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Electrical, magnetic, and structural properties of chemically and

electrochemically synthesized polypyrroles


J. Joo
a,*
, J.K. Lee
a
, J.S. Baeck
a
, K.H. Kim
b
, E.J. Oh
c
, J. Epstein
d
a
Department of Physics and Center for Electro and Photo Responsive Molecules, Korea University, Seoul 136-701, South Korea
b
Department of Chemistry, Yonsei University, Seoul 120-749, South Korea
c
Department of Chemistry, Myongji University, Yong-In 449-728, South Korea
d
Department of Physics and Department of Chemistry, The Ohio State University, Columbus, Ohio 43210, USA
Abstract
We report the results of temperature-dependent dc conductivity (s
dc
(T)), EPR (electron paramagnetic resonance) magnetic susceptibility,
and XPS (X-ray photoelectron spectroscopy) experiments for chemically and electrochemically synthesized polypyrrole (PPy) samples. For
chemically synthesized dodecylbenzenesulfonic acid (DBSA) or naphthalenesulfonic acid (NSA) doped PPy samples (PPy-DBSA or PPy-
NSA, respectively) soluble in m-cresol solvent, dc conductivity and its temperature dependence show the strong localization behavior, while
those of electrochemically synthesized PPy doped with hexauorophosphate (PPy-PF
6
) are in the critical regime. Pauli susceptibility (w
p
)
and the density of states are obtained from the temperature dependence of EPR magnetic susceptibility. The density of states of chemically
synthesized PPy is one-third of that of electrochemically synthesized PPy. From the analysis of the area ratio of carbon 1s XPS peak, the
disorder effect due to interchain links or side chains of PPy-DBSA (m-cresol) samples is ~22%, while that of PPy-PF
6
samples is ~33%.
This result indicates that the percent of interchain links or side chains of chemically synthesized PPy-DBSA (m-cresol) samples is reduced
by ~10% compared to that of electrochemically synthesized PPy-PF
6
samples. We analyze that the side chains or interchain links of
chemically synthesized PPy samples are relatively reduced due to the synthesis method using large size dopants, and subsequently the
interchain interaction weakens. The results of EPR experiments of PPy-DBSA (m-cresol) samples with different doping levels are
discussed. # 2001 Elsevier Science B.V. All rights reserved.
Keywords: Polypyrrole; dc conductivity; Magnetic susceptibility; X-ray photoelectron spectroscopy
1. Introduction
The chemical doping in conjugated polymers such as
polyacetylene, polyaniline (PAN), or polypyrrole (PPy)
induces an insulator-metal transition similar to that of con-
ventional (inorganic) semiconductors [1]. There are funda-
mental distinctions between two systems. While
conventional semiconductors have three-dimensional (3D)
structures, the morphological unit of conducting polymers is
a quasi one-dimensional conjugated polymer chains, with
covalent bonding along the chains and weak bonding
between chains. Anisotropic conductivity, dielectric con-
stant, and thermoelectric power have been reported for
conducting polymers [1,2]. The dopant ions in conducting
polymers are positioned interstitially between polymer
chains, while the dopants in conventional semiconductors
generally are substituted directly in the host lattice. The
interchain hopping with the intrachain charge diffusion has
been emphasized for the charge transport mechanism in
conducting polymers [36].
Doped polyacetylene and PAN have been considered as
quasi 1D structure, in which the effects of interchain links
(connected the nearest polymer backbones) or side chains
(connected one polymer backbone) on physical properties
have not been reported. However, for polypyrrole, Puger
and co-workers reported the existence of ~33% of inter-
chain links or side chains through 2,3 positions in pyrrole
