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Organic Thermoelectric Materials: Emerging Green Energy

REVIEW
Materials Converting Heat to Electricity Directly and
Efficiently
Qian Zhang, Yimeng Sun, Wei Xu,* and Daoben Zhu*

interest from both scientific and industrial

The abundance of solar thermal energy and the widespread demands for communities.
waste heat recovery make thermoelectric generators (TEGs) very attractive in The thermodynamic limit of the energy-
harvesting low-cost energy resources. Meanwhile, thermoelectric refrigeration conversion efficiency (η) of a TEG device
is promising for local cooling and niche applications. In this context there is is defined by reversible Carnot cycles. The
energy-conversion efficiency, namely the
currently a growing interest in developing organic thermoelectric materials
output electrical energy over the input
which are flexible, cost-effective, eco-friendly and potentially energy-efficient. thermal energy, is a function of the mate-
In particular, the past several years have witnessed remarkable progress in rials’ figure-of-merit (ZT), average working
organic thermoelectric materials and devices. In this review, thermoelectric temperature of the device, and temperature
properties of conducting polymers and small molecules are summarized, difference between the hot (TH) and cold
(TC) ends.[2] Although η can be improved
with recent progresses in materials, measurements and devices highlighted.
via thermal engineering[2e] (e.g., increase
Prospects and suggestions for future research efforts are also presented. The TH and TH- TC), it is ZT that fundamen-
organic thermoelectric materials are emerging candidates for green energy tally predominates.[2a-d] The figure-of-merit
conversion. of thermoelectric materials is ZT = S2σT/κ,
where S (V K−1) is Seebeck coefficient or
thermopower, σ (S m−1) is electrical con-
1. Introduction ductivity, κ (W m−1 K−1) is thermal conductivity and T is absolute
temperature. When variation in thermal conductivity is secondary
Energy is indispensible for industrial production and daily life. to modulation in electrical conductivity and Seebeck coefficient,
Currently the majority sources of energy are produced from thermoelectric property of a material can be weighted with a
fossil fuels. These fuels are combusted in heat engines to gen- parameter called power factor (PF) as PF = S2σ in Wm−1 K−2.
erate mechanical energy, which is then transformed through Furthermore, it should be noted that electrical conductivity,
electrical generators into electricity for utilization and storage. Seebeck coefficient and thermal conductivity are not inde-
In contrast, there is a neat heat engine called thermoelectric pendent, namely it is hardly possible to optimize one parameter
generator (TEG) which is able to convert temperature differ- without affecting the other parameters.[2a-d,3] Basically, electrical
ences directly into electrical voltages via the Seebeck effect.[1] conductivity is the product of carrier charge q, carrier concen-
Upon supply of electrical energy, TEG devices can also work tration n (cm−3) and carrier mobility µ (cm2 V−1 s−1) as σ = nqµ.
as heat pumps driven by Peltier effect, which is roughly an Since charge carriers also conduct heat as they move, thermal
inverse process of the Seebeck effect. According to its working conduction is expected to increase with electrical conduction of
principles, a TEG device neither requires moving parts nor con- a given material. Actually according to Wiedemann-Franz rela-
sumes liquid or gas media, implying favorable qualities, such tion, the ratio between its contribution to thermal conduction
as high reliability and eco-friendliness. Moreover, TEG devices and electrical conduction of a charge carrier follows the equa-
can employ low-quality heat, which is otherwise dissipated. tion σT/κ = (3/π)2 (q/kB)2, where kB is Boltzmann constant. As
Therefore, the research of thermoelectricity has attracted great to the Seebeck coefficient, it is a fundamental electronic trans-
port property of materials; specifically it measures the entropy
of a carrier with unit charge. Considering a simple system of
Q. Zhang, Dr. Y. M. Sun, Prof. W. Xu, Prof. D.B. Zhu charge carriers without strong interactions, the entropy of a car-
Beijing National Laboratory for Molecular Sciences
rier is statistically determined to be qS = kBln[(1–ρ)/ρ], where ρ
Key Laboratory of Organic Solids
Institute of Chemistry is the charge density for each state. In the framework of energy-
Chinese Academy of Sciences band theory and Boltzmann distribution, the above equation
Beijing 100190, P. R. China is transformed into S = (kB/q)[(E–Ef)/kBT], where Ef is Fermi
E-mail: wxu@iccas.ac.cn; zhudb@iccas.ac.cn energy level and E is the energy level occupied by the carrier.
Q. Zhang Obviously, Seebeck coefficients largely decrease with increase
University of Chinese Academy of Sciences
Beijing 100049, P. R. China in carrier concentrations.
Experimentally, a Seebeck voltage (ΔV) can be measured
DOI: 10.1002/adma.201305371 between two ends of the sample along with the corresponding

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Qian Zhang graduated with

a B.S.E. in materials sci-
ence and engineering from
Shandong University in 2009.
She is currently a Ph.D.
candidate in chemistry under
the supervision of Professor
Daoben Zhu.

Figure 1. (a) A typical set-up for measurement of Seebeck coefficients

(S = ΔV/ΔT). (b) Schematic illustration of a thermoelectric element com-
posed of a pair of p- and n- type legs. The diffusion of carriers (the inside
narrow lines) under temperature gradient leads to the formation of cur- Yimeng Sun is a research
rent (the outside wide lines) in the circuit and drives the load.
assistant in the Organic
Solids Laboratory. He
temperature difference (ΔT) after the establishment of a
received his B.S. degree in
thermal gradient over the sample, as illustrated in Figure 1a.
chemistry from University
Thereby the Seebeck coefficient of the sample can be obtained
of Science and Technology
via S = ΔV/ΔT. Typically a TEG element consists of a pair of
of China in 2006 and Ph.D.
legs connected electrically in series and thermally in parallel.
in physical chemistry from
As shown in Figure 1b, the two legs are respectively composed
Institute of Chemistry, CAS
of p- and n- type thermoelectric materials, which should meet
in 2012, under the supervi-
the following criteria:
sion of Prof. Daoben Zhu.
a. the thermal conductivity is as low as possible to maintain Currently his research focuses
larger temperature difference, on organic thermoelectric
b. a higher Seebeck coefficient is preferred to achieve higher materials and devices.
Seebeck voltages and
c. a higher electrical conductivity is required for larger short- Wei Xu is a Professor in the
circuit current. Organic Solids Laboratory
in ICCAS. He received his
Ph.D. degree from Wuhan
Generally, insulators and pristine semiconductors are too University in 1997. After
resistive (criterion c); on the other hand, ordinary metals are working with Prof. Daoben
inappropriate because their Seebeck coefficients are small (ca. Zhu as a Postdoc for two
±10 µV K−1) while thermal conductivities are high (criterions a years, he joined Prof. Zhu’s
and b). As a consequence, the most investigated candidates so group in 1999. His research
far are doped semiconductors and semimetals. interests include design,
Taking inorganic thermoelectric materials as an example. In synthesis and transport
the mid of last century, an extensive screening of materials led properties of organic
to the identification of several alloys and intermetallics based semiconductors.
on elements like Bi, Te, Sb, Pb, etc., and ZT of unity at low
temperatures (300–500 K) was achieved.[4] For these materials Daoben Zhu is a Professor
the carrier concentration is tuned to be within the range from and Director of the Organic
1019 cm−3 to 1020 cm−3. As to thermal conductivity, both electrical Solids Laboratory in the
carriers and phonons (quantinization of lattice vibration) are Institute of Chemistry, CAS.
heat carriers. In inorganic materials, the electronic contribution He finished his graduate
to thermal conduction generally follows the Wiedemann-Franz courses at the East China
relation, and the phonon part is determined by composing ele- University of Science and
ments, crystal structures, various microstructure boundaries, Technology in 1968. He was
ect..[2d,4] Actually, suppressing thermal conductivity without selected as an Academician of
sacrificing electrical conductivity has been one of the main the CAS in 1997. His research
driving-forces of enhancement in ZT values of inorganic ther- interests include molecular
moelectric materials. For example, bulk nanocomposites have materials and devices.
been studied extensively since the 1990s, which are designed to
restrict thermal conduction with boundaries between nanocrys-
tallines remained after hot press.[2c,d,4] Nowadays, ZT values devices are still anticipated mainly because of limitations in
above unity are well established in bulk nanocomposites, the materials.[2c,4] Firstly, the composing elements such as Bi,
while the commercialization and wide application of TEG Te, Sb and Pb are toxic and not abundant. Second, laboratory

