Journal of Cluster Science

https://doi.org/10.1007/s10876-020-01783-x (0123456789().,-volV)(0123456789().,-volV)

ORIGINAL PAPER

Theoretical and Conceptual Framework to Design Efficient Dye-

Sensitized Solar Cells (DSSCs): Molecular Engineering by DFT Method
Muhammad Ramzan Saeed Ashraf Janjua1 • Muhammad Usman Khan2 • Muhammad Khalid3 •

Nisar Ullah1 • Rajendra Kalgaonkar4 • Khalid Alnoaimi4 • Nour Baqader4 • Saba Jamil5,6

Received: 26 January 2020

 Springer Science+Business Media, LLC, part of Springer Nature 2020

Abstract
Herein, eight new donor-p-acceptor organic dyes namely M1–M8 have been theoretically investigated for their potential in
optoelectronic properties. The M1–M8 were designed through structural modification of p-conjugated bridge of reference
reported molecule IC2. The designed molecules contain Indolo[3,2,1-jk]carbazole as core donor unit and end capped
cyanoacrylic acid as acceptor unit. DFT and TDDFT calculations using B3LYP, CAM-B3LYP, xB97XD and M062X
functional were performed to evaluate the photophysical and photovoltaic properties. Results indicate that HOMO–LUMO
energy gaps in M1–M8 have been found smaller than IC2. Among all, M7 is a material with lowest energy gap 2.61 eV,
red shifted absorption wavelength value 436 nm. Results of the calculated redox potential of the ground state, vertical
excitation energy of the dye, oxidation potential of the dye in the excited state, free energy change for electron injection,
dye regeneration and open circuit photovoltage and light harvesting efficiency indicates that p-bridges in M1–M8 would
show better power conversion efficiency than IC2. Especially, dye M7 with p-bridge 5-(thiazol-5yl)thiazole is found to be
the most promising candidate for highly effective DSSCs properties. This theoretical framework may provide new ways for
experimentalists to design high-performance DSSCs materials for optoelectronic applications.

Electronic supplementary material The online version of this

article (https://doi.org/10.1007/s10876-020-01783-x) con-
tains supplementary material, which is available to autho-
rized users.
4
EXPEC Advanced Research Center, Saudi Aramco, Dhahran,
& Muhammad Ramzan Saeed Ashraf Janjua Kingdom of Saudi Arabia
Janjua@kfupm.edu.sa 5
Super Light Materials and Nanotechnology Laboratory,
& Saba Jamil Department of Chemistry, University of Agriculture,
sj774@cornell.edu Faisalabad 38000, Pakistan
6
1
Department of Chemistry, King Fahd University of Department of Materials Science and Engineering, Cornell
Petroleum and Minerals (KFUPM), Dhahran 31261, University, Ithaca, NY 14853, USA
Kingdom of Saudi Arabia
2
Department of Applied Chemistry, Government College
University, Faisalabad 38000, Pakistan
3
Department of Chemistry, Khwaja Fareed University of
Engineering & Information Technology,
Rahim Yar Khan 64200, Pakistan

