Efficient solution-processed bulk heterojunction solar cells by antiparallel supramolecular arrangement of dipolar donor-acceptor dyes

Article abstract of DOI:10.1002/anie.201105133

A series of dipolar donor-acceptor (D-A) chromophores with aminothiophene donor and different heterocyclic acceptor units is reported. By modulation of the acceptor strength, absorption bands over the whole visible spectrum are accessible as well as adjustment of the frontier molecular orbital levels. The performance of the chromophores in blends with fullerene acceptors in solution-processed bulk heterojunction solar cells was studied and related to the molecular properties of the dyes. In particular, the effect of the large ground-state dipole moments of these dyes was investigated by single crystal X-ray analysis, which revealed antiparallel dimers, resulting in an annihilation of the dipole moments. This specific feature of supramolecular organization explains the excellent performance of merocyanine dyes in organic solar cells. With blends of HB366:PC₇₁BM, the most efficient solar cell with a V_OC of 1.0 V, a J_SC of 10.2 mAcm^-2, and a power-conversion efficiency of 4.5% was achieved under standard AM1.5, 100 mWcm^-2 conditions. Under reduced lighting conditions, even higher efficiencies up to 5.1% was obtained. Donor-acceptor dyes with an aminothiophene donor show ideal absorption, redox, and packing features in organic photovoltaics (see picture). With blends of HB366:PC₇₁BM, highly efficient solar cells were achieved with a V_OC of 1.0 V, a J _SC of 10.2 mAcm^-2, and a power conversion efficiency of 4.5%. Copyright

Full text of DOI:10.1002/anie.201105133

Communications
DOI: 10.1002/anie.201105133
Supramolecular Photovoltaics
Efficient Solution-Processed Bulk Heterojunction Solar Cells
by Antiparallel Supramolecular Arrangement of Dipolar
Donor–Acceptor Dyes**
Hannah Bꢀrckstꢀmmer, Elena V. Tulyakova, Manuela Deppisch, Martin R. Lenze,
Nils M. Kronenberg, Marcel Gsꢁnger, Matthias Stolte, Klaus Meerholz,* and Frank Wꢀrthner*
Research on small-molecule-based organic semiconductors
has undoubtedly been strongly influenced by xerographic
photoconductors like triarylamines, the first important
organic electronic materials in market products.[1] Their
development was strongly influenced by the Bꢀssler model,
which provided a rationale for the design of amorphous
organic photo- and semiconductors.[2] According to this
model, only compounds that lack dipole moments are
considered promising for charge-carrier transport because
the increased energetic disorder associated with dipole
moments is thought to impede charge hopping. Recently,
we questioned this paradigm in the field of organic photo-
voltaics (OPV) and successfully implemented highly dipolar
merocyanine dyes as active components for light harvesting as
well as exciton and hole transport in solution-cast bulk
heterojunction (BHJ) solar cells.[3] The rationale behind our
concept[4] was that highly dipolar donor–acceptor (D–A)
substituted p systems (also called push-pull dyes) self-assem-
ble into centrosymmetric dimers,[5] thus effectively eliminat-
ing molecular dipole moments on the supramolecular and
material levels.[6] Two drawbacks of our BHJ materials,
however, limited the acceptance of our concept so far. Firstly,
the best solar cells were obtained for merocyanine dyes whose
molecular scaffolds were equipped with rather bulky sub-
stituents that interfere with close face-to-face antiparallel
dimerization.[3] Secondly, the power-conversion efficiencies
(h) under standard AM1.5, 100 mWcmꢀ2 simulated solar
illumination conditions for solution-cast BHJ cells with
fullerenes—although significantly advanced by more sophis-
ticated vacuum processing[7]—could not be improved beyond
2.6%, which is significantly lower than the best solution-
processed small-molecule-based BHJ devices fabricated with
A–D–A and D–A–D chromophores, for example, acceptor-
substituted oligothiophenes (up to 3.7%)[8] and triarylamines
(up to 4.3%),[9] diketopyrrolopyrroles (up to 4.4%),[10] and
squaraines (up to 5.2%).[11] Herein, we introduce dipolar D–
A dyes with flat structures that undoubtedly form centrosym-
metric dimers[5] with perfectly cancelled dipole moments in
the solid state. Solution-processed BHJ solar cells derived
thereof exhibit power-conversion efficiencies up to 4.5–5.1%
(dependent on light intensity), clearly placing D–A dyes now
among the top-performing small molecules in the field of
organic photovoltaics.
