical properties and their tuning are of great importance in
designing solid state electronic devices. Particularly crystalline
semiconductors with definite energy band gap are required in
developing various electronic devices. Polyaniline being a good
FIG. 3. X-ray diffraction pattern of polyaniline coated papers for different
concentration of FeCl3. [Color figure can be viewed at wileyonlinelibrary.
com]
DOI 10.1002/pen
hole transport medium and band gap lying in a suitable range
(2)
attracted our attention to bring a control over the optical proper-
ties along with its electrical properties, when such macromole-
cules are loaded on flexible paper. As we have approached to
prepare polyaniline on paper with different concentration of oxi-
dizing agent, interesting results have been obtained in their opti-
cal properties. With increasing concentration of FeCl3 the
oxidation of aniline takes place more in number in the polymer
chain so that the defect states of polaron and bipolaron appears
with higher concentration. Thus the samples prepared with
higher FeCl3 concentration show higher absorbance correspond-
ing to the fundamental absorbance of polaron and bipolaron in
polyaniline. The results thus show that one can tune the energy
band gap simply by varying the concentration of oxidizing
agent. The UV–vis-NIR absorbance spectra of all the different
samples prepared with different FeCl3 concentrations are shown
in Fig. 6. The UV–vis spectra show three absorptions bands at
340 nm, 440 and 750 nm, respectively. The strong absorption
peaks observed in the UV–vis absorption spectra at 340 nm has
the origin from p–p* interband transition. The absorption band
around 370 nm is ascribed to polaron band transition. On
increasing dopant concentration the number of polarons
increases, thus it creates higher absorption of incident light at
370 nm. The broad absorption band around 750 nm is due to
bipolaron band transition. The occurrence of absorbance peak
FIG. 4. Typical FESEM image of polyaniline loaded paper. [Color figure
can be viewed at wileyonlinelibrary.com]
POLYMER ENGINEERING AND SCIENCE—2018 3

FIG. 5. Photographic view of flexible polyaniline loaded paper. [Color fig-
ure can be viewed at wileyonlinelibrary.com]
also confirms the formation of emeraldine oxidation state of
PANI. One can easily observe that another absorption band
appeared at 370 nm for the higher concentration of FeCl3. The
occurrence of this absorption band depends on the dopant con-
centration, or one can say on higher protonation, the band
observed at 330 nm in the UV–vis spectra polyaniline is shifted
to 370 nm [42].
The energy band gap has been calculated from the absor-
bance spectra using the relation
1 gap changes. The energy band gap changes from 2.45 to 2.65
ðahtÞn 5Aðht2Eg Þ
Where a is the optical absorption coefficient, hm is incident pho-
ton energy and Eg is the band gap and A is a constant. The
energy band gap of the polyaniline semiconductor hole transport
FIG. 6. Optical absorbance spectra of polyaniline coated conducting papers
with different FeCl3 concentration. [Color figure can be viewed at wileyonli-
nelibrary.com]
4 POLYMER ENGINEERING AND SCIENCE—2018
FIG. 7. Energy band gap of polyaniline from (ahm)2 versus hm plot for dif-
ferent samples with different FeCl3 concentration. [Color figure can be
viewed at wileyonlinelibrary.com]
layer has been determined by extrapolating the linear portion of
the (ahm)2 versus hm plot as depicted in Fig. 7. This shows that
the band gap depends on the oxidation state of the polyaniline.
The index n is related to the distribution of the density of states.
The index n 5 1/2 corresponds to the direct allowed transition
energy gap and n 5 2 corresponds to the indirect allowed transi-
tion energy gaps. A significant variation in the band gap has
been observed with the concentration of oxidizing agent. During
oxidation the charged defect states of polaron and bipolarons
are created. These defect states introduce localized electronic
states in the gap, which cause upward shift of the HOMO and
downward shift of the LUMO. Thus, depending on the degree
of oxidation, and the concentration of defect states; the band
eV with increasing concentration.
Electrical Properties
Polyaniline acts as a positive charge transport layer. On ther-
moelectric measurement the Seebeck coefficient of polyaniline
can be obtained with positive sign [31]. It is positive for p-type
material and negative for n type material. Because polyaniline is
a good thermoelectric material, it gives a convenient experimen-
tal evidence for its carrier’s type. This makes it of scientific
worth as p-type semiconductor materials are less explored com-
pared with n-type semiconductors. The selectivity of positive
charge transport layer in different semiconductor devices
requires a good control over its electrical and optical properties.
This work explores an effective and easy way of controlling the
optical and electrical properties of p-type semiconductor of pol-
yaniline. Another significance of this work is lying in bringing
such control on polymer loaded on paper, which may appear
directive in designing paper-based devices. The electrical I–V
plot of the polyaniline loaded paper prepared with different con-
centrations of FeCl3 is shown in Fig. 8. The figure reveals that
initially the electrical conductivity was increased with increasing
concentration of FeCl3, but after certain level the electrical con-
ductivity again starts decreasing. The mechanism of electrical
conductivity in polyaniline includes the formation of spinless
carriers of polaron and bipolaron. The state of oxidation during
DOI 10.1002/pen

FIG. 8. Room temperature I–V characteristics of polyaniline coated papers.
