J. Phys. Chem.

C 2010, 114, 27992805

2799

Structural Modification of Organic Dyes for Efficient Coadsorbent-Free Dye-Sensitized

Solar Cells
Xiao Jiang, Tannia Marinado, Erik Gabrielsson, Daniel P. Hagberg, Licheng Sun,*, and
Anders Hagfeldt*,,
Center of Molecular DeVices, Inorganic Chemistry, and Organic Chemistry, School of Chemical Science and
Engineering, Royal Institute of Technology, 10044 Stockholm, Sweden, and Department of Physical and
Analytical Chemistry, Uppsala UniVersity, 75105 Uppsala, Sweden
ReceiVed: September 4, 2009; ReVised Manuscript ReceiVed: NoVember 27, 2009

Three triphenylamine-based organic sensitizers with different electron-donating substituents (butoxyl chains
or dimethylamine groups) were examined to investigate the effect of bulky alkoxy donor substituents on the
photovoltaic performances of dye-sensitized solar cells (DSCs) in the presence and absence of the coadsorbent
chenodeoxycholic acid (CDCA) in dye-bath solutions. The study showed that, using the D29 dye without
bulky alkoxy substituents, the power conversion efficiency of DSC was significantly increased by about 84%
in the presence of CDCA as compared to that in the absence of CDCA addition during the sensitization.
However, the photovoltaic performance of D35-sensitized DSC having four bulky butoxyl substituents was
not dependent on CDCA at all, probably due to the inherent structural nature of the D35 molecule. The DSC
based on the D37 sensitizer with only two bulky butoxyl chains displayed an expected medium performance
as compared to D29 and D35. The inclusion of bulky alkoxy electron-donating substituents in dye molecules
for efficient DSCs suppressed the electron recombination and reduced the interactions between dye molecules.
This emphasizes the importance of designing novel dyes including functional groups that incorporate the
properties normally needed from an external coadsorbent. The development of a coadsorbent free system is
in particular important for the future economization and simplification of the DSCs assembly process.
Introduction
The dye-sensitized solar cell (DSC) is a molecular system
that consists of a wide band gap semiconductor photoanode,
typically TiO2, an anchored molecular sensitizer, a redox
electrolyte, and a platinized photocathode.15 To increase the
light-to-electricity conversion efficiency as well as the stability,
all of the elements of the photoelectric device need to be
optimized, and there is still substantial potential for further
improvement. Among these elements, the sensitizing dye plays
a vital role for the light harvesting efficiency providing electron
injection into the conduction band of semiconductor upon light
excitation. In recent years, metal-free organic sensitizers, such
as coumarin,69 merocyanine,10,11 indoline,1217 hemicyanine,18,19
fluorene,20,21 carbazole,22,23 perylene,24 oligoene,2527 quinoxaline,28,29
phenothiazine,30 squaraine,31,32 and triphenylamine dyes,3339
have attracted a lot of attention due to many virtues as compared
to noble metal complexes. Some of the benefits with organic
sensitizers are low cost synthesis routes, high molar extinction
coefficients, flexible structural modifications, and the absence
of noble metals. There are, however, still some major problems
for organic dyes used in DSCs, such as dye aggregation, a lack
of directionality in the dye excited state on the TiO2 film,4045
and pronounced recombination of TiO2 conduction-band electrons with oxidized species as compared to ruthenium dyes.4650
These are all obstacles to obtain higher overall conversion
efficiencies (). As a result, a number of research efforts have
been made to overcome these drawbacks and to enhance the
* Corresponding author. E-mail: [email protected].

Inorganic Chemistry, Royal Institute of Technology.

Organic Chemistry, Royal Institute of Technology.

Uppsala University.

CHART 1: Molecular Structure of Chenodeoxycholic

Acid (CDCA)

power conversion efficiency of DSCs based on organic dyes.

