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New Diketopyrrolopyrrole (DPP) Dyes for

Efficient Dye-Sensitized Solar Cells

Article in The Journal of Physical Chemistry C · December 2009

DOI: 10.1021/jp909786k

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 J. Phys. Chem. C 2010, 114, 1343–1349 1343

New Diketopyrrolopyrrole (DPP) Dyes for Efficient Dye-Sensitized Solar Cells

Sanyin Qu, Wenjun Wu, Jianli Hua,* Cong Kong, Yitao Long, and He Tian*
Key Laboratory for AdVanced Materials and Institute of Fine Chemicals, East China UniVersity of Science &
Technology, 130 Meilong Road, Shanghai 200237, People’s Republic of China
ReceiVed: October 12, 2009; ReVised Manuscript ReceiVed: NoVember 29, 2009

Two novel metal-free dyes (DPP-I and DPP-II) with a diketopyrrolopyrrole (DPP) core were synthesized
for dye-sensitized solar cells (DSSCs). The absorption spectra and electrochemical and photovoltaic properties
of DPP-I and DPP-II were extensively investigated. Electrochemical measurement data indicate that the
tuning of the HOMO and LUMO energy levels can be conveniently accomplished by alternating the
π-conjugated systems. Besides, coadsorption of chenodeoxycholic acid (CDCA) can hinder the formation of
dye aggregates and might improve electron injection yield and, thus, Jsc. This has also led to a rise in the
photovoltage, which is attributed to the decrease of charge recombination. The DSSC based on dye DPP-I
showed better photovoltaic performance: a maximum monochromatic incident photon-to-current conversion
efficiency (IPCE) of 80%, a short-circuit photocurrent density (Jsc) of 9.78 mA cm-2, an open-circuit
photovoltage (Voc) of 605 mV, and a fill factor (FF) of 0.69, corresponding to an overall conversion efficiency
of 4.14% under standard global AM 1.5 solar light condition. This work suggests that the metal-free dyes
based on a DPP core are promising candidates for improvement of the performance of DSSCs.

1. Introduction
Dye-sensitized solar cells (DSSCs) have received considerable
attention as the most promising candidates for renewable energy
systems in recent years, owing to their high conversion
efficiency and low cost of production.1 DSSCs based on Ru-
complex photosensitizers, such as N3, N719, and the black dye,
have shown a record solar-energy-to-electricity conversion
efficiency of 11%.2 On the other hand, metal-free organic dyes
have also been developed for DSSCs due to their high molar
absorption coefficient, simple synthesis process, low cost, and
structure adjustability. Metal-free dyes, such as perylene dyes,3
cyanine dyes,4 merocyanine dyes,5 coumarin dyes,6 hemicyanine
dyes,7 and indoline dyes,8 have been investigated as sensitizers
for DSSCs, and great progress has been made in this field.
The sensitizer is a crucial element in DSSCs, exerting
significant influence on the power conversion efficiency as well
as the stability of the cells. Generally, organic dyes used for Figure 1. Molecular structures of DPP-I and DPP-II dyes.
efficient solar cells are required to possess high charge carrier
mobility and broad and intense spectral absorption in the visible-
light region.9 Here, we present two novel efficient dyes (DPP-I concurrent strong H bonding and π-π intermolecular interac-
and DPP-II) (shown in Figure 1) with triphenylamine as the tions in the solid state.12 Soluble derivatives, however, can be
donor, 2,5-dibutylpyrrolo-[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) made by attaching long alkyl chains on the lactam N atom
as a π-conjugated system, and carboxylic acid moiety acting positions of the DPP moiety.13 Also, the introduction of long
as acceptor. The triphenylamine can improve the hole-transport- alkyl chains into DPP rings can also inhibit the charge
ing ability of the materials, and the nonplanar structure of recombination and increase the electron lifetime.14 Finally, the
triphenylamine can also prevent the formation of dye ag- highly absorbing DPP moiety and the extended absorption at
gregates.10 On the other hand, DPP-containing materials are long wavelengths due to intramolecular charge transfer between
bright and strongly fluorescent with exceptional photochemical, the thiophene units and the DPP core increase their potential
mechanical, and thermal stability and are, therefore, used in applicability as dye-sensitizer for DSSCs.15 However, to the best
industrial applications as high performance pigments in paints, of our knowledge, small chromophores containing DPP struc-
plastics, and inks.11 DPP-based molecular materials, however, tural motifs have not been exploited for DSSCs. On the basis
are not soluble in most common organic solvents due to the of the above consideration, we have designed and synthesized
the two novel organic sensitizers, DPP-I and DPP-II, and
* To whom correspondence should be addressed. E-mail: tianhe@
ecust.edu.cn (H.T.), [email protected] (J.H.). Fax: 86-21-64252756 (H.T.), applied them successfully to sensitize nanocrystalline TiO2-based
86-21-64252758 (J.H.). Tel: 86-21-64252756 (H.T.), 86-21-64250940 (J.H.). solar cells.
10.1021/jp909786k  2010 American Chemical Society
Published on Web 12/17/2009
1344 J. Phys. Chem. C, Vol. 114, No. 2, 2010 Qu et al.

