Electrochimica Acta 91 (2013) 246252

Contents lists available at SciVerse ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Quantum dot sensitized solar cells based on an optimized combination of ZnS,

CdS and CdSe with CoS and CuS counter electrodes
Nikolaos Balis a , Vassilios Dracopoulos b , Kyriakos Bourikas c , Panagiotis Lianos a,b,
a
b
c

Engineering Science Department, University of Patras, 26500 Patras, Greece

FORTH/ICE-HT, P.O. Box 1414, 26504 Patras, Greece
School of Science and Technology, Hellenic Open University, Tsamadou 13-15, 26222 Patras, Greece

a r t i c l e

i n f o

Article history:
Received 10 October 2012
Received in revised form
30 December 2012
Accepted 1 January 2013
Available online 8 January 2013
Keywords:
Quantum dot sensitized solar cells
Metal sulde counter electrodes
TiO2
CoS
CuS

a b s t r a c t
Quantum dot sensitized solar cells have been constructed using photoanodes made of nanocrystalline
titania and an optimized combination of ZnS, CdS and CdSe nanoparticles. Pt, CoS and CuS have been
used as electrocatalysts on counter electrodes. Attachment of quantum dot sensitizers on mesoporous
titania was made by successive ionic layer adsorption and reaction and by chemical bath deposition
obeying a certain order, where the rst layer was crucial in dening the quality and the quantity of the
subsequent layers as well as of the ensuing solar conversion efciency. Thus the rst quantum dot layer
consisted of 75% CdS and 25% ZnS and it was followed by a CdSe layer and by an additional ZnS layer on
the top. The quantity of material deposition seems to be affected not only by the employed deposition
method but also and mainly by the nature of the underlying layer. Optimized anode electrodes led to solar
cells producing high current densities but did not much affect open-circuit voltage. The maximum solar
conversion efciency reached in this work was 2.7% and was obtained by using CuS electrocatalyst. Both
CoS and CuS gave high currents and this was in line with the low charge transfer resistances recorded in
their case.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Sensitized solar cells constitute one of the most popular elds of
research, which is being active for several decades [1,2] but continues to attract an ever increasing number of adepts. In a sensitized
solar cell, light is mainly absorbed by the sensitizer. Photogenerated electrons are then rapidly injected into the conduction band
of the coupled semiconductor leading to electronhole separation.
This is the most important asset of sensitized solar cells [3]. Dye
sensitizers of metal oxide semiconductors in combination with
liquid electrolytes have offered the highest photovoltaic efciencies. However, inorganic semiconductor sensitizers, usually
referred to as quantum dot (QD) sensitizers, are recently studied
with great interest that might surpass their dye homologues.
This interest stems from the several attractive features that QD
sensitizers possess [37]: spectral tuning by controlling size due to
the quantum connement effect; high dipole moment that assists
electron injection; high extinction coefcient, etc. In addition,
QDs are easy to synthesize and, since their size is limited to a
few nanometers, they can be easily accommodated within the

Corresponding author at: Engineering Science Department, University of Patras,

26500 Patras, Greece.
E-mail address: lianos@upatras.gr (P. Lianos).
0013-4686/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.01.004

mesoporous structure of nanocrystalline oxide semiconductors,

which is usually one order of magnitude larger.
Several QDs have been studied as sensitizers of nanocrystalline
titania (nc-TiO2 ) and have been used in the construction of the socalled quantum dot sensitized solar cells (QDSSCs) [310]. The most
popular QDs are metal suldes and selenides. Previous works have
shown that combinations of QDs lead to higher efciencies than
pure materials [4,1013]. There are a few reasons for this behavior.
Combination of materials leads to passivation of structure defects,
which are typical sites of electronhole recombination. Mixing of
QDs also leads to charge carrier dispersion impeding charge recombination. Furthermore, combination of QDs by appropriate tting
of energy levels supports cascade charge transfer [11]. Combination then of a few different QDs is an important issue and for this
reason in the present work, we searched for an optimized combination of ZnS, CdS, and CdSe leading to the construction of a QDSSC
with promising characteristics. The main feature of this combination is the careful choice of the rst layer of QDs directly deposited
on nc-TiO2 . We believe that this rst layer is very crucial in dening the characteristics of the photoanode as a whole. For example,
the quantity and the quality of the material forming the upper QD
layer depends on the characteristics of the bottom QD layer. In
the present work, the bottom QD layer was made through a combined deposition of 25%ZnS75%CdS, which is more effective than
plain CdS. ZnSCdS have been previously found [14] to form solid

