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Energy Level Modulation of HOMO, LUMO, and BandGap in Conjugated Polymers for Organic Photovoltaic
Applications
Bong-Gi Kim, Xiao Ma, Chelsea Chen, Yutaka Le, Elizabeth W. Coir, Hossein Hashemi,
Yoshio Aso, Peter F. Green, John Kieffer, and Jinsang Kim*

To devise a reliable strategy for achieving specific HOMO and LUMO energy
level modulation via alternating donor-acceptor monomer units, we investigate a series of conjugated polymers (CPs) in which the electron withdrawing
power of the acceptor group is varied, while maintaining the same donor
group and the same conjugated chain conformation. Through experiment
and DFT calculations, good correlation is identified between the withdrawing
strength of the acceptor group, the HOMO and LUMO levels, and the
degree of orbital localization, which allows reliable design principles for CPs.
Increasing the acceptor strength results in an enhanced charge transfer upon
combination with a donor monomer and a more pronounced decrease of
the LUMO level. Moreover, while HOMO states remain delocalized along
the polymer chain, LUMO states are strongly localized at specific bonds
within the acceptor group. The degree of LUMO localization increases with
increasing polymer length, which results in a further drop of the LUMO level
and converges to its final value when the number of repeat units reaches
the characteristic conjugation length. Based on these insights we designed
PBT8PT, which exhibits 6.78% power conversion efficiency after device optimization via the additive assisted annealing, demonstrating the effectiveness
of our predictive design approach.

Dr. B.-G. Kim, Prof. P. F. Green, Prof. J. Kim

Macromolecular Science and Engineering
University of Michigan
Ann Arbor, Michigan 48109, USA
E-mail: [email protected]
X. Ma, Dr. C. Chen, E. W. Coir, H. Hashemi,
Prof. P. F. Green, Prof. J. Kieffer, Prof. J. Kim
Department of Materials Science and Engineering
University of Michigan
Ann Arbor, Michigan 48109, USA
Prof. Y. Le, Prof. Y. Aso
The Institute of Scientific and Industrial Research
Osaka University
8-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan
Prof. Y. Le
JST-PREST, Kitakyushu Science and Research Park
2-5 Hibikino, Wakamatsu-ku, Kitakyushu city 808-0135, Japan
Prof. P. F. Green, Prof. J. Kim
Department of Chemical Engineering
University of Michigan
Ann Arbor, Michigan 48109, USA

DOI: 10.1002/adfm.201201385

Adv. Funct. Mater. 2012,

DOI: 10.1002/adfm.201201385

1. Introduction

Organic photovoltaic cells incorporating

conjugated polymers (CPs) have drawn
great attention as a cost-effective alternative to silicon-based solar cells. The
power conversion efficiency (PCE) of these
devices has enhanced rapidly during the
last couple of years and currently exceeds
6%.[16] This dramatic improvement of
OPV performance could be ascribed to
the development of new materials, mostly
CPs, and to the growing understanding of
OPV device operation.[111] One of the fundamental requirements for photovoltaic
energy conversion is the collection of as
much sunlight as possible. In this regard,
CPs absorption range should match the
high photon flux region of the solar spectrum, thus the ability to tailor the optical
band-gap of CPs for OPV devices is crucially important for efficient solar energy
harvesting. Nevertheless, effective device
operation requires the CPs energy levels
to move in opposition to a reduced bandgap: CPs should have a low highest occupied molecular orbital (HOMO) to help increase the open
circuit voltage (Voc)[12] and a high lowest unoccupied molecular
orbital (LUMO), compared to the fullerenes LUMO, for efficient charge dissociation in the CP/PCBM bulk heterojunction
device.
The most promising strategy for tailoring the CP band-gap
involves introducing donor (D) and acceptor (A) monomers
together in the polymer framework.[1314] The underlying concept is that the interaction between alternating electron-rich
donors and electron-deficient acceptors results in a compressed
band-gap via molecular orbital hybridization and via intramolecular charge transfer.[15] A drawback of this method, however,
is that too strong an acceptor in the CPs framework could
deteriorate its hole transporting property[16] or could generate
an extremely low LUMO in the CP[17] resulting in poor charge
dissociation. It is therefore clear that achieving specific HOMO
and LUMO energy levels with precision, as well as controlling
the band-gap, is essential for effective material development.
The hybridization of molecular orbitals upon combining
various monomeric groups results in energy levels that are

