Perspective

Cite This: Chem. Mater. 2017, 29, 10248−10283 pubs.acs.org/cm

Polythiophene: From Fundamental Perspectives to Applications

Thaneshwor P. Kaloni,*,† Patrick K. Giesbrecht,‡ Georg Schreckenbach,*,† and Michael S. Freund*,‡
†
Department of Chemistry, University of Manitoba, Winnipeg, MB R3T 2N2, Canada
‡
Department of Chemistry, Florida Institute of Technology, Melbourne, Florida 32901, United States

ABSTRACT: The field of organic electronics has been heavily

impacted by the discovery and development of π-conjugated
conducting polymers. These polymers show great potential for
integration into future optical and electronic devices due to
their capacity to transition between semiconducting and
conducting states as well as the ability to alter mechanical
properties by controlled doping, chemical modification, and
stacking or creating composites with other materials. Among
π-conjugated polymers, polythiophene and its derivatives has
been one of the most extensively studied and is widely
investigated computationally and experimentally for use in
electronic devices such as light-emitting diodes, water
purification devices, hydrogen storage, and biosensors. Various
theoretical modeling studies of polythiophene ranging from an oligothiophene approach to infinite chain lengths (periodic
boundary conditions) have been undertaken to study a variety of electronic and structural properties of these polymers. In this
review, we discuss the recent advances in the understanding of pristine polythiophene and its derivatives from fundamental
perspectives to device applications.

1. INTRODUCTION constituting the π-conjugated polymer can greatly alter the

1.1. Conjugated Polymers. Since the discovery of
polyacetylene by Heeger, MacDairmid, and Sherikawa in
1976,1 a new and emerging class of materials, π-conjugated
conducting organic polymers, has intrigued scientists with their
unique physical and chemical properties. Given the π-
conjugation arising from the alternating single and double
carbon−carbon bonds within the polymer backbone, the π-
electrons are effectively delocalized along the polymer chain,
leading to one unpaired π-electron per carbon atom2−13 and
allowing for charge transport along the polymer chain, and as a
consequence, they display conducting or semiconducting
behavior.14−28 As such, there is great interest toward their
application in electronic and optical semiconducting devi-
ces1,29−39 where the electronic properties of such polymers can
be engineered easily either through doping or chemical
modification.13,40−44
The process of doping induces charge transfer to/from the
conjugated backbone, leaving the system p/n-type doped32,45,46
and changing the polymer electrical properties and thus the
electrochemical potential. Doping can be achieved chemically,
electrochemically, or in the presence of an external electric field,
as discussed in various two-dimensional (2D) materials.47−52
The electronic and optical properties of π-conjugated polymers
can be tuned widely through doping, providing a transition
from insulator to semiconductor to metal based on the dopant
concentration.41,53−56 This paves the way for application of π-
conjugated polymer in transistors, photoresistors, light-emitting
diodes, solid-state lasers, biosensors, and organic solar cells57−67
and sensors.67−80 As such, the selection of the monomer
electronic and optical properties therein. Typical candidates
utilized include acetylene, pyrrole, aniline, and thiophene.3−5
Moreover, it has been suggested that polyselenophene,
polytellurophene, poly(1H-phosphole), and poly(1H-arsole)
can also be developed based on binding energy calcula-
tions,81−87 thereby allowing a wide range of semiconducting
organic materials to be developed.
1.2. Polythiophene and Its Derivatives. Polythiophene
and its derivatives are of great interest in device applica-
tions88−94 due to the high stability of its (un)doped states, ease
of structural modification, and solution processability.95,96 As
such, polythiophene has been extensively studied using
theoretical and experimental approaches.26,97−120 Several
studies on the electronic structure of thiophenes using first-
principles calculations were conducted to elucidate the role
side-chain groups and dopants have on the overall electronic
properties of the polymeric material, where the band gap can be
altered from 3 to 1 eV based on dopant level or side-chain
group employed.121−128 Furthermore, by altering the morphol-
ogy and thus the geometry of the oligomer chains, the band gap
and optical properties of polythiophene-based films can
drastically be altered.127,129−140
In theoretical modeling, the approximation called the
periodic boundary conditions seems to be a sufficient method
with few limitations in its capacity to calculate the band gap in
Received: July 19, 2017
Revised: November 28, 2017
Published: December 12, 2017

© 2017 American Chemical Society 10248 DOI: 10.1021/acs.chemmater.7b03035

Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

relation to experimental values.141,142 There have been only a three decades. Thus, in this review, we focused on the current
few theoretical reports for doped oligothiophene where the developments in pristine polythiophene and its derivatives from
dopants are not covalently bound to oligothio- fundamental perspectives to device applications.
phene.102,103,125,143 Extensive first-principles calculations were
performed to investigate the charge redistribution in Li-doped 2. GEOMETRY AND ELECTRONIC STRUCTURE OF
polyacetylene,144 where it was suggested that a large enhance- POLYTHIOPHENE
ment of the conductivity can be achieved by electron or hole 2.1. Structural Analysis. The structural and electronic
doping.1,145−149 Density functional theory (DFT)-based properties of pristine and doped polythiophene have been
calculations with and without a hybrid functional for Cl or extensively studied.88,102,121,168,169 The structure for the
Cl2 doped polypyrrole150−152 indicated that a hybrid functional monolayer polythiophene using DFT is depicted in Figure
is better at producing the experimental band gap, while the 1a, where the periodic supercell contains 16 C, 8 H, and 4 S
electronic structures of polythiophene-based devices are still
not well-understood. For doped polythiophene, the main
charge carriers are bipolarons or polaron pairs, where the pairs
of the polarons are well-separated by radical cations.153
Moreover, the bipolarons are found to be localized over a
certain portion of the polythiophene chain, while polaron pairs
are found to be well-separated by a nearly undistorted portion
of the polythiophene chain.153−155
Due to various experimental limitations, synthesis and
structural properties of π-conjugated oligomers or polymers
are difficult to understand.155,156 This is also the case for the
theoretical calculations because of the various levels of
theoretical aspects, including the choice of DFT functional
(model chemistry) and, crucially, the choice of a simplified
model for complex experimental situations.125,141,157 It was
proposed that dopants can have a major influence on the
electronic properties, in particular the formation of polarons or
bipolarons in the π-conjugated polymers, which was demon-
strated in experimental findings.149 Recently, the structural and
electronic properties of doped polythiophene were extensively
analyzed for various lengths of the unit cells such as for more
than 10 thiophene rings.96 It has also been proposed that doped
polythiophene can serve as a model for π-conjugated polymers
in general, with its properties applied to other doped π-
conducting polymers.141 Figure 1. Optimized geometry (periodic calculations) of polythio-
The effect of Li or Cl doping on the structural and electronic phene for (a) pristine, (b) Li-doped, and (c) Cl-doped, where the
properties of polythiophene in various stacking geometries green, yellow, cyan, brown, and pink spheres represent S, C, H, Li, and
either in periodic or oligomer forms was studied recently in the Cl atoms, respectively. Adapted with permission from ref 102.
Copyright 2015 American Chemical Society.
framework of first-principles DFT-based model calculations. In
particular, the structural and electronic properties of the
periodic pristine monolayer polythiophene, bilayer polythio-
phene with normal stacking and flipped by 180°, and Li and Cl atoms (i.e., four monomer units), while Figures 1b and c
adsorption/intercalation were investigated.102 The obtained represent the corresponding Li- and Cl-doped polythiophene
result demonstrates that the electronic structure can easily be monolayer. The calculated structural parameters (bond length
tuned and controlled either by adsorption/intercalation or by and angles) were found to be in good agreement with reported
creating multilayers in bulk or bilayer stacking sequences. experimental and theoretical values.88,168,170 Upon doping, the
1.3. Scope and Goals of the Current Review. Due to Li atoms are located above the center of the pentagon, donating
their great capability to be integrated as light-absorbing their fraction of the electrons to the aromatic backbone of the
materials in organic electronic devices, polythiophenes have thiophene unit. In contrast, the Cl atom moves away from the
been the subject of interest for many researchers over the last polythiophene surface due to the electron density along the
three and a half decades. One of the most exciting properties of thiophene backbone.102 No deviation from the planar structure
these materials is the electrical conductivity resulting from the of the pristine monolayer of polythiophene was observed upon
delocalization of electrons along the polymer backbone. doping.
However, the electrical conductivity is not the only interesting The bulk and bilayer polythiophene have also been calculated
property resulting from electron delocalization, but also the (Figure 2), where the interlayer spacing amounts to 3.372 or
optical responses of these materials with dramatic color shifts in 3.371 Å for pristine bulk (periodic stacking of the bilayer) or
response to changes in solvent, temperature, applied potential, bilayer polythiophene, respectively. Only small deviations from
and binding to other molecules. Many interesting and the linear structure of its monolayer counterpart were observed
comprehensive review articles have been published on in the pristine bilayer structure. Introduction of Li, intercalated
polythiophene-based materials, dating from 1981 to into the bilayer (Figure 2b), resulted in a more planar structure,
2010.96,158−167 These reviews are an excellent guide to the with the Li atoms residing in the center of the bilayer and with
highlights of the primary polythiophene literature from the last slightly larger interlayer spacing (3.653−3.881 Å).
10249 DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 2. Top and side views of the optimized structure of periodic bilayer polythiophene for (a) pristine, (b) Li intercalate, and (c) Cl intercalate.
Adapted with permission from ref 102. Copyright 2015 American Chemical Society.
Upon introduction of Cl dopants into the bilayer of
polythiophene (Figure 2c), the polythiophene bilayer was
found to also exhibit a planar structure with slightly larger
interlayer spacing (3.783−3.801 Å). The Cl atoms now reside
between the two layers away from the center of the thiophene
rings, similar to the monolayer case. Computational studies
involving para-toluenesulfonic acid (p-TSA) intercalated in
polythiophene bilayers have also shown this movement of the
anion away from the center of the bilayer, allowing for tighter
packing of the thiophene units.171
Flipping of the second layer of polythiophene by 180° has
also been considered for creating bulk or bilayer structures.
Note that it is speculated a more favorable structure is formed
based on donor−acceptor pair between the S atom and the
carbon backbone, which has not been verified experimentally
yet. The parallel bulk or bilayer structures, however, are
energetically more favorable than their flipped counterparts.
Total ground state energy difference between the parallel and
flipped bulk or bilayer amounted to −0.69 and −1.12 eV,
respectively. Similarly, the parallel bulk or bilayer polythio-
phene is stable by −1.09 or −0.88 eV and −1.03 or −0.36 eV
after Li and Cl intercalation.103
2.2. Electronic Structure. The band structures of pristine,
Li-doped, and Cl-doped monolayer polythiophene are depicted
in Figure 3. A band gap of 1.08 eV is obtained for pristine
Figure 3. Electronic band structure for monolayer polythiophene in
the periodic case for (a) pristine, (b) Li-doped, and (c) Cl-doped
polymers. Adapted with permission from ref 102. Copyright 2015
American Chemical Society.
monolayer of polythiophene (Figure 3a), agreeing well with
available reports.88,127,172 By analyzing the Löwdin populations,
it is found that the C atoms ortho- to the S atom accept 0.09
electrons with the S atom donating 0.41 electrons to the carbon
backbone. The meta-C atoms become positively charged
through donating 0.17 electrons, with the H atoms becoming
negatively charged by 0.13 electrons. Introduction of a Li atom
results in n-doping of the polythiophene monolayer through
electron donation from the Li atom, shifting the band gap 0.68
eV below the Fermi Level (EF; Figure 3b).88 Computational
10250
Perspective
studies of the variation of the Li-doping (Li/C ratios of 0.25,
0.083, and 0.050; Figure 4) can vary the extent to which the
polythiophene is n-doped.88
Similarly, p-doped states are observed when Cl is
incorporated (Figure 3c), with the Cl atom gaining 0.54
electrons, the ortho-C atoms losing a charge of 0.05 electrons,
and the meta-C atoms losing ca. 0.11 electrons. No electron
density was lost from the S and H atoms in comparison to the
undoped polythiophene monolayer. These results indicate that
the band gap in polythiophene can thus be controlled through
doping level of Li or Cl atoms, agreeing with experimental
evidence. The binding energy was found to be −2.01 and −1.49
eV for Li- and Cl-doped polythiophene, respectively. This
indicates that the formation of Cl-doped polythiophene is
easier than that of Li-doped polythiophene.
The band structures of pristine bilayer, pristine bulk, Li/Cl-
intercalated bulk, and Li/Cl-intercalated bilayer polythiophene
were calculated (Figure 5). A band gap of 4 meV was found for
pristine bulk polythiophene, while a band gap of 0.81 eV was
achieved for the bilayer (Figure 5b). Two well-separated bands
close to the conduction regime and two bands close to the
valence regime above/below the EF were found, similar to
previous experimental and theoretical reports for π-stacked
polymers.173 The gap between the two bands is about 0.41 eV,
and due to the splitting of the bands, the band gap in the bilayer
reduces as compared to the corresponding monolayer case. Li
intercalation into the bulk polythiophene results in the film
becoming n-doped, shifting the gap of the pristine case below
the EF by 0.25 eV.
Similarly, Li-intercalated bilayer polythiophene was found to
be shifted by 0.52 eV, resulting in a gap of 0.51 eV, see Figure
5d. It is important to mention that there are two possible
optical transitions (IR polaronic and optical polaronic) for light
absorption; these can be described as π−π* transitions. This
kind of behavior was observed in experiment for doped π-
conjugated polymers.32 Furthermore, the doping can be
understood by two transitions with energies in the range of
IR polaronic absorption for a small band gap and optical
polaronic absorption for a larger band gap. Importantly, by
doping, the conductivity can be increased, allowing such
systems to be used in devices requiring high conductivity, i.e.
photovoltaics, thermoelectrics, and spintronics.32,174,175
2.3. Pristine and Doped Polythiophene: Molecular
Approach. The structure of polythiophene was also analyzed
through molecular calculations, where four different oligomeric
structures (2-ring, 4-ring, 6-ring, and 8-ring) were considered
(HOMO/LUMO molecular orbitals shown in Figure 6). The
2-ring structure is a rather small model for the calculations,
resulting in larger bond lengths and a larger HOMO−LUMO
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 4. Band structures of doped polythiophene. The three middle panels from left to right refer to different concentrations with Li/C ratios of
0.25, 0.083, and 0.050, while the panels on the far right and far left correspond to the undoped polymer. Adapted with permission from ref 88.
Copyright 2009 AIP Publishing LLC.
Figure 5. Electronic band structure for periodic bulk and bilayer
polythiophene: (a and b) pristine, (c and d) Li intercalation, and (e
and f) Cl intercalation. Adapted with permission from ref 102.
Copyright 2015 American Chemical Society.
Figure 6. Calculated HOMO and LUMO of polythiophene oligomers
with an isovalue of ±0.05 electrons/Å3 for (a) 2-ring, (b) 4-ring, (c) 6-
ring, and (d) 8-ring. Adapted with permission from ref 102. Copyright
2015 American Chemical Society.
gap. By increasing the number of rings to 4, 6, and 8, the
structural parameters and band gap become smaller and show
convergence.124,176−179 The HOMO−LUMO gap is found to
10251
Perspective
be 2.94 eV for the 2-ring system and decreases to 1.87 to 1.54
eV to 1.39 eV for 4-ring to 6-ring to 8-ring, respectively. The
HOMO−LUMO gap can easily be engineered by creating
disorder180 or by doping181,182 in polythiophene. The
calculated value of the band gap in the periodic case is similar
to the HOMO−LUMO gap of the 6-ring or 8-ring geometry
(1.2 eV). Formation of a bilayer of polythiophene results in a
decrease in the band gap due to interlayer interactions and
band splitting at EF. Similar to periodic calculations, the flipped
state was also found to be slightly higher in energy (4−116
meV for 2−8 rings) with a larger HOMO−LUMO gap (1.338
eV for 8 rings) but still accessible under experimental
conditions. Experimentally, it was demonstrated that the
stacking of the π-conjugated thiophene is useful to obtain
long-range charge and energy transport in novel nanoscale
polymer-based devices such as optical, electronic switches, and
thin film transistors.183−186
2.3.1. Effects of Chain Lengths and Functionals on the
Electronic Properties. Recently, the effect of the chain length
on the band gap was addressed. 132 The band gaps
(fundamental, optical, and HOMO−LUMO) as a function of
1/N are plotted in Figure 7 for polythiophene derivatives
poly(3-hexylthiophene) and the thieno[3,4-b]thiophene-alt-
benzodithiophene copolymer, where N is the number of C
C bonds along the shortest path along the backbone of the
chain used (N = 2−6). To determine the band gap of the
polymers, an extrapolation of the band gap for planar oligomers
was performed, given that the planar backbone can be assumed
due to the delocalization of the π-electrons. 187 The
fundamental and optical band gaps for an infinite planar
chain of poly(3-hexylthiophene) and thieno[3,4-b]thiophene-
alt-benzodithiophene copolymer were found to be 1.87 and
1.65 eV, respectively, which are fairly close to experimental
values of 1.84 and 1.68 eV, respectively.188 The band gap of
planar poly(3-hexylthiophene) oligomers was found to be
slightly higher than that of planar thieno[3,4-b]thiophene-alt-
benzodithiophene copolymer oligomers.189
In addition, the effects of the chain length on various energy
gaps, orbital energies, ionization potential (IP), and electron
affinity (EA) were addressed for a thiophene dimer (2T) and
hexamer (6T) in comparison with the available experimental
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

lations of excitation energies, the HOMO−LUMO orbital

Figure 7. Chain length versus band gap for polythiophene derivatives
poly(3-hexylthiophene) (dotted lines) and thieno[3,4-b]thiophene-alt-
benzodithiophene copolymer (solid lines). Adapted with permission
from ref 132. Copyright 2014 Elsevier Publishing Company.
data by employing Hartree−Fock (HF) theory and different
hybrid and nonhybrid functionals.176 The orbital energy gap
(Δϵ) was found to be 2.9 to 9.2 eV for 2T, while it becomes 1.6
to 7.0 eV for 6T, depending on the method used. The optical
gaps obtained from a variety of different computational
methods are shown in Table 1. The optical gaps (ΔEO) were
obtained using time-dependent DFT (TDDFT) as a
comparison.190,191 The optical gaps (ΔEO) obtained from HF
and long-range corrected functionals (LC) are larger than the
experimentally measured values; PBE and B3LYP under-
estimate the values, and the LC* approach produces optical
gaps which are close to the experimental findings. It has been
observed that the band gap and other energy parameters
depend on the fraction of exchange correlation in the
functional.192,193 In addition, in some cases, the band gap and
other energy parameters obtained by using the B3LYP
functional provide reasonable agreement with experimental
reports for certain oligomers.
The calculated values of the energy parameters for thiophene
dimer (2T) and hexamer (6T) are discussed in detail in ref 176;
the data are summarized in Table 1. The occupied−unoccupied
orbital pair contribution to the transition density was calculated
based on TDDFT in the framework of the LC-PBE0 and
B3LYP functionals (6-31+G* basis), see Figure 8. The
functionals with low fraction of exact exchange produce an
almost pure HOMO−LUMO transition. For TDDFT calcu-
energy gap (Δϵ) essentially serves as a rough estimate of the
optical gap (ΔEO). The data presented in Table 1 reflect that
for PBE, the TDDFT excitation energy is larger than the
HOMO−LUMO orbital energy gap (Δϵ), while for the LC and
HF functionals, the TDDFT excitation energy is smaller than
the HOMO−LUMO orbital energy gap (Δϵ). For 6T and 12
T, a small HOMO−LUMO orbital energy gap (Δϵ) for PBE in
conjunction with the small admixture of other orbital pairs
renders the calculated optical gaps to be too low. In case of
functionals with a large fraction of exact exchange, the mixing of
the different occupied−unoccupied orbital pairs is in fact
needed to explain the electronic transition. A nice overview of
the HOMOs and LUMOs involved in the transition for
different functionals is addressed in Figure 9, which indicates
that the nature of the transition is totally dependent on the type
of functional used in the calculations.
The effects of electron donating/withdrawing groups on the
electronic structure for oligomers composed of a basic unit
consisting of a thiophene and a pyrrole ring connected by a
−CHN− group were studied by employing DFT/TDDFT.
Oligomers with various substituents in different positions were
also considered.198 The HOMO−LUMO gaps, excitation
energies, and the oscillator strengths were calculated using
five functionals (B3LYP, B2PLYP, PBE0, PW6B95, and
PWPB95). The obtained results indicate that substituents
induce twisting in the conjugated backbone of the oligomers
and thus increase the HOMO−LUMO gaps and the excitation
energies compared to those of the pristine molecule. The
HOMO, LUMO, and HOMO−LUMO gap (ΔH−L) of the
basic monomer unit were calculated using various functionals
and are shown in Figure 9. All of the other functionals provide
larger ΔH−L gaps as compared to the B3LYP functional, while
the ΔH−L obtained from B2PLYP and PWPB95 functionals are
found to be largest among the functionals. Interestingly, all the
functionals were found to have the same trend in the ΔH−L.
2.4. Effects of Substitution. The structural modification
and electronic properties of substitutionally doped polythio-
phene were studied using periodic DFT calculations127 as well
as realized in experiment via NMR studies.199 In particular, the
methyl (CH3), amino (NH2), nitro (NO2) and Cl groups
greatly modify the structural and electronic properties of
thiophene monomers and dimers. In the case of pristine
polythiophene monomers, dimers, and trimers, band gaps of
4.49, 2.93, and 2.21 eV were found computationally, which are
close to the experimental band gaps of 5.37, 4.12, and 3.52 eV,
respectively.200 The obtained values of the HOMO−LUMO
gap for the monomer (dimer) are found to be 4.44 eV (2.97
eV), 4.22 eV (2.87 eV), 4.46 eV (2.75 eV), and 3.21 eV (2.22

Table 1. Values of Negative HOMO Energy (−ϵH), LUMO Energy (−ϵL), IP, EA, Orbital Energy Gap (Δϵ), Fundamental Gap
(ΔEF), and Optical Gap (ΔEO) of Thiophene Dimer/Hexamer (2T/6T) with Experimental Dataa
quantity HF PBE B3LYP HSE LC LC* exptl
−ϵH 7.7/6.6 5.1/4.5 5.7/5.0 5.6/4.9 8.3/7.3 7.7/6.4
IP 6.4/5.6 7.4/5.9 7.5/6.1 7.5/6.1 7.8/6.7 7.7/6.4 7.7/6.4194,195
−ϵL −1.5/-0.4 2.2/2.9 1.6/2.5 1.8/2.7 −0.3/0.9 0.0/1.4
EA −0.8/0.3 −0.03/1.6 −0.05/1.45 −0.05/1.5 −0.04/1.3 −0.01/1.3 −0.05/1.2196
Δϵ 9.2/7.03 2.9/1.6 4.1/2.6 3.7/2.2 8.5/6.4 7.7/5.0
ΔEF 7.2/5.4 7.4/4.3 7.5/4.6 7.6/4.6 7.8/5.4 7.7/5.0
ΔEO 4.2/2.9 3.7/2.01 3.9/2.3 3.9/2.3 4.3/2.9 4.1/2.6 4.1/2.9197

a
LC* = LC−PBE0, and all the parameters are measured in eV. Adapted with permission from ref 176. Copyright 2013 American Chemical Society.

10252 DOI: 10.1021/acs.chemmater.7b03035

Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 8. Contributions of occupied−unoccupied orbital pair to lowest-energy singlet transition obtained from TDDFT for 6T and 12T using the
LC-PBE0 and B3LYP functionals (6-31+G** basis). Adapted with permission from ref 176. Copyright 2014 American Chemical Society.
Figure 9. HOMO−LUMO gaps (ΔH−L) calculated using five different
functionals (B3LYP, B2PLYP, PW6B95, PWPB95, and PBE0).
Adapted with permission from ref 198. Copyright 2013 American
Chemical Society.
eV) for CH3, Cl, NH2, and NO2 substitutions, respectively. The
nitro group induces the smallest HOMO−LUMO gap, which
can be attributed to the fact that the nitro group has the largest
electron-withdrawing capability. The calculated density of states
(DOS) for pristine and substituted polythiophene is shown in
Figure 10. It can be seen that there are few modifications in the
electronic structure with a minor effect of the substituents on
the HOMO−LUMO gap. A HOMO−LUMO gap of 1.19 eV
was obtained for pristine polythiophene and becomes 1.19,
1.22, 1.14, and 1.27 eV for CH 3 , Cl, NH 2 , and NO 2
substitutions, respectively. As observed in the monomer and
dimer calculations, the chloro and nitro groups increase the
HOMO−LUMO gap due to their ability to withdraw electron
density from the thiophene ring. Overall, the influence of the
substituents on the electronic structure of polythiophene is
greatly reduced by the transition from oligo- to polymer
form.121
The structural parameters and electronic structure of
polythiophene are also influenced by steric repulsion between
substituents. The steric repulsion between the substituents can
10253
Perspective
Figure 10. DOS of polythiophene substituted by (a) CH3, (b) Cl, (c)
NH 2 , and (d) NO2 , where dashed lines represent pristine
polythiophene DOS. Adapted with permission from ref 127. Copyright
2012, Rittmeyer and Groβ; licensee Beilstein-Institut.
be reduced by separating the thiophene rings in the backbone
of the polymer by a vinyl bridge (Figure 11a). In this scheme,
the structure remains flat irrespective of the substituent. The
inclusion of a vinyl bridge on polythiophene significantly
reduces the HOMO−LUMO gap from 1.2 to 0.7 eV, see Figure
11b. The vinyl bridges reduce the aromaticity by modifying the
structure toward a quinoid form, where the band gap of
conjugated polymers depends on the degree of the quinoid
versus the aromatic form of the backbone.126,201,202 The trend
is found to be similar for all the substituents on polythiophene
with the largest HOMO−LUMO gap observed for the nitro-
substituted polythiophene. The HOMO−LUMO gap of the
vinyl-bridged polythiophene with an annulated phenyl ring is
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 11. Vinyl-bridged polythiophene derivatives (a) structural
drawing, and (b) HOMO−LUMO gap. Adapted with permission from
ref 127. Copyright 2012, Rittmeyer and Groβ; licensee Beilstein-
Institut.
further reduced to 0.25 eV due to the increased conjugation in
the backbone.
3. POLARONS
Removal of the electrons from the top of the valence band of a
polymer leads to the formation of charged defects such as
polarons (radical cation) and bipolarons (dication), which are
balanced by molecular/atomic counterions.175 The modifica-
tions in the bond lengths around the excess of charge provide
the extent of the wave function of the polarons/bipolarons,
which leads to two new in-gap states (i and i*), where a
localized level is destabilized from the top of the valence
band.175,203,204 For a polaron, the level i contains half-filled
orbitals (Figure 12a), whereas for a bipolaron it is empty
Figure 12. (a) Electronic structure of a polymer for a polaron, (b) the
logarithm of the DOS lnN(E) for an amorphous polaronic polymer
solid containing localized states around the EF, (c) a metallic network
of polarons with the EF lying in a delocalized polaron band, (d)
electronic structure of a polymer for a bipolaron, (e) lnN(E) for an
amorphous bipolaronic polymer solid, and (f) a semimetallic network
of bipolarons with the EF lying between the valence band and the
empty bipolaron band, where i and i* represent the in-gap states
induced by local structural distortions. Adapted with permission from
ref 175. Copyright 2014 Nature Publishing Group.
10254
Perspective
(Figure 12d). Importantly, each of these doping species
possesses distinct optical transitions.205 Due to the unpaired
electrons in the half-filled orbitals, a polaron consists of a 1/2
spin, while a bipolaron has no spin, allowing differentiation of
the two states by electron spin resonance (ESR) spectrosco-
py.206−208
The polaron/bipolaron levels are localized on a segment of
the polymer chain for a polymer in an amorphous phase. The
EF lies in the middle of the localized states of the polaron band
for a disordered polaronic polymer (Figure 12b), while it lies
between the valence band and the bipolaron band for a
disordered bipolaronic polymer (Figure 12e).209,210 When a
polymer exhibits crystalline domains, short interchain distances
occur due to π-electronic density, which promotes the
delocalization of the polaron wave function over several chains,
becoming more metallic in nature.211 Similarly, a highly
oxidized polymer can exhibit metallic behavior212−214 due to
the creation of a polaron network in the half-filled polaron band
(Figure 12c).215
The electronic structure of doped polythiophene was
proposed to be equivalent to a Fermi glass, as depicted in
Figure 12e, where doped polythiophene is described by a
bipolaron network with an empty delocalized bipolaron
band,216 which in fact merges into the delocalized valence
band, see Figure 12f. Furthermore, polythiophene-based
polymers exhibited higher Seebeck coefficients and lower
thermal conductivities compared to those of metals while
maintaining metallic electrical conductivity, forming a semi-
metallic material175 and making them useful for thermoelectric
and spintronic applications.217−222
Analysis of the structure of polythiophene has found that the
benzenoid form of the polythiophene, see Figure 13a, is
Figure 13. Schematic representation of the neutral and charged
polythiophene rings for (a) neutral aromatic benzenoid, (b) neutral
quinonoid, (c) polaron, and (d) bipolaron. Adapted with permission
from ref 88. Copyright 2009 AIP Publishing LLC.
energetically more favorable than its quinonoid form,88 see
Figures 13a and b. The charge transfer due to donor or
acceptor doping introduces polarons or bipolarons into the
polymer, see Figures 13c and d, resulting in the formation of a
localized quinonoid structure.223 Calculations employing
B3LYP DFT using Li donor atoms found the polaron is
energetically more stable than the bipolaron.102 These findings
are in line with previous reports for Li-88 or Cl-doped141
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

Figure 14. (a) Geometrical structure of a single bipolaron doped into a 100-ring polythiophene chain and (b) band gap as a function of the number
of bipolarons in this chain. Adapted with permission from ref 226. Copyright 2010 American Chemical Society.