For example, coadsorbents, such as chenodeoxycholic acid
(CDCA, Chart 1), are routinely added in the dye solutions. The
exact role of coadsorbents in the DSC is still under discussion;
some suggested effects of the coadsorbents are suppressing the
dye aggregation, shifting the TiO2 conduction band edge, and
shielding the TiO2 surface to reduce electron recombination with
the oxidized species in redox electrolyte.51,52 According to
previous studies, addition of CDCA in the dye solution has
proved to improve the performance of DSCs, increasing both
the short-circuit photocurrent density (Jsc) and the open-circuit
voltage (Voc).46,53 In addition, some works showed that the power
conversion efficiency of DSCs based on organic dyes can be
further improved by introducing bulky alkyl or alkoxy chains
into the dye structure to obtain an insulating effect of dye layer
on the TiO2 surface.17,2022 Recently, alkoxy chains located on
the electron-donating part of the dye have resulted in very
promising conversion efficiencies.39,54,55 As a result, strategic
structural modification of organic sensitizers is an effective
approach to enhance the dye performance in DSC and hence
obtain higher conversion efficiencies.

10.1021/jp908552t 2010 American Chemical Society

Published on Web 01/22/2010

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J. Phys. Chem. C, Vol. 114, No. 6, 2010

Jiang et al.

CHART 2: Molecular Structures of Sensitizers D29, D35, and D37

Among the great number of reported organic dyes mentioned

above, sensitizers based on triphenylamine (TPA) moiety have
proved to be a promising alternative. This is due to its excellent
electron-donating nature and nonplanar configuration. In our
recent work, we presented a series of new organic sensitizers
based on TPA functionalized with different donor substituents,
named D29, D35, and D37 (Chart 2).56 These dyes have the
same conjugated bridge units (thiophene) and electron acceptors
(cyanoacrylic acid). The TPA donor was functionalized at the
adjacent phenyl rings of the TPA core with either butoxyl
groups, short dimethylamine groups, or a combination of both
(Chart 2). The different electron donors on respective dye led
to very different photovoltaic performances of DSCs. The overall
conversion efficiencies increased in the order of D29 < D37 <
D35 (Table S1). For the present dyes, the results showed that
structural properties are more determinative than spectral
properties for the photovoltaic performances of DSCs. Despite
the broader and more red-shifted absorption, DSCs based on
D29, without any bulky chains, showed a comparatively low
performance as compared to DSCs based on the less red-shifted
D35 dye with four bulky butoxyl groups. DSCs based on D37
with two bulky butoxyl chains (as compared to four for D35)
exhibited medium efficiencies as compared to the other two
dyes. It is obvious that the presence of long butoxyl chains
contributed to the higher performance of DSCs. It was found
that the longer electron lifetimes were mainly responsible for
the higher value of Voc, resulting in higher power conversion
efficiencies (Figures S1-S3). The reason is probably the
insulating effect of the butoxyl chains protecting the surface of
TiO2 from oxidized species in the redox electrolyte.
As previously mentioned, the dye sensitization needs to be
done in such way so a protecting insulating dye layer is attained.
This is normally done by the introduction of coadsorbents during
the sensitization and/or modification of the dye structure with
bulky alkyl or alkoxy chains. It is noted that even for dyes
capable of leading to respectable conversion efficiencies modified with alkyl or alkoxy chains, the sensitization still requires
coadsorbent in the dye bath to gain better photovoltaic
performances.17,36,54 Thus, the question is how dye modifications
(alkyl or alkoxy chains) perform in comparison to the use of
external coadsorbents in the role of providing effective surface
blocking effect and impeding the electron recombination.
Therefore, the aim of the present study is to compare the
influence of the bulkiness of the dye donor substituents versus
the presence and absence of a coadsorbent (CDCA) during the
sensitization in DSCs, and to study the effect on parameters,
such as electron recombination, dye loads, semiconductor energy
level, and the overall photovoltaic performance. It is noted that

