Organic Electronics 15 (2014) 12051214

Contents lists available at ScienceDirect

Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

Design strategies of metal free-organic sensitizers for dye

sensitized solar cells: Role of donor and acceptor monomers
Chieh-Yu Tseng, Fadlilatul Taufany, Santhanamoorthi Nachimuthu , Jyh-Chiang Jiang ,
Der-Jang Liaw
Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei 106, Taiwan, ROC

a r t i c l e

i n f o

Article history:
Received 28 November 2013
Received in revised form 10 February 2014
Accepted 18 March 2014
Available online 1 April 2014
Keywords:
Organic dyes
DFT/TDDFT
Dual band
Donoracceptor
Absorption spectra

a b s t r a c t
A series of metal free organic sensitizers have been designed and their optoelectronic properties for DSSC applications have been systematically investigated using density functional
theory (DFT) and time dependent density functional theory (TD-DFT) methods. The role of
donor/acceptor monomers on the electron donating/withdrawing abilities has been discussed and promising donoracceptor combinations are screened. Based on this screening,
some of novel metal free sensitizers have been designed and their electronic and spectral
properties have been investigated using DFT/TDDFT methods. Our results show that the
designed molecules are promising candidates to provide good performances as sensitizers
in the DSSC applications.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Considering the environmental issues and renewable
resources, more and more attentions have been paid on
the solar energy utilizations. The dye sensitized solar cells
(DSSCs) have attracted considerable interest after the report of ORegan and Gratzel [1] due to the high photonto-current conversion efciency, easy production and
cost-effective properties. In recent years, number of sensitizer molecules have been developed, which includes metal-free organic dyes [25], non-ruthenium metal dyes
[69] and ruthenium (II)-polypyridly complexes [1012]
and reported their performances in the DSSC applications.
At present, the state-of-the-art DSSCs are based on the
ruthenium metal complexes, such as N3/N719 and black
dye, which hold the record of the overall efciencies up
to 11.5% under standard (Global AM 1.5) irradiation [13
15]. However, there are some snags of ruthenium(II)-based
Corresponding authors. Tel.: +886 2 27376653; fax: +886 2 27376644.
E-mail addresses: santhanamoorthi@gmail.com (S. Nachimuthu),
jcjiang@mail.ntust.edu.tw (J.-C. Jiang).
http://dx.doi.org/10.1016/j.orgel.2014.03.022
1566-1199/ 2014 Elsevier B.V. All rights reserved.

sensitizers, for instance, containing expensive ruthenium

metal, requires careful synthesis and tricky purication
steps [16] which make researchers to nd other possible
solutions. Metal-free sensitizers are prepared rather inexpensively and compared to ruthenium-based complexes,
these have larger molar extinction coefcient and higher
energy absorption bands. Moreover, the major advantage
of metal-free sensitizers is their tunable absorption and
optoelectronic properties through suitable molecular design strategies [16].
Generally, the design of metal-free dyes is based on
linking of electron donor/acceptor (DA) systems through
p-conjugated bridges (i.e., DpA molecular structure).
Many novel DpA metal-free dyes with various donor
moieties, such as coumarin [4,17], indoline [18], triphenylamine [3], phenothiazine [2], carbazole [19], and pyrrole
[20], have been designed and used as efcient sensitizers
for the DSSC applications. However, the photon-to-current
conversion efciency based on those sensitizers has been
achieved up to 9.5% only, which is relatively low compared
to the conventional Ru based sensitizers. In order to increase the efciency of DSSCs, it is important to design

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C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

the suitable dyes, which have reasonable optical properties. This could be possible if we design the sensitizer with
the absorption spectrum covers visible-to-near-infrared
range, have signicant intra-molecular charge separation
after absorbing sun light, and it should stably bind to the
semiconductor surface so that electrons can inject to surface continuously [16,21,22].
Herein, we aimed to design a potential metal-free sensitizer which overcomes the aws of existing dyes and to
nd an efcient way to tune optoelectronic properties.
Nowadays, there are two ways in which the spectral properties of DA or DpA molecules can be improved: changing the conjugation length of the sensitizer, and
substituting different electron -rich and -decient units
to modify the spectrum. Previously it is reported that,
some DA oligomers have dual-band optical absorption
spectra which provide broad absorption characteristics
[23,24]. In general, dual-band absorption spectrum arises
from two separate transitions, which lead to either charge
transfer between the donor and acceptor units along with a
pp* transition (so-called intra-molecular charge transfer,
ICT) [25,26], or reorganization of molecular orbitals to produce accessible low- and high-lying energy levels spread
across both donor and acceptor units (usually named as
pp* transition to make a distinction from ICT) [2729].
In the present study, we selected 12 monomers which
are systematically varied by both in the donor and acceptor-units, to form the different p-conjugated DA oligomers and evaluated their optoelectronic properties. The
selected 12 monomers are thiophene (T), thienopyrazine
(TP), dithienopyrazine (DTP), thiadiazolothienopyrazine
(TDTP), 1,4-dihydro-1-phenylpyrazine (PPP), cyclopentadithiophene (CDT), dicyanomethylidene-cyclopentadithiophene (CDM), 9-phenylcyclopentadithiophene (TPAT),
N,N-bis (4-methoxy-phenyl)-thiophene-2-amine (MPTA),
10-phenyl-10H-phenothiazine (PTAZ), triphenylamine
(TPA), 4-methoxy-N-(4-methoxyphenyl)-N-phenyl- benzeneamine (MPBA), and 9-phenyl-9H-carbazole (PC).
These monomers are derived from the several compounds
[30], which are universally used in the design of DA oligomers, namely thienopyrazine, thiophene, thiazine, carbazole, and phenylamine compounds, thus the resulting 66
DA oligomers could be applied as a model system to represent the general classes of DA oligomers.