ring based upon X-ray photoelectron spectroscopy (XPS)
study of electrochemically synthesized PPy-PF
6
samples,
while most of pyrrole units are linked at the 2,5 positions to
form straight chains [7,8]. It is noted that temperature
dependence of dc conductivity (s
dc
(T)) of highly conducting
PPy samples doped with hexauorophosphate (PPy-PF
6
) is
different from that of PAN doped with camphorsulfonic acid
(CSA) prepared in m-cresol solvent (PAN-CSA (m-cresol)),
although s
dc
of two systems at room temperature (RT) is in
the range of 200400 S/cm [6,911]. The slope of ds
dc
(T)/
dT of PAN-CSA (m-cresol) samples is negative from RT to
~200 K, while that of PPy-PF
6
materials is negative below
Synthetic Metals 117 (2001) 4551
*
Corresponding author. Tel.: 82-2-3290-3103; fax: 82-2-927-3292.
E-mail address: jjoo@kuccnx.korea.ac.kr (J. Joo).
0379-6779/01/$ see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S0 3 7 9 - 6 7 7 9 ( 0 0 ) 0 0 5 3 7 - 3
~30 K [6,911]. That is, temperature ranges to demonstrate
the intrinsic metallic behavior are reversed in two systems.
For heavily perchlorate (ClO
4
) doped stretched oriented
polyacetylene, s
dc
(RT) is 10
4
10
5
S/cm, and its intrinsic
metallic behavior, i.e. ds
dc
(T)adT ` 0 is observed in tem-
perature range from RT to ~200 K, which is similar to that
of PAN-CSA (m-cresol) samples [12].
The structure and the charge transport of doped PPy have
been studied for electrochemically synthesized PPy samples
only. Recent progress in chemical synthesis using various
dopants and organic solvents has contributed to the devel-
opment of soluble PPy [13,14]. The synthesis method using
relatively large dopants such as dodecylbenzenesulfonic
acid (DBSA) or naphthalenesulfonic acid (NSA) reduces
the interchain interaction of polymer chains resulting in the
increase of the solubility in various organic solvents [13,14].
For chemically synthesized soluble PAN materials, the
charge transport properties vary with dopants and solvents
used [15]. The interchain interaction and the conformational
change of polymer chains are important for the conductivity
and its temperature in the PAN systems.
In this report, the results of the temperature dependent dc
conductivity, the density of states, and XPS experiments are
compared for chemically synthesized PPy-DBSA (m-cresol)
and PPy-NSA (m-cresol) samples and electrochemically
synthesized PPy-PF
6
samples. The results of EPR experi-
ments for chemically synthesized PPy-DBSA (m-cresol)
samples with different doping levels are discussed. We
observe that Pauli susceptibility and the density of states
of PPy-DBSA (m-cresol) samples increase as the doping
level increases, which indicates that the system becomes
more highly conducting. FromXPS experiments, the percent
of interchain links or side chains of PPy-DBSA (m-cresol)
samples is reduced by ~10% compared to that of PPy-PF
6
samples. The synthesis method using relatively large
dopants results in weak interchain interaction, low s
dc
,
and strong localization, reecting the insulating state of
soluble PPy systems. However, electrochemically synthe-
sized PPy-PF
6
samples with the relatively high concentra-
tion of interchain links or side chains show critical or
metallic behavior. From the temperature dependence of
the magnetic susceptibility, we obtain that the density of
states of electrochemically synthesized PPy samples is
higher than that of chemically synthesized PPy materials.
We conclude that the synthesis method using relatively large
dopants for PPy samples plays an important role for con-
trolling the degree of interchain links or side chains, the
solubility, and the interchain interaction.
2. Experimental
A four-probe method was used for measuring dc con-
ductivity in order to eliminate the effect of contact resis-
