Polymer 175 (2019) 32–40

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Polymer
journal homepage: www.elsevier.com/locate/polymer

A novel route to synthesis polythiophene with great yield and high electrical T
conductivity without post doping process
David Thanasamya,b, Dominic Jesurajb, Satheesh Kumar Konda kannanb, Vanaja Avadhanama,∗
a
Centre for Societal Missions and Special Technologies, CSIR-National Aerospace Laboratories, Old Airport Road, Kodihalli, Bangalore, 560017, India
b
Department of Chemistry, Gandhigram Rural Institute-Deemed to be University, Gandhigram, Dindigul, 624302, India

H I GH L IG H T S

• Simple one step synthesis of polythiophene at room temperature.

• Higher electrical conductivity value of 9 Scm −1
with greater product yield of 80%.
• Formation of α−α′ polythiophene over α−β′ polythiophene.
• Optical band gap values to supports the electrical conductivity.
• Crystallite size of polythiophene was calculated.

A R T I C LE I N FO A B S T R A C T

Keywords: Polythiophene (PTh) was synthesized by a standard chemical oxidation procedure by using Ferric chloride
Polythiophene (FeCl3) as an oxidizer without any post doping process. The synthesis procedure was optimized by varying
Room temperature synthesis different parameters like reaction temperature, monomer to oxidizer ratio, solvent system, reaction time and
Electrical conductivity oxidizer addition time to realize the maximum electrical conductivity and without compromising on product
Diffuse reflectance spectroscopy
yield. In the optimized synthesis procedure, highest yield of 80% with a maximum electrical conductivity of 9
XRD
Scm−1 was achieved. These results are first of its kind in the literature reported so far for the similar conditions.
The enhancement of electrical conductivity was attributed to the increase in the degree of polymerization under
the optimized reaction conditions and was substantiated with UV–Vis, Diffuse Reflectance Spectroscopy (DRS),
FTIR, NMR solid state, SEM, XRD and DSC studies. This paper is the first of its kind to report the room tem-
perature synthesis procedure of PTh with highest electrical conductivity and yield.

1. Introduction polymerization, ii) metal-catalysed coupling reaction, and iii) chemical

Among various intrinsically conducting polymers, polythiophene
(PTh) has received a greater attention due to its promising electrical
conductivity which can be tailored from insulator to semiconductor to
metal range by doping to extend the potential in various fields [1,2].
PTh having a metallic range of electrical conductivity find applications
in batteries, smart windows, antistatic coatings and various types of
sensors. In contrast, PTh with a semiconducting range of electrical
conductivity find applications in light emitting diodes (LED), field effect
transistors (FET), and photovoltaic cells [3–7]. However, the presence
of inert sulphur in the thiophene ring with high oxidation potential
poses a challenge in the polymerization process [8,9]. Generally, PTh
has been synthesized by following three routes i) electro-
oxidative polymerization [10,11]. Still, chemical oxidative poly-
merization has advantages as compared to other methods such as se-
lection of various monomer and suitable catalyst that favours the good
yield, ease of synthesis with optimum electrical conductivity [7,12–14].
In the chemical oxidative synthesis, reaction conditions and the nature
of the dopant anion dictate the properties of the materials [8]. Number
of studies reported high electrical conductivity for PTh with a post-
doping process by Iodine vapour. Researcher sang soo jeon et al. re-
ported maximum electrical conductivity of 20 Scm−1 without post-
doping process. They have used a facile method where the binary sol-
vent system (dichloromethane and acetonitrile) and sub-ambient tem-
perature played a vital role. However, the product yield was very low
[12]. The high yield can be achieved above 20 °C with a compromise on

∗
Corresponding author.
E-mail addresses: davidthanam@gmail.com (D. Thanasamy), dominiccharleschemist85@gmail.com (D. Jesuraj),
dr.kksatheeshkumar@gmail.com (S.K. Konda kannan), Vanaja@nal.res.in (V. Avadhanam).