2. Experimental Section refluxed for a further 12 h. After cooling to room temperature,

2.1. Materials and Reagents. Tetra-n-butylammonium the mixture was extracted with 30 mL of CH2Cl2. The organic
hexafluorophosphate (TBAPF6), 4-tert-butylpyridine (4-TBP), portion was combined and removed by rotary evaporation. The
lithium iodide, and 2-cyanoacetic acid were purchased from residue was purified by column chromatography on silica
Fluka. THF was predried over 4 Å molecular sieves and distilled (CH2Cl2/ethyl acetate ) 1/70, v/v) to give a red solid. Yield:
under argon atmosphere from sodium benzophenone ketyl 46.6%. 1H NMR (500 MHz, CDCl3) δ: (ppm) 9.90 (s, 1H),
immediately prior to use. All other solvents and chemicals were 7.93 (m, 4H), 7.82 (d, J ) 8.29 Hz, 2H), 7.78 (d, J ) 3.84 Hz,
purchased from Aldrich and used as received without further 1H), 7.71 (d, J ) 8.25 Hz, 2H), 7.51 (d, J ) 3.85 Hz, 1H),
purification. 3,6-bis-(4-bromophenyl)-2,5-di-n-butyl-pyrrolo[3,4- 7.48 (d, J ) 8.57 Hz, 2H), 7.12 (d, J ) 8.81 Hz, 4H), 6.99 (d,
c]-pyrrole-1,4-dione (1), 3,6-bis-(5-bromo-thiophen-2-yl)-2,5- J ) 8.54 Hz, 2H), 6.87 (d, J ) 8.84 Hz, 4H), 3.81 (m, 10H),
di-n-butyl-pyrrolo[3,4-c]-pyrrole-1,4-dione (2), and 4-(bis(4- 1.58-1.69 (m, 4H), 1.21-1.38 (m, 4H), 0.82-0.91 (m, 6H).
13C NMR (125 MHz, CDCl ) δ: 183.4, 163.5, 163.3, 156.9,
methoxyphenyl)-amino)phenylboronic acid were synthesized 3
according to the corresponding literature methods.16 Transparent 153.3, 149.8, 149.6, 147.1, 144.3, 143.9, 141.1, 138.0, 135.8,
FTO conducting glass (fluorine-doped SnO2, transmission >90% 131.7, 130.2, 130.0, 129.7, 128.2, 127.6, 127.3, 127.1, 126.5,
in the visible, sheet resistance ) 15 Ω/square) was obtained 125.7, 120.7, 115.5, 111.2, 110.2, 56.2, 42.6, 42.5, 32.3, 32.2,
from Geao Science and Educational Co. Ltd. of China. Com- 20.7, 14.3.
mercial TiO2 (P25) was used for the preparation of the 2.3.4. Synthesis of 5-[5-[3-[5-(4-(N,N-Bis(4-methoxyphe-
nanocrystalline films. nyl)amino)phenyl)thiophene-2-yl]-2,5-di-n-butyl-pyrrolo[3,4-
2.2. Spectroscopic Measurements. Proton NMR spectra c]pyrrole-1,4-dione]thiophene-2-yl]thiophene-2-carbalde-
were obtained with a Brücker AM 500 spectrometer (relative hyde (6). The synthesis method resembles that of compound 5,
to TMS). Mass spectra were recorded with a Waters Micromass and the compound was purified by column chromatography on
LCT mass spectrometer. The absorption spectra of the dyes in silica (CH2Cl2) to give a green solid. Yield: 43.2%. 1H NMR