N. Balis et al. / Electrochimica Acta 91 (2013) 246252

solutions, without phase separation, allowing for spectral tuning

and modifying the energy levels of the mixed semiconductor with
respect to pure CdS. Such mixture also resulted in a more efcient
solar cell.
In addition, in the present work, nanostructured CoS and CuS
have been used as electrocatalysts on the counter electrode.
Nanocrystalline platinum is the most precious of all electrocatalysts but is not considered a good choice of a catalyst in QDSSCs
employing polysulde electrolytes [15], as in the present case.
The construction of an efcient cathode is important not only for
QDSSCs but for all types of electrochemical cells and for this reason
it attracts a great interest. Alternative catalysts have been proposed by several researchers [1518]. Metal suldes are considered
a good choice. However, their deposition on plain FTO electrodes
does not always produce materials with sufciently high specic
surface or with structural stability. Combination of catalysts, especially, novel nanostructured materials [18] is equally important as
it is in the case of photoanodes. The present work, supports the
existing trends, opts for the employment of CoS and CuS as electrocatalysts and proposes some easy procedures for their deposition
on transparent conductive electrodes.
2. Experimental
2.1. Materials
Unless otherwise indicated, reagents were obtained from
Aldrich and were used as received. Commercial nanocrystalline
titania Degussa P25 (specic surface area 50 m2 /g) was used in
all cell constructions and Millipore water was used in all experiments. SnO2 :F transparent conductive electrodes (FTO, resistance
8 /square) were purchased from Pilkington.
2.2. Construction of nc-TiO2 lms on FTO electrodes
The following procedures were undertaken in order to construct
photoanode electrodes. First, the nc-TiO2 lm was synthesized. It
was deposited in two layers, a bottom compact layer and a top open
structure. The bottom layer was synthesized by the solgel method
while the top layer was deposited by using a paste made of Degussa
P25 nanoparticles. A densely packed nanocrystalline titania layer
was rst deposited on a patterned FTO electrode, cleaned by sonication in acetone, isopropanol and ethanol, according to the following
procedure [19]: 3.5 g of the non-ionic surfactant Triton X-100 was
mixed with 19 ml ethanol. Then 3.4 ml glacial acetic acid (AcOH)
and 1.8 ml of titanium tetraisopropoxide were added under vigorous stirring. After a few minutes stirring, the lm was deposited by
dipping and then it was left to dry in air for a few minutes. Finally,
it was calcined at 550 C. The temperature ramp was 20 C/min up
to 550 C and the sample was left for about 10 min at that temperature. The procedure was repeated once more. Each layer gave a
thin nanostructured lm of about 170 nm thickness, as measured by
its FE-SEM prole [19]. On the top of this compact nanostructured
layer, commercial Degussa P25 was deposited. For this purpose, a
paste of titania P25 was prepared according to Ref. [20]. The paste
was applied by screen printing using a 90 mesh screen. It was nally
calcined again at 550 C. The thickness of the top layer was about
3.4 m as measured by its FE-SEM prole [19]. The procedure was
repeated once more so that the nal nc-TiO2 lm was about 7.5 m
thick. The geometrical size of the lm was 1 cm2 (1 cm 1 cm).
2.3. Formation of the CdSZnS composite layer by the SILAR
method
CdSZnS composite catalysts at various proportions were
deposited on the nc-TiO2 lm by Successive Ionic Layer Adsorption

