Thin Solid Films 511 512 (2006) 187 194

www.elsevier.com/locate/tsf

Different mesoporous titania films for solid-state dye sensitised solar cells
C.S. Karthikeyan a,*, M. Thelakkat b, M. Willert-Porada a
a
Chair of Materials Processing, University of Bayreuth, 95447 Bayreuth, Germany
b
Macromolecular Chemistry-I, University of Bayreuth, 95440 Bayreuth, Germany
Available online 11 May 2006

Abstract

The nature and morphology of titanium dioxide films play a significant role in determining the overall efficiency of the dye sensitised solar cell
(DSSC). The influence of three different nanocrystalline titania films, prepared from three different routes, namely sol gel (FMF), thermal (P-25),
and colloidal-microwave process (CMP), on the performance of solid-state dye sensitised solar cells was studied and discussed here. The
difference in the preparation of nanotitania leads to different surface area, pore size and morphology of the mesoporous films. FMF TiO2
displayed the highest efficiency and IPCE in DSSC among the other two because it possessed pure anatase phase, optimum surface area, pore
volume and pore diameter; and well-connected network of individual nanoparticles. P-25 films exhibited pore structural and morphological
features similar to FMF films but it displayed lower efficiency than FMF TiO2 due to the presence of small percentage of rutile phase besides
major anatase phase. Although, CMP films had high surface area, it possessed smaller pore diameter and pore volume besides agglomerates and
macropores leading to lower efficiency. The work clearly demonstrates the optimal pore and morphological structures required for efficient
functioning of solid-state dye sensitised solar cell.
D 2006 Published by Elsevier B.V.

1. Introduction reports based on inorganic [6] and simple organic p-type

Titanium dioxide, a well-known wide gap semiconductor,
has attracted a lot of interest in applications such as sensors [1],
photocatalysis [2] and photoelectrochemical cells [3] because
of its advantages such as cheap, abundant, non-toxic and
biocompatible. For optical, electrical and catalytic properties,
not only the crystalline phase of titanium dioxide is important,
the pore structure and morphology may also have some
influence [4]. In this respect, mesoporous nanocrystalline
materials are advantageous because of their high surface area
due to optimum pore size [4]. Thus, mesorporous titanium-
dioxide was developed and has gained considerable attention in
the application of dye-sensitised solar cells, the so-called
Gratzel cell [5]. Since 1991 there were many reports on this
topic. Although it was a breakthrough in the field of solar cells
because it is cheaper, the presence of liquid electrolyte in the
system is a major barrier for further development and
commercialisation of this solar cell. Hence, research progressed
towards all solid-state dye sensitised solar cell, where the initial
* Corresponding author.
E-mail address: metcsk@uni-bayreuth.de (C.S. Karthikeyan).
0040-6090/$ - see front matter D 2006 Published by Elsevier B.V.
doi:10.1016/j.tsf.2005.12.152
conductors [7] yielded low incident photon to current
conversion efficiency. In 1998, Gratzel et al. reported a solid-
state DSSC with higher efficiency using a novel amorphous
organic hole-conducting system containing a spiro-compound,
a lithium salt and some dopants [8]. Since then there has been
improvement in efficiency [9 11]. Many investigations have
been carried out on preparing novel dyes and hole conductors
including p-type semi-conducting polymers [12 14] but less
attention has been paid to TiO2. The following are the main and
standard requirements of TiO2 films for its efficient functioning
in solid-state dye sensitised solar cells: (i) pure anatase phase
(ii) optimum porosity leading to high surface area for better dye
absorption and hole conductor (iii) nanoparticle network for
better electronic percolation. Besides the standard require-
ments, the films should also have optimum pore volume and
pore diameter in the nanorange (10 50 nm). In order to
obtain the desired features mentioned above, sintered TiO2
films are generally used as electrodes in DSSC. Therefore, the
work concentrates mainly on the preparation and characterisa-
tion of such mesoporous TiO2 films, besides pristine powders,
for solid-state dye sensitised solar cell. In order to study the
influence of process methodology on the structure, pore
structure and morphology of those films, three different TiO2
188 C.S. Karthikeyan et al. / Thin Solid Films 511 512 (2006) 187 194
prepared by three different routes were utilised. A methodical
investigation on how such films with different structure and
morphology affect the performance of solid-state dye sensitised
solar cell is reported and discussed in this article. To support an
investigation of this nature, X-ray diffraction (XRD) for
structure; Brunauer Emmet Teller (BET) experiments for
surface area and pore size; and Scanning electron microscopy
(SEM) for morphology were performed to gain a clear insight
of the true picture of mesoporous TiO2 films in a typical solid-
state DSSC.