123

Graphic Abstract
Keywords Indolo[3,2,1-jk]carbazole  DSSCs  Molecular modeling  p-conjugated linkers
Introduction
Owing to increasing demands for modern hi-tech applica-
tions, a great deal of scientific efforts has been made in
recent years to explore efficient materials with excellent
optoelectronic properties. The optoelectronic materials are
the leading elements in several device applications
including solar cells, photo diodes, laser diodes, LEDs,
optical communication systems, optical storages and
remote sensing systems [1]. For better photovoltaic
exploration, it is necessary to develop such materials which
would be environment friendly, consistent, efficient, low
cost and nontoxic. Currently, widespread research has been
devoted to dye-sensitized solar cells (DSSCs) because of
their low cost, ease of fabrication and high power con-
version efficiency (PCE) [2]. The DSSCs are commonly
classified into two categories: (i) metal-based complexes
and (ii) metal-free organic dyes. Ruthenium (Ru) based
metal complexes Z907, N719, and N3 [3, 4] have been
widely used as sensitizers since the breakthrough of DSSCs
in 1991 [5]. Under AM1.5-simulated solar light (100 mW
cm-2), DSSCs based on these complexes exhibits impres-
sive PCE up to 10% [3, 4]. However, cost of Ru metal,
rareness and environmental issues of Ru-based dyes ham-
per its wide potential applications. Therefore, researchers
are focusing largely on metal-free organic sensitizers due
to their easier purification and preparation process, low
cost, structural flexibility, high molar extinction coeffi-
cients and environment friendly applications [6]. Gener-
ally, DSSCs contains four major components: a
nanocrystalline wide energy band gap semiconductor
123
M. R. S. A. Janjua et al.
surface of photoanode (generally TiO2 or ZnO etc.), dye
sensitizers, redox liquid electrolyte usually containing
iodide/triiodide (or) hole transport material, and a counter
electrode. The sensitizer that harvests the solar photons is
the most important part of DSSC.
It has been considered that optimal design of highly
efficient organic dyes containing donor-p-acceptor (D-p-A)
configuration in which p-conjugated bridge is linked to
oppositely ends situated electron-donor (D) and acceptor
(A) groups are commonly used for tuning optoelectronic
properties [7–11]. For D units, variety of organic dye
sensitizers such as triphenylamine [12], coumarin [13],
carbazole [14], phenothiazine [15], indoline [16], por-
phyrin [17] and tetrahydroquinoline [18] have been
inspected and applied in DSSCs. Cyanoacrylic acid is
frequently selected as A unit [19, 20] because it facilitates
the electron injection due to binding with semiconductor
surface and its strong electron-withdrawing aptitude.
Although D and A building blocks play a crucial role for
attaining highly efficient D-p-A dyes, but choice of p-
bridge is considered as the key factor [21, 22]. The flour-
ine-containing p-conjugated architectures can also lead to
large NLO and optoelectronic properties [23–25]. Fur-
thermore, some typical p-conjugated structures (such as
(BO2)-chain, etc.) are also beneficial to optical properties
[23, 26]. In order to enhance the cell performance of
DSSCs, there are some successful cases by using spacer
groups in relation up to consistent D-p-A structures [27].
For instance, Liu et al. incorporated thiopehene,
3-hexylthiophene and 3,4-ethyldioxythiophene (EDOT) as
p-bridges to the structure of TH305 which resulted in
Theoretical and Conceptual Framework to Design Efficient Dye-Sensitized Solar Cells (DSSCs):…
different electron recombination, hence, affected the cell
performances [28]. Similarly, Tian et al. showed that
structural tailoring with different p-bridges caused the
considerable differences in the redox potential of dyes [29].
Different reports on computational and theoretical studies
of DSSCs are available in which photovoltaic and opto-
electronic properties are successfully tuned using structural
tailoring of compounds [30–33].
A new class namely indolocarbazole derivatives are
getting much interest recently due to their strong electron
donating capability, good fluorescence quantum yield and
high thermostability [34, 35]. For instance, indolo[3,2-b]-
carbazole is used within copolymers for photovoltaic
applications, as building organic thin film transistor and as
highly efficient electroluminescent material [36].