tance. The measured temperature range for s
dc
was from300
to 10 K using a Janis closed-cycle refrigerator system (CCS-
1 0 0). Four thin gold wires (0.05 mm thick and 99% pure
gold) were attached in parallel on the sample surface by
conducting graphite paint (Acheson Electrodag 502) for
better electrical contact. The EPR spectra were obtained
by using a Bruker Instruments ESP300 (X-band) electron
paramagnetic resonance spectrometer with TE102 resonant
cavity. The samples were put into an EPR tube (Wilmad
707), and pumped under 10
5
Torr for 4 h. The magnetic
susceptibility of the system was estimated from the EPR
integrated intensities calibrated against a LiLiF crystal.
The XPS data were measured using a VG ESCALAB MKII
spectrometer (Mg K
a
X-ray source, 1253.6 eV photons). All
binding energies were referenced by C(1s) neutral carbon
peak at 284.6 eV to compensate for surface charging effects.
The area ratios corrected by the sensitivity factor were used
for quantitative analysis of the XPS data.
For synthesis of soluble PPy, distilled pyrrole monomer
(0.225 mol) and dopant (0.075 mol of DBSA or NSA) were
dissolved in distilled water under magnetic stirring. Fig. 1
shows the chemical structures of DBSA, NSA, and PF
6
dopants. For an oxidant, 0.05 mol of (NH
4
)
2
S
2
O
8
was dis-
solved in distilled water. The solution containing oxidant
was poured into the solution of pyrrole and dopant under
magnetic stirring. Polymerization was carried out for 30 h at
58C in air. PPy powder was ltered and washed with
methanol, and dried under dynamic vacuum for 48 h. Free
standing lm were cast from homogeneous solution of
doped PPy dissolved in m-cresol solvent. Solubility condi-
tions were determined by dopants and solvent used, etc.
However, when small dopant was used, such as sulfosucci-
Fig. 1. Schematic chemical structure of: (a) one-dimensional polypyrrole
(aromatic and quinoid forms) and (b) dodecylbenzenesulfonic acid
(DBSA), naphthalenesulfonic acid (NSA), and hexafluorophosphate
(PF
6
) dopants.
46 J. Joo et al. / Synthetic Metals 117 (2001) 4551
nic acid, the solubility of PPy powder in organic solvents
was reduced resulting in difculty to make free standing
lms. Experimentally, PPy powder with relatively large
dopants was easily soluble in organic solvents.
For synthesis of electrochemical PPy-PF
6
samples, 99%
pure pyrrole was used [16]. Acetronitrile (AN) solvent was
passed into alumina powder at 4008C, and tetraethylammo-
nium hexauorophosphate (TEAPF
6
) was used for an elec-
trolyte. The anodic oxidation of pyrrole was carried out in an
electrolyte bath including TEAPF
6
(0.1 mol), pyrrole
(0.2 mol), and AN solvent. The materials were synthesized
at 1.21 V and for 5 h by using EG & G PAR model 270A
potentiostat/galvanostat. The samples were washed by using
the mixture of water and AN solvent, and dried in vacuum
oven for 72 h. Both chemically and electrochemically pre-
pared samples studied here were in the form of free standing
lm of ~60 and ~200 mm thickness, respectively. The mass
density of chemically synthesized PPy-DBSA (m-cresol)
and electrochemically synthesized PPy-PF
6
was ~1.2 and
~0.9 g/cm
3
, respectively.
3. Experimental results and discussion
Temperature dependence of dc conductivity (s
dc
(T)) for
chemically synthesized PPy-DBSA and PPy-NSA samples
soluble in m-cresol or NMP solvents and electrochemically
synthesized PPy-PF
6
samples is compared in Fig. 2. For
soluble PPy samples, the s
dc
(RT) is _10
1
S/cm. The
s
dc
(RT) of the PPy-PF
6
samples studied here is ~50 S/
cm, much higher than that of the chemically synthesized
PPy samples. The three-dimensional (3D) variable range
hopping (VRH) model [17] provides the best tting for
s
dc
(T) of chemically synthesized PPy samples:
s
dc
(T) = s
0
T
1a2
exp
T
0
T