2. Experimental
2.1. Materials
P-25, nanocrystalline-TiO2 prepared by thermal route,
was purchased from Degussa AG, Germany. FMF TiO2,
screen printable nanotitanium dioxide (prepared by sol
gel method) paste was supplied by Freiburg Materials Research
centre, Germany. The third titanium dioxide, CMP TiO2,
was prepared in our laboratory by colloidal microwave pro-
cess (CMP), the details of which can be found elsewhere [15].
Titanium (IV) bis (acetoacetonato)-di (isopropanoxylate) (TAA)
was purchased from Aldrich. The dye, cis-bis-(isothiocynato)-
bis-(2,2V-bipyridyl-4,4V-dicarboxylato)-Ru (II)-bis-(tetrabutyl
ammonium), namely N-719, was purchased from Solaronix,
Aubonne, Switzerland. 2,2V,7,7V-Tetrakis-(N,N-di-4-methoxy-
phenyl amino)-9,9V-spiro-bifluorene (spiro-OMeTAD) was
obtained from Covion Semiconductors, Germany. The spiro-
OMeTAD radical cation (ox-spiro-OMeTAD) was obtained by
single electron transfer oxidation of spiro-OMeTAD with
excess of AgSbF6 in toluene. N-lithiofluromethane sulfon-
amide, (Li salt) was purchased from Aldrich. Common
solvents and chemicals were purchased from Aldrich. Glass
substrates (Tec 8) covered with 3 mm fluorine-doped tin
oxide (FTO) layer having a sheet resistance of 8 V per square
were purchased from Hartford Glass Co. Inc., Indiana, USA.
The substrates were cut to a size of 25  25 mm to suit the
solar cell size.
2.2. Preparation of TiO2 paste for film
P-25 and CMP TiO2 powders were made into screen
printable paste by following procedure. TiO2 is ground well
using pestle and mortar for about 30 min. Sonication of 6 g of
TiO2 in ethanol was done for 1 h and then the supernatant
system containing fine titania was decanted. Then, 0.1 g of
4-hydroxy benzoic acid and 8 g of ethanol were slowly added
during mixing. The mixture was stirred until a homogeneous
paste was obtained. The system was then milled for about
15 min followed by ethanol evapouration yielding a compact
powder. 3.5 g of 5% ethyl cellulose in a-terpineol was added to
the compact powder and allowed to mix well. After obtaining a
homogeneous system, 4 g of a-terpineol was added to the
dispersion and mixing was continued until a homogenous paste
was obtained. Finally, the paste was milled for about 10 min
and then utilised for subsequent screen-printing process. The
pastes thus prepared using P-25 and CMP TiO2 have nearly
the same viscosity as FMF paste which guarantee identical
thick films.
2.3. Sintering and characterization of the TiO2 films
For all the three samples, films of 4.5 5 Am thickness were
produced by screen-printing and the films were dried and
sintered at 400 -C for 24 h. Brunauer Emmet Teller (BET)
experiments by N2 gas adsorption were performed using
Micromeritics ASAP 2010 instrument, USA on different
TiO2 powder and films utilised in this work. TiO2 powder
and screen printed films before and after sintering were
examined. Surface area, pore volume and pore diameter were
obtained from BET examination for both sintered and non-
sintered samples.
X-ray diffraction of the TiO2 powder and sintered films was
examined in Philips X-Pert MPD instrument, PW 3040 model
with Cu-Ka radiation.
Surface and cross-sectional features of sintered and non-
sintered screen-printed TiO2 films on plain glass were
examined using LEO 1530 Gemini field emission scanning
electron microscope (FE-SEM).