solution and adsorbed on TiO2 films were measured with a (500 MHz, CDCl3) δ: (ppm) 9.90 (s, 1H), 9.08 (d, J ) 4.20
Varian Cary 500 spectrophotometer. Hz, 1H), 8.85 (d, J ) 4.17 Hz, 1H), 7.72 (d, J ) 3.97 Hz, 1H),
2.3. Synthesis of Dyes. 2.3.1. Synthesis of 3-[4-[4-(N,N- 7.49 (d, J ) 2.58 Hz, 2H), 7.48 (d, J ) 1.80, 1H), 7.39 (d, J )
Bis(4-methoxyphenyl)amino)phenyl]phenyl]-6-(4-bromophe- 3.94 Hz, 1H), 7.35 (d, J ) 4.19 Hz, 1H), 7.10 (d, J ) 8.88 Hz,
nyl)-2,5-di-n-butyl-pyrrolo[3,4-c]pyrrole-1,4-dione (3). Com- 4H), 6.92 (d, J ) 8.76 Hz, 2H), 6.86 (d, J ) 8.91, 4H), 4.12
pound 1 (0.84 g, 1.50 mmol), Pd(PPh3)4 (10 mg, 0.01 mmol), (m, 4H), 3.83 (s, 6H), 1.77 (m, 4H), 1.48 (m, 4H), 0.98 (m,
and Na2CO3 (1.02 g, 0.01 mol) in 30 mL of THF and 5 mL of 6H). 13C NMR (500 MHz, CDCl3) δ: 184.0, 163.2, 162.6, 158.2,
H2O were heated to 45 °C under a nitrogen atmosphere for 30 153.4, 151.4, 147.1, 144.5, 142.7, 141.6, 141.5, 139.8, 138.8,
min. A solution of 4-(bis(4-methoxyphenyl)-amino)phenylbo- 138.6, 137.1, 128.8, 128.6, 127.0, 124.9, 121.2, 116.5, 57.2,
ronic acid (0.63 g, 1.80 mmol) in THF (10 mL) was added 55.1, 43.8, 33.8, 33.7, 21.9, 15.4.
slowly, and the mixture was refluxed for a further 12 h. After 2.3.5. Synthesis of 2-cyano-3-[5-[4-[3-[4-(4-(N,N-Bis(4-
cooling to room temperature, the mixture was extracted with methoxyphenyl)amino)phenyl)phenyl]-2,5-di-n-butyl-pyrrolo[3,4-
50 mL of CH2Cl2. The organic portion was combined and c]pyrrole-1,4-dione]phenyl]thiophene-2-yl]acrylic acid (DPP-
removed by rotary evaporation. The residue was purified by I). Compound 5 (0.10 g, 0.12 mmol), 2-cyanoacetic acid (0.11
column chromatography on silica (CH2Cl2/petroleum ether ) g, 1.29 mmol), and piperidine (0.5 mL) in 20 mL of THF were
1/1, v/v) to give an orange solid (0.41 g). Yield: 34.9%. 1H heated to reflux under a nitrogen atmosphere for 6 h. After
NMR (500 MHz, CDCl3) δ: (ppm) 7.89 (d, J ) 8.29 Hz, 2H), cooling to room temperature, the precipitate was filtered. The
7.72 (d, J ) 8.34 Hz, 4H), 7.66 (d, J ) 8.51 Hz, 2H), 7.48 (d, residue was purified by column chromatography on silica
J ) 8.60 Hz, 2H), 7.12 (d, J ) 8.81 Hz, 4H), 6.99 (d, J ) 8.58 (CH2Cl2/ethanol ) 10/1, v/v) to give a dark red solid. Yield:
Hz, 2H), 6.86 (d, J ) 8.82 Hz, 4H), 3.82 (s, 6H), 3.75 (t, J ) 73.4%. 1H NMR (500 MHz, DMSO) δ: (ppm) 8.45 (s, 1H),
7.47 Hz, 7.63 Hz, 4H), 1.55-1.65 (m, 4H), 1.20-1.35 (m, 4H), 8.18 (d, 1H), 7.98 (d, 1H), 7.89-7.96 (m, 4H), 7.82-7.86 (m,