https://doi.org/10.1016/j.polymer.2019.03.042
Received 10 December 2018; Received in revised form 8 March 2019; Accepted 17 March 2019
Available online 20 March 2019
0032-3861/ © 2019 Published by Elsevier Ltd.
D. Thanasamy, et al.
the low value of electrical conductivity [15,16]. This low product yield,
electrical conductivity, and maintenance of sub-ambient reaction tem-
perature limit the interest of researchers and industrialist to choose PTh
for any applications. Thus, it is essential to optimize the synthesis
procedure of PTh to realize high yield with maximum electrical con-
ductivity.
In this context, the present research study is aimed to optimize
polythiophene synthesis by altering the parameters such as i) monomer
to oxidizer ratio, ii) reaction temperature, iii) reaction time and iv)
solvent, to achieve high electrical conductivity without post-doping
process. As per our knowledge, this is the first paper to report the
greater yield of 80% for polythiophene with a maximum electrical
conductivity of 9 Scm−1 synthesized at room temperature. The high
degree of polymerization and the formation of ordered structures
causes the electrical conductivity enhancement. This was substantiated
with FTIR, UV–Vis (DRS), SEM and XRD characterization.
2. Experimental
2.1. Materials
Thiophene, Ferric Chloride anhydrous (FeCl3), Dichloromethane
(CH2Cl2), Chloroform (CH3Cl) and Acetonitrile (CH3CN) were pur-
chased from Sigma-Aldrich, USA. All these chemicals were used in as
received.
2.2. Synthesis
Polythiophene (PTh) was synthesized by a classical chemical oxi-
dation method. Thiophene monomer (0.5 M) was added to 100 ml of
dichloromethane in three-necked round bottom flask. Freshly prepared
anhydrous FeCl3 solution in acetonitrile was mixed to the previously
prepared thiophene solution under vigorous stirring. The formation of
black colour precipitation confirms the polymerization of thiophene.
The polymerization was allowed to proceed for a specific time with
vigorous stirring. The PTh was filtered and washed with acetone and
acetonitrile several times until a colourless filtrate was obtained. Then
the filtered PTh was dried in a vacuum oven at 60 °C for 24 h. Fig. 1
depicts the oxidative polymerization process of thiophene.
In order to realize the maximum electrical conductivity, initially,
the synthesis procedure was optimized for the solvent system, reaction
temperature and reaction time at a constant monomer to oxidizer ratio
(1:5). Table 1 presents the details of different reaction conditions
maintained during the synthesis. Later, the ideal molar ratio of
monomer/oxidizer to realize the highest yield and electrical con-
ductivity was arrived by varying the concentration of the oxidizer
under optimized reaction conditions.
2.3. Characterization
The PTh powder was compressed into a pellet form for electrical
conductivity measurement. The electrical conductivity of PTh samples
was measured by following Vandurpou four-probe method using pro-
grammable Keithley 6221, current source meter and 2187 A nano
voltmeter. The extent of polymerization of thiophene was examined by
Fourier Transform Infrared spectroscopy (FTIR). The IR spectra were
recorded in the range of 4000–400 cm−1 at a resolution of 4 cm−1 using
JASCO FTIR 460 plus model. 13C cross-polarization magic-angle
33
Polymer 175 (2019) 32–40
spinning (CPMAS) NMR experiment was carried out on a Bruker Avance
III HD (Bruker Biospin) spectrometer, equipped with a 4 mm CP/MAS
NMR probe head. The UV–Vis spectra were recorded in the range of
1100–200 nm using Perkin Elmer UV-630 spectrophotometer using
Dichloromethane as a solvent. Diffuse Reflectance Spectroscopy (DRS)
was recorded using JASCO V-670 spectrophotometer equipped with a
JascoISN-723 diffuse reflectance accessory. The surface morphology
analysis was carried out using TESCAN VEGA Scanning Electron
Microscopy (SEM). The XRD patterns of the samples were recorded in
the 2θ range of 10–80° using Bruker binary V3 X-ray diffractometer
with Cu Kα radiation (1.54 Å). Glass transition temperatures of the
samples were measured using a Differential Scanning Calorimetry
(DSC) (Model: TA -Discovery 25) by heating the samples at a heating
rate of 10 °C per minute under inert nitrogen atmosphere in the tem-
perature range of −50 to 200 °C.
3. Results and discussion
3.1. Effect of the solvent system, reaction temperature and polymerization
time on the electrical conductivity of polythiophene
The measured electrical conductivity of PTh samples synthesized
under different reaction conditions is presented in Table 1. From the
table, it is seen that all the samples, when the polymerization is carried
out at 0 °C with varying reaction time from 0.2 to 24 h the electrical
conductivity enhanced from 0.2 to 2.98 Scm−1. The same trend was
observed for the polymerization reaction carried out at RT, which re-
sulted the increase in conductivity from 1.11 to 7.52 Scm−1. This may
be due to the complete polymerization of thiophene with extended
chain formation [17]. At a short reaction time, the polymerization of
thiophene is incomplete and hence resulted in small chain PTh. Further,
when the polymerization is carried out at different temperatures (sub-
ambient and room temperature) for 24 h the samples exhibited in-
creased electrical conductivity from 2.98 to 7.52 Scm−1. This is be-
cause, at elevated temperature, as the number of oxidized thiophene
monomer increases, hence the probability of radical coupling among
these monomers also increases. Especially, the α-position of thiophene
gets activated that leads to the formation of α-α′ coupled lengthy, linear
polythiophene [18]. Fig. 2 shows the schematic representation of pos-
sible α-α′ coupling and α-β’ coupling of thiophene monomers. It is also
seen that the use of the binary solvent system (Dichloromethane and
Acetonitrile) resulted in improved electrical conductivity as compared
to the use of a single solvent (dichloromethane) system. This is due to
the fact that FeCl3 exhibited a better solubility in a binary solvent
system having acetonitrile as compare to dichloromethane alone. Fi-
nally, the polymerization of thiophene with a binary solvent as a
medium at room temperature for 24 h resulted in PTh with a maximum
conductivity of 7.5 Scm−1. These optimized reaction conditions were
followed to study the further effect of oxidizer to monomer ratio on the
electrical conductivity.
3.2. Effect of monomer to oxidizer ratio on the electrical conductivity and
yield
Fig. 3 shows the effect of oxidizer to monomer ratio on electrical
conductivity and yield. From the figure, it is seen that electrical con-
ductivity was increased with increasing thiophene to FeCl3 ratio from
1:1 to 1:6. The maximum electrical conductivity of 9.1 Scm−1 was
Fig. 1. Schematic representation of the oxidation
reaction of thiophene.
D. Thanasamy, et al. Polymer 175 (2019) 32–40