2. Computational details
All the calculations in this study were performed with
Gaussian 09 package [31]. The geometries of neutral
monomers and metal-free sensitizers were optimized
using B3LYP exchange correlation functional [32] combined with the standard double-f plus polarization basis
set, 6-31G(d) [33]. Different basis sets and functionals in
gas phase did not affect the structural parameters much,
but it inuences the optoelectronic properties such as excitation energies and intensities. Hence, we have performed
a benchmark calculation in order to nd the most suitable
method for simulating UVVis absorption. For this, we
considered four DFT methods such as, PBE0, B3LYP,
BHandHLYP and CAM-B3LYP to calculate the UVVis

absorption spectra for TC-1 [34], T2-1 [2] and I-1 [35] molecules of DA type and L1 [36], TAStCA [3] and MK2 [19]
molecules of DpA type. We used 6-31G (d) basis set for
all the benchmark calculations and the calculated excitation energies of DA type and DpA type molecules are
shown in Table 1.
Compared with the experimental values of DA and D
pA types of molecules, the calculated results show that
the absorption energy from B3LYP was more accurate for
DA system and BHandHLYP method show perfect agreements for DpA system which contains longer conjugated
length. Considering that DpA backbone molecules are
main structures in real DSSCs, therefore, we choose
BHandHLYP functional to calculate the optoelectronic
properties of DpA molecules including 20-lowest excitation energies and intensities of all the metal-free sensitizers considered here.
The optoelectronic properties were transformed, using
the SWizard program [37,38], into simulated spectra as described before, using Gauss functions with half-widths of
4000 cm1, as shown in following equation:

X fI
x  x1 2
ex c1
exp 2:773
D
1=2;I
D21=2;I
1

!
1

where e is the molar extinction coefcient given M1 cm1

in unit; the energy x of all the allowed transitions included
in Eq. (1), is expressed in cm1; fI and D1/2 are the oscillator
strength and the half-bandwidths, respectively.
3. Results and discussion
3.1. The classication of donor- and acceptor-monomers
The molecular structures of 12 selected monomers considered in this study are summarized in Fig. 1. These selected monomers are then classied whether they belong
to donor- or acceptor-monomer and then, every possible
combination of different donor- and acceptor-unit is combined together to form 66 DA oligomers. This classication is made on the basis of their vertical ionization
potential (IPv), vertical electron afnity (EAv), and HOMO/
LUMO energy levels. As described by Dixon et al. [39],
stronger donor has smaller IPv (easy to lose an electron)
and higher HOMO level that would lose electrons easily;
and stronger acceptor has more negative value of EAv (easily to gain an electron) and lower LUMO level which would
accept electrons strongly. Therefore, we have calculated

Table 1
The calculated UVVis absorption energies (in nm) for DA and DpA
sensitizers using different DFT methods.

Sensitizers

PBE0

B3LYP

BHandHLYP

CAM-B3LYP

Exptl.a

TC-1
T2-1
I-1

451.7
441.6
435.9

401.7
461.7
453.3

354.3
367.2
374.4

359.0
370.2
381.6

400
452
483

L1
TAStCA
MK2

482.4
504.5
575.2

506.9
534.2
612.8

405.8
409.3
481.5

404.3
403.0
472.6

405
410
480

Taken from Refs. [2,3,19,3436].

C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

1207

Fig. 1. Sketch of molecular structures of thienopyrazine, thiophene, thiazine, carbazole, and phenylamine-based derivative monomers.

the correlations between IPv vs. HOMO and EAv vs. LUMO,
which are shown in Fig. S1. From Fig. S1, we found a linear
relationship between the calculated IPv and HOMO and EAv
with LUMO. From this relationship, we are able to identify
the order of donor- and acceptor-monomers strengths.
The strength of donor from strong to weak is:
PPP > MPBA > MPTA > PTAZ > TPA > PC > CDT > DTP > TPAT >
CDM > TDTP > TP > T and the order of acceptor strength is
TDTP > CDM > DTP > TP > CDT > TPAT > PC > PTAZ > TPA >
MPTA > MPBA > PPP > T.
3.2. Roles of donor and acceptor monomers in optoelectronic
properties
Next, we designed a series of p-conjugated DA oligomers based on the order of electron donating- and electron
withdrawing-abilities. One way to design these DA oligomers is to distinguish what combination of donor and
acceptor could have suitable UVVis absorption for the
practical applications. Accordingly, the present study care-

fully evaluates the impact of the variation in strength of

donor- and acceptor-units on the optoelectronic properties, such as energy gaps and the absorption spectra with
their associated HOMOs-to-LUMOs electronic transitions.
First, we begin with nine representative DA oligomers
such as, the strong donor PPP with ve different-strength
of acceptors (TDTP, DTP, CDT, PTAZ and MPBA) and the
strong acceptor TDTP with different strength of donormonomers (PPP, MPTA, TPA, PC and CDM) and investigated
their optoelectronic properties using TDDFT methods.
Fig. 2 illustrates the electron distribution plots of the designed DA oligomers along with their respective
HOMOLUMO energy gaps, respectively. As mentioned
above, the HOMO/LUMO energy levels are interrelated to
the corresponding electron donating and withdrawing
abilities. Thus, in Fig. 2(b), a dramatic increase of LUMO energy levels is found as weakening the acceptor strength,
which results in an increase in energy gaps. Also, the electron distribution plot (Fig. 2) indicates that the HOMOto-LUMO transitions vary from intra-molecular charge

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C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