1a4
4 5
X (1)
Here T
0
= 16/(k
B
D(E
F
) L
3
), D(E
F
) is the density of states at
the Fermi level, and L is the localization length [17]. The
slope T
0
is estimated to be ~ 9X1 10
7
and ~ 3X0 10
6
K
for PPy-DBSA(m-cresol) and PPy-NSA(m-cresol) samples,
respectively. From the results of D(E
F
) obtained from EPR
experiments, the localization length L is estimated as ~4 and
~2 A

for PPy-NSA (m-cresol) and PPy-DBSA (m-cresol)


samples, respectively, indicating that the charge is strong
localized in soluble PPy systems. The interchain links or
side chains of PPy systems provide the extra doping centers
in addition to the polymer backbones. These might con-
tribute to the 3D VRH of the poorly conducting PPy
materials. The charge transport properties of soluble PPy
materials also vary with solvents used due to the screen
effects of the polar solvents or the interactions between the
solvents, the dopants, and the polymer backbones [14]. Fig. 2
(b) shows the s
dc
(T) of PPy-DBSA and PPy-NSA samples
prepared in NMP solvents. The results demonstrate that s
dc
and its temperature dependence of soluble PPy samples vary
with the solvents and dopants used. A power law provides
the best fitting for s
dc
(T) of electrochemically synthesized
PPy-PF
6
samples:
s
dc
(T) T
b
Y (2)
where 1a3 ` b ` 1. As shown in Fig. 2 (c), the exponent b is
estimated as ~0.5, which implies that the materials are in the
critical regime in the insulator-metal transition, or close to
the metallic regimes [9]. Table 1 compares the charge
transport properties of chemically and electrochemically
synthesized PPy samples studied here. The effects of the
dopant size of the electrochemically synthesized PPy sam-
ples on s
dc
(T) were reported by Sato et al. [19]. They
observed that the system becomes more highly conducting
state as the size of the dopants decreases.
One can determine the insulating, critical, or metallic
state of the materials from the slope of temperature depen-
dence of the reduced activation energy dened as [9,18]
W(T) = log
10
d ln s
dc
(T)
d ln T
!
X (3)
Fig. 2. Comparison of temperature dependence of dc conductivity of: (a)
PPy-DBSA (m-cresol) and PPy-NSA (m-cresol) samples, (b) PPy-DBSA
(NMP) and PPy-NSA (NMP) samples, based on the three-dimensional
variable range hopping model and (c) PPy-PF
6
materials based on the
power law.
J. Joo et al. / Synthetic Metals 117 (2001) 4551 47
Fig. 3 compares the W(T) of the PPy materials studied here.
The slope of soluble PPy samples is negative, i.e. Wincreases
as T decreases, which indicates that the systems are in the
insulating regime. The slope of the W(T) plot of PPy-PF
6
samples is estimated to be 0 or even positive indicating that
the systems are in the critical or the metallic regime.
Fig. 4 presents wT of PPy-DBSA (m-cresol), PPy-NSA
(m-cresol), and PPy-PF
6
samples as a function of tempera-
ture. The density of states, D(E
F
), was obtained from the
measurement of susceptibility (w) through EPRexperiments.
Considering w = w
p
w
c
where w
p
(Pauli susceptibility) is
independent of temperature and w
c
(Curie susceptibility) I/
T, the slope of the straight line of T provides the w
p
. Using the
relation w
p
= 2m
B
2
D(E
F
) where m
B
is the Bohr magneton,
and the density of states, D(E
F
), is estimated as ~0.072
states/(eV ring), ~0.107 states/(eV ring), and ~0.333 states/
(eV ring) for PPy-DBSA (m-cresol), PPy-NSA (m-cresol),
and PPy-PF
6
samples, respectively. The results imply that
the electrochemically synthesized PPy-PF
6
with its rela-
tively small dopant is in highly conducting states compared
to that of the doped soluble PPy materials. It is noted that
Curie constant of w
c
obtained from the y-intercept in Fig. 4 is
9X77 10
4
, 9X72 10
4
, and 1X74 10
4
emu K/mol ring
for PPy-PF
6
, PPy-NSA (m-cresol), and PPy-DBSA (m-cre-
sol) samples, respectively.
The density of states D(E
F
) of soluble PPy systems varies
with the doping levels. Fig. 5 shows the variation of the
D(E
F
) and the w
p
of PPy-DBSA (m-cresol) samples as a
function of doping levels. The concentration of dopants of
the samples is ~0.075, ~0.057, ~0.038 and ~0.028 mol
with 0.225 mol pyrrole monomer. The D(E
F
) and the w
p
increases as the doping level increases. The results demon-
strate that the system becomes more highly conducting with
increasing doping level. This is similar to that of other
conducting polymers such as doped polyacetylene and
polyaniline [1,2]. It is expected that the conductivity of
the system increases with increasing doing level, because
conductivity is controlled by the concentration of conduc-
tion electrons and mobility.
Fig. 6 shows the carbon 1s (C1s) XPS core level spectra of
electrochemically synthesized PPy-PF
6
and chemically
synthesized PPy-DBSA (m-cresol) samples at RT. A stan-
dard line shape analysis with Gaussian tting shows that the
C1s main peak for PPy-PF
6
samples is decomposed into
three lines as shown in Fig. 6 (a). The line due to the pyrrole
b carbons is centered at 284.33 eV, while that of the a
carbons is positioned at 285.27 eV. There is 0.94 eV energy
splitting between two lines, which agrees with the observed
energy separation in pyrrole monomer [7,20]. The C1s
spectrum is not symmetric on the higher binding energy
Table 1
Comparison of the charge transport properties of electrochemically synthesized PPy-PF
6
materials and chemically synthesized PPy-DBSA (m-cresol) and
PPy-NSA (m-cresol) samples
Materials Electrochemically synthesized Chemically synthesized
PPy-PF
6
PPy-DBSA(m-cresol) PPy-NSA(m-cresol)
s
dc
(RT)/s
dc
(100 K) ~2 ~10
3
~2 10
1
Model s
dc
(T ) T
b
s
dc
(T ) T
1/2
exp[(T
o
/T)
1/4
] s
dc
(T ) T
1/2
exp[(T
o
/T)
1/4
]
Constants b 0.5 T
0
9.1 10
7
K, L 2 A

