Thin Solid Films 374 Ž2000.

85᎐91

In situ cyclic voltammetry-surface-enhanced Raman

spectroscopy: studies on the doping᎐undoping of polypyrrole film

Yu-Chuan Liu, Bing-Joe HwangU , Wen-Jie Jian, Raman Santhanam

Department of Chemical Engineering, National Taiwan Uni¨ ersity of Science and Technology, 43, Keelung Road, Section 4, Taipei,
Taiwan, ROC

Received 7 January 2000; received in revised form 7 May 2000; accepted 9 June 2000

Abstract

The redox behavior of polypyrrole ŽPPy. film in 0.2 M aqueous KNO3 solution was investigated by cyclic voltammetry ŽCV. in
situ surface-enhanced Raman spectroscopy ŽSERS.. The results show that the Raman intensity of CsC backbone stretching
decreases and increases regularly with the anodic and cathodic scans, respectively, owing to the change of surface roughness and
the possibility of state transition. The peak position of C᎐H in-plane deformation remains unchanged both in anodic and
cathodic scans. Furthermore, the peak positions of N᎐H in-plane deformation and ring deformation shift to lower and higher
wavenumbers with anodic and cathodic scans, respectively. Also the Raman peak of the NO3y dopant ions appears significant
when PPy is in a more oxidized state. 䊚 2000 Elsevier Science S.A. All rights reserved.

Keywords: Polypyrrole; Cyclic voltammetry; Surface-enhanced Raman spectroscopy; Doping᎐undoping

1. Introduction all conductivity w9᎐12x. In the XPS analysis, the doping

Due to various physical and spectroscopic character-
istics of PPy being demonstrated in its oxidized or
reduced state, which is accompanied by the movement
of dopant ions into or out of PPy matrix, respectively,
many methods w1᎐4x have been employed to measure
the properties of PPy in the doping᎐undoping process.
As we know, the surface of PPy would be rougher in its
more oxidized state or in aging. This can be observed
from SEM or AFM experiments w5,6x. Generally, the
conductivity of doped-PPy is mainly dependent on the
doping level and kinds of dopants. The conductivity of
PPy increases with the increase of the doping level
w7,8x. Larger and more steric counteranions obstruct
interchain electron transport and thus reduce the over-
U to evaluate the structure situation of PPy in various
Corresponding author. Fax: q886-2-27376644.
E-mail address: bjh@ch.ntust.edu.tw ŽB.-J. Hwang..
level is defined as the ratio of oxidized nitrogen to all
nitrogen of PPy ŽNqrN., which is closely related to the
dopant content of PPy. XPS experiments w13,14x re-
vealed that the doping level changed with the treat-
ment of PPy by acid or base. As a result, the corre-
sponding conductivity changed too. Furthermore, in
situ CV-QCM experiments w15,16x provide a method to
monitor the doping process. Conclusively, diffusion is
easy for small anions, namely the anion is doped into
PPy with oxidation of PPy and is undoped from PPy
with reduction of PPy to compensate the opposite
charge in PPy. However, for PPy grown with large
anions with steric hindrance, mostly cations and sol-
vents are inserted and removed with corresponding
reduction and oxidation, respectively, to maintain the
charge neutrality of PPy.
Raman spectroscopy w17᎐20x is an essential method
states. Nevertheless, only poor information can be pro-

