Measurement 92 (2016) 446–452

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Measurement
journal homepage: www.elsevier.com/locate/measurement

Measurement on the structural, morphological, electrical and optical

properties of PANI-CSA nanofilms
D. Geethalakshmi a,⇑, N. Muthukumarasamy b, R. Balasundaraprabhu c
a
Department of Physics, Jansons Institute of Technology, Coimbatore, India
b
Department of Physics, Coimbatore Institute of Technology, Coimbatore, India
c
Department of Physics, PSG College of Technology, Coimbatore, India

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

Article history: Camphorsulfonic acid doped polyaniline (PANI-CSA) prepared by chemical oxidative polymerization is
Received 1 August 2015 spin coated on glass plates with four different PANI:CSA weight ratios (1:1, 1:2, 1:4 and 1:8) and mea-
Received in revised form 17 May 2016 surements on the structural and optical properties are done. Thickness of the films measured <100 nm
Accepted 23 June 2016
are termed as nanofilms. Fourier transform infrared spectroscopy indicated the presence of dopant and
Available online 23 June 2016
an increase in degree of polymerization with increase in dopant ratio. X-ray diffraction studies revealed
the change of amorphous nature of the film to crystalline nature with increase in CSA dopant ratio.
Keywords:
Scanning electron microscopy showed the change of very smooth morphology of the film to rough
PANI-CSA
Chemical synthesis
root-like morphology with increase in CSA dopant ratio. Hall-effect analysis showed that the increase
Spin coating in CSA weight ratio appreciably increases the conductivity of PANI-CSA films due to increase in carrier
Semiconductivity concentration and it also represents the semiconductivity (P-type) nature in all the films. UV–visible
Photoluminescence absorption studies reveal the broadening of absorption spectrum in visible region with maximum CSA
dopant ratio (1:8). Photoluminescence spectra of PANI-CSA films excited using 300 nm, revealed that
the change in intensity and position of emission peaks are due to transition of semiconducting nature
of the film to conducting nature with an increase in CSA dopant ratio from 1:1 to 1:8.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction
Conducting polymers has been observed as the center of scien-
tific interest since last decade, due to their explicit properties such
as conducting/semiconducting mechanism, reversible doping/
dedoping process, controllable chemical and electrochemical prop-
erties, light weight and easy processability. Among all the conduct-
ing polymers, due to high electrical conductivity, charge transport
mechanism, environmental stability and low synthesis cost,
polyaniline (PANI) stands as the most potential conducting poly-
mer. It finds application in bio sensors namely cholesterol sensor
[1], glucose sensor [2], gas sensors [3,4] and in other fields such
as electromagnetic shielding [5], light emitting devices [6,7], pho-
tovoltaic applications [8–11], light weight batteries [12], and
organic displays [13]. PANI can be tuned to either conducting or
insulating nature by doping or dedoping procedure respectively,
through reversible chemical, electrochemical process. By
controlling the quantity of dopants, it can also be tuned to either
conducting or semiconducting nature. The dopants for PANI are
⇑ Corresponding author.
E-mail address: alageelak@gmail.com (D. Geethalakshmi).
hydrochloric acid [14], sulfuric acid [14], phosphoric acid [14],
oleic acid [15], camphor sulfonic acid [16], etc. Compared to inor-
ganic semiconductors, polymer semiconductors generally need
high dopant concentration [17]. Doping of PANI create conjuga-
tional defects like solitons, polarons, and bipolarons in the polymer
chain which produce electron hopping mechanism and generates
high conductivity. PANI is treated equivalent to inorganic P-type
semiconductor due to its positive charge carriers (holes). As most
of the components required for electronic devices are in thin film
form, semiconductor PANI is also being studied in thin film form
by many researchers in recent years. Shuxin Tan et al. in his work
has reported that semiconductor PANI is more suitable than con-
ducting PANI in enhancing the efficiency of solar cells [8]. Also,
semiconducting PANI is well suited for applications like
Schottky-diodes, field-effect transistors, gas sensors, LED’s, etc.
due to its higher carrier mobility and stability [18]. HCl-doped
PANI (PANI-HCl) semiconductor thin films prepared and character-
ized by us in our earlier work, [19] though highly conductive,
shows rapid decrease in conductivity with aging and turn into pure
insulator due to the fast escape of Cl ions. Also, the sticking effi-
ciency of the films to the glass substrate is very weak which may
be due to the strong HCl acid, which is playing the role of both