247

and Reaction (SILAR method) [19,21]. For this purpose, two

aqueous solutions were used, one containing Cd(NO3 )2 4H2 O or
Zn(NO3 )2 6H2 O or mixtures of both, and the second containing
Na2 S9H2 O. The total concentration of metal ions and the corresponding concentration of sulfur ions were 0.1 mol dm3 . The
freshly prepared titania electrode was immersed for 3 min in the
metal salt solution, then copiously washed with triple-distilled
water, then immersed for 3 min in the Na2 S9H2 O solution and
nally washed again. This sequence corresponds to one SILAR cycle.
10 SILAR cycles were performed in all studied cases. Finally, the
electrode with deposited CdSZnS@nc-TiO2 lm was rst dried in a
N2 stream and then it was put for a few minutes in an oven at 100 C.
2.4. Formation of the CdSe layer by CBD
CdSe was deposited by chemical bath deposition (CBD) either
directly on a plain nc-TiO2 lm or on the above CdSZnS@ncTiO2 lm. The procedure was similar to that employed by other
researchers [4,8] and involves the following steps: an aqueous
solution of 0.08 mol dm3 Se powder was rst prepared in the
presence of 0.2 mol dm3 Na2 SO3 by continuous stirring and reuxing at 80 C. The procedure lasted about 15 h and was carried
out overnight. The obtained solution, denoted in the following
as sol A, actually aimed at the formation of sodium selenosulphate (Na2 SeSO3 ), which is a precursor for slow Se2 release.
Two more aqueous solutions were then prepared, containing
0.08 mol dm3 CdSO4 8 /3 H2 O (sol B) and 0.12 mol dm3 nitrilotriacetic acid trisodium salt (sol C), respectively. Sol B was mixed with
an equal volume of sol C and the obtained mixture was stirred
for a few minutes. The combination of sol B with sol C leads to
the formation of a complex, which is used as precursor for slow
release of Cd2+ . Finally, two parts of this last mixture were mixed
with one part of sol A and the thus obtained nal mixture was
used for CBD. The nal concentration of Se2 and Cd2+ ions was
0.08/3 mol dm3 . The idea of the above procedure is to make a mixture of precursors, which slowly release selenium and cadmium
ions so as to make them react after adsorption on the substrate.
Thus the electrodes with substrate lms were dipped in this nal
solution. Subsequently, they were put in a refrigerator at 5 C for
4 h or left at ambient temperature for several hours. The choice
of temperature or residence time is dictated by the substrate. It
was observed that ZnSCdS@nc-TiO2 /FTO electrodes needed only
4 h and low temperature to adsorb substantial quantities of CdSe
and be deeply colored while more than 24 h were required in the
absence of the ZnSCdS layer. The procedure was accelerated if the
CBD was done at ambient temperature.
2.5. Formation of the top ZnS layer
In several recent works [4,12,22,23], researchers have found
that a layer of ZnS added on the top of CdSe greatly improves the
behavior of solar cells. In line with these ndings, we have also prepared samples with added top layer of ZnS, which was deposited
by 2 SILAR cycles as above, using 0.1 mol dm3 aqueous precursor
solutions of the respective Zn2+ and S2 ions.
2.6. Construction of the counter electrodes
Some counter electrodes were functionalized with Pt electrocatalyst. For this purpose, a solution of 0.02 mol dm3 H2 PtCl6 in
isopropanol was spin-coated on properly cleaned FTO at 2000 rpm.
The obtained lm was calcined at 450 C for 15 min. CoS was
directly deposited on FTO by potentiodynamic electrodeposition
[16]. FTO was used as working electrode, a Pt sheet as auxiliary electrode and a Ag/AgCl as reference electrode. The precursor solution
contained 0.005 mol dm3 CoCl2 6H2 O and 0.5 mol dm3 thiourea.

248

N. Balis et al. / Electrochimica Acta 91 (2013) 246252

F(R)

4
3
2
1
0
300

4
3

2
6
1
400

500

600

700

800

Wavelength / nm
Fig. 1. Absorption spectra of various functional lms: (1) plain FTO glass; (2)
nc-TiO2 /FTO; (3) ZnSCdS@nc-TiO2 /FTO; (4) CdSe@ZnSCdS@nc-TiO2 /FTO; (5)
ZnS@CdSe@ZnSCdS@nc-TiO2 /FTO; and (6) CdSe@nc-TiO2 /FTO.

A few drops of diluted NH4 OH may be added [16] to bring pH

close to 6.0. The distance between working and auxiliary electrode was 1 cm. The procedure consisted of 5 cycles of voltage
cycling between 1.2 and +0.2 V at a rate of 5 mV s1 . Afterwards,
the electrode with lm was dried, rst in a N2 stream and then
in an oven at 100 C. CoSCuS mixtures were also deposited by
the same procedure and by utilizing mixtures of CoCl2 6H2 O with
CuCl2 2H2 O (Merck) at a total salt concentration of 0.005 mol dm3 .
Finally, CuS was also deposited on FTO electrodes by a SILAR procedure, by modifying the method presented in Ref. [24]. Precursor
solutions contained 0.5 mol dm3 Cu(NO3 )2 xH2 O in methanol and
1 mol dm3 Na2 S9H2 O in a 1:1 water:methanol mixture. A well
cleaned FTO electrode was immersed for 5 min in the metal salt
solution, then copiously washed with triple-distilled water and
dried in an air stream, then immersed for 5 min in the Na2 S9H2 O
solution and nally washed and dried again. This sequence again
corresponds to one SILAR cycle. 10 SILAR cycles were performed.
Finally, the electrode with deposited CuS lm was rst dried in a
N2 stream and then it was put for a few minutes in an oven at
100 C.
2.7. Cell assembly
The photoanode and the counter electrode were assembled
by using a thermoplastic foil (surlyn type). After assembly, the
distance between the two electrodes was around 60 m. The
space in-between was lled with an aqueous polysulde electrolyte containing 1 mol dm3 Na2 S and 1 mol dm3 S. IV curves
were traced by illuminating the cell through a mask of 0.2 cm2
(0.2 cm 1 cm).
2.8. Methods
Illumination of the samples was made with a PECCELL PECL01 Solar Simulator set at 100 mW cm2 . JV characteristic curves
were recorded under ambient conditions with a Keithley 2601
source meter, which was controlled by Keithley computer software
(LabTracer). IPCE values were measured by using a home-made
apparatus employing a 300 W Oriel xenon lamp and a Jobin-Yvon
monochromator. Radiation intensity for  < 400 nm was measured
with a PMA 2100 Radiant Power meter (Solar Light Co.), calibrated for the near UV spectral range and for  400 nm with
an Oriel Radiant Power meter (70260) calibrated for the visible range. Field emission scanning electron microscope (FE-SEM)