throughout the text the comparisons will be performed for the

cases of with and without CDCA addition in the dye bath during
the sensitization process.
Experimental Section
General Procedure for Preparation of Solar Cells. Fluorinedoped tin oxide (FTO) glass plates (Pilkington-TEC8) were
cleaned in subsequent order of detergent solution, water, and
ethanol using an ultrasonic bath overnight. The conducting glass
substrates were immersed into a 40 mM aqueous TiCl4 solution
at 70 C for 30 min and washed with water and ethanol. The
screen printing procedure was repeated (layers of 3 m) with
TiO2 paste to obtain a transparent nanocrystalline film of
thickness around 10 m and area of 0.25 cm2. The preparation
of TiO2 paste (25 nm colloidal particles) is described elsewhere.57 A scattering layer (3 m, PST-400C, JGC Catalysts
and Chemicals Ltd.) was deposited, and a final thickness of 13.0
( 0.2 m was attained. The TiO2 electrodes were gradually
heated in an oven (Nabertherm Controller P320) at air atmosphere. The temperature gradient program has four levels at 180
C (10 min), 320 C (10 min), 390 C (10 min), and 500 C
(60 min). After sintering, the electrodes once again passed, as
described above, a post-TiCl4 treatment. A second and final
sintering, at 500 C for 30 min, was performed. When the
temperature decreased to 70 C after the sintering, the electrodes
were immersed into 0.2 mM dye solutions and kept for 16-17
h in the dark at room temperature. The solvent was ethanol
(99.5%) for D35, and acetonitrile (99.8%) for D29 and D37,
respectively. After the adsorption of the dyes, the electrode was
rinsed with the same solvent. The electrodes were assembled
with a platinized counter electrode using a hot-melt Surlyn film.
The redox electrolyte consisting of 0.1 M LiI (99.9%), 0.6 M
tetrabutylammonium iodide (TBAI, 98%), 0.05 M I2 (99.9%),
0.5 M 4-tert-butylpyridine (4-TBP, 99%), and 0.05 M guanidinium thiocyanate (GuSCN, 99.8%) in acetonitrile was introduced through a hole drilled in the back of the counter electrode.
Finally, the hole was also sealed with the Surlyn film.
Measurement of Dye-Loading. The preparation of TiO2
films was the same as the procedure above. The adsorbed dyes
were then desorbed in 0.1 M (CH3)4NOH in acetonitrile solution,
and the dye load on the TiO2 film was estimated by means of
a UV-vis absorption spectroscopy.
Photocurrent Density-Voltage (J-V) Measurements. Prepared solar cells were characterized by current-voltage characteristics and incident photon-to-current conversion efficiency
(IPCE). Current-voltage characteristics were carried out with
an AM 1.5G solar simulator, 300 W xenon (ozone free). The
incident light intensity was 1000 W/m-2 calibrated with a

Structural Modification of Organic Dyes

J. Phys. Chem. C, Vol. 114, No. 6, 2010 2801

TABLE 1: Current and Voltage Characteristics of DSCs

Based on D29, D35, and D37 Dyes,a with and without CDCA
Addition during the Sensitization Process
dye
D29b
D35c
D37b

CDCA
(mM)

Jsc
(mA/cm-2)

Voc (V)

FF

(%)

0
6
0
6
0
6

7.98
11.15
12.02
11.84
10.52
11.26

0.66
0.71
0.78
0.77
0.71
0.69

0.47
0.52
0.54
0.56
0.51
0.56

2.22
4.09
5.07
5.10
3.77
4.37

efficiency
improvement
84.2%
0.6%
15.9%

Photovoltaic performance under AM 1.5 irradiation of DSCs

based on D29, D35, and D37 dyes. Electrolyte: 0.6 M
tetrabutylammonium iodide (TBAI), 0.1 M LiI, 0.05 M I2, 0.5 M
4-tert-butylpyridine (4-TBP), 0.05 M guanidinium thiocyanate
(GuSCN) in acetonitrile. b Dye bath: acetonitrile solution (2 10-4
M) with and without the addition of CDCA. c Dye bath: ethanol
solution (2 10-4 M) with and without the addition of CDCA.