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processing of inorganic materials, including melt-spinning,
ball milling, hot pressing, etc., is costly in terms of energy and
instruments, and hence requires a long payback time. Lastly,
most inorganic materials are too heavy and brittle to be of use
in everyday life.
Given the aforementioned obstacles met by current inorganic
thermoelectric materials, organic candidates are attracting
more and more attention. After all, organic materials are poten-
tially abundant, light-weight, flexible, solution-processable and
low-cost. Moreover, the marvelous development of organic elec-
tronics has provided hundreds of organic semiconductors with
the highest field-effect mobilities approaching that of polycrys-
talline silicon.[5] In particular, there are two features of organic
solids that justify serious consideration and devoted endeavor
to exploit organic thermoelectric materials. Firstly, thermal con-
ductivity of organic materials is typically below 1 W m−1K−1,
approaching the lower limit of thermal conductivity of inor-
ganic thermoelectric materials. Second, electronic structures of
organic (semi)conductors are fairly tunable through molecular
chemistry and doping treatments.[6] Therefore, organic ther-
moelectric materials hold much promise in applications at low
temperatures. Despite all the above advantages, further devel-
opment in organic thermoelectric materials is impeded by bot-
tleneck problems including low electrical carrier mobilities and
mediocre Seebeck coefficients.
In fact, research into organic thermoelectric materials is a
topic where new insights accumulated over decades, in that the
thermoelectric measurement of organic materials dates back
to the early days of organic semiconductors[7] and conducting
polymers[8] in the 1970s. Back then Seebeck coefficients
(thermopower) of a wide range of organic electronic mate-
rials were characterized, including organic photo-conducing
dyes,[9] organic charge transfer salts,[10] derivatives of phthalo-
cyanines,[11] conducting polymers,[12] etc., under various condi-
tions of measurements, doping treatments and film processing
methods. Nevertheless, thermoelectric measurements per-
formed at that time were intended for study of electronic struc-
tures rather than the search for potential organic thermoelec-
tric materials. Similarly, in the 1990s Seebeck coefficients were
characterized to learn about doping processes of films of small
molecular semiconductors prepared by thermal deposition,
where doping was performed to improve device performance of
organic light-emitting diodes (OLEDs) or organic photovoltaic
cells (OPVs).[13] Later on, the measurement of Seebeck coeffi-
cients was combined with field-effect transistor (FET) architec-
tures to resolve electrical transport mechanisms in crystalline
organic semiconductors.[14] Therefore, there are both practical
and fundamental interests in the research of organic thermo-
electric materials.
Since the dawn of the 21st century there have been ongoing
efforts to employ organic materials especially conductive poly-
mers as thermoelectric materials.[15] Meanwhile, small conju-
gated molecules like pentacene[16] and fullerene (C60)[17] have
been doped and used as p- and n- type TEG legs respectively.
After incubation over a decade, the highest ZT values achieved
to date are respectively 0.42[18] and 0.20[19] for p- and n- type
organic thermoelectric materials. Moreover, TEG devices fabri-
cated by printing have been demonstrated using organic ther-
moelectric materials.[20] On the molecular level, thermoelectric
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measurement of a series of benzene and fullerene derivatives in
molecular junctions has been experimentally realized through
scanning probe microscopy (SPM).[21] Aside from heterostruc-
turing on the molecular level, hybrid materials that incorporate
organic materials with inorganic thermoelectric materials have
been developed, showing better thermoelectric performance
than either component.[22] Most of these hybrids are fabricated
using conducting polymers as binders or linkers for inorganic
or carbon-based matrixes. Hybridization is important not only
because it provides a pathway to address processing issues
of inorganic materials and to reduce thermal conductivities;
more importantly, it suggests a possibility to utilize advan-
tages of both components of a hybrid through careful design
of the organic/inorganic interfaces.[22] In fact, an analogy can
be drawn between hybrid materials and molecular heterojunc-
tions. And research of the latter model has suggested signifi-
cant influence of energy level alignment between molecular
orbitals and electrode Fermi levels on the thermoelectric perfor-
mance of the junction.[21] There have been several good reviews
published recently with emphasis on hybrid thermoelectric
materials.[23]
In this review, we focus on thermoelectric properties of
organic materials, including that of conductive polymers (Sec-
tion 2), conducting charge transfer complexes and semiconduc-
tors based on small molecules (Section 3). Common methods
of the measurement of Seebeck coefficient, electrical conduc-
tivity and especially thermal conductivity are discussed over
representative examples of organic materials especially conju-
gated polymers (Section 4). Moreover, all-organic thermoelec-
tric devices that have been demonstrated so far are summa-
rized (section 5), with devices in film architectures highlighted.
Finally, approaches for the development of each type of organic
thermoelectric materials are proposed (Section 2 and 3), and a
future outlook of this field is briefly discussed (Section 6).
2. Organic Thermoelectric Materials Based on
Conductive Polymers
The majority of organic thermoelectric materials reported to
date are based on conductive polymers, including conjugated
polymers and certain coordination polymers, where roughly
three types of research objects can be identified.
The first type is highly conducting polymers that have been
well studied previously for other applications. In this case,
thermoelectric properties of the polymers are strongly affected
by the synthesis and/or processing conditions. This efficient
approach is the most adopted, and yet the monomer species
available are relatively limited. The second type of objects is
selected from the tens of solution-processable polymeric semi-
conductors developed in the past two decades for organic elec-
tronics, whose thermoelectric properties are optimized through
doping, blending, and so on. The third approach is to tailor new
molecular structures through derivation and novel design, in
search of potential building blocks appropriate for thermoelec-
tric purposes. This is an elegant demonstration of chemical ver-
satility of organic electronic materials although it is largely trial
and error at the moment. Progress in each of the three research
objects offers a unique perspective, shedding light on the
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Figure 2. Chemical structures of some benchmark conjugated polymers.
ultimate goal of clarifying the structure-property relationships
of polymers for high-performance thermoelectric materials.
2.1. Conjugated Polymers: Materials and Optimization
Strategies
Polymers, widely known as plastics like nylon and resin,
have been commonplaces in our everyday lives. Conjugated
polymers differ from these traditional plastics by the nature
of chemical bonds in the backbones, namely in addition to
covalent σ-bonds the conjugated repeat units are connected
by non-localized π-bonds. Consequently conjugated polymers
are pristinely semiconductive rather than being insulative and
can become conductive and even metallic after appropriate
doping treatments. Since the discovery of metal-like behaviors
in highly doped polyacetylene (PA) films at the end of 1970s,
three generations of conjugated polymers have been devel-
oped.[6,24] For further information readers are referenced to a
recent review presented by Crispin et al. who gave a very good
introduction to most of the fundamental aspects of conjugated
polymers.[25] Herein, we briefly introduce conjugated polymers,
highlighting chemical and physical features that are poten-
tially correlated with thermoelectric performance. Thereafter
research progresses are summarized in an outline classified
into three strategies for optimization of thermoelectric proper-
ties. Finally suggestions on future research efforts are tenta-
tively proposed.
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2.1.1. Materials
Conjugated Polymers: Chemical structures of
some benchmark conjugated polymers ever
employed in thermoelectrics are sketched
in Figure 2. Generally conjugated polymers
have marvelous doping reversibility and
wide doping ranges; they can display supe-
rior mechanical flexibility and decent charge
conductivity along the polymer backbone.
On the other hand, polymeric materials are
often inhomogeneous, because amorphous
and crystalline regions are usually coexistent,
the stacking of polymer chains is hard to
control, and distribution in molecular weight
is broad. To overcome these shortcomings,
various synthesis schemes are developed and
good solubility in common solvents is highly
desired.
Historically, the first generation of conju-
gated polymers is neither soluble nor fusible
because of very strong intermolecular inter-
actions in the absence of side substitutes.
Typical examples include PA, polypyroles
(PPy), polythiophenes (PTh), polyanilines
(PANi) and poly(3,4-ethylenedioxythiophene)
(PEDOT), as shown in Figure 2. These poly-
mers can be prepared by chemical or elec-
trochemical polymerization with or without
catalyses. The as-prepared polymers are
usually highly doped, incorporating coun-
terions to balance charges on the backbones. Moreover, poly-
merization conditions can be tuned to obtain various micro-
scopic and macroscopic morphologies. Thereafter, great efforts
are devoted to addressing the solubility issue. One scheme is
to adopt counterions that can facilitate emulsion polymeriza-
tions. Typical examples are PEDOT: PSS and PANi: CSA, where
PSS− and CSA− are respectively poly(styrenesulfonate) anion
and (±)10-camphorsulfonic acid anion. Nowadays, PEDOT: PSS
of various qualities is commercially available in the form of dis-
persion in water.
The second solution for solublization is to polymerize
monomers with longer side substitutes, leading to the second
generation of conjugated polymers as represented by poly[2-
methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] MEH-
PPV and poly(3-hexylthiophene-2,5-diyl) P3HT shown in
Figure 2. Owing to improved solubility, the purification, pro-
cessing and characterizations of these polymers are facili-
tated. Besides, better solubility makes it easier to synthesize
polymers with higher regioregularity and higher molecular
weights. In particular, it is now possible to include repeat
units with more complex structures into the backbones,
giving rise to the third generation of conjugated polymers. As
a result, the electronic structures of conjugated polymers are
greatly enriched. Moreover, the electronic structures can be
influenced by side substitutes because of their subtle effects
on polymer conformation and stacking manner in solids,
bulk density of conjugated units, chemical/thermal stability
and so on.
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Finally, it should be noted that the as-prepared polymers
of the second and third generations are neutral and soluble,
and can be doped chemically or electrochemically with inser-
tion of counterions and lost of solubility. As such, two basic
mechanisms of (electro)chemical doping are recognized for
conjugated polymers. One is based on redox reactions where
electrons are transferred between polymer backbones and
dopant molecules (in chemical doping) or electrodes (in electro-
chemical doping). The other, often referred to as protonic acid
doping, is a base-acid reaction where proton ions are added to
the polymer backbones without accompanied variation in elec-
tron numbers.
Electrical Conduction: Electrical carriers in conjugated poly-
mers are acknowledged as polarons and bipolarons, which are
approximately the summation of electrons (holes) with local dis-
tortion in molecular structures. Polarons and bipolarons can be
detected with electron spin resonance (ESR) techniques, ultra-
violet-visible and near infrared (UV-vis NIR) spectroscopy, and
Raman spectroscopy. Transport mechanisms of (bi)polarons
in conducting polymers, e.g. localized hopping or delocalized
diffusion, are dependent on crystallinity and morphologies of
materials, doping levels, conformation and stacking manners
of molecules, ect.. In this respect, the values of carrier mobility
can be used as an indicator of the extent of delocalization of
(bi)polarons. Given that electronic structures in the reciprocal
space are determined by the structures of molecules and mate-
rials in the real space, both electrical conductivities and See-
beck coefficients are related with carrier mobility. From this
point of view, not only are carrier concentrations and chemical
structures of monomers and counterions responsible for ther-
moelectric properties, but how the molecules are arranged in
materials is also critical.
Thermal Conduction: Similar to the case in inorganic
materials, heat carriers in conductive polymers include pho-
nons and charge carriers. However, the Wiedemann-Franz
law, which has been widely acknowledged in most inorganic
metals and semiconductors, is often invalid in conjugated
polymers because of their stronger charge-lattice coupling.
Furthermore, the electronic contribution to thermal conduc-
tion is marginally small compared with the phonon part, given
the low electrical conductivities of most polymers. Therefore
thermal conduction in conjugated polymers is generally recog-
nized to be dominated by phonons. For example, only minor
variation in thermal conductivity values was observed in PA,
PANi, and PPy samples, from less than 0.1 W m−1K−1 to below
1.0 W m−1K−1, when electrical conductivity values were tuned
over three orders of magnitudes.[26] Although these results
are desirable for organic thermoelectricity, thermal conduc-
tion property of conductive polymers remains to be studied
extensively. To this end, it seems that thermal conductivity of
polymers is susceptible to synthesis conditions and plausibly
to molecular structures but there are no definite conclusions
for the lack of systematic investigations.[26] Besides, recent
research suggests remarkable impact of crystallinity, alignment
of polymer chains, interfaces or boundaries on thermal con-
ductivity of polymer films or fibers.[27] Given the huge impact
of thermal conductivity on overall ZT value, thermal conduc-
tion property of crystalline conductive polymers deserves fur-
ther investigations.
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2.1.2. Optimization Strategies for Thermoelectric Polymers No.1:
Carrier Concentration
As mentioned in Introduction, it has been well-established in
inorganic thermoelectric materials that the best performance
is found in highly doped semiconductors, typically with carrier
concentration ranging from 1019 to 1020 cm−3. In contrast, the
situation in conjugated polymers is still perplexing.
On the one hand, tuning of carrier concentration has been
proved to be powerful in optimizing thermoelectric properties
of the polymers. Note that instead of specified values of car-
rier concentration, it is doping levels that are mostly cited in
the description of conjugated polymers because accurate meas-
urement of carrier concentration in polymers is nontrivial.
Experimentally more than one definitions can be found for
doping levels, but the basic idea is to identify the number of
counterions per repeat unit of the polymer. Since it is formally
proposed and demonstrated by Crispin et al. in the year 2011
through reducing chemically polymerized PEDOT: Tos (Tos =
tosylate anion) with tetrakis(dimethylamino)ethylene (TDAE)
vapor[20] (Figure 3), intentional tuning of carrier concentration
or doping level has become a routine step to optimize thermo-
electric property of polymers. So far most of the best results
are obtained through tuning doping levels, i.e. step-wisely
increasing or decreasing the apparent ratio of monomer/coun-
terion, as summarized in Table 1.
In the case of PEDOT, various reducing methods have been
reported, such as electrochemical reducing under constant
potentials,[29,30] charge-annialation reducing with gating in elec-
trochemical transistors,[33] solvent-induced removing of counte-
rions[18] and exposure to active agents like TDAE[20] and ammo-
nium formate.[42] In comparison, step-wise oxidation is more
appropriate for polymers with deeper HOMO levels like P3HT
whose oxidized state is less stable than the neutral state.[35,43]
Along with thermoelectric measurement, characterizations of
UV-vis NIR spectroscopy and X-ray photoelectronic spectro-
scopy (XPS) are often performed to infer doping levels and car-
rier nature (polaron and/or bipolaron). Several representative
examples of controlling doping levels with methods aforemen-
tioned are depicted in Figure 3–7, illustrating how thermoelec-
tric property evolves with oxidation or reduction and how the
optical absorption and/or XPS spectra change correspondingly.
On the other hand, mechanisms of the optimization in ther-
moelectric properties by tuning carrier concentration are not
clarified. This judgement is corroborated by three common
observations in published results, which are also evident in
the examples shown in Figure 3–7. Firstly, the optimal doping
levels vary with polymers, counterions and processing methods.
For example, as shown in Figure 3,4 and 6 the optimized
doping levels are around 22%, 14.5%, 20–30% and 30% respec-
tively in PEDOT: Tos, PEDOT: PSS, P3HT: PF6 and P3HT: TFSI
(TFSI− = triflimide anion, inset in Figure 6f).[20,33,35,43] Second,
the evolution of optical absorption spectra as doping proceeds
is indicative of coexsistence of polarons, bipolarons and neu-
tral units. As shown in Figure 3–6, the ratios between either
two of the three components vary with doping levels. It seems
that the PF peak values are achieved around the critical point
where polaron absorption is just beyond its maximum. The
third observation is that electrical conductivity of a sample does
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Figure 3. Optimization of thermoelectric property of PEDOT: Tos by TDAE vapor treatment. Variation in doping levels is verified by XPS (a) and UV-VIS
spectroscopy (b), and the resultant thermoelectric property is maximized at doping level around 22% (c). Adapted with permission.[20] Copyright 2011,
Nature Publishing Group.
not necessarily decrease with reduction in doping levels. Actu-
ally as shown in Figure 5 and 7 both electrical conductivity and
Seebeck coefficient increased with reduction in doping levels
from the highest value.
The summarized three observations imply that thermoelec-
tric properties of conjugated polymers are significantly affected
by the nature of charge carriers, with carrier concentration
being one of all carrier properties. Therefore it is important to
identify other charge carrier natures of key importance to ther-
moelectric performance of conjugated polymers. To this end,
three possible approaches can be generalized as follows:
i. direct characterizations of carrier concentrations are pre-
ferred to indirect methods like XPS or optical absorption,
ii. the ratios between either two of (bi)polarons and neutral seg-
ments should be controlled to clarify their roles on thermo-
electric performance, and
iii. effects of doping mechanisms (redox doping and protonic acid
doping) on thermoelectric properties are subtly important.
However, it should be noted that the second point is very
complicated. Although it has been mentioned previously by
Crispin et al.,[25] the related research is barely reported. Nev-
ertheless, experimental results corresponding to the first and
third points are available and are reviewed in the following.
As characterizations of carrier concentration or doping
level are concerned, the most adopted method is XPS where
the peak area (or height) of distinguishing elements from the
polymer and counterion are compared quantitatively. However,
XPS is highly surface-sensitive, and there are often massive
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ineffective counterions in polymers as well as large amounts of
deep-trapped carriers which barely contribute to electrical trans-
port. As shown in the case of PEDOT: PSS (Figure 7), the con-
centration of free carriers extracted from the measured Seebeck
coefficients via numerical simulation is 0.13N0 while the coun-
terion/monomer ratio (S168/S164) determined by XPS is 0.96,
where N0 is the total density of states of neutral polymer.[18]
Another regular but less common method is to derive injected
charges from electrical signals in electrochemical or transistor
configurations (Figure 4d).
The subtle effect of doping mechanisms on thermoelectric
properties is less noticed. As aforementioned, redox reaction
and proton addition are two basic reaction mechanisms for
chemical doping of conjugated polymers. The former is pre-
dominant in polythiophenes like PEDOT and P3HT while the
latter is primarily observed in polyanilines. Previously Park et al.
measured the Seebeck coefficients of PANi pellets as they sys-
tematically varied doping levels, temperatures, doping methods
(hydrochloride acid HCl and Iodine vapor), and substitutes
including Cl, OCH3, CH3.[44] A transition from positive to nega-
tive in the sign of Seebeck coefficient at high doping levels was
observed in HCl-doped PANi but not in Iodine-doped samples.
Similar transition in the sign of thermopower at high doping
levels was observed in PEDOT: PSS which was used as the
active layer in an electrochemical transistor with PSS: H as the
dielectric layer (Figure 4).[33]
To conclude, tuning carrier concentration is an important
and effective method to modulate thermoelectric property of
conjugated polymers and insights into the working mecha-
nisms require further exploration.
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Table 1. Summary of thermoelectric results of polymers with PF above 1 µW m−1K−2 around 300 K.