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not easily predictable. This is because the HOMO/LUMO

energy levels strongly depend on the degree of electron delocalization within the CPs effective conjugation length (ECL),
and the latter is resolutely affected by the backbones conformation.[1820] Hence, the magnitude of the energy gap in D-A
type CPs cannot be predicted simply based on the HOMO and
LUMO levels of the isolated monomers to be combined in the
CP, but the monomers intrinsic attributes such as shape, side
chains, and functional groups affecting the backbone conformation must be taken into account. In this study, four different
CPs were designed and synthesized in order to identify a way
to modulate and precisely predict the HOMO and LUMO of
CPs. The band-gap narrowing was systematically explored by
monitoring the energy level trends of applied monomers and
resulted CPs. A detailed interpretation of the observed trends
was accomplished through complementary first-principles
calculations. In addition, optical and electrical properties of
obtained CPs were directly correlated with OPV performance,
and an example CP (designated PBT8PT) obtained from the
energy level modulation was suggested and investigated under

different device fabrication conditions to provide a way to optimize the OPV device.

2. Results and Discussion

A comparison of the HOMO/LUMO levels of our series of CPs
with those of their constituent monomers is only meaningful
if all CPs have a similar chain conformation. As shown in
Scheme 1, we designed and synthesized analogous D-A structured CPs which all have the same donor, 4,8-bis(2-ethylhexyloxy)benzo[1,2-b;3,4-b]dithiophene. The CPs main frames were
constructed solely via thiophene derivatives to ensure a rigidplanar conformation.[21,22] Quantum mechanical calculations
(Figure 1) revealed that all of our polymers have exactly the
same zig-zag shaped back-bone geometry. Although PBTCT and
PBTCTO exhibit twist angles between the D-A repeat units of
7.5 and 7.9, respectively, which are slightly larger than for the
other polymers (13 ), they are further planarized in the film
state (PBTCT showed a 40 nm red-shift in its absorption max

Scheme 1. Detailed synthetic scheme of designed CPs. R indicates 2-ethylhexyl group and i) Pd2(dba)3, P(o-tolyl)3, toluene, 110 C, 48 h.

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Figure 1. Chain conformations of designed CPs were expected from their tetramers conformation calculation under minimized energy state, and
their dimers electron distributions both in HOMO/LUMO state are illustrated. R is 2-ethylhexyl group and it was abbreviated as methyl group for the
calculation work.

in solid state compared to its corresponding solution). Thus, all

CPs in this study have similar rigid-planar chain conformations
in solid state and can be expected to have similar ECLs.
The influence of the electron accepting group on the CPs
absorption characteristics was then studied with UV-vis spectroscopy. As depicted in Figure 2a, the absorption of the CPs
red-shifts as stronger acceptor monomers are combined with
the same donor monomer. The absorption edge shifts from
600 nm in PBTCT to 825 nm in PBTFDO, reflecting the narrowing of the optical band-gap in this sequence. As shown in
Figure 2b, the color of the CPs changes from orange (PBTCT)
to purple (PBTCTO), to blue (PBTPDO) and to greenish blue
(PBTFDO), due to the absorption edge shift. To understand the
underlying principles that govern this development, we begin

by comparing the energy levels of the CPs we synthesized, with

those of their constituent D and A groups. In this study, the
CPs energy levels were directly measured by means of cyclic
voltammetry (CV) as shown in Figure S1 (Supporting Information). Furthermore, we used DFT calculations to determine the
HOMO and LUMO levels of the isolated D and A monomers
and of CPs containing 2, 3, 4, and an infinite number of repeat
units, the latter being achieved by constructing a simulation
cell that is periodic in the direction of the polymer backbone
(Figure S2a, Supporting Information). DFT calculations reveal
that upon combining a donor and an acceptor group into a
single D-A repeat unit, the resulting HOMO level approximately
corresponds to that of the donor group and the LUMO level to
that of the acceptor group. Upon combining several of these

Figure 2. a) Absorption spectra of obtained CPs in chloroform solution, and b) energy level diagrams of applied monomers and obtained CPs. All drawn
energy levels are proportional to the scale of the absolute energy level (dashed blue boxes-donor monomers, dashed red boxes- acceptor monomers
and solid black boxes-polymers).