standard Si solar cell. For the J-V curves, the solar cells were
evaluated by using a black mask on the cell surface to avoid
diffusive light (cell area of 0.25 cm2, aperture area of 0.49
cm2).58 IPCE measurements were carried out with a computerized setup consisting of a xenon arc lamp (300 W Cermax, ILC
Technology), followed by a 1/8 m monochromator (CVI
Digikrom CM 110). The data collection was done with a
Keithley 2400 source/meter and a Newport 1830-C power meter
with 818-UV detector head.
Photophysical Measurements. The UV-vis absorption
spectra of the dye-loaded transparent film and the dye solution
(1 10-5 M, in ethanol) were recorded on a Lambda 750
spectrophotometer by using a normal quartz sample cell (1 cm
path length). The fluorescence spectra of dye solution were
recorded on a Cary Eclipse fluorescence spectrophotometer
using the same concentration as the UV-vis measurement.
Electron Lifetime and Extraction Charge Measurements.
Electron lifetimes in the complete dye-sensitized solar cell
devices were measured in a system using a red-light emitting
diode (Luxeon Star 1W, max ) 640 nm) as light source. Voltage
and current traces were recorded using a 16-bit resolution data
acquisition board (DAQ National Instruments) in combination
with a current amplifier (Stanford Research Systems SR570)
and a custom-made system using electromagnetic relay switches.
The relation between potential and charge was investigated by
combining the voltage decay and charge extraction methods.
Extraction charge measurements were performed in the following way: the solar cell was illuminated for 5 s under opencircuit conditions, and then the light was shut off and the voltage
was let to decay to a voltage V. At a certain voltage V, the cell
was short-circuited, and the current was measured under 10 s
and then integrated to obtain Qoc (V). Electron lifetimes were
determined by monitoring the transient voltage responses after
a small light intensity modulation (square wave modulation,
<10% intensity of 0.5 Hz), and the step response was recorded
by the DAQ board. The voltage response was well fitted to firstorder decay, and time constants were hence obtained.
Results and Discussion
1. Effects of Coadsorbent CDCA on the Photovoltaic
Performance of D29-Sensitized DSCs. The photovoltaic
performance characteristics of DSCs based on D29, D35, and
D37 sensitizers with and without the addition of CDCA during
the sensitization, under standard global AM 1.5 illumination,
100 mW cm-2, are summarized in Table 1. As seen from Table
1, D29-sensitized DSC without CDCA addition showed very

TABLE 2: Adsorbed Amount of D29, D35, and D37 Dyes,

Respectively, on the TiO2 Film with and without CDCA
Addition during the Sensitization Process
dye load (10-8 mol/cm2)
dyes
D29
D35
D37

(10 M

-1

7.02
7.01
3.72

-1

cm )

with CDCA

without CDCA

4.10
4.57
8.47

7.51
5.24
12.33

low conversion efficiency. In contrast, the DSC with addition

of CDCA gave a pronounced efficiency enhancement of 84%
by increasing both values of Jsc and Voc as compared to the
case without CDCA addition.
The adsorbed amount of dye on the TiO2 film (determined
by dye desorption) with and without CDCA was listed in Table
2. It was found that the dye amount of D29 sensitizer adsorbed
onto the TiO2 surface was reduced to 54% in the presence of
CDCA, as compared to that without CDCA in the dye bath.
Despite this, higher Jsc was observed (Table 1). The main
possible explanation is that the coadsorption of CDCA prevents
dye aggregation, which can cause intermolecular energy transfer
and sequentially result in the excited-state quenching of the
dyes.5965 As a result, the reduction of dye load on the TiO2
surface in the presence of CDCA in the dye bath consequently
results in more efficient electron injection from the excited dyes
to the TiO2 conduction band.52,66 A more efficient electron
injection thus compensates for the less amount of dye adsorption.
It is noted that there was no direct evidence to support the
coadsorption of CDCA with dyes on the surface, but indirect
results, indicating that it might most probably be present on
the surface.52 The observed changes in Jsc agreed well with the
corresponding incident photon-to-current conversion efficiency
(IPCE) spectra for D29-sensitized DSC with and without the
addition of CDCA during the sensitization process (Figure 1).
However, it is interesting to find that there were almost no
changes between the maximum absorption wavelengths of D29
on the TiO2 film with and without CDCA addition during the
sensitization process (Figure 2). It should be noted that the TiO2
film is thinner in the case of UV-vis measurement as compared
to the actual DSCs condition. To explain this observation, we
propose the following possibilities: (i) The amount of dye was
insufficient to form aggregates, and therefore no spectral shift
was observed, but aggregates might form at higher dye load