http://dx.doi.org/10.1016/j.measurement.2016.06.054
0263-2241/Ó 2016 Elsevier Ltd. All rights reserved.
 D. Geethalakshmi et al. / Measurement 92 (2016) 446–452
dopant (Cl ) and solvent. Moreover, PANI-HCl, if coated on trans-
parent metal electrode (Indium-Tin-oxide-ITO) coated glass plates;
HCl being heavy acid, destroys the metal (ITO) coating on glass
plates, if used to fabricate any thin film optoelectronic devices such
as solar cells. So, solar cell fabrication using PANI-HCl was unsuc-
cessful in our earlier work [19]. So, to sort-out these problems
and to prove the applicability of PANI film in solar cells as photoac-
tive layer, we next concentrate on PANI films with organic dopant
and organic solvent. Camphorsulfonic acid (CSA) doped PANI
(PANI-CSA) thin film find application in bifacial dye sensitized solar
cells as counter electrode, which impart superior photo-voltaic
performances for the device by presenting power conversion effi-
ciency of 5.5% [20]. As it posses metal-like behavior, it was used
as a filler in poly(methylmethacrylate) composites to produce
highly conductive electrospun nanofibers [21]. Due to high con-
ductivity and light weight, PANI-CSA was found to be the most
promising conducting filler material for the production of lightning
strike protection composite coatings [22]. Moreover the most often
used solvent for solution processing of PANI is m-cresol, as it pro-
motes high conductivity through transfer of delocalized polarons
by increasing the aromaticity of the polymer chain [23]. So, here,
we concentrate on the preparation of PANI-CSA semiconductor
nanofilms using chemical oxidative polymerization method. Also,
the effect of CSA dopant concentration on the structural, morpho-
logical, electrical and optical properties of PANI-CSA film has been
studied.
2. Experimental procedures
PANI-CSA was chemically synthesized by oxidative polymeriza-
tion method: First aniline monomer in the solution form is poly-
merized by drop-wise addition of ammonium persulfate (APS)
(NH4)2S2O8 solution in 2 M HCl at 4 °C. This results in the forma-
tion of polyaniline hydrochloride (PANI-HCl) precipitate with high
degree of polymerization as reported in our earlier work [19]. The
resultant precipitate was washed with 0.1 M HCl, deionized water
and dried to get fine PANI-HCl powder. This powder was de-doped
with 0.1 M ammonia solution and stirred using magnetic stirrer for
3 h at room temperature to remove the dopant ion (Cl ). The pre-
cipitate was filtered, washed with de-ionized water until the water
became neutral, and then dried in air for 48 h in order to obtain
PANI Emeraldine base (EB) (de-doped PANI). PANI EB (0.2 g) was
re-doped with camphor sulfonic acid (CSA) (0.2 g, 0.4 g, 0.8 g and
1.6 g) along with the solvent m-cresol (30 ml) to prepare four dif-
ferent samples of PANI:CSA weight ratios (1:1), (1:2), (1:4) and
(1:8) respectively. Doping mechanism was performed by stirring
the solution for 3 days with initial mild heating using magnetic
stirrer and then filtered to get a homogeneous solution. Homoge-
neous PANI-CSA solution was coated on to cleaned glass plates at
1000 rpm for 1 min using spin-coating unit and dried in vacuum
for 24 h.
Thickness of all the films were determined by Profilometer
(Model: Veeco). Fourier transform infra red (FTIR) spectra of the
samples were recorded using FTIR spectrometer (Model: Shi-
madzu). Structural analysis was carried out by means of X-ray
diffraction (XRD) technique (BRUKER DS Advance model) using
Cu Ka radiation (k = 1.5406 Å). The surface morphology was exam-
ined by JEOL JSM-6360LV scanning electron microscope (SEM).
Hall-effect study was carried out using ECOPIA Hall effect mea-
surement system (HMS-2000 Ver.2.0). Absorbance spectra were
recorded using double beam JASCO UV–Visible-NIR Spectropho-
tometer (model V-570) in the wavelength range 200–1200 nm.
Band gap was determined using the absorbance spectra. Photolu-
minescence studies were carried out using FP-6500 Spectroflurom-
eter at room temperature by exciting the films with light of
wavelength 300 nm.
447
3. Results and discussion
The colors of the PANI-HCl, PANI EB and PANI-CSA polymers
appeared as green, deep blue and deep green respectively as
reported in the literature [24,25]. Thickness of PANI-CSA films pre-
pared with different PANI:CSA weight ratios (1:1, 1:2, 1:4 and 1:8)
were found to be in the range of 52–94 nm forming nanofilms
(Table 1). The increase in CSA dopant ratio enhances the thickness
of the polymer film, which may be due to the fact that the increase
of CSA dopant enhances the degree of polymerization which in
turn increases the molecular weight of PANI polymer similar to
PANI-HCl thin films, as reported by us in our earlier work [19].
The film with the highest CSA dopant ratio of (1:8) showed rough
film surface which was not uniform and the determined thickness
was 94 nm which was the maximum among the prepared films.
This shows that CSA quantity is responsible for increase in the
thickness of PANI-CSA films. Compared to the thickness (91–
119 nm) of our earlier dip-coated PANI-HCl films, [19] it was found
that spin-coated PANI-CSA films were very less in thickness, stat-
ing the significance of spin-coating. The sticking efficiency of
PANI-CSA film to the glass substrate was high compared to PANI-
HCl films and this may be due to the organic solvent (m-cresol)
and organic dopant (CSA). Moreover, PANI-CSA solution dip coated
on ITO glass plate firmly stuck to the metal coating without
destroying it, in contrast to PANI-HCl.
Fig. 1a shows the FTIR spectra of PANI-HCl, PANI EB and PANI-
CSA. The spectra were recorded in the wave number range 500–
4000 cm 1. Polymerization of aniline to PANI-HCl, de-doping of
PANI-HCl to PANI EB and re-doping of PANI EB to PANI-CSA were
verified by comparing the FTIR bands observed with the bands
reported in the literature [26,27]. It is clear from the figure that
in each step there is a change in molecular environment of PANI.
The bands at 804 cm 1 and 1302 cm 1 corresponds to PANI-HCl
and the bands at 830 cm 1, 1145 cm 1, 1307 cm 1, 1492 cm 1
and 1589 cm 1 corresponds to PANI EB [28,29]. Similarly, the
bands at 749 cm 1, 1250 cm 1, 2922 cm 1 and 3036 cm 1 corre-
sponds to PANI-CSA [7,30,31]. Table 2 shows the list of observed
bands with their corresponding functional groups.
Fig. 1b shows the FTIR spectra of PANI-CSA samples with differ-
ent PANI:CSA weight ratios (1:1, 1:2, 1:4 and 1:8). The intensity of
Table 1
Thickness of PANI-CSA thin films prepared with different PANI:CSA weight ratio.
PANI:CSA weight ratio Thickness (nm)
1:1 52
1:2 68
1:4 74
1:8 94 (approximate)
Fig. 1a. FTIR spectra of PANI-HCl, PANI EB and PANI-CSA.
448 D. Geethalakshmi et al. / Measurement 92 (2016) 446–452