0040-6090r00r$ - see front matter 䊚 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 0 . 0 1 0 6 1 - 0
86 Y. Liu et al. r Thin Solid Films 374 (2000) 85᎐91
vided due to weak signal or interference from noise
w17,18x. On the whole, the Raman technique cannot be
applied to the analysis of organic compounds that are
present in a system at very low levels. However, there
are two useful exceptions to this rule w21x. Two meth-
ods for increasing the signal of a species present at very
low levels are resonance-enhanced Raman spectro-
scopy ŽRRS. and SERS. One of the major considera-
tions for the formation of a SERS surface is surface
roughness, and this has been achieved in various ways
w6,22x.
To our knowledge, the ex situ technique is clearly
subjected to some restriction. The sample’s surface may
restructure on transfer and measurements. The result
may not reflect the exact property of the as-prepared or
as-treated sample. Nevertheless, the in situ CV-SERS
experiment gives access to the very fast kinetics of
equilibration and structural change of PPy in a new
form when the potential is changed from one value to
another. It provides a prompt insight into the PPy
chemistry as PPy exists in various redox states, because
the SERS spectra are obtained at the same time when
PPy is treated at a certain potential in the correspond-
ing CV experiment. Furthermore, the Raman peak
position and intensity of some scattering mode of PPy
would change due to non-uniformity of the PPy layer in
different areas of the PPy surface being excited by a
He᎐Ne laser beam. However, this shortage, usually
met in the ex situ experiment, can be overcome by
employing an in situ technique. The Raman spectra are
obtained from the same area of the PPy surface during
the in situ CV-SERS experiment. Therefore, the shift,
appearance, disappearance, and change in intensity of
Raman peaks can be meaningful due to the structural
change of PPy, which exists in various states.
Because the in situ experiment is a very reliable
technique, it had been widely used in the literature,
accompanied by the Raman spectroscopy, to study the
structural changes of conducting polymers existing in
various states. Zhong et al. w23x studied the elec-
trochemical redox process of PPy via the in situ tech-
nique of electron spin resonance ŽESR. and Raman
spectroscopy. However, their reports were just focused
on the picture of the polarons and bipolarons involved
in the electrochemical redox process of PPy films.
Bukowska et al. w22x studied the PPy formation on a
roughened silver electrode at different potentials. Since
the structural changes of PPy during the doping᎐un-
doping processes is very important in its application.
The change of Raman scattering intensity of a PPy
film, deposited on an indium tin oxide electrode, during
reversible doping and undoping processes of ClO4y was
studied via in situ Raman spectroscopy by Inoue et al.
w18x. However, the experiment of Inoue et al. was
restricted to two constant anodic and cathodic poten-
tials, and the indium tin oxide electrode could not be
roughened by the ORC treatment. Thus, the doping
and undoping behavior of dopants in the PPy film can
not be distinctly and continuously investigated in their
study.
In situ Raman studies of PPy-deposited electrodes
have recently been reported. However, the Raman
spectroscopy of PPy is not fully understood yet. Mean-
while, no correlation with the in situ CV scans has
been established. Due to the limitation of the potential
window for a silver electrode, in this work, the PPy is
deposited on a gold substrate, which is roughened by
oxidation᎐reduction cycle ŽORC. treatments w24x. The
behavior of PPy films is monitored via in situ CV-SERS
experiments to examine the structural change of PPy
during the redox process.
2. Experimental
2.1. Treatment of Au substrate
In SERS experiments, before the electropolymeriza-
tion of PPy the Au electrode was roughened by oxida-
tion᎐reduction cycle ŽORC. in a separate cell. During
this treatment, the experiment was performed by a
potentiostat ŽModel 273A, EG & G., and the working,
counter and reference electrodes employed were Au
substrate, Pt sheet and saturated calomel electrode
ŽSCE., respectively. The Au electrode was cycled in 0.1
M KCl from y0.3 V Žholding 10 s. to 1.2 V Žholding 5
s. at 500 mV sy1 for 50 times. After the ORC treat-
ment, the electrodes were rinsed throughout with dis-
tilled water, and finally dried in a vacuum dryer for 24
h at room temperature. Then the samples were placed
in a desiccator filled with nitrogen before use. The
surface roughness of gold substrate before and after
ORC treatment was observed by atomic force micros-
cope ŽNanoscope III, Digital Instrument ..
2.2. Electropolymerization of PPy
The electrochemical synthesis of PPy was carried out
on the roughened Au substrate at a constant anodic
potential of 0.85 V vs. SCE in a deoxygenated acetoni-
trile solution containing 0.1 M pyrrole and 0.1 M
LiClO4 . The charge passed for PPy deposition on the
Au substrate with area of 0.238 cm2 is 10 mC. There-
fore, the thickness of PPy is approximately 0.084 ␮m
according to an empirical formula of 500 mCrcm2
corresponding to 1 ␮m estimated by a correlation
between thickness and charge passed w25x.
2.3. CV in situ SERS performance
The in situ CV-SERS measurement was performed
in a three-compartment cell containing 0.2 M KNO3
solution. The working, counter and reference elec-
 Y. Liu et al. r Thin Solid Films 374 (2000) 85᎐91 87

