Polymer International 42 (1997) 380È384

Investigation of Structure and Electrical

Conductivity in Doped Polyaniline
H. K. Chaudhari & D. S. Kelkar*
Institute of Science, Department of Physics, 15 Madam Cama Road, Mumbai 400032, India

(Received 1 October 1996 ; accepted 26 October 1996)

Abstract : Polyaniline (PAn) was synthesized chemically and doped with various
dopants, such as HCl, HCOOH, I and methylene blue (C H ClN S), by an
immersion method. The structure 2of these samples was investigated
16 18 3 infrared
by
(IR) spectroscopy and wide-angle X-ray di†raction (WAXD) analysis. Remark-
able changes have been observed in the IR spectra of doped PAn, indicating that
doping is a†ecting the chemical structure. The percentage crystallinity was also
found to increase after doping. The electrical conductivity (p) of these samples
was measured at various temperatures (T \ 308 K to 423 K). Plots of log p
versus Ty, where y \ [1/2, [1/3, [1/4, were obtained and used to identity the
conduction mechanism. Undoped PAn shows semiconducting behaviour, while
doped samples show a variable range hopping mechanism. A primary cell was
constructed with HCl-doped PAn as one of the electrodes and a copper plate as
the other electrode. It gave an open circuit voltage of 0É38 V and a short circuit
current of about 5É4 mA.

Key words : polyaniline, chemical doping, crystallinity, electrical conductivity,

primary cell.

INTRODUCTION the conductivity in PAn was a†ected. Ohsaka et al.8 dis-

Conducting polymers such as polyacetylene, poly-
pyrrole, polyaniline (PAn) and polythiopene have been
widely investigated over the past few years. PAn has
received great attention because of its good environ-
mental stability and also its interesting electrochemical
properties for the development of light-weight batteries
and electrochromic display devices.1
Polyaniline can be synthesized chemically as well as
electrochemically.2h5 Infrared spectroscopic analysis of
PAn has been widely carried out.3,6h8 IR spectra of
undoped PAn showed main absorption bands at about
3237, 3040, 1587, 1510, 1300, 1250 and 850 cm~1.
Changes in intensities of these bands were observed
after doping the samples. The bands appearing at about
1587 cm~1 and 1510 cm~1 are assigned to non-
symmetric C ring stretching.6,7 It was reported that
6
with di†erent concentrations of HCl, the relative inten-
sities of these two bands changed and simultaneously
* To whom all correspondence should be addressed.
380
Polymer International 0959-8103/97/$09.00 ( 1997 SCI. Printed in Great Britain
cussed the mechanism of polymerization of PAn in
terms of changes in the IR spectra.
According to Wang et al.9 crystallinity (X ) decreased
c
with increasing HCl concentration during synthesis
over the range from 0É001 N to 7 N. The reason for this
was that at high concentrations of HCl addition of Cl
atoms to the quinoid ring occurs. It was reported that
the crystallinity of the sample depends on the size of
both oxidant and dopant. Dopant and oxidant with
smaller sizes lead to higher crystallinity.9 It was also
reported that emeraldine base powder was c. 50%
(orthorhombic) crystalline.10,11 Chen and Lee12 found
that the X-ray di†raction (XRD) pattern of PAn powder
exhibited a broad amorphous peak at 2h \ 19¡ and two
weak crystalline peaks at 2h \ 15¡ and 2h \ 24¡, and
became more crystalline after doping with HCl.
From a literature survey it was found that most of
the studies have concentrated on HCl-doped polyanil-
ine.13,14 It was reported13 that when undoped PAn was
treated with aqueous acid such as HCl, it undergoes an
insulator-to-metal transition involving an increase in
Investigation of doped PAn 381

Fig. 1. Infrared spectra of PAn powder : (a) HCl-doped ;

(b) iodine-doped ; (c) formic acid-doped. Fig. 3. WAXD scans of PAn in powder form : (a) undoped ;
(b) HCl-doped ; (c) formic acid-doped.