Indolo[3,2,1-jk]carbazoles, with an indolo- and a carbazole
ring fused in a strained model, is a special kind of indolo-
carbazole positional isomers which show appealing prop-
erties including strong electron donating ability, good
quantum and fluorescence yield and high thermostability
which led them to be promising components for conducting
thin-film and charge transporting materials [37]. In 2014,
Luo et al. synthesized and reported Indolo[3,2,1-jk]car-
bazole based four organic dyes for DSSCs and illustrated
the effect of different p-bridges on photovoltaic perfor-
mance of these sensitized dyes [38]. Overall, IC-2 exhib-
ited the high PCE of 3.68%, photovoltage of 0.66 V and a
high photocurrent of 9.78 mAcm-2 measured under
AM1.5G illumination [38]. Furthermore, IC-2 displayed a
strong higher molar extinction coefficient and useful
functionalizations that meet the important requirements in
the improvement of highly efficient organic dyes for
DSSCs [38].
IC-2 is a D-p-A organic dye with Indolo[3,2,1-jk]car-
bazole as D unit, thiophene as p-conjugated bridge and
cyanoacrylic acid (CAA) as A unit. Literature suggests that
performance of DSSCs can be finely tuned by modifying
the functional components of the dyes [38]. Therefore, the
rational design of IC-2 should be desirable toward the
development of more efficient organic DSSC dyes. Thus
herein, effect of structural modification by p-linkers on
electronic, photophysical and free energy change for
electron injection (DGinject), dye regeneration (DGreg),
open circuit photovoltage (Voc) and light harvesting effi-
ciency (LHE) have been studied in detail for optoelectronic
applications. Finally we recommended a kind of novel
indolocarbazole dye with highly effective optoelectronic
properties. Hopefully, this theoretical investigation will be
helpful and serve as a springboard for the future experi-
mental studies of these organic dye sensitizers.
Computational Procedure
The photovoltaic properties of IC-2 and M1–M8 were
investigated employing DFT and TDDFT computations.
Gaussian 09 program package [39] was utilized for all
computations of investigated compounds. The optimization
geometry of all compounds in the ground state, gas phase
and without symmetry constraints has been done by DFT
approach combined with B3LYP exchange–correlation
function and 6-31 ? G (d,p) basis set [40, 41]. Frequency
analyses were performed to confirm that the optimized
structures are true local minima (without imaginary fre-
quency) on potential energy surface [42, 43]. Molecular
orbitals including HOMO (highest occupied molecular
orbital) and LUMO (lowest unoccupied molecular orbitals)
were estimated at B3LYP/6-31 ? G(d, p) level of theory.
Photovoltaic properties were also calculated using same
combination.
Literature suggests that TDDFT is efficient in the esti-
mation of optical absorption, electronic properties and
vertical excitation energy. It is also believed that in case of
extended conjugated systems and charge transfer excita-
tions, TDDFT generally show significant effects. Hence, to
simulate the UV–visible absorption spectra of investigated
compounds, it was necessary to opt reliable high level
functional. Therefore, four exchange–correlation (XC)
functionals including B3LYP, CAM-B3LYP, xB97XD and
M06-2X were adopted to estimate the UV–vis absorption
spectra of reference dye IC-2. The conductor-like polar-
izable continuum model (CPCM) was used to check the
solvent (dichloromethane (DCM)) effect. Results obtained
from B3LYP, CAM-B3LYP, xB97XD and M06-2 func-
tionals were 467.90 nm, 394.07 nm, 386.37 nm and
394.10 nm respectively. A comparison of these TDDFT
results with experimental reported value 382 nm of IC-2
dye [38] indicate that B3LYP functional overestimated the
vertical excitation energies of IC-2 with an error of 86 nm.
However, results of CAM-B3LYP and M06-2X functional
are found close to experimental value with a difference of
12 nm. A very good and satisfactory agreement with
experimental value is shown by WB97XD functional with
a minute difference of 3 nm. Therefore, the electronic
absorption spectra of all organic dyes in this work have
been calculated by TDDFT/xB97XD/6-31 ? G(d,p)
method combining CPCM model in DCM solution.
GaussView 5.0 [44] was used to organize the input files.
Output files results were interpreted using Avogadro [45],
ChemCraft [46], GaussSum [47] and GaussView programs.
123