images were recorded with a LEO SUPRA 35VP. Diffuse reectance

spectra (DRS) were recorded with a PerkinElmer Lambda 35
UV/vis spectrophotometer equipped with an integration sphere
accessory. Electrochemical impedance spectra on symmetrical cells
of the type counter-electrode/electrolyte/counter-electrode were
obtained using an Autolab PGSTAT128N potentiostat, equipped
with a frequency response analyzer (FRA), at 0 V bias in the
dark and recorded over a frequency range of 100 kHz100 mHz.
The distance between the two electrodes was 1 cm, their active
size 1.5 cm 1.5 cm and the aqueous electrolyte was the same as
the one lling the above solar cell, i.e. it contained 1 mol dm3
Na2 S and 1 mol dm3 S. XRD patterns were recorded with a D8
ADVANCE (Bruker AXS) diffractometer working with parallel beam
optics (Gobel mirror) in grazing incidence mode. Powder was
scratched from the electrode and was placed on a zero backround holder. The grazing angle was 2 (source: CuKa, power:
1.6 kW).

3. Results and discussion

3.1. Structural and spectroscopic characteristics of the
photoanodes
As it has been described in Section 2, each photoanode electrode was made of a double layer of nc-TiO2 deposited on FTO
glass. The bottom layer was a thin compact layer (about 350 nm)
and the top layer was a relatively thick open structure (about
7 m). Thicknesses were estimated by using the Scanning Electron Microscope proles of the lms. The bottom layer facilitates
stable attachment on the FTO electrode and enhances electric conductivity whereas at the same time prevents the contact of the
electrolyte with the electrode. This is a standard conguration
having been used by us and by others in previous works [19,22].
The top open structure facilitates deep electrolyte penetration and
deep photosensitizer deposition. Images of the nanostructure of
both layers have been presented in a previous publication [19].
The area of each titania lm was 1 cm2 (1 cm x 1 cm) but JV
curves were recorded by employing a mask so that the active area
was 0.2 cm2 . Semiconductor QDs were deposited on freshly prepared titania lms by combining the SILAR method and CBD, as
explained in Section 2. The deposition sequence was the following. First, we deposited ZnSCdS mixtures by the SILAR method,
then CdSe by CBD and nally on the top, ZnS by 2 additional
SILAR cycles. It is of interest to note that the bottom seeds of
ZnSCdS induce rapid CdSe deposition. If CdSe is deposited directly
on titania, i.e. without any ZnSCdS or pure CdS seeds, it is found
that after 24 h of CBD the quantity of CdSe is still very small,
much smaller than that obtained after 4 h of deposition on seeded
substrates. Indeed, as seen in Fig. 1, which depicts absorption
spectra of progressively deposited materials, if we make the reasonable assumption that absorbance and quantity of material grow
in parallel, seeded lms adsorbed relatively large quantities of
CdSe and substantial quantity of ZnS on the top. Non-seeded substrates adsorbed only a very small quantity of CdSe (curve 6 of
Fig. 1).
The rst photosensitizer layer was composed of a mixture of
ZnS and CdS. It has been previously found [14] that the combination of these two semiconductors produces solid solutions, which
allow band gap tuning in a substantial range of the visible spectrum.
This is true both for powdered samples and for thin lms synthesized in situ on nanocrystalline titania [14]. Indeed, as can be seen
in Fig. 2, the absorption onset of the sensitized lm varied up to
500 nm by changing the ratio of Cd and Zn in the SILAR deposited
composite photosensitizer. Composite ZnSCdS photosensitizer is
more efcient than pure CdS or ZnS [14].

N. Balis et al. / Electrochimica Acta 91 (2013) 246252

1.2
1.0

F(R)

0.8

3
2

0.6

0.4

4
0.2
0.0
400

1
420

440

460

480

500

520

wavelength / nm
Fig. 2. Absorption spectra of CdSZnS composite semiconductor nanoparticles
deposited on nanocrystalline TiO2 by the SILAR method at various combinations:
(1) 100% Zn; (2) 75%Zn25%Cd; (3) 50%Zn50%Cd; (4) 25%Zn75%Cd; and (5) 100%
Cd. Spectra were recorded against nanocrystalline TiO2 lm as reference.

249

coating. In the high magnication image of Fig. 3a, one can distinguish the big blocks of FTO covered with Pt nanoparticles [25]
(cf also image of sputtered Pt, shown in Ref. [16]). In the second
case, a CoS lm was obtained by potentiodynamic electrodeposition. The image of Fig. 3b reveals a rough nanostructure similar to
that obtained in a previous work [16] by the same technique. Lin
et al. [16] found that the number of deposition cycles affects lm
structure. 5 cycles have presently been applied in order to obtain
the rough nanostructure of Fig. 3b. Finally, Fig. 3c shows the image
of a CuS lm deposited by SILAR, which also presents a rough nanostructure but very different from that of CoS. It seems that what
denes the CuS nanostructure is not the deposition technique but
the material itself. Indeed, plain CuS and CoSCuS combinations
have also been synthesized by potentiodynamic electrodeposition
where the aspect presented by Fig. 3c prevailed, thus showing that
the material and not the technique denes this aspect.
Both CoS and CuS were studied by XRD to determine their crystallinity. Only CuS gave a detectable signal. The corresponding XRD
spectrum is shown in Fig. 4. The size of CuS nanoparticles, as determined by the Scherrer formula, was approximately 19 nm.