0.85 (m, 6H). 4H), 7.65 (d, J ) 8.47 Hz, 2H), 7.12 (d, J ) 8.76 Hz, 4H),
2.3.2. Synthesis of 3-[5-[4-(N,N-Bis(4-methoxyphenyl)ami- 6.98 (d, J ) 8.82 Hz, 4H), 6.82 (d, J ) 8.61 Hz, 2H), 3.71-3.82
no)phenyl]thiophen-2-yl]-6-(5-bromo-thiophen-2-yl)-2,5-di-n- (m, 10H), 1.64 (m, 4H), 1.20 (m, 4H), 0.69 (m, 6H). 13C NMR
butyl-pyrrolo[3,4-c]pyrrole-1,4-dione (4). The synthesis method (125 MHz, DMSO) δ: 163.1, 162.9, 156.7, 151.1, 149.6, 149.2,
resembles that of compound 3, and the compound was purified 147.1, 143.5, 141.1, 137.5, 135.2, 131.7, 130.1, 130.0, 129.7,
by column chromatography on silica (CH2Cl2/petroleum ether 128.1, 127.5, 126.5, 126.4, 126.3, 125.2, 120.7, 115.4, 110.6,
) 5/1, v/v) to give a blue purple solid. Yield: 33.3%. 1H NMR 109.8, 56.1, 45.4, 42.0, 32.5, 31.9, 30.3, 30.0, 23.4, 23.1, 20.6,
(500 MHz, CDCl3) δ: (ppm) 9.13 (d, J ) 4.20 Hz, 1H), 8.62 14.8, 14.2. HRMS (m/z): [M + H]+ calcd for (C54H48N4O6S),
(d, J ) 4.15 Hz, 1H), 7.47 (d, J ) 8.53 Hz, 2H), 7.34 (d, J ) 881.3295; found, 881.3285.
4.18 Hz, 1H), 7.23 (d, J ) 4.15 Hz, 1H), 7.09 (d, J ) 8.88 Hz, 2.3.6. Synthesis of 2-Cyano-3-[5-[5-[3-[5-(4-(N,N-bis(4-
4H), 6.93 (d, J ) 8.58 Hz, 2H), 6.85 (d, J ) 8.85 Hz, 4H), methoxyphenyl)amino) phenyl)thiophene-2-yl]-2,5-di-n-butyl-
4.12 (m, 4H), 3.83 (s, 6H), 1.72 (m, 4H), 1.43 (m, 4H), 0.96 (t, pyrrolo[3,4-c]pyrrole-1,4-dione]thiophene-2-yl]thiophene-2-
J ) 7.34 Hz, 7.39 Hz, 6H). yl]acrylic acid (DPP-II). The synthesis method resembles that
2.3.3. Synthesis of 5-[4-[3-[4-(4-(N,N-Bis(4-methoxyphe- of compound DPP-I, and the compound was purified by column
nyl)amino)phenyl)phenyl]-2,5-di-n-butyl-pyrrolo[3,4-c]pyrrole- chromatography on silica (CH2Cl2/ethanol ) 10/1, v/v) to give
1,4-dione]phenyl]thiophene-2-carbaldehyde (5). Compound 3 a dark green solid. Yield: 56.8%. 1H NMR (500 MHz, DMSO)
(0.40 g, 0.51 mmol), Pd(PPh3)4 (10 mg, 0.01 mmol), and δ: (ppm) 8.92 (d, J ) 2.92, 1H), 8.78 (d, J ) 3.70, 1H), 8.13
Na2CO3 (1.02 g, 0.01 mol) in 10 mL of THF and 5 mL of H2O (s, 1H), 7.72 (d, 1H), 7.68 (d, 1H), 7.62 (d, 1H), 7.56 (d, 1H),
were heated to 45 °C under a nitrogen atmosphere for 30 min. 7.53 (d, J ) 8.78 Hz, 2H), 7.04 (d, J ) 8.41 Hz, 4H), 6.93 (d,
A solution of 5-formylthiophen-2-yl boronic acid (0.17 g, 1.10 J ) 8.57 Hz, 4H), 6.72 (d, J ) 8.18 Hz, 2H), 4.02 (m, 4H),
mmol) in THF (5 mL) was added slowly, and the mixture was 3.76 (s, 6H), 1.64 (m, 4H), 1.38 (m, 4H), 0.94 (t, J ) 7.13 Hz,
Diketopyrrolopyrrole Dyes for Efficient DSSCs J. Phys. Chem. C, Vol. 114, No. 2, 2010 1345

