Communications

DOI: 10.1002/anie.200903125
Organic Photovoltaics

Outstanding Short-Circuit Currents in BHJ Solar Cells Based on

NIR-Absorbing Acceptor-Substituted Squaraines**
Ulrich Mayerhffer, Kaja Deing, Katrin Gruß, Holger Braunschweig, Klaus Meerholz,* and
Frank Wrthner*
In view of increasing global energy demand and finite employed in initial BHJ cells of this type, recently traditional
resources of fossil fuels, photovoltaic devices are receiving a colorants such as merocyanines,[5a] squaraines,[5b] and dipyr-
great deal of attention. Solution-processable organic semi- romethene boron difluoride (BODIPY)[5c] dyes have been
conductors represent a promising class of new organic introduced, achieving PCE values of up to 1.7 %. As such
photovoltaic (OPV) materials with potential for low manu- chromophore-based materials can be easily optimized, par-
facturing costs and applications ranging from flexible and ticularly in regard to absorbance in the highly desired red and
mobile devices to large-area installations.[1] In the best devices near infrared (NIR) spectral region where the solar photon
constructed to date based on solution-processed organic flux culminates,[6] improvement of tandem devices[2a] and
materials, interpenetrating networks of soluble n-type semi- realization of transparent photovoltaic systems as demanded
conducting fullerenes such as [6,6]-phenyl-C61-butyric acid for the application on window glass are further opportunities
methyl ester (PCBM) as electron acceptor and p-type semi- that might arise from such small-molecule NIR-absorber
conducting polymers such as poly(3- materials.
hexylthiophene) (P3HT) as electron Squaraine dyes are a particularly promising class of
donor moiety form the active interfa- chromophores for NIR OPV cells. They exhibit sharp and
ces. Such bulk heterojunction (BHJ) intense absorption bands in the desired long-wavelength
OPV cells have reached power con- region and possess considerable photo- and thermal stability
version efficiencies (PCEs) of up to under ambient conditions.[7] Thus, squaraines are a widely
6 %.[2] Despite their still lower PCE of used class of functional dyes for a huge variety of applica-
around 4 %, solution-processable tions.[8] Squaraines have been used in single-layer OPVs and,
small-molecule-based BHJ solar cells more recently, in vacuum-deposited and dye-sensitized solar
are becoming increasingly attractive.[3] cells.[9] Lately, Silvestri et al. reported for the first time on the
Owing to their simple purification and use of squaraines in solution-processable BHJ solar cells with
accessibility, paired with their mono- PCEs of up to 1.2 %.[5b]
dispersity and ease of modification, small p-type organic Herein we report on a series of squaraine dyes 5 a–e
semiconductor molecules have overcome many drawbacks (Scheme 1) bearing an additional dicyanovinyl acceptor
associated with their polymer pendants.[4] While established moiety at the central acceptor unit; these species afford
p-type organic semiconductor molecules, for example, oligo- solution-processed BHJ solar cells with PCEs of up to 1.79 %.
thiophenes,[3a,b] triarylamines,[3c] and acenes,[3d] were More importantly, absorption in the highly desired NIR range
and short-circuit current densities up to JSC = 12.6 mA cm 2
[*] U. Mayerhffer, Prof. Dr. F. Wrthner are achieved with these squaraines. To our knowledge, this JSC
Universitt Wrzburg, Institut fr Organische Chemie value is the highest reported for a small-molecule-based BHJ
and solar cell,[3, 5] and compares favorably to JSC of the currently
Rntgen Research Center for Complex Material Systems
best performing polymer-based BHJ solar cells.[2]
Am Hubland, 97074 Wrzburg (Germany)
Fax: (+ 49) 931-318-4756
Squaraines 5 a–e and reference squaraines 7 a,b were
E-mail: wuerthner@[Link] synthesized according to the route outlined in Scheme 1.[10]
K. Deing, Prof. Dr. K. Meerholz For each of these squaraines, a series of BHJ solar cells was
Department of Chemistry, Universitt zu Kln manufactured by spincoating squaraine/PCBM solutions on
Luxemburger Strasse 116, 50939 Kln (Germany) ITO/PEDOT:PSS substrates and subsequent thermal vacuum
E-mail: [Link]@[Link] deposition of Ca/Al cathode (ITO = indium tin oxide,
K. Gruß, Prof. Dr. H. Braunschweig PEDOT = poly(3,4-ethylenedioxythiophene), PSS = poly-
Universitt Wrzburg, Institut fr Anorganische Chemie (styrene sulfonate)). The photovoltaic properties of these
and devices were determined under standard AM (air mass) 1.5
Rntgen Research Center for Complex Material Systems
solar radiation. The characteristic performance values of the
Am Hubland, 97074 Wrzburg (Germany)
BHJ solar cells for the investigated dyes are given in Table 1.
[**] Financial support by the DFG within priority program “Elementary
processes of Organic Photovoltaics” is gratefully acknowledged. The devices based on the reference squaraines 7 a,b show
U.M. thanks the Fonds der Chemischen Industrie for a Ph.D. low PCEs of 0.15 and 0.07 %, respectively, at a squaraine/
scholarship. BHJ = bulk heterojunction. PCBM ratio of 3:7 (w/w), which turned out to be optimal
Supporting information for this article is available on the WWW within a concentration series. These poor efficiency values are
under [Link] accompanied by low short-circuit currents of around