Figure 1. Spectra of incident photon-to-current conversion efficiency

(IPCE) for DSCs based on D29 and D35, respectively, with and without
CDCA addition during the sensitization process.

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Jiang et al.

Figure 2. Absorption spectra of D29 on the TiO2 film with and without
CDCA addition during the sensitization process.
Figure 4. Electron lifetime as a function of extracted charge under
open-circuit conditions for DSCs based on D29 and D35, respectively,
with and without CDCA addition during the sensitization process.

Figure 3. Extracted charge as a function of open-circuit voltage for

DSCs based on D29 sensitizer with and without CDCA addition during
the sensitization process.

conditions for thicker TiO2 films. (ii) The formed aggregates

were of a different character as compared to the well-known H
or J aggregates capable of causing a spectral shift.4244,6769 So,
even if there are complexes of dyes formed on the TiO2 surface
without CDCA addition, they might not be detectable in the
absorption spectra. (iii) In the absence of CDCA, there was a
certain amount of excess dyes, not necessarily forming aggregates, and thus no spectral shift was observed.
The open-circuit voltage (Voc) of DSCs is determined by
the difference between the quasi-Fermi level of TiO2 and the
potential of the redox couple (I-/I3-) in the electrolyte. The
quasi-Fermi level is dependent on both the conduction band
edge position of TiO2 and the electron concentration in
TiO2.45,70,71 The electron concentration is strongly dependent on
the rate of electron recombination often referred to as the
electron lifetime. Figure 3 shows the relation between opencircuit voltage and extracted charge.72,73 A possible shift in this
relation can be interpreted as a shift of the conduction band
edge position of the TiO2. Almost no TiO2 conduction band
shift was found for D29-sensitized DSCs upon addition of
CDCA in the dye bath, indicating that the conduction band edge
of TiO2 was unaffected by the presence of CDCA. Electron

lifetime measurement was subsequently performed to reveal the

influence of CDCA on the electron recombination. Figure 4
shows the electron lifetime as a function of extracted charge of
DSCs based on D29 with and without CDCA addition.74,75 At
a given charge, longer electron lifetime was obtained for D29sensitized DSC with CDCA addition (Figure S4). This implies
that the recombination reaction between electrons in the TiO2
film and the oxidized species in the redox electrolyte is inhibited
by the addition of CDCA in the solar cell. A possible
explanation is that the coadsorption of CDCA with dyes on the
TiO2 surface produces surface passivation, resulting in less
recombination and longer electron lifetimes. Therefore, it can
be concluded that the increased Voc for D29-sensitized DSC was
mainly caused by the longer electron lifetime due to the presence
of CDCA.
On the basis of the above results, it was suggested that the
presence of CDCA in the dye solution during the sensitization
resulted in shielding of the surface against electron recombination and provided a higher concentration of functional dyes on
the TiO2 surface contributing to an efficient electron injection
into the TiO2 conduction band.
2. Effects of Coadsorbent CDCA on the Photovoltaic
Performance of D35-Sensitized DSCs. From Table 1, it is
interesting to find that D35-sensitized DSCs, with and without
the CDCA addition, gave very similar values of Jsc, Voc, and
power conversion efficiency. This means that the photovoltaic
performance of DSCs based on D35 was not dependent on
CDCA. This was further investigated by electron lifetime and
extracted charge measurements. As shown in Figure 4, at a given
charge, almost no differences in electron lifetimes were found
for DSCs based on D35 independent of the presence of
coadsorbent CDCA. This indicates that the recombination of
electrons in the TiO2 film with the oxidized species in the redox
electrolyte is unaffected in D35-sensitized DSCs with and
without CDCA addition. The relation between open-circuit
voltage and charge of D35-sensitized DSCs with and without
CDCA addition is exhibited in Figure 5. For a given charge, a
slight decrease in Voc was found when CDCA was present in
the dye solution, which means that the conduction band-edge
of the TiO2 film was slightly shifted to a more positive potential.
The amount of adsorbed D35 on TiO2 surface with and
without CDCA addition is shown in Table 2. Unlike D29, the