trodes employed were PPy-deposited Au substrate, Pt

wire with a diameter of 0.5 mm, and AgrAgCl elec-
trode, respectively. The scan rate was controlled at 10
mVrs by a potentiostat ŽBas-100B, Bioanalytical sys-
tem. in the CV experiment. In-situ Raman spectra
were obtained using a Renishaw 2000 Raman spec-
trometer employing a He᎐Ne laser of 25 mW and a
charge couple device ŽCCD. detector with 1 cmy1
resolution. Some complex Raman peaks are decon-
volved into component Gaussian peaks with proper
background subtraction using the ‘automatic fitting’
program provided by the Raman spectrometer.

3. Results and discussion

Fig. 1 illustrates the i-E curves recorded in the first

and the last 25th cycles during Au substrate treated
with ORC. The onset potential of Au dissolution is at Fig. 1. I-E curves for the gold electrode recorded during ORC
approximately 0.9 V vs. SCE. However, the cathodic treatment.
peaks for the Au deposition exhibit a more complicated
phenomenon. This may be ascribed to the formation of
can be provided from the Raman spectroscopy if PPy
AuClO4 complex during Au dissolution w26x. Thus, the
deposits on a Au substrate without ORC pre-treat-
Au-containing complex can also be deposited on the
ment. However, almost all of the scattering modes of
Au substrate. On the whole, the main deposition peak
PPy can be markedly demonstrated as sharp peaks in
of Au is located at approximately 0.4 V vs. SCE.
the SERS spectrum.
Generally, the optimum surface-enhanced effect for
A typical cyclic voltammogram obtained for the poly-
Raman spectroscopy is dependent on the cathodic and
pyrrole film in 0.2 M aqueous KNO3 solution at a
anodic scan rates and vertex potentials, duration time
sweep rate of 10 mVrs is shown in Fig. 3. The in situ
at each vertex, the numbers of cycle, and the charge
surface enhanced Raman spectra obtained at different
passed for PPy deposition. The results Ždata not shown
potentials of corresponding voltammograms in the
here. indicate that the strongest Raman intensity can
anodic and cathodic scans are partially shown in Fig. 4.
be obtained under the operation conditions demon-
As illustrated in Fig. 3, the CV experiment is per-
strated as follows. The CV experiment is performed
formed during the cathodic and anodic vertexes of
between y0.3 V and 1.2 V vs. SCE with 25 cycles. The
y0.9 and 0.4 V, respectively. During CV experiment,
cathodic and anodic scan rates are 1 and 0.5 Vrs,
the SERS spectra are measured in situ every 200 mV.
respectively. The duration time for the cathodic and
anodic vertexes are 1 and 10 s, respectively. The charge
passed for PPy deposition is 10 mC.
If the charge passed was less than 10 mC, it would
decrease the Raman intensity since less quantity of
scattering modes of PPy can be excited by the laser
beam. A charge passed that was over 10 mC would
increase the film thickness and also decrease the
Raman intensity. The effect of SERS comes from the
fact that PPy can be deposited on the grains of the
roughened Au substrate. Then the possibility of transi-
tion of vibration modes increases in exciting by laser
beam. It results in a strong enhanced Raman intensity
being obtained. However, the Raman signal is directly
obtained from the bulk of PPy, not from the interface
of Au and PPy, if more ppy is deposited. Thus, no
SERS effect can be demonstrated. As a result, the
Raman intensity decreases with increasing the film
thickness when the charge passed exceeds 10 mC in
SERS experiments. Fig. 2. SERS spectra of PPy films deposited on different Au subs-
As illustrated in Fig. 2, no meaningful information trates. Ža. With ORC treatment. Žb. Without ORC treatment.
88 Y. Liu et al. r Thin Solid Films 374 (2000) 85᎐91

Table 1
Potentials chosen for SERS measurements and their corresponding Raman peaks

Potential ŽV. Wavenumbers Žcmy1 .