Table 1
Optimization Conditions and electrical conductivity of polythiophene.
Sl.No Reaction temperature (°C) Solvent System Reaction time (Hrs) Electrical conductivity (Scm−1) Designation

−5
1. 0 CH2Cl2 24 2.43 × 10 A1
2 RT CH2Cl2 24 1.44 × 10−4 A2
3 0 CH2Cl2/CH3CN 0.2 0.28 B1
4 RT CH2Cl2/CH3CN 0.2 1.11 B2
5 0 CH2Cl2/CH3CN 24 2.98 C1
6 RT CH2Cl2/CH3CN 24 7.52 C2

Fig. 2. Possible structure of formation or coupling of thiophene during oxida-

tion.

Fig. 4. FTIR Spectra of a) A2, b) B1, c) B2, d) C1, and e) C2

3.3. FTIR analysis

The effect of solvent, reaction temperature, reaction time on the

Fig. 3. Effect of molar ratio on electrical conductivity and yield of poly-
thiophene.
obtained at 1:6 M ratio with 80% yield. Further increase in a molar
ratio (1:7) showed an increase in yield 92% but lead to a drastic de-
crease in electrical conductivity 4.46 × 10−1 Scm−1. This could be due
to over-oxidation of PTh when exposed with a higher amount of oxi-
dizer [17]. From these results, it is clearly seen that the dropwise ad-
dition of 6M FeCl3 to 1 mol of thiophene in dichloromethane/acet-
onitrile binary solvent at room temperature for 24 h allowed an
enhanced degree of polymerization of thiophene and imparted high
electrical conductivity to PTh. The enhanced degree of polymerization
was further supported by UV–Visible, FTIR, SEM, XRD and Thermal
analysis.
chemical structure of polythiophene was examined by FTIR spectrum.
Fig. 4 shows FTIR spectra of PTh samples A2, B1, B2, C1, and C2. The
spectrum A2 was showed strong peaks corresponding to C-H stretching
(2921 cm−1), aromatic C=C stretching (1635 cm−1), C=C symmetric
stretching (1428 cm−1), C-H aromatic in-plane bending vibration
(1027 cm−1), C-H out of plane stretching of α-α’ coupling of PTh
(783 cm−1), C-S bending vibration (731 cm−1) and also exhibited weak
peaks corresponding to C-H aromatic in-plane bending vibration (1155
& 1108 cm−1) and C=C stretch of quinoid ring (1385 cm−1) [8,19–24].
The spectrum B1, B2, C1, and C2 were also exhibited similar peaks.
However, as compared to A2, the peak at 1635 cm−1 corresponding to
benzenoid was decreased and the weak peak at 1385 cm−1 corre-
sponding to the quinoid structure of PTh became very strong [20,25].
The increasing quinoid character of polymer chain lead to the decrease
in band gap (HOMO-LUMO) and resulted in enhanced electrical con-
ductivity [26,27]. Further, the peak appeared in A2 at 1428 cm−1 was
shifted to 1485 cm−1 in all other PTh samples. This may be due to the
interaction between C=C and doped Cl− ion [2,28,29]. Moreover, two
new peaks were appeared at 671 cm−1 and 637 cm−1 corresponding to
C-S-C ring stretching and Cl− ions in B1. The peak at 671 cm−1 was
shifted to 669, 667 and 665 cm−1 for B2, C1, and C2 respectively. Si-
milarly, the peak at 637 cm−1 was shifted to 635, 633 and 631 cm−1 for
B2, C1 and C2 respectively. This shift may be due to the formation of a
complex between Cl− and C=C. This clearly validates the electrical
conductivity of PTh prepared by varying the parameters. Further, this
will be authenticated by NMR Solid state, UV–Visible, XRD and SEM
studies.

