J Mater Sci: Mater Electron (2013) 24:1702–1706
DOI 10.1007/s10854-012-1000-6
The thermoelectric performance of carbon black/poly(3,
4-ethylenedioxythiophene):poly(4-styrenesulfonate)
composite films
Yong Du • Ke Feng Cai • Shirley Z. Shen •
Wei Dong Yang • Philip S. Casey
Received: 29 October 2012 / Accepted: 10 November 2012 / Published online: 25 November 2012
Ó Springer Science+Business Media New York 2012
Abstract Carbon black/poly(3,4-ethylenedioxythiophene):
poly(4-styrenesulfonate) (CB/PEDOT:PSS) composite
films have been prepared by a spin-coating method. The
morphology of the composite films was investigated by field
emission scanning electron microscopy and atomic force
microscopy. The thermoelectric properties of CB/PEDOT:
PSS composite films were measured at room temperature. As
the content of CB increased from 0 to 11.16 wt%, the elec-
trical conductivity of the composite films first increased
sharply and then decreased, while the Seebeck coeffi-
cient increased slowly. A highest power factor of
0.96 lWm-1 K-2 was obtained.
1 Introduction
Organic conducting polymer, poly(3,4-ethylenedioxythio-
phene):poly(styrenesulfonate) (PEDOT:PSS), has great
potential for use in thermoelectric (TE) devices mainly
because it has low thermal conductivity and relatively high
electrical conductivity, which are beneficial to the TE
figure of merit, ZT (=a2rT/j, where a is the Seebeck
Y. Du
K. F. Cai (&)
Functional Materials Research Laboratory, Tongji University,
1239 Siping Road, Shanghai 200092, China
e-mail: kfcai@tongji.edu.cn
Y. Du
S. Z. Shen (&)
W. D. Yang
P. S. Casey
Materials Science and Engineering Division, CSIRO, Private
Bag 33, Clayton South, VIC 3169, Australia
e-mail: Shirley.Shen@csiro.au
123
coefficient, r is the electrical conductivity, j is the thermal
conductivity, and S is the absolute temperature) [1].
Recently, it has been found that the electrical conductivity
of PEDOT:PSS films can be raised by several orders of
magnitude by adding dielectric solvents such as dimethyl
sulfoxide (DMSO), N,N-dimethyl formamide (DMF) and
tetrahydrofuran (THF) because these solvents help align
the PEDOT chains and enhance carrier transport [2, 3]. In
addition, PEDOT:PSS films also possess a number of
advantageous properties including low density, low cost,
optical transparency, environmental stability, excellent
thermal stability, easy synthesis and processing into ver-
satile forms. However, PEDOT:PSS films have received
relatively little attention as TE materials mainly because of
their lower power factor (a2r) than that of the state-of-the-
art inorganic TE materials [4].
So far, to improve the TE properties of PEDOT:PSS,
two classes of inorganic materials have been used. The first
class, like carbon nanotube (CNT) [5–7], possesses very
high electrical conductivity. The second class includes Te
nanorods [8], Bi2Te3 [9] and Ca3Co4O9 [10] powder etc.,
which have high Seebeck coefficient values. However, the
high cost and poor processability of these inorganic
materials as well as environmental considerations, limit
their wider application as TE materials [11–14].
Carbon black (CB), a cheap and common material, is an
amorphous form of carbon with a structure similar to dis-
ordered graphite [15] and is typically used as conductive
filler in polymers by forming a continuous network in
polymer matrix leading to high electrical conductivity [16].
Therefore, in this paper, CB/PEDOT:PSS composite
films were prepared and the TE properties of CB/
PEDOT:PSS composite films were studied with different
DMSO dopant concentrations as well as the amount of
CB.
J Mater Sci: Mater Electron (2013) 24:1702–1706
2 Experimental
2.1 Raw materials
Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)
(PEDOT and PSS content 0.5 and 0.8 wt%, respectively,
dispersed in H2O) and dimethyl sulfoxide (DMSO, reagent