A Žy0.9. 941 987 1040 1251 1312 1411 1556

B Žy0.7. 935 987 1040 1249 1314 1407 1556
C Žy0.5. 934 986 1040 1251 1314 1405 1562
D Žy0.3. 930 984 1040 1244 1310 1409 1563 1608
E Žy0.1. 925 980 1040 1237 1310 1409 1567 1608
F Ž0.1. 923 980 1040 1233 1310 1407 1562 1612
G Ž0.3. 921 980 1040 1237 1318 1407 1559 1610
H Ž0.2. 921 980 1040 1231 1319 1407 1553 1610
I Ž0.0. 921 978 1040 1231 1319 1404 1562 1608
J Žy0.2. 923 980 1040 1235 1316 1406 1563 1605
K Žy0.4. 928 984 1040 1244 1314 1406 1563
L Žy0.6. 939 986 1040 1249 1318 1409 1558
M Žy0.8. 939 986 1040 1248 1314 1407 1558

An exposure of 2.54 s is employed for every Raman
spectrum. Namely the potential interval is approxi-
mately 25 mV for every measurement. The potentials
chosen for SERS measurements and their correspond-
ing Raman peaks are demonstrated in Table 1.
As shown in Fig. 4, it can be clearly observed that
the Raman spectrum changes with the change in the
structure of PPy in the redox cycle. The Raman peak
frequencies and corresponding assignments are listed
in Table 2. Significant information can be obtained
from these figures. The peak of C᎐H in-plane deforma-
tion at 1040 cmy1 doesn’t shift both in anodic and
cathodic scans. It indicates that the scattering mode of
C᎐H in-plane deformation is independent of the struc-
tural change of PPy in the redox cycle. Furthermore,
the intensities of all the peaks are found to change
correspondingly with the anodic and cathodic scans, as
discussed later.
It is an exciting observation that the Raman peaks of
Fig. 3. Cyclic voltammograms showing the oxidation᎐reduction be-
haviors of PPy films in 0.2 M KNO3 .
the NO3y dopant at approximately 1049 and 1306 cmy1
w29x appear gradually with the anodic scan from the
potential of y0.5 V, and they disappear again with the
cathodic scan. Although the Raman peaks of the NO3y
dopant and C᎐H in-plane deformation and ring
stretching of PPy somewhat overlap each other, as
shown in Fig. 4, the phenomenon of appearance᎐disap-
pearance of the NO3y dopant in PPy with the
anodic᎐cathodic scan can be illustrated from the de-
convolution of the main peak at 1040 cmy1 . This main
peak is resolved into two component Gaussian peaks
using the ‘automatic fitting’ program provided with the
Raman spectrometer. They are located at approxi-
mately 1040 and 1049 cmy1 , which is assigned to the
C᎐H in-plane deformation of PPy and the NO3y do-
pant, respectively. Therefore, the relative content of
NO3y dopant in PPy can be defined as the ratio of peak
area of NO3y dopant to that of C᎐H in-plane deforma-
tion of PPy. The results reveal that the relative content
of NO3y dopant in PPy increases from 0.32 to 0.59 at
potential increasing from y0.9 to 0.3 V in the anodic
scan. On the contrary, the relative content of NO3y
dopant in PPy decreases from 0.65 to 0.36 at potential
decreasing from 0.2 to y0.8 V in the cathodic scan. In
the anodic sweep, the NO3y anion is doped into the
oxidized PPy to maintain the charge neutrality of the
PPy matrix. Thus, this doping behavior can be moni-
tored by the Raman spectrum. However, the solution
also contains the NO3y ion during the CV experiment,
but the Raman peak of the NO3y ion is insignificant
when it just exists in a state of free ion. This demon-
strates the dramatic effect of SERS for obtaining the
signal of a species present at very low levels.
As shown in Fig. 4, the main peak of the CsC
backbone stretching of reduced PPy at 1560 cmy1
splits into two peaks with the anodic scan from the
potential of y0.3 V. The peaks at 1560 and 1610 cmy1
are assigned to the CsC backbone stretching of re-
duced and oxidized PPy’s, respectively, as shown in a
 Y. Liu et al. r Thin Solid Films 374 (2000) 85᎐91 89

