ARTICLE IN PRESS

Solar Energy Materials & Solar Cells 88 (2005) 341–350

www.elsevier.com/locate/solmat

Enhancement of photovoltage of dye-sensitized

solid-state solar cells by introducing
high-band-gap oxide layers
J. Bandara, H.C. Weerasinghe
Institute of Fundamental Studies, Department of Photochemistry, Hantana Road, Kandy, Sri Lanka
Available online 18 January 2005

Abstract

Electrodes constructed using nanocrystalline TiO2 particulates for dye-sensitized solid-state

solar cells (SS-DSSCs) showed open-circuit voltage (Voc) in the 500–600 mV range, which is
less than the theoretical expected value. Incorporation of high-band-gap semiconducting
oxides with a flatband potential higher than TiO2, such as SrTiO3 or ZnO, results in a
dramatic increase in Voc of SS-DSSC as compared to porous TiO2 nanocrystalline films. The
observed photovoltage difference could be correlated to the difference in the flatband potential
values of the respective oxides and shift of the flatband potentials of the oxide films. Hence,
this method could be used to enhance the Voc and overall cell performance of SS-DSSC.
r 2004 Elsevier B.V. All rights reserved.

Keywords: Dye sensitization; Solid-state solar cell; TiO2; SrTiO3; ZnO; SnO2

1. Introduction

Solid-state dye-sensitized solar cells (SS-DSSCs) constructed using nanocrystalline

films of TiO2 and solid hole collectors are gaining recognition as alternative to the
dye-sensitized liquid junction cells for photovoltaic devices for conversion of solar
energy [1–15]. In this regard, efforts have been made to optimize solar cell

Corresponding author. Tel.: +94 81 2232002; fax: +94 81 2232131.

E-mail address: jayasundera@yahoo.com (J. Bandara).

0927-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2004.11.009
 ARTICLE IN PRESS
342 J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350

performance by using inorganic p-type semiconductors [1,2], p-type oxide semi-

conductors [12] and organic hole transport materials [3,4]. Tennakone et al. [1,2,9]
and Gratzel et al. [10] successfully employed SS-DSSCs using p-type semiconductors
despite the fact that p-type semiconductors often met problems of short-circuit and
mass transport limitation of ions resulting in low conversion efficiency compared
with the liquid version.
The SS-DSSC reported to date exhibit low short-circuit photocurrent (Isc)
because of the presence of shunt paths resulting in low conversion efficiencies
compared with the liquid version. Also, the open-circuit voltage (Voc) of the SS-
DSSC is lower than the theoretical possible value partly because of shunt paths.
Additionally, the following factors also contribute to the low Voc for SS-DSSC,
rather than electrolyte-based DSSC: (a) the rapid recombination of photogenerated
electrons from TiO2 with holes in the hole-conductor; (b) the less favourable
equlibrium Fermi-level position in TiO2 [16]. Attempts have been made to overcome
the short-circuit problem and charge recombination using different techniques, i.e.
by the insertion of oxide film and by the deposition of the organic layer onto spin-
coated TiO2 film, it has been shown that the shunt paths could be minimized
[4,17–19]. Also, the electrodes for DSSC have been prepared using a mixture of TiO2
powder and Ti-isopropoxide [2,9] to minimize the short-circuit paths. Thin films of
TiO2 have been coated on ITO-glass by spray pyrolysis to prevent escape of electrons
from the ITO substrate. However, the blocking layer which acts as a barrier for
short-circuit paths does not function as a blocking layer under open-circuit
conditions because of the rise of Fermi levels of the ITO and TiO2, resulting in
accumulation of the electrons at the surface of TiO2 blocking layer [20]. Therefore,
Voc is lower than the theoretical predicted value. The maximum photovoltage
reported for DSSC constructed using TiO2/dye/CuI is
600 mV and for TiO2/dye/
CuCNS, the photovoltage is 550 mV at one sun illumination. For the solar cell
constructed using hole transport material such as spiro-MeOTD, Kruger et al.
reported Voc of 500 nm. In most cases, when TiO2 is used as the electrode material,
the observed Voc varied between 500 and 600 mV which is far less than the
theoretical possible value.
The theoretical maximum Voc of DSSC could be correlated to the difference
in energy between Fermi level of the photoelectrode semiconducting oxide
and the redox potential of the electrolyte in PEC cells. It has been argued that the
differences in photovoltaic behaviour must arise from intrinsic difference between
these oxides and a strong correlation of flatband and Voc has been reported for solar
cells with an electrolyte [21], i.e. Voc of the PEC cells of ZnO, SrTiO3, Nb2O5
and SnO2 were 750, 750, 750 and 350 mV, respectively [22–24]. Therefore,
attempts have been made to increase Voc of PEC through flatband potential
engineering using high-band-gap semiconductors with high flatband potential
values. Therefore, in this work, we investigated the semiconducting materials
(ZnO, SrTiO3) with high-band-gap and high flatband potential values as electrode
materials as a mean of enhancing Voc of the SS-DSSC cells and the results were
compared with high-band-gap and low flatband potential value semiconducting
oxide (SnO2).
 ARTICLE IN PRESS
J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350 343