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provides a reliable strategy for designing CPs

that exhibit a higher Voc.
Further analysis of the relation between the
energy levels of our CPs and those of their
monomers reveals an interesting feature. To
this effect we define EH as the change in
energy from the midpoint between the HOMO
levels of the isolated donor and acceptor monomers to the HOMO level of the resulting
D-A polymer, and EL as the corresponding
construct for the LUMO levels. As shown in
Figure 3, EH and EL, each are essentially
constant for all CPs we synthesized, and
amount to 0.5 eV and 1.9 eV, respectively. To
Figure 3. a) Energy level diagram and correlation equation. The dashed line indicates the confirm the ubiquity of this observation, we
average energy level of donor (D) monomer and acceptor (A) monomer, and P indicates the
analyzed several CPs (PBTTTT-E, PBTTTTresulting polymer. b) Analyzed energy level correlation both from our series of CPs and three
C and PBTTTT-CF) that likely have a chain
reported CPs in the literature.[1]
conformation[1] similar to those of the CPs in
this study in the same way. These materials
repeat units the HOMO levels decrease only very little, for all
exhibit the same trends, with EH and EL values differing by
CPs investigated, while the LUMO levels decrease more promi0.1 eV from the aforementioned ones. Since molecular orbital
nently. Conversely, the more electronegative the constituents of
hybridization between the monomers during the polymerization
the acceptor group, the more pronounced the decrease in the
occurs only within the CPs ECL, CPs with analogous chain conLUMO level, ultimately leading to a narrowing of the energy
formation should have a similar ECL and are expected to retain
band gap in the sequence from PBTCT to PBTFDO, as shown
a comparable energy level mutation from those of their own
in Figure 2b. This trend is echoed by the localization behavior of
monomeric repeating units. In order to investigate the effect of
electronic orbitals. While for all polymers the HOMO remains
the CPs conformation on EH or EL, another series of CPs[2528]
delocalized along the polymer backbone, the LUMO become
that shares chemical structure similarities but whose conformaincreasingly localized with increasing chain length and the withtions differ from those of the CPs studied above were analyzed,
drawing strength of the acceptor. For example, in PBTCT, sigas shown in Figure S3 (Supporting Information). The applied
nificant LUMO density can be found within the thiophene units
energy levels of each monomer unit are summarized in Figure
of donor and acceptor monomers, while the LUMO is strongly
S2b (Supporting Information). These CPs exhibit different values
concentrated within the connecting bonds between donor and
of EH and EL compared to the series of CPs described in this
acceptor and the sulfur atom of the acceptor in PBTFDO. The
contribution, but still show the same constancy in HOMO and
electron localization induces intramolecular charge separaLUMO level shifts, i.e., EH = 0.9 eV and EL = 1.5 eV. Although
tion, which likely endows an elevated electron affinity to CPs
the same values of EH and EL cannot be universally applicable
via the electron deprived moieties, comparable to the trend
to all D-A type CPs, within a given family of compounds this
of CPs LUMO level decrease when a stronger electron withdesign concept can be adopted to predict CP energy levels from
drawing monomer was incorporated. A similar trend has been
their constituent monomers with reasonable accuracy, as long
observed for a D-A type copolymers: as the degree of polymerias they maintain an analogous chain conformation. To compare
zation increases, the LUMO level decreases more rapidly than
OPV performance depending on the modulated energies of our
the HOMO level due to molecular orbital hybridization of each
CPs, we fabricated OPV devices. The results are summarized in
monomer, finally producing a narrowed band gap.[23] Based on
Table 1. All devices were made after blending the polymer solution
first-principles calculations, it was shown that there is a strong
(10 mg into 2 mL of o-dichlorobenzene) with PCBM[70] (10 mg)
effect of the degree of LUMO localization on the energy gap.[23]
because the CPs had poor solubility (likely due to their rigidFor our system, the fact that the HOMO levels of the CPs are
planar conformation in spite of their low molecular weights (Mn;
essentially controlled by that of the constituent donor group,[24]
10 50013 300 g/mol)). All devices made with our CPs worked
Table 1. Summary of the properties of the OPV devices obtained with the synthesized CPs using different process conditions.