Figure 15. Schematic representation of polythiophene (a) undoped and (b) doped with corresponding energy diagrams for π−π* transitions.
Adapted with permission from ref 227. Copyright 2014 American Chemical Society.

polythiophene. Instead of doping, polarons or bipolarons can
also be created in polythiophene by suppressing and adding
charge to it through application of an electric field.224 The
increased presence of polarons and bipolarons is found to
facilitate large increases in the electrical and thermal
conductivity of conducting polymers from both theoretical
and experimental studies.148,154,225
In addition, the polaronic and bipolaronic defect states in
polythiophene are responsible for excitations as well as charge
storage.226 It was found that the energy of distortion to form
two polarons and one bipolaron are quite similar; however, the
ionization energy decreases significantly for bipolarons
compared to two polarons. As a result, a single bipolaron is
more stable than two polarons.154 In ref 226, the structures of
bipolaron-doped polythiophene containing 100 and 150 rings
and considering a maximum of 12 bipolaronic defects were
studied. The structural symmetry is found to be destroyed by
increasing the concentration of bipolarons. If a single bipolaron
is doped into a large, 100-ring polythiophene chain, the chain
was found to contain four distinct quinonoid rings at the center,
where ∼68% of the total charge is carried by the bipolaronic
defect. Interestingly, the band gap was found to decrease upon
increasing the concentration of bipolarons in polythiophene,
see Figures 14a and b. Moreover, for 4−13 rings, a continuous
transition to an aromatic structure is observed.
The lowest optical absorption for pristine polythiophene
results from π−π* transitions, as shown schematically in Figure
15a. Such a transition lies in the visible region, i.e. the optical
10255
regime.227 However, a polaron, i.e., a positive charge and an
unpaired electron are created on the polythiophene chain after
an electron from the chain is removed, see Figure 15b. In this
situation, two polaron states, namely P1 and P2, arise in the
midgap region between the π−π* bands. The induction of the
P1 and P2 states results in new optical transitions in the
infrared region related to the two new states. This behavior
leads to optical transparency in the visible spectral
region,112,228,229 which can also be demonstrated by analyzing
the absorption spectra of pristine and doped polythiophene. In
addition, the photoluminescence of polarons in doped
polythiophenes was investigated to estimate microscopic carrier
mobility.227 The observed carrier mobility was found to be 2.0
cm2 V−1 s−1, a promising result for the use of polythiophenes in
field-effect transistors constructed from two-dimensional
materials.230−239
4. OPTICAL PROPERTIES
The structural and optical properties of water-soluble
polythiophene derivatives were addressed by Li and Shi70,240
with possible monomer structures shown in Figure 16. The first
water-soluble polythiophene derivatives were synthesized in
1987, poly(3-thiophene-β-ethanesulfonate) and poly(3-(thio-
phene-δ-butanesulfonate)), see 1a and 1b in Figure 16. In
addition, poly(3-[(S)-5-amino-5-carboxyl-3-oxapentyl]-2,5-thi-
ophene hydrochloride) (2) was synthesized in 1991241 and
applied for creating biosensors to monitor DNA hybridization,
peptides, and proteins. 242−244 In 1996, a biotinylated
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 16. Structures of polythiophene derivatives (water soluble).
Adapted with permission from ref 70. Copyright 2014 American
Chemical Society.
copolymer of water-soluble poly(3-alkoxy-4-methylthiophene)
(3) was experimentally studied.245 A large series of cationic
water-soluble poly(3-alkoxy-4-methylthiophenes) was also
prepared later in 1996 (4−12).246−249 It was found that the
above-mentioned polythiophene-based molecules exhibit con-
formational change/aggregation while interacting with DNA,
protein, polysaccharide, and small analytes, which can be
monitored with the help of absorption or emission spectros-
copy. Furthermore, regioregular water-soluble polythiophene-
based molecules were synthesized by cross-coupling reactions
such as 2,5-poly(thiophene-3-propionic acid) (13) with a head-
to-tail regioregular chain250 and a cationic regioregular head-to-
tail 2,5-poly(3-(6-N,N-dimethylhexylammonium thiophene))
(14).251
The optical spectra of water-soluble polythiophene-based
molecules252 are strongly dependent on aggregation in
solutions or solid state, regioregularity, and backbone
conformations. Normally, optical properties are reflections of
the chemical and electronic structures of the π-conjugated
backbones; thus, polythiophene-based molecules with the same
backbone structures and different side groups (either alkyl/
alkoxy or ionic groups) usually show similar optical behavior.253
The colorimetric response of polythiophene-based molecules
(13) can be easily tuned by varying the size of their
countercations.251 By addition of Bu4NOH to polythiophene-
based molecules (13), a base with a cation larger than NH+4 , the
absorption spectrum was found to be blue-shifted by 130 nm.
Thus, a dramatic color change from purple to yellow was
observed. In addition, it has been found that the absorption and
emission spectra of water-soluble polythiophene can be
dramatically changed in aqueous media containing surfactants
due to the formation of ionic complexes through ionic self-
assembly.250,254,255
Recently, the optical properties of polythiophene and various
derivatives were studied theoretically by Samsonidze and co-
workers256 using the GW approximation (quasi-particle self-
energy corrections method) and by solving the Bethe−Salpeter
equation (BSE) to include electron−hole interaction. It was
reported that the band gap obtained using the GW
approximation is larger than that of GGA functionals, and the
GW approximation was found to be a better approach to obtain
10256
Perspective
the experimental band gap in the case of semiconducting
materials.236,257−264 In ref 256, various polymers such as
polythiophene (PT), poly(dithiophene ethyne) (PDTE),
poly(dithiophene vinylene) (PDTV), poly(dithiophene dicya-
novinylene) (PDTDCNV), poly(dithiophene difluorovinylene)
(PDTDFV), poly(dithiophene dichlorovinylene) (PDTDCV),
and fullerene (C60) were studied, see Figure 17. Table 2
provides comparisons of various calculated energies, including
band gap using DFT, G0W0, and BSE, agreeing with
experimental values reported.
Figure 17. Structures of PT and various derivatives (PDTE, PDTV,
PDTDCNV, PDTDFV, and PDTDCV, respectively) and fullerene
(C60), where white, gray, blue, cyan, green, and yellow spheres
represent H, C, N, F, Cl, and S atoms, respectively. Adapted with
permission from ref 256. Copyright 2014 American Physical Society.
Moreover, the polymers listed in Table 2 show larger
structural parameters compared to those of pristine poly-
thiophene, which leads to folded bands. The obtained
macroscopic absorption spectra (χ2) for these polythiophene-
based molecules and fullerene are shown in Figure 18, where χ2
= Aωϵ2 and χ2 = Vωϵ2 for polythiophene-based molecules and
C60, respectively; ϵ2, ω, A, and V are the imaginary part of the
dielectric function, the photon energy, the cross-sectional area,
and the volume of the supercell being used, respectively. The
dashed blue curves in Figure 18 represent the joint density of
quasiparticle states; the dashed green curves represent the
optical transition matrix elements, and the red curves are for the
excitonic effects. The optical excitation energies (Eoee) are
indicated by the peaks observed in the red curves in Figure 18.
The BSE exciton binding energies (Ebin = Egap − Eoee) are
summarized in Table 2. For the C60 molecule, the obtained
lowest peak of the dashed blue curve amounts to 4.56 eV,
which has no matching peak in the dashed green curve,
indicating that the calculated HOMO−LUMO optical tran-
sition for C60 molecule is quenched by symmetry.265 Thereby,
the lowest peak in the red curve at 3.50 eV arises from optical
transitions at higher energies than the HOMO−LUMO gap of
4.56 eV.
A comparison of experimental and theoretical (using various
computational approaches266) absorption energies of 49
different polythiophene-based molecules is addressed in ref
197, see Figure 19. All of the structures were optimized using
the AM1 semiempirical method267 with the GAMESS pack-
age268 or DFT with the B3LYP hybrid functional269,270 in the 6-
31G* basis in the Q-Chem package.271 The ZINDO semi-
empirical method was already tested at the CIS level with the
ZINDO package.272 The 10 highest occupied and 10 lowest
unoccupied orbitals were considered with the random phase
approximation (RPA) method.273,274 First-principles calcula-
tions were performed at both the CIS and RPA levels, and
TDDFT was used with the BLYP functional;270 in fact, it was
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

Table 2. DFT, G0W0, and BSE Results for an Isolated Polythiophene (PT), Poly(methyl thiophene) (PMeT), Poly(3-
hexylthiophene) (P3HT), Poly(dithiophene ethyne) (PDTE), Poly(dithiophene vinylene) (PDTV), Poly(3-hexyldithiophene
vinylene) (P3HDTV), Poly(dithiophene dicyanovinylene) (PDTDCNV), Poly(dithiophene difluorovinylene) (PDTDFV),
Poly(dithiophene dichlorovinylene) (PDTDCV), Fullerene (C60), [6,6]-Phenyl-C61 Butyric Acid Methyl Ester (PCBM),
Polythiophene on Fullerene (PT/C60), and Poly(dithiophene vinylene) on Fullerene (PDTV/C60)a
DFT G0W0 BSE
EVB ECB Egap EVB ECB Egap Eoee Ebin
PT −4.26 −3.21 1.05 −5.35 −2.25 3.10 1.48 1.62
PMeT −3.94 −2.87 1.07 −4.98 −1.97 3.01 1.48 1.53
P3HT −3.79 −2.80 0.99
PDTE −4.44 −3.36 1.08 −5.52 −2.39 3.13 1.79 1.34
PDTV −4.19 −3.36 0.83 −5.14 −2.52 2.62 1.23 1.39
P3HDTV −3.81 −3.12 0.69
PDTDCNV −5.26 −4.63 0.63 −6.04 −3.86 2.18 1.00 1.18
PDTDFV −4.43 −3.46 0.97 −5.48 −2.54 2.94 1.45 1.49
PDTDCV −4.53 −3.52 1.01 −5.58 −2.64 2.94 1.46 1.47
C60 −5.84 −4.19 1.65 7.31 −2.75 4.56 3.50 1.06
PCBM −5.43 −3.96 1.47
PT/C60 −4.49 −4.06 0.43
PDTV/C60 −4.37 −4.08 0.29
a
The EVB (eV), ECB (eV), Egap (eV), Eoee (eV), and Ebin (eV) represent the valence band maximum or HOMO, the conduction band minimum or
LUMO, quasiparticle band gap, optical excitation energy, and binding energy of the lowest bright exciton, respectively. Adapted with permission
from ref 256. Copyright 2014 American Physical Society.

Figure 18. Calculated optical absorption spectra of isolated polythiophene-based molecules and C60 employing the BSE functional. Red, dashed
green, and dashed blue curves represent the macroscopic absorption spectra (χ2) with/without electron−hole interaction and the joint density of
quasiparticle states, respectively. Adapted with permission from ref 256. Copyright 2014 American Physical Society.

shown that the TDDFT-BLYP method is the most accurate for
aromatic hydrocarbons and polyenes.275,276 Six computational
approaches, including ZINDO/CIS, ZINDO/RPA, HF/CIS,
HF/RPA, TDDFT/TDA, and TDDFT, were used to calculate
band gaps and absorption energies for various molecules and
compare the data with experimentally observed values, see
Table 3.277−286 The geometries predicted by the AM1
semiempirical method seem to be unreliable for performing
single-point excited-state calculations, unlike DFT calculations.
On the other hand, the semiempirical ZINDO/CIS method
provides good agreement between experimental and computed
optical absorption energies with small variation. However,
10257
TDDFT methods (TDDFT/CIS and TDDFT/RPA) are quite
accurate after systematic empirical correction.
In addition, the HOMO and LUMO energy levels using
different functionals for another set of polythiophene-based
molecules are addressed in ref 287, see Figure 20, where SW
refers to the square-wave voltammetry method. All of the
molecules investigated exhibit very low-energy HOMO levels
such as −5.94, −5.93, −5.87, and −5.78 eV,288 respectively, for
the structures PBDTA-MIM, PMIM, PBDTO-MIM, and PT-
MIM (details about the structural arrangements can be found
in ref 287). The HOMO level is slightly raised from PMIM to
PT-MIM by providing a lower offset to the LUMO energy level
of PCBM.289 Adding the BDT units results in deeper HOMO
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 19. Various polythiophene-based structures along with corresponding labeling (refer to Table 3). Adapted with permission from ref 197.
Copyright 2002 American Chemical Society.
energy levels of −5.87 and −5.94 eV for PBDTO-MIM and
PBDTA-MIM, respectively, as compared to PT-MIM (−5.78
eV) to PMIM (−5.93 eV). By replacing the alkoxy side chains
with the less electron-donating alkyl chains (from PBDTO-
MIM to PBDTA-MIM), the HOMO energy level is found to
be lower by 0.07 eV. Generally, the HOMO levels of donor−
acceptor polymers are mainly estimated by the electron
deficiency in the system.290−295 The HOMO levels are
relatively less affected by the conjugation length of the
polymers as compared to the LUMO levels, which indicates
that the variation of the HOMO energy level mainly depends
on the nature of the donor units attached. The estimated
HOMO and LUMO energy levels and optical gap for different
systems obtained by using various computational approaches
are shown in Figure 20.
5. THERMOELECTRIC PERFORMANCE
The thermoelectric properties such as Seebeck coefficient and
electric conductivity of polythiophene and its derivatives have
been studied extensively computationally (theoretically) and
experimentally.296−300 The Seebeck coefficient for pristine
polythiophene was found to decrease with increasing electric
conductivity, while the thermoelectric power factor in-
creased.296 The power factor was found to be 1.03 × 10−5
μWm−1 K−2 with a Seebeck coefficient of 23 μV K−1,
comparable to those of other conducting polymers. The figure
of merit (ZT = α 2σT/κ, where α, σ, κ, and T are the Seebeck
coefficient, the electrical conductivity, the thermal conductivity,
and the operating temperature)301 was found to be 1/3 of the
10258
Perspective
well-known Bi−Te system.302 These properties make poly-
thiophene a promising material in the formation of hybrid
organic/inorganic thermoelectric composites.
One such composite involves the incorporation of Bi2Te3
nanoparticles into a polythiophene film, with the temperature
dependence of the Seebeck coefficient, electrical conductivity,
power factor, and thermal conductivity for the composite
shown in (Figure 21).303,304 The Seebeck coefficients for this
system were found to be negative for a large temperature range
(see left top panel of Figure 21), indicating that the
polythiophene/Bi2Te3 composite behaves as n-type thermo-
electric material, where the thermoelectric transport is
dominated by electron carriers. The absolute value of the
Seebeck coefficient increases slightly over the temperature
range from 300 to 473 K with a similar trend also observed for
the electrical conductivity, see right top panel. The highest
absolute value of the Seebeck coefficient was found to be 156
μV K−1 at 423 K, which is 10% larger than that of pristine
Bi2Te3 (120−138 μV K−1) under the same conditions and
much larger than the obtained value for a polyaniline/Bi2Te3
composite (10−30 μV K−1).305 Importantly, the electrical
conductivity for the polythiophene/Bi2Te3 composite decreases
dramatically with increasing polythiophene content (see left
bottom panel of Figure 21), which can be attributed to the
decrease in the carrier concentration and carrier mobility. The
obtained values of the temperature versus thermal conductivity
for the interface of polythiophene/Bi2Te3 are shown in the
right bottom panel of Figure 21. Thermal conductivities of
0.33−0.55 μWm−1 K−2 were found for the temperature range
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

Table 3. Experimentally Observed Absorption Energy and Calculations Using Different Computational Approaches (CIS and
RRA)a
ZINDO HF TDDFT
exptl AM1 DFT AM1 DFT AM1 DFT
1 5.10 0.15, 0.88 0.16, 0.95 1.40, 1.05 1.93, 1.71 0.88, 0.77 1.08, 0.70
2 4.11 −0.17, −1.13 −0.06, −1.03 0.59, 0.31 0.56, 0.28 0.10, −0.20 0.02, −0.28
3 3.50 −0.26, −1.04 −0.14, −0.94 0.46, 0.21 0.44, 0.19 −0.15, −0.41 −0.22, −0.47
4 3.18 −0.33, −1.00 −0.21, −0.90 0.40, 0.18 0.37, 0.15 −0.35, −0.55 −0.41, −0.61
5 2.98 −0.37, −0.97 −0.25, −0.87 0.38, 0.17 0.34, 0.13 −0.51, −0.65 −0.56, −0.71
6 2.87 −0.41, −0.97 −0.30, −0.87 0.34, 0.14 0.30, 0.09 −0.65, −0.76 −0.71, −0.82
7 5.96 −0.28, −0.14 −0.08, −0.01 0.96, 0.56 1.21, 0.83 0.89, 0.44 1.11, 0.68
8 4.49 −0.27, −1.24 −0.04, −1.03 0.60, 0.31 0.91, 0.62 0.16, −0.18 −0.01, 0.05
9 3.91 −0.34, −1.14 −0.11, −0.06 0.45, 0.20 0.76, 0.52 −0.23, −0.47 −0.05, −0.26
10 3.38 −0.33, −1.00 −0.12, −0.81 0.16, 0.88 0.36, 0.69 −0.64, −0.76 −0.34, −0.43
11 3.25 −0.42, −0.58 −0.04, −0.72 0.24, 0.06 0.74, 0.56 −0.95, −1.01 −0.64, −0.69
12 5.93 −0.53, 0.57 −0.39, 0.73 0.73, 0.32 0.99, 0.59 0.71, 0.23 0.94, 0.48
13 4.40 −0.33, −0.81 −0.15, −0.60 0.49, 0.78 0.18, 0.48 0.16, −0.23 0.34, −0.02
14 3.78 −0.42, −0.71 −0.23, −0.49 0.31, 0.59 0.06, 0.35 −0.20, −0.50 −0.05, −0.32
15 3.43 −0.25, −0.63 −0.25, −0.41 0.24, 0.52 0.02, 0.30 −0.44, −0.66 −0.29, −0.49
16 4.90 0.52, 0.62 0.60, 0.75 1.61, 2.03 1.26, 1.80 0.19, 0.16 0.33, 0.24
17 3.76 0.12, −0.87 0.05, −0.94 1.04, 0.79 0.66, 0.39 −0.10, −0.26 −0.27, −0.51
18 3.19 −0.06, −0.84 0.06, −0.74 0.65, 0.41 0.63, 0.39 −0.22, −0.43 −0.31, −0.51
19 2.96 −0.14, −0.81 −0.07, −0.04 0.60, 0.39 0.57, 0.35 −0.37, −0.52 −0.48, −0.62
20 3.81 0.43, −0.66 −0.20, −1.22 1.68, 1.43 0.62, 0.33 −0.04, −0.09 −0.15, −0.44
21 3.23 −0.08, −0.89 −0.15, −0.95 0.92, 0.68 0.58, 0.33 −0.11, −0.27 −0.23, −0.46
22 2.99 −0.20, −0.89 −0.20, −0.89 0.68, 0.46 0.48, 0.25 −0.30, −0.44 −0.42, −0.60
23 2.83 −0.14, −0.77 −0.21, −0.83 0.76, 0.56 0.45, 0.24 −0.37, −0.47 −0.55, −0.68
24 5.58 −0.22, −0.35 −0.15, −0.13 1.25, 0.84 1.60, 1.87 −0.45, −0.46 0.13, 0.03
25 4.96 −0.50, −1.50 −0.20, −1.23 0.46, 0.17 0.86, 0.60 −0.33, −0.57 −0.12, −0.31
26 4.58 −0.69, −1.54 −0.36, −1.26 0.20, −0.04 0.61, 0.38 −0.79, −0.95 −0.56, −0.69
27 4.44 −0.63, −1.46 −0.21, −1.12 0.28, 0.06 0.79, 0.58 −1.09, −1.15 −0.76, −0.81
28 4.35 −0.91, −1.65 −0.60, −1.39 −0.30, −0.10 0.26, 0.07 −1.36, −1.45 −1.13, −0.71
29 4.34 −0.65, −1.46 −0.49, −1.31 0.22, 0.01 0.37, 0.18 −0.58, −0.78 −1.25, −1.28
30 4.32 −0.59, −1.41 −0.25, −1.13 0.29, 0.09 0.71, 0.51 −1.15, −1.18 −0.77, −0.80
31 4.82 0.50, 0.66 0.47, 0.73 1.63, 1.28 1.91, 1.66 0.27, 0.13 0.29, 0.07
32 3.87 −0.11, −1.12 −0.05, −1.08 0.90, 0.62 0.78, 0.49 0.23, −0.08 0.11, −0.23
33 3.10 0.08, −0.84 0.02, −0.79 0.95, 0.70 0.81, 0.56 0.17, −0.07 0.05, −0.20
34 4.38 0.95, 1.09 1.06, 1.26 1.55, 1.25 2.02, 1.81 −0.16, −0.25 −0.15, −0.22
35 3.83 0.38, −0.39 0.33, −0.45 1.41, 1.10 1.22, 0.90 0.38, 0.13 0.34, 0.05
36 5.58 0.16, −0.26 0.27, −0.15 1.29, 0.89 1.48, 1.77 −0.32, −0.32 0.03, 0.54
37 5.93 −0.20, −0.65 −0.04, −0.52 0.93, 0.52 1.17, 0.78 −0.47, −0.56 −0.35, −0.44
38 5.90 −0.15, −0.67 0.02, −0.49 0.90, 0.50 1.19, 0.80 −0.43, −0.50 0.21, −0.34
39 3.45 0.06, −0.80 0.05, −0.80 0.87, 0.62 0.73, 0.48 0.09, −0.12 0.09, −0.24
a
Adapted with permission from ref 197. Copyright 2002 American Chemical Society. The experimental data were adapted from refs 277−281 and
283−286.

300−473 K. While the figure of merit, ZT, is still lower than
that of bulk Bi2Te3, doping the polythiophene film is expected
to increase the electrical conductivity with minimal effects on
its thermal conductivity, allowing for an optimization of the
figure of merit of these polythiophene/inorganic hybrid
thermoelectric composites.306−308
The thermoelectric properties for the interface of poly-
thiophene/multiwalled carbon nanotube (MWCNT), another
promising thermoelectric material, were also investigated, with
the MWCNT content ranging from 30 to 50%.219 The figure of
merit was found to increase by increasing the concentration of
MWCNT, largely due to the large increase in the electrical
conductivity. The highest value of the figure of merit was found
to be 8.71 × 10−4 for the interface of polythiophene/MWCNT
composite with 80% coverage of the MWCNT at 120 °C, while
the Seebeck coefficient was found to be 22.7 μV K−1. These
10259
values can be increased either through doping of the
polythiophene film309 or introduction of a ternary thermo-
electric material such as Bi2Te3.304,310
Polythiophene composites have also been studied for their
thermoelectric properties, namely the superstructures of
poly(3,4-ethylenedioxythiophene) with polythiophene, poly(3-
methylthiophene), and poly(3-hexylthiophene) in the presence
of polystyrenesulfonate.221 The temperature dependence of the
power factor for the three systems mentioned above is
addressed in Figure 22. Power factors of 1.57, 4.43, and 5.79
μWm−1 K−2 were observed for the superstructures of poly(3,4-
ethylenedioxythiophene) with polythiophene, poly(3-methyl-
thiophene), and poly(3-hexylthiophene) in the presence of
polystyrenesulfonate at 300 K, respectively. Moreover, improve-
ments in the electrical conductivity and Seebeck coefficient
were obtained by tailoring the size of the nanostructures
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 20. HOMO and LUMO energy levels using DFT (B3LYP/6-
31G(d) level and SWV) and the optical band gaps. Adapted with
permission from ref 287. Copyright 2013 American Chemical Society.
used.311,312 This study has been followed by several other
research groups to obtain deep understanding and improve the
thermoelectric properties of different varieties of poly-
mers.313−322
Recently, the spin thermoelectric properties of polythio-
phene connected between three-dimensional ferromagnetic
electrodes (see Figure 23 for the model being used) for both
the parallel and antiparallel configurations were studied using a
tight-binding model within the Green’s function approach.323 It
Figure 21. Observed value of the Seebeck coefficient (left top panel), electrical conductivity (right top panel), power factor (left bottom panel), and
thermal conductivity (right bottom panel) as a function of temperature for the interface of polythiophene/Bi2Te3. Adapted with permission from ref
303. Copyright 2011 Springer.
10260
Perspective
Figure 22. Power factor as a function of operating temperature for the
superstructures of poly(3,4-ethylenedioxythiophene) with (a) poly-
thiophene, (b) poly(3-methylthiophene), and (c) poly(3-hexylthio-
phene). Adapted with permission from ref 221. Copyright 2013
American Chemical Society.
was found that by increasing the length of the polythiophene
chain, the oscillation of the spin thermopower increases,
enhancing the spin thermoelectric figure of merit due to the
reduction of the HOMO−LUMO gap. By increasing the length
of the polythiophene chain in the parallel configuration, the
magnitude of the spin thermoelectric figure of merit is
suppressed due to an enhancement in the oscillation at larger
chain lengths, with the situation reversed for the antiparallel
configuration. Moreover, the spin conductance increases and
the thermal conductance decreases with increasing the length of
the polythiophene chain. Thus, the magnitude of the spin figure
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 23. Ferromagnetic/polythiophene/ferromagnetic junction for both the parallel and antiparallel configurations, where n represents the number
of thiophene rings and 4j, 4j-1, 4j-2, and 4j-3 refer to the sites of carbon atoms in thiophene rings. Adapted with permission from ref 323. Copyright
2013 John Wiley and Sons.
of merit decreases for antiparallel and increases for parallel
configurations. This can be attributed to the fact that the value
of the spin conductance and spin thermopower decreases in the
antiparallel configuration due to reduction of the carrier
tunneling between the electrodes via the polythiophene chain.
The insets in Figures 24a and b show the voltage dependence
of the change of maximum value of the spin figure of merit for
the parallel and antiparallel configurations, respectively.
Figure 24. Voltage dependency of the spin figure of merit for various
lengths of thiophene rings for (a) parallel and (b) antiparallel
configurations. The insets refer to the change of maximum value of the
spin figure of merit with voltage for n = 5 thiophene rings. Adapted
with permission from ref 323. Copyright 2013 John Wiley and Sons.
In a recent experiment, it was demonstrated that pristine
polythiophene nanofibers can have a thermal conductivity of
about 4.4 Wm−1 K−1, which is 4 times higher than that obtained
for the bulk polymer so far.324−326 By increasing the
crystallinity as well as aligning the crystallites of the
polythiophene (see Figure 25a for the model being used), the
thermal conductivity was increased.327 For instance, high-
modulus commercial fibers have a thermal conductivity of up to
10 Wm−1 K−1, where the main contribution is coming from the
anharmonic phonon−phonon scattering in the crystalline
regions of the polymers. 328 The amorphous form of
10261
Perspective
polythiophene is illustrated in Figure 25b; it is still unknown
whether chain alignment can be obtained without creating
crystalline domains in the polythiophene.329
The morphology of the polythiophene was also altered to
determine the effect on the resulting thermoelectric properties.
Vertically aligned arrays of polythiophene nanofiber were
synthesized on a metallic substrate (see Figure 25c), and the
transport properties of isolated nanofibers from the array were
studied. Polythiophene nanofibers with 200 nm diameter were
synthesized in a tubular form with wall thicknesses of 40−80
nm, see Figure 25d. Some of the polythiophene nanofibers are
found to be in the solid phase, and these were used to measure
the thermal conductivity on single fibers. On the other hand,
polythiophene nanofibers with diameters of 18−300 nm were
found to be amorphous based on electron diffraction high-
resolution transmission electron microscopy. Interestingly,
polythiophene nanotubes were synthesized for the first time,
see Figure 25e.
The thermal conductivity of individual nanofibers was
measured using the suspended microbridge technique (see
Figures 26a and b).330 The obtained values of the thermal
conductivity of polythiophene nanofiber samples increase upon
decreasing the diameter, see Figure 26a. The thermal
conductivity of the polythiophene nanofibers with diameters
of about 204 to 71 nm were found to increase from 100 to 350
K, see Figure 26b. However, the thermal conductivities of
several other amorphous materials such as carbon black,331
SiO2,332 and hydrogenated silicon films333 were found to
remain constant up to 300 K.332 The fibers exhibit a distinct
behavior with respect to temperature versus the thermal
conductivity as compared to fibers of polyethylene (c-PE) and
polybenzobisoxazole (c-PBO), see Figure 26b.328 Indeed, the
thermal conductivity of polythiophene nanofibers was found to
be increased from 80 to 300 K, whereas c-PE and c-PBO were
found to decrease over the same temperature window. At room
temperature, the phonon scattering in the crystalline
polythiophene fibers is anharmonic phonon−phonon scatter-
ing, whereas the polythiophene nanofibers (Figure 25) were
found to be dominated by interchain scattering resulting from
the increased disorder within the fibers.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

Figure 25. (a) Schematic representation of the chain orientation of the semicrystalline form of polythiophene surrounded by amorphous form, (b)
chain orientation of the amorphous form of polythiophene, (c) scanning electron microscopy image of vertical polythiophene nanofiber arrays on
metallic substrate, (d) transmission electron microscopic image of a polythiophene nanofiber, where the inset shows a selected area of the electron
diffraction patterns, and (e) high-resolution transmission electron microscopic image of a polythiophene nanotube wall in the amorphous form.
Adapted with permission from ref 324. Copyright 2014 Nature Publication Group.