2. Experimental

ZnO, SrTiO3 and SnO2 electrodes were prepared on ITO glasses on which a
compact TiO2 barrier layer [12] was pre-deposited. SnO2 electrode was prepared
using 0.5 ml Alfa Aeser SnO2 colloid with CH3COOH and sprayed onto conducting
glass [25] followed by sintering at 450 1C. SnO2 electrodes were wiped off to remove
loosely bound SnO2 clusters. SrTiO3 and ZnO electrodes were prepared in a similar
manner. Respective oxides were mixed with CH3COOH in an agate motor and
applied on conducting glass by the doctor blade method. In certain cases, oxide
solutions were sprayed onto conducting glass. The oxide layers were sintered in air at
450 1C for 1 h. The porous TiO2 electrodes were prepared mixing 500 mg of Degussa
TiO2, 50 ml of conc. HNO3 and 2 ml of H2O in an agate motor and applied on
conducting glass by the doctor blade method [12].
The films were dyed keeping them immersed in a 5.0  104 M solution of
cis-bis(thiocyanate)bis(2,20 -bipyridyl 4,40 -dicarboxylate) ruthenium(II) in ethanol
for 6 h. CuI was prepared dissolving 1 g of CuI in 30 ml of acetonitrile [2] and
15 mg of triethylamine hydrothiocyanate (THT) was added. The dye-coated
plate was placed on a hot plate (
110 1C) and the CuI solution was lightly spread
over the dyed surface. A Pt-sputtered conducting tin oxide glass plate pressed into
the CuI surface served as the back contact. The energy conversion efficiency was
measured under simulated sunlight (AM 1.5, 1000 W m2 illumination) and the
incident photons to photocurrent conversion efficiency (IPCE) were measured using
a solar cell evaluation system. Rectification curves in the dark were recorded using
dye after coating of CuI. Electron micrographs are taken with a LEO-1400 model
scanning electron microscope (SEM). The I– V characteristics of the cells were
recorded using a solar cell evaluation system (JASCO, CEP-25BX). The flatband
potential of the oxides were determined from Mott–Schottky plots (i.e. a plot of C2
vs. V, where C was the capacitance and V was the potential across the space charge
layer) and on-set potential methods [26,27]. To measure the capacitance, oxide-
coated plates were immersed in Na2SO4 solution and the capacitances were
measured as a function of the potential across the space charge layer at frequencies
of 500 Hz and 1 kHz.

3. Results and discussion

The SEM image of TiO2 compact layer is shown in Fig. 1. The formation
of big TiO2 cluster size ranging from 2 to 3 mm is clearly visible. The TiO2 clusters
look amorphous and XRD analysis (not shown) confirmed the amorphous
nature of TiO2 clusters. The thickness of the TiO2 film calculated from the
cross-section of TiO2 film is
2 mm. The SEM images of porous ZnO, SrTiO3, SnO2
and TiO2 layers coated on the barrier TiO2 layer are shown in Fig. 2a–d, respectively.
In each case, the dense TiO2 layer is fully covered with the spherical shaped
particles and some aggregates of respective oxides. Particle size analysis by
SEM images revealed that particle sizes of ZnO and SrTiO3 are bigger than
 ARTICLE IN PRESS
344 J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350

Fig. 1. SEM image of TiO2 barrier film with a cross-sectional thickness of 3 mm.

Fig. 2. SEM images of (a) ZnO, (b) SrTiO3, (c) SnO2 and (d) TiO2 porous films.
 ARTICLE IN PRESS
J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350 345