REVIEW
Part A Polymers with PF above 100 µW m−1K−2 around 300 K
−1 −1
σ (S cm ) S (µV K ) PF (µW m−1K−2) κ (W m−1K−1)a) Treatmentb)
PA: Ix[26a,28] 11110 28.4 900 0.69 (steady-state) As-synthesized
[28]
PA: FeCl4 7530 15.3 180 / As-synthesized
PEDOT: Tos[20] 238 40 38 / As-synthesized (36%)
80 200 324 0.33 (0.37) TDAE-reduced (22%)
PEDOT: Tos[29] 1354 79.7 861 / As-synthesized (24%)
923 117 1270 / Electrochemically Reduced
PEDOT: PSS[18] 639 27.3 47.6 0.23 (0.52) Spun-casted, EG
(Clevios PH1000)
620 33.4 69.2 0.24 (0.42) Spun-casted, DMSO
830 60 300 0.23 (0.37) EG treated
957 70 469 0.22 (0.31) DMSO treated
PEDOS-C6: ClO4[30] 180 30 16 / As-synthesized
335 103 354.7 / Electrochemically Reduced
Part B Polymers with PF ranging from 10 to 100 µW m−1K−2 around 300 K
σ (S cm−1) S (µV K−1) PF (µW m−1K−2) κ (W m−1K−1) Treatment
EtOPV-co-PV I2 vapor[31] 2.9 40.8 0.48 0.66 (laser-flash) As-synthesized
349.2 47.3 78.1 Stretching ratio 3.1
[32]
PEDOT: PSS (PH1000) 930.4 18 30.1 / DMSO post-treatment
720 23 38.5 / (EMIM)BF4-DMSO
PEDOT: PSS (GmbH)[33] 224 9 2.3 / Spun-casted
23 101 23.5 / PSSH-gated (14.5%)
PEDOT: PSS (PH1000)c)[34] 559 23.3 30.3 0.20 (laser-flash) Batch No. 1
622 34.5 37.3 Batch No. 2
P3HT: TFSI[35] 90 50 22.5 / As-synthesized
Part C Polymers with PF ranging from 1.0 to 10 µW m−1K−2 around 300 K
σ (S cm−1) S (µV K−1) PF (µW m−1K−2) κ (W m−1K−1) Treatment
[36]
PEDOT: PSS (PH750) 570 13.5 10.4 0.34 (TDTR) 5 vol.% DMSO and 10 vol.%
isopropanol
PEDOT: PSS (PH500)[37] 175 23 8.5 / Mixed with (bmim)BF4
123 28.5 9.9 / Mixed with (bmim)Br
PEDOT: ClO4[38] 16.8 74 9.2 / Nano-sized channel
PTh: ClO4[39] 201 23 10.3 / Electrochemical Polymerization
PANi: CSA[40] 260 14 5 / Drawing ratio 78%
PPy: Tos[41] 170 11 2 0.20 (laser-flash) Additional oxidation

a)Cross-plane thermal conductivity values with in-plane conductivity included in brackets. The cross-plane thermal conductivities are obtained with laser-flash method, time

domain thermal reflectance (TDTR) method or differential three-omega (3w) method as detailed in the maintext. In-plane thermal conductivities are obtained with steady-
state method or 3ω method; b)Doping levels experimentally determined are enclosed in brackets; c)Measured at 120 °C.

2.1.3. Optimization Strategies for Thermoelectric Polymers No.2:
Microscopic Morphologies
Microscopic morphologies as characterized with atomic force
microscopy (AFM), scanning electron microscopy (SEM),
transmission electron microscopy (TEM), x-ray diffraction
(XRD), etc., are usually closely correlated with such features
as bulk mobility, density and crystallinity of materials, confor-
mation and ordering of polymer chains and microstructure
heterogeneity. Therefore microscopic morphologies are
expected to remarkably impact thermoelectric property of poly-
meric materials.
Chemically, polymerization methods that improve mate-
rial crystallinity and carrier mobility often change mate-
rial morphologies simultaneously. For example, ZT values
of β-Naphthalene sulfonic acid (β-NSA) doped polyaniline
with and without nanotube structures were respectively
4.86 × 10−5 µW m−1K−2 and 4.58 × 10−7 µW m−1K−2.[45]

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Figure 4. Optimization of the thermoelectric property of PEDOT: PSS (a) with electrochemical transistor architectures (b). The UV-VIS absorption
spectra (c) and doping levels (d) are both varied with gating voltages. (e) (f) The polymer thermoelectric property is optimized at doping level of 14.5%.
Adapted with permission.[33] Copyright 2012, American Chemical Society.