T
0
3.0 10
6
K, L 4 A

Fig. 3. Temperature dependence of reduced activation energy W(T) of PPy-DBSA (m-cresol) and PPy-PF
6
samples.
48 J. Joo et al. / Synthetic Metals 117 (2001) 4551
side of the peak. This asymmetry was assigned to ``disorder
effects'' such as interchain links, side chains, or chain
terminations [7,8]. The measured area ratio of the disorder
effects to the sumof three peaks assigned to a, b sites and the
disorder effects is 0.33, in agreement with the report of
Puger and Street [7]. For the chemically synthesized PPy-
DBSA (m-cresol), the C1s main peak is decomposed into
four lines including the covalent bonded carbon in the
DBSA dopant, which corresponds to the lowest binding
energy centered at 284.66 eV, as shown in Fig. 6 (b). The line
due to the pyrrole b carbons is centered at 285.47 eV, while
that of the a carbons is positioned at 286.37 eV. The overall
shift of the peaks of the a, b carbons and the disorder effects
as compared to those of electrochemically prepared PPy
samples originate from the effects of charging. However, the
0.9 eV energy splitting between the a and the b carbons is
maintained here. The measured area ratio of the disorder
effects assumed due to side chains, interchain links, or chain
terminations is ~22%, which is a one-third reduction as
compared to that of electrochemically synthesized PPy-PF
6
samples. The XPS results support the reduction of the 2,3
coupling modes mainly due to the synthesis method using
large dopants and a resulting relatively weak bonding
between the chains. Based on the analysis of the area ratio
of phosphorous (or sulfur) to nitrogen, we obtain the exis-
tence of one dopant per three pyrrole rings. The error in the
XPS curve tting is ~5%.
Fig. 7 compares the nitrogen 1s (N1s) XPS core level
spectra of PPy materials at RT. The N1s signal originates
Fig. 4. wT vs. T for PPy-DBSA (m-cresol) (solid diamonds), PPy-NSA (m-cresol) (solid triangles), and PPy-PF
6
(circles).
Fig. 5. Comparison of the density of states (D(E
F
)) (left-hand scale) and
the Pauli spin susceptibility (w
p
) (right-hand scale) as a function of doping
level for soluble PPy-DBSA (m-cresol) samples.
Fig. 6. Carbon 1s XPS core level spectrum of: (a) PPy-PF
6
and (b) PPy-
DBSA (m-cresol) samples. The top line through the data represents the
best fit obtained from the superposition of the Gaussian peaks of the lower
lines.
J. Joo et al. / Synthetic Metals 117 (2001) 4551 49
from the nitrogen atoms of the pyrrole rings of the polymer
backbone because of the lack of nitrogen in the dopants
used. The spectrum of the N1s of electrochemically synthe-
sized PPy-PF
6
samples is asymmetric, while that of chemi-
cally synthesized PPy-DBSA (m-cresol) is relatively
symmetric, as shown in Fig. 7. For PPy-PF
6
samples, the
higher binding energy peak is separated from the neutral
nitrogen peak by 2.53 eV as shown in Fig. 7 (a). This
shoulder on the higher energy side is assigned to an electro-
static effect of the nearest PF
6

