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ORGANIC THERMOELECTRICS

Green energy from a blue polymer

Efficient energy harvesting from temperature gradients requires thermoelectric materials with low thermal and high
electrical conductivities. A conducting polymer can fulfil these conditions if its doping level is controlled precisely.

Mario Leclerc and Ahmed Najari

L
ow-temperature gradients are
ubiquitous — they arise naturally
from geothermal and solar energy,
and they can be produced by various
power-generating or -consuming systems.
Thermoelectric materials can turn this
waste heat into pollution-free electricity and
could therefore be a green option for various
energy-harvesting applications ranging from
power generation to microprocessor cooling.
Thermoelectric devices can be operated in
a cooling mode, where their simple leg-type
structures in principle provide enormous
advantages over conventional turbines,
engines and compressors, particularly for
applications that require robust and silent
operation1. The fundamental problem in
creating efficient thermoelectric materials is
that they must be very good at conducting
electricity, but not heat. Only then can
one end of an apparatus get hot while
the other remains cold, maintaining the
temperature gradient that is required for
the thermoelectric effect to be exploited.
However, in most materials, electrical
and thermal conductivities go hand-in-
hand as they are both proportional to the
concentration of the charge carriers. The
Seebeck coefficient, on the other hand, which
corresponds to the change in voltage per
unit temperature difference in a material,
decreases with increasing charge carrier
concentration1. The main goal of research
on thermoelectric materials is therefore to
improve their electrical conductivity without
an increase of their thermal conductivity
while keeping a good Seebeck coefficient.
Writing in Nature Materials, Xavier Crispin
and colleagues now report that the
Some inorganic conductors and
semiconductors, for example bismuth
tellurides, are clearly efficient thermoelectric
materials, but they have drawbacks, such
as high cost of production, scarcity of
materials and toxicity 1. Owing to these
problems, research on conducting polymers
as alternatives has emerged3. Conducting
polymers possess several features that make
them attractive for use as thermoelectrics:
they are lightweight, flexible, easy to process
over large areas and cheap. In general,
conjugated polymers are semiconductors
that show electrical conductivity after
doping with suitable dopants (the so-called
doping reaction is indeed a partial oxidation
or reduction of the neutral conjugated
polymer). Through simple modifications of
their molecular structure, it is also possible to
tune their physical and chemical properties
in a fairly large range, providing great
material flexibility to meet the requirements
of the targeted applications. Finally, polymers
N N
C C
N N
TDAE
– –
O S O O
generally possess a low thermal conductivity,
which gives them a potential advantage over
conventional thermoelectric materials.
As anticipated, first results on polymers
showed that the Seebeck coefficient decreases
when the electrical conductivity increases.
Therefore, it is necessary to balance these
two parameters with a sufficient level
of doping that improves the electrical
conductivity without compromising the
Seebeck coefficient. The study by Crispin and
collaborators shows an impressive example
of such an optimization. They worked on
poly(3,4-ethylenedioxythiophene) (PEDOT),
which is one of the most-studied conducting
polymers4,5. This processable and air-stable
conducting polymer is widely used as an
anti-static coating or as a hole-injecting layer
in light-emitting and photovoltaic devices.
After extensive doping (an oxidation process
where the colour of PEDOT switches from a
dark blue to a light blue-grey), this polymer
can exhibit electrical conductivities up to
TDAE2+
Tos
S O
2e –

thermoelectric performance of a conducting O O

O O O O O O
polymer can be optimized by independently
tuning its electrical properties2.
S + S S
The efficiency of a thermoelectric S +
PEDOT
material is related to the dimensionless S S S n
thermoelectric figure-of-merit ZT, which is
defined by the equation ZT = (S2σ)T/κ, where O O O O O O O O
S is the Seebeck coefficient, σ the electrical
conductivity, T the absolute temperature
and κ the thermal conductivity. Materials
with a ZT of 1 or higher are expected to Figure 1 | Optimization of the doping level in poly(3,4-ethylenedioxythiophene) (PEDOT). The as-prepared
be competitive against other methods of fully oxidized PEDOT is de-doped (that is, partially reduced) using tetrakis(dimethylamino)ethylene
refrigeration and electric-power generation. (TDAE) to maximize the Seebeck coefficient as well as the electrical conductivity.

