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Enhancing the efficiency of a dye sensitized solar cell due to the energy
transfer between CdSe quantum dots and a designed squaraine dye{
Lioz Etgar,*a Jinhyung Park,b Claudia Barolo,*b Vladimir Lesnyak,*c Subhendu K. Panda,c Pierluigi
Quagliotto,b Stephen G. Hickey,c Md. K. Nazeeruddin,a Alexander Eychmüller,c Guido Viscardib and Michael
Grätzela
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Received 2nd February 2012, Accepted 2nd February 2012

DOI: 10.1039/c2ra20192e

The power conversion efficiency of a dye-sensitized solar cell with substituent in the red to near-infrared region,7 and they have been
tailored squaraine dye enhanced by 47%, due to Förster resonance widely and successfully used also in DSSCs in recent years.8 A recent
energy transfer from CdSe quantum dots to the squaraine dye. report on FRET based dye sensitized solar cells showed that the
The incident photons to collection efficiency of electrons indicate acceptor should be anchored to the TiO2. In addition it must have
panchromatic response from the visible to the near-infrared lower excitation energy than the donor, enabling fast and efficient
spectrum. electron transfer to TiO29 upon excitation of the energy relay dye.
Quantum dots (QDs) have high molar extinction coefficients and
broad absorption spectra covering a wide part of the visible
Introduction spectrum. Hence they can be good candidates as donors in FRET
DSSCs in cases where IR dyes that absorb weakly in the visible
Photovoltaic technology is one of the most promising alternative region are used as acceptors.
renewable energy sources, harvesting energy from the sun. Dye On the other hand, QDs can be affected by the electrolyte, one
sensitized solar cells (DSSCs) are inexpensive and use abundant possibility to avoid this was described by Zaban et al.,10–12 who
materials for large-scale solar energy conversion. In a typical DSSC created an amorphous thin TiO2 barrier to avoid direct contact with
the dye absorbs photons and goes to the excited state, generating the electrolyte. Another option is to use a more ‘‘friendly’’ electrolyte,
electron and hole pairs. The electrons are injected into the TiO2 which will not quench the QDs.
conduction band and diffuse to the front contact, simultaneously, the Here, we apply the FRET concept to a hybrid QDs/dye-sensitized
holes are scavenged by a redox couple. Currently DSSCs are solar cell. The donors are TOP/TOPO-capped CdSe QDs, while the
exceeding power conversion of 12%,1 despite the fact that many dyes acceptor is a newly designed symmetric squaraine dye, called VG1-
do not absorb strongly over 700 nm. Therefore, Förster resonance C10, possessing an additional carboxylic group13 as compared to
energy transfer (FRET) has already been demonstrated in a variety standard squaraine dyes, and two C10-chains. This provides better
of optoelectronic applications and recently in DSSCs to harvest dye stability and allows efficient energy transfer. The use of the
visible and near infrared (IR) absorption spectra.2–5 Usually, the cobalt complex (Co+2/Co+3) as an electrolyte in the cells permits
traditional dyes used in DSSCs suffer from low molar extinction direct contact between the QDs and the electrolyte. Moreover, there
coefficients or limited absorption spectra regions.6 Using FRET to is no need to exchange the original ligands of the QDs prior to
transfer energy from donor to acceptor inside the DSSCs paves a deposition, since the two C10 chains of the dye molecules and TOP/
new way for enhancing the photovoltaic performance of DSSCs. TOPO-capping of the QDs provide the optimum distance for FRET
This provides the possibility to employ a cascade combination of and make the preparation and the structure of the cell simple. As a
dyes, which have narrow absorption spectra. result of the energy transfer, the cell power conversion efficiency was
Squaraine dyes are well-known for their remarkable optical increased and its solar response was expanded from the visible to the
behavior because of strong absorption from charge transfer between near infrared spectral region.
an electron-deficient central squaric core and each side of the
a
Results and discussion
Laboratoire de Photonique et Interfaces, Institut des Sciences et Ingénierie
Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Station 6, Different non-symmetric and symmetric squaraines were synthesized
CH-1015, Lausanne, Switzerland. E-mail: lioz.etgar@epfl.ch
b
Dipartimento di Chimica, NIS Centre of Excellence, Università di Torino, and characterized (see ESI{) in order to match their optical and
Via Pietro Giuria 7, I-10125, Torino, Italy. hydrophobic properties with the selected QDs. Their interaction
E-mail: claudia.barolo@unito.it properties have been studied both in solution and on FTO glass,
c
Physical Chemistry, TU Dresden, Bergstr. 66b, 01062, Dresden, avoiding the titania substrate in order to eliminate the injection problem.
{ Electronic supplementary information (ESI) available: Experimental data
includes synthesis of the squaraine dyes and the QDs. See DOI: 10.1039/ Subsequently, the best couple (symmetrical long chain dyes VG1-C10
c2ra20192e and CdSe TOP/TOPO capped QDs) have been used in the cell.

