Materials Chemistry and Physics 117 (2009) 2628

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Materials Chemistry and Physics
j our nal homepage: www. el sevi er . com/ l ocat e/ mat chemphys
Materials science communication
CdS quantum dots sensitized TiO
2
photoelectrodes
K. Prabakar

, Hyunwoong Seo, Minkyu Son, Heeje Kim

Pusan National University, Department of Electrical Engineering, San 30, Jangjeong-Dong, Gumjeong-Ku, Busan 609 735, South Korea
a r t i c l e i n f o
Article history:
Received 10 February 2009
Received in revised form 28 May 2009
Accepted 29 May 2009
Keywords:
Semiconductors
Thin lms
Electron microscopy
Electrical characterization
a b s t r a c t
The CdS quantum dots were deposited on nanoporous TiO
2
by chemical bath deposition technique to
absorb the visible light in the longer wavelength region and are used as photo electrode in the dye sen-
sitized solar cells (DSSC). The CdS quantum dots deposited on nanoporous TiO
2
at 1min deposition time
showed improved short circuit current density (J
sc
) and open circuit voltage (V
oc
) than lms deposited
at higher dipping times. The increase in the CdS dipping time reduces the amount of dye adsorbed on
nanoporous TiO
2
which limits the redox reactions in the electrolyte.
2009 Elsevier B.V. All rights reserved.
1. Introduction
Dyesensitizedsolar cells (DSSC) basedonthephotosensitization
of nanocrystalline TiO
2
semiconductor electrodes by adsorbeddyes
have been studied extensively with respect to improvements of the
power conversion efciencies and relatively inexpensive fabrica-
tion procedure compared with conventional inorganic solar cells
[13]. The efciency of a DSSC is mainly determined by the short
circuit current density (J
sc
) and the open circuit voltage (V
oc
). The
former depends onthe light harvestingpropertyof the dye attached
to the surface of the TiO
2
nanocrystallite [4] and the later is the sub-
ject of optimization studies by means of molecular engineering of
the semiconductor electrolyte interface [5]. The short circuit cur-
rent density could be improved by the sensitization of nanoporous
TiO
2
using CdS [68], CdSe [9], and PbSe [10] nanoparticle quan-
tum dots owing to the high absorption cross-section and ability to
tune the particles sizes withinthe visible andnear-infraredspectral
range. Another advantage of the sensitizers over conventional dyes
is their high extinction coefcient, which is known to reduce the
dark current and increase the overall efciency of a solar cell [11].
However, the solar cells energy conversion efciency is limited due
to the difculty of assembling the sensitizers into the nanoporous
TiO
2
matrix to obtain a well-covered monolayer and the charge
carrier injection into the sensitizer fromthe excited dyes is limited.
Chemical bath deposition (CBD) is the most common method used
for the synthesis of the CdS on TiO
2
[12]. In the CBD process used
to synthesize the semiconductor nanoparticle quantum dots onto
nanoporous TiO
2
lms, the TiO
2
lms were dipped into aqueous
solutions of the reactants. In the present study, a coating of CdS

Corresponding author. Tel.: +82 51 510 7334; fax: +82 51 513 0212.
E-mail address: prabakar@pusan.ac.kr (K. Prabakar).
absorber layer thicknesses of 40100nm were deposited by our
CBD method on lling the pores and report our results by means
of a cell conguration made with a nanoporous TiO
2
lm, a thin
coating of CdS absorber.
2. Experimental
Fluorine doped tin oxide (FTO) having sheet resistances of 10/square was used
tomakeboththeworkingandcounter electrodes. Theworkingphotoelectrodeof the
DSSC was made by pasting 5mmby 5mm(0.25cm
2
active area) nanoporous TiO
2
of
about 20m thicknesses on FTO by doctor blade method followed by annealing at
450

Cfor 30minand the nal thickness was 8mafter the solvent evaporation. The
CdSlms of different thicknesses weredepositedontheabovenanoporous TiO
2
elec-
trodes byour earlier method[7]. Dyesensitizationof theCdScoatednanoporous TiO
2
electrodes was carried out by soaking in N719 dye (Ruthenium 535 bis-TBA cisbis
(isothiocyanato) bis (2,2

-bipyridyl-4,4

-dicarboxylato)-ruthenium(II) bis-tetrabutyl
ammonium) purchased fromSolaronix dissolved in anhydrous ethanol solution. On
counter electrode, platinum of about 120nm thicknesses used to be the catalysis
were sputtered by radio frequency (RF) sputtering at a RF power of 150W and
a sputtering pressure of 2.810
2
Torr. Finally, DSSC was completed by injecting
the electrolyte solution consisted of iodolyte AN-50 (iodide-based low viscosity
electrolyte with 50mM of tri-iodide in acetonitrile) through the counter electrode
pin-hole. Photo anode andcounter electrodes were sealedby using thermoplast hot-
melt sealing sheet of 60m thickness in order to avoid evaporation of electrolyte.
Field emission scanning electron microscopy (FE-SEM, S-4200, Hitachi) operated at
15kV was used to characterize the microstructure of the lms. The currentvoltage
characteristics of the DSSCs were performed under 1 sun illumination (AM 1.5G,
100mWcm
2
) with San Ei Electric (XES 301S, Japan) solar simulator having the
irradiance uniformity of 3% and Keithley 2400 source meter. The intensity of the
incident solar illumination was adjusted to 1 sun condition using AIST certied sil-
icon reference cell. In order to avoid the contribution from non-active area, shadow
mask with an aperture slightly larger than that of TiO
2
active layer was used on the
front side of DSSCs.
3. Results and discussion
The CdS lms deposited on FTOTiO
2
substrates were highly
adherent and yellowish orange in colour. Optical properties of CdS
0254-0584/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2009.05.056
K. Prabakar et al. / Materials Chemistry and Physics 117 (2009) 2628 27
Fig. 1. UVvis absorbance spectra of CdS lms deposited on TiO
2
at (A) 1min, (B)
2min, (C) 5min, and (D) 10min dipping time.
lms were measured by UVvis spectrophotometer in the wave-
length range of 350550nm to evaluate the amount of the CdS
incorporated in a TiO
2
lm. The variation of the absorbance spec-
tra with the CBD dipping time is shown in Fig. 1 for the lms
depositedonthe FTOTiO
2
nanoporous lms sinteredat 450