Table 2
FTIR bands and functional groups of PANI-HCl, PANI EB and PANI-CSA polymers.

Wavenumber Functional group Confirmed

(cm 1) polymer
804 CACl Aromatics out of plain bend
1302 CAN stretch of benzenoid ring PANI-HCl
830 Out-of-plane CAH bending modes
1145 In-plane CAH bending modes PANI EB
1307 NAH bending (or)
1492 Phenylenediamine unit C@C De-doped PANI
stretching
1589 CAC ring stretching vibrations
749 ASO3H vibration PANI-CSA
1250 CAN+ or C@N.+ stretching
vibration
2922 NH asymmetric stretching Fig. 2a. XRD pattern of PANI-CSA and PANI-HCl film.
3036 CH stretching

Fig. 1b. FTIR spectra of PANI-CSA samples with different PANI:CSA weight ratio.

FTIR bands of PANI-CSA were observed to increase gradually with
increase in dopant ions (SO3 ) except the polymer with PANI:CSA
weight ratio of (1:8). This PANI-CSA polymer with PANI:CSA
weight ratio of (1:8) shows sudden decrease in the intensity of
absorption bands, representing a sudden change in the molecular
environment at maximum CSA dopant ratio (1:8). Moreover, bands
in the range (3050–2870) cm 1, (1082–997) cm 1 and (881–856)
cm 1 and bands at 1929 cm 1, 2353 cm 1 and 3354 cm 1 disap-
pear in PANI-CSA polymer with higher CSA dopant ratio (1:8). All
these represent that, if the concentration of CSA dopant in PANI
exceeds a particular level, changes in the molecular structure will
be introduced.
Fig. 2a shows the X-ray diffraction pattern of PANI-CSA nano-
films with PANI:CSA weight ratios (1:1), (1:2) and (1:4) (all appear
similar) along with PANI-HCl film studied earlier. PANI-CSA nano-
films with lower CSA dopant ratios (1:1, 1:2 and 1:4) exhibit high
degree of amorphous nature which was clear from its broad
high-angle asymmetric scattering peak around the diffraction
angle 25°, corresponding to d-spacing of 3.5256 Å. This peak is
the characteristics of the degree of p-conjugation in PANI, as
reported earlier [32–34]. The XRD pattern of PANI-HCl film is not
as broad as the above discussed PANI-CSA nanofilms, due to its
low degree of amorphous nature with nanofiber morphology
[19]. Fig. 2b shows the X-ray diffraction pattern of PANI-CSA nano-
films with different PANI:CSA weight ratios (1:1, 1:2, 1:4 and 1:8).
Among the four films the PANI-CSA film with PANI:CSA weight
ratio of (1:8) shows sharp diffraction peaks which indicates that
the prepared films were of crystalline nature. This crystalline nat-
ure was only due to the higher CSA dopant ratio (1:8) which was
confirmed from the PANI-CSA films below with lower CSA ratios,
Fig. 2b. XRD pattern of PANI-CSA films with different PANI:CSA weight ratio.
which showed amorphous nature. The peaks at 2h = 10.5°, 15.3°,
and 21° (d = 8.44, 5.78 and 4.2 Å respectively) corresponds to PANI
[35,36] and the peaks at 18° and 19° (d = 4.9, and 4.64 Å respec-
tively) corresponds to CSA dopant [37]. So, to obtain high crys-
talline PANI-CSA films, ratio of CSA have to be increased further
which impart crystallinity to PANI polymer films.
Fig. 3a shows the scanning electron microscope image of PANI-
CSA films with different PANI:CSA weight ratios (1:1, 1:2, 1:4 and
1:8). All the PANI-CSA films, except (1:8) ratio, shows smooth sur-
face without any crack. It also reveals that the effect of CSA dopant
ratio is not noticeable in these three SEM image and this may be
due to the very smooth surface of the films with lower CSA dopant
ratio. However, the film with PANI:CSA weight ratio of (1:8) shows
root-like structure spread throughout the film, which was formed
of large number of horizontally grown, short micro-wires, assem-
bled in series (inset of Fig. 3a-(1:8)). This morphology was only
due to higher CSA dopant ratio along with low rate of solvent evap-
oration, which led to self-assembly of atoms and molecules initiat-
ing crystal growth at few points of the film and it extends
throughout the film surface [38]. Fig. 3b shows the scanning elec-
tron microscope image of PANI-HCl film studied by us earlier,
which shows the nanofiber formation with high dense inter-fiber
fusion [19]. This complete change in the morphology of both
PANI-HCl and PANI-CSA films was not only due to the type of
dopants, but also due to the method of film formation. PANI-HCl
film formation was dip-coated with in-situ polymerization process
where purification of the film material is impossible, but PANI-CSA
 D. Geethalakshmi et al. / Measurement 92 (2016) 446–452 449

Fig. 3a. SEM image of PANI-CSA films with different PANI:CSA weight ratio (inset: Magnified image of 1:8 film).

Table 3
Hall effect parameters of PANI-CSA films with different PANI:CSA weight ratio.

Pani:CSA Thickness r l n
wt. ratio (nm) (X 1
cm 1
) (cm2/V s) (cm 3
)
1:1 52 0.34 190.9 1.11  1016
1:2 68 0.59 104.9 8.49  1016
1:4 74 0.73 23.6 1.93  1017
1:8 94 1.21 11.1 6.87  1017

Fig. 3b. SEM image of PANI-HCl film.
nanofilm formation was after many processes such as polymeriza-
tion of aniline to form PANI-HCl, de-doping, purification, re-doping
with CSA followed with long time stirring of doped PANI and then
spin-coated to form nanofilm.
The conductivity (r), carrier mobility (l) and carrier concentra-
tion (n) of PANI-CSA films prepared with different PANI:CSA
weight ratios (1:1, 1:2, 1:4 and 1:8) using Hall-effect study are
shown in Table 3. It is clear from the table that the increase in
CSA dopant ratio, increases the conductivity and carrier concentra-
tion of the films, but the mobility of charge carriers decreases.
Among all the four films, PANI-CSA film with PANI:CSA weight
ratio (1:8) film exhibited maximum conductivity of 1.21 X 1 cm 1
with the carrier concentration 6.87  1017 cm 3 and the carrier
mobility of 11.1 cm2/V s. A sudden increase in the conductivity of
this film with increase in CSA dopant ratio may be due to the for-
mation of crystalline structure of the film with root like morphol-
ogy. Moreover, when comparing the Hall-effect parameters of
crystalline PANI-CSA film (r = 1.21 X 1 cm 1, l = 11.1 cm2/V s,
n = 6.87  1017 cm 3) with that of PANI-HCl amorphous film
(r = 1.08 X 1 cm 1, l = 0.129 cm2/V s, n = 5.23  1019 cm 3) stud-
ied earlier [19], it was found that the crystalline nature of the
PANI-CSA film have enhanced the carrier mobility which was the
main reason for high conductivity at low carrier concentration of
PANI-CSA film. Though the dopant ion (SO3 ) of the CSA doped PANI
films was heavier and was found to be difficult to diffuse into the
polymer backbone unlike the lighter monovalent dopant ions (Cl )
in case of PANI-HCl films [39]; the crystalline nature along with
root like morphology of the PANI-CSA film enhances the diffusion
of dopant ion (SO3 ) into the polymer backbone, which is responsi-
ble for the higher conductivity of PANI-CSA film with lower carrier
concentration. Thus, it is proved that the crystalline structure and
morphology of the film, at the macroscopic level, affects the mobil-
ity of charge carriers and thus controls conductivity. Hall-effect
analysis also revealed that the PANI-CSA films were all P-type
semiconductors, through positive Hall-coefficient (Rh) value.
Fig. 4a shows the absorbance spectra of PANI-CSA nanofilms for
different PANI:CSA weight ratios (1:1, 1:2, 1:4 and 1:8). The
absorption peak observed around 296 nm in the spectra of PANI-
CSA films with lower CSA ratio (1:1, 1:2 and 1:4) represents the
450 D. Geethalakshmi et al. / Measurement 92 (2016) 446–452