2748 | RSC Adv., 2012, 2, 2748–2752 This journal is ß The Royal Society of Chemistry 2012
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The symmetric squaraine VG1-C10 was synthesized via a two step

procedure using commercially available precursors (see Scheme 1).
Symmetrical dyes have the advantage of simple synthesis and easy
purification by crystallization.13 For the synthesis details and NMR
data see the ESI.{
The scheme of the energy transfer cell is presented in Fig. 1A. The
TiO2 electrode was first dipped in the VG1-C10 dye solution
overnight and then the CdSe QDs were spin coated on top of the
dye-coated electrode. Finally the Co+2/Co+3 electrolyte was injected
into the cell.
Fig. 1B shows the energy level diagram of the cell, which is a type I
system. The energy level positions of the QDs and of the dye permit
energy transfer between the QDs as donor and the dye as the
acceptor. Moreover, the mismatch in the conduction band of the
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QDs and the LUMO of the dye does not allow for charge transfer
from the dye to the QDs. As a rule, in the DSSC light is absorbed by
the dye, an electron is excited from the HOMO to the LUMO and
injected to the conduction band of TiO2. In the present hybrid cell,
the QDs act as additional light harvesters absorbing the light and
transferring the energy of their excited state to the LUMO of the dye
via dipole–dipole interaction. Subsequently, as in standard DSSCs,
the electron from the LUMO of the dye is injected to the conduction
band of the TiO2 and the hole is transported to the counter electrode
via the redox couple.
Fig. 2 shows FTIR spectra of the VG1-C10 as dye powder in KBr
Fig. 1 (A) Schematic presentation of the cell structure; (B) energy level
pellets and the VG1-C10 adsorbed on TiO2. The spectra reveal that diagram of the components involved in the cell. Dashed arrows represent
the adsorption of VG1-C10 on TiO2 occurs via carboxy groups, absorption, wavy arrows show energy transfer from the QDs excited state to
showing two bands at 1609 cm21 and 1353 cm21,14 while the the LUMO of the dye via dipole–dipole interaction; (C) the arrangement of
characteristic COOH band around 1730 cm21–1680 cm21 comple- the QDs and the VG1-C10 inside the cell.
tely disappeared. Therefore, the VG1-C10 can be linked by both
COOH groups to the titania surface, in a cis arrangement, probably
directing the hydrocarbon chains far from the TiO2. 9000( ln 10)k2 QD J
R60 ~ (1)
Relying on the FTIR measurements, Fig. 1C presents a possible 128p5 n4 NAV
explanation for the orientation of the QDs and the dye inside the cell,
where n is the refractive index of the medium (typically 1.4–1.5 for
which permits FRET to occur. As discussed above, the VG1-C10
the electrolytes employed in DSSCs), k2 is the orientation factor (2/3
dye anchors the TiO2 by using its two carboxylic groups, as a result
for random orientation), QD is the quantum yield (QY) of the donor
the C10H21-chains are free and away from the TiO2, which allows
(28%), Nav is the Avogadro number, J is the overlap integral:
them to intertwine with the TOP/TOPO ligands of the QDs via
efficient hydrophobic interactions. This kind of a connection results
in an average distance between the donor and the acceptor, which
lies within the Förster radius and allows an efficient energy transfer.
This type of ligand interconnection was demonstrated by Vogel
et al.15 showing FRET between QDs and lipids both containing long
hydrocarbon chains.
Fig. 3 shows the absorption and emission spectra of the CdSe QDs
and the VG1-C10 dye. For FRET it is essential that the emission
spectrum of the donor (QDs) overlap with the absorption spectrum
of the acceptor (dye).
The Förster radius, R0, is the distance at which the probability for
energy transfer is 50%. The Förster radius is given by:16

Fig. 2 FTIR spectra of VG1-C10 in KBr pellets (red), and VG1-C10

Scheme 1 Synthetic pathway for symmetric squaraine VG1-C10. adsorbed on TiO2 electrodes (black).

