PERGAMON Carbon 39 (2001) 101108

Electric conductivity changes of polypyrrole and polythiophene

films with heat-treatment
Eiji Ando 1 , Shinji Onodera, Masashi Iino, Osamu Ito*
Institute for Chemical Reaction Science, Tohoku University, Katahira, Aoba-ku, Sendai, 980 -8577 Japan
Received 30 September 1999; accepted 20 March 2000

Abstract

The electric conductivities of polypyrrole and polythiophene films have been measured as a function of heat-treatment
temperature. From room temperature to 1508C, the conductivity of polypyrrole film remained constant. From 150 to 3008C,
the conductivity dropped due to the decomposition of polypyrrole and the loss of dopant ion (ClO 2 4 ). Above 3008C, the
conductivity increased again. Above 7508C, the conductivity was higher than that of the original film due to the formation of
carbonaceous materials. The polythiophene film showed a similar tendency to the polypyrrole film. Chemical and
spectroscopic methods such as elemental analysis, FT-IR and ESR were employed to determine the origin of the electric
conductivity changes. 2000 Elsevier Science Ltd. All rights reserved.

Keywords: A. Carbon films; B. Pyrolysis; C. Infrared spectroscopy; Electron spin resonance; D. Electrical properties

1. Introduction 2. Experimental

Electrically conductive polymers have been studied 2.1. Materials

extensively [1]. In particular, polypyrrole and poly-
thiophene films exhibit high electric conductivities with
doping. In order to expand their application to devices
under a wide range of conditions, it is necessary to
investigate the thermal stability over a wide temperature
range [2]. Furthermore, the carbonaceous compounds
obtained after appropriate heat treatment of conductive
polymers may be utilized in lithium batteries [3]. In this
study, we measured the electric conductivity changes of
the conductive polymer films with heat-treatment tempera-
ture (HTT). In order to determine the physical and
chemical origin of the changes, various spectroscopic
methods such as ESR and FT-IR were employed in
addition to chemical analysis.
Polypyrrole (PPy) and polythiophene (PT) films were
prepared with polymerization by electrolysis of pyrrole and
thiophene, respectively, as shown in Scheme 1 [4]. These
monomers were purified by distillation under a reduced
pressure just before electropolymerization. Elec-
tropolymerization was performed at constant electric cur-
rent in the range of 0 to 2 V in propylene carbonate with
LiClO 4 as the supporting electrolyte. The films doped with
ClO 42 were deposited on an ITO glass electrode. Dedoping
was performed by dipping the doped film in aqueous
ammonia solution for 1 h. All the film samples were dried
overnight at room temperature in an oven under a reduced
pressure.

2.2. Heat-treatment procedure

*Corresponding author. Tel. / fax: 181-22-217-5610.
E-mail address: ito@icrs.tohoku.ac.jp (O. Ito).
1
Present address: Institute of Applied Electric Technology,
Tohoku Electric Company, Nakayama, Aoba-ku, Sendai 981,
Japan.
A piece (10310 mm) of film was placed in a quartz tube
in an electric furnace under N 2 gas flow (0.2 l / min), and
was heated at a rate of 108C / min. At selected heat-
treatment temperatures, the sample was held for 1 h
followed by cooling to room temperature.

0008-6223 / 01 / $ see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S0008-6223( 00 )00098-1
102 E. Ando et al. / Carbon 39 (2001) 101 108

Scheme 1.

2.3. Measurements the doped sample by a factor of ca. 10 4 . With heat

treatment to 2508C, the electric conductivity decreases
The electric conductivity of a sample was measured by a gradually. In the region of 2505008C, the electric con-
4-terminal method using a Loresta conducting meter for ductivity was too low to measure with our equipment.
films (Mitsubish-Yuka Ltd.). Spectroscopic methods such Above 5008C, the electric conductivity increases again; at
as Fourier transform infra-red spectroscopy (FT-IR; JEOL 5508C, the conductivity reaches the original value for the
J-100) and electron spin resonance spectroscopy (ESR;
Varian E-4) were used. The diffuse reflectance absorption
method was employed for the IR measurements of the
powdered samples. The samples were prepared by pul-
verizing them until the powder passed through a 200 mesh
(,65 mm) Tyler screen. The intensities of the IR bands
were expressed by the Kubelka-Munk function ( f(R ` )),
which is proportional to the absorbance in the transmitt-
ance measurements [5]. ESR measurements were per-
formed with low microwave power to avoid saturation of
the signal intensity [6]. The thermogravimetric measure-
ments were performed under N 2 gas flow (80 ml / min) at a
heating rate of 108C / min.

