Dyes and Pigments 137 (2017) 165e173

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Dyes and Pigments

journal homepage: www.elsevier.com/locate/dyepig

Cyclopentadithiophene bridged organic sensitizers with different

auxiliary acceptor for high performance dye-sensitized solar cells
Weixia Hu, Zemin Zhang, Wei Shen, Ming Li, Rongxing He*
Key Laboratory of Luminescence and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical
Engineering, Southwest University, Chongqing 400715, China

a r t i c l e i n f o a b s t r a c t

Article history: A series of triphenylamine-based dye sensitizers were designed by modifying the auxiliary acceptors and
Received 3 August 2016 their positions for the potential use in dye-sensitized solar cells (DSSCs). The geometrical structures,
Received in revised form photoinduced charge transfer character together with optical properties for these dyes adsorbed on
7 October 2016
(TiO2)6 have been investigated using density functional theory (DFT) and time-dependent density
Accepted 12 October 2016
Available online 13 October 2016
functional theory (TD-DFT) methods. The effects of auxiliary units and their positions on the optoelec-
tronic properties of the dyes are demonstrated. The results illustrate that the dyes with auxiliary ac-
ceptors close to the cyanoacrylic acid show very narrow band gap (HOMO-LUMO), leading to an obvious
Keywords:
Metal-free sensitizers
red-shifted absorption band in contrast to the dyes with additional acceptors next to the donor part.
Cyclopentadithiophene Further analyses of the dye-(TiO2)6 systems manifest that there has strong electronic coupling between
Auxiliary acceptor the dyes and the (TiO2)6 surface. The results are expected to provide a useful reference to the future
High performance design and optimization for new highly efficient metal-free organic dyes.
Dye-sensitized solar cells © 2016 Elsevier Ltd. All rights reserved.

1. Introduction conjunction with Co(II/III) tris-bipyridyl redox shuttle [9].

Tremendous efforts have been devoted to DSSCs due to their
environmental compatibility and low cost, since O'Regan and
Gra€tzel reported the groundbreaking work in the field of dye
sensitized solar cells (DSSCs) based on polypyridyl Ruthenium (Ru)
dye in 1991 [1]. In a typical DSSC, the photovoltaic performance is
mainly determined by sensitizers, photoanode, counter electrode,
electrolyte and their combination [2]. As the key components, the
sensitizer and the redox electrolyte have been confirmed to be
particularly essential for the photoelectric conversion efficiency
and battery properties [3,4]. Over the past decades, numerous dyes
have been used in DSSCs. Comparatively, the metal-free organic
dyes, especially those based on the “push
pull” structure of donor-
p conjugated bridge-acceptor (D-p-A), have displayed rather high
performances considering the advantages of their high molar
extinction coefficient, flexible molecular structures, as well as good
compatibility to the cobalt bipyridyl complex-based electrolytes
[5e10]. It is noteworthy that the power conversion efficiency of
10.65% has been reached by using metal-free organic dyes YA422 in
* Corresponding author.
E-mail address: herx@swu.edu.cn (R. He).
Commonly, iodide/triiodide ðI
=I
3 Þ and [Co(bpy)3]
2þ/3þ
are most
frequently used as redox mediators to attain highly efficient
photovoltaic performances [11]. Recently, Kakiage and co-workers
have successfully achieved high efficiency over 14% by means of
collaborative sensitization [12].
In general, the performance of DSSCs depends on some key
parameters: open-circuit photovoltage (Voc), short-circuit photo-
current density (Jsc), fill factor (FF), and power conversion efficiency
(h) [2]. Structural modification is the common method to improve
the parameters. As is known, most organic sensitizers consist of the
D-p-A configuration, which the electron transfers from the donor
section to the acceptor/anchoring group through a conjugated
linker [13,14]. A novel donor-acceptor-p conjugated bridge-
acceptor (D-A-p-A) configuration which incorporates an electron-
withdrawing auxiliary acceptor such as diketopyrrolopyrrole
[15e18], bithiazole [19,20], isoindigo [9], benzothiadiazole [7,14,21],
benzotriazole [22], and quinoxaline [23e25] was proved to be an
efficient tactic to extend the absorption spectra and improve the
photovoltaic performances.
More recently, Chaurasia et al. [26] focused on incorporating
electron-deficient entity in the conjugated spacer to develop PyT-
based sensitizers. They found that the introduction of an
electron-deficient entity, benzothiadiazole (BT), pyrido[2,1,3]