3.3. Electrochemical characterization of the counter electrodes

3.2. Structural characteristics of the counter electrodes
Three main types of counter electrodes have been studied. Their
synthesis is detailed in Section 2. The FE-SEM images of the corresponding electrocatalytic lms are shown in Fig. 3. In the rst
case, Pt nanoparticles were deposited on an FTO electrode by spin

The three counter electrodes described in Section 3.2 were characterized by electrochemical impedance spectroscopy (EIS) using
symmetric cells and the same electrolyte as the one lling the solar
cells. Fig. 5 shows Nyquist plots for the three counter electrodes.
All presented a single semicircle. By proper tting of the diagrams
with simple electrical equivalent circuits, the following parameters

Fig. 3. FE-SEM images of various electrocatalysts on FTO electrodes: (a) Pt nanoparticles; (b) CoS; and (c) CuS. The corresponding scale bar is: (a) 20 nm; (b) 1 m; and (c)
200 nm.

250

N. Balis et al. / Electrochimica Acta 91 (2013) 246252

Intensity / a.u.

CuS

30

40

50

60

2 degree
Fig. 4. XRD spectrum of CuS nanoparticles deposited on an FTO electrode by the
SILAR method.

Fig. 6. Current density vs. potential curves for solar cells made with various
photoanodes: (1) CdSe@CdS@nc-TiO2 /FTO; (2) CdSe@CdS(75%)ZnS(25%)@ncTiO2 /FTO; (35) ZnS@CdSe@CdS(75%)ZnS(25%)@nc-TiO2 /FTO. Curves (13) correspond to cells using Pt/FTO counter electrodes curve (4) CoS/FTO and (5) CuS/FTO.

3.4. Currentelectric potential characteristics of solar cells made

with the above photoanodes and counter electrodes

Fig. 5. EIS diagrams for three symmetric cells made of FTO electrodes with the following electrocatalysts: (1) Pt nanoparticles; (2) CoS; and (3) CuS. All symmetric
cells contained 1 mol dm3 Na2 S and 1 mol dm3 S aqueous electrolyte. The active
area of each electrode was 1.5 cm 1.5 cm and the distance between the electrodes
was 1 cm. The frequency range was 100 kHz100 mHz. Insert: Magnication of the
horizontal axis revealing curve 3, which corresponds to the shorter charge transfer
resistance.

could be easily determined and they are listed in Table 1. The second column shows the values of the contact resistance Rs , which
also includes the sheet resistance of the electrodes themselves. Rs
values were relatively small. Their variations reect the quality of
the ohmic contact with the electrodes, which was the best in the
case of metal (Pt) nanoparticles and worse (but not very different) in the case of metal suldes. Charge-transfer resistance Rct
at the electrode/electrolyte interface greatly varied from one electrode to the other. The highest resistance was recorded with Pt/FTO
while it was an order of magnitude smaller in the case of CoS and
still one order of magnitude smaller in the case of CuS. These data
show in a rather dramatic manner and in accordance with literature
[7,15,16,22,26,27] that Pt is not a good choice when used with polysulde electrolytes while CuS is the material offering the smallest
charge-transfer resistance and it is expected to offer the best solar
cell functionality, as it is veried in the next section.

Table 1
Data derived by EIS analysis of three symmetric cells made of FTO electrodes with
various electrocatalysts.
Electrocatalyst

Rs (Ohm cm2 )

Rct (Ohm cm2 )

