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Cite this: Dalton Trans., 2012, 41, 7604
www.rsc.org/dalton PAPER
Efficient thiocyanate-free sensitizer: a viable alternative to N719 dye for
dye-sensitized solar cells†
Surya Prakash Singh,*a K. S. V. Gupta,a G. D. Sharma,b Ashraful Islamc and Liyuan Hanc
Received 23rd February 2012, Accepted 16th April 2012
DOI: 10.1039/c2dt30697b
Published on 17 April 2012 on http://pubs.rsc.org | doi:10.1039/C2DT30697B

We have designed and synthesized a new thiocyanate-free sensitizer coded as SPS-01 and used it as the
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sensitizer in a TiO2 based nanocrystalline dye-sensitized solar cell (DSSC). SPS-01 exhibits strong visible
absorption properties with maximum peak around at 532 nm. The overall power conversion efficiency
(PCE) of a DSSC sensitized with SPS-01 (7.96%) is higher than that of N719 (7.30%) under identical
experimental conditions. This high PCE is attributed mainly due to the improvement in the short circuit
current.

Introduction However, thiocyanate ligands are incorporated in most of the

Ru(II) based sensitizers, which reduce the synthetic yield and
The development of cost effective renewable energy alternatives also deteriorate the lifespan of the as-fabricated cell units due to
to current power generation methods is an urgent need because the weak Ru–NCS dative bonding under excessive thermal stress
of the increasing demands and concerns over global warming. or light soaking.5 Few attempts have been made to replace the
Among several new energy technologies, dye sensitized solar SCN donor ligands, however they gave only limited success,6 a
cells (DSSCs) pioneered by O’Regan and Grätzel, have attracted superior conversion efficiency of 10.1% is now documented by
significant attention because of their low cost and high perform- the Grätzel group.7 It is know when extended π-conjugation
ance.1 A DSSC is a photo-electrochemical device which con- is incorporated between the chromophore and the anchoring
tains a photoelectrode, iodine–iodide redox coupled electrolyte group, ruthenium sensitizers are afforded with increased molar
and counter electrode. The photoelectrode consists of a tailor extinction coefficients and enhanced red response in the visible
made light absorbing sensitizer attached to the surface of a large regions.8
band gap nanocrystalline TiO2 film to absorb the light. In light Recently, Chou et al. reported a PCE of 9.54% for DSSCs
harvesting, the choice of a sensitizer should be capable of based on a thiocyanate-free Ru(II) sensitizer containing both 4,4′-
efficient absorption in the visible to NIR light region of the solar carboxy-2,2′-bipyridine and 2-pyrazolate ancillaries.9 As part of
spectrum and is a crucial factor. Therefore, many efforts have our research program in the development of thiocyanate-free sen-
been focused on the design and synthesis of various dyes, sitizers,10 here we report the synthesis of a thiocyanate-free
including metal complexes2 and organic dyes.3 Among them Ru(II) sensitizer, incorporating a phenylethenyl moiety into the
Ru(II) polypyridine complexes have been extensively pursued as anchoring bipyridine, represented as SPS-01 (Scheme 1) and
a potential candidate for efficient sensitizers because of their used it as a potential sensitizer for DSSCs. The DSSC based on
favorable photophysical properties such as intense charge trans- the SPS-01 sensitizer with 20 μm thick transparent nanocrystal-
fer absorption in the visible region and electrochemical pro- line TiO2 layer produced an overall PCE of 7.96% which is
perties which can be systematically fine tuned to achieve optimal higher than the DSSC based on an N719 sensitizer (7.30%),
characteristics. With the certified PCEs more than 11% for under identical conditions.
DSSCs based on stable Ru(II) dyes as the light harvesting
component, this remains the frontier of chemical discovery.4

a
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of
Chemical Technology, Uppal Road, Tarnaka, Hyderabad, 500607,
India. E-mail: spsingh@iict.res.in; Fax: +91(0)40-2716-0921;
Tel: +91(0)40-2719-3186.
b
R & D Centre for Engineering and Science, Jaipur Engineering
College, Kukas, Jaipur (Raj.), India.
c
Photovoltaic Materials Unit, National Institute for Materials Science,
1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan. Fax: +81(0)29 859
2301; Tel: +81(0)29 859 2129.
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c2dt30697b Scheme 1 Chemical structure of SPS-01.