Figure 5. Thermoelectric property of electrochemically polymerized PEDOS-C6. When doping level is tuned electrochemically, both UV-VIS absorption
(a), (b) and thermoelectric property (c), (d) are modified. Morphologies of CVP (e) and CPP (f) films after dedoping at −0.1 V are characterized with
SEM (left) and AFM (right). The scale bar in SEM images is 1µm and the scanning scale of AFM is 3µm. Adapted with permission.[30]

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Figure 6. P3HT films step-wisely doped with NOPF6 (a-c) and Fe(TFSI)3 (d-f). (a) Scheme of carriers generated, (b) UV-VIS absorption spectra, and
(c) variation in thermoelectric property. Adapted with permission.[43] Copyright 2010, American Physical Society. Evolution in (d) XPS, (e) XRD results
with increased doping time and (f) temperature-dependence of thermoelectric property. Adapted with permission.[35] Copyright 2012, The Royal Society
of Chemistry.

Similarly, Taggart et al. reported that PF values of PEDOT
electrochemically deposited in nano-sized channels were
on average three times that of PEDOT deposited on unpat-
terned substrates, owing to improved crystallinity and carrier
mobility.[38] In another case, the Kim group compared PEDOT:
Tos films synthesized with and without triblock copolymer
poly(ethylene glycol)-block-poly(propylene glycol)-85 block-
poly(ethylene glycol) (PEPG) in the precursor solution and
found improved crystallinity (TEM) and higher density (13%
increase) in the former.[29] As a result the PF value was
improved from 861 µW m−1K−2 to 1,270 µW m−1K−2.
More cases demonstrating the necessity to control
polymer morphologies are reported in electrochemical
polymerization. For instance, Hiraishi et al.[39] and Yan
et al.[41] prepared films of PTh and PPy respectively through
electrochemical polymerization. By varying current den-
sity (or oxidation potential), temperature, concentration of
monomer and electrolyte, they found the best thermoelectric
property in films with smoother and denser morphologies.
Recently, Kim et al. prepared poly(3,4-ethylenedioxysele-
nophene) PEDOS-C6 by electrochemical polymerization.[30]
They compared thermoelectric property of films synthe-
sized with cyclic-voltammetric polymerization (CVP) and
constant potential polymerization (CPP), showing that films
obtained under constant potential were smoother and denser
(Figure 5e, f). After electrochemical reducing, the PF was
enhanced from the as-deposited 16.2 µW m−1K−2 to 354.7
µW m−1K−2 (Figure 5c, d).
The impact of morphology is also evident in the most
studied PEDOT: PSS, where secondary doping treatment
(addition of polar solvents, acids or salts) is widely adopted
to increase the electrical conductivity from 0.1 − 1 S cm−1 to
over 1,000 S cm−1. Such remarkable increase in electrical con-
ductivity is primarily ascribed to improvement in mobility as
a result of more extended conformation of polymer chains,
thinning of insulating PSS shells, improved orientation and
coherence of conductive PEDOT grains, etc.[46] Often the
solvent of choice is dimethyl sulfoxide (DMSO) or ethylene
glycol (EG) which leads to more significant fibril morpholo-
gies as revealed by AFM and TEM characterizations.[46a,47] In
contrast, Seebeck coefficients are less sensitive to secondary
doping treatment than electrical conductivity. Since the year
2002,[48] there have been about ten papers published (see a
recent review[49]) suggesting that the effect of solvent treat-
ment be increasing electrical conductivity without remark-
able effects on Seebeck coefficients (specifically around
10 – 20 µV K−1), where solvents including water, EG, DMSO,
dimethylformamide (DMF) and N-Methyl-2-pyrrolidone
(NMP) have been examined.[49,50] Thereafter, ionic liquids
are found to increase Seebeck coefficients to be around
30 µV K−1, accompanied with obvious modifications in film
morphologies, optical absorption spectra and electrical
conductivities.[32]
Very recently for the first time, Pipe et al.[18] proved that See-
beck coefficient of spun-cast PEDOT: PSS film can be increased
from 20 µV K−1 to 60–70 µV K−1 by immersing the film in EG

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Figure 7. Optimization of thermoelectric property of PEDOT: PSS by solvent-induced dedoping treatment. By immersing the polymer film in EG or
DMSO bath, the film thickness is decreased (a) owing to selective removal of PSS as demonstrated by XPS (b). The values of ZT (c), Seebeck coefficient
(d) and electrical conductivity (e) are increased while thermal conductivity is decreased (f) with dedoping. Simulation of variation in S2σ (normalized,
the inset scale bar) as the dopant volume ratio (versus total host volume, rχ) and the carrier concentration (normalized, n/N0) are changed, as shown
in the two-dimensional plot (g) and three-dimensional plot (h). Adapted with permission.[18] Copyright 2013, Nature Publishing Group.

or DMSO bath for a certain time in inert atmosphere. As shown
in Figure 7, owing to the selective removal of counterions PSS−
under such treatment, the film thickness was reduced by half,
the doping level was decreased (according to XPS), and the
thermal conductivity was also suppressed (Table 1). Conse-
quently a maximum ZT value of 0.42 was obtained in DMSO-
treated PEDOT: PSS for which the authors proposed an optimi-
zation scheme based on minimization of the dopant volume.
Nevertheless, it should be noted that commercial sources are
not consistent in all the aforementioned reports, and hence
disparities in molecular weights, fed ratios of 3,4-ethylenedioxy-
thiophene (EDOT) versus PSS and PH values are expected.[51]
Overall, materials morphology is a manifestation of molec-
ular organization in solids, offering another path to optimize
thermoelectric property of conjugated polymers. More impor-
tantly, morphology in real space is closely related with elec-
tronic states in energy space. In this respect, characteriza-
tions related to crystallinity, density and mobility should be
performed along with chemical synthesis and thermoelectric
measurement. Furthermore, morphologies may have additional
impact on thermal conductivities.
2.1.4. Optimization Strategies for Thermoelectric Polymers No.3:
Other Methods Explored
The strategies aforementioned are effective in most cases.
Whenever a polymer is synthesized, carrier concentration and
morphology of the material can be tuned carefully to optimize
thermoelectric performance. There are some other research
results, though yet to achieve high thermoelectric result so far,
revealing information valuable for future optimization of ther-
moelectric properties of polymers.
Enhancement of Seebeck Coefficients: As mentioned in Intro-
duction, Seebeck coefficient would be decreased when electrical
conductivity is increased as carrier concentration or doping
level is increased. However, several research results have dem-
onstrated that it is possible to enhance Seebeck coefficient and
electrical conductivity simultaneously, by means of modulating
transport pathways of charge carriers.
An early example is reported in P3HT which is blended with
poly(3-hexylthiothiophene) (P3HTT). Compared to P3HT, a
sulfur atom is inserted between the hexane side chain and the
backbone in P3HTT, resulting in an upward shift of HOMO