Pt
CoS
CuS

13
18
19

560
48
6

The purpose of the present work is to show that the combination

of various semiconductor quantum dots and the use of metal suldes as electrocatalyst on the counter electrode can offer solar cells
with appreciable efciency. Indeed, the JE plots of Fig. 6 and the data
of Table 2 show that an efciency of around 2.7% is easily obtained
by an optimized combination of these materials. One striking result
is the importance of the presence of Zn in the bottom layer of CdS.
The efciency of the cell almost tripled when we added Zn in the
precursor solution used for the bottom SILAR deposition of QDs
on nc-TiO2 . Improvement of efciency was previously observed by
studying photoactivated fuel cells employing a photoanode made
of ZnSCdS QDs deposited on nanocrystalline titania [14]. In these
cells, the electrolyte was NaOH containing ethanol as fuel. The cell
run by photocatalytic oxidation of ethanol, sensitized by the QD
sensitizers. It was then observed that a mixture of 25% ZnS with
75% CdS makes a more efcient photocatalyst than pure CdS [14].
This result was attributed both to the suppression of electronhole
recombination and to an increase of the oxidative power of the photocatalyst in the presence of ZnS. We believe that similar reasoning
holds true in the present case. The addition of a limited percentage
of ZnS (i.e. 25%) does not greatly affect the light absorbance range
of the ZnSCdS mixture. Thus in Fig. 2, it is seen that the presence of
25% Zn had a minor effect on the blue shift of the absorption spectrum (cf. curves 4 and 5 of Fig. 2). When 25% ZnS was combined with
75% CdS, it offered a bottom QD layer, which created the seeds that
attracted a substantial amount of CdSe and nally of ZnS on top, as
seen in Fig. 1 (curves 4 and 5). On the contrary, absence of this bottom layer resulted in a meager quantity of CdSe on nc-TiO2 (curve
6). The mixture of semiconductors apparently assists electronhole
separation while the high oxidative power of the ZnS valence band
facilitates rapid hole transfer to the surrounding species, which
happen to have favorably located energy levels for hole transfer.
Indeed, as seen in Fig. 7 showing some characteristic energy levels, with the exception of titania, ZnS possesses the most oxidative
valence band thus enhancing the oxidative power of the ZnSCdS
mixture. The positioning of energy levels in Fig. 7 is expected in
bulk. When the nanoparticles come in contact, Fermi level alignment [11] will replace energy levels, particularly in the case of CdSe,
which moves to more negative potentials, thus allowing for cascade
charge transfer [11].
Equally impressive was the efciency increase when an additional ZnS layer was put on the top. The benecial role of the
top ZnS layer has been observed and reported in several previous
works [4,12,22,23]. The top ZnS layer passivates surface states of the
underlying semiconductors while it prevents electron leakage from

N. Balis et al. / Electrochimica Acta 91 (2013) 246252

251

Table 2
Short circuit current density (Jsc ), open circuit potential (Eoc ), ll factor (FF) and efciency data of cells made of a few different photoanodes and counter electrodes.
Photoanode

Electrocatalyst

Jsc (mA cm2 )

Eoc (V)

FF

 (%)

CdSe@CdS@nc-TiO2 /FTO
CdSe@CdS(75%)ZnS(25%)@nc-TiO2 /FTO
ZnS@CdSe@CdS(75%)ZnS(25%)@nc-TiO2 /FTO
//
//

Pt/FTO
Pt/FTO
Pt/FTO
CoS/FTO
CuS/FTO

5.2
7.3
9.1
11.2
13.9

0.32
0.43
0.47
0.52
0.55

0.31
0.39
0.35
0.32
0.35

0.51
1.2
1.6
1.9
2.7

80

60

IPCE / %

3
40
2
20

0
350

Absorbance

titania to the electrolyte. Indeed, the high-lying conduction band of

ZnS (cf. Fig. 7) is expected to block electron leakage. This has been
electrochemically demonstrated by Guijarro et al. [12]. Nevertheless, the same authors consider passivation of surface states as the
most important reason of efciency increase [12].
An equally important nding of the present work was that all
three quantum dot layers, i.e. ZnS@CdSe@ZnSCdS, are necessary
in order to achieve the recorded maximum efciency. Thus in the
absence of CdSe or in the absence of ZnSCdS the efciency dropped
below 1%. Low efciency in the absence of the ZnSCdS layer is
among other reasons also due to the meager CdSe layer formation
(curve 6 of Fig. 1). All QD species applied on the photoanode electrode function as sensitizers of titania. This is seen by comparing
the absorption spectrum of the combined layers (curve 5 of Fig. 1)
with the corresponding IPCE% spectrum shown in Fig. 8. The two
curves are equivalent and show that all QD species are involved in
the sensitization process.
Fig. 5 and Table 2 show that the maximum efciency reached in
the present work, i.e. 2.7% was obtained with CuS on the counter
electrode. Metal sulde electrocatalysts, i.e. CoS, CuS and their
mixtures gave higher current densities than Pt. On the contrary
open-circuit voltage values were practically not affected by the
electrocatalyst. The major problem encountered in the present
work was with the value of the ll factor (FF). It remained below

400

450

500

550

600

650

0
700

wavelength / nm
Fig. 8. IPCE% spectrum (1) and absorption spectrum (2) for a cell made with a
ZnS@CdSe@ZnSCdS@nc-TiO2 /FTO photoanode and a CuS/FTO counter electrode.