Fig. 4b. UV–Vis spectra of PANI-HCl film of 2 M-HCl concentration prepared at 4 °C.

wavelength 300 nm. PL spectra of all films with lower CSA ratio
(1:1, 1:2, 1:4) shows sharp high intense peaks at 361 nm and
Fig. 4a. UV–Vis spectra of PANI-CSA films with different PANI:CSA weight ratio.
494 nm and a broad low intense peak at 410 nm similar to PL spec-
tra of PANI-HCl film studied earlier (Fig. 5b). These PL peaks
observed around the wavelength 361 nm, 410 nm and
p ? p⁄ transition as reported by Varma in his ultrathin PANI-CSA
494 nm were assigned to p⁄ ? p transition, p⁄ ? polaron transi-
films of nanometer thickness [7]. The absorbance spectra of
tion and polaron ? p transition respectively. As reported by Shi-
PANI-CSA nanofilm with PANI:CSA weight ratio of 1:8 exhibits
mano et al. [45] in his work, the combination of broad low
three prominent absorption peaks at 305 nm, 442 nm and
intense peak around 410 nm and a sharp high intense peak around
848 nm confirming it as conducting polymer. These peaks repre-
494 nm of a doped PANI is due to the partial doping which con-
sents p ? p⁄ transition, polaron ? p⁄ transition and p ? polaron
firms its semiconductivity nature as illustrated in Hall-effect anal-
transition of the benzenoid units respectively as reported by earlier
ysis. The disappearance of peak around 410 nm with a sharp high
workers [40–43]. This confirms the polaron band formation in the
intense peak around 494 nm is due to the fully doped state which
band gap of polymer upon CSA doping. Red shift (296 nm ?
305 nm) in absorption spectra takes place due to the transforma-
tion of film from amorphous nature to crystalline with increase
in dopant ratio as represented by Khot et al. in his paper on cad-
mium sulfoselenide thin films about red shift in absorption spec-
trum with enhancement in film crystallinity [44]. Moreover, as
the prepared crystalline PANI-CSA nanofilm showed increase in
the absorption spectrum (305–442 nm) over the visible region, it
is a suitable material to be used as donor in solar cells to enhance
the photo conversion efficiency (PCE) as suggested by Liu et al. [10]
in his work on PANI/TiO2 solar cells. Optical band gap (Eg) of PANI-
CSA films with different PANI:CSA weight ratios (1:1, 1:2, 1:4 and
1:8) were given in Table 4. Increase of dopant weight ratio
enhances the absorption intensity and simultaneously decreases
the optical band gap from 3.8 eV to 2.5 eV. Sudden decrease in
band gap (2.5 eV) of PANI-CSA film with higher CSA dopant ratio
(1:8) was due to the broadening of absorption spectrum estab-
lished by crystalline nature of the film as discussed by Khot et al.
about the decrease in band gap with increase in crystallinity of
cadmium sulfoselenide thin films [44]. The same effect occurs for Fig. 5a. PL spectra of PANI-CSA films with different PANI:CSA weight ratio.
PANI-HCl films with increase in dopant ratio where the spectra
of maximum absorption is represented in Fig. 4b, which was stud-
ied by us earlier [19]. This proved that generally the increase of
dopant ratio in PANI enhances the light absorption capacity along
with decrease in optical band gap.
Photoluminescence (PL) spectra of PANI-CSA nanofilms with
four different PANI:CSA weight ratios (1:1, 1:2, 1:4 and 1:8) are
shown in Fig 5a. These films have been excited with light of

Table 4
Optical properties of PANI-CSA nanofilms with different PANI:CSA weight ratio.