3. Results and discussion

3.1. Polypyrrole ( PPy)

Fig. 1 shows the variation of electric conductivities (s )

with HTT in the form of log 10 s vs. 1 /T. For the film with
dopant (ClO 2 4 ), the samples exhibit a high electric con-
ductivity up to 1508C. This indicates that PPy films are
stable until this temperature for 1-h heat treatment. From
200 to 3008C, the electric conductivity drops drastically by
a factor of ca. 10 4 . Above 3008C, the conductivity
gradually increases again until 5008C. Above 5008C, the
conductivity increases rapidly, reaching the high conduc-
tivity of the original material at 7508C.
In the case of the dedoped PPy sample, the electric Fig. 1. Variation of electric conductivity (s ) of PPy films with
conductivity of the untreated sample is lower than that of HTT; (s) doped PPy and (d) dedoped PPy.
 E. Ando et al. / Carbon 39 (2001) 101 108
Fig. 2. Thermogravimetric curves for PPy; (a) doped PPy, (b)
dedoped PPy, and (c) heat-treated PPy (doped) at 3008C.
untreated sample. At 7508C, the conductivity becomes as
high as that of the doped sample at the same HTT.
In Fig. 2, thermogravimetric curves showing the weight
loss are shown for PPy film. Drastic differences between
the doped PPy and dedoped PPy were observed at 200
3008C. This weight loss in this HTT range occurs for the
doped sample, whereas this weight loss was not observed
for the dedoped sample and for the sample pre-heat treated
at 3008C. Thus, it is suggested that the weight loss between
200 and 3008C is caused by the loss of dopant (ClO 2 4 ),
which was supported by the drop of conductivity in Fig. 1.
Above 3008C, a gradual weight loss was observed up to
10008C, which may be related to the carbonization which
may involve the reactions losing C, H, and N-atoms. For
these three PPy samples, the first weight loss occurs below
1008C, which may be caused by desorption of water. The
electric conductivity was not affected by such desorption
of water, as seen in Fig. 1.
The chemical composition of the residue of the heat-
treated PPy samples was evaluated by elemental analysis.
The data are summarized in Fig. 3 for doped and dedoped
PPy samples. After heat-treatment at 3008C, the weight %
of the actual elements based on original elements can be
evaluated by multiplying the weight % of the residue; i.e.
from the thermogravimetric curve, the weight loss at
3008C of the doped sample is ca. 50 wt.% (Fig. 2). At this
stage the loss of Cl-atoms is prominent (Fig. 3), indicating
the loss of dopant (ClO 42 ). Thus, it is presumed that the
prominent decrease in the electric conductivity (Fig. 1) in
the 2003008C range is due to the loss of dopant, which is
probably accompanied by the decomposition of ClO 2 4 . In
the untreated sample, the unidentified part may come from
103
Fig. 3. Elemental analysis of heat-treated PPy samples; (a) doped
PPy and (b) dedoped PPy.
oxygen or metals such as tin and indium on the electrode
surface.
The loss of N-atoms occurs mainly between 400 and
6008C (Fig. 3). This may correspond to the re-increase in
the electric conductivity in Fig. 1. With the loss of N-
atoms, carbonization reactions occur to produce polycon-
densed aromatic hydrocarbons showing a high electric
conductivity. Since the carbonaceous materials contain
small amounts of H-atoms at this stage, graphite formation
would not be expected. Amorphous carbon may be respon-
sible for the high electric conductivity.
For PPy film without dopant, the loss of N-atoms occurs
between 400 and 6008C resulting in carbon formation with
the evolution of a small amount of H-atoms. This may
correspond to the recovery of the electric conductivity for
the dedoped sample at high HTT. These processes above
4008C were not affected by the dopant, because ClO 2 4 was
decomposed and released at low temperature.
The FT-IR spectra of the heat-treated PPy samples are
shown in Fig. 4. The IR spectrum of an untreated sample
with dopant shows a broad absorption with a sharp band at
1150 cm 21 . This sharp band is attributed to ClO 2
4 , because
such a band was not observed for the dedoped sample. The
broad absorption observed for the untreated sample with
dopant is attributed to the electronic transition extending
from the higher energy region [5]. This broad band may be
characteristic of the highly conductive material [7]. On the
104 E. Ando et al. / Carbon 39 (2001) 101 108
Fig. 4. Fourier-transform infrared (FT-IR) spectra for heat-treated PPy; (a) doped PPy and (b) dedoped PPy.