Figure 26. (a) Thermal conductivity of a single-fiber versus fiber diameter at room temperature, where the inset shows the scanning electron
microscopy image of a polythiophene nanofiber in the suspended microbridge, and (b) the thermal conductivity of a single-fiber versus temperature,
where c-PE, c-PBO, and a-PT refer to crystalline polyethylene, crystalline polybenzobisoxazole, and amorphous polythiophene, respectively. Adapted
with permission from ref 324. Copyright 2014 Nature Publication Group.

6. APPLICATIONS DOT:PSS) and their composites are of great interest for

In this section, we focus mostly on experimental perspectives,
the reason being that this field is not nearly saturated despite
having a long research history. Indeed, there are several
tremendous new directions that have opened recently for both
experimentalists and theoreticians, especially in the area of
device applications of polythiophene-based materials due to
their low cost, solution processability, highly variable
conductivity, and the possible development of three-dimen-
sional stacking devices. Examples include solar cells, field-effect
transistors (FET), light-emitting diodes (LED), hydrogen
storage, water purification, and DNA detection. Thus, there
are indeed lots of possibilities for the study and practical use of
polythiophene-based materials.
6.1. Resistive Memory Devices. Polythiophene and its
derivatives such as tethered alkyl substituted polythiophenes
and block copolymers such as poly(3,4-
ethylenedioxythiophene):poly(styrenesulfonate) (PE-
10262
polymer-based resistive memory storage.334,335 Dynamic
doping of π-conjugated polymers can be obtained by creating
a composite containing a sufficient level of immobilized anions
to accommodate the polymer’s oxidized form as well as mobile
cations to revert the polymer into its neutral state. By forming a
heterojunction with a material that is able to accept these
mobile cations and remain or become conductive, such as metal
oxides, high and low conductive states necessary for a resistive
memory element can be achieved.147,336 The electrodeposition
of these heterojunctions is scalable down to the nanometer
scale to create devices on existing crossbar structures.147,337
Further, recent work has demonstrated the ability to perform
this memory storage along the polymer chain in donor−
acceptor conjugated polymers, allowing access to even smaller
dimensions.338
One such system employs a polythiophene film doped with
both dodecyl sulfate and Li+ placed into a heterojunction with
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
an electrodeposited WO3 film (Figure 27).147,339 Even in the
absence of solvent and electrolyte, Li+ ions are mobile and can
Figure 27. (a) Current−voltage characteristics for sandwiched
structures of polythiophene(dodecyl sulfate−Li+)/polypyrrole(dodecyl
benzenesulfonate) on indium tin oxide. Adapted with permission from
ref 339. Copyright 2012 Royal Society of Chemistry.
drift in response to an applied field.340 The Li+ ions move from
the polythiophene(dodecyl sulfate−Li+ ) film to WO3 (see
Figure 27b), resulting in an oxidized polythiophene and a
reduced WO3 film and a higher conducting state with
increasing current at positive biases, see Figure 27a. To prevent
diffusion of the Li+ ions from the WO3 film into the
polythiophene film and thereby retain the high conductive
state, an oxidized polypyrrole(dodecyl benzenesulfonate) layer
is deposited between the films. Any mechanism by which Li
ions go through the polypyrrole(dodecyl benzenesulfonate)
layer will result in an increase in the energy of the system,
amounting to a barrier to ion transport. The slow ion motion
observed between the films can be understood by analyzing the
hysteresis curve in Figure 27a. It is expected that, by optimizing
the barrier thicknesses and the applied voltage, these systems
can be utilized as memory devices such as dynamic random-
access memory (DRAM) or static random-access memory
(SRAM).59,66
Very recently, a polyelectrolyte-gated memory device based
on a poly(3-carboxypentylthiophene) was synthesized. It was
demonstrated that the device can display nonvolatile bistable
memory characteristics with low operating voltage (±3 V).341
Figure 28. (a) Structure of the proposed Al/PEDOT:PSS/poly(methyl methacrylate)/indium−tin−oxide/polyethylene terephthalate memory
device. (b) Switching behavior of the input voltage (top) and output current (bottom) for write-read-erase cycles. Adapted with permission from ref
348. Copyright 2012 AIP Publishing LLC.
10263
Perspective
In this experiment, the conductivity of the polythiophene layer
was reversibly switched between the high and low conductance
states with write and erase bias, respectively. The retention time
of the ON state was found to be 1 × 104 s, and the write-read-
erase-read switching was found to be stable over 100 cycles.
Moreover, a fast switching speed was observed by simultaneous
monitoring of both write and read operations. It is expected
that such devices are dimensionally stable. Therefore, they are
promising candidates for next generation nonvolatile memory
application.
High hole mobility of poly(3-hexylthiophene) thin films has
been demonstrated.342 Thus, the thin films of poly(3-
hexylthiophene) are expected to be potential candidates for
studying charge transport phenomena.343,344 In addition,
poly(3-hexylthiophene) has also been proposed as a potential
material to construct junction diodes.59,66,345−347
The switching behavior of the Al/PEDOT:PSS/poly(methyl
methacrylate)/indium−tin−oxide/polyethylene terephthalate
memory device was addressed in ref 348. The writing, reading,
and erasing voltage pulses for the current−time characteristics
were considered as −4, +1, and +4 V, respectively, see Figure
28. The value of the applied voltage−time for the writing,
erasing, and reading processes was 1 ms, while the erasing
voltage pulse can be applied to change the device from the ON
to the OFF state. The current at the reading voltage pulse is
found to be about 2 × 10−11 A. The current at the reading
voltage is found to be about 1 × 10−8 A after the writing voltage
pulse was applied to turn the device from the OFF to ON state.
A significant difference between ON and OFF currents
demonstrates that the proposed device has good switching
behavior. The I−V curves for the device indicate that the
current bistability with an ON/OFF current ratio is found to be
about 1× 103, which in fact is larger than that of the device
without a poly(methyl methacrylate) buffer layer. The obtained
results indicated that the device has strong potential for read-
only memory (ROM) applications.
Moreover, bipolar switching behavior of nonvolatile polymer-
based memory devices made of PEDOT:PSS with glycerol was
demonstrated.349 It was found that the OFF-current of the
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

Figure 29. Measured I−V characteristics of the indium−tin−oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) + functionalized

multiwalled carbon nanotubes/Al devices for various concentrations of the functionalized multiwalled carbon nanotubes. Device schematic is shown
on the right. Adapted with permission from ref 350. Copyright 2012 ScienceDirect.

memory devices increases without any effect on ON-current

levels, which can be understood by achieving highly conductive
current paths on the ON-state. The write-read-erase-read cycle
test could be operated 105 times, and the ON-retention time is
dependent on the amount of glycerol in the PEDOT:PSS film
as well as the annealing temperature.
Another type of memory device made of a small amount of
up to 0.01 wt% of functionalized MWCNTs embedded in
PEDOT:PSS with Al as the top electrodes on indium−tin−
oxide substrates was synthesized.350,351 Even for the low
resistance ON-state and the high resistance OFF-state, the
information can be stored for hours. The system was found to
be stable even after hundreds of write-read-erase-read cycles,
which makes it a candidate for erasable and rewritable volatile
memory devices. The threshold voltage for OFF to ON
switching can be maintained just by adjustment through
changing the concentration of functionalized MWCNTs within Figure 30. Schematic for the formation of a polymer-based solar cell.
the polymer film. In this design, a bulk heterojunction is formed between the p-type and
The device performance for various concentrations of n-type polymers employed. Adapted with permission from ref 352.
functionalized MWCNTs for indium−tin−oxide/PEDOT:PSS Copyright 2015 American Chemical Society.
+ functionalized MWCNTs/Al is pictured in Figures 29a−f.
The devices showed bistability even for very small concen- potential route to increase the efficiency of such organic solar
tration of the functionalized MWCNTs. By reducing the cells has been suggested by many groups,163,355−358 which
concentration of the functionalized MWCNTs, an enhance- involves developing new organic materials with a high dielectric
ment on the threshold voltage was found, which in fact allows constant. This type of research focuses on lowering the
the tuning of memory retention. Devices made of only of Coulomb potential between the electrons and holes by
PEDOT:PSS do not show the bistability, which indicates that increasing the concentration of free charges, which is useful
the functionalized MWCNTs composite is an essential for the solar cells. Given the promising electrical, optical, and
utilization of single polymer film memory devices. physical properties of polythiophene films, their use in organic
6.2. Photovoltaics and Photoelectrochemistry. Solar solar cells359−361 and dye-sensitized solar cells362−364 has
energy conversion, including the use of organic solar cells, significantly grown in the scientific community over recent
could be a potential route to tackle the energy crisis in the years.
future.353,354 A schematic of an organic solar cell is shown in The heterostructure of poly(3-hexylthiophene) and [6,6]-
Figure 30, where a bulk heterojunction is formed between a p- phenyl-C61-butyric acid methyl ester was proposed as a
type and n-type organic small molecules or polymers.352 One potential candidate to construct organic solar cells with
10264 DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
reasonable characteristic carrier lifetimes, and hence reasonable
extraction efficiencies.365−372 Theoretically, it was proposed
that incorporation of permanent dipole moments in the organic
materials in fact lowers the Coulomb attraction/potential.372
One method of introducing this dipole into conjugated
polymers is by linking the polymer with a fullerene derivative,
resulting in large dipole moments in the polymer side
chains.373−375 Fullerene-based polythiophene solar cells suffer
from narrow absorption profiles, however, leading to the
development of fullerene-free solar cells376−378 which show
improved efficiencies (ca. 10%). Alternatively, introduction of a
donor/acceptor pair within the polymer chain can also result in
this necessary dipole moment,379 such as poly(thiophene-block-
perylene diimide) copolymers.380
In addition, semiconducting conjugated polymers were
fabricated through Stille polymerization, where the structures
combined unsubstituted or (triisopropylsilyl)ethynyl substi-
tuted 2,6-bis(trimethylstannyl)benzo[1,2-b:4.5-b′]dithiophene
that acts as a donor unit and benzotriazole with a symmetrically
branched alkyl side chain that act as an acceptor unit.381 Power
conversion efficiencies of 5.5 and 2.9% for (triisopropylsilyl)-
ethynyl substituted 2,6-bis(trimethylstannyl)benzo[1,2-b:4.5-
b′]dithiophene and benzotriazole-based devices, respectively,
were obtained. While lower than state-of-the-art power
conversion efficiencies (7−10%),382,383 the difference in
power conversion efficiencies can be understood by the
differences in the optimal morphology and carrier mobility,
which in fact provides a potential route to improve the
performance of the solar cells.378,384,385
Polythiophene films have also shown their use in photo-
electrochemical cells. Preliminary work investigated the ability
of polythiophene films such as poly(3-hexylthiophene) to
photoelectrochemically or photocatalytically reduce water to
hydrogen.387−390 Further work has shown the ability of a
poly(3-hexylthiophene) film to reduce an organic substrate,
anthraquinone-2,7-disulfonate, directly (Figure 31).386 Due to
Figure 31. Schematic for a photoelectrochemical system involving a
polythiophene film for the reduction of anthraquinone-2,7-disulfonate
(AQ27DS). Adapted with permission from ref 386. Copyright 2016
John Wiley and Sons.
10265
Perspective
the placement of the valence and conduction bands relative to
the reduction potential for hydrogen, the photoexcited electron
upon illumination can be utilized to drive the reductive process
in solution, provided no large energy barrier exists toward the
reduction process. The band position of polythiophene films
also allows their use in oxygen reduction to water390−397 for
fuel cell applications. Given the large degree that these polymer
films can be adjusted, the light absorption and extraction
efficiency as well as the catalytic ability of the film can be
optimized. However, due to the potential for degradation of the
polymer film under the applied conditions, current avenues
being explored involve the incorporation of protective layers,
additional light absorbers, and introduction of solution-based
electrocatalysts to help mitigate this issue and improve the cell’s
efficiency.
Alternatively, thiophene and its derivatives can also form
heterostructures with other semiconducting materials for solar
energy conversion. Experimentally, using the Heck reaction,
coupling of olefins to the Si(111) surface functionalized by a
mixed single layer consisting of methyl and thienyl groups was
proposed.398 In this method, conjugated linkage was developed
between the Si(111) surface and olefinic surface functionality,
which indeed allows charge redistribution easily from the
Si(111) surface to the mixed monolayer of methyl and thienyl
groups. Such a synthetic method would be useful to construct
surface derivatizable, air-stable silicon photoelectrodes.399
Alternatively, thiophene adsorption on a Si(111) surface can
also tune the electronic band gap over a wide range, which
could be a significant step toward applications in photo-
electrochemistry.400 Furthermore, introduction of a PE-
DOT:PSS layer at an n-doped silicon surface results in the
formation of a p-n diode,401−403 where the barrier to charge
transport and the overall photovoltaic properties can be tuned
based on the organic moiety present.404−408
Recently, the charge injection rates in nanosilicon-poly-
thiophene bulk heterojunction solar cells were determined
experimentally as well as theoretically.409−412 Characteristic
times of the order of ∼10−100 fs were found for the electron
injection from the photoexcited dodecathiophene or poly-
thiophene to a hydrogen-passivated silicon clusters of ∼2.2 nm
diameter if the thiophene chain lies approximately parallel to
the silicon surface (physisorption). The chemisorption of the
thiophene chain with an ethyl linker significantly improves the
electron injection time as compared to the physisorption of the
thiophene on the silicon surface. Moreover, the electron
injection time was found to be much larger when the
oligothiophene chain anchors perpendicularly to the silicon
surface. This is attributed to the low weight of the
oligothiophene LUMO on the chain end and the small overlap
of this state with the unoccupied electron states of the
nanocrystal, see Figure 32 for the model that was used.
Therefore, chemisorption of the thiophene on the silicon
surface has the advantage of offering more anchoring points per
chain in oligothiophenes as compared to physisorption (see
right panel of Figure 32), ensuring a smaller spacing between
the oligothiophene chain and the silicon surface and improving
the electronic coupling. Such a system has recently been
realized experimentally by constructing hybrid photovoltaic
thin films.413
6.3. Organic Light-Emitting Diodes. Polymer-based
(organic) light-emitting diodes have attracted significant
research interest because of their low power consumption,
light weight, fast response, and comparative ease of integration
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Figure 32. (a) Physiosorption (left panel) and chemisorption (right
panel) of a polythiophene chain on H-passivated silicon clusters.
Adapted with permission from ref 409. Copyright 2013 American
Chemical Society.
into electronic devices.66,414,415 The charge transport is an
important factor to determine the performance of these devices.
To achieve high performance of the organic light-emitting
devices (OLEDs), the charge injection and transport from both
anode and cathode should be balanced by excitons that were
induced in the light emission layer.415 A light-emitting diode
mainly consists of three layers embedded between two
electrodes: (i) the hole injection/transport layer, (ii)
electron-emitting layer, and (iii) electron-transporting layer,
where each layer has to be optimized individually for charge
injection, transport, and emission. A schematic of a typical
OLED is shown in Figure 33. Due to the high conductivity,
Figure 33. Schematic for an OLED. Adapted with permission from ref
416. Copyright 2009 American Chemical Society.
reasonable ionization potential, wettability, and fair hole-
injection ability, PEDOT:PSS is typically employed in
OLEDs as a hole injection layer, similar to the ITO anode in
Figure 33.
However, the electrical properties of such a device can
thereby become dependent on the presence of oxygen and
water during fabrication. Alternative thiophene derivatives such
as bithiophene vinylene have shown promise as light-emitting
materials, where the color of the light-emitting can be tuned
from red to purple to white simply by the monomer or
substituent employed on the thiophene unit.416,417 Alterna-
tively, a suspended single layer of pristine polythiophene
molecule between the tip of a scanning tunneling microscope
(STM) and a gold substrate was proposed as polythiophene-
based light-emitting diode.418,419
Figure 34a shows the suspended polythiophene wire in the
junction, where the STM tip is first located on the top of
polythiophene deposited on a Au(111) surface, see Figure
34b.420 The total conductance can be defined as G(z) ∝
Gcexp−βz, where Gc is the conductance at contact, z is the
10266
Perspective
Figure 34. (a) STM image of a polythiophene wire embedded on a
Au(111) surface, (b) normalized conductance (G/G0) as a function of
the distance between the tip and the sample for a polythiophene wire
embedded in the junction for different voltages, (c) conductance (dI/
dV) spectrum, (d) light emission efficiency as a function of the voltage,
and (e) atomistic structure of the polythiophene embedded between
the gold electrode and linked on the top by the STM tip. Adapted with
permission from ref 418. Copyright 2014 American Physical Society.
distance between tip and sample, and β determines the ability
of the wire to transport current and becomes smaller and
smaller upon increasing the applied voltage.421,422 The obtained
dI/dV spectra for suspended polymers of various lengths are
shown in Figure 34c. It is clear from this figure that the first
resonance appears at V = −0.8 V and a second one occurs at V
= 1.25 V, while another highly intense resonance was found at 2
V. For V = 1.4 eV, the quantum yield of the emission process
was found to be 10−7 photon/electron. It increases up to 10−5
at higher voltage, see Figure 34d, which can be attributed to the
larger emission bandwidth. An atomistic structure of the
polythiophene embedded between the gold electrode and
linked to the top by the STM tip is shown in Figure 34e. The
authors of ref 418 suggest that the strong similarity of their
experiment with OLEDs opens up the possibility to realize
single-molecular optoelectronic devices made of polythiophene.
6.4. Field-Effect Transistors. The basic function of a
transistor is to work as a switch and an amplifier, where the
amount of current flowing between two terminals is determined
by a voltage applied to a gate; thus, the transistor can function
as ON/OFF or as a very sensitive transducer, providing
memory elements similar to those discussed above in Section
6.1. This basic function makes transistors the fundamental
building block of all logic circuits necessary for electronic
devices. Thin film field-effect transistors (FETs) generally
consist of a semiconducting layer separated from a gate
electrode by a thin insulating gate dielectric.58,424,425 Exper-
imentally, it was demonstrated that polythiophene and
derivatives have played an important role in the development
of printable electronics, organic electronics, and molecular
electronic devices.426
In recent years, polythiophene films have been used in
polymer-based FETs.423,427−431 In one study, the authors
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

Figure 35. (a) I−V characteristics of a PBTTT/PMMA transistor, where the PBTTT molecular structure is shown in the upper right inset, and the
transistor structure is shown in lower left inset. (b) CMS spectra for the accumulation region for isotropic nanoribbon PBTTT/PMMA transistors,
where the inset shows the delocalized states, (c) CMS of a nanoribbon PBTTT film in accumulation and full depletion regimes, and (d) UV−visible
absorption spectrum (red line) and first derivative of the absorption (black line) at 300 K. Adapted with permission from ref 423. Copyright 2013
American Chemical Society.

investigated the charge carriers induced in FETs based on a Figures 36a−c. The source electrode is usually grounded when
uniaxially aligned polythiophene derivative poly(2,5-bis(3- voltage is applied through the gate electrode and drain
alkylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT) using
electro-optical charge modulation spectroscopy (CMS). The
I−V characteristics of a PBTTT/polymethymethalacrylate
(PMMA) transistor are shown in Figure 35a, where linear
and saturation mobilities of 0.10 and 0.32 cm2 V−1 s−1,
respectively, were found. The CMS spectra for an isotropic
nanoribbon of PBTTT transistors are addressed in Figure 35b;
the obtained spectra agree well with a previous report.432
Neutral absorption is found to about 2.2 eV, which shows a
positive peak in the ΔT/T plot, whereas charge induced,
polaron-based absorption with two significant negative peaks at
about 1.2−1.3 and 1.8−1.9 eV was observed.
These two peaks might be originating from the same charged
species because the shape of the spectra was independent of the
magnitude of the applied gate voltage.222 The CMS spectra
were measured for aligned nanoribbons of PBTTT films that
were prepared by zone-casting and measured in accumulation
regime of −30 V and full depletion regime of +10 V, where the Figure 36. Molecular structure of self-doped polythiophene (rr-
modulating voltage was ±1 V, see Figure 35c. Neutral UV− P3HT) and different transistor prototypes: (a) bottom contact/top
visible absorption spectroscopy was carried out on PBTTT gate, (b) top contact/bottom gate, and (c) bottom contact/bottom
films at room temperature, see Figure 35d. Interestingly, the gate. (d) Working principle of electrolyte-gated transistors. Adapted
with permission from ref 434. Copyright 2014 Springer Berlin
charge-induced absorption spectrum suggests that polymer- Heidelberg.
based field-effect transistors can be constructed and operated at
room temperature.433
The working principles of polythiophene-based transistors electrode. The source−drain voltage can be estimated just by
are demonstrated in ref 434. A source and a drain electrode, measuring the potential difference between the source and
also called channel width, are separated by a distance called the drain, where the source acts as the charge-injecting electrode. A
channel length, and are directly connected to the semi- symbolic representation of the working principles of the
conducting layer. Commonly used structures of the transistors polythiophene-based field-effect transistor is shown in Figure
include (i) bottom contact/top gate, (ii) top contact/bottom 36d. When a positive gate voltage is applied with respect to the
gate, and (iii) bottom contact/bottom gate geometries, see source, electrons are injected, while holes are injected for
10267 DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

negative gate voltage. The applied gate voltage determines the

amount of accumulated charges in the channel and the current
flow between the source and the drain electrode which, in
principle, is the product of the charge carrier density, mobility,
and the lateral electric fields. Normally, the charges accumulate
only within a minute distance from the semiconductor−
dielectric interface (within the first molecular layer). It is not
necessary that all the induced charges are mobile and contribute
to the current in the field-effect transistors. Such transistors
have been realized experimentally, where SiO2 acts as a
substrate, and a polythiophene-based polymer behaves as
sample. It has been demonstrated that such transistors are
highly stable in air.435−438
More recently, investigations have begun looking at organic
FETs involving thiophene copolymers.440−446 In one such
study, a high field-effect mobility of ∼3.6 cm2 V−1 s−1 was
demonstrated experimentally for an organic transistor made of
an indacenodithiophene−benzothiadiazole copolymer, creating
a donor−acceptor pair within the polymer backbone. The
molecular structure of the copolymer is shown in Figure 37.

Figure 37. Molecular structure of an indacenodithiophene−

benzothiadiazole copolymer. Adapted with permission from ref 439.
Copyright 2013 Nature Publishing Group.
The conjugated planes are found to exhibit a common as well
as comprehensive orientation in both the noncrystalline regions
and the ordered crystallites. The charge transport in high-
mobility semiconducting polymers is found to be quasi one-
dimensional, indicating only intermolecular hopping through
the short π-stacking bridges.439 An organic FET constructed
from indacenodithiophene−benzothiadiazole copolymer is
addressed in Figure 38a, with its I−V characteristics shown in
Figure 38b. The carrier mobility can be estimated by taking the
first as well as second derivatives of the drain current for the
linear and saturation regimes, see Figure 38c. The obtained
values of the mobilities are 1.5 ± 0.2 cm2 V−1 s−1 for the linear
and 2.0 ± 0.2 cm2 V−1 s−1 for the saturation regimes at room
temperature with ON/OFF ratios of about 106, which depends
on the lengths of the devices. A mobility 2−3 times higher was
achieved in contrast to the earlier studies;447,448 the enhance-
ment can be attributed to the larger molecular mass and smaller
polydispersity.449 The mobilities could be further increased by
employing fractionated materials with higher molecular masses
and narrower polydispersity such that the quality and efficiency
of the organic field-effect transistors can be improved.
6.5. Biosensors. Clean water with good microbiological
quality is essential to keep humans healthy and free from
diseases that are transferred by water.450−453 It has been
reported that diarrheal diseases due to poor microbiological
quality result in the deaths of about 4000−6000 children per
day; a large percentage of these deaths are children.454 Water
purification techniques are being developed and employed day
10268
Figure 38. Organic FET constructed from indacenodithiophene−
benzothiadiazole copolymer: (a) top-gate, bottom-contact device, (b)
transfer curves, and (c) mobility obtained based on the first derivative
of the linear and second derivative of the saturation regime. Adapted
with permission from ref 439. Copyright 2013 Nature Publishing
Group.
by day to improve hygiene and reduce the occurrence of
waterborne diseases, but water distribution systems are
increasingly contaminated by a wide range of microbes.455,456
Drinking water naturally contains viruses, bacteria, fungi, and
parasites, and they can survive (i) even in the filtration and
chlorination process, (ii) in the distribution system, such as
household pipes or reservoirs, (iii) from retention or
stagnation, and (iv) in the distribution system following a
structural failure.454,457−459 To tackle the problem properly, a
cationic water-soluble polythiophene was used for the rapid and
direct assessment of the microbiological quality of water based
on the heterotrophic plate count criteria applied in North
America, especially in the United States and Canada.76,166,460 In
the presence of polyanionic macromolecules such as DNA,
RNA, and negatively charged particles, the cationic poly-
thiophene shows a diminution of its initial fluorescence, see
Figure 39 for the detailed steps involved. It also shows a
wavelength shift in fluorescence and colorimetry when its
conformation changes from a nonplanar to a planar form. The
interactions between the cationic polythiophene biosensor and
intact microbial particles decrease the magnitude of the
fluorescence intensity without inducing a fluorescence wave-
length shift, which indicates that this technique is useful for
biosensing.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials Perspective

A schematic description of a polythiophene-based fluorescent

Figure 39. Operating principle of a polymer-based biosensor. The
fluorescence is optimal when the cationic polythiophene biosensors is
by itself; after addition of a microbial particle, a reduction in
fluorescence without any wavelength shift is observed. Adapted with
permission from ref 76. Copyright 2013 American Chemical Society.
DNA biosensor is presented in Figure 40. The fluorescent
hybridization detection signal can be achieved upon conforma-
tional change of the cationic poly(3-alkoxy-4-methylthiophene)
from a planar (duplex) form to a nonplanar (triplex) form.80,461
The polythiophene biosensor measured after 30 min of triplex
formation shows that some DNA sequences emitted higher
fluorescence signals than others. Moreover, the absorbance
measurements showed that the difference in fluorescence signal
is reflected by a faster switch from 530 nm (duplex) to 420 nm
(triplex) absorbance peak for the high fluorescence signal
sequences compared to the weak fluorescence signal, which
indicates that the polythiophene conformational change is
indeed affected by the sequence of the DNA components. The
difference in fluorescence emission signal upon hybridization
can be understood by the structure adopted in the duplex. The
absence of intermolecular hydrogen bonding stabilizes the
dsDNA structure, while ssDNA shows various structures
directly mediated by its sequence; therefore, the variations
might be responsible for the polythiophene-based biosensor
structure in the duplex form.462
6.6. Batteries, Hydrogen Storage, and Supercapaci-
tors. A polythiophene-based flow battery was realized
experimentally with the goal of achieving a high cell
potential.464 In ref 464, polythiophene microparticles were
used for both anodic and cathodic redox couples. The
polythiophene electrochemical redox potential was found to
be −2.0 and +0.5 V for n-doping and p-doping, respectively.
This indicates that the polythiophene-based flow battery can be
operated at a cell potential of 2.5 V, which is the highest cell
potential in a metal-free and all-organic redox flow battery.
Such a battery also showed stable charge/discharge perform-
ance with a high energy efficiency of about 70%.

