Synthesis and Application of New Ru(II) Complexes

Bull. Korean Chem. Soc. 2007, Vol. 28, No. 8

1311

Synthesis and Application of New Ru(II) Complexes for Dye-Sensitized

Nanocrystalline TiO2 Solar Cells
Won K. Seok,* A. K. Gupta, Seung-Jae Roh, Wonjoo Lee, and Sung-Hwan Han,*
Contribution from Department of Chemistry, Dongguk University, Seoul 100-715, Korea. *E-mail: [email protected]

Department of Chemistry, Hanyang University, Seoul 133-791, Korea. *E-mail: [email protected]

Received May 5, 2007
To develop photo-sensitizers for dye-sensitized solar cells (DSCs) used in harvesting sunlight and transferring
solar energy into electricity, we synthesize novel Ru(II) polypyridyl dyes and describe their characterization.
We also investigate the photo-electrochemical properties of DSCs using these sensitizers. New dyes contain
chromophore unit of dafo (4,5-diazafluoren-9-one) or phen-dione (1,10-phenanthroline-5,6-dione) instead of
the nonchromophoric donor unit of thiocyanato ligand in cis-[RuII(dcbpy)2(NCS)2] (dcbpy = 4,4'-dicarboxy2,2'-bipyridine) coded as N3 dye. For example, the photovoltaic data of DSCs using [RuII(dcbpy)2(dafo)](CN)2
as a sensitizer show 6.85 mA/cm2, 0.70 V, 0.58 and 2.82% in short-circuit current (Jsc), open-circuit voltage
(Voc), fill factor (FF) and power conversion efficiency (Eff), which can be compared with those of 7.90 mA/
cm2, 0.70 V, 0.53 and 3.03% for N3 dye. With the same chelating ligand directly bonded to the Ru metal in the
complex, the CN ligand increases the Jsc value by double, compared to the SCN ligand. The extra binding
ability in these new dyes makes them more resistant against ligand loss and photo-induced isomerization within
octahedral geometry.
Key Words : DSCs, New photosensitizers, Chromophore

Introduction
Dye-sensitized solar cells (DSCs) consist of a cathode
coated with Pt, a transparent oxide thin-film anode having a
nanoporous structure anchored with monolayers of dye, and
an iodine redox electrolyte.1 The generally accepted
mechanism for the photocurrent generation of DSCs results
from the initial injection of an electron from the photoexcited dye to the semiconductor oxide conduction band.
The electron can flow into an external circuit through a
resistor and the energy is utilized, and then connected to the
cathode making a closed circuit. The oxidized form of the
dye on the semiconductor surface is reduced to its original
state by accepting electron from an electron donor I in the
electrolyte, which completes the cycle.
After the discovery of cis-[RuII(dcbpy)2(NCS)2] (dcbpy =
4,4'-dicarboxy-2,2'-bipyridine) referred to as N3 dye,2 there
has been growing interest among chemists and physicists to
develop a new generation of sensitizers for DSCs. It has also
been reported that black dye as a photo-sensitizer showed
spectacular stability as well as high power conversion
efficiency around 10.4%.3 It is recognized that the higher
conversion efficiency of the DSCs is also dependent on the
productive light capturing antenna. Absorption by these dyes
in the visible and near-IR regions is attributed to metal to
ligand charge transfer (MLCT) transition. The highest occupied
molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO) are mainly derived from the d
orbitals of the Ru metal and the * orbital of the chelate
ligand. The thiocyanato ligand shifts the ground state level
negatively, leading to a red shift in the absorption property of
the complex, and also contributes to the electron acceptance