Sample

PBTCT

PBTCTO

PBTPDO

PBTFDO

Applied method

additive

additive

additive

additive

heat

none

additive

additive heat

Layer thickness

80 nm

80 nm

80 nm

80 nm

120 nm

120 nm

120 nm

120 nm

Jsc (mA/cm2)

3.39

8.76

10.68

1.20

10.03

10.27

12.37

Voc (V)

0.62

0.72

0.73

0.79

0.85

0.91

0.88

Fill Factor

0.53

0.62

0.62

0.45

0.49

0.48

0.62

PCE (%)

1.13

3.90

4.84

0.27

4.22

4.48

6.78

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PBT8PT

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N/A

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the HOMO level (0.04 eV), our results demonstrate that EH and EL still converge to
the same values if the CP conformation is
similar. When OPV devices were fabricated
with newly devised PBT8PT under various
process conditions, as summarized in Table 1,
we obtained over 4% PCE and 6.78% PCE
after optimization with an additive (1.3 vol%
1,8-octanedithiol). The improved PCE can be
attributed to an increased molecular weight
(Mn = 23 000 g/mol) and enhanced solubility.
For example, dissolving PBT8PT (10 mg) in
o-dichlorobenzene (1.5 mL) yields the best
performance with a 120-nm-thick active layer,
which is 40 nm thicker than the devices fabricated from PBTPDO.
In order to verify how the OPV performance depends on the fabrication process, the
obtained active layers were characterized with
energy filtered transmission electron microFigure 4. a) Chemical structure of PBT8PT (R; 2-ethylhexyl) and energy diagram (dashed scopy (EF-TEM). As shown in Figure 5, both
blue box: donor monomer; dashed red box: acceptor monomer; solid black box: polymer zero-loss and energy-filtered (27 3 eV) confrom CV; and dashed black box: polymer from calculation). b) Absorption spectra in solution ditions were conducted to interpret the film
(CHCl3) and dried film. c) Absorption spectra of obtained devices and EQE, and d) OPV device morphology of PBT8PT/PCBM[70], because
performance.
less conducting PBT8PT is bright under the
zero-loss state and becomes dark under the
successfully, except for PBTFDO because its LUMO level (3.9 eV)
energy-filtered state. Based on the diffraction patterns and the
is too low for PCBM[70] to dissociate excitons. This emphasizes
obtained EF-TEM images, the thermally annealed PBT8PT/
how important selecting a proper acceptor monomer is when
PCBM[70] device exhibits better crystallinity than the nonandesigning D-A type CPs. As the CPs absorption shifts to a longer
nealed device, which facilitates carrier transport. However, the
wavelength region from PBTCT to PBTPDO, photocurrent genthermally annealed device exhibits poor performance as Voc and
eration improves due to its absorption adjustment in the high
Jsc are reduced. As described in our previous work, a fast drying
photo-flux region (600800 nm). The Voc increases as the CPs
condition does not allow enough time for the phase separation
HOMO level decreases, as explained by the modified Shockley
between PBT8PT and PCBM[70], resulting in an island or a culequation.[12] Among the CPs tested in this study, PBTPDO exhibits
de-sac domain including a narrow intermolecular distance. This
the best OPV performance with about 5% PCE, because it has a
causes a strong recombination, and ultimately decreases V oc and
good absorption region to harvest solar radiation and because its
impairs the charge collection efficiency.[31] In case of the addilower HOMO level results in a higher Voc. Although their energy
tive assisted annealed device, it exhibits a much stronger crystallevels (including the optical band-gap) were systematically conline phase of PBT8PT, compared to the nonannealed condition,
trolled, the OPV performance from our series of CPs still lags
though both samples were evenly treated except for the additive.
behind reported CPs having similar absorption region.[1,4] We
We believe that the additive removes PCBM[70] from polymerbelieved that this is due to a low molecular weight which is not
rich domains through its orthogonal solubility, which facilihelpful for long range percolation pathways for charge carrier
tates PBT8PT aggregation because small size PCBM[70] acts as
transfer[29,30] and due to a poor solubility which limits an active
a plasticizer in the polymer matrix. Thus, the additive assisted
layer thickness (80 nm) for better light harvesting.
annealing method is useful to produce a percolation pathway
To demonstrate the reliability of the established energy level
including a highly crystalline polymer domain.[13] As shown
prediction and to further improve OPV device performance, a
in Figure 4c, absorption spectra of the fabricated OPV devices
new CP (PBT8PT, Figure 4a), which is expected to have a rigidunder different process conditions are similar, but the additive
planar conformation similar to that of the four CPs studied in
assisted annealed device exhibited higher external quantum effithis contribution, was designed. An extra octyl side chain was
ciency (EQE) through overall wavelength and an enhanced fill
introduced to increase the molecular weight through improved
factor (FF) (Table 1 and Figure 4d). This implies that the additive
solubility. As shown in Figure 4b, PBT8PT exhibits nearly the
assisted annealed device has a superior charge dissociation and
same absorption properties both in solution (CHCl3) and in the
carrier collection pathway, because the absorption and the dissodried film, indicating a rigid-planar polymer conformation. We
ciation energy offset are likely similar, regardless of the device
predicted PBT8PTs energy levels assuming 0.5 eV for EH and
fabrication process for the same material composition. Interest1.9 eV for EL. As shown in Figure 4a, these predicted energy
ingly, when the additive assisted annealed device was thermally
levels (based on the monomers energy levels confirmed with
treated further it did not exhibit photovoltaic behavior. As shown
CV) agree well with the measured values using CV. Although
in Figure 5g, the pristine crystalline phase generated by the addithe LUMO level showed slightly larger deviation (0.09 eV) than
tive assisted annealing manifested in Figure 5e was deteriorated