http://dx.doi.org/10.1016/j.dyepig.2016.10.011
0143-7208/© 2016 Elsevier Ltd. All rights reserved.
166 W. Hu et al. / Dyes and Pigments 137 (2017) 165e173

thiadiazole (PyT), as the auxiliary acceptor in the conjugated bridge
of the D-p-A framework [27], was an effectual way to broad the
light absorption band. Wang et al. reported the D-A-p-A sensitizers
D2 (named BT-CPDT as the model molecule in our work) with a
broad visible light absorption range up to 800 nm and a power
conversion efficiency over 9% using cobalt electrolytes [28]. The
bulky triphenylamine donor offers the probability to inhibit charge
recombination and hinder molecular aggregation, especially for the
cobalt redox system. Meanwhile, the cyclopentadithiophene
(CPDT) unit has been documented as an effective building block for
organic photovoltaics [29e31]. The entirely rigid coplanar structure
together with good electron-donating ability is anticipated to
decrease the energy gap and boost the intramolecular charge
transfer process. More importantly, evidence from recent research
shows that the insertion of long alkyl chain into dye structure can
effectively offer double protection [32]. However, the absorption
bands of most organic dyes are restricted to a comparatively nar-
row absorption range compared with Ru dyes and other dyes.
Until now, the effects of auxiliary acceptors and their positions
near the anchor group or close to the donor group on the photo-
voltaic properties have not been systematically studied. Based on
the previous study, we begin with a cyclopentadithiophene unit as
the spacer to design efficient DSSCs dyes with cobalt electrolytes
(Fig. 1). PyNT (the N atom facing toward the acceptor) and NPyT
(the N atom facing away from the acceptor), which are just one
atom of difference from BT, have a higher electron affinity than BT.
In order to extend the absorption range, we incorporate PyNT and
NPyT entities as additional acceptors into D-A-p-A molecule owing
to the following reasons: (1) the more electron affinity than BT is
helpful for red shifting of the absorption spectra; (2) the asym-
metric feature of pyridine ring can form two isomers. With the
purpose of finding the potential sensitizers, the absorption spectra,
electronic properties and energy gap for these dyes are considered
using DFT and TD-DFT methods. What's more, to simulate the real
working conditions, the optical properties of investigated dyes
adsorbed on (TiO2)6 surface are further calculated. It is hoped that
the perceptions obtained in this study will offer guidance for the
future experimental research on design and optimization of new
efficient dyes for DSSC applications.
2. Computational methods
2.1. Theoretical background
As described above, the power conversion efficiency (h) of the
DSSCs is closely associated with three factors: short-circuit
photocurrent density (Jsc), open-circuit photovoltage (Voc) and the
fill factor (FF). And it can be expressed as follows [33]:
Voc Jsc
h ¼ FF (1)
Pinc
where Pinc represents the incident solar power on the cell.
Correspondingly, Jsc can be described as the following equation
[11,34,35]:
Z
Jsc ¼ e LHEFinject hreg hcollect Is ðlÞdl (2)
l
where LHE is the light-harvesting efficiency. Finject is the electron
injection efficiency, and hreg and hcollect denote the regeneration
efficiency of the oxidized dye and the charge collection efficiency,
respectively. The LHE can be expressed as
LHE ¼ 1
10
f (3)
where f is the oscillator strength of the dye molecule at the
maximum wavelength. Finject can be estimated through the driving
force of electron injection (DGinject) from the excited dye to the
semiconductor. Additionally, hreg can also be evaluated by the
driving force of regeneration (DGreg) between the oxidized dye and
the electrolyte. They are defined as [36,37]

DGinject ¼ Edye
ECB (4)

 . 
DGreg ¼ E Co2þ Co3þ
ECB (5)

where Edye* is the excited-state oxidation potential energy of the

dye and ECB is the redox potential of the excited dye. Edye* can be
expressed as [38]

Edye* ¼ Edye
Elmax (6)

where Edye is the ground-state oxidation potential energy of the dye

and Elmax is the vertical transition energy [39].
As for Voc in DSSCs, it can be described by Ref. [38]
 