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level by 0.15 eV.[52] The solution of P3HT - P3HTT blend is
doped by gradual addition of 2,3,5,6-tetrafluoro-7,7,8,8- tetracy-
anoquinodimethane (F4TCNQ) solution and is thereafter casted
into films. In the blend of P3HT - 20 wt.% P3HTT, electrical
conductivity and Seebeck coefficient were increased simul-
taneously with addition of F4TCNQ when the dopant ratio is
below 1.0 wt.%. It is suggested by the authors that Fermi level
is pinned by P3HTT while the major contribution to electrical
conductivity is from carriers in P3HT given its higher weight
ratio and carrier mobility.
A second method is to utilize vertical architectures where
a thin polymer film is sandwiched between electrode layers,
with temperature gradient applied vertically over the top and
bottom electrodes.[53] This device architecture was designed to
suppress thermal conductivity while keeping electrical conduc-
tivity intact so as to improve Seebeck coefficient.[53a] Specifically,
thermal conduction is prohibited because of acoustic mismatch
between polymers and inorganic electrodes. Meanwhile, Ohm
contact is established to insure electrical conduction. Seebeck
coefficient is improved because the disparity in carrier entropy
at given temperature difference is enlarged between carriers at
the hot end and carriers at the cold, in the presence of charge-
phonon interactions which is expected to occur at the polymer-
electrode interface.[53] Furthermore, it is shown that film thick-
ness, working temperature, and electrode materials at the hot
end should be considered together to maximize the benefits
from the interface. So far this sandwich device architecture
has been demonstrated in films of Ppy[53a] and PEDOT: PSS[53b]
with thickness around 200 nm. Recently, this multilayer struc-
ture is applied to MEH-PPV, showing that light illumination
can simultaneously increase Seebeck coefficient and electrical
conductivity in the ITO/MEHPPV/Au device.[53c]
Orientation of Polymer Chains: The shortcoming shared by
the above two methods is undesirable electrical conductivity
(below 10−4 S cm−1), which is primarily caused by low carrier
concentrations of chosen materials. So it remains whether
these methods would be effective at higher density of charge
carriers. A third method achieving high thermoelectric per-
formance is to utilize anisotropy of polymers, e.g., to induce
orientation of polymer chains through mechanical stretching.
Toshima et al.[31,54] synthesized a series of copolymers of phe-
nylenevinylene and dialkoxyphenylenevinylene ROPV-co-PV
(RO = MeO, EtO, BuO). After systematic optimization in the
ratio of the two monomers (ca. 30 mol.% of dialkoxy-substi-
tuted units) and in the length of side-chain substitutes, the PF
of polymer EtOPV-co-PV were optimized to 78.1 µW m−1K−2
with elongation ratio of 3.1. Anisotropy in conductive polymers
is an interesting attribute for thermoelectricity.
Effects of Chemical Structures: Last but not least, reports
related to the relationships between chemical structures and
thermoelectric properties of the materials are summarized.
In the year 2005, Gao et al.[55] proposed carbazole unit as
a promising building-block for high Seebeck coefficients.
Because according to their band structure calculation, oxidation
was expected to firstly occur on nitrogen atom where electron
cloud was more localized. Thereafter, poly(2,7-carbazole), poly-
indolocarbazole and a series of their derivatives were designed,
synthesized and doped.[56] Regretfully, electrical conductivities
of these soluble polymers were below 1.0 S cm−1 except for
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poly(2,7-carbazole-alt-bithiophene)s. By introducing a benzothi-
adiazole unit between the carbazole and bithiophene units, the
PF value was optimized to be 19 µW m−1K−2.[57] Similarly, Xu
et al. synthesized a series of polymers with monomers com-
posed of units including carbazole, thiophene, thieno[3,2-b]thio-
phene (TT), EDOT, and 3,4-ethylenedithiathiophene (EDTT) by
electrochemical polymerization or solid-state polymerization.[58]
The best performance around 1.0 µW m−1K−2 was obtained in
poly(thieno[3,2-b]thiophene).[58b]
In addition to molecular structures of the backbones, side
substitutes and counterion species are also reported to affect
thermoelectric properties significantly. Shinohara et al. com-
pared thermoelectric property of electrochemically polymer-
ized polythiophene, poly(3-hexylthiophene), poly(3-octylthio-
phene) and poly(3-dodecylthiophene), and found that PF values
decreased with increasing length of side chains.[39,59] Zhu et al.
found that PF values of P3HT: TFSI and PBTTT: TFSI (TFSI− =
triflimide anion, inset in Figure 6f) were roughly ten times that
of P3HT: PF6 and PBTTT: PF6 respectively (Figure 6).[35,43,60]
Meanwhile, stability of the polymers against moisture and heat
was obviously improved. Besides, Park prepared heavily-doped
PA samples with iodine complexes, FeCl4−, ZrCl4-, MoCl5-,
NbCl5- as counterions and found different temperature depend-
ence of Seebeck coefficients assumingly caused by different
scattering effects from counterions.[28]
In summary, much more extensive research is required to
generalize the effect of chemical structures of polymers (both
backbones and side substitutes) and counterions on the ther-
moelectric properties. At the moment, it seems that once decent
carrier mobility is insured by crafting polymer structures for
appropriate molecular stacking and materials microstructures,
polymer backbones with relatively localized distribution of elec-
tron cloud are preferred for higher Seebeck coefficients.[57,60b]
2.2. Thermoelectric Generators Based on Coordination Polymers
Coordination polymers (CPs) are polymers constructed from
metal ions and ligands, with metal ions acting as connectors
and ligands as linkers. CPs can also be regarded as polymers
whose repeat units are coordination complexes. Since the
1960s, CPs have been widely studied in chirality, luminescence,
non-linear optics, electrical conductivity, magnetism, catalysis,
molecular storage, etc.[61] However, the research on thermoelec-
tric and related properties is very limited, much less than that
on traditional conjugated polymers.[62]
In 1979, D’Sa et al. prepared a series of CPs based on
4,4′-dihydroxy-3,3′-diacetyl biphenyl bis-thiosemicarbazone
(L-1) and 4,4′-dihydroxy-3,3′-dipropionyl biphenyl bis-thiosem-
icarbazone (L-2),[63] as shown in Figure 8a. The electrical con-
ductivity of Cu(L-1) was around 10−5 S cm−1. Its Seebeck coef-
ficient was positive with values around 1.1 – 1.2 mV K−1 in the
temperature range of 310 - 450 K, indicating that Cu(L-1) was
a p-type semiconductor. Then Patel[64] found that the Seebeck
coefficient of the polymer barely changed in the given tem-
perature range, implying a hopping mechanism for charge car-
riers in the material. A second type of CPs of interest is based
on bisphenolic ligands, and the general formula are given in
Figure 8b. Electrical conductivities of these polymers were rather
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Figure 8. Chemical structures of (a) Cu(L-1), Cu(L-2), M = Cu(II), Co(II), Ni(II), R = CH3, C2H5;
(b) bisphenolic CPs; (c) PSF-Cs; (d) poly[Ax(M-ett)].
low (<10−7 S cm−1) and Seebeck coefficients were positive.[65] In
another case, Rusu et al. prepared modified polysulfones (PSF-
Cs) from chloro-terminated polysulfones and bis (2,4-dihy-
droxybenzaldehyde) Cu2+ (Figure 8c), and found that electrical
conductivities of this material were below 10−7 S cm−1. Fur-
thermore, the Seebeck coefficients were around 50–200 µV K−1
and decreased obviously with increasing temperatures, indi-
cating that the polymers were p-type semiconductors.[66]
In the year 2012, the Zhu’s group reported an inspiring
result, showing that CPs could be promising thermoelectric
materials. As shown in Figure 8d, they prepared a series of
CPs poly[Ax(M-ett)] with 1,1,2,2-ethenetetrathiolate (ett) as the
linking bridge, where A is the counter cation including tetrade-
cyltrimethyl ammonium, tetrabutyl ammonium, Na+, K+, Ni2+
and Cu2+ while M is the coordination metallic ion of Ni or Cu.
Furthermore, thermoelectric properties of the CPs were charac-
terized and an “all-organic” TEG device was fabricated based on
the as-prepared polymers, as is shown in Figure 9.[19]
It should be noted that research on CPs with structures
similar to poly[Ax(M-ett)] started about 30 years ago. Despite of
numerous reports on synthesis, structure analysis, and char-
acterizations of electrical and magnetic properties,[67] thermo-
electric properties of poly[Ax(M-ett)] were seldom studied. In
their work, Zhu et al. found that thermoelectric properties of
poly[Ax(M-ett)] containing Na+ and K+ were much better than
those of polymers with tetraalkylammonium as counter cat-
ions. It was suggested that close packing of polymer chains
were blocked by the alkyl groups of tetraalkylammonium and
thus interchain charge transport was impeded. In particular,
the polymer Poly[Kx(Ni-ett)] showed remarkable performance:
the electrical conductivity was as high as 63 S cm−1 at 440 K, the
Seebeck coefficients were in the range of -50 to -200 µV K−1
and increased with temperature, and the thermal conductivity
was as low as 0.15 W m−1 K−1. As a result, the ZT values of
poly[Nax(Ni-ett)] and poly[Kx(Ni-ett)] were 0.1 and 0.2 at
400 K respectively, with the latter being the most efficient n-type
organic thermoelectric material. Furthermore, the sign of See-
beck coefficient was tunable via metal ions, e.g., the sign was
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negative for poly[Nax(Ni-ett)] and poly[Kx(Ni-
ett)] while was positive for poly[Cux(Cu-ett)].
Regretfully, these poly[Ax(Ni-ett)] mate-
rials were prepared as powders and were
barely soluble in any solvents. Thereafter, a
modified synthesis scheme was reported by
Faulmann et al., whereby smaller and soluble
nanoparticles of CPs based on the ett ligand
were obtained.[68] Recently, the Zhu’s group
successfully fabricated a flexible thermoelec-
tric device by printing with solution com-
posite of the poly[Ax(M-ett)] powders.[69] The
powders of poly[Kx(Ni-ett)] and poly[Cux(Cu-
ett)] were ball-milled with polyvinylidene flu-
oride (PVDF) pre-dissolved in DMSO. There-
after the solution of the composites was fed
into an ink-jet printer that delivered a proper
TEG device on polyethylene terephthalate
(PET) substrates.
2.3. Prospects of Thermoelectric Materials Based
on Conductive Polymers
As aforementioned, the past few years have witnessed exciting
progress in thermoelectricity based on conductive polymers,
including materials, devices and theoretical works.[18,25,49,70]
However, research in this area is still in its infancy and exten-
sive efforts are needed to understand and utilize thermoelectric
properties of conductive polymers.
Materials Screening: Conductive polymers can be viewed as
a complex system with hierarchical structures, from chemical
structures on the molecular level, to polymer chains with var-
ious conformations and assemblies on the nano-scale, to the
material microstructures on the micron scale and above. Addi-
tional freedom is endowed with doping that modifies mate-
rials properties (i.e. strength, density, heat capacity, etc.) and
electronic structures. To achieve efficient screening of material
candidates and establishment of structure-property relation-
ships, it is indispensible to discriminate the dominant factors
from all the experimental freedoms. One possible route is to
synthesize crystalline conductive polymers where comprehen-
sive information of polymer chains, counterions, and crystal-
lites can be clearly characterized. Another promising method
is to exert modulations over transistors with traditional, electro-
chemical and novel geometries. Finally, it is desired to combine
synthesis, structure characterizations and thermoelectric meas-
urements coherently.
Seebeck Coefficients: Seebeck coefficient (thermopower) is
both simple and complex. It is simple because thermopower
is insensitive to energy-independent scattering like that arising
from most boundaries in materials. On the other hand, ther-
mopower is fundamentally related with entropy of charge car-
riers, including configuration entropy determined by energy
levels that hold the charges and migration entropy when
charges transport. Additional source of entropy is from the
spin freedom of charge carriers, e.g., d-electrons of transition
metals in CPs and unpaired polarons in conjugated polymers.
In this respect, origins of thermopower in conductive polymers
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Figure 9. Structure and performance of the thermoelectric device prepared with coordination polymers poly[Ax(M-ett)]. Reproduced with permission.[19]
should be clarified, preferably in a quantitative manner. Quali-
tative information may be obtained from characterizations like
UV-vis NIR absorption, ESR, IR and Raman spectroscopies, as
well as temperature-dependent measurement of electrical and
magnetic properties.
Thermal and Electrical Conductivity: Thermal conduction
properties of conductive polymers are much less studied com-
pared with electrical properties. Given the significant impact of
thermal conductivity on ZT values, more attention should be
paid to thermal conduction properties of polymers, such as the
dependence of thermal conductivity on counterions and doping
levels, thermal anisotropy in polymer films, and novel effects
specific to interfaces. Furthermore, it may be interesting to find
possible correlations between thermal physical properties and
Seebeck coefficients of thermoelectric polymers. As to electrical
conduction, direct characterizations of carrier concentrations
and carrier mobilities are desired, and simultaneous measure-
ment of Seebeck coefficients would be valuable. Given the noto-
rious difficulty of Hall measurement on polymers, the tran-
sistor strategy may be more feasible.
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Processing and Devices: Thermoelectric devices based on con-
ductive polymers are substantial to the development of the
overall organic thermoelectric field. Current status of thermoe-
lectric devices based on conductive polymers will be summarized
along with the devices based on small molecules in Section 5.
In the long run, clever design and synthesis of thermoelec-
tric building-blocks, stability of conductive polymers at opti-
mized doping levels, high performance n-type thermoelec-
tric polymers, and novel design of thermoelectric devices are
envisioned.
3. Organic Thermoelectric Materials Based
on Small Molecules
Currently research on thermoelectric materials based on small
molecules is lagging behind that of polymers. However, small
molecular thermoelectric materials are very attractive in that
small molecules are easier to be purified and crystallized.
Besides, it may be more feasible to achieve n-type conduction
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Figure 10. Chemical structures of some small molecules studied as
organic thermoelectric materials.
in small molecules. In the following two types of small mole-
cules, namely charge transfer complexes and molecular semi-
conductors, are discussed as potential thermoelectric materials.
3.1. Charge Transfer Complexes
3.1.1. TTF-TCNQ
In parallel with conductive polymers, charge transfer complexes
or radical cation salts are another type of highly conducting
organic material, as shown in Figure 10. Most of these materials
are prepared based on derivatives of tetrathiafulvalenes (TTFs),
which have attracted great research interests in the 80s and 90s
of the last century for the development of organic supercon-
ductors.[71] In the well-known organic conductor TTF-TCNQ, a
charge transfer complex is formed between electron donor TTF
and electron acceptor tetracyanoquinodimethane (TCNQ) with
donor and acceptor molecules stacking into one-dimensional
columns separately. There are strong intermolecular electronic
couplings between adjacent molecules along the stacks which
serve as the transport path for charge carriers; whereas the cou-
pling between neighboring columns is negligibly small. This
material displays quasi-one-dimensional characters in struc-
tures and electronic properties. Recently, conducting charge
transfer complexes have found applications in the study of
organic FET as solution-processable electrodes.[72] Thermoelec-
tric properties of these materials also attract some attention due
to their intrinsically high electrical conductivities.
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In fact, theoretical simulations showed that the ZT value could
be very high (∼20) in such low-dimensional conducting sys-
tems.[73] This unusually high value of ZT was obtained based on
the assumption that two types of electron-phonon interactions
exist simultaneously in this quasi-one-dimensional system. One
of the interactions is related to fluctuation in transfer energy of
the conduction electrons from one molecule to the neighboring
one, and the other is fluctuation in polarization energy of mole-
cules surrounding the conduction electrons. Under specific con-
ditions the interference between these two interactions could
occur, resulting in the significant enhancement of conductivity
and thermopower simultaneously. However, experimental
results are far below this theoretical prediction.
Although electrical conductivities are relatively high in such
charge transfer complexes, thermopower values are always quite
low. For TTF-TCNQ single crystals, the reported conductivities
at room temperature were in the range of 300–500 S cm−1 with
a thermopower of about -28 µV K−1.[74] Such small thermopower
was suggested to be caused by co-existence of n- and p- chan-