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© 2011 Macmillan Publishers Limited. All rights reserved

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1,000 S cm–1. However, in those conditions,
the Seebeck coefficient is so low that the ZT
remains about 10–2–10–3. The nice and simple
idea of Crispin’s team was to slightly de-dope
the fully oxidized PEDOT — a process that
brings back a blue colour to the polymer
(Fig. 1)2. The authors slightly reduced the
as-prepared fully oxidized PEDOT with
tetrakis(dimethylamino)ethylene (TDAE)
to achieve a remarkable value of ZT = 0.25.
Perhaps, more importantly, they were able to
stabilize the optimized doping level at room
temperature in air and up to temperatures of
100 °C. With the exception of polyacetylene,
which is not stable and not processable, this
is the best ZT value reported so far for a
conducting polymer.
To further improve the practical
and commercial prospects of polymeric
thermoelectric materials, recent
research efforts have been devoted to
organic–inorganic composites6–8. Such
composites have gained importance
because they can be tuned to combine
high electrical conductivity, which is
characteristic of inorganic materials, with
poor thermal conductivity, which is an
inherent property of organic polymers. For
instance, some researchers have worked on
the improvement of electrical conductivity
by incorporating carbon nanotubes in a
conducting polymer matrix 6. As carbon
nanotubes are very stiff and tough, they
also enhanced the mechanical strength of
the polymer composites. Finally, recent
studies have shown improved thermoelectric
properties in ultralong electrodeposited
PEDOT nanowires9. Both approaches
could be tested on Crispin’s material,
and they could soon lead to air-stable,
processable and environmentally friendly
thermoelectric devices. ❐
Mario Leclerc and Ahmed Najari are at the
Department of Chemistry at the Université Laval,
Quebec City, Quebec G1V 0A6, Canada.
e-mail: mario.leclerc@chm.ulaval.ca
References
1. Snyder, G. J. & Toberer, E. S. Nature Mater. 7, 105–114 (2008).
2. Bubnova, O. et al. Nature Mater. 10, 429–433 (2011).
3. Dubey, N. & Leclerc, M. J. Polym. Sci. Polym. Phys.
49, 467–475 (2011).
4. Gronendaal, L., Jonas, F., Freitag, D., Pielartzik, H. &
Reynolds, J. R. Adv. Mater. 12, 481–494 (2000).
5. Kirchmeyer, S. & Reuter, K. J. Mater. Chem. 15, 2077–2088 (2005).
6. Kim, D., Kim, Y., Choi, Y. K., Grunlan, J. C. & Yu, C. ACS Nano
4, 513–523 (2010).
7. See, K. C. et al. Nano Lett. 10, 4664–4667 (2010).
8. Zhang, B., Sun, J., Katz, H. E., Fang, F. & Opila, R. L.
ACS Appl. Mater. Interfaces 2, 3170–3178 (2011).
9. Taggart, D. K., Yang, Y., Kung, S-C., McIntire, T. M. &
Penner, R. M. Nano Lett. 11, 125–131 (2011).

COLLOIDAL SELF-ASSEMBLY

Designed to yield
Maximum yield of self-assembly for a target structure can be attained with simple rules for the interactions
between the structure’s building blocks.

Daan Frenkel and David J. Wales

O
ur success in designing nano- or
microsized building blocks that a b c
spontaneously assemble from
solution into a targeted ordered structure is
meagre compared with what living systems
are capable of. Aside from the case of a few
simple structures — a hexagonally close-
packed arrangement, for instance — we
lack general guiding rules for the design of
the properties of the building blocks and
the interactions among them. Effective d
rules should fulfil two general design
requirements: the target structure needs
to be thermodynamically the most stable
among all possible arrangements, as well
as kinetically accessible under the same
conditions to avoid the self-assembly
process getting trapped in unwanted, Figure 1 | Packings of a designable eight-block cluster. a–c, Hormoz and Brenner chose a high-symmetry
metastable structures1,2. As reported in cluster to test their proposed design rules4. The cluster, which has achiral tetrahedral symmetry and
Proceedings of the National Academy of belongs to a degenerate set of sixteen packings (thirteen of which are shown in panel d; the remaining
Sciences, using concepts that were developed three are chiral enantiomers), consists of eight building blocks (spheres) that interact in pairs through
in the context of the random energy model3 contact. All the interactions between the blocks are characterized by three parameters: the number
for protein folding1, Sahand Hormoz of energetically distinct blocks (distinct interactions are indicated by different colours), the number of
and Michael Brenner propose simple attractive interactions, and the standard deviation of the interaction energies. If all building blocks are
design rules for the self-assembly of identical (a), the cluster’s yield is less than 1%, a result of entropy favouring more asymmetric packings.
three-dimensional clusters that satisfy the For clusters with two (b) and eight (c) distinct blocks, the yield increases up to approximately 50% and
design requirements4. 70%, respectively. The maximum enhancement in yield is obtained if the interactions are equal within
Hormoz and Brenner chose to study each type (attractive or repulsive), and if the standard deviation of the interaction energies is at the
clusters containing a fixed number of practical maximum, which occurs at the onset of kinetic freezing. For stability reasons, the spheres in
building blocks that have only isotropic cluster a are all attractive, cluster b has two attractive interactions (red–red and red–blue) and cluster c
nearest-neighbour interactions, and has 18. Figure reproduced with permission from ref. 4, © 2011 NAS.

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