8776  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2009, 48, 8776 –8779
 Angewandte
Chemie

nearly unchanged, suggesting that the annealing process leads

to improved device morphology.[11]
The other acceptor-substituted squaraines 5 c–e also
exhibit superior photovoltaic properties compared to those
of 7 a,b (Table 1). In particular, squaraine 5 d features quite
unique photovoltaic properties. While the reference com-
pound 7 b shows the poorest performance, the corresponding
dicyanovinyl-functionalized derivative 5 d exhibits a PCE of
1.79 %, which is the highest of the present series. However,
this good photovoltaic performance is only achieved upon
annealing at 110 8C for 15 min, which slightly reduces VOC but
strongly increases JSC. This behavior again indicates dramatic
changes in the device morphology.[11] The best performing
devices for 5 d and 5 c were obtained for a squaraine/PCBM
ratio of 6:4 (w/w). Such large optimum dye content is quite
unusual for BHJ materials. It is, however, highly beneficial,
because by increasing the proportion of squaraine in the
active layer, more photons can be absorbed without increas-
ing the layer thickness. These favorable material properties of
5 d manifest themselves in the short-circuit current density of
JSC = 12.6 mA cm 2 (Figure 1).
These high photocurrents are attributed to the presence of
Scheme 1. Synthesis of acceptor-substituted squaraines 5 a–e and well-packed domains of PCBM and squaraine 5 d (for a
reference squaraines 7 a,b. discussion of packing properties, see below) that enable well-
balanced charge-carrier mobilities
for electrons and holes. Indeed, thin
Table 1: Electronic properties of the investigated squaraine dyes and the characteristic performance
films of 5 d exhibit appreciable
values for the respective BHJ solar cells with Ca/Al top electrode and a typical device thickness of about
80 nm. hole-carrier mobility in organic
[c] [g]
field-effect transistors of mh = 1.5 
Dye lmax [nm] E1/2(Ox) EHOMO ELUMO wt % VOC JSC FF PCE 5
10 cm2 V 1 s 1, which further
(emax [L mol 1 cm 1]) [V][d] [eV][e] [eV][f ] PCBM [V] [mA cm 2] [%]
increases upon annealing to mh =
7 a[a] 646 (250 000) 0.013 5.16 3.24 70 0.44 1.08 0.31 0.15 1.3  10 3 cm2 V 1 s 1 (for details,
7 b[b] 685 (210 000) 0.167 4.98 3.17 70 0.22 1.02 0.30 0.07
see the Supporting Information).
5 a[b] 683 (185 000) 0.101 5.25 3.42 70 0.63 3.28 0.36 0.74
[b]
5 b 683 (195 000) 0.120 5.27 3.45 70 0.66 3.49 0.37 0.84 Further evidence for the relatively
5 c[b] 625 (142 000) 0.009 5.16 3.18 40 0.42 2.79 0.42 0.49 high charge-carrier mobility of 5 d
5 d[b] 701 (170 000) 0.013 5.14 3.37 40 0.31 12.6 0.47 1.79 in the devices is given by the largest
5 e[b] 688 (180 000) 0.015 5.17 3.37 70 0.54 3.00 0.39 0.64 fill factor (FF) of 47 % within this
[12]
[a] Best device for squaraine/PCBM blend as cast. [b] Best device for squaraine/PCBM blend after series.
annealing at 110 8C for 15 min. [c] UV/Vis measurements in CH2Cl2 solutions (c = 10 5 m). [d] Deter- From the above photovoltaic
mined by cyclic voltammetry calibrated against the ferrocene/ferrocenium redox couple. [e] EHOMO = data it becomes evident that the
5.15 eV EOx ; [f] ELUMO = EHOMO + (h c/lmax), see Figures S5–S8 in Supporting Information; [g] FF = fill
factor.