SCHEME 1: Synthesis of the DPP Sensitizers

7.38 Hz, 6H). 13C NMR (125 MHz, DMSO) δ: 162.8, 162.2, the counter electrode by capillary force and was driven into the
158.0, 151.2, 151.0, 146.8, 144.5, 142.3, 141.9, 141.5, 137.9, cell by means of vacuum backfilling. Finally, the hole was sealed
137.2, 136.2, 136.0, 134.3, 128.8, 128.5, 127.0, 124.9, 121.1, using a UV-melt gum and a cover glass. Two electrolytes were
116.4, 57.1, 56.5, 54.6, 43.3, 34.0, 33.4, 32.1, 31.8, 24.6, 24.3, used for device evaluation, in which one was composed of 0.1
21.8, 15.9, 15.3. HRMS (m/z): [M + H]+ calcd for M lithium iodide, 0.6 M 1,2-dimethyl-3-n-propylimidazolium
(C50H44N4O6S3), 893.2501; found, 893.2502. iodide (DMPImI), 0.1 M I2, and 0.5 M 4-tert-butylpyridine (4-
2.4. Electrochemical Measurements. The oxidation poten- TBP) in acetonitrile; the other was composed of 0.1 M lithium
tials of dyes adsorbed on TiO2 films were measured in a normal iodide, 0.6 M methyl-propylimidazolum iodide (MPII), and 0.05
three-electrode electrochemical cell. TiO2 films stained with M I2 in the mixed solvent of acetonitrile and 3-methoxypropi-
sensitizer were used as the working electrode, a platinum wire onitrile (7:3, v/v).
was the counter electrode, and a regular calomel electrode in 2.6. Photoelectrochemical Measurements. Photovoltaic mea-
saturated KCl solution was the reference electrode. The surements employed an AM 1.5 solar simulator equipped with
measurements were performed using a potentiostat/galvanostat a 300 W xenon lamp (model no. 91160, Oriel). The power of
model K0264 (Princeton Applied Research). The supporting the simulated light was calibrated to 100 MW/cm2 using a
electrolyte was 0.1 M TBAPF6 (tetra-n-butylammonium hexaflu- Newport Oriel PV reference cell system (model 91150 V). I-V
orophosphate) in acetonitrile as the solvent. curves were obtained by applying an external bias to the cell
2.5. Preparation of Solar Cells. The dye-sensitized TiO2 and measuring the generated photocurrent with a Keithley model
electrode was prepared by following the procedure reported in 2400 digital source meter. The voltage step and delay time of
the literature.17 A TiO2 colloidal dispersion was made employing photocurrent were 10 mV and 40 ms, respectively. The cell
commercial TiO2 (P25, Degussa AG, Germany) as material. active area was tested with a mask of 0.158 cm2. The
Films of nanocrystalline TiO2 colloidal on FTO were prepared photocurrent action spectra were measured with an IPCE test
by sliding a glass rod over the conductive side of the FTO. system consisting of a model SR830 DSP Lock-In Amplifier
Sintering was carried out at 450 °C for 30 min. Before and model SR540 Optical Chopper (Stanford Research Corpora-
immersion in the dye solution, these films were soaked in the tion, U.S.A.), a 7IL/PX150 xenon lamp and power supply, and
0.2 M aqueous TiCl4 solution overnight in a closed chamber, a 7ISW301 spectrometer. Impedance spectra were done using
which can significantly increase the short-circuit photocurrent. a CHI-660c electrochemical station.)
The thickness of the TiO2 film was about 12 µm. After being 2.7. Electrical Impedance Measurements. Electrical im-
washed with deionized water and fully rinsed with ethanol, the pedance experiments were performed in the dark with a
films were heated again at 450 °C, followed by cooling to 80 CHI660C electrochemical workstation, with a frequency range
°C and dipping into a 3 × 10 -4 M solution of dyes in CH2Cl2 from 0.01 Hz to 100 kHz and a potential modulation of 10 mV.
for 12 h at room temperature. For the coadsorption, chenode- The applied bias potential was held at -0.5 V.
oxycholic acid was added. The adsorbed TiO2 electrode and Pt
counter electrode were assembled into a sealed sandwich-type 3. Results and Discussion
cell by heating with a hot-melt ionomer film (Surlyn 1702, 3.1. Synthesis. The synthetic route to DPP dyes containing
DuPont). The redox electrolyte was placed in a drilled hole in thiophene is depicted in Scheme 1. The butyl chain on the DPP
1346 J. Phys. Chem. C, Vol. 114, No. 2, 2010 Qu et al.