Fig. 4. SERS spectra of PPy in situ CV experiment at various potentials vs. AgrAgCl. Ža. y0.9, y0.5, y0.1 and 0.3 V for spectra a᎐d,
respectively, in the anodic scan. Žb. 0.2, y0.2, y0.4 and y0.8 V for spectra a᎐d, respectively, in the cathodic scan.

previous study w24x. A similar phenomena were also the tendency of the relative content of oxidized PPy in
observed on the roughened silver electrode reported by PPy with anodic and cathodic scans can be roughly
Bukowska et al. w22x and on the Pt or Au electrode in expressed by the ratio of peak area of oxidized PPy to
situ ESR observations reported by Zhong et al. w23x. that of oxidized and reduced PPy. The results reveal
Therefore, the peak at 1610 cmy1 , representing the that the relative content of oxidized PPy in PPy in-
PPy in an oxidized state, appears more significantly in a creases from 0.16 to 0.57 at potential increasing from
regular pattern with anodic scan than the peak at 1560 y0.9 to 0.3 V in the anodic scan. On the contrary, the
cmy1 , representing the PPy in a reduced state. On the relative content of oxidized PPy in PPy decreases from
contrary, the reduced peak dominates the whole peak 0.60 to 0.18 at a potential decreasing from 0.2 to y0.8
of CsC backbone stretching with cathodic scan. This V in the cathodic scan.
is consistent with the observation of Fig. 4. Meanwhile, In order to understand the intensity differences of
in order to establish a quantitative estimation, the the Raman peaks, obtained at different potentials dur-
somewhat overlapped double peaks are resolved into ing the CV experiment, the spectrum recorded for
two component peaks. They are located at approxi- doped PPy film during the anodic scan can be clearly
mately 1560 and 1610 cmy1 , which are assigned to the distinguished from the cathodic scan by the variation in
reduced and the oxidized PPy, respectively. Therefore, the peak intensities. Fig. 5 shows the change of Raman
intensity of the CsC backbone stretching with time
Table 2
Band frequencies in SERS of PPy on Au electrodes and assignments
and potential in CV experiments. Generally, the sur-
face of PPy film becomes roughened and smooth with
Peaks Žcmy1 . Peaks Žcmy1 . shown Peaks assignments oxidation and reduction, respectively. It results from
in this work in the literature the repelling action between oxidized units of PPy. As
930 939 C᎐H out-of-plane
we know, the Raman intensity is influenced by the
deformation w27x scattering of the exciting light from the surface of
984 998 Ring deformation w28x sample and the possibility of transition of vibration
1040 1044 C᎐H in-plane deformation modes. PPy film with a rougher surface is always ac-
w28x companied by a high extent of scattering of exciting
1049, 1306 1048, 1304 NOy w x
3 dopant ions 29
1244 1249 N᎐H in-plane deformation
light from the surface. It results in lower intensity at
w28x the detector. Therefore, the Raman intensity decreases
1314, 1407 1326, 1392 Ring stretching w27x with the increase of surface roughness of PPy. This is
1560, 1610 1560 ; 1630 CsC backbone stretching consistent with the observation from Fig. 5. Actually,
w23x other vibration modes of PPy exhibit similar behavior
90 Y. Liu et al. r Thin Solid Films 374 (2000) 85᎐91
Fig. 5. Change of Raman intensity of the main peak of CsC
backbone stretching at approximately 1560 or 1610 cmy1 with time
and potential in CV experiment.
in intensities as the CsC backbone stretching with
oxidation and reduction. However, the possibility of
transition of CsC backbone stretching may also cause
the change in Raman intensity. In order to demon-
strate this effect and ignore the factor due to scatter-
ing, the relative Raman intensity of CsC backbone
stretching, referred to that of other vibration mode of
PPy, is conducted to reach this goal.
Because the peak of C᎐H in-plane deformation at
1040 cmy1 doesn’t shift both in anodic and cathodic
scans, the intensity of the C᎐H in-plane deformation is