those of SnO2 and TiO2. Also, well-crystalline ZnO and SrTiO3 particles are clearly
noticeable compared to less-crystalline SnO2 and TiO2 particles. Further, it is clear
that thin films of SnO2 and TiO2 are densely and uniformly formed on the barrier
layer compared to less dense and non-uniform ZnO and SrTiO3 thin films. The
formation of densely and uniformly formed thin films probably could be due to small
particle sizes of SnO2 and TiO2.
The major task of this investigation is to find a solution for low Voc of the SS-
DSSC, which arises mainly due to less favourable equilibrium Fermi-level position in
TiO2, by using high-band-gap oxide materials with high flatband potential values
replacing the TiO2 layer. Performances of the solar cells fabricated using different
oxides were tested by IV, rectification and flatband measurements. IV characteristics
of the solar cells constructed with ZnO, SrTiO3 and SnO2 on a compact layer, Ru-
bypridyal dye as light absorbing unit and CuI as hole transport material (MO/dye/
CuI) under 1.5 AM illumination are shown in Fig. 3. For comparison, IV
characteristics of the solar cell prepared using a porous TiO2 layer on a compact
layer is also shown. The Isc, Voc and calculated fill factors and efficiencies measured
under the same conditions are shown in Table 1. The solar cell made with a porous
TiO2 layer (TiO2/dye/CuI cell) generated a Isc of 6 mA cm2 and Voc of
500 mV at
the illumination intensity of 1000 W m2. The solar cell constructed with ZnO and

Fig. 3. I– V characteristics of SS-DSSC made from (a) ZnO/dye/CuI, (b) SrTiO3/dye/CuI, (c) SnO2/dye/
CuI and (d) TiO2/dye/CuI at an illumination intensity of 1000 W m2 1.5 AM.
 ARTICLE IN PRESS
346 J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350

Table 1
Solar cell performance of the cell type MO/dye/CuI at illumination intensity of 1000 W m2 1.5 AM
(MO–TiO2, ZnO, SrTiO3 and SnO2)

Electrode Voc (mV) Isc (mA cm2) FF (%) Effi. (%)

TiO2 500 6.0 58 1.7

ZnO 760 4.7 57 1.9
SrTiO3 700 2.0 56 0.7
SnO2 259 2.1 37 0.2

SrTiO3 electrode materials showed Voc of 760 and 700 mV, respectively, while with
SnO2 electrode, the observed Voc was 250 mV. However, lower short-circuit currents
(Isc) were noted for ZnO (4.7 mA cm2) and SrTiO3 (2.0 mA cm2) cells than those of
TiO2 electrodes which could be due to differences in dye adsorption amounts, i.e.
dye-adsorbed amounts were 5.12  1015, 4.88  1015 and 5.82  1015 molecules cm2,
respectively, for ZnO, SrTiO3 and TiO2. Similar fill factors were noticed for ZnO,
SrTiO3 and TiO2 cells but a lower fill factor was observed for SnO2 cells. Despite
high dye-adsorbed amount (5.78  1015) on SnO2 film, it showed very low Isc
(2.1 mA cm2) which will be discussed later.
Compared with the literature results and our own results, SS-DSSC fabricated
with TiO2 electrode showed Voc in the 500–600 mV range. From the results presented
in Table 1, measured Voc’s were roughly 150–200 mV higher for solar cells fabricated
using ZnO or SrTiO3 films than for solar cells fabricated using TiO2 films. However,
for solar cells constructed with SnO2 nanocrystalline film, lower Voc was noticed
than TiO2 electrode. Such a variation of Voc could arise due to differences in particle
size or surface area of the respective oxides [21], i.e. higher Voc could be observed
with the thin films prepared with smaller particle size materials. However, SEM
images shown in Fig. 2a–d for ZnO, SrTiO3, SnO2 and TiO2, respectively, and solar
cell performances shown in the Table 1 revealed contradictory results where lower
Voc’s were observed for smaller particle sizes of SnO2 and TiO2. Therefore, higher
Voc obtained for ZnO and SrTiO3 could not be assigned to their differences in
particle sizes. Thus, the differences in photovoltaic behaviour must arise from
intrinsic differences between TiO2 and respective oxides as explained by Gratzel et al.
[21] and this intrinsic difference could be correlated to flatband variation of the
semconducting oxides.
Flatband potentials of these oxides were measured by Mott–Schottky plots
and on-set potential methods [26,27] and the measured flatband values by
both methods were in good agreement. The calculated flatband values from the
above measurements are shown in Table 2. The flatband potentials of bare
and porous ZnO, SrTiO3, SnO2 and TiO2 materials are situated at 0.40, 0.30,
0.10 and 0.20 (vs. SCE at pH 5), respectively [28]. The measured flatband
potential of compact barrier TiO2 layer is situated at
0.10 eV. Coating of a
porous TiO2 layer on it results in a shift in flatband potential value to 0.35 eV.
The reported flatband potentials of ZnO and SrTiO3 are situated above the
 ARTICLE IN PRESS
J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350 347

Table 2
Measured flatband potentials of thin films of TiO2, ZnO, SrTiO3 and SnO2 on the TiO2 barrier layer