34
D. Thanasamy, et al. Polymer 175 (2019) 32–40

13
Fig. 5. C Solid state NMR spectrum of sample C2

3.4. NMR analysis (Solid state)

13
C solid state (CPMAS) NMR was carried out for the sample C2 to
understand the chemical structure of the doped polythiophene. Fig. 5
shows the 13C solid state NMR spectrum of sample C2. Although the
thiophene is expected to show four distinct bands corresponding to four
kinds of carbon atoms with different electronic structures theoretically,
the spectrum clearly shows a single sharp peak at 198 ppm. This ob-
servation was earlier reported by Hotta et al., and Devreux et al.
[30–32]. The presence of sharp peak rather than broader peak (β−α
carbon) is attributed to non proton-bonded 13C spins (α-α carbons)
[32]. This evidence strongly supports the formation of regular α-poly-
merization which is further substantiated by appearance of peak at
783 cm−1 corresponding to 2,5 substituted thiophene in FTIR char-
acterization. Generally, the peak corresponding to α-carbons appears at
136 ppm for undoped polythiophene. For the sample C2, the peak was
shifted to downfield at 198 ppm which could be due to possible high
electron density of thiophene ring rendered from electron rich dopant
as Cl− etc. Hotta etc, also reported this kind of chemical shift using
ClO4− and BF4−. This is results in concurrence with the FTIR analysis
where a peak at 631 cm−1corresponding to presence of dopant Cl− is Fig. 6. Uv–Vis Spectrum of a) A2, b) B1, c) B2, d) C1, and e) C2 in
observed. Dichloromethane.

Table 2
3.5. UV–visible spectrum Uv–Vis absorption bands with possible assignments in polythiophene and
measured optical band gap.
Further, the UV–vis spectroscopic analysis was carried out for A2,
Samples Wavelength of absorption band (nm) Egopt (eV)
B1, B2, C1, and C2 in Dichloromethane medium to understand the
mechanism that was responsible for the enhancement of electrical π – π* n-π*/Polaran- π*
conductivity. Fig. 6(a–e) shows UV–vis spectra of various PTh synthe-
sized. Table 2 shows the absorption peaks of PTh with its possible as- A2 275 368, 588 3.6
B1 271 362, 601 2.6
signments. The UV–Vis spectrum of A2 exhibits a strong peak around B2 269 355, 601 2.5
275 nm corresponding to π-π* transition of 2,5 substituted thiophene, a C1 266 355, 603 2.3
medium peak around 368 nm and a weak peak around 588 nm belongs C2 262 353, 670 2.0
to n-π* transition of 2,5 substituted thiophene [15] respectively. The
peak at 588 nm signifies the extension of large π-conjugation of PTh. All

35
D. Thanasamy, et al. Polymer 175 (2019) 32–40

Fig. 7. Plot of (αhν)2 vs. hν for polythiophene samples.