grade) were purchased from Sigma–Aldrich Chem. Co. CB
(22 wt% dispersion in H2O) was purchased from Chro-
maScape, Inc. The as received materials were used without
further treatment or purification.
2.2 Preparation of DMSO doped PEDOT:PSS films
Glass substrates (2 9 2 cm) were ultrasonicated in acetone
for 15 min, oxidized in Piranha solution (98 % H2SO4:
30 % H2O2 = 7: 3) for 1 h (h) before rinsing with distilled
water. Various amounts of DMSO were mixed with the
PEDOT/PSS solution to form 5, 10, 15 or 20 wt% of
DMSO/PEDOT/PSS mixtures. These mixtures were soni-
cated for 1 h at room temperature and then filtered through
a membrane with 0.45 lm micropores to remove any traces
of undissolved aggregates. DMSO doped PEDOT:PSS
films were prepared by spin coating the above mixed
solutions on a glass substrate. Spin coating was performed
at 1,000 rpm for 60 s followed by 2,000 rpm for 60 s. The
films were dried under vacuum at 60 °C for 1 h. Pure
PEDOT:PSS film was prepared using the same procedure
as described above but without adding DMSO.
2.3 Preparation of CB/PEDOT:PSS composite films
A 10 wt% DMSO in PEDOT/PSS mixture was prepared.
The mixed solution was sonicated for 1 h at room tem-
perature and then filtered through a 0.45 lm membrane to
remove any traces of undissolved aggregates. An appro-
priate amount of CB was added to the above mixed solu-
tions to produce a 0–11.16 wt% mix which were sonicated
for 1 h. CB/PEDOT:PSS composite films were prepared by
spin coating the mixed solutions on a glass substrate
(2 9 2 cm) and dried in a similar manner to that described
above. The thicknesses of the CB/PEDOT:PSS composite
films were *90–120 nm.
2.4 Characterization
The morphologies of the CB/PEDOT:PSS composite films
were observed by field emission scanning electron micros-
copy (FE-SEM, Quanta 200 FEG) and atomic force
microscopy (AFM), which was performed with Digital
Instruments Nanoscope III operating in tapping mode. The
thickness of the CB/PEDOT:PSS composite films was
measured by XP-plus stylus profilometer (AMBIOS,
1703
XP-2000). The Hall effect of the samples was measured
using an HMS-3000 (Ecopia) system with a magnetic field of
0.55 Tesla at room temperature. The electrical conductivity
was measured using a steady-state four-probe technique with
a square wave current (*10 mA in amplitude). The Seebeck
coefficient was determined by the slope of the linear rela-
tionship between the thermal electromotive force and tem-
perature difference (*10–15 K) between the two points of
each film. The error of the measured Seebeck coefficient
values is\10 %.
3 Results and discussion
Figure 1 shows the variation of electrical conductivity of
PEDOT:PSS films with different DMSO concentrations.
The electrical conductivity of the films increased quickly
from 0.0032 to 36.17 S cm-1 as the DMSO content
increased from 0 to 10 wt%, before decaying slowly at
higher DMSO levels 15.96 S cm-1 at 30 wt%. The
increase in electrical conductivity of PEDOT:PSS films on
adding dielectric solvent DMSO is mainly due to the
reorientation of the PEDOT:PSS chains [17] and the strong
screening effects between the PEDOT and PSS dopant
caused by DMSO [2]. The highest electrical conductivity
of the films is 36.17 S cm-1 (DMSO concentration is
10 wt%), which is four orders of magnitude higher than
that of the pure PEDOT:PSS film (0.0032 S cm-1).
Therefore, the content of DMSO mixed with PEDOT:PSS
for the CB/PEDOT:PSS composite films was kept at
10 wt%.
Figure 2a presents an FESEM image of the prepared
DMSO doped PEDOT:PSS film, while Fig. 2b, c present
FESEM images of CB/PEDOT:PSS composite films with
2.52 and 8.90 wt% CB, respectively. FESEM observations
Fig. 1 Electrical conductivity of PEDOT:PSS films with different
DMSO concentrations
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1704 J Mater Sci: Mater Electron (2013) 24:1702–1706