counter ion [7]. This


electrostatic effect is not observed for chemically synthe-
sized PPy-DBSA (m-cresol) samples. Comparing the size of
the counter ions, the electric eld due to the large size
DBSA

counter ion may be negligible. This implies that the


interchain interaction of soluble PPy systems with the
DBSA dopants is relatively weak compared to that of
electrochemically synthesized PPy-PF
6
samples.
Experimentally, the effects of interchain links or side
chains on physical properties have not been reported for
doped polyacetylene and PAN, which have been considered
as quasi 1D structures. The chemically and electrochemi-
Fig. 7. Nitrogen 1s XPS core level spectrum of: (a) PPy-PF
6
and (b) PPy-
DBSA (m-cresol) samples.
Fig. 8. Schematic chemical structure of interchain links or side chains through 2,3 coupling modes of polypyrrole. Inset: pyrrole monomer with the
conventional labeling of atom positions shown.
50 J. Joo et al. / Synthetic Metals 117 (2001) 4551
cally synthesized PPy systems can be considered as quasi
network systems through the 2,3 coupling modes as shown
in Fig. 8, which are supported by the 3DVRH for s
dc
(T) and
the disordered effect obtained from XPS experiments. The
2,3 coupling modes might increase the mechanical strength,
and provide extra doping centers, which induce the 3DVRH
and relatively high density of states for poorly conducting
soluble PPy samples. The interchain links or side chains
through the 2,3 coupling modes induce the reduction of the
solubility of PPy in organic solvents and the variation of the
conjugation length. Theoretical study by Prigodin and co-
workers for a random network model of metallic wires
demonstrated the insulator-metal transition which can be
determined by the concentration of the junctions such as
interchain links or side chains in conducting polymers
[21,22]. For soluble PPy systems, the reduction of the
interchain links or side chains encourages charge localiza-
tion.
4. Conclusion
Electrical, magnetic, and structural properties for chemi-
cally and electrochemically synthesized PPy samples are
compared. From the results of s
dc
(T), the density of states,
and XPS experiments, chemically synthesized PPy systems
are in an insulating state associated with the reduction of the
interchain links or side chains and the weaker interchain
interaction. We observe that the density of states of PPy-
DBSA (m-cresol) samples increases as the doping level
increases. The electrochemically synthesized PPy-PF
6
mate-
rials have higher concentration of interchain links or side
chains, and are in the critical or the metallic regime. The
density of states of electrochemically prepared PPy-PF
6
samples is higher than that of soluble PPy materials. The
synthesis method using relatively large dopants for soluble
PPy samples controls the solubility, the structure, and the
charge transport mechanism.
Acknowledgements
This work was supported in part by the CRM-KOSEF
(1998).
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