Fig. 2. Infrared spectra of PAn powder : (a) undoped ; Fig. 4. WAXD scans of PAn in powder form : (a) undoped ;
(b) methylene blue-doped. (b) iodine-doped ; (c) methylene blue-doped.

POLYMER INTERNATIONAL VOL. 42, NO. 4, 1997

382 H. K. Chaudhari, D. S. Kelkar

conductivity of the order of 10. Hence it was thought
interesting to investigate the structure and electrical
conduction in PAn when it is doped with various
dopants such as formic acid, iodine, methylene blue as
well as HCl. The structure of these samples has been
investigated using infrared (IR) spectroscopic analysis
and wide-angle X-ray di†raction (WAXD) analysis.
Electrical conductivity study of these samples at various
temperatures has been undertaken. An attempt has also
been made to use HCl-doped PAn as one of the elec-
trodes in a primary cell.
EXPERIMENTAL
Sample preparation
The PAn used was synthesized chemically using aniline
as monomer and ammonium peroxodisulphate as an
oxidant in aqueous media.5 The PAn thus obtained was
in the doped form, which was converted into the base
form by treatment with aqueous ammonia.
Doping
Undoped PAn powder was doped by immersion in
various solutions, such as 1 M aqueous HCl, 10%
aqueous formic acid, 1% iodine solution in acetone and
1% aqueous methylene blue solution, for 24 h, followed
by drying under dynamic vacuum at room temperature.
It was then pressed into pellets of about 1 cm diameter
and 1 mm thickness.
IR spectroscopy
pellet, while the other electrode was a copper plate of
about the same area (1 cm2).
RESULTS AND DISCUSSION
Figure 1 shows the IR spectra of HCl-, iodine- and
formic acid-doped PAn and Fig. 2 shows the IR spectra
of undoped and methylene blue-doped PAn. Remark-
able changes are observed after doping ; the most
important described below.
In the NwH stretching region, a band appears at
about 3237 cm~1. This band shifts towards higher
wavenumbers in the case of all doped samples, except
that doped with formic acid where there is a slight shift
towards lower wavenumbers. The shift in this band
indicates a hydrogen amine (NH) group.6 In the CwH
stretching region, the peak at about 3060 cm~1 for
undoped PAn is reduced after doping, which indicates
reduction in the number of H atoms bonded to the
benzene ring.6 The CwN stretching band at about
1300 cm~1 shifts slightly towards lower wavenumbers
and becomes stronger than the key bands in the case of
HCl-, HCOOH- and I -doped samples. Simultaneous
2
changes are observed in the NwH and CwN stretching
bands, indicating the possibility of the dopant molecules
becoming attached to the more reactive amine nitrogen
sites of PAn.
After doping, the key bands assigned to the quinoid
and benzenoid units are at about 1582 cm~1 and
1496 cm~1, respectively, showing slight shifts towards
lower wavenumbers. The relative intensity of these two
bands increases after doping.
In the case of methylene blue-doped samples, unlike
the other doped samples, almost all the peaks shift

The IR absorption spectra were obtained for pristine

and modiÐed PAn samples in the spectral range 4000È
400 cm~1 using a Perkin Elmer FTIR model 1600
spectrometer.

WAXD scans

The X-ray di†raction parameters were recorded using a

JEOL JDX-8030 X-ray di†ractometer. From the radial
scans of intensity versus 2h, the lateral order or the crys-
tallinity index of these samples was calculated using
ManjunathÏs formula.15

Electrical conductivity measurements

A two-probe method was used to measure the electrical

conductivity of the PAn pellets in a sandwich conÐgu-
ration.16
A very simple primary cell was constructed, which
consisted of an aqueous CuCl solution as electrolyte.
2
One of the electrodes used was an HCl-doped PAn Fig. 5. Plot of log p versus 1/T for undoped PAn powder.