Fig. 2 FESEM images of a DMSO doped PEDOT:PSS film, b, c CB/ respectively. d AFM image of CB/PEDOT:PSS composite film with
PEDOT:PSS composite film with 2.52 and 8.90 wt% CB, respec- 2.52 wt% CB. The panel e is high-magnification AFM image of the
tively. The insets in panel b and c are high-magnification SEM area marked by the blue square in panel d (Color figure online)
images of the area marked by the blue squares in panel b and c,

indicate that the DMSO doped PEDOT:PSS film has agglomerated CB (see Fig. 2b, c) consistent with the
a uniform morphology (see Fig. 2a), while the CB/ agglomerated CB structure reported in Ref. [18]. AFM
PEDOT:PSS composite films are not smooth due to the image (Fig. 2d) shows the distribution of the CB in the

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J Mater Sci: Mater Electron (2013) 24:1702–1706 1705

Table 1 Room temperature carrier concentration (n), mobility (lH)

and Hall coefficient (RH) of the composite films with different con-
tents of CB
CB Carrier Carrier mobility Hall coefficient
concentration concentration (lH/ (RH/(cm3 C-1))
(n cm-3) (cm2V-1s-1))

2.52 3.7974E?21 8.9496E-02 1.6438E-03

5.60 6.4654E?21 4.8718E-02 9.6547E-04
8.90 1.1519E?21 7.1408E-02 5.4188E-03
11.16 6.6960E?20 5.9836E-02 9.3223E-03

PEDOT/PSS matrix with 2.52 wt% CB. The calculated

root-mean-square roughness of this composite film is
21.4 nm (see Fig. 2e). The morphology of the composite
films with a CB content[2.52 wt% is similar to that shown
in Fig. 2b but with greater amounts of agglomerated CB
with a consequent increase in the root-mean-square
roughness in these films.
Table 1 presents the carrier concentration, mobility and
Hall coefficient at room temperature of composite films
with different CB content. Figure 3a presents the room-
temperature electrical conductivity and Seebeck coefficient
as a function of CB content of the CB/PEDOT:PSS com-
posite films, while Fig. 3b provides the calculated power
factor.
The CB/PEDOT:PSS composite film with 2.52 wt% CB
had the highest electrical conductivity of all the composite
films 61.20 S cm-1 (see Fig. 3a). Electrical conductivity is
given by the following equation r = nelH, where n is
carrier concentration, e is the charge, lH is the carrier
mobility with this sample having the highest carrier
mobility (see Table 1). As the content of CB increases
from 5.60 to 11.16 wt%, the electrical conductivity of the
composite films decreases, mainly because the carrier
concentration of the composite films decreased signifi-
cantly while the carrier mobility remained almost the same
(see Table 1).
The electrical conductivity (61.20 S cm-1) of the com-
posite film with 2.52 wt% CB at room temperature is higher
than either that of the DMSO doped PEDOT:PSS film pre-
pared under the same procedure (36.17 S cm-1) or a CB
pellet cold pressed from CB powder (12.06 S cm-1). This
conductivity value is also higher than that of a reported
PEDOT:PSS/Te composite film (*19.3 S cm-1) [8].
However, it is still lower than that of a PEDOT:PSS/single
walled carbon nanotube (SWCNT) composite (280–
400 S cm-1) [5] and a PEDOT:PSS (Clevios PH1000)/
Bi2Te3 composite (55–250 S cm-1) [9]. The reasons for this
may be (1) the electrical conductivity of the SWCNT and
Bi2Te3 is much higher than that of the CB and (2) the
PEDOT:PSS used in the Refs. [5] and [9] are new products
from H.C.Stark, Inc., which have very high electrical
Fig. 3 a electrical conductivity and Seebeck coefficient, and b power
factor of CB/PEDOT:PSS composite films with different CB contents
conductivity (*945 S cm-1 when doped with 5 wt%
DMSO, which is *50 times higher than that of the PE-
DOT:PSS doped with 5 wt% DMSO used in the present
work).
The Seebeck coefficient of the CB/PEDOT:PSS com-
posite films increases by \8 % from 12.51 to
13.41 lV K-1 as the content of CB increases from 0 to
11.16 wt%. The positive values indicate that the compos-
ites are p-type conductors in agreement with the Hall effect
measurement results. The room temperature Seebeck
coefficients of the composite films are higher than those of
the DMSO doped PEDOT:PSS film (12.51 lV K-1) pre-
pared under the same procedure and the CB pellet
(5.58 lV K-1) but lower (in some cases by an order of
magnitude) than that of a PEDOT:PSS/Te composite
film (*163 lV K-1) [8], a PEDOT:PSS/SWCNT com-
posite film (*21 lV K-1) [5] or a PEDOT:PSS/Bi2Te3
(*-125–150 lV K-1) composite [9].
Figure 3b shows as the content of CB increases form 0
to 11.16 wt%, the power factor of the CB/PEDOT:PSS
composite films first increases sharply and then decreases
mainly because the electrical conductivity of the composite
films increases sharply and then decreases, while the

123
1706
Seebeck coefficient increases gradually. The composite
film containing 2.52 wt% CB shows the highest power
factor value of *0.96 lWm-1 K-2, which is much higher
than that of DMSO doped PEDOT:PSS film
(0.57 lWm-1 K-2) and CB pellet (0.04 lWm-1 K-2).
The power factor value of the CB/PEDOT:PSS composite
films is lower than that of the PEDOT:PSS/Te composite
film [8], the PEDOT:PSS/SWCNT composite film [5] or
the PEDOT:PSS (Clevios PH1000)/Bi2Te3 composite [9]
due mainly to the relatively low electrical conductivity of
the CB and PEDOT:PSS raw materials used.
Given that the Seebeck coefficient of the CB/
PEDOT:PSS composites increased slowly in comparison to
the DMSO doped PEDOT:PSS, the enhancement of the
electrical conductivity using a high conductivity
PEDOT:PSS product such as the new products, PH500 or
PH1000, from H.C.Stark, Inc. could be a principal way of
improving the TE properties of the CB/PEDOT:PSS
composite films.
4 Conclusions
Carbon black/poly(3,4-ethylenedioxythiophene):poly(4-sty-
renesulfonate) (CB/PEDOT:PSS) composite films were
prepared by a spin-coating method. As the content of CB
increased form 0 to 11.16 wt%, the power factor of the CB/
PEDOT:PSS composite films increased sharply to a max-
imum and then slowly decreased. The composite contain-
ing 2.52 wt% CB showed the highest power factor value of
*0.96 lWm-1 K-2, which is a much higher power factor
value than either a pure CB pellet or the DMSO doped
PEDOT:PSS films.
Acknowledgments This work was supported by research Fund for
the Doctoral Program of Higher Education of China and foundation of
the State Key Lab of Advanced Technology for Materials Synthesis
and Processing (Wuhan University of Technology).
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J Mater Sci: Mater Electron (2013) 24:1702–1706
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