ECB þ DECB kb T nc E
Voc ¼ þ ln
redox (7)
q q NCB q

Fig. 1. Molecular structures of the metal-free organic sensitized dyes investigated in
this work.
where q is the unit charge, ECB is the conduction band edge of the
semiconductor substrate, kb is the Boltzmann constant, T is the
absolute temperature, nc is the number of electrons in conduction
band, NCB is the density of accessible states in the conduction band.
DECB is the shift of ECB when the dyes are absorbed on substrate and
can be expressed as [40]
 W. Hu et al. / Dyes and Pigments 137 (2017) 165e173
qmnormal g
DECB ¼
(8)
ε0 ε
Here, mnormal denotes the dipole moment of individual dye molec-
ular perpendicular to the surface of the semiconductor substrate. g
is the surface concentration of dyes. ε0 and ε represent the vacuum
permittivity and the dielectric permittivity, respectively. It can be
drawn from Eqs. (7) and (8) that nc and mnormal show vital influence
on Voc.
2.2. Computational details
All the calculations were implemented with DFT and TD-DFT
using the Gaussian 09 package [41]. With the intention of select-
ing an appropriate HOMO energy which will agree well with the
experiment value, a series of hybrid functional including B3LYP,
BHandHLYP, PBE0, and M062X together with different basis sets
were applied to optimize the ground-state (S0) geometry of
investigated model compound BT-CPDT (shown in Table S1, Sup-
plementary material). We find that PBE0/6-311G(d,p) method is
proper for the present work. The frequency analyses were also
carried out at the same theoretical level as geometry optimization
to guarantee the local minimum of potential energy surface. In the
process of TD-DFT calculation, optical absorption spectra at the
optimized ground-state geometries with the 30 lowest singlet-
singlet excitations were calculated. To find a proper functional,
we used different exchangeecorrelation (XC) functional including
BMK, PBE0, and CAM-B3LYP. By comparing the theoretical
maximum absorption wavelength with the experimental data, it is
found that the Boese and Martin's s-dependent hybrid functional
(BMK) together with 6-311G(d,p) is the most suitable one used for
their vertical electronic excitation energies (listed in Table S2). In
addition, to study the coupling interaction between dye and TiO2
surface further, the geometry optimizations and TD-DFT calcula-
tions for dyes binding to (TiO2)6 were explored by using the same
functional as isolated dyes for the C, H, O, N, S, and LANL2DZ basis
set [42] for Ti atoms. The conductor-like polarized continuum
model (C-PCM) (in dichloromethane environment) was also taken
into consideration [43]. Besides, the electron density differences
were calculated with the code Multwfn 2.5 to assess the efficiency
of charge separation [44]. The distance of charge transfer and the
fraction of charge exchange were calculated with DctViaCube [45].
3. Results and discussion
3.1. Geometrical structures and electronic properties
The geometrical structures of investigated sensitizers are shown
in Fig. 1, in which triphenylamine is used as electron-donating unit
(D), BT, PyNT, NPyT acting as auxiliary acceptors (A), a cyclo-
pentadithiophene unit as spacer (p), and cyanoacrylic acid as
electron acceptor (A), respectively. A potential dye molecule must
have a high LUMO energy level for efficient electron injection into
TiO2, a sufficiently low HOMO energy level for efficient regenera-
tion of the oxidized state dye and a low energy gap to ensure the