Fig. 2. The roles of (a) donor and (b) acceptor in governing the energy gap preferences of the selected p-conjugated DA oligomers. In gures (a) and (b), the
strength of donor- and acceptor-units, is varied from strong (left) to weak (right).

transfer (ICT) to pp* transition while the strengths of

acceptors are weaken. Contrarily, the HOMO levels gradually decrease while the strength of the donor becomes
weaker, but the inuence is not obvious as like acceptors
and all the HOMO-to-LUMO transitions are having ICT
character. These results indicate that, if two monomers
are combined together to form an oligomer, the HOMO
LUMO energy gaps are more dominated by the acceptor
counterpart.
Although energy gaps are important indices when estimating the optoelectronic properties, UVVis absorption
spectra are more reliable and direct data to evaluate how
these sensitizers will perform in the solar cells. Thus, we
have simulated the UVVis absorption of the designed D
A molecules and the spectra with corresponding transition
assignments are shown in Fig. 3 and Table 2. As can be seen
from the Fig. 3(a), the variation of donor strengths, i.e.,
from weak (CDM) to strong (PPP), does not affect the
absorption spectra appreciably; the spectra remain dualband character, one absorption band is located at nearinfrared region, while the other is in the range of UVVis.
Increasing the strength of donors makes the rst absorption band red shifted and increases the intensities very little, (see Table 2) which are due to an increase in the degree

of charge separation. It has been observed for CDMTDTP,

TPATDTP, PPPTDTP molecules, the transition characters
below 400 nm are mainly contributed from pp* transitions, whereas, PPPTDTP has a low-lying satellite band
which corresponds to ICT transition (k = 412 nm). The
dual-band characteristic makes the absorption broad,
which is benecial for light-harvesting if the absorption
spectrum covers visible region.
On the other hand, the variation on the acceptor-monomers strength from weak-to-strong cases, the absorption
band characteristics are transformed from mono- to dualband. The nding of this dual-band absorption characteristic is vital for the various applications in light harvesting
and light-emitting devices. The strong donor (PPP) with
different acceptors strengths (MPBA, CDT and TDTP) has
been used for this illustration (Fig. 3(b)). From Table 2,
the absorption of strong donor-weak acceptor (PPPMPBA)
oligomer is found only at UV region and it is mono-band
characteristic which is due to pp* transitions. However,
when the strength of the acceptor counterpart increased,
as represented in the case of PPPTDTP molecule, a strong
absorption band is noticed in the near-IR region
(k = 1205.6 nm; originated from a ICT transition (Table.
2)) and also it has absorption band in the UV region as well

Fig. 3. The roles of (a) donor and (b) acceptor-units in governing the UVVis absorption spectra of the selected p-conjugated DA oligomers. In gures (a)
and (b), the strength of donor and acceptor -units, is varied from strong (top) to weak (bottom).

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C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

Table 2
The calculated absorption energies (k), oscillator strengths (f), light harvesting efciency (LHE) and transition characters of ve representative DA oligomers:
CDMTDTP, TPATDTP, PPPTDTP, PPPCDT and PPPMPBA molecules. The states with f > 0.1 are shown.
DA molecule

Electronic transition

k (nm)

f (a.u)

LHE

Transition assignment

CDMTDTP

S0 ? S1
S0 ? S7
S0 ? S8

1011.7
388.5
377

0.13
0.48
0.11

0.259
0.669
0.224

S0 ? S12
S0 ? S13

341.7
336.1

0.33
0.33

0.532
0.532

H?L (+100%)a
H ? L + 2(+75%)b
H-4 ? L (+64%)a
H ? L + 2(+13%)b
H-2 ? L + 1(+74%)b
H-5 ? L (+49%)a

TPATDTP

PPPTDTP

H-4 ? L (18%)a
H-5 ? L (+20%)a

H-4 ? L + 1(12%)b

S0 ? S1
S0 ? S6
S0 ? S11
S0 ? S13

1058.7
388.4
332
317.2

0.15
0.58
0.29
0.27

0.292
0.737
0.487
0.463

H ? L (+100%)
H ? L + 1(+92%)a
H-8 ? L (+47%)b
H ? L + 3(+94%)b

S0 ? S1
S0 ? S4
S0 ? S9
S0 ? S11

1205.6
412.3
333.6
321.9

0.19
0.47
0.27
0.25

0.354
0.661
0.463
0.438

H ? L (+100%)a
H ? L + 1(+92%)a
H-5 ? L (+67%)b
H ? L + 4(+57%)b

H-7 ? L (37%)a

H ? L + 3(38%)b

PPPCDT

S0 ? S1
S0 ? S3

435.9
339.4

0.81
0.44

0.845
0.637

H ? L (+100%)
H-1 ? L (+86%)b

PPPMPBA

S0 ? S2
S0 ? S7

370.6
321.6

1.05
0.11

0.911
0.224

H ? L (+92%)b
H ? L + 3(+75%)a

H represents HOMO and L represents LUMO.

a
ICT transition.
b
p ? p* Transition.

(Fig. 3(b)). The appearance of the absorption band at both

UV and visible to near-IR region, thus justies the dualband absorption characteristics.
From the above results, it has been noticed that the
inuence of acceptors is more signicant in determining
the optoelectronic properties of designed DA oligomers
and also the overall spectra can be red shifted by increasing the strength of the donor. However, the simulated
UVVis absorption spectra of the designed molecules are
not enough to use as efcient sensitizer in DSSCs since,
for efcient sensitizer, the absorption band should be
broader and cover the whole visible region. Thus, we try
to employ the molecules which have only dual-band characteristic to broaden the absorption spectrum in the visible
region.