thiophenes instead of the benzene in the π-conjugated linker

part. Compared with the spectrum in dichloromethane solution,
the absorption spectra of the two dyes attached to TiO2 film
were broadened significantly and a nearly 100 nm red shift of
the maxima absorption peak was observed, which can be
attributed to the formation of a J-type aggregate. We have
measured the adsorbed amount of DPP dyes for the electrodes
with and without addition of the CDCA, in which there is further
proof to support this comment that the coadsorption of CDCA
can retard the aggregation of the DPP dyes. As seen in Table
3, when TiO2 films were exposed to DPP dye solutions
containing CDCA, the DPP dyes adsorption was reduced
gradually with increasing the CDCA content in the dye solution.
The drop of DPP dyes’ adsorption indicates that CDCA
competes for the TiO2 surface sites with the DPP dye molecules.
Strong interaction between the adsorbed dye molecules and the
oxide molecules in the TiO2 surface leads to aggregate forma-
tion, and consequently, broadening of the absorption spectrum
was observed during the dye absorption. This might be
correlated with dyesTiO2 interactions, dyesdye interactions,
or both, and coadsorption of CDCA diminished these interac-
tions on the TiO2 surface.18 The broadened absorption of two
dyes loaded on the TiO2 film is advantageous for light harvesting
of the solar spectrum. The absorption peak showed smaller red
shifts when two DPP dyes coadsorbed with CDCA compared
with the spectrum on TiO2 film, revealing that the aggregation
of DPP dye molecules on TiO2 is true. This result further proved
the comment that the coadsorption of CDCA can retard the
aggregation of DPP dyes.
3.3. Electrochemical Properties. To evaluate the possibility
Figure 2. Normalized absorption spectra of DPP-I and DPP-II in of electron transfer from the excited dye to the conduction band
CH2Cl2 and on TiO2 film. of TiO2, cyclic voltammetry was performed in acetonitrile
solution, using 0.1 M tetra-n-butylammonium hexafluorophos-
nucleus can improve the solubility and form a tightly packed phate as the supporting electrolyte and TiO2 films stained with
insulating monolayer blocking the I3- or cations approaching sensitizer as the working electrode. The examined highest
the TiO2.14 A 4-methoxy-N-(4-methoxyphenyl)-N-phenylben- occupied molecular orbital (HOMO) levels and the lowest
zenamine group as donor is attached to the core DPP by the unoccupied molecular orbital (LUMO) levels are collected in
Suzuki coupling reaction. The reaction produced the disubsti- Table 1. The SCE reference electrode was calibrated using a
tuted side products; fortunately, monocapped compounds can ferrocene/ferrocenium (Fc/Fc+) redox couple as an external
be easily separated by column chromatography. In the next step, standard. The excitation transition energy (E0-0) of DPP-I and
this bromo-exposed intermediate reacted with 5-formylthiophen- DPP-II was estimated from their absorption thresholds of dye-
2-ylboronic acid by the Suzuki coupling reaction. Finally, the sensitized TiO2 films to be 1.65 and 1.55 eV, respectively. The
target products (DPP-I and DPP-II) were synthesized via the HOMO values of DPP-I and DPP-II corresponding to their
Knoevenagel condensation reaction of the respective carbalde- first redox potential are 0.78 and 0.99 V versus NHE, respec-
hydes with cyanoacetic acid in the presence of piperidine. All tively. The HOMO levels of the two dyes are much more
the key intermediates and two novel organic DPP sensitizers positive than the iodine/iodide redox potential value (0.4 V),
have been confirmed by 1H NMR, 13C NMR, and HRMS. ensuring that there is enough driving force for the dye
3.2. Absorption Properties in Solutions and on TiO2 Film. regeneration efficiently through the recapture of the injected
Normalized absorption spectra of the two dyes, DPP-I and DPP- electrons from I- by the dye cation radical. As listed in Table
II, in a diluted solution of CH2Cl2 and TiO2 films were shown 1, the HOMO value of DPP-II is significantly higher than that
in Figure 2. The absorption maxima of the dyes, DPP-I and of DPP-I, which should be ascribed to the better electron-
DPP-II, appeared at 524 and 627 nm in diluted solution, transfer character of the two thiophene units. The estimated
respectively. The latter was observed to be largely shifted to a excited-state potential corresponding to the LUMO levels of
longer wavelength than the former DPP-I because of the two DPP-I and DPP-II, calculated from EHOMO s E0s0, are -0.87

TABLE 1: Photophysical Parameters of the Dyes

dye λmaxa/nm (ε × 10-4 M-1 cm-1) λmaxb (nm) HOMOc/V (vs NHE) E0s0d (eV) LUMOe/V (vs NHE)
DPP-I 524(4.21) 605 0.78 1.65 -0.87
DPP-II 627(3.32) 702 0.99 1.55 -0.56
a
Absorption maximum in CH2Cl2 solution (3 × 10-5 M). b Absorption maximum on TiO2 film (without CDCA). c The HOMO was
measured in acetonitrile with 0.1 M tetra-n-butylammonium hexafluorophosphate (TBAPF6) as electrolyte (working electrode, FTO/TiO2/dye;
reference electrode, SCE; calibrated with ferrocene/ferrocenium (Fc/Fc+) as an external reference. Counter electrode: Pt). d E0-0 was estimated
from the absorption thresholds from absorption spectra of dyes adsorbed on the TiO2 film. e The LUMO is estimated by subtracting E0-0 from
the HOMO.
Diketopyrrolopyrrole Dyes for Efficient DSSCs J. Phys. Chem. C, Vol. 114, No. 2, 2010 1347

Figure 3. Photocurrent action spectra of the TiO2 electrodes sensitized

by DPP-I and DPP-II.