other hand, the dedoped sample shows the rather sharp IR
bands in the region of 6001700 cm 21 . It is evident that
the sample with high electric conductivity tends to lose the
IR bands characteristic of organic material. With HTT
accompanying the loss of electric conductivity of the
doped sample, the IR bands characteristic of aromatic
compounds appear around 1600 cm 21 .
Between 300 and 4008C, a band appears at 2210 cm 21 ,
which is characteristic of C=N [8]. By further heat-
treatment above 6008C, the sharp IR bands were replaced
by a broad band spreading over the entire IR region. This
HTT range seems to be consistent with that for N-atom
loss as seen in Fig. 3. This broad band was attributed to the
electronic transition of the polycondensed aromatic hydro-
carbons stacked upon each other [9]; this implies that
carbonaceous materials have a relatively ordered structure,
which is still quite low compared with the graphite
structure.
For the dedoped sample below 3008C, the relatively
sharp bands around 8001700 cm 21 are attributed to the
vibrations of the pyrrole moiety [10]. After the appearance
of the 2200 cm 21 band at 2508C, the band around 800
1700 cm 21 disappeared at about 5508C. After the dis-
appearance of the sharp band at 2200 cm 21 , a broad
absorption band increases above 6008C, suggesting the
formation of the conductive carbonaceous materials.
Each ESR spectrum for the untreated and heat-treated
PPy samples consists of a symmetric single signal. Fig. 5
shows the dependence of the spin concentration and line
width of the ESR signal on HTT. The spin concentration
for the dedoped PPy sample is almost constant from room
temperature to HTT at 3008C; then, the spin concentration
increases monotonously with HTT up to 8008C. This
suggests that the origin of the paramagnetism above 3008C
is different from that below 3008C; i.e. some reactions take
place above 3008C. For the doped PPy sample, the spin
concentration increases from room temperature to 2008C;
then, from 200 to 3008C, the spin concentration decreases,
probably due to the decomposition of the dopant. From
300 to 8008C, the spin concentration increases again in a
 E. Ando et al. / Carbon 39 (2001) 101 108
Fig. 5. Variation of electron spin concentration and line width
(DHpp ) with HTT; (s) doped PPy and (d) dedoped PPy.
similar manner to the dedoped sample, which is attributed
to the increase in the radical species formed during the
carbonization reactions.
The temperature change of the line width of the ESR
signal suggests that the radical species in the region of
2004508C have different characters from that below
Fig. 6. (a) Variation of electric conductivity (s ) of PT film with
HTT; (s) doped PT and (d) dedoped PT.
105
Fig. 7. Thermogravimetric curves for PT; (a) doped PT and (b)
dedoped PT.
2008C. The broad line width for the dedoped sample in the
HTT region of 2004008C may be related to the decrease
in the electric conductivity in the same HTT region in Fig.
1. At ca. 6508C, a steep inflection point of the line width
Fig. 8. Elemental analysis of heat-treated PT; (a) doped PT and
(b) dedoped PT.
106 E. Ando et al. / Carbon 39 (2001) 101 108
indicates that a drastic change occurs in the origin of
paramagnetism; the degree of carbonization becomes quite
different at this temperature for both the doped and
dedoped PPy samples.
3.2. Polythiophene ( PT)
The electric conductivity changes of the PT samples
with HTT are shown in Fig. 6. The electric conductivity of
the doped PT sample drops at 1008C; the thermal stability
of PT is less than that of PPy. In the HTT range between
200 and 6008C, the conductivity of the doped sample was
too low to measure. Above 6008C, the conductivity
increases again up to a value similar to that before heat-
treatment; this may be accompanied by the formation of
carbonaceous compounds, because the brown film became
black during heat-treatment above 6008C. The electric
conductivity of the dedoped PT sample was too low to
measure for HTTs below 6008C. At a heat-treatment above
Fig. 9. FT-IR spectra for heat-treated PT; (a) doped PT and (b) dedoped PT.
6008C, the conductivities increased in a similar way to the
doped sample.
In the thermogravimetric curves shown in Fig. 7, the
weight loss of the doped PT sample begins at 1502258C,
which corresponds to the decrease in electric conductivity.
Since the weight loss at this temperature range was not
observed for the dedoped sample, this weight loss is
attributed to the loss of dopant (ClO 2
4 ). The main weight