PANI:CSA Thickness Eg
wt. ratio (nm) (eV) (1:1)
(1:1) 52 3.8
(1:2) 68 3.72
(1:4) 74 3.67
(1:8) 94 2.5
Fig. 5b. PL spectra of PANI-HCl film of 2 M-HCl concentration prepared at 4 °C.
 D. Geethalakshmi et al. / Measurement 92 (2016) 446–452
confirms the conducting PANI [45] which was found for PANI-CSA
film with PANI:CSA weight ratio of (1:8) in our PL analysis. This
PANI-CSA film shows peaks both in UV (359 nm) and visible region
(491 nm) with slight shift from the peaks of PANI films with lower
CSA ratio. One of the prominent peaks around 410 nm was not pre-
sent in this crystalline PANI thin film compared to amorphous
PANI-CSA nanofilm of lower CSA dopant weight ratio. The reason
for these changes may be the formation of crystalline PANI film
as a result of high CSA dopant with PANI:CSA weight ratio of 1:8.
Varma [7] too has already reported similar emission for PANI-
CSA films of nano-thickness. Comparing the PL emission peaks of
PANI-CSA nanofilms of four different PANI:CSA weight ratio, it is
obvious that intensity of all the peaks increases with increase in
dopant ratio as reported by us in our earlier work of PANI-HCl films
for increasing dopant concentration [19].
4. Conclusion
PANI-CSA samples were prepared by chemical oxidative poly-
merization method and spin coated on glass slides to form nano-
films. Measurements on structural and optical properties of PANI-
CSA films were done by varying the PANI:CSA weight ratio. Sticking
efficiency of the film to glass plate was good due to organic solvent
and organic dopant. FTIR studies reveal the presence of dopants and
change in molecular environment of the film with high CSA dopant
ratio (1:8). XRD studies indicate the change in amorphous nature to
crystalline structure of the PANI films with increase in CSA dopant
ratio and SEM represents the change in smooth morphology to
rough root-like morphology of the PANI films with increase in
CSA dopant ratio. Hall-effect analysis shows that the films are P-
type semiconductors with high conductivity for PANI film of
PANI:CSA weight ratio (1:8). UV–visible absorption study reveals
that with increase in CSA-dopant weight ratio, absorption spectra
of PANI-CSA nanofilms broadens over visible region along with
increased absorption. Photoluminescence studies represent that
with increase in CSA dopant ratio, PANI-CSA films shows changes
in the emission intensity and peak positions revealing the transition
of films from semiconducting nature to conducting nature. Subse-
quently, the prepared PANI-CSA films can be used as a P-type layer
in solar cells, which is the next part of our work.
References
[1] D. Chetna, D. Maumit, S. Gajjala, S. Avanish Kumar, P. Manoj Kumar, K. Cheol
Gi, D. Monika, M. Bansi Dhar, Preparation, characterization and application of
polyaniline nanospheres to biosensing, Nanoscale 2 (2010) 747–754.
[2] T. Sowmiya, A. Ananthi, S. Anandhakumar, J. Mathiyarasu, Potentiometric
glucose biosensing using camphor sulfonic acid doped polyaniline, Anal.
Methods 4 (2012) 1838–1842.
[3] A. Terbouche, C. Ait-Ramdane-Terbouche, S. Djebbar, O. Benali-Baitich, D.
Hauchard, Effectiveness study of sensor based on modified cavity
microelectrode by Algerian humic acid-polyaniline composites using square
wave voltammetry, Sens. Actuat. B: Chem. (2012) 297–304.
[4] S.G. Pawar, S.L. Patil, M.A. Chougule, B.T. Raut, P.R. Godase, R.N. Mulik,
Shashwati Sen, V.B. Patil, New method for fabrication of CSA doped PANi-TiO2