7604 | Dalton Trans., 2012, 41, 7604–7608 This journal is © The Royal Society of Chemistry 2012
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Experimental details Preparation of TiO2 electrode

Synthesis of thiocyanate free dye, SPS-01 Nanocrystalline TiO2 photoelectrodes of about 20 μm thickness
(area: 0.25 cm2) were prepared using a variation of a method
2-(3-(Trifluoromethyl)-1H-pyrazol-5-yl)pyridine (149.76 mg, reported by Grätzel and co-workers.2a Fluorine-doped tin oxide-
0.70 mmol) and [Ru(4,4′-bis( p-methylcarboxystyryl)-2,2′- coated (FTO) glass electrodes (Nippon Sheet Glass Co., Japan)
bipyridine)( p-cymene)Cl]·Cl (250 mg, 0.33 mmol) were dis- with a sheet resistance of 8–10 ohm m−2 and an optical trans-
solved in 2-methoxyethanol (30 mL), and the reaction mixture mission of >80% in the visible range were used. Anatase TiO2
was heated to 130 °C under stirring for 12 h. After evaporating colloids ( particle size ∼13 nm) were obtained from commercial
the solvent, the aqueous phase was separated and extracted sources (Ti-Nanoxide D/SP, Solaronix). The nanocrystalline
with dichloromethane (3 × 25 mL). The crude compound was TiO2 thin films of approximately 20 μm thickness were depos-
purified by silica gel column chromatography (CH2Cl2–EtOAc = ited onto the conducting glass by screen-printing. The film was
5 : 1). Finally, the resulting solid was dissolved in a mixture of then sintered at 500 °C for 1 h. The film thickness was measured
Published on 17 April 2012 on http://pubs.rsc.org | doi:10.1039/C2DT30697B

acetone (5 mL) and 1 M sodium hydroxide (5 mL). The solution with a Surfcom 1400A surface profiler (Tokyo Seimitsu Co.
was heated to 100 °C under N2 for 24 h. After completing the Ltd). The electrodes were impregnated with a 50 mM titanium
hydrolysis, the solvent was removed and the solid was dissolved tetrachloride solution and sintered at 500 °C. The dye solutions
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in basic H2O solution (10 mL) and was titrated with 2 M HCl to (2 × 10−4 M) were prepared in 1 : 1 acetonitrile and tert-butyl
pH 3 to afford a brown precipitate. This brown product was then alcohol solvents. Deoxycholic acid (DCA) as a co-adsorbent
taken into a minimum amount of methanol and purified on a was added to the dye solution at a concentration of 20 mM. The
Sephadex LH-20 column using methanol as the eluent. The electrodes were immersed in the dye solutions and then kept
main band was collected and solvent was evaporated to dryness. at 25 °C for 20 h to adsorb the dye onto the TiO2 surface.
After then, the brown precipitate was washed with deionized
water and diethyl ether in sequence, giving SPS-01 as a
powdery material. The procedure of the synthesis of SPS-01 is Fabrication of dye-sensitized solar cell
shown in Scheme 2. 1H NMR (CD3OD, 600 MHz): δ 8.1
(s, 2H), 8.0 (m, 3H), 7.94 (t, 2H), 7.86 (d, 2H), 7.57–7.78 Photovoltaic measurements were performed in a two-electrode
(m, 12H), 7.35 (3H, d), 7.2 (d, 2H), 7.07–6.93 (m, 2H); FR-IR sandwich cell configuration. The dye-deposited TiO2 film was
(KBr, cm−1): 3418, 1587, 1540, 1383, 1249, 1137, 991; ESI-MS used as the working electrode and a platinum-coated conducting
(M−): 972 (expected 973). glass as the counter electrode. The two electrodes were separated
Electrochemical data were recorded using Autolab potentio- by a surlyn spacer (40 μm thick) and sealed up by heating
stat/Galvanostat PGSTAT30 having three electrodes. The cyclic the polymer frame. The electrolyte was composed of 0.6 M
voltammogram curves were obtained from a three electrode cell dimethylpropyl-imidazolium iodide (DMPII), 0.05 M I2, and
in 0.1 M Bu4NPF6 acetonitrile solution at a scan rate of 100 mV 0.1 M LiI and TBP 0.5 M in acetonitrile.
s−1, using a dye coated on glassy carbon as a working electrode,
Pt wire as a counter electrode and an Ag/AgCl reference elec-
Photovoltaic characterization
trode and calibrated with ferrocene. All the measured potentials
were converted to the NHE scale. The optical spectra of SPS-01 The current–voltage characteristics were measured using the
in solution and adsorbed onto TiO2 surface were recorded with a previously reported method11 with a solar simulator (AM-1.5,
UV-visible spectrophotometer (Shimarzu). 100 mW cm−2, WXS-155S-10: Wacom Denso Co., Japan).