nels, leading to compensation in thermopower from electrons
and holes. The thermal conductivity of TTF-TCNQ crystals at
300 K was dominated by the phonon part as it was experimen-
tally determined to be 1 W m−1K–1.[75] Therefore, a calculated ZT
value of 0.7 – 1.1 × 10−2 at 300 K could be obtained for TTF-
TCNQ crystals based on those reported parameters.
Due to the tiny size and weak mechanical strength of TTF-
TCNQ crystals, thermoelectric measurements of the crystals
are difficult and the potential applications are doubtful. In
this respect, compressed powder samples or composites with
polymers are more convenient for characterizations and appli-
cations. However, G. Saito[76] found that the electrical conduc-
tivity of compressed TTF-TCNQ samples was decreased to
6.62 S cm−1, almost two orders of magnitudes lower than
that of the corresponding single crystals. Moreover, the tem-
perature dependence of conductivity displayed variable-range-
hopping (VRH) behavior, indicating that transport of charge
carriers was dominated by inter-particle hopping process.
The Seebeck coefficient was −18 µV K−1, comparable to that
observed in single crystals. The consistency in Seebeck coef-
ficients between single crystals and compressed powders con-
forms to the fact that Seebeck coefficient is barely affected by
grain boundaries, as in theory it is measured under open-cir-
cuit condition. The thermal conductivity was determined to be
0.34 W m−1K−1, one-third of that of the single crystals. The final
ZT value (1.83 × 10−4) was two orders of magnitudes lower
than that of the single crystals, mainly due to the reduction in
electrical conductivity.[76]
As a demonstration of employing organic materials for
future thin-film TEG devices on flexible substrates, J. Wüsten
et al. prepared a series of composites of poly(vinyl chloride)
(PVC) blended with graphite or charge transfer complexes.
Then a first thick-film prototype of TEG was built by screen
printing with the PVC composites as active materials. Due to
the low conductivity of these blend systems (typically in the
range of 0.1 – 10−3 S cm−1), the device performance was quite
low.[77] Recently, along with PEDOT: Tos as the p-type leg, the
TTF-TCNQ/PVC blend system was used as the n-type leg, ful-
filling the construction of a well-behaved TEG device through
ink-jet printing.[20]
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3.1.2. EDO-S,S-DMEDT-TTF
Another type of low-dimensional organic conductor worthy
of noting is τ-(EDO-S,S-DMEDT-TTF)2(AuBr2)1+y, (y ≤ 0.875),
where EDO-S,S-DMEDT-TTF is ethylenedioxy- S,S-dimethy-
lethylenedithio- tetrathiafulvalene, because this material dis-
plays large thermopower as a metallic organic conductor.
H. Yoshino et al. simultaneously determined the σ, S and
κ of a small crystal of τ-(EDO-S,S-DMEDT-TTF)2(AuBr2)1+y
(y < 0.875) with a homemade measurement apparatus. They
found that the conductivity of this material was as high as
200 S cm−1 at 300 K and observed temperature dependence
typical of metals down to 150 K; meanwhile, the thermopower
was −85 µV K−1 at 300 K and reached a maximum value of
about −140 µV K−1 between 120 and 140 K.[78] Thermal conduc-
tivity of the single crystal was 7 W m−1K−1 at 300 K, typical of
single-crystalline organic conductors. The calculated contribu-
tion from charge carrier to thermal conductivity was very small
(0.5–2 %) in the investigated temperature range. So the max-
imum ZT value of this crystal was determined to be 1.1 × 10−2
around 160 K, comparable to that of TTF-TCNQ crystals.
Furthermore, the origin of such large thermopower was ana-
lyzed by the authors based on ab initio band calculation and
calculation of Seebeck coefficient using Boltzmann’s equation.
It was found that the band structure of τ-(EDO-S,S-DMEDT-
TTF)2(AuBr2)2 was very peculiar, in that the band profile near
the Γ point was very flat but was highly dispersive around the
X and Y points. Such band structure was named as ‘‘inverted
pudding mold type band’’ on top of a ‘‘pudding mold type
band’’, justifying the coexistence of high conductivity and high
thermopower.[79] This work presents a possibility to search for
promising organic thermoelectric materials in organic conduc-
tors through theoretical calculations of band structures.
3.2. Small Molecular Semiconductors
In the past decade, large numbers of organic
semiconductors (OSCs) with charge car-
rier mobilities exceeding that of amorphous
silicon have been developed. For small mol-
ecules, mobilities as high as 31 cm2 V−1 s−1
and 11 cm2 V−1 s−1 have been achieved
respectively for solution-processed films
of p-type molecules and single crystals of
n-type molecules.[80] Such progress may pro-
vide new candidates for high-performance
organic thermoelectric (TE) materials, since
one of the main challenges in organic TE
materials is ascribed to the lower carrier
mobility of OSCs compared to their inor-
ganic counterparts.
3.2.1. Pentacene Films as P-Type TE Materials
As the benchmark of p-type OSCs, penta-
cene is the most studied small molecule Figure 11. Thermoelectric parameters of pentacene samples doped by (a) co-evaporation with
for TE applications up to date. A notable F4TCNQ and (b) forming pentacene/F4TCNQ bilayer structures. Adapted with permission.[82]
attribute of pentacene is its high mobility Copyright 2010, American Institute of Physics.
Adv. Mater. 2014, © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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up to 3 cm2 V−1 s−1 in thin film transistors.[81] Due to the low
REVIEW
carrier concentration of pentacene in neutral state, appro-
priate doping treatment is critical to the optimization of its TE
properties.
F4TCNQ is a strong electron acceptor that is frequently used
as a p-type dopant in organic electronics. In 2010, K. Harada
et al. reported the TE performance of thin films of pentacene
doped with F4TCNQ. The films were prepared by thermal
deposition, where blends of pentacene and F4TCNQ in single-
layer structure and pentacene/F4TCNQ bilayer structure were
compared.[82] In the case of the blended samples, the doping
level was varied from 0.5 to 10 mol.%. The electrical conduc-
tivities firstly increased with doping, but saturated and even
decreased at higher doping levels. In contrast, the field-effect
mobility decreased constantly with increase of dopant concen-
tration because of scattering from dopants. As a result, they
got a maximum electrical conductivity of 4.1 × 10−2 S cm−1
and a maximum PF of 0.16 µW m−1K−2 at doping level of
2.0 mol.% (Figure 11a). In the bilayer samples, the carriers
were supposed to be generated through charge transfer at the
pentacene/F4TCNQ interface, since the F4TCNQ layer was
merely 2-nm thick. Therefore, scattering from the dopant could
be minimized as much as possible. In fact, a conductivity of
0.43 S cm−1 was derived from the measured sheet conduct-
ance, ten times that of the blended samples. Furthermore,
when the thickness of the pentacene layer was varied, electrical
conductivity was optimized while the Seebeck coefficient was
unaffected (around 200 µV K−1). Finally, the maximum PF of
2.0 µW m−1K−2 was obtained in the 6-nm thick pentacene
sample (Figure 11b).
Iodine is another efficient dopant for pentacene. In 1991, T.
Minakata et al. found that vacuum-deposited pentacene thin
films could be doped with iodine vapor to realize conductivity
as high as 110 S cm−1. The formation of pentacene-iodine
charge transfer complex was proposed according to structure
and spectroscopic characterizations.[83] Recently, K. Hayashi
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Figure 12. Thickness dependence of (a) carrier concentration n, (b)
mobility µ, (c) electrical conductivity σ, and (d) Seebeck coefficient S
of the iodine-doped pentacene films grown at different substrate tem-
peratures (Tsub = RT or 80 °C). Reproduced with permission. Copyright
2011,[84] American Institute of Physics.
et al. employed the similar doping method to optimize TE per-
formance of pentacene thin films.[84] As shown in Figure 12,
they got a highest electrical conductivity of 60 S cm−1 with the
thermopower in the range of 40 – 60 µV K−1. As a result, the
highest PF could reach 13 µW m−1K−2 which was more than six
times that of pentacene/F4TCNQ bilayer sample. This improve-
ment was mainly due to the increase in electrical conductivity
by two orders of magnitudes. The smaller S value than that of
the F4TCNQ-doped samples was caused by higher carrier con-
centration in this case. The disadvantage of such iodine-doped
thin films of pentacene is the poor stability.[16] K. Hayashi
et al. demonstrated that the decay in PF due to iodine desorp-
tion could be suppressed by covering the initially doped film
with an insulating polyimide tape.[84]
3.2.2. Pentacene Films Investigated in FET Architectures
In addition to the aforementioned doping through charge
transfer at donor-acceptor interface, carrier concentration of
OSCs can be adjusted with gate voltages in transistor archi-
tectures at the semiconductor/dielectric interface, whereby the
thermopower can be modulated accordingly. In this context, TE
measurement is combined with FET modulation and has been
proved to be powerful in revealing transport mechanisms of
OSCs.
In 2007, based on their research into the dependence of ther-
mopower on gate voltages and temperatures in thin films of
pentacene, Mühlenen et al. proposed a mechanism to enhance
thermopower based on lattice hardening, originating from
substantial lattice vibrational entropy (3kB per carrier) in the
the presence of charge carriers.[85] Later on, by measuring the
temperature and carrier-density dependence of thermopower
of rubrene single crystals and pentacene thin films with FET
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architectures, Pernstich et al. found that the Seebeck coeffi-
cients were well within the range of electronic contribution typ-
ical of conventional inorganic semiconductors, implying high
similarity in charge transport mechanisms between organic
and inorganic semiconductors.[14b] Recently, Germs et al. deter-
mined the critical temperature of transition from hopping
transport to band-like transport in pentacene films, based on
detailed analysis on thermopower – temperature relationships
obtained with a similar measurement configuration.[14c]
Although the transistor geometry may be difficult to find
applications in practical organic TE modules, it can be a pow-
erful tool for efficient screening of high performance organic
TE materials from the latest developed OSCs.
3.2.3. Fullerene Films as N-Type TE Materials
Currently, most of the conductive polymers studied for TE
applications are p-type materials. Although high perfor-
mance n-type polymeric semiconductors have been developed
recently,[86] transport behaviors of n-type doped polymers are
rarely reported.[87] To meet the requirement of n-type organic
TE materials for the fabrication of TEG devices, molecular
OSCs such as C60 have attracted much attention.
According to the early work on C60-based materials, C60 can
be doped by alkali metals to achieve high conductivities and
even superconductors.[88] Seebeck coefficient measurements
were used to characterize the electronic structures of such
doped C60, e.g., thermopower of K and Rb-doped C60 were deter-
mined to be -11 and -18 µV K−1 at 300 K.[89] Given the low elec-
trical conductivity (below 100 S cm−1), PF values of these mate-
rials are expected to be no larger than 2 µW m−1K−2 at 300 K.
Further improvement in TE properties is reported by two
groups using nonstoichiometric doping of C60 with Cs2CO3
as the dopant. Therein either bilayer structure or single-
layer blend was fabricated by thermal evaporation, and the
achieved maximum PF values were respectively 20.5 and
28.8 µW m−1K−2.[17,90] The improvement in PF is mainly due
to the high thermopower up to around 200 µV K−1 with con-
ductivities of about 5 S cm−1. Similar results are reported in C60
samples doped with Cr2(hpp)4 or W2(hpp)4 (hpp = 1, 3, 4, 6, 7,
8-hexahydro- 2H-pyrimido [1, 2-a] pyrimidinato).[87a] These PF
values of doped films of C60 are comparable to that of P3HT
based p-type materials.[35]
3.3. Future Chances for Small Molecular Thermoelectric
Materials
Compared with conductive polymers, thermoelectric properties
of small molecules are relatively less explored and require fur-
ther investigations.
Charge Transfer Complexes: Considering their well-defined
crystal structures, charge transfer complexes are of special sig-
nificance in figuring out the relationship between material
structures and thermoelectric behaviors. In terms of TTFs-based
organic conductors, it is relatively difficult to adjust carrier con-
centrations because of the well-defined stoichiometries and struc-
tures. In this respect, A. Casian et al. analyzed the conducting
Adv. Mater. 2014,
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Figure 13. Schematic illustration of thermoelectric measurement architectures. (a) Four-contact method for measurement of electrical conductivity
and (b) measurement of Seebeck coefficient (ΔV/ΔT). (c) Two-contact method with smaller channel distances where linear regression is verified (d).
Adapted with permission.[18,20] Copyright 2011, 2013, Nature Publishing Group.
crystal of tetrathiotetracene-iodide (TTT2I3), and found that ZT
value up to 1.4 at 300 K could be obtained if the carrier concen-
tration was reduced by 2.5 times from the stoichiometry.[91] How-
ever, no nonstoichiometric crystal of TTTIx has been reported
up to date. Adjusting carrier concentration for such crystalline
materials may be realized by nonstoichiometric doping process.
Besides, a systematic screening is possibly helpful given the
large amounts of organic conductor crystals available.
Small Molecular Semiconductors: As the benchmark of molec-
ular OSCs, pentacene is highly promising as organic TE mate-
rials. Recently, Z. G. Shuai et al. performed first-principle band
structure calculations coupled with Boltzmann transport theory
to analyze thermoelectric properties of pentacene and rubrene
crystals.[92] The calculated thermopower and its dependence
on temperature and carrier density agreed well with those
experimental results reported by Pernstich et al.. According to
their calculations, peak ZT values in the range of 0.8 – 1.8 at
294 K and 1.1 - 2.4 at 248 K are predicted respectively for pen-
tacene and rubrene. Therefore, further research is expected for
more efficient and stable agents and methods of doping so as to
better utilize these small molecular semiconductors.
4. Thermoelectric Measurement Methods
for Organic Materials
Generally electrical conductivity, Seebeck coefficient, and
thermal conductivity are measured respectively, and thereafter
ZT is calculated from the three parameters. Therefore, errors
in each measurement could be superimposed. In the following
we summarize common measurement methods for organic
thermoelectric materials with representative examples of con-
jugated polymers especially those prepared as films. Possible
errors in each measurement method are underlined and the
measurement of thermal conductivity is highlighted. Brief
review on current status of thermoelectric measurement of
small molecular materials is made at the end of this section as
compared with that of polymers.
4.1. Measurement of Electrical Conductivity
Firstly, four-contact measurement is preferred to two-contact
methods because contact resistance can be excluded in the
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REVIEW
former. Second, four-probe measurement with mechanical
point contact or van-der Pauw layout should be used with
caution because organic materials are generally soft, inhomo-
geneous and potentially anisotropic. Third, work functions of
electrode materials should be examined to insure Ohm contact,
because Fermi levels of organic materials can vary with doping
levels. Currently patterned stripes of gold are most adopted as
electrodes for reliable measurement. In Figure 13 are shown
four- and two- contact architectures adopted in recent reports,
for which possible errors are latent in the sizes and inter-
distances of electrodes versus the samples’ geometries and
homogeneity.
4.2. Measurement of Seebeck Coefficients
Errors in measurement of Seebeck coefficients can cause broad
distribution in ZT values because the coefficient is squared. In
principle, Seebeck coefficient is derived by dividing the voltage
difference ΔV with its corresponding temperature difference ΔT
as shown in Figure 1 and Figure 13a, b. In experiments, how-
ever, it is nontrivial to accurately measure each parameter (ΔV
and ΔT) while making sure that they are precisely matched. So
far there have been several commercial devices available, e.g.,
the ZEM-3 system from ULVAC Tech. is suitable for bulk mate-
rials with dimensions of centimeters, and the SB-100 system
from MMR Tech. is more appropriate for smaller samples on
millimeter scales.[45] And yet homemade apparatuses are pre-
ferred when customized controls over the measurements are
imposed, such as field-effect gating[33] and light illumination.[53c]
In this case the measurement validity is verified either using a
reference whose Seebeck coefficient is well-known or by linear
regression of thermo-voltages obtained under different tem-
perature differences, as shown in Figure 13d. Moreover, elec-
trical conductivity can be obtained with the same measurement
set-up (Figure 13a–c).
4.3. Measurement of Thermal Conductivity
Basically there are two types of measurement methods for
thermal conductivity, namely the steady-state measurement and
the transient-state measurement. The former was previously
used to measure in-plane thermal conductivity of 100-µm-thick
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free-standing films of PA at room temperature.[26a] It was found