from reduced redox species. The Ru complexes are adsorbed

on the semiconductor oxide surface via either carboxylate
bidentate coordination or ester bonding. The presence of
functionalized anchoring groups is necessary to ensure
monolayer distribution of the dye on the oxide surface,
which causes a large electronic interaction between the
ligand and the conduction band of TiO2, resulting in
effective electron injection from LUMO into the conduction
band.4
The ideal sensitizer should absorb all of the solar light
including UV and visible wavelengths including that in the
near IR region. For these goals major emphasis has been
given on the preparation of bidentate heterocyclic ligands
with aromatic ring system such as 4,4'-di(3-methoxystyryl)2,2'-bipyridine, phenanthroline and biquinoline derivatives
instead of dcbpy ligand, which are capable of coordinating
with a variety of metal ions including Ru(II).5 The choice of
Ru(II) complexes is of particular interest due to their
octahedral geometry with a variety of specific ligands in a
controlled manner. Their excited states have long lifetime
and long-term chemical stability.6
Many attempts have also been made to improve the photoconversion efficiency by introducing donor ligands into the
central ruthenium metal instead of the thiocyanato ligand.7
Although some of the non-thiocyanato complexes improved
absorption of visible light, their conversion performance was
not satisfactory.8 There have also been many efforts to
modify the properties of the sensitizers and the arrangement
of the donor and acceptor ligands of the proposed complexes.9 All of these works suggest that the development of
new photo-sensitizers is still needed at this stage.
In this work, we focus on the design of new ruthenium

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Bull. Korean Chem. Soc. 2007, Vol. 28, No. 8

sensitizers to understand the effects of photochemical and

photophysical nature of molecules on photo-conversion
efficiency. Here, we synthesize novel Ru(II) dyes containing
two chromophore units of dafo (4,5-diazafluoren-9-one) and
phen-dione (1,10-phenanthroline-5,6-dione) instead of nonchromophoric donor for N3 dye and describe their characterization using spectroscopic techniques. We also investigate their photo-electrochemical properties for nanocrystalline TiO2 solar cells.10 Two ancillary ligands can be
regarded as classical chelating reagents, but they exhibit
significantly different electronic properties due to the
presence of the carbonyl functional group. The more
coordinating ability of these ligands makes the complex
more resistant against its ligand loss and/or photo-induced
isomerization within octahedral geometry than those of the
two monodentate ligands.11 The chemical and stereochemical
robustness of the dye can increase the long-term stability in a
solar cell, which is one of main requirements for its practical
application. The binding ability of nitrogen lone pair of these
ligands destabilizes the ground state level of the dye, which
leads to lower energy shift of MLCT transitions. The
presence of carbonyl functional group in the dafo and phendione ligands also enhances the coordinating ability to
nanocrystalline the TiO2 surface. They can also tune the
metal t2g orbital of Ru(II) and possibly stabilize the hole that
is being generated on the metal, after having injected an
electron into the TiO2 conduction band.12
Experimental
Materials. All the solvents used in the reactions were of
the reagent grade. NaOD/D2O and phen-dione were purchased from Aldrich and used as received. The following
compounds were prepared according to literature methods:
dafo and Ru(dcbpy)2Cl2.13 Nanocrystalline TiO2 were obtained
from Degussa (P-25). Tin-doped indium oxide (ITO, 10
cm) electrode was supplied from Samsung Corning Co. in
Korea. The ITO substrates were successively washed with
acetone, ethanol and deionized water in an ultrasonicator
bath for 15 min, and finally rinsed with iso-propanol.
Instrumentations. Routine UV-vis spectra were recorded
on a Hewlett-Packard 8452 A Diode Array spectrophotometer.
FT IR spectra were obtained on a Bomen MB 100 spectrophotometer on KBr disc. 1H spectra were measured on a
Varian Gemini 200 MHz FT NMR spectrometer. The
chemical shift of spectra was presented in parts per million
( ) and referenced to TMS in NaOD/D2O. Elemental
analysis data were obtained from the analytical laboratory of
the Basic Science Institute of Korea. Redox properties of Ru
complexes were monitored by a cyclic voltammetry (BAS
100B, Bioanalytical Systems, Inc.). Electrochemical measurements were performed using a single compartment with
a standard three-electrode glass cell of Ag/AgCl and Pt as
reference and a standard electrode under nitrogen atmosphere. In order to measure the photocurrent, sandwich-type
DSCs were assembled with Ru complex/TiO2 /ITO and Ptsputtered ITO electrode in electrolyte composed of 0.1 mol/

Won K. Seok et al.