3.3. Design strategy based on dual-band characteristics

Here, we proposed a design strategy on the basis of the
requirements of high-efciency metal-free sensitizer,
including signicant intra-molecular charge transfer,
broad UVVis absorption spectra with high molar extinction coefcients and appropriate excitation energies, and
proper geometries. In order to increase the degree of
charge transfer when electronic excitation occurs, it is
preferable to choose strong donors and strong acceptors
counterparts for efcient sensitizers; for instance, the combinations of strong donors (PPP, MPBA and TPA) and strong
acceptors (TDTP, CDM and TP). However, from the results
shown in Fig. 3(b), even though the strongest acceptor,
TDTP possess dual-band character and broad absorption

Fig. 4. UVVis absorption spectra of (a) MPBACDM based and (b) MPBATP based oligomers. The black solid line represents donor and acceptor system
with anchoring group (DA*CN), blue dash one is for donor and acceptor system with p-linker (DpA), and the red dash line is DpA*CN system.

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C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

Table 3
Absorption energy (k), oscillator strength (f), light harvesting efciency (LHE) and transition character of the singlet excited states of MPBACDM series
calculated by BHandHLYP/6-31G(d) level of theory. The states with k > 300 nm and f > 0.1 are shown.
Molecule

Electronic transition

k (nm)

f (a.u)

LHE

Transition assignment

MPBACDM*CN

S0 ? S1
S0 ? S2
S0 ? S3
S0 ? S5

733.3
472.9
405
323.6

0.22
0.12
1.25
0.20

0.397
0.241
0.944
0.369

S0 ? S6

312.6

0.64

0.771

H-1 ? L (+28%)a
H ? L (30%)a
H-1 ? L+1(+17%)a
H-3 ? L (+25%)a
H-1 ? L+1(10%)a
H-6 ? L (+20%)a
H ? L+2(+13%)b
H-2 ? L (+17%)a

S0 ? S7

305.3

0.22

0.397

H ? L (+68%)a
H-1 ? L (+58%)a
H ? L+1(+71%)a
H-6 ? L (+32%)a
H-5 ? L (11%)a
H-1 ? L+1(+21%)a
H-3 ? L (20%)a
H ? L+2(+45%)b

MPBATCDM

S0 ? S1
S0 ? S3
S0 ? S5

729.3
374
309.2

0.09
1.52
0.54

0.187
0.970
0.712

H ? L (+46%)a
H ? L+1(+79%)a
H-6 ? L (+87%)a

H-1 ? L (+45%)a

MPBATCDM*CN

S0 ? S1
S0 ? S3
S0 ? S6

760.7
429.2
340.9

0.29
1.65
0.42

0.487
0.978
0.620

H-1 ? L (+39%)a
H-1 ? L+1(+20%)a
H-1 ? L+1(30%)a

S0 ? S7

313.9

0.45

0.645

H ? L (+55%)a
H ? L+1(+60%)a
H ? L+1(+33%)a
H ? L+2(20%)b
H-8 ? L (+45%)a

H-7 ? L (+18%)a

Excitations in bold are assigned to important transitions.

H represents HOMO and L represents LUMO.
a
ICT transition.
b
p ? p*.

spectrum, its long-wavelength absorption band observed

at 1200 nm, which is far away from the visible region.
Whereas, the acceptor, CDT which is not so strong, its rst
absorption peak shifted to visible region and also exhibits
charge transfer character which is necessary for DSSCs (Table 2). According to these observations, we suggest design
strategies as follows; it is better to consider the acceptor
which has electron withdrawing ability between TDTP
and CDT (i.e. CDM, DTP, and TP), substitute p-conjugated
linker between electron-rich and electron-decient groups
and decorate acceptors with an anchoring group. Moreover, it is easy to tune the spectrum of CDT-based molecules by employing stronger donor. As discussed in
previous section, the overall spectra of DA oligomers have
bathochromic shift when increasing the strength of donor
counterpart (shown in Fig. 3(a)). In this work, thiophene
is employed as a p linker to extent the conjugation, which
results in high absorption intensities. Thiophene is among
the most frequently used p-spacer in organic dyes due to
its high structural stability, effective for the controlling
intramolecular charge separation and optical properties
[40,41]. Recent studies report the better performances of
thiophene based dyes for DSSC application [42,43]. The
2-cyanoacrylic acid is commonly used as anchoring group
for metal-free DSSCs and is a well-known electron acceptor
which can help charge separation and bind strongly on
TiO2 surface [5,4446]. In brief, we selected strong donors,
like PPP, MPBA and TPA, and strong acceptors, CDM, TP and
CDT, with thiophene (p-bridge) and 2-cyanoacrylic acid
(anchoring group), to design new sensitizers and investigated their optoelectronic properties.

3.4. The optoelectronic properties of designed DpA

sensitizers
The molecular structures of the selected MPBACDM,
MPBATP, and MPBACDT oligomers are modied through