Scheme 1 outlines the synthetic route that follows our
earlier work on merocyanine dyes for photorefractive mate-
rials[12] and the simple access to 5-dialkylamino-thiophene-2-
carbaldehydes by Hartmann.[13] Detailed synthetic proce-
dures and characterization data are described in the Support-
ing Information.
Scheme 1. Synthesis and molecular structures of the investigated D–A
dyes (yields are given in parentheses). The substituents are R=nBu
and R’=Et for HB366 and R=R’=nBu for all other dyes.
[*] H. Bꢀrckstꢀmmer, Dr. E. V. Tulyakova, M. Deppisch, M. Gsꢁnger,
Dr. M. Stolte, Prof. Dr. F. Wꢀrthner
Universitꢁt Wꢀrzburg, Institut fꢀr Organische Chemie and
Rçntgen Research Center for Complex Material Systems
Am Hubland, 97074 Wꢀrzburg (Germany)
E-mail: wuerthner@chemie.uni-wuerzburg.de
The optical properties of the synthesized dyes were
investigated by UV/Vis and electro-optical absorption spec-
troscopy.[14] Furthermore, cyclic voltammetry was performed
for each dye to obtain information about their highest
occupied molecular orbital (HOMO) and lowest unoccupied
molecular orbital (LUMO) levels.[15] Figure 1a displays
representative absorption spectra of the reported dye series
in dichloromethane, and Figure 1b depicts the position of the
frontier molecular orbital (FMO) energies of the chromo-
phores with regard to the electron acceptor PC61BM. The
M. R. Lenze, Dr. N. M. Kronenberg, Prof. Dr. K. Meerholz
Department of Chemistry, Universitꢁt zu Kçln
Luxemburger Strasse 116, 50939 Kçln (Germany)
E-mail: klaus.meerholz@uni-koeln.de
[**] We gratefully acknowledge funding of our project by the German
Ministry of Science and Education (BMBF, OPEG project) and the
German Science Foundation (DFG, priority programme SPP1355
“Elementary Processes of Organic Photovoltaics”).
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201105133.
11628
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2011, 50, 11628 –11632

cycles entails a significant red-shift of the absorption maxima
from 517 nm (MD352) to 654 nm (MD357) and 660 nm
(HB239), respectively. Thus, by varying the acceptor unit, the
absorption properties are tunable over the entire visible
spectrum. The absorption coefficients at lmax vary from
approximately 5 ꢁ 104 Lmolꢀ1 cmꢀ1 for HB239 to approxi-
mately 1.5 ꢁ 105 Lmolꢀ1 cmꢀ1 for MD333 (Figure 1a). How-
ever, this result does not necessarily reflect the absorption
strength of a chromophore since a dye with a sharp and
intense absorption profile can absorb the same amount of
photons as one with a broad, but less intense UV/Vis band. To
evaluate the absorption strength, we define the figure-of-
ꢀ1
merit m2
M
(absorption density), which represents the
ag
transition dipole moment m2ag divided by the molar mass M of
the compound and is, therefore, directly related to the
tinctorial strength of the respective dye. The absorption
densities of the reported dyes all fall in the range of (0.22 ꢁ
0.02) D2 molgꢀ1, except for HB239, which displays a signifi-
cantly reduced tinctorial strength. If we apply the same
procedure to determine the absorption density of P3HT
(poly-3-hexylthiophene),[16] we obtain a distinctly lower value
of only 0.14 D2 molgꢀ1. Regarding the electro-optical proper-
ties, we found that dyes MD333, HB238, and MD357 show
large ground-state dipole moments (mg) of 12–13 D and small
changes of the dipole moment upon optical excitation (Dm),
whereas MD352, EL86, HB366, and HB239 exhibit distinctly
lower mg and higher Dm values. As expected,[12] the dyes close
to the cyanine limit (Dm = 0 D)[17] show the largest transition
dipole moments (Table 1).