2.4. Solar cell preparation and characterisation
Solid-state dye sensitised solar cells for the present work
were prepared according to the procedure reported earlier [16].
TiO 2 blocking layer was produced by spray pyrolysis
deposition (SPD) process. The preparation conditions of TiO2
blocking layers by SPD are well optimised in our lab to obtain
reproducible and smooth films. 0.2 M solution of TAA in
ethanol was used as a spraying solution for SPD process. The
spray pyrolysis was carried out at 400 -C. After performing the
required number of spraying cycles, the substrates containing
layers were annealed at 500 -C for 1 h and cooled down to
room temperature. In the present work, 10 spraying cycles were
performed leading to 150 nm of TiO2 blocking layers on the
FTO-coated glass substrates. Mesoporous nanocrystalline TiO2
film was produced on the compact TiO2 layer by screen-
printing using 186 Am net. The TiO2 film was subsequently
sintered at 400 -C for 24 h. The thickness of the films was
maintained in 4.5 5.0 Am range (determined by Dektak
profiliometer) in order to obtain maximum charge carrier
diffusion in the films.
The sintered mesoporous TiO2 films were immersed in
N-719 dye solution of 0.3 mM concentration for 18 h. The
physisorbed dye molecules were washed away and the dye
coated TiO2 electrode was dried at 40 -C for 3 4 h.
The hole transport layer (HTL) was deposited on the
dye coated TiO2 mesoporous electrode by spin coating. Hole
conducting system is a mixture of spiro-OMeTAD, ox-
spiro-OMeTAD and Li-salt. The ox-spiro acts as a dopant to
enrich the charge concentration and Li-salt is added to increase
the conductivity as well as to manipulate the surface potential
of TiO2 for better electron injection. Finally, a thin Au film was
vapour deposited to complete the cell.
 C.S. Karthikeyan et al. / Thin Solid Films 511 512 (2006) 187 194 189

Fig. 1. XRD patterns of FMF TiO2, CMP TiO2 and P-25 sintered films.

The solar cells thus prepared were characterised for give an unambiguous idea about the structure of TiO2 in a
current voltage measurements using white light source with typical DSSC. Thus, Fig. 1 shows the XRD patterns of sintered
an intensity of 77 mW/cm2 by Keithley 6517 source measure films of P-25, FMF TiO2 and CMP TiO2. It is evident from
unit under AM 1.5G conditions. the figure that the crystals of FMF TiO2 and CMP TiO2 are
pure anatase (101) phase while P-25 has a little amount of rutile
(110) phase along with the major anatase phase. How this
3. Results and discussion
structural difference existing in all three TiO2 films used in this
work influences solar cell performance from one of the subjects
An interesting aspect in this study is that results based on
of study in the present investigation.
sintered films are compared with the non-sintered ones so that
one can get an idea about how the structure and morphology
3.2. Sintering and BET
changes upon sintering. A report of this nature could give a
clear picture about the actual situation prevailing in the solar
Screen-printed nanocrystalline TiO2 films are normally
cell environment.
sintered to obtain an interconnected and mechanically stable
In order to obtain maximum efficiency the thickness of the
film for overall stability of the solar cell. Hence, sintering is
n-TiO2 should be optimum [11]. For instance, if the film is too
one of the crucial steps in solar cell preparation. Sintering
thin (< 1 Am), the amount of absorbed light in the active cell
process in this work involves the following steps. Films were
area is smaller and hence only a fraction of the sunlight can be
screen printed (set-up described under solar cell preparation) on
converted to current. On increasing the film thickness, the
a plain glass using the paste prepared from all three TiO2
amount of light absorbed increases and therefore efficiency
powders. Sufficiently thick films (about 5 6 layers) were
improves. But at higher thickness (> 6 Am), the amount of
produced suitable for BET measurements. All the films were
absorbed light increases but the path for the charges to reach
sintered at 400 -C for 24 h similar to the condition adopted for
the electrodes is increasing as well. This leads to higher series
solar cell preparation. BET measurements were carried out for
resistance and more charge recombination in the cell so that
both powder and sintered films of TiO2. Table 1 gives the BET
fewer charges will reach the counter electrode. This exchange
results such as BET surface area, pore volume and pore
between light harvesting and series resistance leads to an
optimal thickness in the range 3 6 Am for obtaining maximum
Table 1
photocurrent. In the present work, TiO2 film thickness in DSSC BET results of powder and sintered films of different TiO2 samples
was, therefore, maintained between 4.5 and 5 Am.