Semiconductor Measured flatband potential of Measured flatband potential of thin films of

bare oxide film (eV) (vs. SCE) oxides on the barrier layer (eV) (vs. SCE)

TiO2 0.20 0.35

ZnO 0.40 0.60
SrTiO3 0.30 0.60
SnO2 0.10 0.15

flatband potential of TiO2 while the flatband of SnO2 is situated below that of
TiO2. Coating of ZnO or SrTiO3 on the dense TiO2 barrier layer results in a
negative shift in flatband potential compared to that of TiO2 while for SnO2 a
positive shift of flatband potential is noticed at pH 5.0, i.e. flatband potential of
ZnO, SrTiO3 and SnO2 thin films coated on a barrier layer are 0.60, 0.60 and
0.15, respectively.
Voc of a PEC cell is equal to the difference in energy between the quasi-Fermi level
of the photoelectrode semiconductor oxide and the redox potential of the electrolyte
[21]. Similarly, Voc of SS-DSSC is equal to the energy difference in quasi-Fermi levels
of semiconductor oxide and the hole-conducting semiconductor. Schematic diagram
illustrating the energy-level diagram showing the relative positions of ZnO, SrTiO3,
SnO2, TiO2, dye and CuI are shown in Fig. 4. The measured quasi-Fermi levels of
ZnO and SrTiO3 are situated above the quasi-Fermi level of TiO2. Hence, the
increase in open-circuit voltage of ZnO and SrTiO3 electrodes as compared to that of
TiO2 could be assigned to the increase in flatband potential of the respective oxides.
Similarly, the decrease in open-circuit voltage of SnO2 compared to that of TiO2
could be assigned to lower flatband potential of SnO2 materials. Further, it has been
reported that the negative shift of the flatband potential results in a decrease in back
electron transfer process because of increase in free energy of back electron transfer.
In such a way, retardation of back electron transfer has been noticed [29]. Therefore,
increase in Voc of the solar cell fabricated with ZnO and SrTiO3 could be assigned to
favourable flatband potential and decrease in back electron transfer process.
Additionally, the different particle sizes of ZnO and SrTiO3 particles may block the
additional shunt paths by depositing in the barrier layer and thereby further reduce
the short-circuit paths.
The dark I– V curves for the cells ZnO, SrTiO3, TiO2 and SnO2 in the forward and
reverse bias are presented in Fig. 5. Poor diode behaviour was noted for SnO2-coated
film as expected and was in agreement with the poor solar cell performance of SnO2
electrode. Better rectifications were noted for the solar cells fabricated using ZnO,
SrTiO3 and TiO2 and the solar cell results presented for those electrodes justifying
the increased rectification. The IPCE measurements show lower IPCE values for
ZnO and SrTiO3 solar cells than the TiO2 solar cell in spite of their high Voc. The
lower IPCE of those cells could be due to their poor dye adsorption as explained
earlier [21].
 ARTICLE IN PRESS
348 J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350

Fig. 4. Energy-level diagram showing the relative CB positions of (a) ZnO, (b) SrTiO3, (c) SnO2, (d) TiO2
with the energy positions of CuI and ground and excited energy levels of the dye.

4. Conclusions

The use of ZnO and SrTiO3 as electrode materials in SS-DSSC results in increase
in Voc while with SnO2 nanocrystalline material, decrease in Voc was noted. The
observed photovoltage difference could be correlated to the difference in the flatband
potential values of the respective oxides and shift of the flatband potentials of the
composite films. The reported IPCE values for ZnO and SrTiO3 are less than those
of TiO2 due to poor dye adsorption on larger well-crystalline particles of ZnO and
SrTiO3. From the results presented above, it is evident that Voc of SS-DSSC can be
improved by using appropriate high-band-gap semiconductors with high flatband
potential values. If the dye adsorption amount could be improved by changing the
 ARTICLE IN PRESS
J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350 349

Fig. 5. Dark I– V characteristics of SS-DSSC made from (a) ZnO/dye/CuI, (b) SrTiO3/dye/CuI, (c) SnO2/
dye/CuI and (d) TiO2/dye/CuI.

surface modification of these materials, semiconducting materials with high-band-

gap semiconductors and high flatband potential could be used to enhance Voc and Isc
and thereby overall cell performance.