Structural Modification of Organic Dyes

Figure 5. Extracted charge as a function of open-circuit voltage for

DSCs based on D35 sensitizer with and without CDCA addition during
the sensitization process.

dye load of D35 on the TiO2 surface was less dependent on the
CDCA. There was a small decrease in dye load when CDCA
was added into the dye bath. As previously mentioned, the D29
dye load on the TiO2 surface was decreased by about 50% in
the presence of CDCA, whereas the D35 dye load was reduced
only about 10%. When using CDCA, the exact ratio of dye/
CDCA on the TiO2 surface is unknown,52 but the dye load
reduction in the presence of CDCA implies that the competitive
coadsorption of CDCA with D35 sensitizer on the TiO2 film is
weaker than that with D29 sensitizer. In other words, it is
suggested that D35 forms an ordered dye layer on TiO2 surface
and binds more strongly to the TiO2 surface than CDCA. Thus,
D35 shows less dependence on the presence of CDCA.
Generally, one would expect that a self-assembly property of
the dye during the sensitization of TiO2 film is important to
obtain efficient surface coverage and efficient electron injection
and thus obtain high photovoltaic performance of DSCs.
The essential reason for higher DSCs performance based on
the D35 sensitizer can be ascribed to its intrinsic structural
properties. As shown in Chart 2, the D35 sensitizer contains
four long butoxyl chains in ortho and para positions of the
phenyl rings, which are further linked in para position with the
TPA phenyl rings by single bonds, allowing free rotation. These
rotatable bulky groups may produce surface blocking through
steric hindrance, preventing the access of electrons to the redox
electrolyte, which will be in favor of higher Voc. On the other
hand, the twisted three-dimensional structure may not only
facilitate the ordered molecular arrangement on the TiO2 surface,
but also keep dye molecules at a distance, which may suppress
possibly intermolecular dye interaction, favoring higher Jsc. Even
when comparing the results of complete DSC devices based on
only D35 dye (no CDCA) with the DSCs based on D29 dye
and CDCA, D35-based DSCs still resulted in better performance. The main difference is still the significantly longer
electron lifetimes observed for DSCs based on D35 resulting
in higher Voc. The protection by the butoxyl chains is proven to
be more efficient as compared to the coadsorption of CDCA
under the examined conditions. However, the less efficient
surface protection due to the small donating groups in D29
sensitizer directly resulted in relatively poor photovoltaic
performance. In conclusion, markedly higher power conversion
efficiencies were obtained for DSCs based on D35 with

J. Phys. Chem. C, Vol. 114, No. 6, 2010 2803

Figure 6. Electron lifetime as a function of extracted charge under

open-circuit conditions for DSCs based on D37 with and without CDCA
addition during the sensitization process.