Scheme 2 Conditions: (i) 2-Methoxyethanol, 130 °C, 12 h. (ii) Acetone, NaOH, reflux.

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Monochromatic incident photon-to-current conversion efficiency

(IPCE) for the solar cell, plotted as a function of excitation wave-
length, was recorded on a CEP-2000 system (Bunkoh-Keiki Co.
Ltd). Incident photon-to-current conversion efficiency (IPCE) at
each incident wavelength was calculated from eqn (1), where Jsc
is the photocurrent density at short circuit in mA cm−2 under
monochromatic irradiation, λ is the wavelength of incident
radiation in nm, and Pin is the incident radiative flux in W m−2.

IPCEðλÞ ¼ ð1240Jsc =λPin Þ ð1Þ

The electrochemical impedance spectra (EIS) measurements
were carried out by applying bias equivalent to the Voc of the
device and recorded over a frequency of 0.01 Hz to 105 Hz with
Published on 17 April 2012 on http://pubs.rsc.org | doi:10.1039/C2DT30697B

an ac amplitude of 10 mV. The above measurements were

recorded with an electrochemical impedance analyser equipped
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with FRA.

Results and discussion

SPS-01 structural drawing is depicted in Scheme 1. SPS-01 was
prepared by direct treatment of [Ru(4,4′-bis( p-methylcarboxy-
styryl)-2,2′-bipyridine)( p-cymene)Cl]·Cl and 2-(3-(Trifluoro-
methyl)-1H-pyrazol-5-yl)pyridine in refluxing 2-methoxy-
ethanol. After chromatographic separation, it was then
hydrolyzed with 1 M NaOH solution at 100 °C for 24 h.
The normalized absorption spectra of SPS-01 in 1 : 1 aceto-
Fig. 1 (a) Optical absorption spectra of SPS-01 and N719 dye in sol-
nitrile and tert-butyl alcohol solvents is shown in Fig. 1a along ution. (b) Solid state optical absorption spectra of SPS-01 and N719
with the absorption spectra of N719 for comparison. In addition dyes adsorption in 12 μm TiO2 thin film.
to higher energy π–π* absorption around 334 nm, the SPS-01
exhibits two absorption at 418 nm and 532 nm attributable to the
metal-to-ligand charge transfer (MLCT) bands mixed with a energy gap is −0.93 V, sufficiently more negative than the con-
small amount of ligand to ligand charge transfer contribution. duction band edge of the TiO2 (−0.5 V vs. NHE).2a We have not
The optical band gap of the SPS-01 is estimated from the onset observed any shift in the peak at different cycles, which shows
of the optical absorption which is 1.83 eV. The absorption that the material is electrochemically stable in solution.
spectra of SPS-01 adsorbed on TiO2 film is shown in Fig. 1b, The cyclic voltammograms of SPS-01 were also measured
along with the N719. After adsorbing these dyes on the TiO2 at different scan rates i.e. 50 mV s−1, 200 mV s−1, 500 mV s−1
film, the optical absorption shows the redshift in the absorption and 1000 mV s−1 and are shown in Fig. 2b. The oxidation onset
band and an increase in intensity of the red tail. This was con- potential does not change with the scan rate, however, the anodic
sidered desirable as it increases the overlap with the solar spec- current increases linearly with the scan rate voltage. This obser-
trum and should result in a larger photocurrent. vation also indicates the electrochemical stability of SPS-01.
In order to check the photo-stability of SPS-01, we have also The IPCE spectra of the DSSCs based on SPS-01 and N719
measured the optical spectra of SPS-01 in solution at different sensitizers are shown in Fig. 3. The onset of IPCE spectra for the
time intervals as shown in Fig. S1, ESI†. There was little DSSCs based on SPS-01 and N719 are close to 810 nm and
observed change in the shape of the absorption band and any 780 nm, respectively and excellent IPCE performance was
shift in the absorption edge. These observations indicate that observed from 380 nm to 760 nm, for with 92.3% at 500 nm and
SPS-01 is photostable. 83% at 550 nm, for DSSCs based on SPS-01 and N719, respect-
Cyclic voltammetry was also performed to ensure that the ively. These results indicates that the SPS-01 dye exhibits
LUMO level of SPS-01 is suited for injecting electrons into the superior light harvesting capability than that of N719.
conduction band of TiO2 and to verify whether the HOMO level Fig. 4 shows the current–voltage (J–V) characteristics of the
match the redox potential of electrolyte. The cyclic voltammo- DSSCs under AM 1.5 G simulated light of 100 mW cm−2. The
grams of SPS-01 for three cycles at a scan rate of 50 mV s−1, are photovoltaic parameters i.e. short circuit photocurrent (Jsc), open
shown Fig. 2a. The onset oxidation potential is about 0.90 V (vs. circuit voltage (Voc), fill factor (FF) and power conversion
NHE) which is due to the Ru(II) metal oxidation. This indicates efficiency (PCE) are summarized in Table 1. Under standard AM
that the oxidation potential of I−/I3− redox couple (ca. 0.4 V vs. 1.5 solar conditions, the SPS-01 sensitized solar cell gave a Jsc
NHE)2a is more negative than the oxidation potential (HOMO value of 17.74 mA cm−2, Voc of 0.66 V, and FF of 0.68, yielding
level) of SPS-01 and is able to regenerate the dye effectively. an overall PCE of 7.96%. Under the same conditions, the N719
The LUMO energy level of SPS-01 estimated from the differ- sensitized solar cell gave a Jsc value of 15.35 mA cm−2, Voc
ence between the HOMO level and the onset of the optical value of 0.67 V and FF of 0.71, yielding a PCE of 7.30%. The