TiO2 BET surface area Pore volume Pore diameter
(m2/g) (cm3/g) (nm)
3.1. XRD
CMP powder 110.59 0.124876 3.67
CMPa, sintered film 77.01 0.164317 6.37
XRD patterns of powder and sintered films revealed no P-25 powder 48.37 0.344120 25.75
difference with respect to the phases in each type; hence results P-25a, sintered film 29.11 0.258069 29.64
based only on sintered films are reported here to avoid FMFa, sintered film 30.40 0.259423 44.23
a
repetition. Moreover, XRD results on sintered films would Sintering done at 400 -C for 24 h.
190 C.S. Karthikeyan et al. / Thin Solid Films 511 512 (2006) 187 194
Fig. 2. BET adsorption desorption isotherm of mesoporous CMP TiO2 sintered film.
diameter of TiO2 pristine and sintered film samples. From the
table it is clear that in all three types (CMP TiO2, FMF TiO2,
P-25), BET surface area decreases upon sintering indicating the
formation of a compact interconnected TiO2 film desirable for
the solar cell. It is also evident that CMP TiO2 film displays
higher surface area value (77 m2/g) than P-25 and FMF TiO2,
where the latter two have nearly the same values (about 30). It
is known that one of the main requirements for efficient
functioning of DSSC is high surface area of TiO2 film after
sintering. TiO2 prepared by CMP method fulfils this require-
ment. Besides the surface area, the adsorption desorption
isotherm obtained from BET experiments can give more
evidence for the mesoporous nature of the films. To cite an
example, Fig. 2 is the isotherm plot of sintered CMP TiO2
film. It is evident that the isotherm displays a hysteresis instead
of simply retracing the adsorption curve. This behaviour is
typical of mesoporous materials [17], hence, CMP film is
mesoporous. The other two films namely, FMF and P-25, also
exhibited similar hysteresis in the BET isotherm thus confirm-
ing the mesoporous nature.
Other interesting aspects in BET results are pore volume and
pore diameter. The pore diameter and pore volume values for
powder samples and films are also shown in Table 1. In the case
of CMPTiO2 there is a slight increase in pore volume and
diameter after sintering. In P-25 the pore volume slightly
decreases after sintering but there is an increase in diameter.
These values become more significant when compared among
three TiO2 samples. It is obvious that FMFTiO2 and P-25 have
pore volume and diameter values higher than CMP. Although
CMPTiO2 has higher BET surface area, it has lower pore
volume and pore diameter. In other words, CMPTiO2 has
largely very small pores (<10 nm), in addition to small amount
of large pores, while the other two have predominantly
mesoporous structure. P-25 and FMFTiO2 have lower BET
surface area than CMPTiO2 but higher pore volume and
diameter values. This is a significant finding with respect to the
electrode structure in DSSC. Whether these pore-structural and
surface area differences existing in three films are vital in
determining the efficiency of DSSC will be evident when dealing
with solar cells characterization results in the following section.
3.3. Solid-state dye sensitised solar cell
Solid-state dye sensitised solar cell is represented by FTO/
bl-TiO2/nc-TiO2/Ru-dye/HTL/Au where / denotes the inter-
face and solid-state HTL is comprised of spiro-OMeTAD, ox-
spiro-OMeTAD and Li-salt. In order to make a comparative
study, solar cells were prepared with different TiO2 films (P-25,
FMF TiO2, CMP TiO2) but with same dye and HTL. The
performance of such solid-state dye sensitised solar cells are
reported and discussed in this section. The method of
preparation of mesoporous TiO2 layer is not the optimum for
the performance of solar cells, but it is in close conformity with
the sample preparation for BET and SEM analysis.