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by changing the electron withdrawing power of the acceptor

monomers, while using the same donor monomer. Stronger
electron withdrawing groups in the acceptor monomer result in
lower HOMO and LUMO energy levels in the resulting CP. The
LUMO level drops more rapidly than the HOMO level, which
ultimately produces a narrowed band-gap. Furthermore, the
shift in the HOMO level of the CP compared to the midpoint
value between the HOMO levels of the constituent monomers,
EH, converges towards a constant value regardless of the difference in the monomers HOMO values. The same holds true
for the LUMO as well. This trend is universally applicable to
similarly structured CPs, with different constant values for different CP conformations. Conversely, this method may be used
to predict CP energy levels, given a set of monomers energy
levels. We demonstrate these predictive capabilities using the
example of PBT8PT. The energy levels of the newly obtained
PBT8PT show good agreement with the anticipated energy
levels from the suggested energy level correlation between CP
and its own monomers. Using OPV devices fabricated with the
obtained CPs, we verify that Voc increases as CPs HOMO level
decreases and J sc increases as CPs absorption approaches a
high photon flux region. After OPV device optimization with
the additive, the PBT8PT/PCBM[70] blend achieved 6.78% PCE
mostly due to the combined effects including enlarged molecular weight, enhanced solubility and an improved charge collection pathway. Finally, the morphology of the active layers
generated by different fabrication conditions was characterized
with EF-TEM. Both the thermal and additive treatments are
useful to enhance the crystallinity of PBT8PT, but the thermally
annealed device cannot utilize the advantage of the enhanced
crystallinity because of the accompanied strong recombination.
The additive assisted annealed device exhibits highly crystalline
PBT8PT, which results in best OPV performance among the
applied device fabrication conditions.