Figure 40. Schematic representation of polymer-based hybridization detection system. The cationic poly(3-alkoxy-4-methylthiophene) biosensor is
electrostatically attracted by DNA with different optical spectra for single-stranded (ss) DNA (duplex) and double-stranded (ds) DNA (triplex). The
free cationic poly(3-alkoxy-4-methylthiophene) shows a nonplanar conformation with high fluorescence intensity (λmax = 400 nm). For the duplex
form, it shows a planar conformation with very low fluorescence (λmax = 530 nm). Whereas, upon hybridization of the duplex with a dsDNA, the
cationic poly(3-alkoxy-4-methylthiophene) conformation transfers from planar to nonplanar and thus regains much of its fluorescence emission
properties (λmax = 420 nm). DNA detection is based on the fluorescence difference between duplex and triplex. Adapted with permission from ref 80.
Copyright 2013 John Wiley and Sons.

10269 DOI: 10.1021/acs.chemmater.7b03035

Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
The synthesis of activated carbon derived from polythio-
phene is addressed in Figure 41. In this process, 2-
Figure 41. Schematic representation of the synthesis process of
polythiophene-based activated carbon with the following steps: (1)
synthesis and (2) chemical activation of polythiophene. SEM images of
(a) polythiophene and (b) activated carbon and (c) TEM image of the
activated carbon. Adapted with permission from ref 463. Copyright
2011 ScienceDirect.
thiophenemethanol is first polymerized with the help of
FeCl3. The scanning electron microscopy (SEM) image is
shown in Figure 41a, where the diameter of the polythiophene
polymer was found to be about 0.3−1.3 μm. The
polythiophene is then converted into activated carbon by
chemical activation with KOH. The morphology of the
activated carbon exhibits a graphene-like structure with highly
vesiculated irregularly shaped particles of relatively large size of
about 40 μm, see Figure 41b. The porosity of the activated
carbon was found to be randomly distributed but uniformly
sized, see Figure 41c. Highly porous carbon materials with
tunable pore size, surface area, and pore volume of up to 3000
m2/g and 1.75 cm3/g, respectively, were synthesized for the
first time with relatively high hydrogen storage capacity. The
hydrogen storage capacity of the material was found to be
about 5.71 wt%, which is indeed superior to the hydrogen
uptake of other types of activated carbon having similar or even
higher surface area, which is a great achievement in the area of
hydrogen storage.465
A large enhancement in charge capacity was found for
ultrathin polythiophene films, which preserves the high surface
area and pore space of the nanostructures in which they were
developed, ideal for application as pseudocapacitors.466,467 One
such design is shown in Figure 42, where polythiophene
nanofibers are electropolymerized within the pores of a
titanium dioxide nanotube array.466 The nanostructures were
found to exhibit excellent long-term cycling stability (>5000
cycles) with high Coloumbic efficiencies (99.76%) and high
specific capacitance (1052 g−1), very important for application
as pseudocapacitors. Furthermore, pseudocapacitors made of
ultrathin polythiophene within activated carbon increase by up
to 50 and 250% in specific and volumetric capacitance,
respectively, as compared to the bare activated carbon, which
indeed is a great step toward increasing the charge capacity for
polythiophene-based materials.468−470
10270
Perspective
Figure 42. Schematic representation of 1D polythiophene nanofibers
grown within a titanium dioxide nanotube array. Adapted with
permission from ref 466. Copyright 2017 Royal Society of Chemistry.
7. CONCLUSION AND OUTLOOK
In this review, we covered the material properties and possible
applications of pristine polythiophene and its derivatives in light
of theoretical modeling and experimental realization with a view
of future directions. Polythiophene-based polymers have been
used in molecule-based electronic devices because of their
capacity to transition from semiconductor to conductor and the
fact that the material properties can be easily controlled by
doping or chemical modification by creating superlattices with
other materials or by stacking. Polythiophene-based polymers
have already been widely used and extensively studied in
electronic devices such as in field-effect transistors, memory
devices, organic light-emitting diodes, solar cells, biosensors/
hydrogen storage, and batteries. As such, polythiophene-based
molecules do have significant potential to be fully integrated
into a wide range of next generation electronic devices.
However, due to various experimental limitations, synthetic
and structural properties of π-conjugated oligomers or
polymers are still difficult to understand.155,156 As such, there
has been a big push to predict the ability of polythiophene films
and various derivatives for use in organic solar cells, FETs, and
LEDs through computational approaches471−475 rather than
experimental approaches, effectively creating a catalog of
potential polythiophene-based materials. The challenge then
lies in the effectiveness of the theoretical models used, which is
limited by the various levels of approximations that have to be
chosen and the difficulty of building physically meaningful yet
tractable models of complex experimental situations.157,476 In
the end, it should be noted that the B3LYP, HSE, LC, and LC*
levels of computational approaches reproduced experimental
parameters very well compared to those of HF and PBE;
therefore, our suggestion is to employ B3LYP, HSE, LC, and
LC* levels of computational approaches while dealing with π-
conducting polymers such as polythiophene and its derivatives.
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: thaneshwor.kaloni@umanitoba.ca.
*E-mail: schrecke@cc.umanitoba.ca.
*E-mail: msfreund@fit.edu.
ORCID
Patrick K. Giesbrecht: 0000-0003-2039-4791
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Georg Schreckenbach: 0000-0002-4614-0901
Michael S. Freund: 0000-0003-1104-2292
Notes
The authors declare no competing financial interest.
Biographies
Dr. Thaneshwor P. Kaloni obtained his M.Sc. from Tribhuvan
University, Nepal in 2007. He received a Ph.D. in materials science
and engineering from King Abdullah University of Science and
Technology in 2013. He then moved to the University of Manitoba
Department of Chemistry as a postdoctoral fellow in 2014 and worked
on polythiophene-based conducting polymers for one and half years.
In 2016, he moved to California State University Northridge as a
research scientist. Currently, he is a postdoctoral fellow at the
University of Arkansas, Fayetteville, where he is working on two-
dimensional structural phase transition and ferroelectricity in
monochalcogenide monolayers. To date, he has published 37 papers.
Patrick K. Giesbrecht received his B.Sc. and M.Sc. degrees from the
University of Manitoba (Winnipeg, Canada) in 2015 and 2017,
respectively. During his time there, he conducted research on the
growth and surface functionalization of silicon microrods under the
supervision of Professor Michael S. Freund as well as investigations
into electrocatalysts for CO2 reduction for solar fuels applications
under the supervision of Professor David E. Herbert. He is now a
member of the professional staff at the Florida Institute of Technology
in the Freund Group, where he is working on the development of
membranes for solar fuel generation.
Dr. Georg Schreckenbach is a Professor of Chemistry at the University
of Manitoba, Canada. He received his Ph.D. in 1996 from the
University of Calgary, Canada, under the supervision of the late Tom
Ziegler. From 1997 to 2000, he was a Seaborg Institute Postdoctoral
Fellow at Los Alamos National Laboratory, United States, working
with Jeffrey Hay and Richard Martin. After holding positions at the
CCLRC Daresbury Laboratory (UK) and Concordia University
(Canada), he joined the University of Manitoba in 2003. Dr.
Schreckenbach’s research interests span a wide range of computational
and theoretical chemistry. They include quantum-chemical method
development, chemistry of heavy elements (actinides and Hg), and
materials (solar energy conversion, polymers, and 2D materials).
Dr. Michael S. Freund has been Professor and Head of Chemistry at
the Florida Institute of Technology since 2015. From 2002 to 2015, he
was faculty at the University of Manitoba, where he attained the rank
of tenured Professor of Chemistry and held the Canada Research
Chair in Electronic Materials (Tier 1 and 2). He has published over
100 papers and has supervised approximately 50 students and
postdoctoral associates. His research interests include electro-
chemistry, conducting polymers, and surface science.
■
ACKNOWLEDGMENTS
G.S. acknowledges funding from the Natural Sciences and
Engineering Council of Canada (NSERC, Discovery Grant).
M.S.F. acknowledges support by the Natural Sciences and
Engineering Research Council (NSERC) of Canada, the
Canada Research Chair program, Canada Foundation for
Innovation (CFI), the Manitoba Research and Innovation
Fund, the University of Manitoba, and the United States
National Science Foundation (NSF) under the CCI Solar Fuels
Program, Grant No. CHE-1305124.
■
REFERENCES
(1) Chiang, C. K.; Fincher, C. R.; Park, Y. W.; Heeger, A. J.;
Shirakawa, H.; Louis, E. J.; Gau, S. C.; MacDiarmid, A. G. Electrical
10271
Perspective
Conductivity in Doped Polyacetylene. Phys. Rev. Lett. 1977, 39, 1098−
1101.
(2) Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G.; Chiang, C. K.;
Heeger, A. J. Synthesis of Electrically Conducting Organic Polymers:
Halogen Derivatives of Polyacetylene (CH). J. Chem. Soc., Chem.
Commun. 1977, 16, 578−580.
(3) Kumar, M. R.; Freund, M. S. In Self-Doped Polymers; K. Mullen,
T. M., Reynolds, J. R., Ed.; Royal Society of Chemistry: London, 2013.
(4) Freund, M. S.; Deore, B. A. Self-Doped Conducting Polymers;
Wiley and Sons: Hoboken, NJ, 2007.
(5) Skotheim, T. A. In Handbook of Conducting Polymers; Dekker:
New York, 1986; Vol. I and II.
(6) McGehee, M. D.; Miller, E. K.; Moses, D.; Heeger, A. J. In
Advances in Synthetic Metals: Twenty Years of Progress in Science and
Technology; Bernier, P., Ed.; Elsevier: Amsterdam, 1999.
(7) Plausinaitis, D.; Sinkevicius, L.; Mikoliunaite, L.; Plausinaitiene,
V.; Ramanaviciene, A.; Ramanavicius, A. Electrochemical polypyrrole
formation from pyrrole ’adlayer’. Phys. Chem. Chem. Phys. 2017, 19,
1029−1038.
(8) Pham-Cong, D.; Park, J.; Kim, J.; Kim, J.; Braun, P.; Choi, J.; Kim,
S.; Jeong, S.; Cho, C. Enhanced cycle stability of polypyrrole-derived
nitrogen-doped carbon-coated tin oxide hollow nanofibers for lithium
battery anodes. Carbon 2017, 111, 28−37.
(9) Tan, Q.; Lu, S.; Lv, Y.; Xu, X.; Si, J.; Xiang, Y. Doping structure
and degradation mechanism of polypyrrole-Nafion composite
membrane for vanadium redox flow batteries. RSC Adv. 2016, 6,
103332−103336.
(10) Kadac, K.; Nowaczyk, J. Polythiophene nanoparticles in aqueous
media. J. Appl. Polym. Sci. 2016, 133, 1.
(11) Raichman, D.; Ben-Shabat Binyamini, R.; Lellouche, J.-P. A new
polythiophene-driven coating method on an inorganic INT/IF-WS2
nanomaterial surface. RSC Adv. 2016, 6, 4490−4504.
(12) Brédas, J. L.; Street, G. B.; Thémans, B.; André, J. M. Organic
Polymers Based on Aromatic Rings (Polyparaphenylene, Polypyrrole,
Polythiophene): Evolution of the Electronic Properties as a Function
of the Torsion Angle between Adjacent Rings. J. Chem. Phys. 1985, 83,
1323−1329.
(13) Brédas, J. L.; Thémans, B.; Fripiat, J. G.; André, J. M.; Chance,
R. R. Highly Conducting Polyparaphenylene, Polypyrrole, and
Polythiophene Chains: An ab initio Study of the Geometry and
Electronic-Structure Modifications upon Doping. Phys. Rev. B:
Condens. Matter Mater. Phys. 1984, 29, 6761−6773.
(14) Heeger, A. J. Semiconducting and Metallic Polymers: The
Fourth Generation of Polymeric Materials (Nobel Lecture). Angew.
Chem., Int. Ed. 2001, 40, 2591−2611.
(15) MacDiarmid, A. G. Synthetic Metals”: A Novel Role for Organic
Polymers (Nobel Lecture). Angew. Chem., Int. Ed. 2001, 40, 2581−
2590.
(16) Shirakawa, H. The Discovery of Polyacetylene Film: The
Dawning of an Era of Conducting Polymers (Nobel Lecture). Angew.
Chem., Int. Ed. 2001, 40, 2574−2580.
(17) Zhao, X.; Zhan, X. Electron Transporting Semiconducting
Polymers in Organic Electronics. Chem. Soc. Rev. 2011, 40, 3728−
3743.
(18) Hoofman, R. J.; de Haas, M. P.; Siebbeles, L. D.; Warman, J. M.
Highly Mobile Electrons and Holes on Isolated Chains of the
Semiconducting Polymer Poly(phenylene Vinylene). Nature 1998,
392, 54−56.
(19) Noriega, R.; Salleo, A.; Spakowitz, A. J. Chain Conformations
Dictate Multiscale Charge Transport Phenomena in Disordered
Semiconducting Polymers. Proc. Natl. Acad. Sci. U. S. A. 2013, 110,
16315−16320.
(20) Nicolai, H.; Kuik, M.; Wetzelaer, G.; de Boer, B.; Campbell, C.;
Risko, C.; Brédas, J.; Blom, P. Unification of Trap-Limited Electron
Transport in Semiconducting Polymers. Nat. Mater. 2012, 11, 882−
887.
(21) Sotzing, G. A.; Lee, K. Poly(thieno[3,4-b]thiophene): A p- and
n-Dopable Polythiophene Exhibiting High Optical Transparency in
the Semiconducting State. Macromolecules 2002, 35, 7281−7286.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(22) Sotzing, G. A.; Thomas, C. A.; Reynolds, J. R.; Steel, P. J. Low
Band Gap Cyanovinylene Polymers Based on Ethylenedioxythiophene.
Macromolecules 1998, 31, 3750−3752.
(23) Sotzing, G. A.; Reynolds, J. R.; Katritzky, A. R.; Soloducho, J.;
Belyakov, S.; Musgrave, R. Poly[bis(pyrrol-2-yl)arylenes]: Conducting
Polymers from Low Oxidation Potential Monomers Based on Pyrrole
via Electropolymerization. Macromolecules 1996, 29, 1679−1684.
(24) Jang, S.-Y.; Sotzing, G. A.; Marquez, M. Intrinsically Conducting
Polymer Networks of Poly(thiophene) via Solid-State Oxidative
Cross-Linking of a Poly(norbornylene) Containing Terthiophene
Moieties. Macromolecules 2002, 35, 7293−7300.
(25) Lee, B.; Yavuz, M. S.; Sotzing, G. A. Poly(thieno[3,4-
b]thiophene)s from Three Symmetrical Thieno[3,4-b]thiophene
Dimers. Macromolecules 2006, 39, 3118−3124.
(26) Kumar, A.; Buyukmumcu, Z.; Sotzing, G. A. Poly(thieno[3,4-
b]furan). A New Low Band Gap Conjugated Polymer. Macromolecules
2006, 39, 2723−2725.
(27) Dey, T.; Invernale, M. A.; Ding, Y.; Buyukmumcu, Z.; Sotzing,
G. A. Poly(3,4-propylenedioxythiophene)s as a Single Platform for
Full Color Realization. Macromolecules 2011, 44, 2415−2417.
(28) Kumar, A.; Bokria, J. G.; Buyukmumcu, Z.; Dey, T.; Sotzing, G.
A. Poly(thieno[3,4-b]furan), a New Low Band Gap Polymer:
Experiment and Theory. Macromolecules 2008, 41, 7098−7108.
(29) Niwa, O.; Tamamura, T. Polythiophene/Polyvinylchloride
Conducting Polymer Alloy Films and their Redox Properties. Synth.
Met. 1987, 20, 235−243.
(30) Krische, B.; Zagorska, M. The Polythiophene Paradox. Synth.
Met. 1989, 28, 263−268.
(31) Waltman, R. J.; Bargon, J.; Diaz, A. F. Electrochemical Studies of
some Conducting Polythiophene Films. J. Phys. Chem. 1983, 87,
1459−1463.
(32) Gasiorowski, J.; Boudiba, S.; Hingerl, K.; Ulbricht, C.; Fattori,
V.; Tinti, F.; Camaioni, N.; Menon, R.; Schlager, S.; Boudida, L.; et al.
Anthracene-Containing Conjugated Polymer Showing Four Optical
Transitions Upon Doping: A Spectroscopic Study. J. Polym. Sci., Part
B: Polym. Phys. 2014, 52, 338−346.
(33) Liu, Y.; Scully, S. R.; McGehee, M. D.; Liu, J.; Luscombe, C. K.;
Fréchet, J. M. J.; Shaheen, S. E.; Ginley, D. S. Dependence of Band
Offset and Open-Circuit Voltage on the Interfacial Interaction
between TiO2 and Carboxylated Polythiophenes. J. Phys. Chem. B
2006, 110, 3257−3261.
(34) Pandey, L.; Doiron, C.; Sears, J. S.; Brédas, J.-L. Lowest Excited
States and Optical Absorption Spectra of Donor-Acceptor Copolymers
for Organic Photovoltaics: A New Picture Emerging from Tuned
Long-Range Corrected Density Functionals. Phys. Chem. Chem. Phys.
2012, 14, 14243−14248.
(35) Arroyave, F. A.; Richard, C. A.; Reynolds, J. R. Efficient
Synthesis of Benzo[1,2-b:6,5-b′]dithiophene-4,5-dione (BDTD) and
Its Chemical Transformations into Precursors for π-Conjugated
Materials. Org. Lett. 2012, 14, 6138−6141.
(36) Wang, L.; Puodziukynaite, E.; Grumstrup, E. M.; Brown, A. C.;
Keinan, S.; Schanze, K. S.; Reynolds, J. R.; Papanikolas, J. M. Ultrafast
Formation of a Long-Lived Charge-Separated State in a Ru-Loaded
Poly(3-hexylthiophene) Light-Harvesting Polymer. J. Phys. Chem. Lett.
2013, 4, 2269−2273.
(37) Estrada, L. A.; Deininger, J. J.; Kamenov, G. D.; Reynolds, J. R.
Direct (Hetero)arylation Polymerization: An Effective Route to 3,4-
Propylenedioxythiophene-Based Polymers with Low Residual Metal
Content. ACS Macro Lett. 2013, 2, 869−873.
(38) Beaujuge, P. M.; Vasilyeva, S. V.; Liu, D. Y.; Ellinger, S.;
McCarley, T. D.; Reynolds, J. R. Structure-Performance Correlations
in Spray-Processable Green Dioxythiophene-Benzothiadiazole Donor-
Acceptor Polymer Electrochromes. Chem. Mater. 2012, 24, 255−268.
(39) Brown, P. J.; Thomas, D. S.; Köhler, A.; Wilson, J. S.; Kim, J.-S.;
Ramsdale, C. M.; Sirringhaus, H.; Friend, R. H. Effect of Interchain
Interactions on the Absorption and Emission of Poly(3-hexylth-
iophene). Phys. Rev. B: Condens. Matter Mater. Phys. 2003, 67, 064203.
(40) Roth, S.; Bleier, H. Solitons in polyacetylene. Adv. Phys. 1987,
36, 385−462.
10272
Perspective
(41) Heeger, A. J.; Kivelson, S.; Schrieffer, J. R.; Su, W. P. Solitons in
Conducting Polymers. Rev. Mod. Phys. 1988, 60, 781−850.
(42) Deore, B. A.; Yu, I.; Freund, M. S. A Switchable Self-Doped
Polyaniline: Interconversion between Self-Doped and Non-Self-Doped
Forms. J. Am. Chem. Soc. 2004, 126, 52−53.
(43) Wang, W.; Chen, C.; Tollan, C.; Yang, F.; Qin, Y.; Knez, M.
Efficient and controllable vapor to solid doping of the polythiophene
P3HT by low temperature vapor phase infiltration. J. Mater. Chem. C
2017, 5, 2686−2694.
(44) Bulumulla, C.; Du, J.; Washington, K. E.; Kularatne, R. N.;
Nguyen, H. Q.; Biewer, M. C.; Stefan, M. C. Influence of
functionalized side chains of polythiophene diblock copolymers on
the performance of CdSe quantum dot hybrid solar cells. J. Mater.
Chem. A 2017, 5, 2473−2477.
(45) Borjas, R.; Buttry, D. A. EQCM Studies of Film Growth, Redox
Cycling, and Charge Trapping of n-Doped and p-Doped Poly-
(Thiophene). Chem. Mater. 1991, 3, 872−878.
(46) Mastragostino, M.; Soddu, L. Electrochemical Characterization
of N Doped Polyheterocyclic Conducting Polymers-I. Polybithio-
phene. Electrochim. Acta 1990, 35, 463−466.
(47) Xu, Y.; Berger, P. R. High Electric-Field Effects on Short-
Channel Polythiophene Polymer Field-Effect Transistors. J. Appl. Phys.
2004, 95, 1497−1501.
(48) Kaloni, T. P.; Singh, N.; Schwingenschlögl, U. Prediction of a
quantum anomalous Hall state in Co-decorated silicene. Phys. Rev. B:
Condens. Matter Mater. Phys. 2014, 89, 035409.
(49) Kaloni, T. P.; Gangopadhyay, S.; Singh, N.; Jones, B.;
Schwingenschlögl, U. Electronic properties of Mn-decorated silicene
on hexagonal boron nitride. Phys. Rev. B: Condens. Matter Mater. Phys.
2013, 88, 235418.
(50) Kaloni, T.; Tahir, M.; Schwingenschlögl, U. Quasi Free-Standing
Silicene in a Superlattice with Hexagonal Boron Nitride. Sci. Rep. 2013,
3, 3192.
(51) Kaloni, T. P.; Schreckenbach, G.; Freund, M. S.;
Schwingenschlö g l, U. Current developments in silicene and
germanene. Phys. Status Solidi RRL 2016, 10, 133−142.
(52) Kaloni, T.; Kahaly, M. U.; Faccio, R.; Schwingenschlögl, U.
Modelling magnetism of C at O and B monovacancies in graphene.
Carbon 2013, 64, 281−287.
(53) Chiang, C. K.; Gau, S. C.; Fincher, C. R.; Park, Y. W.;
MacDiarmid, A. G.; Heeger, A. J. Polyacetylene, (CH)x: N-Type and
P-Type Doping and Compensation. Appl. Phys. Lett. 1978, 33, 18−20.
(54) Chiang, C. K.; Park, Y. W.; Heeger, A. J.; Shirakawa, H.; Louis,
E. J.; MacDiarmid, A. G. Conducting Polymers: Halogen Doped
Polyacetylene. J. Chem. Phys. 1978, 69, 5098−5104.
(55) Moon, Y. B.; Winokur, M.; Heeger, A. J.; Barker, J.; Bott, D. C.
X-ray Scattering from Oriented Durham Polyacetylene: Structural
Changes after Electrochemical Doping. Macromolecules 1987, 20,
2457−2461.
(56) Winokur, M.; Moon, Y. B.; Heeger, A. J.; Barker, J.; Bott, D. C.;
Shirakawa, H. X-Ray Scattering from Sodium-Doped Polyacetylene:
Incommensurate-Commensurate and Order-Disorder Transforma-
tions. Phys. Rev. Lett. 1987, 58, 2329−2332.
(57) Ma, C.-Q.; Mena-Osteritz, E.; Debaerdemaeker, T.; Wienk, M.;
Janssen, R.; Bäuerle, P. Functionalized 3D Oligothiophene Dendrons
and Dendrimers-Novel Macromolecules for Organic Electronics.
Angew. Chem., Int. Ed. 2007, 46, 1679−1683.
(58) Kline, R. J.; McGehee, M. D.; Toney, M. F. Highly Oriented
Crystals at the Buried Interface in Polythiophene Thin-Film
Transistors. Nat. Mater. 2006, 5, 222−228.
(59) Ziebarth, J.; Saafir, A.; Fan, S.; McGehee, M. Extracting Light
from Polymer Light-Emitting Diodes Using Stamped Bragg Gratings.
Adv. Funct. Mater. 2004, 14, 451−456.
(60) McGehee, M. D.; Heeger, A. J. Semiconducting (Conjugated)
Polymers as Materials for Solid-State Lasers. Adv. Mater. 2000, 12,
1655−1668.
(61) McGehee, M. D.; Dıáz-Garcıá, M. A.; Hide, F.; Gupta, R.;
Miller, E. K.; Moses, D.; Heeger, A. J. Semiconducting Polymer
Distributed Feedback Lasers. Appl. Phys. Lett. 1998, 72, 1536−1538.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(62) Coakley, K. M.; McGehee, M. D. Conjugated Polymer