The absorption patterns of the chemisorbed N719 dye on
three mesoporous TiO2 films were recorded using UV Visible
 C.S. Karthikeyan et al. / Thin Solid Films 511 512 (2006) 187 194 191

Fig. 3. Absorption spectra of N-719 ruthenium dye on TiO2 films.

spectroscopy. Fig. 3 shows the UV Visible spectra of the dye- In order to have a better understanding of the fundamental
adsorbed films of FMF TiO2, P-25 and CMP TiO2. It is process of photoinduced charge separation, incident photon to
known that dye N-719 shows absorption peaks at 550 and current conversion (IPCE) or external quantum efficiency
370 nm. We observe peaks at similar wavelengths in all three (EQE) was measured besides the current voltage measure-
cases in Fig. 3. In Fig. 3 the nature of dye adsorption on three ments for the solar cells prepared in this work. The IPCE
different TiO2 films is also evident, where FMF TiO2 and P- results are also given in Table 2. The maximum efficiency was
25 shows clear absorption patterns. The spectrum of dye on obtained at the wavelength 360 nm, where the efficient light
CMP TiO2 displays both absorption and strong scattering. In absorption by the dye takes place. It is evident that DSSC
the cases of FMF TiO2 and P-25, the spectra span the whole based on FMF has IPCE of about 32%, which is higher than P-
visible region followed by an intensity decrease at the end of 25 (28%) and CMP (12%). The IPCE results of these three
visible region. The decrease is more prominent for FMF TiO2 solid-state DSSC are similar to trend followed by the current
than P-25. The decrease in absorption pattern from FMF TiO2 voltage characteristics of these cells where the efficiency
to CMP TiO2 through P-25 may be attributed to particle size decreases from FMF to CMP. The IPCE values correlate well
and morphology of these three TiO2 films. The morphology of with the dye absorption pattern observed for all three films
the films will be discussed in detail under SEM section. (Fig. 3) where dye absorbed on CMP showed a scattering
The performance of DSSC is normally reported in terms of pattern yielding lower IPCE. The power conversion efficiency
Power conversion efficiency (g). g is governed by three and external quantum efficiency or IPCE results of all three
parameters namely open circuit voltage, short circuit current different solid-state DSSCs thus obtained are discussed as
and fill factor. Table 2 displays the results from photovoltaic follows.
performance of three solid-state DSSCs based on P-25, FMF The BET results of powder and sintered films were already
TiO2 and CMPTiO2 films at an illumination intensity of about compared and discussed earlier. It was clear that surface area
77 mW/cm2 under AM 1.5 solar conditions. It is clear that of the material decreases upon sintering. It is believed that
DSSC based on FMF has higher efficiency than other two cells surface area of the sintered TiO2 films influences the
(P-25 and CMPTiO2). FMF has an open circuit voltage of performance of DSSC. However, in order to understand the
665 mV, which is higher than both P-25 and CMP. A higher mechanism better, pore volume and pore diameter values
photocurrent (1.2 mA/cm2) and better fill factor (49%) for FMF obtained from BET experiments should also be taken in
than the other two led to a power conversion efficiency of 0.5%.
One can also notice that although open circuit voltage and Table 2
photocurrent values of P-25 based solar cells are only slightly Photovoltaic performance of three solid-state dye sensitised solar cells prepared
inferior to FMF based cell, the fill factor is strikingly lower using different mesoporous TiO2 films
(32%) leading to efficiency of 0.2%. CMP based DSSC displays Device U OC J SC Fill factor g IPCE [%]
the lowest efficiency compared to FMF and P-25 based cells. (mV) (mA/cm2) [%] [%] 360 nm
This may be attributed to noticeably lower photocurrent, open FMF TiO2 665 1.2 49 0.5 32
circuit voltage and fill factor values. Thus, all three parameters P-25 635 0.8 32 0.2 28
mentioned earlier determine solar cell efficiency. CMP TiO2 487 0.3 39 0.07 12
192 C.S. Karthikeyan et al. / Thin Solid Films 511 512 (2006) 187 194
Fig. 4. SEM pictures of surface views of the a) non-sintered and b) sintered
FMF TiO2 films.
account. This approach was chosen because no similar
investigation could be found in the literature. As mentioned
earlier, there exists a pore structural and surface area
difference among the three TiO2 layers utilised in this work.