redshift of the absorption band. The incorporation of an auxiliary
electron-withdrawing acceptor between the donor and conjugated
bridge can tune energy level, extend light absorption range, and
promote electron transfer from the donor part to anchor group. In
this paper, the influence of the electron withdrawing ability and
their positions of the auxiliary acceptor was taken into account in
detail.
The dihedral angles between donor group and auxiliary acceptor
(a), between auxiliary acceptor and cyclopentadithiophene unit (b)
167
as well as between cyclopentadithiophene unit and cyanoacrylic acid
moiety (g) are listed in Table 1. The results indicate that the donor
and acceptor moieties are fully conjugated through the p bridge. For
all the dyes, the dihedral angles (a) are computed to be 33.0 ,
22.8 ,
14.8 , 19.7,
31.2 , and
19.3 . It can be easily found that the
changes of auxiliary groups not only can be benefit to the increase of
conjugation but also can inhibit the p-aggregation due to the decline
of the a. For the dyes of auxiliary group near the anchor group, CPDT-
PyNT has the smaller a than that of CPDT-BT and CPDT-NPyT, which
perhaps due to the strong electron withdrawing ability of N atom.
This may lead to the bathochromic shift of the absorption band. The
dihedral angles b are 14.7, 1.2 ,
7.9 , 0.3 ,
0.3 , and 0.7,
respectively. The results indicate that the good coplanarity may be
beneficial to the electron injection process. As for the dihedral angles
g, all are close to 0 .
Generally, intramolecular charge transfer characteristics have
close relation to the orbital spatial distribution and the composi-
tions of the frontier molecular orbital [46], which have a substantial
impact on the electronic excitation of dyes. For a suitable sensitizer,
the HOMO is mostly localized on the donor segment whereas the
LUMO is localized on the acceptor part. The orbital spatial distri-
bution and components of the HOMO and LUMO for these mole-
cules are depicted in Fig. 2. For the investigated dyes BT-CPDT,
PyNT-CPDT, the HOMO orbitals are almost populated over the
donor and additional moiety, while the LUMOs are centered at the
“A-p-A” segment, with primely overlap on the auxiliary acceptors.
As for the dyes CPDT-BT, CPDT-NPyT and CPDT-PyNT, the HOMOs
mainly show localization at electron-donor and linker moiety,
while LUMOs primarily are centered at the p-conjugated bridge
and acceptor part. The electron transfer from HOMO to LUMO in-
duces efficient charge separations, and can be visually displayed by
the electronic density difference (EDD) plots in Table 2. On the
contrary, the dye NPyT-CPDT exhibits an insufficient spatial charge
distribution, the HOMO shows location at the “A-p-A” segment,
whereas the LUMO extends over the “A-p-A” section. Such a
delocalized HOMO is considered to produce electron-hole recom-
bination, which is disadvantageous to cell performance.
Besides, the energy level is another pivotal feature. To gain a
deep insight into the driving force for the electron injection and the
regeneration of the sensitizers, Fig. 3 and Table S3 illustrate the
energy levels of HOMOs and LUMOs of designed dyes BT-CPDT,
Table 1
Brief structure and calculated dihedral angles between the neighbouring units of
dyes.
Dyes a b g
BT-CPDT 33.0 14.7
0.2
CPDT-BT
22.8 1.2
0.1
NPyT-CPDT 14.8
7.9 1.8
CPDT-NPyT 19.7 0.3 0.2
PyNT-CPDT
31.2
0.3 1.1
CPDT-PyNT
19.3 0.7
0.1
168 W. Hu et al. / Dyes and Pigments 137 (2017) 165e173