Photovoltaic Cells. Chem. Mater. 2004, 16, 4533−4542.
(63) McGehee, M. D. Materials Science: Fast-Track Solar Cells.
Nature 2013, 501, 323−325.
(64) Hardin, B. E.; Snaith, H. J.; McGehee, M. D. The renaissance of
Dye-Sensitized Solar Cells. Nat. Photonics 2012, 6, 162−169.
(65) Miller, N. C.; Cho, E.; Gysel, R.; Risko, C.; Coropceanu, V.;
Miller, C. E.; Sweetnam, S.; Sellinger, A.; Heeney, M.; McCulloch, I.;
et al. Factors Governing Intercalation of Fullerenes and Other Small
Molecules Between the Side Chains of Semiconducting Polymers
Used in Solar Cells. Adv. Energy Mater. 2012, 2, 1208−1217.
(66) Gélinas, S.; Rao, A.; Kumar, A.; Smith, S. L.; Chin, A. W.; Clark,
J.; van der Poll, T. S.; Bazan, G. C.; Friend, R. H. Ultrafast Long-Range
Charge Separation in Organic Semiconductor Photovoltaic Diodes.
Science 2014, 343, 512−516.
(67) Kumar, M. R.; Ryman, S.; Tareq, O.; Buchanan, D. A.; Freund,
M. S. Chemical Diversity in Electrochemically Deposited Conducting
Polymer-Based Sensor Arrays. Sens. Actuators, B 2014, 202, 600−608.
(68) English, J. T.; Deore, B. A.; Freund, M. S. Biogenic Amine
Vapour Detection Using Poly(Anilineboronic Acid) Films. Sens.
Actuators, B 2006, 115, 666−671.
(69) Nambiar, S.; Yeow, J. T. W. Conductive Polymer-Based Sensors
for Biomedical Applications. Biosens. Bioelectron. 2011, 26, 1825−1832.
(70) Li, C.; Shi, G. Polythiophene-Based Optical Sensors for Small
Molecules. ACS Appl. Mater. Interfaces 2013, 5, 4503−4510.
(71) Shin, Y.; Lin, X. Modeling Photoinduced Charge Transfer
Across π-Conjugated Heterojunctions. J. Phys. Chem. C 2013, 117,
12432−12437.
(72) Teh, S.-L.; Linton, D.; Sumpter, B.; Dadmun, M. D. Controlling
Non-Covalent Interactions to Modulate the Dispersion of Fullerenes
in Polymer Nanocomposites. Macromolecules 2011, 44, 7737−7745.
(73) Ludwig, K. A.; Uram, J. D.; Yang, J.; Martin, D. C.; Kipke, D. R.
Chronic Neural Recordings using Silicon Microelectrode Arrays
Electrochemically Deposited with a Poly(3,4-ethylenedioxythiophene)
(PEDOT) film. J. Neural Eng. 2006, 3, 59.
(74) Richardson-Burns, S. M.; Hendricks, J. L.; Foster, B.; Povlich, L.
K.; Kim, D.-H.; Martin, D. C. Polymerization of the Conducting
Polymer Poly(3,4-ethylenedioxythiophene) (PEDOT) Around Living
Neural Cells. Biomaterials 2007, 28, 1539−1552.
(75) Kim, D.-H.; Richardson-Burns, S.; Hendricks, J.; Sequera, C.;
Martin, D. Effect of Immobilized Nerve Growth Factor on Conductive
Polymers: Electrical Properties and Cellular Response. Adv. Funct.
Mater. 2007, 17, 79−786.
(76) Plante, M.-P.; Bérubé, E.; Bissonnette, L.; Bergeron, M. G.;
Leclerc, M. Polythiophene Biosensor for Rapid Detection of Microbial
Particles in Water. ACS Appl. Mater. Interfaces 2013, 5, 4544−4548.
(77) Bér a-Abérem, M.; Ho, H.-A.; Leclerc, M. Functional
Polythiophenes as Optical Chemo- and Biosensors. Tetrahedron
2004, 60, 11169−11173.
(78) Kumpumbu-Kalemba, L.; Leclerc, M. Electrochemical Charac-
terization of Monolayers of a Biotinylated Polythiophene: Towards the
Development of Polymeric Biosensors. Chem. Commun. 2000, 1847−
1848.
(79) Ho, H.-A.; Boissinot, M.; Bergeron, M. G.; Corbeil, G.; Doré,
K.; Boudreau, D.; Leclerc, M. Colorimetric and Fluorometric
Detection of Nucleic Acids Using Cationic Polythiophene Derivatives.
Angew. Chem., Int. Ed. 2002, 41, 1548−1551.
(80) Charlebois, I.; Gravel, C.; Arrad, N.; Boissinot, M.; Bergeron, M.
G.; Leclerc, M. Impact of DNA Sequence and Oligonucleotide Length
on a Polythiophene-Based Fluorescent DNA Biosensor. Macromol.
Biosci. 2013, 13, 717−722.
(81) Hollinger, J.; DiCarmine, P. M.; Karl, D.; Seferos, D. S.
Heterocycle-Induced Phase Separation in Conjugated Polymers.
Macromolecules 2012, 45, 3772−3778.
(82) Jahnke, A. A.; Djukic, B.; McCormick, T. M.; Buchaca Domingo,
E.; Hellmann, C.; Lee, Y.; Seferos, D. S. Poly(3-alkyltellurophene)s
Are Solution-Processable Polyheterocycles. J. Am. Chem. Soc. 2013,
135, 951−954.
10273
Perspective
(83) Jahnke, A. A.; Yu, L.; Coombs, N.; Scaccabarozzi, A. D.; Tilley,
A. J.; DiCarmine, P. M.; Amassian, A.; Stingelin, N.; Seferos, D. S.
Polytellurophenes provide imaging contrast towards unravelling the
structure-property-function relationships in semiconductor:insulator
polymer blends. J. Mater. Chem. C 2015, 3, 3767−3773.
(84) Kynaston, E. L.; Fang, Y.; Manion, J. G.; Obhi, N. K.; Howe, J.
Y.; Perepichka, D. F.; Seferos, D. S. Patchy Nanofibers from the Thin
Film Self-Assembly of a Conjugated Diblock Copolymer. Angew.
Chem., Int. Ed. 2017, 56, 6152−6156.
(85) Li, L.; Hollinger, J.; Guerin, G.; Seferos, D. S. Synthesis and
Network-Like Self-Assembly of Porphyrin-Polyselenophene Com-
plexes. ChemPhysChem 2012, 13, 4110−4115.
(86) Li, L.; Hollinger, J.; Jahnke, A. A.; Petrov, S.; Seferos, D. S.
Polyselenophenes with distinct crystallization properties. Chem. Sci.
2011, 2, 2306−2310.
(87) Razzell-Hollis, J.; Fleischli, F.; Jahnke, A. A.; Stingelin, N.;
Seferos, D. S.; Kim, J.-S. Effects of Side-Chain Length and Shape on
Polytellurophene Molecular Order and Blend Morphology. J. Phys.
Chem. C 2017, 121, 2088−2098.
(88) Ramírez-Solís, A.; Kirtman, B.; Bernal-Jáquez, R.; Zicovich-
Wilson, C. M. Periodic Density Functional Theory Studies of Li-
Doped Polythiophene: Dependence of Electronic and Structural
Properties on Dopant Concentration. J. Chem. Phys. 2009, 130,
164904.
(89) Ho, H.-A.; Najari, A.; Leclerc, M. Optical Detection of DNA and
Proteins with Cationic Polythiophenes. Acc. Chem. Res. 2008, 41, 168−
178.
(90) Béra-Abérem, M.; Najari, A.; Ho, H.-A.; Gravel, J.-F.; Nobert, P.;
Boudreau, D.; Leclerc, M. Protein Detecting Arrays Based on Cationic
Polythiophene-DNA-Aptamer Complexes. Adv. Mater. 2006, 18,
2703−2707.
(91) le Floch, F.; Ho, H. A.; Leclerc, M. Label-Free Electrochemical
Detection of Protein Based on a Ferrocene-Bearing Cationic
Polythiophene and Aptamer. Anal. Chem. 2006, 78, 4727−4731.
(92) LeFloch, F.; Ho, H.-A.; Harding-Lepage, P.; Bédard, M.; Neagu-
Plesu, R.; Leclerc, M. Ferrocene-Functionalized Cationic Polythio-
phene for the Label-Free Electrochemical Detection of DNA. Adv.
Mater. 2005, 17, 1251−1254.
(93) Bernier, S.; Garreau, S.; Béra-Abérem, M.; Gravel, C.; Leclerc,
M. A Versatile Approach to Affinitychromic Polythiophenes. J. Am.
Chem. Soc. 2002, 124, 12463−12468.
(94) Granström, M. M.; Harrison, G.; Friend, R. H. In Electro-Optical
Polythiophene Devices; Fichou, D., Ed.; Wiley-VCH: Weinheim, 1998;
pp 405−458.
(95) Coppo, P.; Cupertino, D. C.; Yeates, S. G.; Turner, M. L.
Synthetic Routes to Solution-Processable Polycyclopentadithiophenes.
Macromolecules 2003, 36, 2705−2711.
(96) Mehmood, U.; Al-Ahmed, A.; Hussein, I. A. Review on recent
advances in polythiophene based photovoltaic devices. Renewable
Sustainable Energy Rev. 2016, 57, 550−561.
(97) Parente, V.; Pourtois, G.; Lazzaroni, R.; Brédas, J.-L.; Ruani, G.;
Murgia, M.; Zamboni, R. The Vibrational Signature of the Aluminum/
Polythiophene Interface. Adv. Mater. 1998, 10, 319−324.
(98) Parente, V.; Pourtois, G.; Lazzaroni, R.; Brédas, J. Theoretical
Investigation of the Chemical Structure and Vibrational Signature at
the Aluminum-Polythiophene Interface. Synth. Met. 1997, 85, 1031−
1034.
(99) Wang, F.; Gu, H.; Swager, T. M. Carbon Nanotube/
Polythiophene Chemiresistive Sensors for Chemical Warfare Agents.
J. Am. Chem. Soc. 2008, 130, 5392−5393.
(100) Sugiyasu, K.; Song, C.; Swager, T. M. Aromaticity in Tropone-
Containing Polythiophene. Macromolecules 2006, 39, 5598−5600.
(101) Kingsborough, R. P.; Swager, T. M. Electrocatalytic
Conducting Polymers: Oxygen Reduction by a Polythiophene-Cobalt
Salen Hybrid. Chem. Mater. 2000, 12, 872−874.
(102) Kaloni, T. P.; Schreckenbach, G.; Freund, M. S. The Structural
and Electronic Properties of Pristine and Doped Polythiophene:
Periodic Versus Molecular Calculations. J. Phys. Chem. C 2015, 119,
3979−3989.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(103) Kaloni, T. P.; Schreckenbach, G.; Freund, M. S. Band Bap
Modulation in Polythiophene and Polypyrrole-based Systems. Sci. Rep.
2016, 6, 36554.
(104) Kingsborough, R. P.; Swager, T. M. Polythiophene Hybrids of
Transition-Metal Bis(salicylidenimine)s: Correlation between Struc-
ture and Electronic Properties. J. Am. Chem. Soc. 1999, 121, 8825−
8834.
(105) Zhu, S. S.; Kingsborough, R. P.; Swager, T. M. Conducting
Redox Polymers: Investigations of Polythiophene-(Ru(bpy)3 Hybrid
Materials. J. Mater. Chem. 1999, 9, 2123−2131.
(106) Marsella, M. J.; Newland, R. J.; Carroll, P. J.; Swager, T. M.
Ionoresistivity as a Highly Sensitive Sensory Probe: Investigations of
Polythiophenes Functionalized with Calix[4]arene-Based Ion Recep-
tors. J. Am. Chem. Soc. 1995, 117, 9842−9848.
(107) Marsella, M. J.; Swager, T. M. Designing Conducting Polymer-
Based Sensors: Selective Ionochromic Response in Crown Ether-
Containing Polythiophenes. J. Am. Chem. Soc. 1993, 115, 12214−
12215.
(108) Zhu, S. S.; Swager, T. M. Design of Conducting Redox
Polymers: A Polythiophene-(Ru(bipy)3;n@Hybrid Material. Adv.
Mater. 1996, 8, 497−500.
(109) Suppes, G.; Ballard, E.; Holdcroft, S. Aqueous Photocathode
Activity of Regioregular Poly(3-hexylthiophene). Polym. Chem. 2013,
4, 5345−5350.
(110) Gholamkhass, B.; Peckham, T. J.; Holdcroft, S. Poly(3-
hexylthiophene) Bearing Pendant Fullerenes: Aggregation vs. Self-
Organization. Polym. Chem. 2010, 1, 708−719.
(111) Brédas, J. L.; Silbey, R.; Boudreaux, D. S.; Chance, R. R. Chain-
Length Dependence of Electronic and Electrochemical Properties of
Conjugated Systems: Polyacetylene, Polyphenylene, Polythiophene,
and Polypyrrole. J. Am. Chem. Soc. 1983, 105, 6555−6559.
(112) Groenendaal, L.; Zotti, G.; Aubert, P.-H.; Waybright, S.;
Reynolds, J. Electrochemistry of Poly(3,4-alkylenedioxythiophene)
Derivatives. Adv. Mater. 2003, 15, 855−879.
(113) Salzner, U. Theoretical Design of Conjugated Organic
Polymers. Curr. Org. Chem. 2004, 8, 569−590.
(114) Forrest, S. R.; Thompson, M. E. Introduction:Organic
Electronics and Optoelectronics. Chem. Rev. 2007, 107, 923−925.
(115) Heinze, J.; Frontana-Uribe, B. A.; Ludwigs, S. Electrochemistry
of Conducting Polymers-Persistent Models and New Concepts. Chem.
Rev. 2010, 110, 4724−4771.
(116) Kertesz, M.; Choi, C. H.; Yang, S. Conjugated Polymers and
Aromaticity. Chem. Rev. 2005, 105, 3448−3481.
(117) Coropceanu, V.; Cornil, J.; da Silva Filho, D. A.; Olivier, Y.;
Silbey, R.; Brédas, J.-L. Charge Transport in Organic Semiconductors.
Chem. Rev. 2007, 107, 926−952.
(118) Casanovas, J.; Alemán, C. Comparative Theoretical Study of
Heterocyclic Conducting Oligomers: Neutral and Oxidized Forms. J.
Phys. Chem. C 2007, 111, 4823−4830.
(119) Toussaint, J. M.; Brédas, J. L. Theoretical Analysis of the
Geometric and Electronic Structure of Small-Band-Gap Polythio-
phenes: Poly(5,5′-bithiophene methine) and its Derivatives. Macro-
molecules 1993, 26, 5240−5248.
(120) dos Santos, D. A.; Brédas, J. L. Influence of Polymerization
Irregularities on the Electronic Properties of Polythiophene. J. Chem.
Phys. 1991, 95, 6567−6575.
(121) Salzner, U. Does the Donor-Acceptor Concept Work for
Designing Synthetic Metals? 1. Theoretical Investigation of Poly(3-
cyano-3′-hydroxybithiophene). J. Phys. Chem. B 2002, 106, 9214−
9220.
(122) Radhakrishnan, S.; Parthasarathi, R.; Subramanian, V.;
Somanathan, N. Quantum Chemical Studies on Polythiophenes
Containing Heterocyclic Substituents: Effect of Structure on the
Band Gap. J. Chem. Phys. 2005, 123, 164905.
(123) Radhakrishnan, S.; Ananthakrishnan, S.; Somanathan, N.
Structure-Property Relationships of Electroluminescent Polythio-
phenes: Role of Nitrogen-Based Heterocycles as Side Chains. Bull.
Mater. Sci. 2011, 34, 713−726.
10274
Perspective
(124) Zade, S. S.; Bendikov, M. Theoretical Study of Long
Oligothiophene Polycations as a Model for Doped Polythiophene. J.
Phys. Chem. C 2007, 111, 10662−10672.
(125) Zamoshchik, N.; Salzner, U.; Bendikov, M. Nature of Charge
Carriers in Long Doped Oligothiophenes: The Effect of Counterions.
J. Phys. Chem. C 2008, 112, 8408−8418.
(126) Patra, A.; Wijsboom, Y. H.; Leitus, G.; Bendikov, M. Tuning
the Band Gap of Low-Band-Gap Polyselenophenes and Polythio-
phenes: The Effect of the Heteroatom†. Chem. Mater. 2011, 23, 896−
906.
(127) Rittmeyer, S. P.; Groß, A. Structural and Electronic Properties
of Oligo- and Polythiophenes Modified by Substituents. Beilstein J.
Nanotechnol. 2012, 3, 909−919.
(128) Zhou, W.; Hernández-Burgos, K.; Burkhardt, S. E.; Qian, H.;
Abruña, H. D. Synthesis and Electrochemical and Computational
Analysis of Two New Families of Thiophene-Carbonyl Molecules. J.
Phys. Chem. C 2013, 117, 6022−6032.
(129) Mena-Osteritz, E.; Zhang, F.; Götz, G.; Reineker, P.; Bäuerle,
P. Optical Properties of Fully Conjugated Cyclo[n]thiophenes-An
Experimental and Theoretical Approach. Beilstein J. Nanotechnol. 2011,
2, 720−726.
(130) Gao, J.; Niles, E. T.; Grey, J. K. Aggregates Promote Efficient
Charge Transfer Doping of Poly(3-Hexylthiophene). J. Phys. Chem.
Lett. 2013, 4, 2953−2957.
(131) Hogan, C.; Palummo, M.; Gierschner, J.; Rubio, A. Correlation
Effects in the Optical Spectra of Porphyrin Oligomer Chains: Exciton
Confinement and Length Dependence. J. Chem. Phys. 2013, 138,
024312.
(132) Bhatta, R. S.; Tsige, M. Chain Length and Torsional
Dependence of Exciton Binding Energies in P3HT and PTB7
Conjugated Polymers: A First-Principles Study. Polymer 2014, 55,
2667−2672.
́
(133) Swiergiel, J.; Bouteiller, L.; Jadżyn, J. Concentration Evolution
of the Dielectric Response of Hydrogen-Bonded Supramolecular
Polymers Formed by Dialkylurea in Non-Polar Medium. Macro-
molecules 2014, 47, 2464−2470.
(134) Jenkins, I. H.; Rees, N. G.; Pickup, P. G. Conducting
Bipyridine-Bithiophene Copolymers. Chem. Mater. 1997, 9, 1213−
1216.
(135) Lefebvre, M.; Qi, Z.; Rana, D.; Pickup, P. G. Chemical
Synthesis, Characterization, and Electrochemical Studies of Poly(3,4-
ethylenedioxythiophene)/Poly(styrene-4-sulfonate) Composites.
Chem. Mater. 1999, 11, 262−268.
(136) Qi, Z.; Rees, N. G.; Pickup, P. G. Electrochemically Induced
Substitution of Polythiophenes and Polypyrrole. Chem. Mater. 1996, 8,
701−707.
(137) Huang, H.; Pickup, P. G. Oxygen-Modified Poly(4-dicyano-
methylene-4H-cyclopenta[2,1-b;3,4-b′]dithiophene): A Tunable Low
Band Gap Polymer. Chem. Mater. 1999, 11, 1541−1545.
(138) Kean, C. L.; Miller, D. O.; Pickup, P. G. Thiophene-
Substituted Nickel Dithiolene Complexes. Precursors for Low Band
Gap Conjugated Metallopolymers. J. Mater. Chem. 2002, 12, 2949−
2956.
(139) Loganathan, K.; Cammisa, E. G.; Myron, B. D.; Pickup, P. G.
Δ4,4′-Dicyclopenta[2,1-b:3,4-b′]dithiophene. A Conjugated Bridging
Unit for Low Band Gap Conducting Polymers. Chem. Mater. 2003, 15,
1918−1923.
(140) Loganathan, K.; Pickup, P. G. Electrochemistry and Electron
Transport Properties of Copolymers of Electron Deficient Fluorenes
with Thiophene. Electrochim. Acta 2007, 52, 4685−4690.
(141) Zamoshchik, N.; Bendikov, M. Doped Conductive Polymers:
Modeling of Polythiophene with Explicitly Used Counterions. Adv.
Funct. Mater. 2008, 18, 3377−3385.
(142) Hutchison, G. R.; Zhao, Y.-J.; Delley, B.; Freeman, A. J.;
Ratner, M. A.; Marks, T. J. Electronic structure of Conducting
Polymers: Limitations of Oligomer Extrapolation Approximations and
Effects of Heteroatoms. Phys. Rev. B: Condens. Matter Mater. Phys.
2003, 68, 035204.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(143) Salzner, U. Electronic structure of conducting organic
polymers: insights from time-dependent density functional theory.
Wiley Interdisciplinary Reviews: Computational Molecular Science 2014,
4, 601−622.
(144) Sun, G.; Kürti, J.; Kertesz, M.; Baughman, R. H. Dimensional
Changes as a Function of Charge Injection for Trans-Polyacetylene: A
Density Functional Theory Study. J. Chem. Phys. 2002, 117, 7691−
7697.
(145) Schimmel, T.; Rieβ, W.; Gmeiner, J.; Denninger, G.;
Schwoerer, M.; Naarmann, H.; Theophilou, N. DC-Conductivity on
a New Type of Highly Conducting Polyacetylene, N-(CH)x. Solid
State Commun. 1988, 65, 1311−1315.
(146) Yoo, J. E.; Cross, J. L.; Bucholz, T. L.; Lee, K. S.; Espe, M. P.;
Loo, Y.-L. Improving the Electrical Conductivity of Polymer Acid-
Doped Polyaniline by Controlling the Template Molecular Weight. J.
Mater. Chem. 2007, 17, 1268−1275.
(147) Rahman, G. M. A.; Zhao, J.-H.; Thomson, D. J.; Freund, M. S.
Compensation Doping in Conjugated Polymers: Engineering Dopable
Heterojunctions for Modulating Conductivity in the Solid State. J. Am.
Chem. Soc. 2009, 131, 15600−15601.
(148) Pomerantz, Z.; Zaban, A.; Ghosh, S.; Lellouche, J. P.; Garcia-
Belmonte, G.; Bisquert, J. Capacitance, Spectroelectrochemistry and
Conductivity of Polarons and Bipolarons in a Polydicarbazole Based
Conducting Polymer. J. Electroanal. Chem. 2008, 614, 49−60.
(149) Chiu, W. W.; Travaš-Sejdić, J.; Cooney, R. P.; Bowmaker, G. A.
Spectroscopic and Conductivity Studies of Doping in Chemically
Synthesized Poly(3,4-ethylenedioxythiophene). Synth. Met. 2005, 155,
80−88.
(150) Varela-Á lvarez, A.; Sordo, J. A.; Scuseria, G. E. Doping of
Polyaniline by Acid-Base Chemistry: Density Functional Calculations
with Periodic Boundary Conditions. J. Am. Chem. Soc. 2005, 127,
11318−11327.
(151) López Cascales, J. J.; Fernández, A. J.; Otero, T. F.
Characterization of the Reduced and Oxidized Polypyrrole/Water
Interface: A Molecular Dynamics Simulation Study. J. Phys. Chem. B
2003, 107, 9339−9343.
(152) López Cascales, J. J.; Otero, T. F. Molecular Dynamic
Simulation of the Hydration and Diffusion of Chloride Ions from Bulk
Water to Polypyrrole Matrix. J. Chem. Phys. 2004, 120, 1951.
(153) Zade, S. S.; Bendikov, M. Theoretical Study of Long
Oligothiophene Dications:Bipolaron vs Polaron Pair vs Triplet State.
J. Phys. Chem. B 2006, 110, 15839−15846.
(154) Brédas, J. L.; Street, G. B. Polarons, Bipolarons, and Solitons in
Conducting Polymers. Acc. Chem. Res. 1985, 18, 309−315.
(155) Tautz, R.; Da Como, E.; Limmer, T.; Feldmann, J.; Egelhaaf,
H.; von Hauff, E.; Lemaur, V.; Beljonne, D.; Yilmaz, S.; Dumsch, I.;
et al. Structural Correlations in the Generation of Polaron Pairs in
Low-Bandgap Polymers for Photovoltaics. Nat. Commun. 2012, 3, 970.
(156) Furukawa, Y. Electronic Absorption and Vibrational Spectros-
copies of Conjugated Conducting Polymers. J. Phys. Chem. 1996, 100,
15644−15653.
(157) Schreckenbach, G.; Shamov, G. A. Theoretical Actinide
Molecular Science. Acc. Chem. Res. 2010, 43, 19−29.
(158) Street, G. B.; Clarke, T. C. Conducting Polymers: A Review of
Recent Work. IBM J. Res. Dev. 1981, 25, 51−57.
(159) Schopf, G.; Kobmehl, G. Thermoreversible Networks; Adv.
Polym. Sci.; Springer Berlin: Heidelberg, 1997; Vol. 130; pp 1−12.
(160) Roncali, J. Conjugated Poly(thiophenes): Synthesis, Function-
alization, and Applications. Chem. Rev. 1992, 92, 711−738.
(161) Roncali, J. Synthetic Principles for Bandgap Control in Linear
π-Conjugated Systems. Chem. Rev. 1997, 97, 173−206.
(162) McCullough, R. D. The Chemistry of Conducting Poly-
thiophenes. Adv. Mater. 1998, 10, 93−116.
(163) Cheng, Y.-J.; Yang, S.-H.; Hsu, C.-S. Synthesis of Conjugated
Polymers for Organic Solar Cell Applications. Chem. Rev. 2009, 109,
5868−5923.
(164) Yamamoto, T. Molecular Assembly and Properties of
Polythiophenes. NPG Asia Mater. 2010, 2, 54−60.
10275
Perspective
(165) Kim, B. C.; Hong, J.-Y.; Wallace, G. G.; Park, H. S. Recent
Progress in Flexible Electrochemical Capacitors: Electrode Materials,
Device Configuration, and Functions. Adv. Energy Mater. 2015, 5,
1500959.
(166) Das, S.; Routh, P.; Ghosh, R.; Chatterjee, D. P.; Nandi, A. K.
Water-soluble ionic polythiophenes for biological and analytical
applications. Polym. Int. 2017, 66, 623−639.
(167) Meng, Q.; Cai, K.; Chen, Y.; Chen, L. Research progress on
conducting polymer based supercapacitor electrode materials. Nano
Energy 2017, 36, 268−285.
(168) Casado, J.; Hernández, V.; Hotta, S.; López Navarrete, J. T.
Vibrational Spectra of Charged Defects in a Series of α,α′-Dimethyl
End-Capped Oligothiophenes Induced by Chemical Doping with
Iodine. J. Chem. Phys. 1998, 109, 10419−10429.
(169) Casado, J.; Hernández, V.; López Navarrete, J. T. Vibrational
Raman Shifts and Aromaticity: The Case of Oligothiophenes. Chem.
Rec. 2015, 15, 1110−1118.
(170) Irle, S.; Lischka, H. An ab initio Investigation of the
ChargeTransfer Complexes of Alkali Atoms with Oligo (α, α′)
Thiophenes and Oligoparaphenylenes: A Model Calculation on
Polaronic and Bipolaronic Defect Structures. J. Chem. Phys. 1995,
103, 1508−1522.
(171) Chaalane, A.; Mahi, D.; Dkhissi, A. Structural and electronic
properties of doped oligothiophenes in the presence of p-
toluenesulfonate acids. Theor. Chem. Acc. 2015, 134, 66.
(172) Asaduzzaman, A. M.; Schmidt-D’Aloisio, K.; Dong, Y.;
Springborg, M. Properties of Polythiophene and Related Conjugated
Polymers: a Density-Functional Study. Phys. Chem. Chem. Phys. 2005,
7, 2714−2722.
(173) Houk, K. N.; Lee, P. S.; Nendel, M. Polyacene and Cyclacene
Geometries and Electronic Structures: Bond Equalization, Vanishing
Band Gaps, and Triplet Ground States Contrast with Polyacetylene. J.
Org. Chem. 2001, 66, 5517−5521.
(174) Banerji, N.; Gagnon, E.; Morgantini, P.-Y.; Valouch, S.;
Mohebbi, A. R.; Seo, J.-H.; Leclerc, M.; Heeger, A. J. Breaking Down
the Problem: Optical Transitions, Electronic Structure, and Photo-
conductivity in Conjugated Polymer PCDTBT and in Its Separate