1 mA cm 2 and open-circuit voltages of VOC = 0.44 V for 7 a

and VOC = 0.22 V for 7 b. It is worth mentioning that neither
temperature nor duration of annealing has an influence on the
device performance.
In contrast, the introduction of the dicyanovinyl func-
tional group at the squaric acid unit in 5 a evoked a drastic
(fivefold) increase in efficiency to a PCE value of 0.74 % at
the same squaraine/PCBM ratio of 3:7 (w/w). The open-
circuit voltage and the short-circuit current of the device
increased to VOC = 0.63 V and JSC = 3.28 mA cm 2. Similar
values are obtained for 5 b with VOC = 0.66 V and JSC =
3.49 mA cm 2, resulting in a PCE value of 0.84 %. For 5 a
Figure 1. J–V characteristics of 5 a (black solid line), 5 b (black dotted
and 5 b, annealing at 110 8C for 15 min enhances the PCE by line), 5 c (blue solid line), 5 d (red solid line), 5 e (green solid line), 7 a
about 10 %. This improvement in PCE goes hand in hand with (black dashed line), and 7 b (red dashed line) for the respective best
an increase in the short-circuit current, while the VOC remains solar cell devices measured under AM 1.5 illumination.

Angew. Chem. Int. Ed. 2009, 48, 8776 –8779  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 8777
Communications
introduction of the dicyanovinyl moiety influences the molecular structure inhibits such an advantageous spatial
molecular and material properties of squaraines to a great arrangement in the solid state.
extent. The structural influence of this group is revealed by X- The dicyanovinyl acceptor also favorably changes the
ray analysis of single crystals of 5 a and 5 d (see Figure 2 and absorption properties of compounds 5 a–e (Figure 3 and

Figure 3. UV/Vis absorption spectra of squaraines 7 a (black solid

line), 5 a (red solid line), and 5 d (blue solid line) in CH2Cl2
(c = 10 5 m) and of 5 d in films (blue dotted line: as cast; blue dashed
line: after annealing at 110 8C for 15 min).