Fig. 2. Frontier molecular orbitals of all the dyes at level of PBE0/6-311G(d,p).

Table 2
Electron density difference plots of the electronic transition S0/S1 for all the dyes performed in dichloromethane solvent using the BMK functional together with the 6-
311G(d,p) basis set.

Scheme BT-CPDT CPDT-BT NPyT-CPDT CPDT-NPyT PyNT-CPDT CPDT-PyNT

Picture

L (Ang) 10.046 11.816 3.744 11.353 8.529 12.281

De 1.063 1.101 0.950 1.076 1.102 1.140
U 0.2536 0.0539 0.3665 0.0891 0.3380 0.0445

L is the electron transfer distance (Å), De is the fraction of electron exchange (je
j), U is overlap between the regions of density depletion and increment (isovalue: 4  10
4 e
au
3).

Fig. 3. Energy level diagram of the sensitizers relative to TiO2 and [Co(bpy)3]2þ/3þ in
CH2Cl2.
CPDT-BT, NPyT-CPDT, CPDT-NPyT, PyNT-CPDT, CPDT-PyNT at
PBE0/6-311G(d,p) level in CH2Cl2. The LUMO levels of all of the
sensitizers are established above the conduction band (CB) of TiO2
semiconductor, thus ensuring an effective electron injection from
the excited state dye to TiO2 surface, whereas the corresponding
HOMO levels are adequately lower than these of the Cobalt (II/III)
electrolyte redox potential so that all dyes can be restored by
electrons from electrolyte [47].
As Fig. 3 demonstrated, for all the designed dyes, the HOMO
energies are all up-shifted and the LUMO energies are down-
shifted considerably except for the dye NPyT-CPDT in comparison
with the model molecule BT-CPDT. That is to say, due to their much
lower LUMO energies, the HOMO-LUMO energy gaps of all the dyes
become narrower than that of BT-CPDT except for the dye NPyT-
CPDT. As testified in other literature, sensitizers with smaller en-
ergy gaps may lead to the electrons being more easily excited and
thus favorable for providing broader wavelength light range [39].
The band gaps between HOMO and LUMO in CH2Cl2 for the dyes are
in the sequence of NPyT-CPDT > BT-CPDT > PyNT-CPDT > CPDT-
BT > CPDT-NPyT > CPDT-PyNT. The outcome reveals that the
calculated band gaps of different complexes are determined by the
position of the additional acceptors. The additional acceptors
adjacent to the anchor side can lead to narrow band gaps. We
speculate that the reason why the band gap of the dyes with
auxiliary group next to the anchor group is narrower than that of
near the donor part is the good planarity of the p-bridge. It is
evident that the dyes with the additional moiety close to the anchor
group have the potential for getting bathochromic shift of the ab-
sorption band, which may make contributions to higher power
conversion efficiency [48].
In this work, in order to study the charge transfer properties
deeply, electron density difference plots of all isolated dyes were
calculated. Besides, three parameters including the electron
transfer distance (L in Å), the fraction of electron exchange (De in
je
j), together with the overlap between the zones of density
depletion and increment (U, isovalue: 4  10
4 e au
3 ) are summed
up in Table 2 [45].
Apparently, the region of the electron density depletion (green
color) mostly localizes on the donor part, while the region of the
 W. Hu et al. / Dyes and Pigments 137 (2017) 165e173
electron density increment (purple color) is largely aligned with
the p-conjugation spacer and acceptor regions. Therefore, the
intramolecular charge transfer (ICT) excitation is important for
reaching fast electron injection from the excited dye to the TiO2
conduction band. Normally, with the longer distance and less
electron density overlap, a better charge separation can be ach-
ieved. The electron transfer distance is in the following order:
CPDT-PyNT (12.281) > CPDT-BT (11.816) > CPDT-NPyT
(11.353) > BT-CPDT (10.046) > PyNT-CPDT (8.529) > NPyT-CPDT
(3.744). When the electron-withdrawing entities of sensitizers are
in the vicinity of the acceptor, the fraction of electron exchange is
larger than that of near the donor. Moreover, we can observe that
the electron density depletion of CPDT-PyNT whose PyNT is
directly connected to the anchoring group is the largest, which may
be caused by an enhanced charge accumulation around the cya-
noacrylic acid and its surrounding area. It also can be demonstrated
by the largest fraction of charge exchange De for CPDT-PyNT
(1.140). In addition, the longer electron transfer distance (L) of
CPDT-PyNT (12.281) is also the evidence of the better charge sep-
aration when PyNT (the N atom facing toward the acceptor) is
directly linked to acceptor part. In addition to De and L, the overlaps
between the regions of density depletion and increment also can
well evaluate the charge separation. Notably, weak overlap is ad-
vantageous to good charge separation. As presented in Table 2, with
the changes of the additional acceptors, the overlaps decrease in
the order of NPyT-CPDT (0.3665) > PyNT-CPDT (0.3380) > BT-CPDT
(0.2536) > CPDT-NPyT (0.0891) > CPDT-BT (0.0539) > CPDT-PyNT
(0.0445). All in all, when a series of strong electron-withdrawing