Building Blocks. J. Phys. Chem. C 2012, 116, 11456−11469.
(175) Bubnova, O.; Khan, Z. U.; Wang, H.; Braun, S.; Evans, D. R.;
Fabretto, M.; Hojati; Dagnelund, D.; Arlin, J.; Geerts, Y. H.; Desbief,
S.; et al. Semi-Metallic Polymers. Nat. Mater. 2013, 13, 190−194.
(176) Sun, H.; Autschbach, J. Electronic Energy Gaps for π-
Conjugated Oligomers and Polymers Calculated with Density
Functional Theory. J. Chem. Theory Comput. 2014, 10, 1035−1047.
(177) Guay, J.; Kasai, P.; Diaz, A.; Wu, R.; Tour, J. M.; Dao, L. H.
Chain-Length Dependence of Electrochemical and Electronic Proper-
ties of Neutral and Oxidized Soluble.Alpha.,.Alpha.-Coupled Thio-
phene Oligomers. Chem. Mater. 1992, 4, 1097−1105.
(178) Zhang, L.; Colella, N. S.; Cherniawski, B. P.; Mannsfeld, S. C.
B.; Briseno, A. L. Oligothiophene Semiconductors: Synthesis,
Characterization, and Applications for Organic Devices. ACS Appl.
Mater. Interfaces 2014, 6, 5327−5343.
(179) Colella, N. S.; Zhang, L.; McCarthy-Ward, T.; Mannsfeld, S. C.
B.; Winter, H. H.; Heeney, M.; Watkins, J. J.; Briseno, A. L. Controlled
integration of oligo- and polythiophenes at the molecular scale. Phys.
Chem. Chem. Phys. 2015, 17, 26525−26529.
(180) Vukmirović, N.; Wang, L.-W. Electronic Structure of
Disordered Conjugated Polymers: Polythiophenes. J. Phys. Chem. B
2009, 113, 409−415.
(181) Ding, H.; Pan, Z.; Pigani, L.; Seeber, R.; Zanardi, C. p- and n-
Doping Processes in Polythiophene with Reduced Bandgap. An
Electrochemical Impedance Spectroscopy Study. Electrochim. Acta
2001, 46, 2721−2732.
(182) Takechi, K.; Shiga, T.; Motohiro, T.; Akiyama, T.; Yamada, S.;
Nakayama, H.; Kohama, K. Solar Cells Using Iodine-Doped
Polythiophene-Porphyrin Polymer Films. Sol. Energy Mater. Sol. Cells
2006, 90, 1322−1330.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(183) Niles, E. T.; Roehling, J. D.; Yamagata, H.; Wise, A. J.; Spano,
F. C.; Moulé, A. J.; Grey, J. K. J-Aggregate Behavior in Poly-3-
hexylthiophene Nanofibers. J. Phys. Chem. Lett. 2012, 3, 259−263.
(184) Gao, J.; Roehling, J. D.; Li, Y.; Guo, H.; Moule, A. J.; Grey, J. K.
The effect of 2,3,5,6-Tetrafluoro-7,7,8,8-Tetracyanoquinodimethane
Charge Transfer Dopants on the Conformation and Aggregation of
Poly(3-Hexylthiophene). J. Mater. Chem. C 2013, 1, 5638−5646.
(185) Li, X.-C.; Sirringhaus, H.; Garnier, F.; Holmes, A. B.; Moratti,
S. C.; Feeder, N.; Clegg, W.; Teat, S. J.; Friend, R. H. A Highly π-
Stacked Organic Semiconductor for Thin Film Transistors Based on
Fused Thiophenes. J. Am. Chem. Soc. 1998, 120, 2206−2207.
(186) Sirringhaus, H.; Friend, R. H.; Li, X. C.; Moratti, S. C.;
Holmes, A. B.; Feeder, N. Bis(dithienothiophene) Organic Field-Effect
Transistors with a High ON/OFF Ratio. Appl. Phys. Lett. 1997, 71,
3871−3873.
(187) Torras, J.; Casanovas, J.; Aleman, C. Reviewing Extrapolation
Procedures of the Electronic Properties on the pi-Conjugated Polymer
Limit. J. Phys. Chem. A 2012, 116, 7571−7583.
(188) Liang, Y.; Xu, Z.; Xia, J.; Tsai, S.-T.; Wu, Y.; Li, G.; Ray, C.; Yu,
L. For the Bright Future-Bulk Heterojunction Polymer Solar Cells
with Power Conversion Efficiency of 7.4%. Adv. Mater. 2010, 22, 135−
138.
(189) Richter, T. V.; Braun, C. H.; Link, S.; Scheuble, M.; Crossland,
E. J. W.; Stelzl, F.; Wü r fel, U.; Ludwigs, S. Regioregular
Polythiophenes with Alkylthiophene Side Chains. Macromolecules
2012, 45, 5782−5788.
(190) Runge, E.; Gross, E. K. U. Density-Functional Theory for
Time-Dependent Systems. Phys. Rev. Lett. 1984, 52, 997−1000.
(191) Laurent, A. D.; Jacquemin, D. TDDFT benchmarks: A review.
Int. J. Quantum Chem. 2013, 113, 2019−2039.
(192) Zade, S. S.; Bendikov, M. From Oligomers to Polymer:
Convergence in the HOMO-LUMO Gaps of Conjugated Oligomers.
Org. Lett. 2006, 8, 5243−5246.
(193) Salzner, U.; Karaltı, O.; Durdaği, S. Does the Donor-Acceptor
Concept Work for Designing Synthetic Metals? J. Mol. Model. 2006,
12, 687−701.
(194) Jones, D.; Guerra, M.; Favaretto, L.; Modelli, A.; Fabrizio, M.;
Distefano, G. Determination of the Electronic Structure of Thiophene
Oligomers and Extrapolation to Polythiophene. J. Phys. Chem. 1990,
94, 5761−5766.
(195) da Silva Filho, D. A.; Coropceanu, V.; Fichou, D.; Gruhn, N.
E.; Bill, T. G.; Gierschner, J.; Cornil, J.; Brédas, J.-L. Hole-Vibronic
Coupling in Oligothiophenes: Impact of Backbone Torsional
Flexibility on Relaxation Energies. Philos. Trans. R. Soc., A 2007,
365, 1435−1452.
(196) Siegert, S.; Vogeler, F.; Marian, C. M.; Weinkauf, R. Throwing
Light on Dark States of α-Oligothiophenes of Chain Lengths 2 to 6:
Radical Anion Photoelectron Spectroscopy and Excited-State Theory.
Phys. Chem. Chem. Phys. 2011, 13, 10350−10363.
(197) Hutchison, G. R.; Ratner, M. A.; Marks, T. J. Accurate
Prediction of Band Gaps in Neutral Heterocyclic Conjugated
Polymers. J. Phys. Chem. A 2002, 106, 10596−10605.
(198) Sahu, H.; Panda, A. N. Computational Study on the Effect of
Substituents on the Structural and Electronic Properties of Thiophene-
Pyrrole-Based π-Conjugated Oligomers. Macromolecules 2013, 46,
844−855.
(199) le Bouch, N.; Auger, M.; Leclerc, M. Structure and Segmental
Motions in a Substituted Polythiophene: A Solid-State NMR Study.
Macromol. Chem. Phys. 2008, 209, 2455−2462.
(200) Diaz, A.; Crowley, J.; Bargon, J.; Gardini, G. P.; Torrance, J. B.
Electrooxidation of aromatic oligomers and conducting polymers. J.
Electroanal. Chem. Interfacial Electrochem. 1981, 121, 355−361.
(201) Hong, S. Y.; Marynick, D. S. Understanding the Conforma-
tional Stability and Electronic Structures of Modified Polymers Based
on Polythiophene. Macromolecules 1992, 25, 4652−4657.
(202) Marshall, J.; Hooton, J.; Han, Y.; Creamer, A.; Ashraf, R.;
Porte, Y.; Anthopoulos, T.; Stavrinou, P.; McLachlan, M.; Bronstein,
H.; Beavis, P.; Heeney, M. Polythiophenes with Vinylene Linked
10276
Perspective
Ortho, Meta and Para-Carborane Sidechains. Polym. Chem. 2014, 5,
6190−6199.
(203) Beljonne, D.; Cornil, J.; Sirringhaus, H.; Brown, P. J.; Shkunov,
M.; Friend, R. H.; Brédas, J.-L. Optical Signature of Delocalized
Polarons in Conjugated Polymers. Adv. Funct. Mater. 2001, 11, 229−
234.
(204) Brédas, J. L.; Wudl, F.; Heeger, A. J. Polarons and Bipolarons
in Doped Polythiophene: A Theoretical Investigation. Solid State
Commun. 1987, 63, 577−580.
(205) Jeuris, K.; Groenendaal, L.; Verheyen, H.; Louwet, F.; De
Schryver, F. C. Light Sability of 3,4-ethylenedioxythiophene-Based
Derivatives. Synth. Met. 2003, 132, 289−295.
(206) Devreux, F.; Genoud, F.; Nechtschein, M.; Villeret, B. ESR
Investigation of Polarons and Bipolarons in Conducting Polymers:
The Case of Polypyrrole. Synth. Met. 1987, 18, 89−94.
(207) Helton, J. S.; Pajerowski, D. M.; Qiu, Y.; Zhao, Y.; Shulyatev,
D. A.; Mukovskii, Y. M.; Bychkov, G. L.; Barilo, S. N.; Lynn, J. W.
Polaron-Mediated Spin Correlations in Metallic and Insulating
La1−xAxMnO3 A = (Ca, Sr, Ba). Phys. Rev. B: Condens. Matter Mater.
Phys. 2014, 90, 214411.
(208) Watanabe, S.; Ando, K.; Kang, K.; Mooser, S.; Vaynzof, Y.;
Kurebayashi, H.; Saitoh, E.; Sirringhaus, H. Polaron Spin Current
Transport in Organic Semiconductors. Nat. Phys. 2014, 10, 308−313.
(209) Lavarda, F. C.; dos Santos, M. C.; Galvão, D. S.; Laks, B.
Insulator-to-Metal Transition in Polythiophene. Phys. Rev. B: Condens.
Matter Mater. Phys. 1994, 49, 979−983.
(210) Bussac, M. N.; Zuppiroli, L. Bipolaron Singlet and Triplet
States in Disordered Conducting Polymers. Phys. Rev. B: Condens.
Matter Mater. Phys. 1993, 47, 5493−5496.
(211) Koller, G.; Berkebile, S.; Oehzelt, M.; Puschnig, P.; Ambrosch-
Draxl, C.; Netzer, F. P.; Ramsey, M. G. Intra- and Intermolecular Band
Dispersion in an Organic Crystal. Science 2007, 317, 351−355.
(212) Lee, K.; Cho, S.; Heum Park, S.; Heeger, A.; Lee, C.; Lee, S.
Metallic Transport in Polyaniline. Nature 2006, 441, 65−68.
(213) Mentbayeva, A.; Ospanova, A.; Tashmuhambetova, Z.;
Sokolova, V.; Sukhishvili, S. Polymer-Metal Complexes in Polyelec-
trolyte Multilayer Films as Catalysts for Oxidation of Toluene.
Langmuir 2012, 28, 11948−11955.
(214) Wang, R.-M.; Zhang, Z.-L.; Lou, J.-F.; Wang, Y.-P.; Song, P.-F.;
Xia, C.-G. Preparation and Catalytic Oxidation Properties of Inorganic
Polymer Encapsulated Metal Complexes. Polym. Adv. Technol. 2004,
15, 48−51.
(215) Stafström, S.; Brédas, J. L.; Epstein, A. J.; Woo, H. S.; Tanner,
D. B.; Huang, W. S.; MacDiarmid, A. G. Polaron Lattice in Highly
Conducting Polyaniline: Theoretical and Optical Studies. Phys. Rev.
Lett. 1987, 59, 1464−1467.
(216) Muñoz, W. A.; Singh, S. K.; Franco-Gonzalez, J. F.; Linares,
M.; Crispin, X.; Zozoulenko, I. V. Insulator to semimetallic transition
in conducting polymers. Phys. Rev. B: Condens. Matter Mater. Phys.
2016, 94, 205202.
(217) Majumdar, S.; Laiho, R.; Laukkanen, P.; Väyrynen, I. J.;
Majumdar, H. S.; Ö sterbacka, R. Application of Regioregular
Polythiophene in Spintronic Devices: Effect of Interface. Appl. Phys.
Lett. 2006, 89, 122114.
(218) Ao, W.; Wang, L.; Li, J.; Pan, F.; Wu, C. Synthesis and
Characterization of Polythiophene/Bi2Te3 Nanocomposite Thermo-
electric Material. J. Electron. Mater. 2011, 40, 2027−2032.
(219) Wang, L.; Jia, X.; Wang, D.; Zhu, G.; Li, J. Preparation and
Thermoelectric Properties of Polythiophene/Multiwalled Carbon
Nanotube Composites. Synth. Met. 2013, 181, 79−85.
(220) Wang, Y.; Cai, K.; Yao, X. Facile Fabrication and Thermo-
electric Properties of PbTe-Modified Poly(3,4-ethylenedioxythio-
phene) Nanotubes. ACS Appl. Mater. Interfaces 2011, 3, 1163−1166.
(221) Shi, H.; Liu, C.; Xu, J.; Song, H.; Lu, B.; Jiang, F.; Zhou, W.;
Zhang, G.; Jiang, Q. Facile Fabrication of PEDOT:PSS/Polythio-
phenes Bilayered Nanofilms on Pure Organic Electrodes and Their
Thermoelectric Performance. ACS Appl. Mater. Interfaces 2013, 5,
12811−12819.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(222) Clark, J.; Silva, C.; Friend, R. H.; Spano, F. C. Role of
Intermolecular Coupling in the Photophysics of Disordered Organic
Semiconductors: Aggregate Emission in Regioregular Polythiophene.
Phys. Rev. Lett. 2007, 98, 206406.
(223) Di Nuzzo, D.; Fontanesi, C.; Jones, R.; Allard, S.; Dumsch, I.;
Scherf, U.; von Hauff, E.; Schumacher, S.; Da Como, E. How
intermolecular geometrical disorder affects the molecular doping of
donor-acceptor copolymers. Nat. Commun. 2015, 6, 6460.
(224) Puvanatvattana, T.; Chotpattananont, D.; Hiamtup, P.;
Niamlang, S.; Sirivat, A.; Jamieson, A. M. Electric field induced stress
moduli in polythiophene/polyisoprene elastomer blends. React. Funct.
Polym. 2006, 66, 1575−1588.
(225) Kelkar, D.; Chourasia, A. Effect of dopant on thermal
properties of polythiophene. Indian J. Phys. 2012, 86, 101−107.
(226) Sarkar, K.; Sharma, R.; Bhattacharyya, S. P. Blending
Determinism with Evolutionary Computing: Applications to the
Calculation of the Molecular Electronic Structure of Polythiophene. J.
Chem. Theory Comput. 2010, 6, 718−726.
(227) Koyama, T.; Nakamura, A.; Kishida, H. Microscopic Mobility
of Polarons in Chemically Doped Polythiophenes Measured by
Employing Photoluminescence Spectroscopy. ACS Photonics 2014, 1,
655−661.
(228) Patil, A. O.; Heeger, A. J.; Wudl, F. Optical Properties of
Conducting Polymers. Chem. Rev. 1988, 88, 183−200.
(229) Furukawa, Y. Electronic Absorption and Vibrational Spectros-
copies of Conjugated Conducting Polymers. J. Phys. Chem. 1996, 100,
15644−15653.
(230) Mei, J.; Diao, Y.; Appleton, A. L.; Fang, L.; Bao, Z. Integrated
Materials Design of Organic Semiconductors for Field-Effect
Transistors. J. Am. Chem. Soc. 2013, 135, 6724−6746.
(231) Perera, M. M.; Lin, M.-W.; Chuang, H.-J.; Chamlagain, B. P.;
Wang, C.; Tan, X.; Cheng, M. M.-C.; Tománek, D.; Zhou, Z.
Improved Carrier Mobility in Few-Layer MoS2 Field-Effect Transistors
with Ionic-Liquid Gating. ACS Nano 2013, 7, 4449−4458.
(232) Sun, H.; Wang, Q.; Li, Y.; Lin, Y.; Wang, Y.; Yin, Y.; Xu, Y.;
Liu, C.; Tsukagoshi, K.; Pan, L.; Wang, X.; Hu, Z.; Shi, Y. Boost Up
Carrier Mobility for Ferroelectric Organic Transistor Memory via
Buffering Interfacial Polarization Fluctuation. Sci. Rep. 2015, 4, 07227.
(233) Podzorov, V.; Sysoev, S. E.; Loginova, E.; Pudalov, V. M.;
Gershenson, M. E. Single-crystal organic field effect transistors with
the hole mobility 8cm2/Vs. Appl. Phys. Lett. 2003, 83, 3504−3506.
(234) Kaloni, T. P.; Cheng, Y. C.; Schwingenschlögl, U. Electronic
Structure of Superlattices of Graphene and Hexagonal Boron Nitride.
J. Mater. Chem. 2012, 22, 919−922.
(235) Kaloni, T. P.; Joshi, R. P.; Adhikari, N. P.; Schwingenschlögl,
U. Band Gap Tunning in BN-Doped Graphene Systems with High
Carrier Mobility. Appl. Phys. Lett. 2014, 104, 073116.
(236) Kaloni, T. P.; Schreckenbach, G.; Freund, M. S. Large
Enhancement and Tunable Band Gap in Silicene by Small Organic
Molecule Adsorption. J. Phys. Chem. C 2014, 118, 23361−23367.
(237) Kaloni, T. P.; Cheng, Y. C.; Kahaly, M. U.; Schwingenschlögl,
U. Charge Carrier Density in Li-Intercalated Graphene. Chem. Phys.
Lett. 2012, 534, 29−33.
(238) Kaloni, T. P.; Kahaly, M. U.; Cheng, Y. C.; Schwingenschlögl,
U. K-Intercalated Carbon Systems: Effects of Dimensionality and
Substrate. EPL 2012, 98, 67003.
(239) Sonar, P.; Oldridge, L.; Grimsdale, A. C.; Müllen, K.; Surin, M.;
Lazzaroni, R.; Leclére, P.; Pinto, J.; Chua, L.-L.; Friend, R. H.; et al.
Synthesis, Characterization and Comparative OFET Behaviour of
Indenofluorene-Bithiophene and Terthiophene Alternating Copoly-
mers. Synth. Met. 2010, 160, 468−474.
(240) Li, C.; Numata, M.; Takeuchi, M.; Shinkai, S. A Sensitive
Colorimetric and Fluorescent Probe Based on a Polythiophene
Derivative for the Detection of ATP. Angew. Chem., Int. Ed. 2005,
44, 6371−6374.
(241) Andersson, M.; Ekeblad, P. O.; Hjertberg, T.; Wennerstroem,
O.; Inganaes, O. Polythiophene with a Free Amino Acid Side Chain.
Polym. Commun. 1991, 32, 546.
10277
Perspective
(242) Nilsson, K. P. R.; Rydberg, J.; Baltzer, L.; Inganäs, O. Self-
Assembly of Synthetic Peptides Control Conformation and Optical
Properties of a Zwitterionic Polythiophene Derivative. Proc. Natl. Acad.
Sci. U. S. A. 2003, 100, 10170−10174.
(243) Nilsson, K. P. R.; Inganäs, O. Optical Emission of a
Conjugated Polyelectrolyte: Calcium-Induced Conformational
Changes in Calmodulin and Calmodulin-Calcineurin Interactions.
Macromolecules 2004, 37, 9109−9113.
(244) Nilsson, K. R.; Inganas, O. Chip and Solution Detection of
DNA Hybridization Using a Luminescent. Nat. Mater. 2003, 2, 419−
424.
(245) Tanaka, K.; Mihara, T.; Koide, N. Synthesis and Physical
Properties of Regioregular Poly(3-alkoxy-4-methylthiophene)s. Polym.
J. 2004, 36, 628−633.
(246) Ho, H.-A.; Boissinot, M.; Bergeron, M. G.; Corbeil, G.; Doré,
K.; Boudreau, D.; Leclerc, M. Colorimetric and Fluorometric
Detection of Nucleic Acids Using Cationic Polythiophene Derivatives.
Angew. Chem., Int. Ed. 2002, 41, 1548−1551.
(247) Ho, H. A.; Leclerc, M. New Colorimetric and Fluorometric
Chemosensor Based on a Cationic Polythiophene Derivative for
Iodide-Specific Detection. J. Am. Chem. Soc. 2003, 125, 4412−4413.
(248) Yao, Z.; Li, Y.; Li, C.; Shi, G. Disassembly of Conjugated
Polyelectrolyte Aggregates and their Application for Colorimetric
Detection of Surfactants in Water. Chem. Commun. 2010, 46, 8639−
8641.
(249) Lukkari, J.; Salomäki, M.; Viinikanoja, A.; Ä ar̈ italo, T.;
Paukkunen, J.; Kocharova, N.; Kankare, J. Polyelectrolyte Multilayers
Prepared from Water-Soluble Poly(alkoxythiophene) Derivatives. J.
Am. Chem. Soc. 2001, 123, 6083−6091.
(250) Zhai, L.; McCullough, R. Layer-by-Layer Assembly of
Polythiophene. Adv. Mater. 2002, 14, 901−905.
(251) McCullough, R. D.; Ewbank, P. C.; Loewe, R. S. Self-Assembly
and Disassembly of Regioregular, Water Soluble Polythiophenes:
Chemoselective Ionchromatic Sensing in Water. J. Am. Chem. Soc.
1997, 119, 633−634.
(252) Wang, F.; Li, M.; Wang, B.; Zhang, J.; Cheng, Y.; Liu, L.; Lv,
F.; Wang, S. Synthesis and characterization of water-soluble
polythiophene derivatives for cell imaging. Sci. Rep. 2015, 5, 7617.
(253) Leclerc, M.; Faid, K. Electrical and optical properties of
Processable Polythiophene Derivatives: Structure-Property relation-
ships. Adv. Mater. 1997, 9, 1087−1094.
(254) Li, Y.; Bai, H.; Li, C.; Shi, G. Colorimetric Assays for
Acetylcholinesterase Activity and Inhibitor Screening Based on the
Disassembly-Assembly of a Water-Soluble Polythiophene Derivative.
ACS Appl. Mater. Interfaces 2011, 3, 1306−1310.
(255) Evans, R. C.; Knaapila, M.; Willis-Fox, N.; Kraft, M.; Terry, A.;
Burrows, H. D.; Scherf, U. Cationic Polythiophene-Surfactant Self-
Assembly Complexes: Phase Transitions, Optical Response, and
Sensing. Langmuir 2012, 28, 12348−12356.
(256) Samsonidze, G.; Ribeiro, F. J.; Cohen, M. L.; Louie, S. G.
Quasiparticle and optical properties of polythiophene-derived
polymers. Phys. Rev. B: Condens. Matter Mater. Phys. 2014, 90, 035123.
(257) Faleev, S. V.; van Schilfgaarde, M.; Kotani, T. All-Electron Self-
Consistent GW Approximation: Application to Si, MnO, and NiO.
Phys. Rev. Lett. 2004, 93, 126406.
(258) Hamann, D. R.; Vanderbilt, D. Maximally Localized Wannier
Functions for GW Quasiparticles. Phys. Rev. B: Condens. Matter Mater.
Phys. 2009, 79, 045109.
(259) Shi, H.; Pan, H.; Zhang, Y.-W.; Yakobson, B. I. Quasiparticle
Band Structures and Optical Properties of Strained Monolayer MoS2
and WS2. Phys. Rev. B: Condens. Matter Mater. Phys. 2013, 87, 155304.
(260) Shishkin, M.; Kresse, G. Self-Consistent GW Calculations for
Semiconductors and Insulators. Phys. Rev. B: Condens. Matter Mater.
Phys. 2007, 75, 235102.
(261) Chang, Y.-W.; Jin, B.-Y. Correlation Effects of π Eectrons on
the Band Structures of Conjugated Polymers using the Self-Consistent
GW Approximation with Vertex Corrections. J. Chem. Phys. 2012, 136,
024110.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(262) Romaniello, P.; Guyot, S.; Reining, L. The Self-Energy Beyond
GW: Local and Nonlocal Vertex Corrections. J. Chem. Phys. 2009, 131,
154111.
(263) Amin, B.; Kaloni, T. P.; Schwingenschlö gl, U. Strain
Engineering of WS2 WSe2 and WTe2. RSC Adv. 2014, 4, 34561−
34565.
(264) Kaloni, T. P. Tuning the Structural, Electronic, and Magnetic
Properties of Germanene by the Adsorption of 3d Transition Metal
Atoms. J. Phys. Chem. C 2014, 118, 25200−25208.
(265) Bertsch, G. F.; Bulgac, A.; Tománek, D.; Wang, Y. Collective
Plasmon Excitations in C60 Clusters. Phys. Rev. Lett. 1991, 67, 2690−
2693.
(266) Sun, H.; Hu, Z.; Zhong, C.; Zhang, S.; Sun, Z. Quantitative
Estimation of Exciton Binding Energy of Polythiophene-Derived
Polymers Using Polarizable Continuum Model Tuned Range-
Separated Density Functional. J. Phys. Chem. C 2016, 120, 8048−8055.
(267) Dewar, M. J. S.; Zoebisch, E. G.; Healy, E. F.; Stewart, J. J. P.
Development and use of Quantum Mechanical Molecular Models. 76.
AM1: A New General Purpose Quantum Mechanical Molecular
Model. J. Am. Chem. Soc. 1985, 107, 3902−3909.
(268) Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.;
Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.;
Su, S.; et al. General Atomic and Molecular Electronic Structure
System. J. Comput. Chem. 1993, 14, 1347−1363.
(269) Becke, A. D. DensityFunctional Thermochemistry. III. The
Role of Exact Exchange. J. Chem. Phys. 1993, 98, 5648−5652.
(270) Lee, C.; Yang, W.; Parr, R. G. Development of the Colle-
Salvetti Correlation-Energy Formula into a Functional of the Electron
Density. Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 785−789.
(271) Kong, J.; White, C. A.; Krylov, A. I.; Sherrill, D.; Adamson, R.
D.; Furlani, T. R.; Lee, M. S.; Lee, A. M.; Gwaltney, S. R.; Adams, T.
R.; et al. Q-Chem 2.0: a High-Performance Ab initio Electronic
Structure Program Package. J. Comput. Chem. 2000, 21, 1532−1548.
(272) Ridley, M.; Zerner, J. An Intermediate Neglect of Differential
Overlap Technique for Spectroscopy: Pyrrole and the Azines. Theor.
Chim. Acta 1973, 32, 111−134.
(273) Tretiak, S.; Saxena, A.; Martin, R. L.; Bishop, A. R. CEO/
Semiempirical Calculations of UV-Visible Spectra in Conjugated
Molecules. Chem. Phys. Lett. 2000, 331, 561−568.
(274) Mukamel, S.; Tretiak, S.; Wagersteiter, T.; Chernyak, V.
Electronic Coherence and Collective Optical Excitations of Con-
jugated Molecules. Science 1997, 277, 781−787.
(275) Hsu, C.-P.; Hirata, S.; Head-Gordon, M. Excitation Energies
from Time-Dependent Density Functional Theory for Linear Polyene
Oligomers: Butadiene to Decapentaene. J. Phys. Chem. A 2001, 105,
451−458.
(276) Hirata, S.; Lee, T. J.; Head-Gordon, M. Time-Dependent
Density Functional Study on the Electronic Excitation Energies of
Polycyclic Aromatic Hydrocarbon Radical Cations of Naphthalene,
Anthracene, Pyrene, and Perylene. J. Chem. Phys. 1999, 111, 8904−
8912.
(277) Groenendaal, L.; Jonas, F.; Freitag, D.; Pielartzik, H.; Reynolds,
J. R. Poly(3,4-ethylenedioxythiophene) and Its Derivatives: Past,
Present, and Future. Adv. Mater. 2000, 12, 481−494.
(278) Garcia, P.; Pernaut, J. M.; Hapiot, P.; Wintgens, V.; Valat, P.;
Garnier, F.; Delabouglise, D. Effect of End Substitution on
Electrochemical and Optical Properties of Oligothiophenes. J. Phys.
Chem. 1993, 97, 513−516.
(279) Hicks, R. G.; Nodwell, M. B. Synthesis and Electronic
Structure Investigations of α, ω-Bis(arylthio)oligothiophenes:Toward
Understanding Wire-Linker Interactions in Molecular-Scale Electronic
Materials. J. Am. Chem. Soc. 2000, 122, 6746−6753.
(280) Seixas de Melo, J.; Elisei, F.; Gartner, C.; Aloisi, G. G.; Becker,