used as a reference to express the relative intensity of
other peaks, shown in the Raman spectrum in their
corresponding redox states. Fig. 6 exhibits the change
of relative Raman intensity of the CsC backbone
stretching referred to the intensity of C᎐H in-plane
Fig. 7. Raman peaks shift with time and potential in CV experiment. Ža. Peak of ring deformation at approximately 984 cmy1 . Žb. Peak of N᎐H
in-plane deformation at approximately 1244 cmy1 .
Fig. 6. Change of relative Raman intensity of the main peak of CsC
backbone stretching at approximately 1560 or 1610 cmy1 with time
and potential in CV experiment.
deformation with time and potential in CV experi-
ments. As shown in this figure, the intensity of CsC
backbone stretching is normalized by that of C᎐H
in-plane deformation, so the relative intensity only
represents the transition possibility of CsC backbone
stretching shown in Raman spectra, ignoring the scat-
tering effect, as mentioned before. Fig. 6 shows a
similar trend as Fig. 5. The relative intensity decreases
and increases with the anodic and cathodic scans in
CV, respectively. It means that the surface roughness
also demonstrates a remarked influence on the en-
hancement of Raman peaks. Namely a rougher surface,
resulting from an anodic scan, causes a decrease in the
intensity of the Raman peak.
Meanwhile, the peaks of ring deformation and N᎐H
in-plane deformation at approximately 984 and 1244
 Y. Liu et al. r Thin Solid Films 374 (2000) 85᎐91
cmy1 , respectively, reveal some meaningful informa-
tion. Both peaks shift to a lower wavenumber with the
anodic scan. On the contrary, these peak positions
again shift to a higher wavenumber with the cathodic
scan, as illustrated in Fig. 7. These may be ascribed to
the change in chemical structure of PPy due to oxida-
tion and reduction cycles. The oxidized PPy increases
with the anodic scan. Then more counterions, NO3y,
are doped into positively charged PPy to neutralize the
excess charge. As shown in the previous study w24x, the
positive charges of oxidized PPy locate at nitrogen and
carbon atoms of PPy, and at the whole PPy ring. Thus
the NO3y is doped without certain localization into
oxidized PPy with the anodic scan. That is why the
doped NO3y may influence the Raman peak positions
of ring deformation and N᎐H in-plane deformation of
PPy with redox cycles. Furthermore, the peak position
of the C᎐H out-of-plane deformation, as demonstrated
in Table 1, also shifts with a similar tendency as the
ring deformation and N᎐H in-plane deformation do.
These strongly indicate that Raman peak positions are
dependent on the redox state of PPy.
4. Conclusion
The in situ CV-SERS investigation on the redox
behavior of PPy film in 0.2 M aqueous KNO3 solution
was performed in this study. The Raman signals of PPy
deposited at the highly roughened Au electrode surface
are greatly enhanced. The results indicate that SERS
provides a deep insight into the structural change of
PPy during CV. The Raman intensity of CsC back-
bone stretching decreases and increases regularly with
the anodic and cathodic scans, respectively. It results
from the changes of surface roughness and the possibil-
ity of state transition during redox cycles. The peak
position of C᎐H in-plane deformation of PPy remains
unchanged both in anodic and cathodic scans. Further-
more, the peak positions of N᎐H in-plane deformation
and ring deformation shift to lower and higher
wavenumbers with anodic and cathodic scans, respec-
tively. These result from the structural changes of PPy
as it undergoes redox reactions. Meanwhile, the Raman
peak of the NO3y dopant ions appears significantly
when PPy is at more oxidized state.
Acknowledgements
We thank the National Science Council of the Re-
91
public of China ŽNSC-88-2214-E-011-020. and National
Taiwan University of Science and Technology for their
financial support.
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