[Color figure can be viewed at wileyonlinelibrary.com]
synthesis process plays the key role in controlling the electrical
conductivity.
The band theory of inorganic semiconductors that is, occur-
rence of valence and conduction bands in inorganic semiconduc-
tors translates to p or bonding and p* or antibonding bands in
FIG. 9. Different forms of polyaniline it its different oxidation states.
[Color figure can be viewed at wileyonlinelibrary.com]
DOI 10.1002/pen
conducting polymers, respectively. The charge is said to be
excited from a lower energy (bonding molecular orbital) to a
state of higher energy (anti-bonding molecular orbital) within
the molecular matrix. Thus, it attains the electronic band struc-
ture with semiconducting properties; however the semiconduct-
ing properties can be controlled by introducing polaronic and
bipolaronic bands through defect incorporation during oxidation
process. Depending on the doping level, polyaniline can be in
leucoemeraldine, pernigraniline, and emeraldine base, or emeral-
dine salt forms (Fig. 9). Polyaniline in leucoemeraldine form is
fully reduced state. Polyaniline in pernigraniline form is fully
oxidized state with imine links instead of amine links. Both the
forms are poor conductors, even when doped with an acid. Poly-
aniline in emeraldine salt form is a p-type semiconductor with
hole as charge carriers and are of our interest, which has been
found to be formed on paper. During oxidation electrons are
removed from the top of the valence band that is, highest occu-
pied molecular orbitals (HOMO) and thus holes are created.
This charge appeared in the chain can induce a local distortion
in the polymer chain. This creates localized electronic states in
the gap, which cause upward shift of the HOMO and downward
shift of the LUMO. Thus, a lattice distortion around a charge
becomes energetically favorable in polyaniline chain leading
towards charge localization with lattice distortion, which we call
polaron. The presence of this localized electronic states are
called polaron states. When the second electron is removed
from the polaron in the polymer chain a bipolaron is formed. A
bipolaron is defined as a pair of like charges coupled through
strong local lattice distortion analogous to Cooper pair in BCS
theory, where two electrons are coupled through lattice vibra-
tion. The formation of both the polaron and bipolaron are ener-
getically favorable in polyaniline. However, the formation of
bipolaron is thermodynamically more favorable than the forma-
tion of two separate polaron in the polymer chain [43]. The
schematic energy band diagram for polaron and bipolaron in
polyaniline is shown in Fig. 10. The polaron and bipolaron
assisted charge transport in polyaniline induce a motion of hole
in the polyaniline and p-type conductivity is achieved [44–47].
The conductivity however depends on the oxidation level and
can easily be achieved by varying the concentration of FeCl3.
With increase in FeCl3 concentration, first the conductivity
increases and then with further increase it decreases. This is
FIG. 10. Schematic energy band diagram of neutral state, polaron state and
bipolaron state of polyaniline. [Color figure can be viewed at wileyonlineli-
brary.com]
POLYMER ENGINEERING AND SCIENCE—2018 5
TABLE 1. Sheet resistance of polyaniline incorporated papers prepared
with different FeCl3 concentration.
Concentration of
Sl. No. Sample name FeCl3 used Sheet resistance
1 Polyaniline_paper 1 0.25 M 4.33 3 107
2 Polyaniline_paper 2 0.35 M 2.65 3 106
3 Polyaniline_paper 3 0.50 M 1.00 3 105
4 Polyaniline_paper 4 0.70 M 4.60 3 105
5 Polyaniline_paper 5 0.90 M 1.35 3 106
because, with extreme higher concentration of FeCl3, some of
polymer transformed towards the fully oxidized pernigraniline
form. The sheet resistance of different polyaniline coated paper
has been measured in order to draw a comparison of their con-
ductivity level and is shown in Table 1. One can observe that
the I–V plot is nonlinear for the samples indicating non-Ohmic
transport through the sample. The nonlinear behavior is due to
the polaronic and bipolaronic type of carriers. With the increas-
ing applied electric field, the applied electric potential domi-
nates over the lattice distortion potential and thus current
increases nonlinearly. Another significantly important property
is its flexibility and it has been observed that the electrical
behavior retains even after repeated cycle of bending.
CONCLUSIONS
Polyaniline has been synthesized on paper through oxidative
chemical polymerization of aniline with an objective to control
the electrical and optical behavior of the samples. This work
thus reports to bring a successful control over the electrical
properties of conductive polyaniline loaded on paper as a p-type
semiconductor. The conductivity is reported to be controlled
within a wide range of two degree of its value. The appearance
of polaron and bipolaron energy levels within the energy bands
of molecular orbitals is responsible for the excellent p-type con-
ductivity of the samples. Depending on the level of oxidation,
polyaniline show controllable electrical conductivity. The hole
transport in polyaniline chain occurs with the propagation of
charged defects like polaron and bipolaron under the interaction
of applied electric potential coupled with lattice distortion
potential. The band gap also lies in an appropriate range (2.45–
2.65 eV) for all the samples making those suitable for optoelec-
tronic devices. Thus, it can be a significant approach towards
paper-based flexible electronic devices, where polyaniline
loaded papers can be employed as p-type semiconductor.
ACKNOWLEDGMENT
The authors acknowledge the Central Research Facility,
National institute of Technology Agartala for extending X-ray
diffraction facility.
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