C. The
absorbance spectra increase with an increase of CBD dipping time,
indicating an increased adsorption amount of CdS. Furthermore,
it is seen that the absorption edge shifts towards longer wave-
length with increasing dipping times implies the growth of the CdS
nanoparticles [12]. The adsorption amount of CdS is increased until
5min dipping time; however, it is saturated when deposited more
than 5min. It indicates that up to 5min dipping time, higher sur-
face area is available for the adsorption, attributable to the better
penetration and wetting of the solution in the nanoporous TiO
2
matrix. The CdS lms could be formed well into the inner region
of the nanoporous lm, leading to a better-covered layer on the
TiO
2
surface during the rst 5min dipping time. If the dipping
time was more than 5min, the uncovered surface area of the TiO
2
lm decreases as and hence the amount of CdS absorbed is almost
saturated. Fig. 2 shows the SEM images of the (A) doctor blade
coated TiO
2
on FTO substrates and CdS lms deposited on TiO
2
at
(B) 1, (C) 2 and (D) 10min dipping times respectively. The images
of TiO
2
lms before and after 1min dipping of CdS lm deposi-
tion showed the presence of nanoparticles evenly distributed all
over the nanoporous TiO
2
crystals and the overall surface area
has remarkably increased without affecting the surface nature.
However, as the CdS dipping time was more than 1min, the TiO
2
nanopores are completely lled by the CdS deposition and form a
chain-like continuous surface structure after 2min deposition. At
theCdSdippingtimeof 10min, cracks areformedonthesurfaceand
the nanoporous structures of the TiO
2
are completely destroyed.
The photocurrentvoltage (IV) characteristics of the DSSCs
prepared by the standard Gratzel cells (S) and CdS-sensitized at dif-
ferent deposition times on TiO
2
photoelectrodes (AD) are shown
in Fig. 3. It is observed contrary to the expectation that, CdS sensi-
tization as wells as dipping time decreases the overall conversion
efciencies of the dye sensitized solar cells. The higher J
sc
and ll
factor values for the CdS sensitized cells were obtained in which
the CdS depositiontimes were 1min. It indicates that as the dipping
time increases more than 1min, CdS thickness increases along with
complete coverage on the TiO
2
surface and higher amount of CdS
incorporated on the TiO
2
lm, which in turn reduces the amount of
dye adsorbed on the TiO
2
surfaces and hence limits the light har-
vesting as well as the redox reaction. As a function of CBD dipping
time, the maximum overall efciency was for 1min (A), and then
decreases for further increase in the dipping time. The decrease in
efciency is mainly caused by the reduction of the ll factor due to
the blocking of the nanopores by the additional loading of the CdS
as is in agreement with the earlier report [13]. Even though 1 and
2min CdS dipped cells showed improved efciencies, the overall
Fig. 2. SEM images of (A) nanoporous TiO
2
pastes, CdS lms deposited on nanoporous TiO
2
at (B) 1min, (C) 2min and (D) 10min dipping time.
28 K. Prabakar et al. / Materials Chemistry and Physics 117 (2009) 2628
Fig. 3. IV characterization of (S) standard Gratzel cell and CdS lms sensitized on
TiO
2
at (A) 1min, (B) 2min, (C) 5min and (D) 10min dipping time.
performance of the cells were not increased signicantly. It may
be because of the limitation by the diffusion length of electrons
along the longer pathways of the CdS phase. Another reason could
be the increase of electron recombination at the interface between
the nanoporous TiO
2
and CdS lms due to the increase of the inter-
face pathway along the lm and the open circuit voltage is greatly
reduced [14]. It is evidenced from SEM measurement that at 1min
CdS dipped lms, higher surface area was evidenced and further
increase in the dipping time reduces the surface to be available
for the dyes adsorption. At 10min dipping time (D), the cells did
not showstandard IV characterization because of the poor surface
nature. From the experimental evidence, it is proposed that CdS
sensitization should be done during the soaking of TiO
2
lms in the
dyes to improve the cell efciencies. If the CdS are deposited prior
to soaking, less amount of dyes are adsorbed over TiO
2
surfaces and
the over all cell performance would be decreased due to either the
increased surface recombination or the reduced redox reaction.
4. Conclusion
In order to increase the incident photon to current conver-
sion efciency (IPCE) of the dye sensitized solar cells, the effects
of CdS as sensitizer layer on TiO
2
have been investigated. With
increase in the CdS lms thickness over nanoporous TiO
2
, the
short circuit current density as well as the open circuit voltage
are decreased. The decrease in efciency is mainly caused by the
reduction of the ll factor due to the blocking of the nanopores
by the additional loading of the CdS. Therefore, it is suggested
that CdS lms deposition should be carried while the nanoporous
TiO
2
were soaked in the dye in order to have optimized amount
of the sensitizer as well the dye to increase the redox reac-
tion.
Acknowledgements
The author K. Prabakar would like to thank the Pusan National
University for the nancial support and the grand-in-aid for basic
research. The authors are grateful to Professor Young-Son Choe for
the IV characterization.
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