the samples exhibited a red shift of this peak (towards higher wave- 1240
Egopt (eV ) = (nm)
length) and a maximum shift to around 670 nm was observed for the λ edge (1)
sample C2. This reveals that the sample C2 is having the lengthy con-
jugative polymer chain than other samples. The existence of lengthy where Egopt is the optical band gap, λedge is the absorption edge and the
conjugation is responsible for higher electrical conductivity. The peaks number 1240 is obtained from the relationship between frequency and
at around 275 and 368 nm are blue shifted (towards lower wavelength) wavelength as described following equation (2).
for all other PTh which could be due to a high degree of polymerization c
E (eV ) = hv = h
[33] or presence of Cl-dopant (electron withdrawing group) [34]. eλ (2)
Further Diffuse Reflectance Spectra (DRS) was recorded for A2, B1, B2,
C1, and C2 to calculate optical band gap (HOMO-LUMO). Fig. 7 shows Where ‘h’ is Planck's constant, ‘c’ is the speed of light in a vacuum, ‘e’ is
plot of (αhν)2 versus photon energy hν (eV) for PTh. the electron charge, and ‘λ’ is wavelength in the unit of meter, then
The optical band gap (difference between the valence band and the 1240 can be obtained from hc/e. To obtain the corresponding band gap,
conduction band) can be obtained by the equation [8,35–39]. one can plot (αhν)2 vs hν and extrapolate the linear portion of it to
α = 0 value. Accordingly, the bandgaps were calculated. The calculated
bandgaps are presented in Table 2.

36
D. Thanasamy, et al.
Fig. 8. SEM image of various polythiophene samples a) A2, b) B1, c) B2, d) C1, and e) C2
From the table it is seen that PTh synthesized by dropwise addition
of oxidizer using binary solvent at RT for 24 h (C2) exhibited very low
band gap of 2.0 eV which was in agreement with reported literature
[40]. This can be explained by the fact that increased amount of dopant
Cl− which causes the maximum quinoid character in polythiophene
conjugation chain [26,27,41]. This result is well in agreement with the
measured electrical conductivity values of PTh samples.
3.6. SEM analysis
The morphology of various PTh samples synthesized was analysed
by Scanning Electron Microscopy (SEM). Fig. 8(a–e) shows the SEM
images of the morphology of (A2, B1, B2, C1, and C2) samples. From
the Fig. 8a, it is seen that sample A2 exhibited nonporous and irregular
macro-granular structure, reflecting the amorphous nature of PTh. The
sample B1 showed an aggregated semi-sphere structure as shown in
Fig. 8b. This could be due to the formation of the ordered structure of
37
Polymer 175 (2019) 32–40
PTh. Further, sample B2 exhibited a sphere-shaped structure as shown
in Fig. 8c with the particle radius size of 180–200 nm (Fig. S1). Simi-
larly, the samples C1 and C2 were also exhibited sphere-like structures
as shown in Fig. 8d–e. The particle radius size of C1 and C2 samples
were 150–180 nm and 110–130 nm (Figs. S2 and S3) respectively. From
these results, it is evident that the thiophene polymerization carried out
in a binary solvent system at room temperature for 24 h resulted in the
formation of polythiophene (C2) with an ordered structure and nano
sized particles, which were responsible for enhanced electrical con-
ductivity. These results were further confirmed with X-ray diffraction
study.
3.7. XRD analysis
The structural difference of PTh samples was investigated by X-ray
diffraction analysis to cognize the influence of solvent system, reaction
temperature, and reaction time etc., Fig. 9 shows the diffraction pattern
D. Thanasamy, et al. Polymer 175 (2019) 32–40

samples were estimated using the Bragg's (Eq. (3)) and Debye-Scherrer
(Eq. (4)) equations.
Lattice space ‘d’ is calculated from Bragg's equation.
nλ = 2d sinθ (3)
where n is an integer, λ is the wavelength of incident wave (1.5405 Å
for Cu Ka), d is the spacing between the planes in the atomic lattice and
θ is the angle between the incident ray and the scattering planes. The
crystal size ‘D’ can be calculated from Debye-Scherrer equation.
D = 0.9λ /β cos θ (4)

where β is full width at half maximum (FWHM) of the diffraction peak,

and D is crystal size.
The calculated crystal sizes and lattice spaces for PTh samples are
presented in Table 3.
From the Table 3, it is seen that the FWHM of the common peak
observed at approximately 2θ = 25° is decreased and the crystallite size
is increased from B1 to C2. This substantially supports the highest
electrical conductivity of C2.