units of the dyes are linked to the acceptor entities, the charge
separation efficiency can be substantially improved.
3.2. Photophysical properties
The UVevis absorption spectra are more trustworthy to evaluate
their light-harvesting performances in the solar cells. The simu-
lated electronic spectra of the sensitizers in CH2Cl2 which were
obtained at the TDDFT/BMK/6-311G(d,p) level are shown in Fig. 4,
and it has been demonstrated previously that the absorption peak
was in good agreement with the experimental result. The relevant
electronic transition data of the dyes are summarized in Table 3,
more detailed analyses of the molecular orbital compositions with
the transition information including the excitation energies, the
maximum wavelength (lmax), oscillator strengths (f) and major
electron transitions, together with absorption bands with f > 0.1
Fig. 4. Simulated absorption spectra and oscillator strength of the free dyes at the
BMK/6-311G(d,p) level of theory in CH2Cl2.
169
and l > 350 nm in the UVevis regions for all the dyes in CH2Cl2 are
listed in Table S4. Obviously, the absorption spectrum displays two
major intense bands in the ranges of 320e450 nm for B band and
520e750 nm for Q band, respectively. The prominent Q band can be
attributed to the intramolecular charge transfer from the triphe-
nylamine donor to the cyanoacrylic acid acceptor, while the B band
can be ascribed to the localized p-p* electron transition within the
whole dyes.
From Fig. 4, it is easy to observe that the different sites of the
auxiliary group have a great influence on the absorption spectra.
The maximum absorption wavelength of BT-CPDT appears at
560 nm. Apparently, the absorption spectra of the designed dyes
have significantly broadened and red-shifted, whereas dye NPyT-
CPDT is blue-shifted owing to insufficient charge separation.
Particularly, for each isometric pair molecules, the large red-shift
can be achieved for the dyes CPDT-BT, CPDT-NPyT, CPDT-PyNT
with additional acceptors next to the anchor moiety, which are in
well agreement with their narrow HOMO-LUMO energy gaps. We
conjecture that the reason for the broaden absorption range is the
higher coplanarity and lower energy gaps. Furthermore, albeit
weak intensity of the absorption peak, the dye CPDT-PyNT with the
wavelength at 736 nm has a great bathochromic shift compared
with the reference dye BT-CPDT, which is beneficial for light har-
vesting. By comparison, the intensities of the absorption peak for
CPDT-BT, CPDT-NPyT are increasing gradually by substituting H
atom for N atom on the auxiliary receptor, which is possibly caused
by the growing contribution of electron transition from HOMO to
LUMO. Moreover, we can see from Table 3 that the orbital contri-
butions of electronic transition for designed dyes are larger than
the experimental molecule. As we all known, f reveals the light-
harvesting efficiency (LHE) to some degree. As described in Eq.
(3), a larger f will lead to a larger LHE. Obviously, the largest LHE of
0.9858 achieved in CPDT-NPyT is not conspicuous in contrast to the
reference dye. As a whole, we can draw the conclusion that the LHE
has no marked changes for dyes in the maximum absorption bands.
3.3. Charge injection (DGinject) and dye regeneration (DGreg)
According to the above discussion, Finject and hreg are also
important means to estimate the photoelectric conversion effi-
ciency, and it can be roughly reckoned by means of DGinject and
DGreg. Based on the related reference, we know that the ground
state oxidation potential energy (Edye) can be evaluated as negative
EHOMO and Edye* can be calculated by Eq. (4). As shown in Table 4,
the free energy changes DGinject of all the designed dyes are slightly
lower than that of BT-CPDT, suggesting an efficient electron in-
jection from the dyes into the conduction band.
Beyond that, low DGreg is required for the fast electron transfer.
The spin density distributions for the oxidized systems were ana-
lysed to study dye regeneration [49]. Based on the (U) DFT/PBE0/6-
311G(d,p) calculations, the contour plots of the spin densities as
well as the contributions from the donor moiety and bridge are
presented in Fig. 5. The spin density for all oxidized dyes is mainly
populated over the donor and p-conjugated spacer. Meanwhile, the
contribution from the electron donor and p-linker is in the
sequence of NPyT-CPDT (88.1%) < CPDT-PyNT (95.5%) < CPDT-BT
(96.8%) < CPDT-NPyT (97.9%) < BT-CPDT (98.8%) < PyNT-CPDT
(98.9%), which shows a very faintly difference between the refer-
ence dye and the new designed ones. At the same time, from
Table 4, the DGreg values show a small changes between the refer-
ence dye BT-CPDT and other dyes except for NPyT-CPDT. More
importantly, the favorable spin density distribution of the cationic
radical, sufficient DGreg, and the larger absorption spectra ranges
can induce a higher Jsc which may contribute to the improvement of
the cell performance.
170 W. Hu et al. / Dyes and Pigments 137 (2017) 165e173