L of LiI and 0.05 mol/L of I2 in CH3CN. The Ru complex/

TiO2/ITO was irradiated by 80 mW/cm2 white light with air
mass 0 and 1.5 filters as a solar simulator in the presence of a
water filter (450 W Xenon lamp, Oriel Instruments), and the
photocurrent was measured with a Kiethley 2400 source
meter. The incident-photon-to-current conversion efficiency
(IPCE) measurements were carried out without bias illumination with respect to a calibrated Melles-Friot silicon diode.
IPCE was measured by changing the excitation wavelength
(Photon counting spectrometer, ISS Inc. and Kiethley 2400
source meter).
General Procedure.
[Ru(dcbpy)2(L-L)](Cl)2 (L-L = dafo or phen-dione). A
solution of 0.033 g of Ru(dcbpy)2Cl2 (0.05 mmol) containing
0.07 g of KOH (1.25 mmol) in 15 mL water/15 mL MeOH
was refluxed with continuous stirring for 5 h. It was cooled
off and 0.014 g of dafo (0.075 mmol) or 0.016 g of phendione (0.075 mmol) was added to the solution. The reaction
mixture was again refluxed with continuous stirring for 5 h.
It was filtered to remove any unwanted impurities and
evaporated to dryness using a rotatory evaporator. It was
dissolved in methanol and precipitated by using diethyl ether
and centrifuged out. Dissolution in methanol and precipitation
was repeated several times until free of any turbidity. It was
again dissolved in methanol and yellow orange colored
compound precipitated by using 0.5 M nitric acid solution at
pH in the range of 3 and 3.5. Finally, it was filtered by using
glass frit and successively washed with ~15 mL aqueous
HNO3 solution containing pH 3.5, methanol and diethyl
ether.
[Ru(dcbpy)2(dafo)](Cl)2. Yield: 65%. UV-vis: 480 (14.0
103), 454sh (12.4 103), 366 (10.0 103), 304 (39.1 103),
248 (22.8 103), 210 (37.9 103). Anal Calcd. For
C35H22N6O9Cl2Ru: C, 49.89; H, 2.63; N, 9.98. Found: C,
47.55; H, 2.47; N, 10.28.
[Ru(dcbpy)2(phen-dione)](Cl)2. Yield: 60%. UV-vis: 482
(14.3 103), 454sh (12.3 103), 364 (12.0 103), 310 (45.0
103), 254 (30.0 103), 220 (45.0 103). Anal Calcd. For
C36H22N6O10Cl2Ru: C, 49.66; H, 2.55; N, 9.66. Found: C,
48.85; H, 2.86; N, 9.14.
[Ru(dcbpy)2(L-L)](X)2 (L-L = dafo or phen-dione and
X = CN, NCS). To a solution of 0.033 g of Ru(dcbpy)2Cl2
(0.05 mmol) containing 0.07 g of KOH (1.25 mmol) in 15
mL water/15 mL MeOH was added 0.1 mmol of AgX (X =
CN, NCS) salt respectively. The reaction mixture was
refluxed with continuous stirring for 5 h. It was cooled and
filtered to remove AgCl. 0.014 g of dafo (0.075 mmol) or
0.016 g of phen-dione (0.075 mmol) was added to a clear red
solution. The reaction mixture was again refluxed with
continuous stirring for 5 h. It was filtered to remove any
unwanted impurities and evaporated to dryness using a
rotatory evaporator. It was dissolved in methanol and
precipitated by using diethyl ether and centrifuged out.
Dissolution in methanol and precipitation was repeated
several times until free of any turbidity. It was again
dissolved in methanol and yellow orange colored compound
precipitated by using 0.5 M nitric acid solution at pH in the