R. S. Comprehensive Investigation of the Photophysical Behavior of
Oligopolyfurans. J. Phys. Chem. A 2000, 104, 6907−6911.
(281) Sotzing, G. A.; Reynolds, J. R.; Steel, P. J. Electrochromic
Conducting Polymers via Electrochemical Polymerization of Bis(2-
(3,4-ethylenedioxy)thienyl) Monomers. Chem. Mater. 1996, 8, 882−
889.
10278
Perspective
(282) Lee, K.; Sotzing, G. A. Poly(thieno[3,4-b]thiophene). A New
Stable Low Band Gap Conducting Polymer. Macromolecules 2001, 34,
5746−5747.
(283) Fichou, D.; te Ulade-Fichou, M.-P.; Horowitz, G.; Demanze, F.
Thermal and Optical Characterization of High Purity α-Octithio-
phenk. Adv. Mater. 1997, 9, 75−80.
(284) Wang, C.; Schindler, J. L.; Kannewurf, C. R.; Kanatzidis, M. G.
Poly(3,4-ethylenedithiathiophene). A New Soluble Conductive
Polythiophene Derivative. Chem. Mater. 1995, 7, 58−68.
(285) Schottland, P.; Zong, K.; Gaupp, C. L.; Thompson, B. C.;
Thomas, C. A.; Giurgiu, I.; Hickman, R.; Abboud, K. A.; Reynolds, J.
R. Poly(3,4-alkylenedioxypyrrole)s: Highly Stable Electronically
Conducting and Electrochromic Polymers. Macromolecules 2000, 33,
7051−7061.
(286) Demanze, F.; Cornil, J.; Garnier, F.; Horowitz, G.; Valat, P.;
Yassar, A.; Lazzaroni, R.; Brédas, J.-L. Tuning of the Electronic and
Optical Properties of Oligothiophenes via Cyano Substitution: A Joint
Experimental and Theoretical Study. J. Phys. Chem. B 1997, 101,
4553−4558.
(287) Zhuang, W.; Bolognesi, M.; Seri, M.; Henriksson, P.; Gedefaw,
D.; Kroon, R.; Jarvid, M.; Lundin, A.; Wang, E.; Muccini, M.;
Andersson, M. R. Influence of Incorporating Different Electron-Rich
Thiophene-Based Units on the Photovoltaic Properties of Isoindigo-
Based Conjugated Polymers: An Experimental and DFT Study.
Macromolecules 2013, 46, 8488−8499.
(288) Scharber, M.; Mühlbacher, D.; Koppe, M.; Denk, P.; Waldauf,
C.; Heeger, A.; Brabec, C. Design Rules for Donors in Bulk-
Heterojunction Solar Cells-Towards 10% Energy-Conversion Effi-
ciency. Adv. Mater. 2006, 18, 789−794.
(289) Ma, Z.; Wang, E.; Jarvid, M. E.; Henriksson, P.; Inganas, O.;
Zhang, F.; Andersson, M. R. Synthesis and Characterization of
Benzodithiophene-Isoindigo Polymers for Solar Cells. J. Mater. Chem.
2012, 22, 2306−2314.
(290) Zhou, H.; Yang, L.; You, W. Rational Design of High
Performance Conjugated Polymers for Organic Solar Cells. Macro-
molecules 2012, 45, 607−632.
(291) Pandey, L.; Risko, C.; Norton, J. E.; Brédas, J.-L. Donor-
Acceptor Copolymers of Relevance for Organic Photovoltaics: A
Theoretical Investigation of the Impact of Chemical Structure
Modifications on the Electronic and Optical Properties. Macro-
molecules 2012, 45, 6405−6414.
(292) Saberi Moghaddam, R.; Huettner, S.; Vaynzof, Y.; Ducati, C.;
Divitini, G.; Lohwasser, R. H.; Musselman, K. P.; Sepe, A.; Scherer, M.
R. J.; Friend, R. H.; et al. Polymer Crystallization as a Tool To Pattern
Hybrid Nanostructures: Growth of 12 nm ZnO Arrays in Poly(3-
hexylthiophene). Nano Lett. 2013, 13, 4499−4504.
(293) Huettner, S.; Hodgkiss, J. M.; Sommer, M.; Friend, R. H.;
Steiner, U.; Thelakkat, M. Morphology-Dependent Charge Photo-
generation in Donor-Acceptor Block Copolymer Films Based on
Poly(3-hexylthiophene)-block-Poly(perylene bisimide acrylate). J.
Phys. Chem. B 2012, 116, 10070−10078.
(294) Sharber, S. A.; Baral, R. N.; Frausto, F.; Haas, T. E.; Müller, P.;
Thomas, S. W., III Substituent Effects That Control Conjugated
Oligomer Conformation through Non-covalent Interactions. J. Am.
Chem. Soc. 2017, 139, 5164−5174.
(295) Kim, J.-H.; Park, J. B.; Yoon, S. C.; Jung, I. H.; Hwang, D.-H.
Enhanced and controllable open-circuit voltage using 2D-conjugated
benzodithiophene (BDT) homopolymers by alkylthio substitution. J.
Mater. Chem. C 2016, 4, 2170−2177.
(296) Kentaro, H.; Akito, M.; Hachiro, N.; Hidetoshi, O.; Yosikazu,
S. Evaluation of Thermoelectric Properties of Polythiophene Films
Synthesized by Electrolytic Polymerization. Jpn. J. Appl. Phys. 2009, 48,
071501.
(297) Famili, M.; Grace, I. M.; Al-Galiby, Q.; Sadeghi, H.; Lambert,
C. J. Toward High Thermoelectric Performance of Thiophene and
Ethylenedioxythiophene (EDOT) Molecular Wires. Adv. Funct. Mater.
2017, 1703135.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(298) Zhang, B.; Wang, K.; Li, D.; Cui, X. Doping effects on the
thermoelectric properties of pristine poly(3,4-ethylenedioxythio-
phene). RSC Adv. 2015, 5, 33885−33891.
(299) Ihnatsenka, S.; Crispin, X.; Zozoulenko, I. V. Understanding
hopping transport and thermoelectric properties of conducting
polymers. Phys. Rev. B: Condens. Matter Mater. Phys. 2015, 92, 035201.
(300) Wei, Q.; Mukaida, M.; Kirihara, K.; Naitoh, Y.; Ishida, T.
Photoinduced Dedoping of Conducting Polymers: An Approach to
Precise Control of the Carrier Concentration and Understanding
Transport Properties. ACS Appl. Mater. Interfaces 2016, 8, 2054−2060.
(301) DiSalvo, F. J. Thermoelectric Cooling and Power Generation.
Science 1999, 285, 703−706.
(302) Hu, L.; Zhu, T.; Wang, Y.; Xie, H.; Xu, Z.; Zhao, X. Shifting up
the Optimum Figure of Merit of P-Type Bismuth Telluride-Based
Thermoelectric Materials for Power Generation by Suppressing
Intrinsic Conduction. NPG Asia Mater. 2014, 6, 88.
(303) Ao, W.; Wang, L.; Li, J.; Pan, F.; Wu, C. Synthesis and
Characterization of Polythiophene/Bi2Te3 Nanocomposite Thermo-
electric Material. J. Electron. Mater. 2011, 40, 2027−2032.
(304) Lai, C.; Li, J.; Pan, C.; Wang, L.; Bai, X. Preparation and
Characterization of Bi2Te3/Graphite/Polythiophene Thermoelectric
Composites. J. Electron. Mater. 2016, 45, 5246−5252.
(305) Mateeva, N.; Niculescu, H.; Schlenoff, J.; Testardi, L. R.
Correlation of Seebeck Coefficient and Electric Conductivity in
Polyaniline and Polypyrrole. J. Appl. Phys. 1998, 83, 3111−3117.
(306) Glaudell, A. M.; Cochran, J. E.; Patel, S. N.; Chabinyc, M. L.
Impact of the Doping Method on Conductivity and Thermopower in
Semiconducting Polythiophenes. Adv. Energy Mater. 2015, 5, 1401072.
(307) Kroon, R.; Mengistie, D. A.; Kiefer, D.; Hynynen, J.; Ryan, J.
D.; Yu, L.; Muller, C. Thermoelectric plastics: from design to
synthesis, processing and structure-property relationships. Chem. Soc.
Rev. 2016, 45, 6147−6164.
(308) Li, Z.; Sun, L.; Zhang, Y.; Dove, A. P.; O’Reilly, R. K.; Chen, G.
Shape Effect of Glyco-Nanoparticles on Macrophage Cellular Uptake
and Immune Response. ACS Macro Lett. 2016, 5, 1059−1064.
(309) Fan, L.; Xu, X. A simple strategy to enhance electrical
conductivity of nanotube-conjugate polymer composites via iodine-
doping. RSC Adv. 2015, 5, 78104−78108.
(310) Meer, S.; Kausar, A.; Iqbal, T. Trends in Conducting Polymer
and Hybrids of Conducting Polymer/Carbon Nanotube: A Review.
Polym.-Plast. Technol. Eng. 2016, 55, 1416−1440.
(311) Dresselhaus, M.; Chen, G.; Tang, M.; Yang, R.; Lee, H.; Wang,
D.; Ren, Z.; Fleurial, J.-P.; Gogna, P. New Directions for Low-
Dimensional Thermoelectric Materials. Adv. Mater. 2007, 19, 1043−
1053.
(312) Meng, C.; Liu, C.; Fan, S. A Promising Approach to Enhanced
Thermoelectric Properties Using Carbon Nanotube Networks. Adv.
Mater. 2010, 22, 535−539.
(313) Wang, L.; Jiang, F.; Xiong, J.; Xu, J.; Zhou, W.; Liu, C.; Shi, H.;
Jiang, Q. Effects of Second Dopants on Electrical Conductivity and
Thermopower of Poly(3,4-Ethylenedioxythiophene):Poly-
(styrenesulfonate)-Filled Carbon Black. Mater. Chem. Phys. 2015,
153, 285−290.
(314) Chen, Y.; Zhao, Y.; Liang, Z. Solution Processed Organic
Thermoelectrics: Towards Flexible Thermoelectric Modules. Energy
Environ. Sci. 2015, 8, 401−422.
(315) Ming, S.; Zhen, S.; Lin, K.; Zhao, L.; Xu, J.; Lu, B.; Wang, L.;
Xiong, J.; Zhu, Z. Thermoelectric Performance of Donor-Acceptor-
Donor Conjugated Polymers Based on Benzothiadiazole Derivatives. J.
Electron. Mater. 2015, 44, 1−8.
(316) Wang, J.; Cai, K.; Shen, S. Enhanced thermoelectric properties
of poly(3,4-ethylenedioxythiophene) thin films treated with H2SO4.
Org. Electron. 2014, 15, 3087−3095.
(317) Ma, S.; Anderson, K.; Guo, L.; Yousuf, A.; Ellingsworth, E. C.;
Vajner, C.; Wang, H.-T.; Szulczewski, G. Temperature Dependent
Thermopower and Electrical Conductivity of te Nanowire/Poly(3,4-
Ethylenedioxythiophene):Poly(4-styrene Sulfonate) Microribbons.
Appl. Phys. Lett. 2014, 105, 073905.
10279
Perspective
(318) Gu, H.; Ming, S.; Lin, K.; Liu, H.; Chen, S.; Lu, B.; Xu, J.
Thermoelectric Properties of Poly(selenophene-co-3,4-ethylenediox-
ythiophene) via Electropolymerization. J. Electron. Mater. 2017, 46,
3124−3130.
(319) Ye, G.; Xu, J.; Ma, X.; Zhou, Q.; Li, D.; Zuo, Y.; Lv, L.; Zhou,
W.; Duan, X. One-step electrodeposition of free-standing flexible
conducting PEDOT derivative film and its electrochemical capacitive
and thermoelectric performance. Electrochim. Acta 2017, 224, 125−
132.
(320) Shi, H.; Liu, C.; Jiang, Q.; Xu, J. Effective Approaches to
Improve the Electrical Conductivity of PEDOT:PSS: A Review. Adv.
Elect. Mater. 2015, 1, 1500017.
(321) Lee, H. J.; Anoop, G.; Lee, H. J.; Kim, C.; Park, J.-W.; Choi, J.;
Kim, H.; Kim, Y.-J.; Lee, E.; Lee, S.-G.; Kim, Y.-M.; Lee, J.-H.; Jo, J. Y.
Enhanced thermoelectric performance of PEDOT:PSS/PANI-CSA
polymer multilayer structures. Energy Environ. Sci. 2016, 9, 2806−
2811.
(322) Wang, J.; Cai, K.; Song, H.; Shen, S. Simultaneously enhanced
electrical conductivity and Seebeck coefficient in Poly (3,4-ethyl-
enedioxythiophene) films treated with hydroiodic acid. Synth. Met.
2016, 220, 585−590.
(323) Golsanamlou, Z.; Tagani, M. B.; Soleimani, H. R. Spin
Thermoelectric Properties of Polythiophene Molecular Junction.
Macromol. Theory Simul. 2014, 23, 311−319.
(324) Singh, V.; Bougher, T. L.; Weathers, A.; Cai, Y.; Bi, K.; Pettes,
M. T.; McMenamin, S. A.; Lv, W.; Resler, D. P.; Gattuso, T. R.; et al.
High Thermal Conductivity of Chain-Oriented Amorphous Poly-
thiophene. Nat. Nanotechnol. 2014, 9, 384−390.
(325) Kim, G.-H.; Lee, D.; Shanker, A.; Shao, L.; Kwon, M. S.;
Gidley, D.; Kim, J.; Pipe, K. P. High thermal conductivity in
amorphous polymer blends by engineered interchain interactions. Nat.
Mater. 2014, 14, 295−300.
(326) Shanker, A.; Li, C.; Kim, G.-H.; Gidley, D.; Pipe, K. P.; Kim, J.
High thermal conductivity in electrostatically engineered amorphous
polymers. Science Adv. 2017, 3, e1700342.
(327) Choy, C. Thermal Conductivity of Polymers. Polymer 1977,
18, 984−1004.
(328) Wang, X.; Ho, V.; Segalman, R. A.; Cahill, D. G. Thermal
Conductivity of High-Modulus Polymer Fibers. Macromolecules 2013,
46, 4937−4943.
(329) Kurabayashi, K.; Asheghi, M.; Touzelbaev, M.; Goodson, K. E.
Measurement of the Thermal Conductivity Anisotropy in Polyimide
Films. J. Microelectromech. Syst. 1999, 8, 180−191.
(330) Li, S.; Deyu, L.; Choongho, Y.; Wanyoung, J.; Dohyung, K.;
Zhen, Y.; Philip, K.; Arunava, M. Measuring Thermal and Thermo-
electric Properties of One-Dimensional Nanostructures Using a
Microfabricated Device. J. Heat Transfer 2003, 125, 881−888.
(331) Bullen, A. J.; O’Hara, K. E.; Cahill, D. G.; Monteiro, O.; von
Keudell, A. Thermal Conductivity of Amorphous Carbon Thin Films.
J. Appl. Phys. 2000, 88, 6317−6320.
(332) Cahill, D. G.; Watson, S. K.; Pohl, R. O. Lower Limit to the
Thermal Conductivity of Disordered Crystals. Phys. Rev. B: Condens.
Matter Mater. Phys. 1992, 46, 6131−6140.
(333) Liu, X.; Feldman, J. L.; Cahill, D. G.; Crandall, R. S.; Bernstein,
N.; Photiadis, D. M.; Mehl, M. J.; Papaconstantopoulos, D. A. High
Thermal Conductivity of a Hydrogenated Amorphous Silicon Film.
Phys. Rev. Lett. 2009, 102, 035901.
(334) Yen, H.-J.; Shan, C.; Wang, L.; Xu, P.; Zhou, M.; Wang, H.-L.
Development of Conjugated Polymers for Memory Device Applica-
tions. Polymers 2017, 9, 25.
(335) Li, Y.; Shen, Y. Polythiophene-based materials for nonvolatile
polymeric memory devices. Polym. Eng. Sci. 2014, 54, 2470−2488.
(336) Pillai, R. G.; Zhao, J.; Freund, M. S.; Thomson, D. J. Field-
Induced Carrier Generation in Conjugated Polymer Semiconductors
for Dynamic, Asymmetric Junctions. Adv. Mater. 2008, 20, 49−53.
(337) Barman, S.; Deng, F.; McCreery, R. L. Conducting Polymer
Memory Devices Based on Dynamic Doping. J. Am. Chem. Soc. 2008,
130, 11073−11081.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
(338) Elsawy, W.; Son, M.; Jang, J.; Kim, M. J.; Ji, Y.; Kim, T.-W.; Ko,
H. C.; Elbarbary, A.; Ham, M.-H.; Lee, J.-S. Isoindigo-Based Donor-
Acceptor Conjugated Polymers for Air-Stable Nonvolatile Memory
Devices. ACS Macro Lett. 2015, 4, 322−326.
(339) Kumar, M. R.; Rahman, G. M. A.; Thomson, D. J.; Freund, M.
S. Controlling Volatility in Solid-State Redox-Based Memory Devices
Using Heterojunction Barriers to Ion Transport. Chem. Commun.
2012, 48, 9409−9411.
(340) Wang, X.; Smela, E. Experimental Studies of Ion Transport in
PPy(DBS). J. Phys. Chem. C 2009, 113, 369−381.
(341) Li, Y.; Song, Y.; Zhang, X.; Wu, X.; Wang, F.; Wang, Z.
Programmable Polymer Memory Device Based on Hydrophilic
Polythiophene and Poly(ionic liquid) Electrolyte. Macromol. Chem.
Phys. 2015, 216, 113−121.
(342) Coakley, K.; Srinivasan, B.; Ziebarth, J.; Goh, C.; Liu, Y.;
McGehee, M. Enhanced Hole Mobility in Regioregular Polythiophene
Infiltrated in Straight Nanopores. Adv. Funct. Mater. 2005, 15, 1927−
1932.
(343) Duong, D. T.; Toney, M. F.; Salleo, A. Role of Confinement
and Aggregation in Charge Transport in Semicrystalline Polythio-
phene Thin Films. Phys. Rev. B: Condens. Matter Mater. Phys. 2012, 86,
205205.
(344) McCulloch, I.; Heeney, M.; Bailey, C.; Genevicius, K.;
MacDonald, I.; Shkunov, M.; Sparrowe, D.; Tierney, S.; Wagner, R.;
Zhang, W.; et al. Liquid-Crystalline Semiconducting Polymers with
High Charge-Carrier Mobility. Nat. Mater. 2006, 5, 328−333.
(345) Aizawa, M.; Yamada, T.; Shinohara, H.; Akagi, K.; Shirakawa,
H. Electrochemical Fabrication of a Polypyrrole-Polythiophene p-n
Junction Diode. J. Chem. Soc., Chem. Commun. 1986, 1315−1317.
(346) Goh, C.; Kline, R. J.; McGehee, M. D.; Kadnikova, E. N.;
Fréc het, J. M. J. Molecular-Weight-Dependent Mobilities in
Regioregular Poly(3-Hexyl-Thiophene) Diodes. Appl. Phys. Lett.
2005, 86, 122110.
(347) Dai, M. Z.; Chen, Y. H.; Chuang, M. Y.; Zan, H. W.; Meng, H.
F. Achieving a Good Life Time in a Vertical-Organic-Diode Gas
Sensor. Sensors 2014, 14, 16287.
(348) Min Son, J.; Seung Song, W.; Ho Yoo, C.; Yeol Yun, D.; Whan
Kim, T. Electrical Stabilities and Memory Mechanisms of Organic
Bistable Devices Fabricated Utilizing a Poly(3,4-Ethylene-Dioxythio-
phene): Poly(Styrenesulfonate) Layer with a Poly(methyl Methacry-
late) Buffer Layer. Appl. Phys. Lett. 2012, 100, 183303.
(349) Park, B.; Lee, J.; Kim, O. Effect of Glycerol on Retention Time
and Electrical Properties of Polymer Bistable Memory Devices Based
on Glycerol-Modified PEDOT:PSS. J. Nanosci. Nanotechnol. 2012, 12,
469−474.
(350) Avila-Nino, J. A.; Machado, W. S.; Sustaita, A. O.; Segura-
Cardenas, E.; Reyes-Reyes, M.; Lopez-Sandoval, R.; Hummelgen, I. A.
Organic Low Voltage Rewritable Memory Device Based on
PEDOT:PSS/f-MWCNTs Thin Film. Org. Electron. 2012, 13, 2582−
2588.
(351) Sun, Y.; Li, L.; Wen, D.; Bai, X.; Li, G. Bistable electrical
switching and nonvolatile memory effect in carbon nanotube-poly(3,4-
ethylenedioxythiophene):poly(styrenesulfonate) composite films.
Phys. Chem. Chem. Phys. 2015, 17, 17150−17158.
(352) Lu, L.; Zheng, T.; Wu, Q.; Schneider, A. M.; Zhao, D.; Yu, L.
Recent Advances in Bulk Heterojunction Polymer Solar Cells. Chem.
Rev. 2015, 115, 12666−12731.
(353) Lewis, N. S.; Nocera, D. G. Powering the planet: Chemical
challenges in solar energy utilization. Proc. Natl. Acad. Sci. U. S. A.
2006, 103, 15729−15735.
(354) Cook, T. R.; Dogutan, D. K.; Reece, S. Y.; Surendranath, Y.;
Teets, T. S.; Nocera, D. G. Solar Energy Supply and Storage for the
Legacy and Nonlegacy Worlds. Chem. Rev. 2010, 110, 6474−6502.
(355) Günes, S.; Neugebauer, H.; Sariciftci, N. S. Conjugated
Polymer-Based Organic Solar Cells. Chem. Rev. 2007, 107, 1324−
1338.
(356) Grätzel, M. Recent Advances in Sensitized Mesoscopic Solar
Cells. Acc. Chem. Res. 2009, 42, 1788−1798.
10280
Perspective
(357) Clarke, T. M.; Durrant, J. R. Charge Photogeneration in
Organic Solar Cells. Chem. Rev. 2010, 110, 6736−6767.
(358) Facchetti, A. π-Conjugated Polymers for Organic Electronics
and Photovoltaic Cell Applications. Chem. Mater. 2011, 23, 733−758.
(359) Liang, Y.; Yu, L. A New Class of Semiconducting Polymers for
Bulk Heterojunction Solar Cells with Exceptionally High Performance.
Acc. Chem. Res. 2010, 43, 1227−1236.
(360) Treat, N. D.; Brady, M. A.; Smith, G.; Toney, M. F.; Kramer, E.
J.; Hawker, C. J.; Chabinyc, M. L. Interdiffusion of PCBM and P3HT
Reveals Miscibility in a Photovoltaically Active Blend. Adv. Energy
Mater. 2011, 1, 82−89.
(361) Zhang, S.; Ye, L.; Hou, J. Breaking the 10Photovoltaics:
Morphology and Device Optimization of Well-Known PBDTTT
Polymers. Adv. Energy Mater. 2016, 6, 1502529.
(362) Lee, W.; Roh, S.-J.; Hyung, K.-H.; Park, J.; Lee, S.-H.; Han, S.-
H. Photoelectrochemically polymerized polythiophene layers on
ruthenium photosensitizers in dye-sensitized solar cells and their
beneficial effects. Sol. Energy 2009, 83, 690−695.
(363) Zhang, W.; Zhu, R.; Li, F.; Wang, Q.; Liu, B. High-
Performance Solid-State Organic Dye Sensitized Solar Cells with
P3HT as Hole Transporter. J. Phys. Chem. C 2011, 115, 7038−7043.
(364) Kwon, T.-H.; Armel, V.; Nattestad, A.; MacFarlane, D. R.;
Bach, U.; Lind, S. J.; Gordon, K. C.; Tang, W.; Jones, D. J.; Holmes, A.
B. Dithienothiophene (DTT)-Based Dyes for Dye-Sensitized Solar
Cells: Synthesis of 2,6-Dibromo-DTT. J. Org. Chem. 2011, 76, 4088−
4093.
(365) Liu, T.; Troisi, A. Absolute Rate of Charge Separation and
Recombination in a Molecular Model of the P3HT/PCBM Interface. J.
Phys. Chem. C 2011, 115, 2406−2415.
(366) Liu, T.; Cheung, D. L.; Troisi, A. Structural Variability and
Dynamics of the P3HT/PCBM Interface and its Effects on the
Electronic Structure and the Charge-Transfer Rates in Solar Cells.
Phys. Chem. Chem. Phys. 2011, 13, 21461−21470.
(367) Caruso, D.; Troisi, A. Long-Range Exciton Dissociation in
Organic Solar Cells. Proc. Natl. Acad. Sci. U. S. A. 2012, 109, 13498−
13502.
(368) Yamamoto, S.; Orimo, A.; Ohkita, H.; Benten, H.; Ito, S.
Molecular Understanding of the Open-Circuit Voltage of Polymer:-
Fullerene Solar Cells. Adv. Energy Mater. 2012, 2, 229−237.
(369) Koster, L. J. A.; Shaheen, S. E.; Hummelen, J. C. Pathways to a
New Efficiency Regime for Organic Solar Cells. Adv. Energy Mater.
2012, 2, 1246−1253.
(370) Few, S.; Frost, J. M.; Nelson, J. Models of Charge Pair
Generation in Organic Solar Cells. Phys. Chem. Chem. Phys. 2015, 17,
2311−2325.
(371) Korona, T.; Rutkowska-Zbik, D. A Theoretical Study on
Elementary Building Blocks for Organic Solar Cells-Influence of a
Donor Molecule on Electronic Spectrum of PCBM. Comput. Theor.
Chem. 2014, 1040, 243−258.
(372) Kolemen, S.; Cakmak, Y.; Ozdemir, T.; Erten-Ela, S.;
Buyuktemiz, M.; Dede, Y.; Akkaya, E. U. Design and Characterization
of Bodipy Derivatives for Bulk Heterojunction Solar Cells. Tetrahedron
2014, 70, 6229−6234.
(373) de Gier, H. D.; Broer, R.; Havenith, R. W. A. Non-Innocent
Side-Chains with Dipole Moments in Organic Solar Cells Improve
Charge Separation. Phys. Chem. Chem. Phys. 2014, 16, 12454−12461.
(374) Li, S.-B.; Duan, Y.-A.; Geng, Y.; Li, H.-B.; Zhang, J.-Z.; Xu, H.-
L.; Zhang, M.; Su, Z.-M. A Designed Bithiopheneimide-Based
Conjugated Polymer for Organic Photovoltaic with Ultrafast Charge
Transfer at Donor/PC71BM Interface: Theoretical Study and
Characterization. Phys. Chem. Chem. Phys. 2014, 16, 25799−25808.
(375) Dattani, R.; Bannock, J.; Fei, Z.; MacKenzie, R.; Guilbert, A.;
Vezie, M.; Nelson, J.; de Mello, J. C.; Heeney, M.; Cabral, J.; Nedoma,
A. A General Mechanism for Controlling thin Film Structures in All-
Conjugated Block Copolymer: Fullerene Blends. J. Mater. Chem. A
2014, 2, 14711−14719.
(376) Qin, Y.; Uddin, M. A.; Chen, Y.; Jang, B.; Zhao, K.; Zheng, Z.;
Yu, R.; Shin, T. J.; Woo, H. Y.; Hou, J. Highly Efficient Fullerene-Free
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Polymer Solar Cells Fabricated with Polythiophene Derivative. Adv.
Mater. 2016, 28, 9416−9422.
(377) Zhang, H.; Li, S.; Xu, B.; Yao, H.; Yang, B.; Hou, J. Fullerene-
free polymer solar cell based on a polythiophene derivative with an
unprecedented energy loss of less than 0.5 eV. J. Mater. Chem. A 2016,
4, 18043−18049.
(378) Liu, D.; Yang, B.; Jang, B.; Xu, B.; Zhang, S.; He, C.; Woo, H.
Y.; Hou, J. Molecular design of a wide-band-gap conjugated polymer
for efficient fullerene-free polymer solar cells. Energy Environ. Sci. 2017,
10, 546−551.
(379) Huettner, S.; Hodgkiss, J. M.; Sommer, M.; Friend, R. H.;
Steiner, U.; Thelakkat, M. Morphology-Dependent Charge Photo-
generation in Donor-Acceptor Block Copolymer Films Based on
Poly(3-hexylthiophene)-block-Poly(perylene bisimide acrylate). J.
Phys. Chem. B 2012, 116, 10070−10078.
(380) Zhang, Q.; Cirpan, A.; Russell, T. P.; Emrick, T. Donor-
Acceptor Poly(thiophene-block-perylene diimide) Copolymers: Syn-
thesis and Solar Cell Fabrication. Macromolecules 2009, 42, 1079−
1082.
(381) Kim, J.-H.; Song, C. E.; Shin, N.; Kang, H.; Wood, S.; Kang, I.-
N.; Kim, B. J.; Kim, B.; Kim, J.-S.; Shin, W. S. a. a. High-Crystalline
Medium-Band-Gap Polymers Consisting of Benzodithiophene and
Benzotriazole Derivatives for Organic Photovoltaic Cells. ACS Appl.
Mater. Interfaces 2013, 5, 12820−12831.
(382) Li, G.; Zhu, R.; Yang, Y. Polymer solar cells. Nat. Photonics