loss appears in the wide range of 400 to 6008C for both the
doped and dedoped samples, which is ascribed to the
carbonization reaction.
In Fig. 8, the weight % of the elements for the PT
samples is summarized for the representative HTTs. Most
of the Cl-atoms were lost up to 2008C for the doped
sample, showing that the dedoping occurs at this tempera-
ture. This is the main reason why the electric conductivity
decreases at relatively low HTTs. In the range of the main
weight loss (4006008C), no appreciable change was
observed for the fractions of the elements. It is noticeable
that the S atom persists even at 6008C for both the doped
 E. Ando et al. / Carbon 39 (2001) 101 108
and dedoped samples. Until 6008C, the electric conduc-
tivity does not recover as seen in Fig. 6; thus, the S-atom
may retard the formation of the carbonaceous compounds
which exhibit high electric conductivity.
Fig. 9 shows the FT-IR spectra of heat-treated PT
samples. The electrically conductive doped PT films (Fig.
9a) show a broad band in the entire IR region from room
temperature to 1508C [11]. The weak but sharp band at
1150 cm 21 is attributed to ClO 2 4 . As the electrical
conductivity decreases with the loss of dopant in the HTT
region from 200 to 6008C, the IR bands characteristic of
organic materials appear in the region of 8001600 cm 21
and ca. 3000 cm 21 . These strong IR bands are attributed to
the aromatic CH (3030 cm 21 , 800 cm 21 etc.) and
aromatic C=C (1600 cm 21 ) vibrations. The weak bands at
2970 and 1550 cm 21 are attributed to aliphatic CH
vibrations [8]. The band at 1650 cm 21 may be attributed to
C=O groups. Above 6008C, the IR bands are replaced
again with the broad band characteristic of the electrically
conductive carbonaceous materials [5,9].
In the case of dedoped PT samples (Fig. 9b), the IR
bands are sharp even below 1508C, indicating low electric
Fig. 10. Electron spin resonance (ESR) spectra of heat-treated PT;
(a) doped PT and (b) dedoped PT.
107
conductivity. The thiophene moiety in the polymer seems
to be stable for HTTs up to 5508C. Electrically conductive
carbonaceous material was produced from the dedoped PT
sample above 6008C, which is a similar HTT to that for the
doped sample.
Fig. 10 shows the ESR spectra for the heat-treated PT
samples. For the doped PT sample, a narrow signal was
observed at the low temperature range in which the
material exhibits high electric conductivity. Above a HTT
of 2008C, where electric conductivity is lost, the signal
becomes broad as seen in the spectrum at 2508C. At
4508C, the signal intensity decreases by a factor of 2
compared with that at 2508C, keeping the line width
almost constant. With the recovery of the electric con-
ductivity above 6008C, the signal remains broad as the spin
concentration begins to increase.
For the dedoped PT sample, the ESR signal is weak and
broad at room temperature, which is in good agreement
with its low electric conductivity. With heat-treatment up
to 4508C, the signal intensity increases slightly while the
line width remains broad. At 6508C, the ESR signal
intensity increases whereas the line width decreases. The
carbonaceous material produced from the dedoped PT
sample may be quite different from that formed from the
doped PT sample, because the line widths are different.
4. Conclusion
Electrically conductive polymers were changed drasti-
cally with heat-treatment. The first-stage change occurs at
1002008C, accompanying the decrease in the conduc-
tivity when ClO 2 4 was used as dopant. The second-stage
change is the re-increase in the conductivity with the
formation of electrically conductive carbonaceous materi-
als. The FT-IR spectra observed by the diffuse reflectance
method afford useful information about the electric con-
ductivity in terms of the broad absorption over the entire
wavenumber region, in addition to the functional group
changes with heat-treatment. The ESR signals also give
some clues for the origin of the variation of the electric
conductivity during heat treatment of the conductive
polymers. The carbonaceous materials obtained from these
electrically conductive polymers may have uniquely new
characteristics; research on these materials is in progress.
Acknowledgements
The present work was partly supported by a Grant-in-
Aid on Priority-Area-Research on Carbon Alloys (No.
11124202) from the Ministry of Education, Science, Sports
and Culture.
108 E. Ando et al. / Carbon 39 (2001) 101 108
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