thin-film ammonia sensor, IEEE Sens. J. 11 (2011) 2980–2985.
[5] Young-E. Moon, Jumi Yun, Hyung-Il Kim, Synergetic improvement in
electromagnetic interference shielding characteristics of polyaniline-coated
graphite oxide/c-Fe2O3/BaTiO3 nanocomposites, J. Ind. Eng. Chem. 19-2 (2013)
493–497.
[6] C. Dispenza, M.A. Sabatino, D. Chmielewska, C.L. Presti, G. Battaglia, Inherently
fluorescent polyaniline nanoparticles in a dynamic landscape, React. Funct.
Polym. 72–3 (2012) 185–197.
[7] S.J. Varma, J. George, P.P. Jeeju, S. Jayalekshmi, Quantum confinement effects in
highly conducting, ultrathin polyaniline films pursued through spectroscopic
investigations, J. Lumin. 132–3 (2012) 801–805.
[8] S. Tan, J. Zhai, B. Xue, M. Wan, Q. Meng, Y. Li, L. Jiang, D. Zhu, Property influence
of polyanilines on photovoltaic behaviors of dye-sensitized solar cells,
Langmuir 2 (2004) 2934–2937.
[9] H. Bejbouji, L. Vignau, J.L. Miane, M.T. Dang, E.M. Oualim, M. Harmouchi, A.
Mouhsen, Polyaniline as a hole injection layer on organic photovoltaic cells,
Sol. Energy Mater. Sol. Cells 94 (2010) 176–181.
451
[10] Z. Liu, J. Zhou, H. Xue, L. Shen, H. Zang, W. Chen, Polyaniline/TiO2 solar cells,
Synth. Met. 156 (2006) 721–723.
[11] S.E. Mavundla, G.F. Malgas, D.E. Motaung, E.I. Iwuoha, Synthesis of flower-like
zinc oxide and polyaniline with worm-like morphology and their applications
in hybrid Solar cells, Cryst. Res. Technol. 47–5 (2012) 553–560.
[12] X. Zhao, J.K. Kim, H.J. Ahn, K.K. Cho, J.H. Ahn, A ternary sulfur/
polyaniline/carbon composite as cathode material for lithium sulfur
batteries, Electrochim. Acta 109–30 (2013) 145–152.
[13] F.M. Kelly, L. Meunier, C. Cochrane, V. Koncar, Polyaniline: application as solid
state electrochromic in a flexible textile display, Displays 34–1 (2013) 1–7.
[14] I. Sedenkova, M. Trchova, N.V. Blinova, J. Stejskal, In-situ polymerized
polyaniline films. Preparation in solutions of hydrochloric, sulfuric, or
phosphoric acid, Thin Solid Films 515 (2006) 1640–1646.
[15] P. Liu, Synthesis and characterization of organo-soluble conducting polyaniline
doped with oleic acid, Synth. Met. 159 (1–2) (2009) 148–152.
[16] Y.N. Xia, J.M. Wiesinger, A.G. MacDiarmid, A.J. Epstein, Camphorsulfonic acid
fully doped polyaniline emeraldine salt: Conformations in different solvents
studied by an ultraviolet/visible/near-infrared spectroscopic method, Chem.
Mater. 7 (1995) 443–445.
[17] Sadia Ameen, M. Shaheer Akhtar, Young Soon Kim, Hyung-Shik Shin,
Fabrication, Doping and Characterization of Polyaniline and Metal Oxides:
Dye Sensitized Solar Cells, Solar Cells – Dye-Sensitized Devices, in: Leonid A.
Kosyachenko (Ed.), InTech Publishers, 2011, p. 98.
[18] S.J. Varma, S. Jayalekshmi, On the prospects of polyaniline and polyaniline/
MWNT composites for possible pressure sensing applications, J. Appl. Polym.
Sci. 117 (2010) 138–142.
[19] D. Geethalakshmi, N. Muthukumarasamy, R. Balasundaraprabhu, Effect of
dopant concentration on the properties of HCl-doped PANI thin film prepared
at different temperatures, Optik 125 (2014) 1307–1310.
[20] S.H. Park, K.H. Shin, J.Y. Kim, S.J. Yoo, K.J. Lee, J. Shin, J.W. Choi, J. Jang, Y.E. Sung,
The application of camphorsulfonic acid doped polyaniline films prepared on
TCO-free glass for counter electrode of bifacial dye-sensitized solar cells, J.
Photoch. Photobio. A 245 (2012) 1–8.
[21] V. Jagadeesh Babu, D.V.B. Murthy, V. Subramanian, V.R.K. Murthy, T.S.