Figure 1b illustrates one of the major benefits of D–A
dyes with regard to organic solar cells: all dyes—even the low-
bandgap ones—show favorable low-lying HOMO levels
(ꢀ5.45 to ꢀ5.7 eV vs. vacuum). Low-lying HOMO levels
enable high open-circuit voltages and are, therefore, desir-
able.[18] Within the presented dye series, the HOMO energies
vary by only 0.25 eV. On the other hand, the respective
acceptor unit has a significantly stronger influence on the
LUMO level, which is shifted by 0.57 eV from MD352 to
HB239. Although the dyes with stronger acceptor units
exhibit low-lying LUMO levels, the energy offsets from the
dye LUMO levels to the LUMO of PC61BM are still close to
the ideal value of 0.3–0.4 eV.[18b] Hence, the energetics of
these dyes match ideally with PC61BM to minimize energy
loss upon electron transfer from the donor dye to the
fullerene acceptor. By modulating the acceptor unit, we are
able to tune not only the absorption properties, but also the
FMO levels of the respective chromophores.
Figure 1. a) UV/Vis spectra of MD352 (orange), MD333 (red), EL86
(violet), MD357 (blue), and HB239 (green) in CH2Cl2 (cꢂ10ꢀ5 molLꢀ1
at 298 K and solar photon flux at AM 1.5 conditions (black). The
spectra of HB366 and HB238 are similar to those of EL 86 and
MD357, respectively; b) FMO levels and band gap (solid area) of dyes
and their relative position to the LUMO of PC61BM.
)
Table 1: Electro-optical and redox properties of investigated D–A dyes.
ꢀ1
Dye
m2
m2
M
ag
mg
[D][b]
Dm
[D][b]
EHOMO
ELUMO
ag
[D2][a]
[D2 molgꢀ1
]
[eV][c]
[eV][d]
MD352
MD333
EL86
HB366
HB238
MD357
HB239
82
95
97
94
102
104
74
0.22
0.20
0.23
0.24
0.24
0.21
0.15
5.7
12.6
8.6
4.2
1.7
4.1
4.0
2.5
2.3
4.6
ꢀ5.56*
ꢀ5.65
ꢀ5.70
ꢀ5.69
ꢀ5.52
ꢀ5.45*
ꢀ5.61*
ꢀ3.17
ꢀ3.36
ꢀ3.56
ꢀ3.54
ꢀ3.62
ꢀ3.55
ꢀ3.74
8.5
13.1
12.1
6.1
[a] UV/Vis measurements for dilute solution (cꢂ10ꢀ5 m) in CH2Cl2 at
298 K. Absorption maxima (lmax) and coefficients (e) are given in the
Supporting Information. [b] In 1,4-dioxane (cꢂ10ꢀ6 m) at 298 K. [c] Cal-
culated from CV measurements (E1/2ox/*Ep) in CH2Cl2 calibrated against
the ferrocene/ferrocenium couple (Fc/Fc+, ꢀ5.15 eV) as internal stan-
dard. [d] ELUMO =EHOMO +(hc/lmax). *=Irreversible oxidation.
For two characteristic dyes of our series, EL86 and
HB239, we have grown single crystals that could be resolved
by single-crystal X-ray diffraction analysis.[19] As shown in
Figure 2 and 3, the chromophores are located in planes
parallel to each other arranged in discrete stacks. Each
molecule features one close and one distant neighbor, hence
forming close and distant centrosymmetric dimeric units. The
ꢀ
relevant electro-optical and electrochemical properties are
summarized in Table 1.
Increasing the length of the polymethine chain and
acceptor strength from indandione (MD352) to thiazole
(HB238, MD357) and bis-indandione (HB239) based hetero-
C C bond lengths of the methine bridges to the two
heterocycles change only marginally, thus indicating fully
conjugated p systems close to the cyanine limit.[12,17]
In the single-crystal structure of EL86, the molecule itself
is only slightly distorted from planarity, with a torsion angle
Angew. Chem. Int. Ed. 2011, 50, 11628 –11632
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org 11629

Communications
combination with the commonly used fullerene acceptor
PC61BM in solution-processed BHJ solar cells using the
simple device structure ITO/PEDOT:PSS (40 nm)/
dye:PC61BM/Al (120 nm) at an AM1.5 illumination intensity
of 100 mWcmꢀ2. The dye:PC61BM layers were prepared by
spin-coating and only optimized with respect to their layer
thickness and the dye:PC61BM ratio. VOC and FF were mostly
unaffected by different dye:PC61BM ratios whilst JSC and
consequently h displayed maxima at a certain PC61BM
content. Optimized film thicknesses were found to be 50–
60 nm. A comparison of the solar cell characteristics is listed
in Table 2, details on the device fabrication are given in the
Supporting Information.