4. Experimental Section

Figure 5. EF-TEM images of active layers of the PBT8PT/PCBM[70] film

formed under different fabrication conditions. a,b) thermally annealed;
c,d) non-annealed; e,f) additive assisted annealed; and g,h) thermally
annealed after additive assisted annealing. Insets indicate diffraction
patterns.

by an additional thermal treatment. It is probable that the

remnant additive causes PCBM[70] to rediffuse into PBT8PT
domains during the additional thermal annealing, because the
additive has a decent solubility towards PBT8PT at the applied
thermal annealing condition (130 C for 15 min).

3. Conclusions
A series of CPs with alternating D-A monomer units to predictably modulate the HOMO and the LUMO of CPs were successfully synthesized. The CPs energy levels were modified
6

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Synthesis: All starting materials were purchased from commercial

suppliers (Aldrich and Fisher Sci.). Detailed synthetic procedures are
summarized in the Supporting Information and synthesized compounds
were fully characterized with 1H-NMR and GC-mass spectroscopy.
Molecular weights of the final polymers were measured with gel permeation
chromatography (GPC) using polystyrene calibration standards.
Molecular Geometry Calculations: Electronic structure calculations and
spatial relaxation of the molecules were performed using Gaussian03.[32]
Pre-optimizations of the molecules were carried out using AM1
semiempirical quantum chemistry model.[33] The resulting molecular
configurations were then further optimized in the density functional
theory (DFT) framework. We used B3LYP as the exchange-correlation
functional, that is, a Hartree-Fock-DFT hybrid where the exchange energy
is explicitly calculated using the Hartree-Fock approach.[34] The molecular
geometries were optimized in the Cartesian coordinate system without
any symmetry (maximum degrees of freedom) using 6-31G contracted
Gaussian basis set with polarization functions.[35,36]
Cyclic Voltammetry Measurements: Ag/AgNO3 served as the pseudo
reference electrode, ferrocene was used for calibration, and the
supporting electrolyte was tetrabutylammonium hexafluorophosphate in
acetonitrile. Oxidation and reduction potentials of each CP were directly
measured after casting them on top of ITO coated glass.
OPV Device Fabrication: PCBM[70] was purchased from SES research
and used without further purification. After dissolving obtained CPs
(10 mg) and PCBM[70] (10 mg) into o-dichlorobenzene (2.0 mL) and

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Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.

Acknowledgements
We thank Dr. Chang-Gua Zhen for the energy level calculation of applied
monomers. This research was supported as part of the Center for Solar
and Thermal Energy Conversion, an Energy Frontier Research Center
funded by the U.S. Department of Energy, Office of Science, Office of
Basic Energy Sciences under Award No. DE-SC0000957.
Received: May 22, 2012
Published online:

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1,8-octanedithiol (26 L), the mixture was filtered with a syringe filter
(0.45 m pore diameter) and used to form the active layer by means of
spin casting. In case of PBT8PT, 1.5 mL of o-dichlorobenzene and 20 L
of 1,8-octanedithiol were used for the blend solution. ITO-coated glass
was cleaned with acetone and IPA followed by UV ozone treatment for
10 min. PEDOT:PSS (Baytron PH 500) was spin cast on the substrate
and baked at 140 C for 15 min. Different polymer/PCBM[70] blend
solutions were spin cast at 700 rpm for 30 s and used for metal electrode
evaporation without further treatment. Final devices were fabricated by
depositing a 1-nm-thick LiF and a 70 nm Al layer (9.6 mm2) sequentially
under 5 107 Torr (1 Torr = 133.32 Pa). All devices were characterized
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(AM 1.5G Oriel solar simulator).
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floated from deionized water and picked up onto copper grids (Ted
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using an energy slit width of 8 eV and a step width of 0.8 eV, from 5 to
40 eV, covering the zero-loss regime and plasmon-loss regime on the
energy loss spectra.

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