Figure S1–S4 in the Supporting Information). Reference dye

7 a shows a sharp and intense absorption band typical of
Figure 2. a) Molecular structure and b) front view of the squaraine symmetrical squaraines at 646 nm with an absorption coef-
plane of 5 a. c) Molecular structure and d) front view of the squaraine
ficient of about e = 2.5  105 m 1 cm 1.[7b] The increased
plane of 5 d. Thermal ellipsoids are set at the 50 % probability level.
Hydrogen atoms, the disorder of one alkyl chain in 5 d, and solvent
acceptor strength of the dicyanovinyl moiety in 5 a causes a
molecules in 5 a are omitted for clarity. C black, N blue, O red, S yellow. red shift of the absorption maximum by about 40 nm to
e) Spatial arrangement of 5 d in the crystal lattice (for clarity, only the 683 nm (e = 1.85  105 m 1 cm 1). Furthermore, a second
squaraine p system is shown). absorption band with a maximum at 380 nm (e = 3.2 
104 m 1 cm 1) evolves. The same absorption characteristics
are observed for all other acceptor-substituted squaraines
the Supporting Information).[13] For the parent squaraines of (Table 1) and accordingly can be attributed to the molecular
the type 7 a,b, it was observed that the molecules are placed symmetry change of the dyes.
across an inversion center in the middle of the squarate ring Owing to a pronounced excitonic coupling of these
with a trans arrangement of the donor groups, as shown in densely packed chromophores (Figure 2 e), a substantial red
Scheme 1.[14] By introduction of the dicyanovinyl group, the shift and band broadening is observed in the solid state
inversion center is inevitably destroyed. Furthermore, the (dotted and dashed lines in Figure 3). Both of these spectral
increased steric demand of the additional acceptor groups features are highly desirable, because they increase the
forces the donor groups into a cis-like arrangement. absorption cross section for solar radiation and, eminently
Despite this mutuality, the structures of squaraines 5 a and important for the application on window glass, expand the
5 d also exhibit significant differences. Thus, the p backbone absorption far into the NIR region for the annealed film
of squaraine 5 a is bent, with one indolenine ring in plane with (Figure 3).[11] These beneficial properties manifest themselves
the central squarate ring and the other one twisted out of the in the external quantum efficiency (EQE). Thus, the 5 d/
plane with a torsion angle of around 128 (Figure 2 b). PCBM cell shows a maximum EQE of around 41 % at
Furthermore, the dicyanovinyl unit is twisted about 98 relative 750 nm, which belongs to the best EQEs reported for small-
to the plane of the squarate ring. Squaraine 5 d, in contrast, molecule-based BHJ cells (Figure S10 in the Supporting
exhibits an almost planar p skeleton (Figure 2 d). Information).
This planarity allows squaraine 5 d to arrange in a densely The only limitation for the efficient exploitation of solar
packed “brickwork” arrangement with a closest interplanar irradiation arises from quite low open-circuit voltages, in
distance of only 3.4  in the monoclinic space group C2/c particular for devices based on squaraines 7 a,b and 5 c,d
(Figure 2 e). This brickwork arrangement provides an excel- (Table 1). One explanation for these low VOC values comes
lent contact between the p systems, as demanded for efficient from the rather high-lying HOMO energy levels of squar-
exciton and charge-carrier transport through the material. aines, which could be lowered by 0.1–0.2 eV by means of the
This beneficial arrangement explains the observed superior dicyanovinyl substituents in derivatives 5 a–e. Another reason
conductivity values[12] of 5 d compared to 5 a, whose bent seems to be related to a strong interaction of these dyes in the

8778 [Link]  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2009, 48, 8776 –8779
 Angewandte
Chemie

solid state that alters not only the optical properties but the G. G. Malliaras, J. Am. Chem. Soc. 2007, 129, 9144 – 9149; d) S.
frontier molecular orbital levels as well.[5a] It is, however, Roquet, A. Cravino, P. Leriche, O. Aleveque, P. Frere, J. Roncali,
worth mentioning that the exploitation of the NIR spectral J. Am. Chem. Soc. 2006, 128, 3459 – 3466.
[4] M. Brumbach, D. Placencia, N. R. Armstrong, J. Phys. Chem. C
range always leads to a decrease of the utilizable excitation
2008, 112, 3142 – 3151.
energy per absorbed photon, which is 3.1 eV at 400 nm but [5] a) N. M. Kronenberg, M. Deppisch, F. Wrthner, H. W. A.
only 1.4 eV at 900 nm. Lademann, K. Deing, K. Meerholz, Chem. Commun. 2008,
To conclude, we have achieved highly desired NIR- 6489 – 6491; b) F. Silvestri, M. D. Irwin, L. Beverina, A. Fac-
absorbing dyes for BHJ solar cells by a rational molecular chetti, G. A. Pagani, T. J. Marks, J. Am. Chem. Soc. 2008, 130,
engineering approach. Using these dyes, we could manufac- 17640 – 17641; c) T. Rousseau, A. Cravino, T. Bura, G. Ulrich, R.
Ziessel, J. Roncali, Chem. Commun. 2009, 1673 – 1675.
ture devices with PCEs up to 1.79 % and maximum JSC values
[6] M. M. Wienk, M. G. R. Turbiez, M. P. Struijk, M. Fonrodona,
of 12.6 mA cm 2 ; the latter is the highest value reported for R. A. J. Janssen, Appl. Phys. Lett. 2006, 88, 153511.
solution-processed small-molecule BHJ cells and is close to [7] a) D. Keil, H. Hartmann, T. Moschny, Dyes Pigm. 1991, 17, 19 –
the JSC values of the best polymer-based BHJ cells. Further 27; b) S. Sreejith, P. Carol, P. Chithra, A. Ajayaghosh, J. Mater.
investigations are currently underway to improve the device Chem. 2008, 18, 264 – 274.
morphology and the electronic properties of the dyes towards [8] a) G. J. Ashwell, G. Jefferies, D. G. Hamilton, D. E. Lynch,
higher VOC values. Moreover, with their high JSC in the NIR M. P. S. Roberts, G. S. Bahra, C. R. Brown, Nature 1995, 375,
385 – 388; b) D. Ramaiah, I. Eckert, K. T. Arun, L. Weidenfeller,
spectral range, 5 d/PCBM layers feature promising character-
B. Epe, Photochem. Photobiol. 2002, 76, 672 – 677; c) K.-Y. Law,
istics for application in tandem cell devices with established Chem. Rev. 1993, 93, 449 – 486; d) J. V. Ros-Lis, R. Martnez-
polymer-based materials such as P3HT/PCBM that exploit Mez, F. Sancen n, J. Soto, M. Spieles, K. Rurack, Chem. Eur. J.
the shorter wavelength range of solar light. 2008, 14, 10101 – 10114.
[9] a) D. L. Morel, A. K. Ghosh, T. Feng, E. L. Stogryn, P. E.
Received: June 10, 2009 Purwin, R. F. Shaw, C. Fishman, Appl. Phys. Lett. 1978, 32, 495 –
Published online: October 13, 2009 497; b) S. Wang, E. I. Mayo, M. D. Perez, L. Griffe, G. Wei, P. I.
Djurovich, S. R. Forrest, M. E. Thompson, Appl. Phys. Lett.