Results and Discussion
The screening of p-conjugated group is an important factor
and plays a key role in D-p-A organic dyes for achieving
promising photovoltaic properties [11]. Different reports
are available in the literature in which structural tailoring
by different p-conjugated bridges is proven as important
strategy to tune the optoelectronic properties [48–50]. The
focus of present probe was to theoretically design novel
Indolo[3,2,1-jk]carbazole based more efficient organic
dyes with promising p-conjugated bridges and predict their
electronic, photophysical and photovoltaic properties for
solar cell applications. For systematic designing, experi-
mentally synthesized D–p–A based metal free organic dye
IC-2 was used. IC-2 structure is composed of three blocks:
Indolo[3,2,1-jk]carbazole as D unit, thiophene as p-conju-
gated bridge and CAA as A unit. The M1–M8 were
designed by structural substitution of p-conjugated bridge
(thiophene) of IC-2 with eight new p-bridges namely;
thiazole, furan, thieno[3,2-b]thiophene, thiazolo[5,4-d]thi-
azole, furo[3,2-b]furan, 2-(thiophen-2yl)thiophene, 5-(thi-
azol-5yl)thiazole and 2,20 -bifuran respectively. The
structures of M1–M8 are displayed in Fig. 1. DFT and
TDDFT computations were performed on IC-2 and M1–
M8 to describe how bridging core modification affects the
optical absorption spectra and photovoltaic properties of
the organic sensitizers.
Electronic Structure and Energy Level
Alignment
It is known that charge transfer is strongly influenced by
the distribution of frontier molecular orbitals (FMOs) of
sensitizer. In terms of band theory, HOMO refers as
valence band, while LUMO corresponds to the conduction
band. The FMOs energy gap (Egap = ELUMO - EHOMO) is a
representative signature found on photovoltaic materials.
PCE of solar cells are intimately associated to FMOs
energies and their energy band gaps. Egap predicts the
driving force for exciton dissociation and Voc. It also
characterize the electron transport properties, dynamic
stability, chemical hardness, chemical reactivity and soft-
ness of the molecules [51]. Molecular systems with smaller
Egap offers significant ICT from pendant D group to the A
unit through p-conjugated bridge which broadens the
absorption range toward longer wavelength, hence, lead to
robust photovoltaic performance [52, 53]. In DSSCs,
organic dye act as a photosensitizer and its major role is to
sensitize the photoelectrode with large band gaps (such as
TiO2). After adsorption of the dye on photoelectrode sur-
face, excited electron upon illumination is injected into the
123
M. R. S. A. Janjua et al.
photoelectrode surface. For better optical transitions which
lead to photo-induced electron transfer from dye to the
semiconductor, dye sensitizers HOMO–LUMOs location