0.4 and this limited the overall efciency, even though, the current
densities presently recorded were high. The search for a higher FF
is an open question and has occupied many other researchers. It is
believed that higher FFs will be obtained with even better electrocatalysts and more functional counter electrodes. Thus higher FFs
have been obtained with PbS/Pb [15], a Cu2 Sgraphene composite [5,10,18] and carbon nanostructures [26,27]. All these different
possibilities are on stage and they are currently studied in our laboratories.
4. Conclusions
QDSSCs have been constructed and optimized by combining
nc-TiO2 with ZnS, CdS and CdSe QDs on the anode electrode. Pt,
CoS or CuS were used as electrocatalysts on counter electrodes
in combination with a polysulde electrolyte. The maximum solar
conversion efciency of 2.7% was obtained with a CuS counter electrode. The most important nding of this work is the importance of
the rst QD layer deposited on the mesoporous titania lm, which
affected the quantity and the quality of the subsequent QD layers and the ensuing cell efciency. Thus the rst layer consisted
of 75%CdS25%ZnS, deposited by the SILAR method. High current
densities were obtained with all cells having optimized anode electrodes. Among them, the highest currents were obtained with metal
sulde electrocatalysts. Electrochemical impedance spectroscopy
showed that the lowest charge transfer resistance was recorded
with metal suldes and this directly reected on the electric current
values. Finally, it must be stressed that the methods of metal sulde
electrocatalyst deposition in the present work were easy one-step
procedures that provide well shaped nanostructured materials.

Fig. 7. Approximate energy levels for a few semiconductors and the polysulde
redox couple. The positioning of the levels refers to values of isolated nanocrystallites. When the nanoparticles come in contact, Fermi level alignment [11] is expected
to approximately locate CdSe to a higher level (more negative potentials, red frame).
This will allow cascade charge transfer [11]. Values are adapted to data from Refs.
[11,28,29] and correspond to pH 7.0. (For interpretation of the references to color
in this gure legend, the reader is referred to the web version of this article.)

Acknowledgments
This research has been co-nanced by the European Union
(European Social Fund ESF) and Greek national funds through
the Operational Program Education and Lifelong Learning of
the National Strategic Reference Framework (NSRF) Research

252

N. Balis et al. / Electrochimica Acta 91 (2013) 246252

Funding Program: Thales, MIS377756. Investing in knowledge

society through the European Social Fund.
References
[1] M.P. Dare-Edwards, J.B. Goodenough, A. Hamnett, K.R. Seddon, D.R. Wright,
Sensitisation of semiconducting electrodes with ruthenium-based dyes, Faraday Discussions of the Chemical Society 70 (1980) 285.
[2] B. OReagan, M. Grtzel, A low-cost, high-efciency solar cell based on dyesensitized colloidal TiO2 lms, Nature 353 (1991) 737.
[3] P.P. Boix, G. Larramona, A. Jacob, B. Delatouche, I. Mora-Ser, J. Bisquert,
Hole transport and recombination in all-solid Sb2 S3 -sensitized TiO2 solar cells
using CuSCN as hole transporter, Journal of Physical Chemistry C 116 (2012)
1579.
[4] Q. Shen, J. Kobayashi, L.J. Diguna, T. Toyoda, Effect of ZnS coating on the photovoltaic properties of CdSe quantum dot-sensitized solar cells, Journal of Applied
Physics 103 (2008) 084304.
[5] M.P. Genovese, I.V. Lightcap, P.V. Kamat, Sun-believable solar paint. A transformative one-step approach for designing nanocrystalline solar cells, ACS Nano
6 (2012) 865.
[6] S. Rhle, M. Shalom, A. Zaban, Quantum-Dot-Sensitized Solar Cells,
Chem.Phys.Chem. 11 (2010) 2290.
[7] I. Mora-Ser, J. Bisquert, Breakthroughs in the development of SemiConductor Sensitized Solar Cells, Journal of Physical Chemistry Letters 1 (2010)
3046.
[8] S. Gorer, G. Hodes, Quantum size effects in the study of chemical solution deposition mechanisms of semiconductor lms, Journal of Physical Chemistry 98
(1994) 5338.
[9] D.R. Pernik, K. Tvrdy, J.G. Radich, P.V. Kamat, Tracking the adsorption and
electron injection rates of CdSe quantum dots on TiO2 : Linked versus direct
attachment, Journal of Physical Chemistry C 115 (2011) 13511.
[10] P.K. Santra, P.V. Kamat, Mn-Doped Quantum Dot Sensitized Solar cells: A strategy to Boost Efciency over 5%, Journal of the American Chemical Society 134
(2012) 2508.
[11] Y.-L. Lee, Y.-S. Lo, Highly efcient quantum-dot-sensitized solar cell based on
co-sensitization of CdS/CdSe, Advanced Functional Materials 19 (2009) 604.
Q. Shen, T. Toyoda, T. Lana-Villarreal, R. Gomez,
[12] N. Guijarro, J.M. Campina,
Uncovering the role of the ZnS treatment in the performance of quantum dot
sensitized solar cells, Physical Chemistry Chemical Physics 13 (2011) 12024.
[13] O. Niitso, S.K. Sarkar, C. Pejoux, S. Rhle, D. Cahen, G. Hodes, Chemical bath
deposited CdS/CdSe-sensitized porous TiO2 solar cells, Journal of Photochemistry and Photobiology A: Chemistry 181 (2006) 306.
[14] M. Antoniadou, V.M. Daskalaki, N. Balis, D.I. Kondarides, C. Kordulis, P.
Lianos, Photocatalysis and photoelectrocatalysis using (CdS-ZnS)/TiO2 combined photocatalysts, Applied Catalysis B: Environmental 107 (2011) 188.
[15] Z. Tachan, M. Shalom, I. Hod, S. Rhle, S. Tirosh, A. Zaban, PbS as a highly catalytic counter electrode for polysulde-based quantum dot solar cells, Journal
of Physical Chemistry C 115 (2011) 6162.