an introduction of p-linker, thiophene (T), and electron

withdrawing substituent, 2-cyanoacrylic acid, (*CN) to form
their subsequent analogue oligomers, termed as MPBAT
CDM*CN, MPBATTP*CN, and MPBATCDT*CN, respectively.
The schematic illustrations of the designed sensitizers are
shown in Fig. S2 of Supplementary material. Fig. 4 shows
the calculated UVVis absorption spectra of MPBACDM
and MPBATP based series and their related transition data
including absorption energies, oscillator strengths and
transition assignments are summarized in Tables 3 and 4
(The results of MPBACDT series and other combinations
of designed dyes are given in Tables S1S2 and Figs. S3S6
of Supplementary material). It has been observed that the
UVVis absorption spectra of these two systems have dual
band character. In MPBACDM series, long-wavelength
band, named as Band 1, is located around 750 nm; and
short-wavelength band, named as Band 2, is about
400 nm. Both absorption bands are in the visible region.
But for MPBATP series, Band 1 and Band 2 are located at
530 nm and 350 nm, respectively. As can be seen from
Fig. 4, the absorption intensity of the visible-region band
is found to be increased due to the incorporation of the
p-linker, which is in agreement with the previous experimental results [47,48]. Apart from this, it also red shifts
the overall spectra of both the series signicantly. On the
other hand, considering the effect of electron withdrawing
anchoring group, the intensities of Band 1 in both cases are
found to be increased largely. Also, the overall absorption
spectra of MPBACDM and MPBATP are bathochromic
shift around 30 and 90 nm, respectively. It has been noted
that the substitution of p-linker and electron withdrawing
anchoring group with strong donors and strong acceptors
can increase the molar extinction coefcients as well as
red-shift the overall spectra. Also, we have calculated the
light harvesting efciency (LHE) of the designed dyes using
the formula:

LHE 110f

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C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

Table 4
Absorption energy (k), oscillator strength (f), light harvesting efciency (LHE) and transition character of the singlet excited states of MPBATP series calculated
by BHandHLYP/6-31G(d) level of theory. The states with k > 300 nm and f > 0.1are shown.
Molecule

Electronic transition

k (nm)

f (a.u)

LHE

Transition assignment

MPBATP*CN

S0 ? S1
S0 ? S4

514.2
326

0.99
0.36

0.898
0.563

H ? L (+92%)a
H ? L+1(+72%)a
a

MPBATTP

S0 ? S1
S0 ? S2
S0 ? S4

472.6
349
319.3

0.63
0.12
0.65

0.766
0.241
0.776

H ? L (+77%)
H-1 ? L (+64%)a
H ? L+1(+73%)b

MPBATTP*CN

S0 ? S1
S0 ? S4

563.6
335

1.24
0.54

0.942
0.712

S0 ? S5

320.4

0.21

0.383

H ? L (+84%)a
H ? L+1(+46%)a
H ? L+2(+16%)b
H ? L+2(+69%)b

H-1 ? L+1(+18%)a
H-1 ? L (+20%)a
H ? L (17%)a

H-1 ? L+1(+27%)a
H ? L+1(14%)a

Excitations in bold are assigned to important transitions.

H represents HOMO and L represents LUMO.
a
ICT transition.
b
p ? p*.

where f is the oscillator strength of the designed dyes corresponds to the wavelength and the calculated values are
given in the respective tables. As can be seen from those
values, the LHE of the designed dyes are large, which is required to enhance the photocurrent response of the DSSCs.
Figs. 5 and 6 show the high-lying and low-lying molecular orbitals of the most important excitations, which illustrate the either charge transfer or pp* character, of
MPBACDM and MPBATP based systems, respectively.
For both the cases, the main assignment of Band 1 is due
the transition from HOMO to LUMO, whereas for Band 2
is HOMO to LUMO+1. It can be seen from Fig. 5, all the
transitions of MPBACDM series show the ICT character,
which is required for the highly efcient sensitizers. However, in the HOMO to LUMO transition, the electrons are
transferred from donor (MPBA) to acceptor counterpart
(CDM) whereas, in the HOMO to LUMO+1 transition, the
electrons are transferred to both acceptor and anchoring

groups, except in MPBATCDM case. This indicates that,

in MPBACDM*CN and MPBATCDM*CN, the Band 2 is well
charge separated and also it is in the visible region (405,
429 nm see Table 3), hence, it is expected that the excited
electrons efciently inject into the TiO2 surface. On the
other hand, Band 1 of MPBACDM series is an ineffective
for DSSC applications, since the electrons are localized in
acceptor unit rather than the anchoring group after excitation. Compared with MPBACDM series, MPBATP series
have better charge transfer characters because excited
electrons are delocalized at both acceptor (TP) and anchoring group (shown in Fig. 6). This may be due to the electron
withdrawing ability of CDM is relatively stronger than TP,
which may compete the electron withdrawing ability of
anchoring groups. This indicates that, the strength of the
considered acceptor is too strong, some ineffective transitions may appear in the spectrum. It has been noticed
that the calculated absorption spectra for the designed

Fig. 5. Representations of HOMO, LUMO and LUMO+1 corresponding to the important excitations of MPBACDM series shown in Table 3. Both HOMO to
LUMO and HOMO to LUMO+1 reveal ICT character in all the cases.

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C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

Fig. 6. Representations of HOMO, LUMO and LUMO+1 corresponding to the important excitations of MPBATP series shown in Table 4. Both HOMO to
LUMO and HOMO to LUMO+1 reveal ICT character in all the cases.

sensitizers signicantly red-shifted as compared to the

conventional Ru based dyes (N3, C101, C106 and CYCB11) [4952] which is ideal for the DSSCs. The results reveal that the optical properties of the metal free sensitizers
can be tuned in accordance with the requirements by
means of combining suitable donor and acceptor moieties.
For instance, if we combine the strong acceptor and strong
donor monomers, the long wavelength band may not be
suitable for DSSC due to its less electron injection ability,
but the short wavelength band shifted to visible region because of donor effect and it can be used to harvest the sun
light. Also, the incorporation of thiophene and 2-cyanoacrylic acid enhances the intensity of the overall absorption
spectra and making the spectra bathochromic shift
through increasing conjugation length.
4. Conclusions
In this contribution, we proposed a design strategy to
improve the photon-to-current conversion efciency of
DSSCs based on the metal-free sensitizers using DFT calculations. From these theoretical results, we identied the
electron -donating and-withdrawing abilities of selected
monomers and investigated their roles in the optoelectronic properties. Further, we have systematically investigated the UVVis absorption spectra and electronic
transition characters of selected DpA sensitizers and reported their spectral properties for DSSC applications.
From our results, we found that the acceptor monomers
play an important role in determining the optoelectronic
properties. Further it is evident that the substitution of thiophene and 2-cyanoacrylic acid enhances the intensity of
the absorption signicantly and the overall absorption
spectrum can be red shifted. The simulated spectra reveal
that the characteristic of dual-band is present in the selected sensitizers, which is highly required for the efcient
sensitizer. Particularly, in the MPBATP based series, the