and their energy level must need to match the conduction
band edge (CBE) level of the TiO2 semiconductor and
iodine/iodide redox potential. Thus analysis for distribution
of charges on FMOs particularly the charge-separated
between virtual and occupied orbitals is important to
understand the optical properties and electronic behavior of
the investigated compounds during the excitation process.
To investigate the effect of p-spacers part on the elec-
tronic properties of the studied dyes, the energy levels
diagram consisting of HOMOs, LUMOs of IC-2 and M1–
M8, redox potential energy of the electrolyte and Ecb of
TiO2 are shown in Fig. 2. The EHOMO values are computed
to be - 5.71 eV and - 5.82 eV, - 5.60 eV, - 5.62 eV,
- 5.81 eV, - 5.42 eV, - 5.44 eV, - 5.69 eV, - 5.25 eV
for IC-2 and M1–M8 respectively. Similarly, the LUMO
energies (ELUMO) for IC-2 and M1–M8 are found to be
- 2.60 eV and - 2.79 eV, - 2.49 eV, - 2.64 eV,
- 3.06 eV, - 2.54 eV, - 2.70 eV, - 3.08 eV, - 2.51 eV
correspondingly. The energy gap (Eg) value of reference
IC-2 is found to be 3.11 eV which is noted as highest value
of band gap among all investigated molecules (IC-2 and
M1–M8). In designed molecule M1, energy gap shortly
reduced to 3.03 eV indicating the effect of thiazole bridge
as compared to thiophene bridge present in R. The Eg value
of M2 is found 3.11 eV similar to reference IC-2. The Eg is
found to be narrow in M3 2.98 eV which is 0.13 eV
smaller than reference IC-2 molecule. This reduction in Eg
value might due to the effect of p-spacer thieno[3,2-
b]thiophene. The effect of p-spacers modification is
observed sharply in M4 molecule where energy gap
become abridged to 2.75 eV which is 0.36 eV smaller than
reference IC-2 molecule due to thiazolo[5,4-d] thiazole
bridge effect. The Eg is found to be narrow in M5 as
compared to reference IC-2 and M1–M3 molecules but
slightly larger than M4, M6–M8 value. This indicate that
performance of p-spacer furo[3,2-b]furan present in M5 is
better than IC-2 and M1–M3 molecules p-spacer groups
but lower than p-spacer groups of M4, M6–M8 molecules.
Similarly in M6, M8 molecules, energy gap is reduced to
2.74 eV. The effect of 2-(thiophen-2yl) thiopehene and
2,20 -bifuran p-spacers present in M6 and M8 molecules
respectively for reduction in energy gap is proved better
than IC-2 and M1–M5 molecules p-spacer groups but
lower than p-spacer groups of M7 molecule. The lowest
energy gap value of 2.61 eV is observed in designed
molecule M7. The Eg value of M7 is 0.50 eV less as
compared to reference IC-2 molecule Eg value. This
reduction in Eg value validates that p-spacer 5-(thiazol-
5yl)thiazole present in M7 molecule successfully lowers
the Eg value. The energy gap is also the most vital factor in
Theoretical and Conceptual Framework to Design Efficient Dye-Sensitized Solar Cells (DSSCs):…