[16] J.-Y. Lin, J.J-H. Liao, S.-W. Chou, Cathodic electrodeposition of highly porous
cobalt sulde counter electrodes for dye-sensitized solar cells, Electrochimica
Acta 56 (2011) 8818.
[17] Z. Yang, C.-Y. Chen, C.-W. Liu, C.-L. Li, H.-T. Chang, Quantum DotSensitized
Solar Cells Featuring CuS/CoS Electrodes Provide 4.1% Efciency, Advanced
Energy Materials 2 (2011) 259.
[18] J.G. Radich, R. Dwyer, P.V. Kamat, Cu2 S Reduced Graphene Oxide Composite for
High-Efciency Quantum Dot Solar Cells. Overcoming the Redox Limitations of
S-2(-) /S-n(2-) at the Counter Electrode, Journal of Physical Chemistry Letters
2 (2011) 2453.
[19] N. Balis, V. Dracopoulos, E. Stathatos, N. Boukos, P. Lianos, A solid state hybrid
solar cell made of nc-TiO2 , CdS quantum dots and P3HT with 2-amino-1methylbenzimidazole as interface modier, Journal of Physical Chemistry C
115 (2011) 10911.
[20] S. Ito, P. Chen, P. Comte, M.K. Nazeeruddin, P. Liska, P. Pechy, M. Gratzel, Fabrication of screen-printing pastes from TiO2 powders for dye-sensitised solar
cells, Progress in Photovoltaics: Research and Applications 15 (2007) 603.
[21] H.M. Pathan, C.D. Lokhande, Deposition of metal chalcogenide thin lms by
successive ionic layer adsorption and reaction (SILAR) method, Bulletin of
Materials Science 27 (2004) 85.
[22] S. Gimenez, I. Mora-Sero, L. Macor, N. Guijarro, T. Lana-Villareal, R. Gomez,
L.J. Diguna, Q. Shen, T. Toyoda, J. Bisquert, Improving the performance
of colloidal quantum-dot-sensitized solar cells, Nanotechnology 20 (2009)
295204.
[23] E.M. Barea, M. Shalom, S. Gimenez, I. Hod, I. Mora-Sero, A. Zaban, J. Bisquert,
Design of injection and recombination in quantum dot sensitized solar cells,
Journal of the American Chemical Society 132 (2010) 6834.
[24] T.-L. Li, Y.-L. Lee, H. Teng, High-performance quantum dot-sensitized solar cells
based on sensitization with CuInS 2 quantum dots/CdS heterostructure, Energy
and Environmental Science 5 (2012) 5315.
[25] N. Balis, T. Makris, V. Dracopoulos, T. Stergiopoulos, P. Lianos, Quasi-Solid-State
Dye-Sensitized Solar Cells made with poly(3,4-ethylenedioxythiophene)functionalized counter-electrodes, Journal of Power Sources 203 (2012) 302.
[26] S.Q. Fan, B. Fang, J.H. Kim, J.-J. Kim, J.-S. Yu, J. Ko, Hierarchical nanostructured spherical carbon with hollow core/mesoporous shell as a highly efcient
counter electrode in CdSe quantum-dot-sensitized solar cells, Applied Physics
Letters 96 (2010) 063501.
[27] B. Fang, M. Kim, S.-Q. Fan, J.H. Kim, D.P. Wilkingson, J. Ko, J.-S. Yu, Facile synthesis
of open mesoporous carbon nanobers with tailored nanostructure as a highly
efcient counter electrode in CdSe quantum-dot-sensitized solar cells, Journal
of Materials Chemistry 21 (2011) 8742.
[28] I. Mora-Sero, S. Gimenez, T. Moehl, F. Fabregat-Santiago, L. Lana-Villareal, R.
Gomez, J. Bisquert, Factors determining the photovoltaic performance of a CdSe
quantum dot sensitized solar cell: The role of the linker molecule and of the
counter electrode, Nanotechnology 19 (2008) 424007.
[29] P. Lianos, Production of electricity and hydrogen by photocatalytic degradation
of organic wastes in a photoelectrochemical cell: The concept of the Photofuelcell: A review of a re-emerging research eld, Journal of Hazardous Materials
185 (2011) 575.