Synthesis and Application of New Ru(II) Complexes

range of 3 and 3.5. Finally it was filtered by using glass frit

and successively washed with ~15 mL aqueous HNO3
solution containing pH 3.5, methanol and diethyl ether.
[Ru(dcbpy)2(dafo)](CN)2. Yield: 42%. UV-vis: 504 (15.5
103), 380 (15.3 103), 310 (38.5 103), 250 (26.8 103),
212 (38.8 103). FT IR: 2079, 1718, 1562, 1406, 1266,
1232. 1H NMR: 9.21 (2H, d), 8.69-8.19 (8H, m), 7.89-7.15
(8H, m). Anal Calcd. For C37H22N8O9Ru: C, 53.95; H, 2.69;
N, 13.61. Found: C, 55.22; H, 2.82; N, 12.95.
[Ru(dcbpy)2(phen-dione)](CN)2. Yield: 40%. UV-vis: 508
(13.8 103), 384 (11.7 103), 310 (45.7 103), 250sh (24.1
103), 212 (39.7 103). FT IR: 2079, 1718, 1560, 1406,
1269, 1232, 773. 1H NMR: 8.72 (2H, d), 7.99-7.42 (8H, m),
7.29-7.11 (8H, m). Anal Calcd. For C38H22N8O10Ru: C,
53.58; H, 2.60; N, 13.16. Found: C, 52.06; H, 2.44; N, 13.52.
[Ru(dcbpy)2(dafo)](NCS)2. Yield: 57%. UV-vis: 480 (8.10
103), 454sh (7.10 103), 362sh (4.80 103), 306 (26.7
103), 248sh (14.5 103), 208 (26.8 103). FT IR: 2104,
1718, 1610, 1406, 1232, 770. 1H NMR: 8.71 (2H, d), 7.997.43 (8H, m), 7.29-7.11 (8H, m). Anal Calcd. For C37H22N8O9S2Ru: C, 49.83; H, 2.42; N, 12.24. Found: C, 47.80; H,
2.66; N, 11.90.
[Ru(dcbpy)2(phen-dione)](NCS)2. Yield: 52%. UV-vis:
484 (23.0 103), 456sh (18.3 103), 364sh (18.4 103), 308
(80.0 103), 250sh (40.0 103), 222 (73.0 103). FT IR:
2109, 1719, 1593, 1383, 1230, 771. 1H NMR: 8.71 (2H, d),
7.99-7.43 (8H, m), 7.29-7.11 (8H, m). Anal Calcd. For
C38H22N8O10S2Ru: C, 49.83; H, 2.42; N, 12.24. Found: C,
47.80; H, 2.66; N, 11.90.
Preparation of Film Electrode. Transparent films of
electrodes were obtained by spin coating TiO2 colloidal
solution on conducting glass plates (ITO). Then, the films
were sintered for 30 min at 450 oC in air. The thickness of
the TiO2 layer was about 7 m determined using the surface
profiler (P-10, TENCOR. Co.). The annealed films were
impregnated with 0.5 mM Ru(II) sensitizer in MeOH for
24h at room temperature. Each dye-coated film was soaked
in MeOH for 3h to remove unattached dye molecules. The
resulting sensitizer-coated TiO2 film was washed with
ethanol and then used to fabricate the DSCs.
Results and Discussion
Scheme 1 shows the chemical structure of each new Ru(II)
dye. Since the dye molecules play a key role in harvesting
sunlight and solar energy conversion into electricity, many
efforts have been made to develop new sensitizers. Many
Ru(II) polypyridyl complexes have been employed to sensitize nanocrystalline titanium oxide semiconductors, since
they have intense and highly efficient absorption band of
MLCT in the visible region and a long excited lifetime.
Although one of them, cis-[RuII(dcbpy)2(NCS)2], is the most
frequently used as a sensitizer in DSCs systems, the photoconversion performance still shows that there is room for
improvement.1-8
New Ru(II) complexes, [RuII(dcbpy)2(dafo)]X2 or [RuII
(dcbpy)2(phen-dione)]X2 (X=Cl, CN, NCS), which contain

Bull. Korean Chem. Soc. 2007, Vol. 28, No. 8

1313

Scheme 1. Chemical Structures of New Ru(II) Dyes.