long wavelength absorption band is due to the ICT character and importantly excited electrons not only localized on
the acceptor, but also on the anchoring group: hence it is
easy to inject the excited electrons into the TiO2 surface.
In summary, we suggested some potential sensitizers
which have suitable optoelectronic properties and we believe that these molecules can be used as an efcient sensitizes for the new generation of DSSCs.
Acknowledgements
We acknowledge the nancial support from the National Science Council of Taiwan (NSC 101-2113-M-011004-MY3). We are also thankful to the National Center of
High-Performance Computing (NCHC) for donating computer time and facilities.
Appendix A. Supplementary material
Supplementary material: the plots of vertical ionization
potential (IPv), electron afnity (EAv), schematic illustrations of selected fragments and optoelectronic properties
of MPBACDT based series are shown. Supplementary data
associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.orgel.2014.03.022.
References
[1] B. ORegan, M. Gratzel, A low-cost, high-efciency solar cell based on
dye-sensitized colloidal TiO2 lms, Nature 353 (1991) 737739.
[2] H.N. Tian, X.C. Yang, R.K. Chen, Y.Z. Pan, L. Li, A. Hagfeldt, L.C. Sun,
Phenothiazine derivatives for efcient organic dye-sensitized solar
cells, Chem. Commun. (2007) 37413743.
[3] S. Hwang, J.H. Lee, C. Park, H. Lee, C. Kim, C. Park, M.H. Lee, W. Lee, J.
Park, K. Kim, N.G. Park, C. Kim, A highly efcient organic sensitizer
for dye-sensitized solar cells, Chem. Commun. (2007) 48874889.
[4] Z.S. Wang, Y. Cui, Y. Dan-Oh, C. Kasada, A. Shinpo, K. Hara,
Thiophene-functionalized coumarin dye for efcient dye-sensitized

C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]
[14]

[15]

[16]

[17]

[18]
[19]

[20]

[21]

[22]

[23]

[24]

[25]

solar cells: electron lifetime improved by coadsorption of

deoxycholic acid, J. Phys. Chem. C 111 (2007) 72247230.
N. Santhanamoorthi, K.H. Lai, F. Taufany, J.C. Jiang, Theoretical
investigations of metal-free dyes for solar cells: effects of electron
donor and acceptor groups on sensitizers, J. Power Sources 242
(2013) 464471.
N. Santhanamoorthi, C.M. Lo, J.C. Jiang, Molecular design of
porphyrins for dye-sensitized solar cells: a DFT/TDDFT study, J.
Phys. Chem. Lett. 4 (2013) 524530.
D. Kuciauskas, M.S. Freund, H.B. Gray, J.R. Winkler, N.S. Lewis,
Electron transfer dynamics in nanocrystalline titanium dioxide solar
cells sensitized with ruthenium or osmium polypyridyl complexes, J.
Phys. Chem. B 105 (2001) 392403.
E.A.M. Geary, L.J. Yellowlees, L.A. Jack, I.D.H. Oswald, S. Parsons, N.
Hirata, J.R. Durrant, N. Robertson, Synthesis, structure, and
properties of [Pt(II)(diimine)(dithiolate)] dyes with 3,30 -,4,40 -, and
5,50 -disubstituted bipyridyl: applications in dye-sensitized solar
cells, Inorg. Chem. 44 (2005) 242250.
Q. Wang, W.M. Carnpbell, E.E. Bonfantani, K.W. Jolley, D.L. Ofcer, P.J.
Walsh, K. Gordon, R. Humphry-Baker, M.K. Nazeeruddin, M. Gratzel,
Efcient light harvesting by using green Zn-porphyrin-sensitized
nanocrystalline TiO2 lms, J. Phys. Chem. B 109 (2005) 1539715409.
M.K. Nazeeruddin, P. Pechy, T. Renouard, S.M. Zakeeruddin, R.
Humphry-Baker, P. Comte, P. Liska, L. Cevey, E. Costa, V. Shklover,
L. Spiccia, G.B. Deacon, C.A. Bignozzi, M. Gratzel, Engineering of
efcient panchromatic sensitizers for nanocrystalline TiO2-based
solar cells, J. Am. Chem. Soc. 123 (2001) 16131624.
M.K. Nazeeruddin, F. De Angelis, S. Fantacci, A. Selloni, G. Viscardi, P.
Liska, S. Ito, T. Bessho, M. Gratzel, Combined experimental and DFT
TDDFT computational study of photoelectrochemical cell ruthenium
sensitizers, J. Am. Chem. Soc. 127 (2005) 1683516847.
F.F. Gao, Y. Wang, J. Zhang, D. Shi, M.K. Wang, R. Humphry-Baker, P.
Wang, S.M. Zakeeruddin, M. Gratzel, A new heteroleptic ruthenium
sensitizer enhances the absorptivity of mesoporous titania lm for a
high efciency dye-sensitized solar cell, Chem. Commun. (2008)
26352637.
M. Gratzel, Photoelectrochemical cells, Nature 414 (2001) 338344.
Y. Chiba, A. Islam, Y. Watanabe, R. Komiya, N. Koide, L.Y. Han, Dyesensitized solar cells with conversion efciency of 11.1%, Jpn. J. Appl.
Phys. 45 (2006) L638L640.
M.K. Nazeeruddin, T. Bessho, L. Cevey, S. Ito, C. Klein, F. De Angelis, S.
Fantacci, P. Comte, P. Liska, H. Imai, M. Graetzel, A high molar
extinction coefcient charge transfer sensitizer and its application in
dye-sensitized solar cell, J. Photochem. Photobiol., A 185 (2007)
331337.
A. Mishra, M.K.R. Fischer, P. Bauerle, Metal-free organic dyes for dyesensitized solar cells: from structure: property relationships to
design rules, Angew. Chem., Int. Ed. 48 (2009) 24742499.
Z.S. Wang, Y. Cui, Y. Dan-Oh, C. Kasada, A. Shinpo, K. Hara, Molecular
design of coumarin dyes for stable and efcient organic dyesensitized solar cells, J. Phys. Chem. C 112 (2008) 1701117017.
J.Y. Kim, Y.H. Kim, Y.S. Kim, Indoline dyes with various acceptors for
dye-sensitized solar cells, Curr. Appl. Phys. 11 (2011) S117S121.
N. Koumura, Z.S. Wang, S. Mori, M. Miyashita, E. Suzuki, K. Hara,
Alkyl-functionalized organic dyes for efcient molecular
photovoltaics, J. Am. Chem. Soc. 128 (2006) 1425614257.
P. Qin, X.C. Yang, R.K. Chen, L.C. Sun, T. Marinado, T. Edvinsson, G.
Boschloo, A. Hagfeldt, Inuence of pi-conjugation units in organic
dyes for dye-sensitized solar cells, J. Phys. Chem. C 111 (2007) 1853
1860.
W.R. Duncan, O.V. Prezhdo, Temperature independence of the
photoinduced electron injection in dye-sensitized TiO(2)
rationalized by ab initio time-domain density functional theory, J.
Am. Chem. Soc. 130 (2008) 97569762.
V. Thavasi, V. Renugopalakrishnan, R. Jose, S. Ramakrishna,
Controlled electron injection and transport at materials interfaces
in dye sensitized solar cells, Mater. Sci. Eng. R 63 (2009) 8199.
P.M. Beaujuge, C.M. Amb, J.R. Reynolds, Spectral engineering in piconjugated polymers with intramolecular donoracceptor
interactions, Acc. Chem. Res. 43 (2010) 13961407.
G.L. Gibson, T.M. McCormick, D.S. Seferos, Atomistic band gap
engineering in donoracceptor polymers, J. Am. Chem. Soc. 134
(2012) 539547.
Y. Zhu, A.P. Kulkarni, P.T. Wu, S.A. Jenekhe, New ambipolar organic
semiconductors. 1. Synthesis, single-crystal structures, redox
properties, and photophysics of phenoxazine-based donor
acceptor molecules, Chem. Mater. 20 (2008) 42004211.