TABLE 2: Influence of 4-TBP on the Photovoltaic

Performance Parametersa
dye 4-TBP Jsc/mA cm-2 Voc/V FF η (%)
DPP-I 0 10.81 0.483 0.52 2.70
0.5 M 9.78 0.531 0.62 3.24
0.8 M 3.89 0.532 0.64 1.32
DPP-II 0 7.65 0.346 0.55 1.45
0.5 M 1.71 0.419 0.64 0.46
0.8 M 0.85 0.443 0.56 0.21
a
Illumination: 100 mW cm-2 simulated AM 1.5 G solar light.
Other redox electrolyte contained 0.1 M LiI + 0.6 M MPII + 0.05
M I2 in the mixed solvent of acetonitrile and 3-methoxypropionitrile
(7:3, v/v). Figure 5. Photocurrent density vs voltage curves for DSSCs based
on DPP-I and DPP-II with various concentrations of CDCA under
irradiation of AM 1.5 G simulated solar light (100 mW cm-2) with
liquid electrolyte.

and -0.56 V versus NHE, respectively. Judging from the

LUMO value, the two dyes are more negative than the bottom
of the conduction band of TiO2 (-0.5 V), indicating that the
electron injection process from the excited dye molecule to TiO2
conduction band is energetically permitted.19
3.4. Photovoltaic Performance of DSSCs. Figure 3 shows
the action spectra of incident photon-to-current conversion
efficiency (IPCE) for DSSCs based on DPP-I and DPP-II. The
IPCE data of DPP-I sensitizer exhibit a high efficiency of more
than 60% in the range of 400-600 nm with a maximum value
of 80% at 550 nm. On the other hand, the IPCE value for DPP-
II was obviously decreased at 400 to 600 nm, suggesting the
worst electron injection ability from the excited dye of DPP-II
to the TiO2 conduction band. The IPCE spectra of them are
consistent with the absorption spectra on the TiO2 film. The
maximum IPCE value of DPP-II is significantly lower than that
of DPP-I, while in the long-wavelength region, DPP-II shows
higher IPCE. To be mentioned, owing to the two thiophene units
in the molecule, the action spectra of DPP-II even extend to
the near-infrared region (>800 nm), which is rare in previous
studies.
The photovoltaic performance of the DSSCs was measured
at 100 mW cm-2 under simulated AM 1.5 G solar light
conditions. The DPP-I-sensitized cell gave a short-circuit
photocurrent density (Jsc) of 10.81 mA cm-2, an open-circuit
voltage (Voc) of 0.483 V, and a fill factor (FF) of 0.50,
Figure 4. Photocurrent density vs voltage curves for DSSCs based
corresponding to an overall conversion efficiency (η) of 2.70%.
on DPP-I and DPP-II with various concentrations of 4-TBP in the Under the same conditions, the DPP-II-sensitized cell gave a
redox electrolyte under irradiation of AM 1.5 G simulated solar light Jsc value of 7.65 mA cm-2, a Voc of 0.346 V, and an FF of
(100 mW cm-2). 0.53, corresponding to the η value of 1.45% (see Table 2). The
1348 J. Phys. Chem. C, Vol. 114, No. 2, 2010 Qu et al.

TABLE 3: Influence of CDCA on the Photovoltaic Performance Parametersa,b

dye CDCA Jsc/mA cm-2 Voc/V FF η (%) amount (10-8 mol cm-2)
DPP-I 0 9.36 0.572 0.64 3.44 5.80
1.5 mM 9.78 0.605 0.70 4.14 4.98
saturated 9.74 0.588 0.67 3.81 3.08
DPP-II 0 1.39 0.459 0.67 0.43 6.36
1.5 mM 2.39 0.508 0.68 0.83 4.79
saturated 2.09 0.483 0.68 0.69 4.17
N719 16.10 0.689 0.67 7.47
a
Illumination: 100 mW cm-2 simulated AM 1.5 G solar light. b Electrolyte containing 0.1 M LiI + 0.6 M DMPImI + 0.1 M I2 + 0.5 M
4-TBP in acetonitrile.