Figure 2. a) Molecular structure of EL86 in the crystal. b) p stack of
EL86 with antiparallel packing motif. c) Space-filling view of the close
dimer of EL86 (alkyl chains and protons in (b) and (c) are omitted).
d) Schematic representation of EL86 stack showing the antiparallel
orientation of the dipole moments (arrows).
Table 2: Photovoltaic characteristics of chlorobenzene solution-cast
dye:PC61BM BHJ solar cells for the optimized ratio.
Dye
lmax
[nm][b]
PCBM
[wt%]
VOC
[V]
JSC
FF
h
[%][c]
[mAcmꢀ2
]
MD352
MD333
EL86
532
556
595
595
682
689
700
70
70
60
55
75
70
75
0.63
0.73
0.96
0.94
0.72
0.47
0.68
2.9
4.0
5.8
8.3
4.5
4.0
4.0
0.27
0.32
0.41
0.38
0.35
0.27
0.36
0.5
0.9
2.3
3.0
1.1
0.5
1.0
HB366[a]
HB238
MD357
HB239
Figure 3. a) Molecular structure of HB239 in the crystal. b) p stack of
HB239 with antiparallel packing motif. c) Space-filling view of the close
dimer of HB239 (alkyl chains and protons in (b) and (c) are omitted).
d) Schematic representation of a HB239 stack showing the antiparallel
orientation of the dipole moments (arrows).
[a] Cast from chloroform solution owing to solubility problems in
chlorobenzene. [b] UV/Vis measurements of a thin film of the blend.
[c] AM1.5 conditions, 100 mWcmꢀ2
.
between the donor and acceptor unit of 138. Within the stacks,
almost equal distances of the close (3.48 ꢂ) and the distant
(3.60 ꢂ) antiparallel neighbors result in a one-dimensional
p stack of closely packed chromophores (Figure 2b). These
show only small longitudinal displacements with respect to
each other, thus leading to a pronounced contact area
between the p surfaces of neighboring molecules. A tightly
bound antiparallel dimer unit is also observed in the solid-
state packing of HB239 (3.47 ꢂ distance); however, the
distance to the other neighbor is significantly increased
(4.89 ꢂ) as shown in Figure 3b. Adjoining molecules in the
close dimer also show a more pronounced longitudinal
displacement with respect to each other, and transverse
displacements are observed regarding the more distant
neighbor, further reducing the p–p contact between adjacent
molecules. Both effects are probably caused by the strongly
distorted molecular structure of HB239, as the torsion angle
between the two indandione units of the acceptor is 328. Thus,
the twisted acceptor moiety acts like a spacer between the
centrosymmetric distant dimers and prevents the formation of
a closely packed p stack as it is provided in the case of EL86.
The power conversion efficiency (h) of solar cells is
defined as:
The open-circuit voltages determined for this series of
dyes are centered at around 0.7 V. MD357 shows the lowest
VOC of 0.47 V, which is consistent with this dye having the
highest HOMO level within the series (Figure 1b). Likewise,
the dyes with the lowest HOMO levels, EL86 and HB366,
give the highest VOC of 0.94 and 0.96 V, respectively. The
short-circuit current density is directly related to the light-
harvesting efficiency as well as the charge-carrier properties
of the active layer of a photovoltaic cell. Most devices
investigated here have moderate JSC values of approximately
4 mAcmꢀ2. Cells built with MD352 exhibited a lower
performance with a JSC of 2.9 mAcmꢀ2, whereas significantly
higher JSC values of 5.8 and 8.3 mAcmꢀ2 were determined for
devices prepared with EL86 and HB366, respectively. Nota-
bly, for these dyes, higher dye loadings resulted in the best
solar cell performances. Fill factors of most devices were
around 0.3, with the highest FF observed again for cells based
on EL86 and HB366. Accordingly, applying Equation (1),
typical power-conversion efficiencies range between 0.5–
1.1% with two clear outliers, the structurally very similar
EL86 and HB366, showing 2.3% and 3.0%, respectively.