1213

[26] S.A. Jenekhe, L.D. Lu, M.M. Alam, New conjugated polymers with
donoracceptor architectures: synthesis and photophysics of
carbazolequinoline and phenothiazinequinoline copolymers and
oligomers exhibiting large intramolecular charge transfer,
Macromolecules 34 (2001) 73157324.
[27] U. Salzner, Does the donor-acceptor concept work for designing
synthetic metals? 1. Theoretical investigation of poly(3-cyano-30 hydroxybithiophene), J. Phys. Chem. B 106 (2002) 92149220.
[28] U. Salzner, M.E. Kose, Does the donor-acceptor concept work for
designing synthetic metals? 2. Theoretical investigation of
copolymers of 4-(dicyanomethylene)-4H-cyclopenta[2,1-b: 3,4-b
]dithiophene and 3,4-(ethylenedioxy)thiophene, J. Phys. Chem. B
106 (2002) 92219226.
[29] U. Salzner, O. Karalti, S. Durdagi, Does the donoracceptor concept
work for designing synthetic metals? III. Theoretical investigation of
copolymers between quinoid acceptors and aromatic donors, J. Mol.
Model. 12 (2006) 687701.
[30] H.A.M. van Mullekom, J.A.J.M. Vekemans, E.E. Havinga, E.W. Meijer,
Developments in the chemistry and band gap engineering of donoracceptor substituted conjugated polymers, Mater. Sci. Eng. R 32
(2001) 140.
[31] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R.
Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H.
Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino,
G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J.
Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T.
Vreven, J.A. Montgomery, Jr.; J.E. Peralta, F. Ogliaro, M. Bearpark, J.J.
Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J.
Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J.
Tomasi, M. Cossi, N. Rega, N.J. Millam, M. Klene, J.E. Knox, J.B. Cross,
V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O.
Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin,
K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J.
Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V.
Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision A.1, in: Gaussian
Inc., Wallingford, CT, 2009.
[32] A.D. Becke, Density-functional thermochemistry. III. The role of
exact exchange, J. Chem. Phys. 98 (1993) 56485652.
[33] V.A. Rassolov, M.A. Ratner, J.A. Pople, P.C. Redfern, L.A. Curtiss, 6
31G*basis set for third-row atoms, J. Comput. Chem. 22 (2001) 976
984.
[34] W. Xu, B. Peng, J. Chen, M. Liang, F. Cai, New triphenylamine-based
dyes for dye-sensitized solar cells, J. Phys. Chem. C 112 (2008) 874
880.
[35] T. Horiuchi, H. Miura, S. Uchida, Highly efcient metal-free organic
dyes for dye-sensitized solar cells, J. Photochem. Photobiol., A 164
(2004) 2932.
[36] D.P. Hagberg, T. Marinado, K.M. Karlsson, K. Nonomura, P. Qin, G.
Boschloo, T. Brinck, A. Hagfeldt, L. Sun, Tuning the HOMO and LUMO
energy levels of organic chromophores for dye sensitized solar cells,
J. Org. Chem. 72 (2007) 95509556.
[37] S.I. Gorelsky, A.B.P. Lever, Electronic structure and spectral, of
ruthenium diimine complexes by density functional theory and
INDO/S. Comparison of the two methods, J. Organomet. Chem. 635
(2001) 187196.
[38] S.I. Gorelsky, SWizard program, in: <http://www.sg-chem.net/>,
University of Ottawa, Ottawa, Canada, 2013.
[39] C.G. Zhan, J.A. Nichols, D.A. Dixon, Ionization potential, electron
afnity, electronegativity, hardness, and electron excitation energy:
molecular properties from density functional theory orbital
energies, J. Phys. Chem. A 107 (2003) 41844195.
[40] K. Hara, T. Sato, R. Katoh, A. Furube, T. Yoshihara, M. Murai, M.
Kurashige, S. Ito, A. Shinpo, S. Suga, H. Arakawa, Novel conjugated
organic dyes for efcient dye-sensitized solar cells, Adv. Funct.
Mater. 15 (2005) 246252.
[41] H. Choi, C. Baik, S.O. Kang, J. Ko, M.S. Kang, M.K. Nazeeruddin, M.
Gratzel, Highly efcient and thermally stable organic sensitizers for
solvent-free dye-sensitized solar cells, Angew. Chem., Int. Ed. 47
(2008) 327330.
[42] S. Jungsuttiwong, T. Yakhanthip, Y. Surakhot, J. Khunchalee, T.
Sudyoadsuk, V. Promarak, N. Kungwan, S. Namuangruk, The effect of
conjugated spacer on novel carbazole derivatives for dye-sensitized
solar cells: density functional theory/time-dependent density
functional theory study, J. Comput. Chem. 33 (2012) 15171523.
[43] K. Srinivas, C.R. Kumar, M.A. Reddy, K. Bhanuprakash, V.J. Rao, L.
Giribabu, D-pi-A organic dyes with carbazole as donor for dyesensitized solar cells, Synth. Met. 161 (2011) 96105.