References

[1] K. Tennakone, G.R.R.A. Kumara, I.R.M. Kottegoda, K.G.U. Wijayantha, V.P.S. Perera, J. Phys.
D: Appl. Phys. 31 (1998) 1492.
[2] K. Tennakone, G.R.R.A. Kumara, K.G.U. Wijayantha, I.R.M. Kottegoda, V.P.S. Perera, G.M.L.P.
Aponsu, J. Photochem. Photobiol. A 108 (1997) 175.
[3] U. Bach, D. Lupo, P. Comte, J. Moser, F. Weissortel, J. Salbeck, H. Spreitzer, M. Gratzel, Nature
395 (1998) 583.
[4] J. Kruger, R. Plass, Le. Cevey, M. Piccirelli, M. Gratzel, Appl. Phys. Lett. 79 (2001) 2085.
[5] B. O’Regan, D.T. Schwartz, J. Appl. Phys. 80 (1996) 4749.
[6] M. Matsomuto, H. Miyazaki, K. Matsuhiro, Y. Kumashiro, Y. Takaoa, Solid State Ionics 89 (1996)
263.
[7] W. Kubo, T. Kitamura, K. Hanabusa, Y. Wada, S. Yanagida, Chem. Commun. (2002) 374.
[8] N. Papageorgiou, Y. Athanassov, M. Armand, P. Bonhote, H. Pettersson, A. Azam, M. Gratzel,
J. Electrochem. Soc. 143 (1996) 3099.
[9] K. Tennakone, G.R.R.A. Kumara, I.R.M. Kottegoda, V.P.S. Perera, P.S.R.S. Weerasundara,
J. Photochem. Photobiol. A 117 (1998) 137.
 ARTICLE IN PRESS
350 J. Bandara, H.C. Weerasinghe / Solar Energy Materials & Solar Cells 88 (2005) 341–350

[10] B. O’Regan, D.T. Schwartz, S.M. Zakeeruddin, M. Gratzel, Adv. Mater. 12 (2000) 1263.
[11] T. Taguchi, X. Zhang, I. Sutanto, K. Tokuhiro, T.N. Rao, H. Watanabe, T. Nakamori, M. Uragami,
A. Fujishima, Chem. Commun. 19 (2003) 2480.
[12] J. Bandara, H.C. Weerasinghe, Sol. Energy Mater. Sol. Cells 85 (2005) 385.
[13] G. Kron, T. Egerter, G. Nelles, A. Yasuda, Werner, U. Rau, Thin Solid Films 403 (2002) 242.
[14] T. Stergiopoulos, I.M. Arabatzis, H. Cachet, P. Falaras, J. Photochem. Photobiol. A: Chem. 155
(2003) 163.
[15] G. Katsaros, T. Stergiopoulos, I.M. Arabatzis, K.G. Papadokostaki, P. Falaras, J. Photochem.
Photobiol. A: Chem. 149 (2002) 191.
[16] G. Kron, T. Egerter, J.H. Werner, U. Rau, J. Phys. Chem. B 107 (2003) 3556.
[17] Y. Kurosaka, N. Tada, Y. Ohmori, K. Yoshino, Jpn. J. Appl. Phys. 37 (1998) L872.
[18] B.A. Gregg, Chem. Phys. Lett. 258 (1996) 376.
[19] A.C. Arango, L.R. Johnson, V.N. Bliznyuk, Z. Shlesinger, S.A. Carter, H.H. Horhold, Adv. Mater.
12 (2000) 1689.
[20] P.J. Cameron, L.M. Peter, J. Phys. Chem. B 107 (2003) 14394.
[21] S. Burnside, J.E. Moser, K. Brookes, M. Gratzel, J. Phys. Chem. B 103 (1999) 9328.
[22] H. Rensmo, K. Keis, H. Lindstrom, H. Sodergren, S. Solbrand, A. Hagfeldt, S.-E. Lindquist, L.N.
Wang, M. Muhammed, J. Phys. Chem. B 101 (1997) 2598.
[23] I. Bedja, S. Hotchandanai, P.V. Kamat, J. Phys. Chem. 98 (1994) 4133.
[24] K. Sayama, H. Sugihara, H. Arakawa, Chem. Mater. 10 (1998) 3825.
[25] J. Bandara, K. Tennakone, P. Binduhewa, New J. Chem. 25 (2001) 1302.
[26] A.J. Bard, L.R. Faulkner, Electrochemical Methods. Fundamentals and Applications, first ed.,
Wiley, New York, 1980.
[27] J.F. McCann, J. Pezy, J. Electrochem. Soc. 128 (1981) 1735.
[28] Y. Xu, M.A.A. Schoonen, Am. Mineral. 85 (2000) 543.
[29] G. Ramakrishna, A.J. Singh, D.K. Palit, H.N. Ghosh, J. Phys. Chem. B 108 (2004) 1701.