two ancillary ligands of dafo and phen-dione instead of

nonchromophoric thiocyanato ligand are synthesized. The
ligands exhibit distinct properties such as containing a
reactive exocyclic ketone and having a more rigid structure
compared to analogue 2,2'-bipyridine. Ru(II) heterocyclic
complexes were obtained in the traditional way by reaction
of cis-[RuII(dcbpy)2Cl2] with dafo or phen-dione in a basic
solution of water and methanol. For example, [RuII(dcbpy)2
(dafo)]2+ was prepared by metathesis as follows. The
procedure required the prior preparation of the Ag+ complex
of the heterocyclic ligand and then its reaction with the
appropriate ruthenium precursor. The driving force in the
reaction is precipitation of AgCl.14
cis-[RuII(dcbpy)2Cl2] + 2Ag(dafo)2+
[RuII(dcbpy)2(dafo)]2+ + 2AgCl + 2dafo
The complexes were initially characterized by electronic
spectra. UV-vis absorption spectra of Ru(II) complexes are
shown in Figure 1. Each 5 105 M stock solution for the
spectra was prepared in 50 cm3 of 5:1 H2O:EtOH mixture
containing 0.1 M NaNO3. NaNO3 was added to avoid
precipitation while performing acid-base titration; complexes were insoluble in H2O, but sparingly soluble in
aqueous basic medium. The pH of the solution was made to
11 by using 0.2 M NaOH solution and then by adding
diluted nitric acid gradually decreased its pH. Generally the
bands in the UV region at 300 and 250 nm are assigned to
intra ligand -* charge-transfer transitions of dcbpy as well
as dafo or phen-dione ligand, respectively.
For [RuII(dcbpy)2(dafo)](X)2 and [RuII(dcbpy)2(phendione)] (X)2 (X=Cl, CN, NCS) complexes, most of them
show two broad visible bands around 480 and 360 nm,
which are assigned to MLCT origin. However, the broad
MLCT bands shift to around 500 and 380 nm for the
complexes of cyanate anions. The bands in the UV region
around 310 and 250 nm for all the Ru complexes are

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Bull. Korean Chem. Soc. 2007, Vol. 28, No. 8

Figure 1. UV-vis Absorption Spectra of Ru(II) Complexes.

assigned to intra ligand -* charge transfer transitions of

dcbpy as well as dafo or phen-dione ligands.
Deprotonation of the COOH groups in the [RuII(dcbpy)2
(dafo)](NCS)2 complex blue shifts the lower energy MLCT
d-* charge-transfer bands from 480 to 466 nm and from
360 to 348 nm as shoulder peak with a higher molar
absorption coefficient. The blue shift is due to an increase in
the energy of LUMO of ligand, causing the -* and d-*
transitions to occur at higher energies. However, the band at
250 nm due to -* charge-transfer transitions of the dcbpy
ligand, is unaffected in the pH range of 2 to 11.15 The molar
extinction coefficient of the prepared complexes is generally
higher than that of cis-[RuII(dcbpy)2(NCS)2]. There are also
two shoulder peaks around 346 and 440 nm, which are
tentatively attributed to MLCT transitions.
FT IR spectra of all the prepared complexes show a strong
broad band in the region of around 1720 cm1 due to the
C=O stretching on the carboxylate group.16 The weak peak
around 1230 cm1 is due to v(CO) stretching. The spectra
of the complexes also shows the presence of carboxylate
asymmetric (v(COOas)) between 1560 and 1610 cm1 and
symmetric (v(COOs)) around 1400 cm1 together with a
strong v(NC) of the cyanate anions at 2079 cm1 and of the
thiocyanate anions at 2104 cm1.16a The C-H stretching
vibrations of the heteroaromatic pyridines expected about
3100 cm1 are weak because of a very strong moisture
background.
The 1H NMR spectra of the complexes [RuII(dcbpy)2
(dafo)]X2 where X is CN or NCS show a strong doublet at
9.21 and 8.71 ppm for 6,6-positioned two protons of bisdcbpy and a singlet at 8.69 and 7.99 ppm for 3,3-positioned
four protons of bis-dcbpy ligands.3b,3c,17 The doublet at 8.48
and 7.78 ppm is assigned to 1,8-protons of the dafo ligand
chelated to the ruthenium metal center. The multiplet around
8.30 and 7.50 ppm is assigned to two 2,7-protons of the dafo
ligand. There are multiple peaks between 7.89-7.15 ppm and
7.29-7.11 ppm, which are assigned to the mixing of the
coupling of four protons 6,6-positioned protons of the bisdcbpy ligands as well as the 3,6-protons of the dafo ligand.
The 1H NMR spectra of the complexes [RuII(dcbpy)2
(phen-dione)](X)2 (X = CN, NCS) also show a strong