Natarajan, S. Ramakrishna, Microwave hall mobility and electrical properties
of electrospun polymer nanofibers, J. Appl. Phys. 109 (2011) 74305.
[22] K. Krukiewicz, A. Katunin, The effect of reaction medium on the conductivity
and morphology of polyaniline doped with camphorsulfonic acid, Synth. Met.
214 (2016) 45–49.
[23] K.H. Lee, B.J. Park, D.H. Song, I.J. Chin, H.J. Chin, The role of acidic m-cresol in
polyaniline doped by camphorsulfonic acid, Polymer 50 (2009) 4372–4377.
[24] Yong Cao, Paul Smith, Alan J. Heeger, Counterion induced processibility of
conducting polyaniline, Synth. Met. 57 (1993) 3514–3519.
[25] Chin-Tsou Kuo, Chun-Hua Chen, Characterization of polyaniline doped with
diphenyl phosphate, Synth. Met. 99 (1999) 163–167.
[26] G.E. Asturias, A.G. MacDiarmid, R.P. McCall, A.J. Epstein, The oxidation state of
‘‘emeraldine” base, Synth. Met. 29 (1989) 157–162.
[27] T.L.A. Campos, D.F. Kersting, C.A. Ferreira, Chemical synthesis of polyaniline
using sulphanilic acid as dopant agent into the reactional medium, Surf. Coat.
Technol. 122 (1999) 3–5.
[28] Y. Geng, Ji Li, Z. Sun, X. Jing, F. Wang, Polymerization of aniline in an aqueous
system containing organic solvents, Synth. Met. 96 (1998) 1–6.
[29] J. Tang, X. Jing, B. Wang, F. Wang, Infrared spectra of soluble polyaniline, Synth.
Met. 24 (1988) 231–238.
[30] A.J. Epstein, A.G. MacDiarmid, Polyanilines: from solitons to polymer metal,
from chemical currosity to technology, Synth. Met. 69 (1–3) (1995) 179–182.
[31] Y. Wang, M.F. Rubner, An investigation of the conductivity stability of acid-
doped polyanilines, Synth. Met. 47 (1992) 255–266.
[32] M. Amrithesh, S. Aravind, S. Jayalekshmi, R.S. Jayasree, Polyaniline doped with
orthophosphoric acid – a material with prospects for optoelectronic
applications, J. Alloys Compd. 458 (2008) 532–535.
[33] X. Zhang, J. Zhang, Z. Liu, Tubular composite of doped polyaniline with multi-
walled carbon nanotubes, Appl. Phys. A. 80 (2005) 1813–1817.
[34] S.W. Liu, J. Yue, R.J. Wehmschulte, Large thick flattened carbon nanotubes,
Nano Lett. 2 (12) (2002) 1439–1442.
[35] Ahmed M. Youssef, Morphological studies of polyaniline nanocomposite based
mesostructured TiO2 nanowires as conductive packaging materials, RCS Adv. 4
(2014) 6811–6820.
[36] Y. He, A novel emulsion route to sub-micrometer polyaniline/nano–ZnO
composite fibers, Appl. Surface Sci. 249 (2005) 1–4.
[37] S.G. Pawar, S.L. Patil, M.A. Chougule, B.T. Raut, V.B. Patil, CSA doped PANi–TiO2
nanocomposite: synthesis, structural, morphological and electrical properties,
Int. J. Polym. Mater. 60 (2011) 979–987.
[38] Junna Li, Daohong Zhang, Shunhai Li, Xu Zhicai, Sufang Chen, Tingcheng Li,
Junheng Zhang, Shenghui Chen, Aiqing Zhang, 2D self-assembly of an amido-
ended hydrophilic hyperbranched polyester by copper ion induction,
Macromol. Chem. Phys. 214 (2013) 1724–1733.
[39] R. Singh, V. Arora, R.P. Tandon, S. Chandra, Transport and structural properties
of polyaniline doped with monovalent and multivalent ions, Polymer 38 (19)
(1997) 4897–4902.
[40] H.C. Pant, M.K. Patra, S.C. Negi, A. Bhatia, S.R. Vadera, N. Kumar, Studies on
conductivity and dielectric properties of polyaniline-zinc sulphide composites,
Bull. Mater. Sci. 29 (2006) 379–384.
[41] T.K. Sarma, A. Chattopadhyay, Reversible encapsulation of nanometer-size
polyaniline and polyaniline-Au-nanoparticle composite in starch, Langmuir 20
(2004) 4733–4737.
452 D. Geethalakshmi et al. / Measurement 92 (2016) 446–452