Table 3
Main electron transitions, oscillator strengths (f), and absorption bands with f > 0.1 and l > 350 nm in the UVevis regions at the BMK/6-311G(d,p) level for all the dyes in
CH2Cl2. (H¼HOMO, L ¼ LUMO, Lþ1 ¼ LUMOþ1, etc.)

Sensitizer Excited energy (eV) lmax (nm) f Composition

BT-CPDT 2.21(S0/S1) 560 1.7899 H-1/L (15%) H/L (75%)

H/Lþ1 (7%)
CPDT-BT 1.84(S0/S1) 675 1.7447 H-1/L (12%) H/L (85%)
NPyT-CPDT 2.33(S0/S1) 531 1.8409 H/L (96%) H-3/Lþ1 (2%)
CPDT-NPyT 1.79(S0/S1) 692 1.8478 H-1/L (10%) H/L (87%)
PyNT-CPDT 2.06(S0/S1) 603 1.5695 H/L (84%) H-1/L (10%)
H/Lþ1 (4%)
CPDT-PyNT 1.68(S0/S1) 736 1.5396 H-1/L (10%) H/L (88%)

Table 4
Calculated electronic properties of the isolated dyes.

Sensitizer LHEa Edye (eV)b Edye* (eV)c DGinject (eV)d DGreg (eV)e mnormal (Debye)f
BT-CPDT 0.9838 5.25 3.04
0.96 0.25 19.559
CPDT-BT 0.9820 5.14 3.30
0.70 0.14 25.451
NPyT-CPDT 0.9856 5.82 3.49
0.51 0.82 21.404
CPDT-NPyT 0.9858 5.21 3.42
0.58 0.21 23.412
PyNT-CPDT 0.9731 5.28 3.22
0.78 0.28 15.981
CPDT-PyNT 0.9711 5.16 3.48
0.52 0.16 22.466
a
The light-harvesting efficiency at maximum wavelength (LHE).
b
The oxidized potential of ground state (Edye, in eV).
c
The oxidized potential of the first excited state (Edye*, in eV).
d
The injection driving force (DGinject, in eV) related to the electronic transition in Q band.
e
The regeneration energy (DGreg, in eV).
f
The dipole moment for the free dyes absorbed on (TiO2)6 cluster (mnormal, in debye).

Fig. 5. Contour plot of the spin density for the optimized geometry of the investigated dyes.

3.4. Dye absorption on (TiO2)6
In addition to Jsc, possessing a high Voc value would lead to high
h. The Voc is directly related to the CB energy (ECB). It has been re-
ported that the shift of ECB is closely correlated with mnormal of the
absorbed dyes [50,51]. From Eqs. (7) and (8), we can find that the
larger mnormal can exert a significant impact on Voc. In the previous
work, Sa nchez-de-Armas performed real-time calculations on
different model (TiO2)n (n ¼ 1, 2, 3, 6, 9, 15, and 38) nanoclusters.
They regarded that a unit of (TiO2)6 as the smallest nanocluster
model was able to simulate semiquantitatively all the features in
the electronic structure of the system [52,53]. The (TiO2)6 cluster
has also been employed to study the influence of position of
auxiliary acceptor in D-A-p-A photosentitizers on photovoltaic
performances of dye-sensitized solar cells [54]. Therefore, we used
a (TiO2)6 cluster which was proved to be reasonable to simply
simulate the dye-TiO2 systems. Typically, there are three possible
modes through which dyes are adsorbed onto a TiO2 surface:
monodentate, chelated, and bridged bidentate [55,56]. Bidentate
bridging, in which one hydrogen atom (H) is bound to the oxygen
surface, is proved to be the most stable [57,58]. Therefore, we
employed the bidentate chelation for all the sensitizers absorbed
on the TiO2 film, and the corresponding optimized structures for
the dye-(TiO2)6 complexes are presented in Fig. 6. As shown in
Table 4, the decreased mnormal for the dyes with additional acceptor
closing to the triphenylamine moiety may result in a lower Voc. On
the contrary, the great increased mnormal for the dyes with addi-
tional acceptor next to the cyanoacrylic acid may induce more
 W. Hu et al. / Dyes and Pigments 137 (2017) 165e173 171

Fig. 6. The optimized structures together with the HOMO and LUMO energy levels (in eV) of all the dyes when adsorbed on the (TiO2)6 surface, as obtained by the PBE0 functional
with the 6-311G(d,p) basis set (a); contour plots of the HOMO and LUMO of dyes on (TiO2)6 surface (b).