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Fig. 3 Absorption and emission spectra of the CdSe QDs and VG1-C10 Fig. 5 Incident photon to current efficiency (IPCE) curves of the three cells.
dye. The CdSe cell (brown line); the VG1-C10 cell (green line) and the hybrid cell
ð
? composed of the donor and acceptor (purple line).
J~ ID (l)eA (l)l4 dl, ID is the emission profile spectrum of the
0 the main evidences for FRET is the shortening of the donor lifetime
donor and eA is the molar extinction coefficient of the acceptor. in the presence of the acceptor and the increase of the lifetime of the
According to this formula, R0 in our system is 3.7 nm, which agrees acceptor in the presence of the donor.
well with our suggested orientation of the QDs and the dye. One of In order to show the energy transfer from the CdSe QDs to the
VG1-C10 dye, mixed composite films of different QDs/VG1-C10
ratios were prepared. Absorption and photoluminescence (PL)
spectra of the CdSe QDs and the VG1-C10 dye in solution are
presented in Fig. 3. As is seen from the figure, the QDs sample
chosen for the experiments as a potential energy donor meets two
main requirements for investigation of energy relations in the system
by means of optical spectroscopy: on the one hand, its emission
spectrum overlaps with the absorption of the dye, on the other hand
its PL maximum is quite distant from that of the dye, which allows
for the separate detection of the time resolved emissions from the
donor and from the acceptor, at 600 and 700 nm, respectively.
Moreover, excitation sources for time resolved measurements (pulse
laser diodes) allow for separate excitation of the QDs and the dye. As
is seen from Fig. 3, neither the QDs absorb light at 670 nm (used for
the dye emission measurements), nor does the dye absorb at 470 nm
(used for the QDs PL excitation). Thus, emissions of the QDs and
the dye do not interfere and consequently do not account for time
resolved traces of each other.
As is clearly seen from Fig. 4A and B, an increase in the QDs
content in the mixed films leads to strong enhancement of both

Fig. 4 Time resolved PL spectra of the composite QDs/VG1C10 films with

different ratios recorded at 600 nm (QDs emission) (A) and at 700 nm (VG1-
C10 emission) (B); lex = 470 nm for all the samples except the pure VG1-C10
film excited at 635 nm (black curve in Fig. 4B). Note, QDs emission
measured at 700 nm (ex. 470 nm) is very weak (not shown). The arrows Fig. 6 Photovoltaic response of the VG1-C10 cell and the VG1-C10 +
indicate an increase in the QD/VG1 ratio. CdSe QDs cell.

2750 | RSC Adv., 2012, 2, 2748–2752 This journal is ß The Royal Society of Chemistry 2012
 View Article Online

Table 1 Photovoltaic performance of the VG1-C10 dye (acceptor) cell and of the donor/acceptor cell, showing the improvement of the performance
due to the FRET
Cell type Jsc/mA cm22 Voc/mV FF g @ 1 sun