lower efficiency of the DSSC based on DPP-II as compared

with the DPP-I-based DSSC is due to its lower extinction
coefficient, photocurrent, and IPCE data in the range of
400-600 nm. To improve the open-circuit potential (Voc), 0.5
and 0.8 M 4-tert-butylpyridine (4-TBP) were added to the
electrolyte, and the data were summarized in Table 2. As shown
in Figure 4, the cell voltages in the DSSCs with both DPP-I
and DPP-II were largely improved with an addition of 4-TBP
in the electrolyte, while the photocurrent density was decreased.
This is because the tert-butyl chain of 4-TBP prevents recom-
bination between the injected electrons and I3- ions on the TiO2
surface, resulting in an improved voltage. However, 4-TBP
adsorbed on the TiO2 surface negatively shifts the conduction
band level of TiO2, which suggests that relatively large energy
gaps between the LUMO levels of the dyes and the conduction
band edge level of TiO2 should be requested in the use of
4-TBP.20 The reduction potential of DPP-I obtained in CH2Cl2
is -0.87 V (Table 1), which is largely more negative than the
value of -0.5 V for the TiO2 electrode, indicating an improve-
ment of total efficiency with the use of 4-TBP at a suitable
concentration. It was found that 0.5 M 4-TBP was optimal for
DPP-I with respect to power conversion. On the contrary, the
TiO2 conductive band levels are relatively close in energy to
the excited-state levels of the dye DPP-II (Table 1) when 4-TBP
is present in the electrolyte, so the Jsc value of DPP-II is
drastically decreased. As a consequence, the highest power
conversion efficiency of DPP-II was obtained without 4-TBP
contained in the redox electrolyte (Table 2).
Chenodeoxycholic acid (CDCA) is a transparent, organic
compound that binds strongly to the surface of nanostructured
TiO2, being able to displace dye molecules from the semicon- Figure 6. Electrochemical impedance for DSSCs sensitized by DPP-I
and DPP-II containing various concentrations of CDCA.
ductor surface, therefore, hindering the formation of dye
aggregates.21 It is known to improve DSSC efficiency, generally
attributed to its preventing dye aggregation, resulting in concentration to saturated lead to a decrease in the Voc value;
improved electron injection efficiency and thus leading to an this is because adsorption of CDCA leaves protons on the TiO2
increase in the device photocurrent.22 Moreover, in some cases, surface and, hence, charges the surface positively shifted by
the use of CDCA has also led to a rise in the photovoltage. the coadsorption of CDCA, resulting in Voc loss.24 The enhance-
This latter effect has been attributed to a decrease of recombina- ment of the Voc is usually associated with the negative shift of
tion of the injected electrons.23 To solve the problem of dye the conduction band edge or suppression of charge recombina-
aggregation, the effect of CDCA content in the dye solution on tion. In consequence, suppression of charge recombination may
the solar cell performance was also investigated, and the data be counteracted by the Voc loss because of proton exchange from
were summarized in Table 3. As shown in Figure 5, the short- CDCA to the TiO2 surface,6a Thus, the open-circuit voltage
circuit photocurrent (Jsc) of DPP-I and DPP-II increased with would be somewhat determined by the concentration of CDCA.
1.5 mM CDCA and then slightly decreased with further As shown in Table 3, the highest power conversion efficiency
increasing CDCA to a saturated concentration. One explanation could be obtained at 1.5 mM CDCA.
is that the amount of adsorbed dye on the TiO2 surface was 3.5. Electrochemical Impedance Spectroscopy. Electro-
reduced by coadsorbents of CDCA, resulting in a loss in light chemical impedance spectroscopy (EIS) analysis was performed
harvesting and thus decreased short-circuit photocurrent. The to clarify the CDCA effect on the Voc further. Figure 6 compares
open-circuit voltage in the DSSCs with both DPP-I and DPP- the impedance spectra for DPP-I- and DPP-II-sensitized cells
II was improved, indicating that the charge recombination measured in the dark under a forward bias of -0.50 V with a
process was effectively prohibited with a content of chenode- frequency range of 0.1 Hz to 100 kHz, respectively. The
oxycholic acid. However, further increases in the CDCA important differences for the two organic dye solar-sensitized
Diketopyrrolopyrrole Dyes for Efficient DSSCs J. Phys. Chem. C, Vol. 114, No. 2, 2010 1349

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