Based on our initial results, several steps in the solar-cell
fabrication were optimized with the best performing dye
HB366. Whereas little effect was observed by post-treatments
such as thermal annealing, clear improvements could be
achieved by replacing PC61BM with PC71BM (enhanced
absorption), replacement of the hole-collecting PEDOT:PSS
layer by MoO3, and applying a Ba/Ag metal electrode. The
result of this optimization afforded a highly improved solar
FFJSCVOC
ð1Þ
h ¼
Pin
where FF is the fill factor, JSC the short-circuit current density,
VOC the open-circuit voltage, and Pin the power density of the
incoming light. All described D–A dyes were evaluated in
11630 www.angewandte.org
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2011, 50, 11628 –11632

cell with a power-conversion efficiency of 4.5% under
standard AM1.5, 100 mWcmꢀ2 conditions. Under reduced
lighting conditions, an even higher efficiency of 5.1% was
obtained (for details, see the Supporting Information). For a
direct comparison, BHJ solar cells were also manufactured
for Nguyenꢃs diketopyrrolopyrrole (DPP, Figure 4), which is a
the dye HB238 (4 ꢁ 10ꢀ4 cm2 Vꢀ1 sꢀ1), which exhibits the
largest dipole moment within our series (Table 1). Interest-
ingly, these values are not much smaller than those of
amorphous nondipolar triarylamine-based photoconduc-
tors.[1,2] As our results indicate, charge-transport properties
are not necessarily impaired by large ground-state dipole
moments of monomeric molecules, if the molecules are
assembled in a suitable fashion in the bulk material.
In conclusion, this study provides a strong impetus to
reconsider established design concepts in organic semicon-
ductor research, particularly in the area of small-molecule-
based OPV, but also beyond (i.e. in other areas of organic
electronics or polymeric OPV as well). Our studies show that
highly dipolar D–A dyes are applicable as p-type hole-
conducting components in BHJ solar cells. These cells have
been optimized in a rather short time to reach power-
conversion efficiencies similar to those obtained with estab-
lished nonpolar small-molecule materials. Thus, a serious
restriction in the design of small molecules for OPV has been
overcome, opening investigation up to a much larger variety
of chemical structures. For us and other researchers working
on optoelectronic applications of push-pull chromophores, it
may appear as an odd anecdote that these dyes widely failed
in nonlinear optical applications despite their outstanding
suitability on the molecular level owing to dipolar aggregation
in the bulk, which has now shown to be the pathway to success
in OPV.
Figure 4. J–V response of the solar cells built with HB366 (solid line,
55 wt% PC71BM) and DPP (dashed line, 40 wt% PC71BM) measured
under simulated solar illumination (AM1.5, 100 mWcmꢀ2).
leading dye in the field of solution-processed small molecule
BHJ solar cells.[10] Figure 4 compares the J–V curves of the
optimized devices containing HB366/PC71BM and DPP/
PC71BM as reference. Although we use significantly lower
dye content (45 wt% compared to 60 wt%), a higher JSC and
VOC, 10.2 mAcmꢀ2 and 1.0 V, respectively, are observed for
HB366 compared to DPP (9.6 mAcmꢀ2 and 0.91 V). The fill
factors are quite similar (0.44 and 0.47, respectively), thus, the
resulting power-conversion efficiency under standard condi-
tions amounts to 4.5% for HB366 and 4.1% for DPP.[20]
Notably, devices that contain DPP need to be annealed at
1108C for 10 min to reach this high performance, whereas
cells built with HB366 afford 4.5% without post treatment.
With this result, dipolar D–A dyes are now positioned
among the most promising small molecules for organic
photovoltaics despite the obvious contradiction with the
Bꢀssler model. To avoid large energetic disorder caused by
their dipolarity, organization into favorable antiparallel
aggregate structures is, however, crucial. This concept has
been demonstrated in the solid state for dyes EL86 and
HB239 that exhibit slightly different packing features, likely
contributing to their varying performance in solar cells. While
EL86 assembles into p stacks with two close-by antiparallel
neighbor molecules, such favorable packing is impeded for
HB239 because of steric hindrance. Attempts to measure the
hole mobility of HB239 in organic field-effect transistors
(OFETs) failed for both, pristine films and blends with
PC61BM. In contrast, for EL86, hole mobilities of 1 ꢁ
10ꢀ5 cm2 Vꢀ1 sꢀ1 and 1 ꢁ 10ꢀ6 cm2 Vꢀ1 sꢀ1 were measured for
pure films and blends with PC61BM, respectively. Slightly
reduced values were obtained for the structurally related
HB366 (0.7 ꢁ 10ꢀ5 cm2 Vꢀ1 sꢀ1 and 0.9 ꢁ 10ꢀ6 cm2 Vꢀ1 sꢀ1). Even
higher hole mobilities were measured for spin-coated films of
Received: July 21, 2011
Revised: September 9, 2011
Published online: October 14, 2011
Keywords: aggregation · centrosymmetric dimers · dyes/
.
pigments · merocyanines · organic solar cells
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