Won K. Seok et al.

Figure 2. Cyclic Voltammogram of Ru(II) Complexes in 0.1 M

[N(Bu)4][BF4] as Supporting Electrolyte with a Scan Rate of 50
mV/s.

doublet at 8.72 ppm for 6,6-positioned two protons of bisdcbpy and a strong singlet at 7.90 ppm for four protons of
bis-dcbpy ligands. The doublet around 7.80 ppm and the
sextet around 7.50 ppm are assigned to 4,7-protons and 3,8protons of the phen-dione ligand chelated to the ruthenium.
Multiplet peaks between 7.29-7.11 ppm result from the
mixing of coupling of four protons 6,6-positioned protons of
the bis-dcbpy ligands as well as the 3,6-protons of the phendione ligand. The 1H NMR spectra of both complexes are
complicated in nature and show a similar pattern of splitting
except 4,7-positioned protons of the phen-dione ligand to
more or less upfield chemical shift in comparison to the 1,8protons of dafo ligand.
The redox properties of the prepared Ru complexes are
monitored by cyclic voltammetry of Pt standard electrode in
MeOH containing 0.1 M of [N(Bu)4][BF4] as supporting
electrolyte with a scan rate of 50 mV/s. As shown in Figure
2, each ruthenium complex indicates Ru(II)/Ru(III).18 The
Eox of four different complexes with CN, NCS, dafo, phendione showed small changes on the HOMO level. The
[Ru(dcbpy)2(dafo)](CN)2 gives oxidation potential of 833
mV, which is the lowest value among them. [Ru(dcbpy)2
(phen-dione)](CN)2 shows 816 mV, and the difference between them is only 20 mV. The phen-dione ligand generally
increases the oxidation potential by lowering HOMO level.
Upon irradiation, the oxidation peak of ruthenium complex
shifts to Ru(III)/Ru(IV), which is independently monitored
by the chemical oxidation with Ce(IV) sulfate.18,19 However,
LUMO level of newly prepared dyes are different depending
on the combination of ligands as shown in Table 1. The
maximum absorptions of the dyes are blue shifted from the
one of N3 dye, 536 nm. [Ru(dcbpy)2(phen-dione)](NCS)2
shows the maximum absorption at 463 nm with a band gab
of 1.70 eV. [Ru(dcbpy)2(dafo)](CN)2 has the biggest band
gab of 1.89 eV with an absorption maximum at 460 nm.
The photovoltaic performance of the DSCs with new Ru
dyes on TiO2 films is investigated by measuring the J-V
characteristics. A sandwich-type cell is prepared in the
presence of LiI/I2 /acetonitrile. The cell is illuminated by 80

Synthesis and Application of New Ru(II) Complexes

Bull. Korean Chem. Soc. 2007, Vol. 28, No. 8

1315

Table 1. Photo-electrical Parameters of New Dyes

Dye
[RuII(dcbpy)2(dafo)](CN)2
[RuII(dcbpy)2(dafo)](NCS)2
[RuII(dcbpy)2(phen-dione)](CN)2
[RuII(dcbpy)2(phen-dione)](NCS)2
a