POLYMER INTERNATIONAL VOL. 42, NO. 4, 1997

Investigation of doped PAn 383

Fig. 6. Plot of log p versus T ~1@4 for : (a) HCl-doped ; (b) HCOOH-doped ; (c) I -doped.
2

towards higher wavenumbers and the bands become
broad.
The WAXD patterns of all the PAN samples are well
resolved and show distinct peaks (Figs 3 and 4). For
calculation of the crystallinity index, ManjunathÏs
formula was used.15
For undoped samples, peaks appeared at about
2h \ 9É5¡, 14É7¡, 20É4¡ and 25É1¡, and the percentage,
crystallinity calculated using ManjunathÏs formula was
45%. This indicates that undoped PAn is not fully
amorphous, but partially crystalline. It is also observed
that the crystalline peak at 2h \ 25¡ is more prominent

Fig. 7. Plot of log p versus T ~1@4 for methylene blue-doped PAn powder.

POLYMER INTERNATIONAL VOL. 42, NO. 4, 1997

384
than the amorphous peak, which is reported at
2h \ 19É5¡.
After doping with HCl and formic acid, PAn becomes
more crystalline. The percentage crystallinity increases
remarkably for HCl- and HCOOH-doped samples
(Table 1). In the case of iodine-doped samples, peaks are
not as distinct and sharp as they are for undoped PAn.
Furthermore, the amorphous peak is more intense than
the crystalline one. The percentage crystallinity reduces
to 35%, which is even less than that of the undoped
material. After doping with methylene blue, the crys-
tallinity of the sample does not show as much improve-
ment as is observed in HCl- and HCOOH-doped PAn.
From these observations it can be concluded that the
dopant species a†ects the structure and also the crys-
tallinity of PAn.
For undoped PAn, variation of conductivity (p) with
temperature (T ) was studied in the temperature range
308 K to 423 K. A plot of log p versus 1/T for this
sample shows a straight line Ðt (Fig. 5).
A straight line relationship between log p and 1/T
indicates that the behaviour is semiconducting. Similar
plots of log p versus 1/T were obtained for the other
doped samples, but good Ðts were not observed. For
HCl, HCOOH and I dopants, a plot of log p versus
2
T ~1@4 shows a good Ðt (Fig. 6), while for methylene
blue-doped PAn a plot of log p versus T ~1@3 shows a
good Ðt (Fig. 7). These observations indicate that after
doping the conduction mechanism does not remain
semiconducting, but changes to variable range hopping.
An attempt was made to construct a primary cell
containing 40% CuCl solution as an electrolyte. It
2 1468.
gave an open circuit voltage of 0É38 V and a short
circuit current of about 5É4 mA.
It was observed that the PAn electrode becomes posi-
tive when a voltage is developed. This shows that PAn
loses electrons, which may then recombine with metal
TABLE 1. Percentage crystallinity, X and electrical
c
conductivity (measured at room temperature) of
PAn in powdered form
PAn powder X (%) Conductivity (S cmÉ1)
c
Undoped 45 5·27 Ã 10É7
HCl-doped 74 6·0 Ã 10É2
Formic acid-doped 65 2·0 Ã 10É1
Iodine-doped 35 3·68 Ã 10É4
Methylene blue-doped 52 7·18 Ã 10É7
H. K. Chaudhari, D. S. Kelkar
cations. The reaction may be as follows :
At the anode (polymer) : PAn ] PAn` ] e~
CuCl ] Cu2` ] 2Cl~
2
At the cathode metal) : Cu2` ] 2e~ ] Cu
Copper ions then deposit on the metal electrode
making it negative.
During the course of this study, it was seen that the
PAn electrode was not visibly a†ected and could be
reused after washing.
CONCLUSIONS
From the IR spectra and WAXD scans it can be con-
cluded that the dopant species a†ect the structure and
also the crystallinity of PAn. Pristine PAn has semicon-
ducting behaviour, which changes to variable range
hopping after doping. PAn can be used as the anode for
constructing a primary cell.
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POLYMER INTERNATIONAL VOL. 42, NO. 4, 1997