REVIEW

With this manner, Toshima et al. investigated thermal property

that thermal conductivity of trans-isomer PA was higher than
its cis-isomer, i.e. 0.38 W m−1K−1 versus 0.21 W m−1K−1, which
was further increased to 0.69 W m−1K−1 after heavy doping
with iodine (Table 1). The steady-state method is very time-con-
suming and is seldom used today.
Compared with the steady-state method, transient-state
methods are much more efficient and are well-developed.
Nowadays, thermal conduction properties of both bulk and
film materials can be characterized with transient methods.
Herein three most widely adopted methods, namely laser-
flash, time domain thermal reflectance (TDTR) and differential
three-omega (3ω) are summarized and compared. As such, it
should be noted that although in-plane thermal conductivity
of PA films was obtained with the steady-state strategy,[26a] it is
difficult to be determined using most transient-state methods
mainly because of the measurement principles. Specifically,
only cross-plane thermal conductivity is available using laser-
flash and TDTR methods, while both cross-plane and in-plane
thermal conductivities can be obtained with 3ω method.
Laser-flash method measures thermal conductivity indirectly.
Typically, disk samples with thickness of microns are irradi-
ated with a laser pulse on the surface, and thermal diffusivity is
experimentally extracted. Thereafter thermal conductivity is cal-
culated according to the formula κ = ραCp, where ρ is material
density, Cp is specific heat capacity, and α is thermal diffusivity.
(thermal diffusivity, thermal conductivity and their temperature
dependence) of PANi with different counterions; however, no
systematic results were generalized.[26c,93] Similar to the laser-
flash scenario, sample surfaces are also exposed to a laser pulse
in the TDTR approach. A special attribute of this method is its
high spatial resolution, facilitating measurement of crystalline
polymer fibers with diameter of ten microns.[27e] There are also
commercial apparatuses available for immediate measurement
of thermal conductivity utilizing modified plane source of heat
instead of laser heating.[19] The cross-plane thermal conductivi-
ties obtained with laser-flash or TDTR methods reported in the
cited references are listed in Table 1.
Owing to its convenience, high accuracy and in-plane meas-
urement capability, 3-ω method has been widely adopted
for films of conductive polymers in the past few years. For
example, thermal conductivities of films of PEDOT: Tos and
PEDOT: PSS were characterized with 3-ω method by different
groups,[18,20] as listed in Table 1. The measurement principles
are shown in Figure 14. Firstly metallic heaters are deposited
onto the polymer surface which has been protected in advance
to insure electrical insulation. Then thermal conduction is
induced by passing electrical current (at frequency ω) through
the metallic stripes (heat generators). As a result of the current,
joule heating at frequency 2ω is produced and temperature of
the heaters is also modulated at frequency 2ω, leading to a 3ω

Figure 14. Device architectures for the measurement of (a), (d) one-dimensional (1D) and (b), (e) 1D and 2D cross-plane heat conduction in films of
(a)-(c) PEDOT: Tos and (d)-(f) PEDOT: PSS. In-plane thermal conductivity λ||(or κ||) is derived from 1D cross-plane thermal conductivity λ⊥(or κ⊥) and
anisotropy ratio λ⊥/λ|| (c), (f). Adapted with permission.[18,20] Copyright 2011, 2013, Nature Publishing Group.