multibulky butoxyl donor substituents due to the inherent

properties of the dye molecule.
3. Effects of Coadsorbent CDCA on the Photovoltaic
Performance of D37-Sensitized DSCs. D37 sensitizer is a good
example to consolidate the above conclusions. As illustrated in
Chart 1, the structure of D37 is a combination of the two parent
chromophores from D29 and D35. There are two bulky butoxyl
groups and one small amino group. Thus, an expected intermediate performance for D37-sensitized DSC was obtained in
comparison with D29 and D35 under both conditions, with and
without the CDCA addition. The changes in the values of Jsc
and Voc (Table 1) can also be explained by electron lifetime
measurement and extracted charge measurement. We found that
the decrease in Voc, when adding CDCA, was a result of
collective effects of a slightly increased electron recombination
and a small positive band-edge shift of TiO2 (Figures 6 and 7).
From Table 2, it is clear that the dye load of D37 dropped
by about 30% (about 50% for D29, 10% for D35) due to the
addition of CDCA in the dye bath. However, like D29, the value
of Jsc increased with decreasing dye coverage, probably due to
the same reason as mentioned for D29.
It is interesting and noticeable that the molar extinction
coefficient of D37 is only about one-half of D29 and D35,
although these three dyes have similar structures. The lower
molar extinction coefficient is possibly due to the breakage of
symmetry of the molecule.56,76 As a result, although there is a
higher dye load in the D37 system relative to the other two
cases (twice as much as D35 and D29), only a medium
performance was obtained due to the poor molar extinction
coefficient and relatively few bulky electron-donating groups
(two butoxyl groups as compared to four for D35) in the
molecule.
Conclusions
According to previous reports, the addition of coadsorbent
in dye bath and/or functionalization of organic dyes with bulky
alkyl/alkoxy electron-donating chains can effectively enhance
the photovoltaic performances of DSCs. The role of bulky
substituents in dye molecules and the use of coadsorbents have

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Jiang et al.
AG Ludwigshafen. We also thank Dr. Leif Haggman for
supplying the TiO2 paste and TiO2 electrodes.
Supporting Information Available: Current and voltage
characteristics of DSCs based on D29, D35, and D37. Electron
lifetime and extracted charge measurements for DSCs based
on D29, D35, and D37. This material is available free of charge
via the Internet at http://pubs.acs.org.
References and Notes

Figure 7. Extracted charge as a function of open-circuit voltage for

DSCs based on D37 sensitizer with and without CDCA addition during
the sensitization process.

common purposes: reducing the presence of aggregated dyes

and providing surface protection suppressing electron recombination. Three dyes D29, D35, and D37, with different electrondonating substituents (butoxyl chains or dimethylamine groups),
showed gradually enhanced photovoltaic performance with
increasing the length and the number of electron-donating
chains. To better understand the influence of the bulky electrondonating butoxyl dye substituents on the photovoltaic performance of DSCs, we investigated the photovoltaic performances
of D29-, D35-, and D37-sensitized DSCs with and without
CDCA addition in the dye bath. The studies showed that the
photovoltaic performance of D35-sensitized DSC containing
four bulky butoxyl chains was independent of the coadsorbent
CDCA. By comparison, the D37 bearing two bulky butoxyl
chains and D29 without butoxyl chains showed 16% and 84%,
respectively, improvement in photovoltaic performance in the
presence of the coadsorbent CDCA. In the absence of CDCA,
D35-based DSCs were still superior to both D37 and D29 in
the presence of CDCA. This is probably due to the inherently
structural nature of D35 molecule, functionalized with four bulky
butoxyl electron-donating substituents, which resulted in excellent photovoltaic performance. The aims of the bulky butoxyl
substituents are proven to be 2-fold. The first is to provide selfassembly and aggregate-free dye layer on the TiO2 surface.
Second, an insulating hydrophobic dye layer will keep oxidized
species in the redox electrolyte at a distance from the TiO2
surface suppressing the electron recombination. This study
elucidates the role and the importance of bulky alkoxy electrondonating substituents in dye molecules for efficient dyesensitized solar cells. The protection by the butoxyl chains is
proven to be more efficient as compared to the coadsorption of
CDCA under the examined conditions. Additionally, improved
dye design incorporating the properties of coadsorbent into the
dye structure is important for future economization of cost and
simplification of the coadsorbent-free DSCs assembly process.
Acknowledgment. Financial support of this work from the
following sources is gratefully acknowledged: the Swedish
Energy Agency, the Swedish Research Council, Knut and Alice
Wallenberg Foundation, the Carl Trygger Foundation, the
Swedish Foundation for Strategic Research (SSF), and BASF

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