Eox a Band
LUMOb HOMOb
(mV) gap (eV)
833
836
816
819

1.89
1.92
1.81
1.70

3.56 5.45
3.52 5.45
3.63 5.44
3.75 5.45

vs. Ag/AgCl. b vs. vacuum

Figure 4. Incident photon-to-current conversion efficiency (IPCE)

of [RuII(dcbpy)2(dafo)](CN)2 and N3 dye on TiO2/ITO.

efficiency, IPCE (%), which is defined and calculated using

equation
IPCE = ( 1240*I sc ) ( P in )

Figure 3. J-V curve of DSCs with Ru(II) Complexes.

mW/cm2 white light with air mass 0 and 1.5 filters as a solar
simulator in the presence of a water filter. Figure 3 shows the
typical J-V curves of the DSCs. The solar cell with the
[RuII(dcbpy)2(dafo)](CN)2 shows the highest conversion
efficiency of 2.98% with Jsc of 7.33 mA/cm2, Voc of 0.66 V,
and FF of 0.61 shown in Table 2. As a reference, a solar cell
with N3 dye is prepared under the identical conditions.
Compared to the cell with N3 dye, new dyes show good FF
in the range of 0.56-0.61. However, Jsc is relatively decreased
from 7.33 mA to 2.07 mA. With the same chelating ligand,
the Jsc of Ru complex with CN ligand almost doubled in
value compared to SCN ligand. Voc of cells with NCS was
also smaller than that of CN ligand. Though the number of
compounds prepared is not enough to draw any definitive
conclusion, the CN ligand seems to be a good choice to
design an efficient photosensitizer.
The photocurrent is determined by the amount of absorbed
light and the internal conversion efficiency. An experimentally accessible value is the incident photon to current
Table 2. Performance Parameters of DSCs Containing Ru(II) Dyes
Dye

Isc a
(mA/cm2)

Vocb
(V)

FFc

Eff d
(%)

[RuII(dcbpy)2(NCS)2]
[RuII(dcbpy)2(dafo)](CN)2
[RuII(dcbpy)2(dafo)](NCS)2
[RuII(dcbpy)2(phen-dione)](CN)2
[RuII(dcbpy)2(phen-dione)](NCS)2

8.01
7.33
3.46
4.97
2.07

0.70
0.66
0.65
0.69
0.69

0.60
0.61
0.54
0.56
0.60

3.31
2.98
1.22
1.92
0.86

short-circuit current. bopen-circuit voltage. cfill factor. dpower conversion efficiency

where [nm] is the incident photon wavelength, Isc [uA/

cm2] is the photocurrent of the device and PIn [W/m2] is the
incident power. Figure 4 shows the IPCE spectra of the
RuII(dcbpy)2(dafo)](CN)2 and N3 dye on TiO2/ITO. The
IPCE spectrum of RuII(dcbpy)2(dafo)](CN)2 reaches up to
70% by the monochromatic illumination at 490 nm. As a
reference, IPCE of N3 dye on TiO2/ITO is 76%, which is
smaller than previously reported value.1a
Conclusion
New types of ligand were used to prepare photosensitizers
for the nanocrystalline DSCs. Chelating ligands of dafo and
phen-dione were coordinated with the octahedral Ru complex containing either CN or SCN anion. The Ru complexes
showed similar HOMO and LUMO level compared to those
of N3 dye. Compared to cells with N3 dye, new dyes
showed good fill factor in the range of 0.54-0.61. With the
same chelating ligand on Ru complex, the CN ligand
increased the Jsc up to double the value compared with the
SCN ligand.
Acknowledgement. Won K. Seok thanks Dongguk
University for supporting the research. S.-J. Roh and W. Lee
wish to thank Brain Korea 21 for the award of financial
support. S.-H. Han thanks the Korean Science and Engineering Foundation (ABRL R14-2003-014-01001-0) for
supporting the research. The research was partially supported by ITEP.
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Kuang, D.; Ito, S.; Wenger, B.; Klein, C.; Moser, J.; HumphreyBaker, R.; Zakeeruddin, S. M.; Gratzel, M. J. Am. Chem. Soc.
2006, 128, 4146.
2. ORegan, B.; Gratzel, M. Nature 1991, 353, 737.

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