18 wileyonlinelibrary.com © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2014,
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component in the voltage across the heater. Then thermal con-
ductivity across the polymer film can be analytically extrapo-
lated from the ω and 3ω voltages at the low-frequency limit.
Experimentally the same heaters are fabricated on the under-
lying substrates to exclude thermal contribution of the sub-
strates (Figure 14a, d).
To get in-plane thermal conductivity, a second narrower
heater is patterned on the sample surface (Figure 14b, e), that
is there are two heaters in total on the polymer films. Also the
same pair of heaters should be patterned on the underlying sub-
strates to eliminate the substrate effect. The wide and narrow
heaters are utilized to respectively induce one-dimensional (1D)
and two-dimensional (2D) heat conduction in the polymer film.
Moreover, the width of the narrow heater (w) and the thickness
of the polymer film (d) are varied to generate several geometry
ratios (w/d). Then by means of the geometry ratio and the cor-
responding 2D/1D thermal conduction ratio, the ratio between
cross-plane and in-plane thermal conductivities (λ⊥/λ|| or κ⊥/κ||
in Figure 14c, f) can be extracted with formulae in a mathemat-
ical way.
Following the procedures described above, both cross-plane
and in-plane thermal conductivities of PEDOT films were
measured and reported recently.[18,20] The measurement set-ups
are shown in Figure 14 and the results are included in Table 1.
Obviously, in-plane thermal conductivities are higher than the
corresponding cross-plane values, indicating strong anisotropy
in thermal conduction property of PEDOT films. In specific, the
in-plane/cross-plane ratio (λ||/λ⊥) is respectively 1.11 and 1.62
(1.40) for PEDOT: Tos film and PEDOT: PSS films treated with
EG (DMSO). However, it should be noted that repeated spin-
coating was used to prepare the thick films for in-plane meas-
urement of PEDOT: PSS, and anisotropy in thermal conduc-
tivity of conductive polymer films needs further investigations.
Recently, Haque et al. developed a modified 3-ω method
whereby they were able to measure in-plane thermal con-
ductivity directly, and electrical conductivity was obtained at
the same time.[27a,94] With this technique, they studied PANi
films with thickness ranging from 20 nm to one micron, and
observed significant reduction in thermal conductivity when
the film thickness was below 50 nm.[95] Since film processing
is probably the dominant technology for future applications of
organic thermoelectric materials, the effects of interfaces and
sizes on thermal conduction deserve more attention.
4.4. Thermoelectric Measurement of Small Molecular Materials
Thermoelectric measurement of small molecular materials is
somewhat different from their polymer counterparts, in part
because of features specific to the materials and in part because
transistor modulation is often incorporated in previous reports.
More extensive investigations into the corresponding measure-
ments are required for future development of small molecular
candidates for thermoelectrics.
As aforementioned, crystals of charge transfer complexes
are generally tiny and brittle, and hence measurement of single
crystals requires delicate apparatuses as well as much exper-
tise.[78] For convenience compressed pellets can be prepared
from these crystals and the resultant bulks are expected to show
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REVIEW
comparable Seebeck coefficients but much lower electrical and
thermal conductivities.[75,76]
In contrast to charge transfer complexes and conductive
polymers, small molecular semiconductors are often pro-
cessed with vacuum thermal evaporation. The resultant films
are expected to be thinner, more electrical resistant, and insep-
arable from the substrates. As such, most of the thermoelec-
tric measurements of molecular semiconductors are accom-
plished with architectures similar to that shown in Figure 11.
Therefore, the measurement configurations and general prin-
ciples are in line with that of conductive polymers (Figure 13)
as clarified in previous sub-sections. However, thermal con-
ductivity of the molecular films is barely studied due to the
small thickness of evaporated films. Recently, by means of
traditional 3-ω method, Jin et al. determined the cross-plane
thermal conductivity of multilayer thin films of copper phth-
alocyanine (CuPc) and Ag or Al. As the density of CuPc/Ag
(Al) interface was increased, large thermal boundary resist-
ance was observed.[96]
5. Fabrication of TEG Based on Organic
Thermoelectric Materials and Extended
Applications
The fabrication of TEG based on organic thermoelectric mate-
rials is an integral part of this field. In the respect of funda-
mental researches, characterizations of organic materials with
TEG devices help to clarify the structure-property relationships.
From the application point of view, solution-processability of
organic materials makes it possible to produce TEG devices
with printing technologies. In addition, novel designs of
device architectures are necessary to exert the full potential of
organic materials while circumventing their disadvantages.[70a]
For example, further enhancement of thermoelectric perfor-
mance can be brought by engineering the interfaces in TEG
devices.[73,97]
To begin with, the most straightforward approach is to repro-
duce the configuration of inorganic TEG. Based on compressed
pellets of powders of poly[Kx(Ni-ett)] and poly[Cux(Cu-ett)], Zhu
et al. fabricated a TEG device composed of 35 p-n couples with
leg dimensions of 5 mm in height and 2 mm × 0.9 mm in
cross-section.[19] Under a temperature difference ΔT = 80 K, an
open-circuit voltage of 0.26 V, a short-circuit current of 10.1 mA
were generated by the device. Assuming the optimum packing
density of 0.94, the output power per area was extrapolated
to be 2.8 µW cm−2 under a ΔT = 30 K (Figure 9). This is the
highest power density ever reported for TEG using all-organic
materials.
Another type of TEG device was demonstrated by Crispin
et al. by means of ink-jet printing. The p-type ink was a mixture
of the monomer EDOT with the oxidant solution containing
polymerization inhibitor; while for n-type ink the crystalline
powders of TTF-TCNQ were blended with PVC in toluene.[20]
The extrapolated output of the TEG consisting of 54 thermo-
couples (leg dimensions: 30 µm in height and 25 mm × 25 mm
in cross-section) was 0.27 µW cm−2 at optimum packing density
and ΔT = 30 K (Figure 15a, b).
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Figure 15. (a) Fabrication of an all-organic TEG consisting of 54 modules through photolithography patterning and ink-jet printing. (b) Maximum
power output per area of the TEG with packing density of 0.47 (solid line) and 0.94 (dashed line). Reproduced with permission.[20] Copyright 2011,
Nature Publishing Group. (c) Four-terminal prototype TEG fabricated by thermal deposition of pentacene (p-leg) and C60 (n-leg). Reproduced with
permission.[17] Copyright 2011, American Insititute of Physics. (d) Film-based TEG employing only one type of thermoelectric material processed by
roll-to-roll printing. (e) The final rolled-up device and heat-flow direction therein. Reproduced with permission.[70a]

A prototype TEG based on small molecules fabricated by
thermal deposition is reported by Sumino et al. (Figure 15c),
using F4TCNQ-covered pentacene and Cs2CO3-covered C60
as p-type and n-type legs respectively.[17] This is a device with
thin-film architecture; however, no effective output is generated
owing to large internal resistance.
Very recently Krebs et al. have performed a proof-of-prin-
ciple research by applying large-area roll-to-roll (R2R) printing
to produce TEG with p-type materials PEDOT: PSS only.[70a] A
total of 18,000 serially connected junctions of silver/PEDOT:
PSS (1.2 µm)/silver were stacked on a 60-µm thick PET foil,
which was then divided into smaller stretches and rolled up on
an aluminum cylinder (Figure 15d, e). This novel structure was
developed for R2R processing while eliminating the require-
ment of both p- and n-type materials simultaneously. Although
the device output power is too low (on the pW scale) to be prac-
tical, it shows the possibility to produce flexible TEG with poly-
mers at very low cost.
In summary, the fabrication of well-performed flexible
organic TEG devices is as challenging as it is attractive. In addi-
tion to the numerous technological issues to be addressed,
supply of organic thermoelectric materials with much higher
ZT values are decisive. Furthermore, it should be noted that
thermoelectric properties of the materials prepared as inks are
probably different from their pristine properties. At present
several methods to deliver inks are available, including solu-
tion mixtures containing monomers,[20] solution composites
impregnated with organic powders,[20,68] polymer emulsions
similar to PEDOT: PSS solutions,[33,70a] and soluble polymers to
be doped afterwards.
In addition to printing technologies and vacuum depositions,
other strategies like electrochemical deposition and massive
assembly of nano-sized building-blocks could be useful under
different circumstances.[98] Besides, it is interesting to combine
organic thermoelectric devices with other electronic or optoe-
lectric devices as is currently studied in the inorganic counter-
parts.[99] Last but not the least, organic thermoelectric materials
can be used in sensors based on Seebeck effect for the detec-
tion of heat, light, bio(chemical) agents and so on.[29,100]
6. Conclusions and Outlook
In the past several years the research on organic thermoelec-
tric materials has made remarkable progresses. ZT values
of 0.42 (p-type) and 0.20 (n-type) have been demonstrated,
respectively, in PEDOT: PSS and coordination polymers
poly[Kx(Ni-ett)], which are comparable to those of inorganic
nanomaterials employed to generate thermoelectricity from
window glasses.[101] Moreover, all-organic TEG devices fabri-
cated by printing technologies have been demonstrated with
screen-printing, ink-jet printing and R2R printing as well.
In the quest for green energy sources from organic TEG
devices, more efficient organic thermoelectric materials and
n-type organic candidates should be developed, and novel
design and engineering of organic thermoelectric devices
are expected. Furthermore, fundamental understanding
of the structure-property relationships of various types of
organic thermoelectric materials is valuable. The research in
organic thermoelectrics is an emerging and promising field

20 wileyonlinelibrary.com © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2014,
DOI: 10.1002/adma.201305371

www.MaterialsViews.com
waiting for cooperation of scientists and engineers from all
backgrounds.
Acknowledgements
Financial support from the Ministry of Science and Technology of China
(project number: 2013CB632506) and the Chinese Academy of Sciences
are gratefully acknowledged.
Received: October 29, 2013
Revised: February 11, 2014
Published online:
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