During the solar cell preparation, since all films formed by
screen-printing are sintered before the dye absorption, it is
relevant and essential to discuss the BET results of the all
three sintered TiO2 films alone. Comparing the surface area
values of three films, CMP TiO2 has the higher surface area
than the other two, which have comparable values. In
principle, higher surface area should yield higher efficiency
in DSSC but in the present work DSSC based on CMP TiO2
displays inferior solar cell performance compared to DSSCs
with P-25 and FMF TiO2 films. Although CMP TiO2 has
higher surface area it has yielded lower efficiency emphasis-
ing surface area value alone is not sufficient to determine the
performance of DSSC. There must be another factor, which
may govern the performance. First reason for lower perfor-
mance for CMP TiO2 film may be attributed to lower pore
volume compared to FMF TiO2 and P-25 films. The second
reason is due to the pore diameter decrease from FMF TiO2
through P-25 to CMP TiO2. In other words, FMF TiO2 has
larger pores (44 nm) than P-25 (29 nm) and CMP TiO2
(6 nm). Interestingly, g and EQE increase with increasing
pore diameter i.e. FMF with larger pore diameter has higher g
and EQE than P-25 and CMP TiO2 films (Tables 1 and 2).
Due to smaller pore diameter present in CMP TiO2 films, the
hole-transport layer (HTL) was not able to fill the pores
effectively. This situation leads to deficiency of HTL on
TiO2-dye suppressing the process of hole-transfer from the
dye to HTL. Consequently, the charges get accumulated in
the dye layer and recombine thus reducing g and EQE of the
system. On the contrary, the presence of larger pore diameter
in FMF TiO2 leads to effective filling of HTL into the pores
enhancing the hole transfer from the dye to HTL to facilitate
better charge separation. This better charge separation
resulted in better efficiency for DSSC containing FMF
TiO2 films than the other two cells (P-25 and CMP TiO2).
Since pore diameter of P-25 film lies in between FMF TiO2
and CMP TiO2, obviously, intermediate efficiency values
were obtained. From the present result it is clear that surface
area of the films alone is not sufficient, the pore volume and
diameter are also important in determining the overall
performance of the DSSC.
XRD investigations revealed a structural difference among
the three TiO2 films. FMF TiO2 and CMP TiO2 have pure
anatase phase whereas P-25 has a small percentage of rutile
component. It was reported [18] that rutile phase of TiO2 would
show lower efficiency than the anatase phase. From the
literature it is known that close packing nature in rutile phase
leads to lower surface area compared to anatase [19].
Moreover, the electron transport in anatase is relatively faster
than in rutile [18,19] in which the short circuit current (I sc) was
reported to be 30% lower than that of anatase TiO2 [18].
Hence, anatase is the preferred phase for efficient functioning
of DSSC. In addition, any small amount of rutile phase would
decrease the overall performance of the cell. This is explicitly
shown in the present work where DSSC based on P-25 has
slightly lower power conversion efficiency than FMF TiO2,
due to the presence of small percentage of rutile phase. Thus,
XRD studies on different TiO2 films are very essential and
helpful in explaining the DSSC performance.
3.4. SEM investigations
Morphology study by SEM is supportive and helpful in
discussing the quantitative results obtained by various mea-
surements in order to obtain a true picture of the material
system. FE-SEM examination was done on both non-sintered
and sintered films of all three types of TiO2 utilised in this
work. To cite an example, Fig. 4a and b shows the surface
features of the non-sintered and sintered FMF TiO2 films. The
individual nano-TiO2 particles are visible in both the pictures.
The effect of sintering is obvious in Fig. 4b wherein less
porosity and connected nanoparticles are visible. The influence
of sintering was observed in P-25 and CMP TiO2 films too.