negative charges populated closer to the TiO2 surface than that of

the reference dye BT-CPDT, resulting in a greater ECB upshift and a
larger Voc values.
Besides, the total and partial densities of states [59] for dye-TiO2
complexes were conducted to elucidate electronic coupling be-
tween the dye and cluster (shown in Fig. S2). For all dye-TiO2
complexes, the electronic densities of LUMO orbitals are primarily
localized on the dyes with subtle contribution on adsorbates, sug-
gesting weak electronic coupling between dye and TiO2. The small
contribution plays a key role in electron transfer. The contributions
from the LUMOs of the designed dyes are higher than these of the
model molecule as we can see from Table S5 which shows the
collected contributions of selected unoccupied molecular orbitals.
We can conclude that dyes with additional acceptors adjacent to
cyanoacrylic acid have stronger electronic coupling with the CB film
than others, which will boost electron injection.
To simulate the performance of the DSSCs more vividly, we Fig. 7. Simulated absorption spectra and oscillator strength of the dyes absorbed
explore the electronic and optical properties of the dyes adsorbed systems at the BMK/6-311G(d,p) level of theory in CH2Cl2.
on the (TiO2)6 based on wholly optimized structures of dye-(TiO2)6.
Bond distances between the carboxylic oxygen atoms and the Ti
dyes are located on the triphenylamine section, whereas the HOMO
atoms (TieO bond lengths) of the dyes are gathered in Table S6. The
of dye NPyT-CPDT spreads across the whole dye molecule which
calculated bond distances between the Ti and O atoms of dyes are in
hampers the efficient electron transfer. LUMO þ 2 and LUMO þ 3
the range of 2.007e2.043 Å. The results suggest that all the dyes are
(see Table S7) are centered on the TiO2 substrate, which manifest
adsorbed on the TiO2 substrate tightly which will certainly increase
the dyes have the capacity of electron injection from dyes to the
the electron-transfer rate and improve the photovoltaic perfor-
semiconductor. Furthermore, there are puny changes about 0.13 eV
mance. The optical properties of dye-(TiO2)6 are presented in Fig. 7.
in the HOMO when dyes binding to the TiO2 surface in comparison
The spectral character is well simulated and their spectra
to the HOMO of the isolated sensitizer. The LUMO energy of each
comply with the isolated dyes. We can obviously observe that the
dye-(TiO2)6 system is much lower (by about 0.25 eV) than the
maximum absorption wavelength of the investigated dyes is red-
corresponding LUMO of the isolated dye, indicating that the LUMO
shifted in the scope of 10e75 nm contrasted with the isolated
has the major contribution to the relatively strong electron
dyes. The largest absorption peaks for the isomers of dye CPDT-BT
coupling of each dye with the TiO2 surface, which facilitates elec-
and CPDT-NPyT are redshifted by 50 nm and 34 nm, respectively. In
tron injection.
addition, the relevant molecular orbitals for dye-TiO2 systems
during photoexcitation are depicted in Fig. S3. The HOMOs of the
172 W. Hu et al. / Dyes and Pigments 137 (2017) 165e173
4. Conclusions
In summary, we have designed a series of sensitizers by
changing the auxiliary acceptors and their positions using DFT and
TD-DFT approaches. The geometrical structures, photoinduced
charge transfer character, optical properties are analysed in detail.
The additional acceptors positions have a significant influence on
the absorption wavelength because of differences in the geomet-
rical structures and the energy gaps together with the MO contri-
butions. It is found that the dyes with the auxiliary acceptors close
to the cyanoacrylic acid exhibit an improved DSSC photovoltaic
performance with a larger short-circuit current density JSC and a
higher open-circuit photovoltage VOC. By comparison, the dyes with
additional acceptors next to the donor part may lead to a lower VOC
due to possessing a smaller dipole moment, which could be
detrimental to the performance of DSSCs. Analyses of the
geometrical structures and frontier molecular orbitals of the dye-
(TiO2)6 system demonstrate that there has strong electronic
coupling between the dyes and the TiO2 semiconductor. It is hoped
that this theoretical approach will provide guideline for the future
design of pushepull organic dyes towards more efficient dye-
sensitized solar cells.
Acknowledgement
We acknowledge generous financial support from Natural Sci-
ence Foundation of China (21173169, 20803059), Chongqing
Municipal Natural Science Foundation (cstc2013jcyjA90015). And
program for Innovation Team Building at Institutions of Higher
Education in Chongqing (CXTDX201601011).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.dyepig.2016.10.011.
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