7606 | Dalton Trans., 2012, 41, 7604–7608 This journal is © The Royal Society of Chemistry 2012
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Fig. 4 Current–voltage characteristics of DSSCs under illumination

intensity of 100 mW cm−2.

Table 1 Photovoltaic parameters of DSSCs based on SPS-01 and

N719 dyes

Dye Jsc (mA cm−2) Voc (V) FF PCE (%)

SPS-01 17.74 0.66 0.68 7.96

N719 15.35 0.67 0.71 7.30

Fig. 2 (a) Cyclic voltammogram of SPS-01. Oxidation potential of the

dyes was measured in DMF with 0.1 m (nBu)4NPF6 and with a scan rate
of 50 mV s−1 (vs. the normal hydrogen electrode, NHE (three cycles). shows the electrochemical impedance spectra for the DSSCs
(b) Cyclic voltammograms of SPS-01 at different scan rates. based on SPS-01 and N719 dyes under a forward bias of −0.65
V in the dark. Two semicircles are observed in Nyquist plots
(Fig. 5a). The small and large semicircles respectively located in
the high and middle frequency regions are assigned to the charge
transfer at the Pt/electrolyte and the TiO2/dye/electrolyte inter-
face, respectively.13 The charge recombination resistance (Rrec) at
the TiO2 surface can be deduced by fitting curves from the range
of middle frequency using Z-view software. Rrec is related to
the charge recombination rate between injected electron and I3−
ions in the electrolyte, estimated from the large semicircle width.
A large Rrec means the small charge recombination rate and
vice versa. The Nyquist plots (Fig. 5a) in the dark under a
forward bias of 0.65 V show the radius of the middle semicircle
to increase in order SPS-01 > N719, indicating that the electron
recombination resistance is higher for the DSSC based on
SPS-01 than that for N719. The higher value of the recombina-
tion resistance leads to slower recombination process in the
Fig. 3 IPCE spectra of the DSSCs sensitized with SPS-01 and N719 DSSCs which is beneficial for a higher PCE value. The electron
dyes. lifetime values derived from these curves fitting are 35 ms
and 28 ms for SPS-01 and N719, respectively. The Bode
phase plots shown in Fig. 5b also supports the difference in
PCE of DSSCs sensitized with N719 dye is inferior to that of the electron lifetime for TiO2 films sensitized with these two
SPS-01, although FF for the former is higher. The higher PCE dyes. The middle frequency peaks of the DSSCs based on
value of the SPS-01 solar cell compared to that of its N719 SPS-01 shift to lower frequency relative to that of N719, indicat-
counterpart comes from the higher Jsc value, which can be ing shorter recombination lifetime for the latter dye. The increase
rationalized by the high absorption coefficient and red shifted in recombination lifetime in the TiO2 film is associated with
absorption of the MLCT band. a pronounced rise in the charge transfer resistance, implying
Electrochemical impedance spectra (EIS) analysis was also that the sensitization with SPS-01 decrease the interfacial
performed to elucidate the above photovoltaic findings.12 Fig. 5 rate constant for electron capture by I3− ions. In addition, at a

This journal is © The Royal Society of Chemistry 2012 Dalton Trans., 2012, 41, 7604–7608 | 7607
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Notes and references

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Published on 17 April 2012 on http://pubs.rsc.org | doi:10.1039/C2DT30697B

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7608 | Dalton Trans., 2012, 41, 7604–7608 This journal is © The Royal Society of Chemistry 2012