The sintering effect is evident in cross-sectional views too. To
gain better and clear understanding of the morphology of the
sintered films, which in turn governs the performance in DSSC,
SEM examination was carried out at for all three films. The
cross-section view of the sintered FMF films is depicted in
Fig. 5a. It is interesting to note that the nanoparticles in FMF
film are not only individual but also are also well connected to
make a compact film with optimum pore structure. Such well-
 C.S. Karthikeyan et al. / Thin Solid Films 511 512 (2006) 187 194
Fig. 5. SEM pictures of cross-section views of the sintered films of FMF TiO2
(a); P-25 (b); CMP TiO2 (c).
connected nanoparticle network is desirable for efficient
functioning of DSSC because it will improve electron
percolation of the system. In brief, FMF films are mesoporous
and have separate nanoparticles, which are connected to form a
network structure. It also has optimum pore diameter and pore
volume for efficient filling of HTL. Fig. 5b shows the FE-SEM
picture of the sintered P-25 film. The individual nanoparticles
are also evident in the case of P-25. The morphology of the
sintered P-25 film is somewhat similar to FMF film i.e. P-25
film is also of mesoporous nature with individual and
connected nanoparticles network. When the cross-section view
(Fig. 5c) of the CMP TiO2 film was examined it was visible
that the nanoparticles were joined together to form agglomer-
193
ates in the sub-micron range. Another feature in CMP TiO2 is
that besides nanopores, the film also has macropores. These
agglomerates and macropores are the major reasons for
lowering the performance of DSSC based on CMP TiO2.
The higher surface area for CMP film is a result of both meso-
and macroporous structures. Moreover, it has no network of
well-connected nanoparticles similar to FMF TiO2 and P-25.
Although DSSC based on CMP TiO2 diplays higher fill
factor due to the presence of agglomerates of TiO2 in which the
internal resistance for electron transport may be less, it
exhibited lower short-circuit current and open circuit voltage
leading to lower efficiency for the same reason. To summarise,
FMF TiO2 and P-25 have higher efficiencies compared to
CMP TiO2 due to the following reasons: optimum surface
area and pore structure, well-connected individual nanoparti-
cles suitable for electron percolation. CMP exhibits the lowest
performance because it has agglomerates and macropores
besides nanoparticles and nanopores. Thus, SEM clearly
brought out the morphology difference that exists in FMF
TiO2, P-25 and CMP TiO2 films. It also reveals the desirable
and essential features of TiO2 films in solid-state DSSC for
better performance.
Finally a point worthy to be mentioned is that by adopting a
new and proper preparation methodology for obtaining TiO2
film with higher surface area, pore volume and pore diameter;
and better network of nanoparticles than the one reported in
this work, it is possible to achieve even higher efficiency for
the same dye and solid-state hole conductor.
4. Conclusions
A systematic study focusing on the fundamental aspects of
nanocrystalline TiO2 films namely structure and morphology
was carried out in this work. From the foregoing results on the
preparation and characterisation of different mesoporous films
possessing variation in structure, pore structure, morphology
and thickness for solid-state dye sensitised solar cells (DSSC),
the following conclusions emerge. Mesoporous films based on
nanocrystalline titanium dioxide prepared by sol gel method
(FMF) displayed better performance in solid-state DSSC than
the other two namely, the commercial P-25 and colloidal
microwave process (CMP), due to following reasons. FMF film
possessed proper crystalline phase namely anatase, optimal
surface area, pore diameter and pore volume essential for
efficient functioning of DSSC. In addition, SEM investigation
proved that FMF film has separate and well-connected network
of nanoparticles suitable for better electron percolation. It was
clear, although CMP films had high surface area; it possessed
lower pore diameter and pore volume besides agglomerates and
macropores leading to lower efficiency. P-25 films exhibited
pore structural and morphological features similar to FMF
films but it displayed lower efficiency than FMF TiO2 due to
the presence of small percentage of rutile phase besides major
anatase phase. The work clearly demonstrates the proper
crystal phase, optimal pore and morphological structure
required for the efficient functioning of solid-state dye
sensitised solar cell.
194 C.S. Karthikeyan et al. / Thin Solid Films 511 512 (2006) 187 194
Acknowledgements
The authors thank Bayrische Forshungsstiftung (BFS) and
SFB-481 (Deutsche Forschungsgemeinschaft) for the financial
support. The assistance of Mrs. Ingrid Otto for the BET
measurements and Mrs. Clarissa Abetz for the SEM examina-
tions is kindly acknowledged.
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