1214

C.-Y. Tseng et al. / Organic Electronics 15 (2014) 12051214

[44] K.F. Chen, Y.C. Hsu, Q.Y. Wu, M.C.P. Yeh, S.S. Sun, Structurally simple
dipolar organic dyes featuring 1,3-cyclohexadiene conjugated unit
for dye-sensitized solar cells, Org. Lett. 11 (2009) 377380.
[45] K. Srinivas, K. Yesudas, K. Bhanuprakash, V.J. Rao, L. Giribabu, A
combined experimental and computational investigation of
anthracene based sensitizers for DSSC: comparison of cyanoacrylic
and malonic acid electron withdrawing groups binding onto the TiO2
anatase (1 0 1) surface, J. Phys. Chem. C 113 (2009) 2011720126.
[46] R.Z. Li, J.Y. Liu, N. Cai, M. Zhang, P. Wang, Synchronously reduced
surface states, charge recombination, and light absorption length for
high-performance organic dye-sensitized solar cells, J. Phys. Chem. B
114 (2010) 44614464.
[47] Z.S. Wang, N. Koumura, Y. Cui, M. Takahashi, H. Sekiguchi, A. Mori, T.
Kubo, A. Furube, K. Hara, Hexylthiophene-functionalized carbazole
dyes for efcient molecular photovoltaics: tuning of solar-cell
performance by structural modication, Chem. Mater. 20 (2008)
39934003.
[48] K.R.J. Thomas, Y.C. Hsu, J.T. Lin, K.M. Lee, K.C. Ho, C.H. Lai, Y.M.
Cheng, P.T. Chou, 2,3-disubstituted thiophene-based organic dyes
for solar cells, Chem. Mater. 20 (2008) 18301840.

[49] M.K. Nazeeruddin, S.M. Zakeeruddin, R. Humphry-Baker, M. Jirousek,

P. Liska, N. Vlachopoulos, V. Shklover, C.H. Fischer, M. Gratzel, Acidbase equilibria of (2,20 -bipyridyl-4,40 -dicarboxylic acid)ruthenium(II)
complexes and the effect of protonation on charge-transfer
sensitization of nanocrystalline titania, Inorg. Chem. 38 (1999)
62986305.
[50] F. Gao, Y. Wang, D. Shi, J. Zhang, M.K. Wang, X.Y. Jing, R. HumphryBaker, P. Wang, S.M. Zakeeruddin, M. Gratzel, Enhance the optical
absorptivity of nanocrystalline TiO(2) lm with high molar extinction
coefcient ruthenium sensitizers for high performance dyesensitized solar cells, J. Am. Chem. Soc. 130 (2008) 1072010728.
[51] Y.M. Cao, Y. Bai, Q.J. Yu, Y.M. Cheng, S. Liu, D. Shi, F.F. Gao, P. Wang,
Dye-sensitized solar cells with a high absorptivity ruthenium
sensitizer
featuring
a
2-(hexylthio)thiophene
conjugated
bipyridine, J. Phys. Chem. C 113 (2009) 62906297.
[52] C.Y. Chen, M.K. Wang, J.Y. Li, N. Pootrakulchote, L. Alibabaei, C.H.
Ngoc-le, J.D. Decoppet, J.H. Tsai, C. Gratzel, C.G. Wu, S.M.
Zakeeruddin, M. Gratzel, Highly efcient light-harvesting
ruthenium sensitizer for thin-lm dye-sensitized solar cells, ACS
Nano 3 (2009) 31033109.