2012, 6, 153.
(383) Guo, X.; Zhou, N.; Lou, S. J.; Smith, J.; Tice, D. B.; Hennek, J.
W.; Ortiz, R. P.; Navarrete, J. T. L.; Li, S.; Strzalka, J.; Chen, L. X.;
Chang, R. P. H.; Facchetti, A.; Marks, T. J. Polymer solar cells with
enhanced fill factors. Nat. Photonics 2013, 7, 825.
(384) Yao, H.; Ye, L.; Zhang, H.; Li, S.; Zhang, S.; Hou, J. Molecular
Design of Benzodithiophene-Based Organic Photovoltaic Materials.
Chem. Rev. 2016, 116, 7397−7457.
(385) Kim, J.-H.; Park, J. B.; Yang, H.; Jung, I. H.; Yoon, S. C.; Kim,
D.; Hwang, D.-H. Controlling the Morphology of BDTT-DPP-Based
Small Molecules via End-Group Functionalization for Highly Efficient
Single and Tandem Organic Photovoltaic Cells. ACS Appl. Mater.
Interfaces 2015, 7, 23866−23875.
(386) Chowdhury, P.; Fortin, P.; Suppes, G.; Holdcroft, S. Aqueous
Photoelectrochemical Reduction of Anthraquinone Disulfonate at
Organic Polymer Films. Macromol. Chem. Phys. 2016, 217, 1119−
1127.
(387) El-Rashiedy, O. A.; Holdcroft, S. Photoelectrochemical
Properties of Poly(3-alkylthiophene) Films in Aqueous Solution. J.
Phys. Chem. 1996, 100, 5481−5484.
(388) Nanda, K. K.; Swain, S.; Satpati, B.; Besra, L.; Mishra, B.;
Chaudhary, Y. S. Enhanced Photocatalytic Activity and Charge Carrier
Dynamics of Hetero-Structured Organic-Inorganic Nano-Photocata-
lysts. ACS Appl. Mater. Interfaces 2015, 7, 7970−7978.
(389) Yang, S.; Fan, L.; Yang, S. Langmuir-Blodgett Films of Poly(3-
hexylthiophene) Doped with the Endohedral Metallofullerene Dy@
C82: Preparation, Characterization, and Application in Photo-
electrochemical Cells. J. Phys. Chem. B 2004, 108, 4394−4404.
(390) Mosconi, E.; Salvatori, P.; Saba, M. I.; Mattoni, A.; Bellani, S.;
Bruni, F.; Santiago Gonzalez, B.; Antognazza, M. R.; Brovelli, S.;
Lanzani, G.; Li, H.; Brédas, J.-L.; De Angelis, F. Surface Polarization
Drives Photoinduced Charge Separation at the P3HT/Water Interface.
ACS Energy Lett. 2016, 1, 454−463.
(391) Maria Giron, R.; Marco-Martinez, J.; Bellani, S.; Insuasty, A.;
Comas Rojas, H.; Tullii, G.; Antognazza, M. R.; Filippone, S.; Martin,
N. Synthesis of modified fullerenes for oxygen reduction reactions. J.
Mater. Chem. A 2016, 4, 14284−14290.
(392) Rojas, H. C.; Bellani, S.; Fumagalli, F.; Tullii, G.; Leonardi, S.;
Mayer, M. T.; Schreier, M.; Gratzel, M.; Lanzani, G.; Di Fonzo, F.;
Antognazza, M. R. Polymer-based photocathodes with a solution-
processable cuprous iodide anode layer and a polyethyleneimine
protective coating. Energy Environ. Sci. 2016, 9, 3710−3723.
10281
Perspective
(393) Kirner, J. T.; Finke, R. G. Water-oxidation photoanodes using
organic light-harvesting materials: a review. J. Mater. Chem. A 2017, 5,
19560−19592.
(394) Bourgeteau, T.; Tondelier, D.; Geffroy, B.; Brisse, R.; Cornut,
R.; Artero, V.; Jousselme, B. Enhancing the Performances of
P3HT:PCBM-MoS3-Based H2-Evolving Photocathodes with Inter-
facial Layers. ACS Appl. Mater. Interfaces 2015, 7, 16395−16403.
(395) Bellani, S.; Najafi, L.; Capasso, A.; Del Rio Castillo, A. E.;
Antognazza, M. R.; Bonaccorso, F. Few-layer MoS2 flakes as a hole-
selective layer for solution-processed hybrid organic hydrogen-evolving
photocathodes. J. Mater. Chem. A 2017, 5, 4384−4396.
(396) Liao, X.; Liu, Z.; Ding, L.; Chen, J.; Tang, W. Photo-
electrocatalytic activity of flexible PEDOT-PSS/silicon carbide nano-
wire films. RSC Adv. 2015, 5, 99143−99147.
(397) Guerrero, A.; Haro, M.; Bellani, S.; Antognazza, M. R.; Meda,
L.; Gimenez, S.; Bisquert, J. Organic photoelectrochemical cells with
quantitative photocarrier conversion. Energy Environ. Sci. 2014, 7,
3666−3673.
(398) O’Leary, L. E.; Rose, M. J.; Ding, T. X.; Johansson, E.;
Brunschwig, B. S.; Lewis, N. S. Heck Coupling of Olefins to Mixed
Methyl/Thienyl Monolayers on Si(111) Surfaces. J. Am. Chem. Soc.
2013, 135, 10081−10090.
(399) Yu, M.; Doak, P.; Tamblyn, I.; Neaton, J. B. Theory of
Covalent Adsorbate Frontier Orbital Energies on Functionalized
Light-Absorbing Semiconductor Surfaces. J. Phys. Chem. Lett. 2013, 4,
1701−1706.
(400) Li, Y.; O’Leary, L. E.; Lewis, N. S.; Galli, G. Combined
Theoretical and Experimental Study of Band-Edge Control of Si
through Surface Functionalization. J. Phys. Chem. C 2013, 117, 5188−
5194.
(401) Liang, Z.; Zeng, P.; Liu, P.; Zhao, C.; Xie, W.; Mai, W.
Interface Engineering To Boost Photoresponse Performance of Self-
Powered, Broad-Bandwidth PEDOT:PSS/Si Heterojunction Photo-
detector. ACS Appl. Mater. Interfaces 2016, 8, 19158−19167.
(402) Walter, M. G.; Liu, X.; O’Leary, L. E.; Brunschwig, B. S.; Lewis,
N. S. Electrical Junction Behavior of Poly(3,4-ethylenedioxythio-
phene) (PEDOT) Contacts to H-Terminated and CH3-Terminated
p-, n-, and n+-Si(111) Surfaces. J. Phys. Chem. C 2013, 117, 14485−
14492.
(403) Yang, Z.; Gao, P.; He, J.; Chen, W.; Yin, W.-Y.; Zeng, Y.; Guo,
W.; Ye, J.; Cui, Y. Tuning of the Contact Properties for High-
Efficiency Si/PEDOT:PSS Heterojunction Solar Cells. ACS Energy
Lett. 2017, 2, 556−562.
(404) Bruce, J. P.; Oliver, D. R.; Lewis, N. S.; Freund, M. S. Electrical
Characteristics of the Junction between PEDOT:PSS and Thiophene-
Functionalized Silicon Microwires. ACS Appl. Mater. Interfaces 2015, 7,
27160−27166.
(405) Bruce, J. P.; Asgari, S.; Ardo, S.; Lewis, N. S.; Oliver, D. R.;
Freund, M. S. Measurement of the Electrical Resistance of n-Type Si
Microwire/p-Type Conducting Polymer Junctions for Use in Artificial
Photosynthesis. J. Phys. Chem. C 2014, 118, 27742−27748.
(406) Giesbrecht, P. K.; Bruce, J. P.; Freund, M. S. Electric and
Photoelectric Properties of 3,4-Ethylenedioxythiophene-Function-
alized n-Si/PEDOT:PSS Junctions. ChemSusChem 2016, 9, 109−117.
(407) Yahyaie, I.; Ardo, S.; Oliver, D. R.; Thomson, D. J.; Freund, M.
S.; Lewis, N. S. Comparison between the electrical junction properties
of H-terminated and methyl-terminated individual Si microwire/
polymer assemblies for photoelectrochemical fuel production. Energy
Environ. Sci. 2012, 5, 9789−9794.
(408) Yahyaie, I.; McEleney, K.; Walter, M. G.; Oliver, D. R.;
Thomson, D. J.; Freund, M. S.; Lewis, N. S. Characterization of the
Electrical Properties of Individual p-Si Microwire/Polymer/n-Si
Microwire Assemblies. J. Phys. Chem. C 2011, 115, 24945−24950.
(409) Carvalho, A.; Martsinovich, N.; Vieira, R.; Troisi, A. Charge
Injection Rates in Hybrid Nanosilicon-Polythiophene Bulk Hetero-
junction Solar Cells. J. Phys. Chem. C 2013, 117, 110−115.
(410) Vaynzof, Y.; Brenner, T. J. K.; Kabra, D.; Sirringhaus, H.;
Friend, R. H. Compositional and Morphological Studies of
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
Polythiophene/Polyflorene Blends in Inverted Architecture Hybrid
Solar Cells. Adv. Funct. Mater. 2012, 22, 2418−2424.
(411) Humphry-Baker, N.; Driscoll, K.; Rao, A.; Torres, T.; Snaith,
H. J.; Friend, R. H. Time-Evolution of Poly(3-Hexylthiophene) as an
Energy Relay Dye in Dye-Sensitized Solar Cells. Nano Lett. 2012, 12,
634−639.
(412) McNeill, C. R.; Halls, J. J. M.; Wilson, R.; Whiting, G. L.;
Berkebile, S.; Ramsey, M. G.; Friend, R. H.; Greenham, N. C. Efficient
Polythiophene/Polyfluorene Copolymer Bulk Heterojunction Photo-
voltaic Devices: Device Physics and Annealing Effects. Adv. Funct.
Mater. 2008, 18, 2309−2321.
(413) Couderc, E.; Greaney, M. J.; Brutchey, R. L.; Bradforth, S. E.
Direct Spectroscopic Evidence of Ultrafast Electron Transfer from a
Low Band Gap Polymer to CdSe Quantum Dots in Hybrid
Photovoltaic Thin Films. J. Am. Chem. Soc. 2013, 135, 18418−18426.
(414) Galperin, M.; Nitzan, A. Molecular Optoelectronics: the
Interaction of Molecular Conduction Junctions with Light. Phys. Chem.
Chem. Phys. 2012, 14, 9421−9438.
(415) Chu, Y.-L.; Cheng, C.-C.; Yen, Y.-C.; Chang, F.-C. A New
Supramolecular Hole Injection/Transport Material on Conducting
Polymer for Application in Light-Emitting Diodes. Adv. Mater. 2012,
24, 1894−1898.
(416) Grimsdale, A. C.; Leok Chan, K.; Martin, R. E.; Jokisz, P. G.;
Holmes, A. B. Synthesis of Light-Emitting Conjugated Polymers for
Applications in Electroluminescent Devices. Chem. Rev. 2009, 109,
897−1091.
(417) Perepichka, I.; Perepichka, D.; Meng, H.; Wudl, F. Light-
Emitting Polythiophenes. Adv. Mater. 2005, 17, 2281−2305.
(418) Reecht, G.; Scheurer, F.; Speisser, V.; Dappe, Y. J.; Mathevet,
F.; Schull, G. Electroluminescence of a Polythiophene Molecular Wire
Suspended between a Metallic Surface and the Tip of a Scanning
Tunneling Microscope. Phys. Rev. Lett. 2014, 112, 047403.
(419) Klopper, A. Tiny lights. Nat. Phys. 2014, 10, 177−177.
(420) Reecht, G.; Bulou, H.; Scheurer, F.; Speisser, V.; Carrière, B.;
Mathevet, F.; Schull, G. Oligothiophene Nanorings as Electron
Resonators for Whispering Gallery Modes. Phys. Rev. Lett. 2013,
110, 056802.
(421) Koch, M.; Ample, F.; Joachim, C.; Grill, L. Voltage-Dependent
Conductance of a Single Graphene Nanoribbon. Nat. Nanotechnol.
2012, 7, 713−717.
(422) Magoga, M.; Joachim, C. Conductance and Transparence of
Long Molecular Wires. Phys. Rev. B: Condens. Matter Mater. Phys.
1997, 56, 4722−4729.
(423) Lee, M. J.; Chen, Z.; Pietro, R. d.; Heeney, M.; Sirringhaus, H.
Electrooptical Spectroscopy of Uniaxially Aligned Polythiophene Films
in Field-Effect Transistors. Chem. Mater. 2013, 25, 2075−2082.
(424) Kline, R.; McGehee, M.; Kadnikova, E.; Liu, J.; Fréchet, J.
Controlling the Field-Effect Mobility of Regioregular Polythiophene
by Changing the Molecular Weight. Adv. Mater. 2003, 15, 1519−1522.
(425) Sandberg, H. G. O.; Frey, G. L.; Shkunov, M. N.; Sirringhaus,
H.; Friend, R. H.; Nielsen, M. M.; Kumpf, C. Ultrathin Regioregular
Poly(3-hexyl thiophene) Field-Effect Transistors. Langmuir 2002, 18,
10176−10182.
(426) Usta, H.; Yilmaz, M. D.; Avestro, A.-J.; Boudinet, D.; Denti,
M.; Zhao, W.; Stoddart, J. F.; Facchetti, A. BODIPY−Thiophene
Copolymers as p-Channel Semiconductors for Organic Thin-Film
Transistors. Adv. Mater. 2013, 25, 4327−4334.
(427) Tsumura, A.; Koezuka, H.; Ando, T. Macromolecular
electronic device: Field-effect transistor with a polythiophene thin
film. Appl. Phys. Lett. 1986, 49, 1210−1212.
(428) Wang, C.; Dong, H.; Hu, W.; Liu, Y.; Zhu, D. Semiconducting
π-Conjugated Systems in Field-Effect Transistors: A Material Odyssey
of Organic Electronics. Chem. Rev. 2012, 112, 2208−2267.
(429) Ebata, H.; Izawa, T.; Miyazaki, E.; Takimiya, K.; Ikeda, M.;
Kuwabara, H.; Yui, T. Highly Soluble [1]Benzothieno[3,2-b]-
benzothiophene (BTBT) Derivatives for High-Performance, Solu-
tion-Processed Organic Field-Effect Transistors. J. Am. Chem. Soc.
2007, 129, 15732−15733.
10282
Perspective
(430) Sawamoto, M.; Kang, M. J.; Miyazaki, E.; Sugino, H.; Osaka, I.;
Takimiya, K. Soluble Dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene
Derivatives for Solution-Processed Organic Field-Effect Transistors.
ACS Appl. Mater. Interfaces 2016, 8, 3810−3824.
(431) Fei, Z.; Boufflet, P.; Wood, S.; Wade, J.; Moriarty, J.; Gann, E.;
Ratcliff, E. L.; McNeill, C. R.; Sirringhaus, H.; Kim, J.-S.; Heeney, M.
Influence of Backbone Fluorination in Regioregular Poly(3-alkyl-4-
fluoro)thiophenes. J. Am. Chem. Soc. 2015, 137, 6866−6879.
(432) Zhao, N.; Noh, Y.-Y.; Chang, J.-F.; Heeney, M.; McCulloch, I.;
Sirringhaus, H. Polaron Localization at Interfaces in High-Mobility
Microcrystalline Conjugated Polymers. Adv. Mater. 2009, 21, 3759−
3763.
(433) Brown, P. J.; Sirringhaus, H.; Harrison, M.; Shkunov, M.;
Friend, R. H. Optical Spectroscopy of Field-Induced Charge in Self-
Organized High Mobility Poly(3-Hexylthiophene). Phys. Rev. B:
Condens. Matter Mater. Phys. 2001, 63, 125204.
(434) Zaumseil, J. In P3HT Revisited-From Molecular Scale to Solar
Cell Devices; Ludwigs, S., Ed.; Springer Berlin: Heidelberg, 2014; Vol.
265; pp 107−137.
(435) Sun, Y.; Lu, X.; Lin, S.; Kettle, J.; Yeates, S. G.; Song, A.
Polythiophene-Based Field-Effect Transistors with Enhanced Air
Stability. Org. Electron. 2010, 11, 351−355.
(436) Murphy, A. R.; Liu, J.; Luscombe, C.; Kavulak, D.; Fréchet, J.
M. J.; Kline, R. J.; McGehee, M. D. Synthesis, Characterization, and
Field-Effect Transistor Performance of Carboxylate-Functionalized
Polythiophenes with Increased Air Stability. Chem. Mater. 2005, 17,
4892−4899.
(437) Kazarinoff, P. D.; Shamburger, P. J.; Ohuchi, F. S.; Luscombe,
C. K. OTFT performance of air-stable ester-functionalized poly-
thiophenes. J. Mater. Chem. 2010, 20, 3040−3045.
(438) Sun, Y.; Lu, X.; Lin, S.; Kettle, J.; Yeates, S.; Song, A.
Polythiophene-based field-effect transistors with enhanced air stability.
Org. Electron. 2010, 11, 351−355.
(439) Zhang, X.; Bronstein, H.; Kronemeijer, A. J.; Smith, J.; Kim, Y.;
Kline, R.; Richter, L. J.; Anthopoulos, T. D.; Sirringhaus, H.; Song, K.;
et al. Molecular Origin of High Field-Effect Mobility in an
Indacenodithiophene-Benzothiadiazole Copolymer. Nat. Commun.
2013, 4, 3238.
(440) Wang, J.-T.; Takashima, S.; Wu, H.-C.; Chiu, Y.-C.; Chen, Y.;
Isono, T.; Kakuchi, T.; Satoh, T.; Chen, W.-C. Donor-Acceptor
Poly(3-hexylthiophene)-block-Pendent Poly(isoindigo) with Dual
Roles of Charge Transporting and Storage Layer for High-Perform-
ance Transistor-Type Memory Applications. Adv. Funct. Mater. 2016,
26, 2695−2705.
(441) Fang, Y.-K.; Liu, C.-L.; Li, C.; Lin, C.-J.; Mezzenga, R.; Chen,
W.-C. Synthesis, Morphology, and Properties of Poly(3-hexylthio-
phene)-block-Poly(vinylphenyl oxadiazole) Donor-Acceptor Rod-Coil
Block Copolymers and Their Memory Device Applications. Adv. Funct.
Mater. 2010, 20, 3012−3024.
(442) Chou, Y.-H.; You, N.-H.; Kurosawa, T.; Lee, W.-Y.;
Higashihara, T.; Ueda, M.; Chen, W.-C. Thiophene and Selenophene
Donor-Acceptor Polyimides as Polymer Electrets for Nonvolatile
Transistor Memory Devices. Macromolecules 2012, 45, 6946−6956.
(443) Bronstein, H.; et al. Thieno[3,2-b]thiophene-Diketopyrrolo-
pyrrole-Containing Polymers for High-Performance Organic Field-
Effect Transistors and Organic Photovoltaic Devices. J. Am. Chem. Soc.
2011, 133, 3272−3275.
(444) Ashraf, R. S.; Kronemeijer, A. J.; James, D. I.; Sirringhaus, H.;
McCulloch, I. A new thiophene substituted isoindigo based copolymer
for high performance ambipolar transistors. Chem. Commun. 2012, 48,
3939−3941.
(445) Fan, J.; Yuen, J. D.; Cui, W.; Seifter, J.; Mohebbi, A. R.; Wang,
M.; Zhou, H.; Heeger, A.; Wudl, F. High-Hole-Mobility Field-Effect
Transistors Based on Co-Benzobisthiadiazole-Quaterthiophene. Adv.
Mater. 2012, 24, 6164−6168.
(446) Luo, H.; Yu, C.; Liu, Z.; Zhang, G.; Geng, H.; Yi, Y.; Broch, K.;
Hu, Y.; Sadhanala, A.; Jiang, L.; Qi, P.; Cai, Z.; Sirringhaus, H.; Zhang,
D. Remarkable enhancement of charge carrier mobility of conjugated
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283
Chemistry of Materials
polymer field-effect transistors upon incorporating an ionic additive.
Sci. Adv. 2016, 2, e1600076.
(447) Zhang, W.; Smith, J.; Watkins, S. E.; Gysel, R.; McGehee, M.;
Salleo, A.; Kirkpatrick, J.; Ashraf, S.; Anthopoulos, T.; Heeney, M.;
et al. Indacenodithiophene Semiconducting Polymers for High-
Performance, Air-Stable Transistors. J. Am. Chem. Soc. 2010, 132,
11437−11439.
(448) Tsao, H. N.; Cho, D. M.; Park, I.; Hansen, M. R.; Mavrinskiy,
A.; Yoon, D. Y.; Graf, R.; Pisula, W.; Spiess, H. W.; Müllen, K.
Ultrahigh Mobility in Polymer Field-Effect Transistors by Design. J.
Am. Chem. Soc. 2011, 133, 2605−2612.
(449) Kline, R. J.; McGehee, M. D.; Kadnikova, E. N.; Liu, J.;
Fréchet, J. M. J.; Toney, M. F. Dependence of Regioregular Poly(3-
hexylthiophene) Film Morphology and Field-Effect Mobility on
Molecular Weight. Macromolecules 2005, 38, 3312−3319.
(450) Yuan, H.; Xing, C.; Fan, Y.; Chai, R.; Niu, R.; Zhan, Y.; Peng,
F.; Qi, J. Carbon Dioxide-Controlled Assembly of Water-Soluble
Conjugated Polymers Catalyzed by Carbonic Anhydrase. Macromol.
Rapid Commun. 2017, 38, 1600726.
(451) Mishra, A. K.; Agrawal, N. R.; Das, I. Synthesis of water
dispersible dendritic amino acid modified polythiophenes as highly
effective adsorbent for removal of methylene blue. J. Environ. Chem.
Eng. 2017, 5, 4923−4936.
(452) Yuan, H.; Fan, Y.; Xing, C.; Niu, R.; Chai, R.; Zhan, Y.; Qi, J.;
An, H.; Xu, J. Conjugated Polymer-Based Hybrid Materials for Turn-
On Detection of CO2 in Plant Photosynthesis. Anal. Chem. 2016, 88,
6593−6597.
(453) Yang, S.; Meng, D.; Sun, J.; Hou, W.; Ding, Y.; Jiang, S.;
Huang, Y.; Huang, Y.; Geng, J. Enhanced electrochemical response for
mercury ion detection based on poly(3-hexylthiophene) hybridized
with multi-walled carbon nanotubes. RSC Adv. 2014, 4, 25051−25056.
(454) Christine, L. M.; Rheingans, R. D. Global Challenges in Water,
Sanitation and Health. J. Water Health 2006, 04, 42−57.
(455) Reynolds, K. A.; Mena, K. D.; Gerba, C. P. Risk of Waterborne
Illness Via Drinking Water in the United States. Rev. Environ. Contam.
Toxicol. 2008, 192, 117−158.
(456) Völker, S.; Schreiber, C.; Kistemann, T. Drinking Water
Quality in Household Supply Infrastructure-A Survey of the Current
Situation in Germany. Int. J. Hyg. Environ. Health 2010, 213, 204−209.
(457) Juhna, T.; Birzniece, D.; Larsson, S.; Zulenkovs, D.; Sharipo,
A.; Azevedo, N. F.; Ménard-Szczebara, F.; Castagnet, S.; Féliers, C.;
Keevil, C. W. Detection of Escherichia coli in Biofilms from Pipe
Samples and Coupons in Drinking Water Distribution Networks. Appl.
Environ. Microbiol. 2007, 73, 7456−7464.
(458) Lindsay, D.; von Holy, A. Bacterial Biofilms within the Clinical
Setting: What Healthcare Professionals should Know. J. Hosp. Infect.
2006, 64, 313−325.
(459) Otterholt, E.; Charnock, C. Identification and Phylogeny of the
Small Eukaryote Population of Raw and Drinking Waters. Water Res.
2011, 45, 2527−2538.
(460) Yan, W.; Yuan, H.; Li, R.; Fan, Y.; Zhan, Y.; Qi, J.; An, H.; Niu,
R.; Li, G.; Xing, C. Conjugated Polythiophene/Porphyrin Complex for
Rapid and Simple Detection of Bacteria in Drinking Water. Macromol.
Chem. Phys. 2015, 216, 1603−1608.
(461) Rajwar, D.; Ammanath, G.; Cheema, J. A.; Palaniappan, A.;
Yildiz, U. H.; Liedberg, B. Tailoring Conformation-Induced Chromism
of Polythiophene Copolymers for Nucleic Acid Assay at Resource
Limited Settings. ACS Appl. Mater. Interfaces 2016, 8, 8349−8357.
(462) Isaksson, J.; Acharya, S.; Barman, J.; Cheruku, P.;
Chattopadhyaya, J. Single-Stranded Adenine-Rich DNA and RNA
Retain Structural Characteristics of Their Respective Double-Stranded
Conformations and Show Directional Differences in Stacking Pattern.
Biochemistry 2004, 43, 15996−16010.
(463) Sevilla, M.; Fuertes, A.; Mokaya, R. Preparation and Hydrogen
Storage Capacity of Highly Porous Activated Carbon Materials
Derived from Polythiophene. Int. J. Hydrogen Energy 2011, 36,
15658−15663.
(464) Oh, S. H.; Lee, C.-W.; Chun, D. H.; Jeon, J.-D.; Shim, J.; Shin,
K. H.; Yang, J. H. A metal-Free and All-Organic Redox Flow Battery
10283
Perspective
with Polythiophene as the Electroactive Species. J. Mater. Chem. A
2014, 2, 19994−19998.
(465) Moseley, P. T., Garche, J., Eds. Electrochemical Energy Storage
for Renewable Sources and Grid Balancing; Elsevier Science:
Amsterdam, 2014.
(466) Ambade, R. B.; Ambade, S. B.; Shrestha, N. K.; Salunkhe, R. R.;
Lee, W.; Bagde, S. S.; Kim, J. H.; Stadler, F. J.; Yamauchi, Y.; Lee, S.-H.
Controlled growth of polythiophene nanofibers in TiO2 nanotube
arrays for supercapacitor applications. J. Mater. Chem. A 2017, 5, 172−
180.
(467) Nejati, S.; Minford, T. E.; Smolin, Y. Y.; Lau, K. K. S. Enhanced
Charge Storage of Ultrathin Polythiophene Films within Porous
Nanostructures. ACS Nano 2014, 8, 5413−5422.
(468) Shown, I.; Ganguly, A.; Chen, L.-C.; Chen, K.-H. Conducting
Polymer-Based Flexible Supercapacitor. Energy Sci. Eng. 2015, 3, 2−26.
(469) Qin, L.; Zhang, Y.; Wu, X.; Nian, L.; Xie, Z.; Liu, L.; Ma, Y. In
Situ Electrochemical Synthesis and Deposition of Discotic Hexa-peri-
hexabenzocoronene Molecules on Electrodes: Self-Assembled Struc-
ture, Redox Properties, and Application for Supercapacitor. Small
2015, 11, 3028−3034.
(470) Yadav, S. K.; Kumar, R.; Sundramoorthy, A. K.; Singh, R. K.;
Koo, C. M. Simultaneous reduction and covalent grafting of
polythiophene on graphene oxide sheets for excellent capacitance
retention. RSC Adv. 2016, 6, 52945−52949.
(471) Kanal, I. Y.; Owens, S. G.; Bechtel, J. S.; Hutchison, G. R.
Efficient Computational Screening of Organic Polymer Photovoltaics.
J. Phys. Chem. Lett. 2013, 4, 1613−1623.
(472) Sokolov, A. N.; Atahan-Evrenk, S.; Mondal, R.; Akkerman, H.
B.; Sánchez-Carrera, R. S.; Granados-Focil, S.; Schrier, J.; Mannsfeld, S.
C. B.; Zoombelt, A. P.; Bao, Z.; Aspuru-Guzik, A. From computational
discovery to experimental characterization of a high hole mobility
organic crystal. Nat. Commun. 2011, 2, 437.
(473) Lan, Y.-K.; Yang, C. H.; Yang, H.-C. Theoretical investigations
of electronic structure and charge transport properties in poly-
thiophene-based organic field-effect transistors. Polym. Int. 2010, 59,
16−21.
(474) Huong, V. T. T.; Nguyen, H. T.; Tai, T. B.; Nguyen, M. T. Π-
Conjugated Molecules Containing Naphtho[2,3-b]thiophene and
Their Derivatives: Theoretical Design for Organic Semiconductors. J.
Phys. Chem. C 2013, 117, 10175−10184.
(475) Risko, C.; Brédas, J.-L. In Multiscale Modelling of Organic and
Hybrid Photovoltaics; Beljonne, D., Cornil, J., Eds.; Springer Berlin
Heidelberg: Berlin, Heidelberg, 2014; pp 1−38.
(476) Schreckenbach, G. Differential Solvation. Chem. - Eur. J. 2017,
23, 3797−3803.
DOI: 10.1021/acs.chemmater.7b03035
Chem. Mater. 2017, 29, 10248−10283