3.8. Thermal analysis

Fig. 9. XRD of various polythiophene samples a) A2, b) B1, c) B2, d) C1, and e)
C2
The effect of various reaction conditions on thermal properties of
PTh was studied by DSC. Fig. 10 shows DSC thermograms of PTh
Table 3 samples. From the figure, it is seen that the sample (A2) synthesized in
Crystallite size, FWHM and Lattice spacing of PThs to the corresponding 2θ mono-solvent medium exhibited the lowest glass transition temperature
values. (Tg) at ≈ 42 °C. When the reaction medium was changed to a binary
Samples 2θ FWHM Lattice Spacing (d)A° Crystallite Size (D) A° solvent system, the glass transition temperature of all the samples, in
general, exhibited higher glass transition temperature as compared to
A2 23.57 1.8822 3.7696 0.7522 A2. Further, when the reaction temperature was raised from 0 °C to
B1 22.27 0.7173 3.9866 1.9693
24.92 1.3658 3.5684 1.0393
room temperature the sample C1 exhibited, higher Tg (≈56 °C) as
B2 21.42 0.8156 4.1428 1.7296 compared to sample B1 (≈53 °C). When the reaction time was extended
24.82 1.1324 3.5825 1.2532 from 0.2 to 24 h, the Tg of B2 (≈54 °C) was further enhanced and
C1 16.02 0.2843 5.5248 4.9238 highest Tg of 60 °C was realized for sample C2 due to the presence of
18.27 0.5323 4.8492 2.6371
more orderly chain structure. In addition, the samples that were syn-
24.82 1.2130 3.5825 1.1700
27.27 0.4855 3.2660 2.9373 thesized with an extended period of polymerization time (C1 and C2)
C2 15.27 0.4089 5.7943 3.4196 exhibited additional endothermic peaks at 109° and 138° respectively.
23.07 0.7565 3.8501 1.8700 This could be due to the evacuation of strongly bounded Cl− to the
25.17 1.0996 3.5335 1.2916 polymer chain [45].
31.17 0.5062 2.8657 2.8429
33.62 0.3378 2.6623 4.2859
4. Conclusion

of PTh samples prepared under various conditions. Table 3 shows the A novel method of synthesis for PTh having highest conductivity
XRD peaks appeared for PTh samples. It is known that the poly- without post doping process was arrived through the optimization of
thiophene samples are amorphous and contains less percentage of
crystallinity (approximately < 10%). However, in this study, only the
relative improvement in crystallinity among the samples is reported.
From the table, it is seen that A2 had only one peak at 2θ ≈ 23.57°. All
other PTh samples were had two or more than two peaks. This reveals
that the A2 is highly amorphous in structure than other PTh samples.
The sample B1 had two different peaks at 2θ ≈ 22.27° and 24.92°. Si-
milarly, the sample B2 also had two peaks at 2θ ≈ 21.42°, 24.82°. The
sample C1 had four peaks at 2θ ≈ 16.02, 18.27, 24.82, and 27.27°. The
sample C2 had five peaks at 2θ ≈ 15.27, 23.07, 25.17, 31.17, and
33.62°. All these peaks were observed in various literatures [42–44]. A
common peak is existing in all four PTh samples except A2 at ap-
proximately 2θ = 25°. This might be due to the effect of a binary sol-
vent (Dichloromethane and Acetonitrile) system on the structure of the
polymer chain. Similarly, A2 and C2 had a common peak at approxi-
mately 2θ = 23°. This might be due to the effect of reaction tempera-
ture (RT) and reaction time (24hr). Except these similarities, each
sample show peaks at different 2θ. These results indicate that para-
meters such as reaction temperature, solvent system, reaction time are a
most influencing factor of crystal structure in the polymer chain.
In order to support this fact, Lattice spaces and crystal sizes of PTh Fig. 10. DSC thermograms of various polythiophene samples a) A2, b) B1, c)
B2, d) C1, and e) C2

38
D. Thanasamy, et al.
various reaction parameters viz solvent medium, reaction temperature,
polymerization time and monomer to oxidizer ratio. From the studies, it
was found that, the room temperature polymerization of thiophene
monomer for 24 h in presence oxidizer FeCl3 with 1:6 ratio in a binary
solvent system was the most ideal procedure for synthesizing the PTh to
acquire highest electrical conductivity without post doping process.
80% yield and maximum electrical conductivity of 9 Scm−1 was
achieved for PTh with this optimized procedure. This achievement was
substantiated by NMR solid state, FTIR, UV–Vis, Diffuse Reflectance
Spectroscopy (DRS), XRD and DSC studies.
Acknowledgment
One of the authors T. David acknowledges the CSIR-National
Aerospace Laboratories, Bangalore for the Award of Senior Research
Fellow (SRF). Authors also acknowledge the encouragement and sup-
port received from Mr. Shyamchetty, former Director CSIR-NAL, Mr.
Jitendra J Jadhav, Director-CSIR-NAL and Dr. G. N. Dayananda, Head,
CSMST, CSIR-NAL to carry out this research work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.polymer.2019.03.042.
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