[42] M.A. Chougule, S.L. Patil, S.G. Pawar, B.T. Raut, P.R. Godse, S. Sen, V.B. Patil,
Facile and efficient route for preparation of polypyrrole-ZnO nanocomposites:
microstructural, optical and charge transport properties, J. Appl. Polym. Sci.
125 (2012) E541–E547.
[43] E. Konyushenko, J. Stejkal, M. Trchova, J. Hradil, J. Kovarova, J. Prokes, M.
Cieslar, J.Y. Hwang, K.H. Chen, I. Sapurina, Multi-wall carbon nanotubes coated
with polyaniline, Polymer 47 (2006) 5715–5723.
[44] Kishorkumar V. Khot, Sawanta S. Mali, Nita B. Pawar, Rohini R. Kharade, Rahul
M. Mane, Pallavi B. Patil, Pramod S. Patil, Chang Kook Hong, Jin Hyeok Kim,
Jaeyeong Heoe, Popatrao N. Bhosale, Simplistic construction of cadmium
sulfoselenide thin films via a hybrid chemical process for enhanced
photoelectrochemical performance, RSC Adv. 5 (2015) 40283–40296.
[45] J.Y. Shimano, A.G. Mac Diarmid, Polyaniline, a dynamic block copolymer: key
to attaining its intrinsic conductivity, Synth. Met. 123 (2001) 251–262.