.
Keywords: bulk heterojunction solar cells · donor–
acceptor systems · dyes/pigments · squaraines · thin films
2009, 94, 233304; c) J.-H. Yum, P. Walter, S. Huber, D. Rentsch,
T. Geiger, F. Nesch, F. De Angelis, M. Grtzel, M. K. Nazeer-
uddin, J. Am. Chem. Soc. 2007, 129, 10320 – 10321.
[10] For synthetic details and compound characterization, see the
Supporting Information.
[1] a) R. M. Nault, Basic Research Needs for Solar Energy Utiliza- [11] For details on the device morphology, see the Supporting
tion—Report of the Basic Energy Sciences Workshop on Solar Information.
Energy Utilization, April 18 – 21, 2005; [Link] [12] One limiting factor for BHJ cells is known to be the buildup of
bes/reports/files/SEU_rpt.pdf; b) C. J. Brabec, N. S. Sariciftci, space charge, which may occur if the charge-carrier mobility
J. C. Hummelen, Adv. Funct. Mater. 2001, 11, 15 – 26. difference between the donor and acceptor phase exceeds two
[2] a) J. Y. Kim, K. Lee, N. Coates, D. Moses, T.-Q. Nguyen, M. orders of magnitude. Under this condition the FF value is less
Dante, A. J. Heeger, Science 2007, 317, 222 – 225; b) J. Peet, J. Y. than 42 %, see: a) V. D. Mihailetchi, J. Wildeman, P. W. M. Blom,
Kim, N. E. Coates, W. L. Ma, D. Moses, A. J. Heeger, G. C. Phys. Rev. Lett. 2005, 94, 126602; b) L. J. A. Koster, V. D.
Bazan, Nat. Mater. 2007, 6, 497 – 500. Mihailetchi, P. W. M. Blom, Appl. Phys. Lett. 2006, 88, 052104.
[3] a) B. Walker, A. B. Tamayo, X.-D. Dang, P. Zalar, J. H. Seo, A. [13] CCDC 734983 (5 a) and 734984 (5 d) contain the supplementary
Garcia, M. Tantiwiwat, T.-Q. Nguyen, Adv. Funct. Mater. 2009, crystallographic data for this paper. These data can be obtained
19, 3063 – 3069; b) C.-Q. Ma, M. Fonrodona, M. C. Schikora, free of charge from The Cambridge Crystallographic Data
M. M. Wienk, R. A. J. Janssen, P. Buerle, Adv. Funct. Mater. Centre via [Link]/data_request/cif.
2008, 18, 3323 – 3331; c) M. T. Lloyd, A. C. Mayer, S. Subrama- [14] D. E. Lynch, K. A. Byriel, Cryst. Eng. 1999, 2, 225 – 239.
nian, D. A. Mourey, D. J. Herman, A. V. Bapat, J. E. Anthony,

Angew. Chem. Int. Ed. 2009, 48, 8776 –8779  2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim [Link] 8779