VG1-C10 dye 2.73 542 0.536 0.79

VG1-C10 dye + CdSe QDs (FRET cell) 3.25 653.4 0.69 1.48
D +16% +17% +23% +47%

emission lifetimes. Thus the more donors present in the system, the
more efficient energy pumping of the acceptor is realized. FRET
from the donors (QDs) is clearly shown by the appearance of a slow
component in the acceptor PL lifetime.
FRET efficiency can be calculated according to the following
equation:17 E = 1 2 (tDA/tD), where tDA and tD are the lifetime of
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the donor in the presence of the acceptor and the lifetime of the
donor alone, respectively. In our case, the PL lifetime was fitted by
bi-exponential equation and the weighted average lifetime of each
decay curve was calculated. The donor lifetime is 9.7 ¡ 0.1 ns and
the lifetime of the donor in the presence of acceptor drops to 3 ¡
0.1 ns. For the lifetime of the donor in the presence of the acceptor,
we considered the QD/VG1-C10 ratio, which is the same as their
Fig. 7 Dark current measurements of the VG1-C10 cell and the VG1-C10
ratio in the cell. The calculated FRET efficiency is E # 69%.
+ CdSe QDs cell (FRET cell).
Fig. 5 shows the incident photon to current efficiency (IPCE) of
three different DSSCs: CdSe QDs donor cell, VG1-C10 acceptor cell
visible photons in the 350–650 nm region resulting from energy
and hybrid cell composed of the donor (QDs) and the acceptor (dye).
transfer.
The QDs cell (one layer of QDs deposited on the titania electrode)
shows a very week response for the whole wavelength range. The dye
cell exhibits an IPCE response between 500 nm to 750 nm, which Conclusion
matches well the absorption spectrum of the dye (see Fig. 3). As is We demonstrated an enhancement of the light harvesting in dye
seen from Fig. 5, the hybrid cell containing both the dye and the QDs sensitized solar cell due to Förster resonance energy transfer. The
layers has the best efficiency and demonstrates response over the donors are CdSe QDs and the acceptor is a new designed symmetric
whole visible range, reaching its maximum at 360 nm and 660 nm, squaraine dye with two carboxy groups and two long hydrocarbon
corresponding to IPCE intensity of 36% and 30%, respectively. The chains. The use of the cobalt complex (Co+2/Co+3) as the electrolyte
coverage of the whole visible spectrum in the hybrid cell is evidence in the cells permits direct contact between the QDs and the
for the efficient FRET interaction between the constituents of the electrolyte without affecting the QDs, which results in a simple
light-absorbing layer. Moreover, the cell fabrication method, structure FRET system employed in a hybrid QDs/dye-sensitized
consisting of dipping the TiO2 electrode in the dye solution with solar cell. PL lifetime measurements revealed FRET from the QDs to
subsequent deposition of the QDs via spin coating, minimizes the the dye. IPCE curves of the device exhibit a full coverage of the
possibility of co-sensitization. During the QDs deposition the whole visible region. In addition, all the cell photovoltaic parameters were
TiO2 surface is already covered by the dye molecules, which prevents enhanced, proving efficient energy transfer within the QD–dye-
direct injection of electrons from the QDs to the TiO2 conduction sensitized solar cell.
band.
The photovoltaic performance (PV) of the acceptor cell composed Acknowledgements
of the VG1-C10 dye only and the donor-acceptor cell (composed of
the dye and the QDs) is shown in Fig. 6 and Table 1. The acceptor This research was funded by the European Community’s
cell exhibits a power conversion efficiency (PCE) of 0.79% under AM Seventh Framework Programme (FP7/2007-2013) under grant
1.5 G and short circuit current (Jsc), open circuit voltage (Voc), and agreement nu 227057, Project ‘‘INNOVASOL’’. L. E. acknowl-
fill factor (FF) of 2.73 mA cm22, 542 mV, and 0.53, respectively. edges the Marie Curie Actions-Intra-European Fellowships
Upon incorporation of CdSe QDs into the device, the Jsc increases by (FP7-PEOPLE-2009-IEF) under grant agreement nu 252228,
16% to 3.25 mA cm22 with an increase in the PCE up to 1.48%. The project ‘‘Excitonic Solar Cell’’. We gratefully acknowledge
Voc increased by 111 mV (17% increase) and the FF increased by Christian Waurisch (TU Dresden) for providing the samples. J.
23%. The increase in the Voc is mainly due to an upward shift of the P., C. B., P. Q. and V. G. thank Compagnia di San Paolo and
TiO2 conduction band. This can be explained in the difference of the Fondazione CRT for continuous equipment supply.
dark current measurements shown in Fig. 7 (assuming the same
recombination behaviour), and by the higher current density of the References
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2752 | RSC Adv., 2012, 2, 2748–2752 This journal is ß The Royal Society of Chemistry 2012