CN

N
S COOH

IC-2

N CN CN

N N
S COOH O COOH

M1 M2

S S
N

N CN
N CN N
S
S
HOOC
HOOC

M3 M4

S
CN CN
N N
O S
HOOC
HOOC

M5 M6

S O
CN CN
N N
S O
N
HOOC HOOC

M7 M8

Fig. 1 Structures of studied dyes

conduction of solar cells, as it provides valuable informa- molecules (M1–M8) have energy gap lower as compared
tion for charge transfer. In present studies all designed to reference molecule IC-2.

123

Fig. 2 Schematic energy
diagram of dyes, TiO2 and
electrolyte (I-/I3-), EHOMO and
ELUMO of the dyes
Results indicate that, simulated HOMOs of IC-2 and
M1–M8 lie below the I-/I3- redox potential (2 4.8 eV)
which results in fast dye regeneration and avoiding the
geminate charge recombination between oxidized dye
molecules and photo-injected electrons in the nanocrys-
talline TiO2 film. On the other hand, LUMOs of IC-2 and
M1–M8 are found above the CBE of TiO2 (- 4.0 eV)
providing the thermodynamic driving force for favorable
electron injection from the excited state dye to the TiO2
conduction band edge. Thus, all dyes have sufficient
driving force for use as sensitizers in DSSCs.
Beside the energy levels of HOMO and LUMO, ICT
from D to A through p-linkers is an added decisive feature
of compounds. So, contour surfaces for electron density
distributions of FMOs used to describe charge transfer are
drawn in Fig. 3. The pictorial representation depicts that
HOMOs in all dyes are populated mostly over donor unit
(indolo[3,2,1-jk]carbazole) and p-spacer units. On the
other hand, LUMOs are concentrated mostly over A unit
(cyanoacrylic acid) and partially on the p-spacer unit. This
indicates that efficient charge/electrons are moving from
HOMO delocalized on D part to LUMO delocalized over A
part via p-conjugated bridges and then to TiO2 during the
excitation process.
Photovoltaic Properties
The FMOs analysis of IC-2 and M1–M8 suggests that all
dyes have HOMOs level below I-/I3- redox potential and
LUMOs level above CBE of TiO2. From these levels, we
deduce the donor behavior of these dyes in the face of TiO2
123
M. R. S. A. Janjua et al.
and their electron injection capability in the excited state to
the conduction band of the semiconductor. Thus, investi-
gated compounds contain sufficient driving force for use as
sensitizers in DSSCs and in photovoltaic devices. Assum-
ing these considerations, photovoltaic properties of IC-2
and M1–M8 were calculated and results are collected in
Table 1.
Power Conversion Efficiency
The most commonly used parameter to compute the per-
formance of solar cell for converting the sunlight into
electricity is its power conversion efficiency (PCE or g).
The PCE of DSSCs is determined according to the Eq. 1.
JSC VOC FF
PCE=g ¼ ð1Þ
Pinc
Where FF represents fill factor, Voc is the open circuit
voltage, JSC is the short-circuit current density and Pinc
indicates the incident photon to current efficiency.
Open Circuit Voltage (Voc)
Voc is an auspicious photovoltaic parameter and perfor-
mance of DSSCs is strongly affected by Voc value. Dif-
ferent factors on which Voc mainly depends are; external
fluorescence efficiency, charge-carrier recombination,
work functions of the electrodes, light source, temperature
of solar cell device, light intensity, environmental factors,
types and energy levels of materials. However, many
studies exhibits that Voc can be determined by examining
Theoretical and Conceptual Framework to Design Efficient Dye-Sensitized Solar Cells (DSSCs):…

Fig. 3 HOMOs and LUMOs of

the studied compounds

the energy difference between LUMO of the dye and ECB The calculated values for Voc of IC-2 and M1–M8 are
of TiO2 using Eq. 2 [54]. presented in Table 1. The Voc values are found to be in the
eVoc ¼ ELUMO ECB ð2Þ range of 0.92 to 1.51 eV for all studied compounds. It is
also noteworthy that all Voc values are positive. This

123
 M. R. S. A. Janjua et al.

Fig. 3 continued

Table 1 The calculated redox potential of the ground state ( EOX dye
in implies that electrons will be easily transferred from dyes
ICT
eV), vertical excitation energy of the dye (kmax in eV), oxidation to the ECB of TiO2. These values are sufficient for a
dye potential efficient electron injection process. Therefore, all
potential of the dye in the excited state (EOX in eV), free energy
change for electron injection (DGinject in eV), dye regeneration (DGreg the designed molecules can be used as the dye sensitized.
in eV) and open circuit photovoltage (Voc) of IC-2 and S1–S8

Dye dye
EOX kICT
max
dye
EOX DGinject DGreg LHE Voc
Short-Circuit Current Density (JSC)
IC-2 5.71 3.21 2.50 - 1.49 0.91 0.96 1.40
M1 5.82 3.19 2.63 - 1.37 1.02 0.95 1.21 In DSSCs, JSC can be determined using Eq. 3 [55];
M2 5.60 3.13 2.47 - 1.53 0.80 0.96 1.51 0
M3 5.62 3.09 2.52 - 1.47 0.82 0.98 1.36 JSC ¼ r LHEðkÞUinject gcollect dk ð3Þ
M4 5.81 2.94 2.87 - 1.12 1.01 0.97 0.94 k

M5 5.42 2.94 2.48 - 1.51 0.62 0.98 1.46 In this Eq. 3, LHE denotes the light harvesting effi-
M6 5.44 2.86 2.58 - 1.41 0.64 0.97 1.30 ciency at a given wavelength, gcollect represents the effi-
M7 5.69 2.86 2.82 - 1.17 0.89 0.99 0.92 ciency of charge collection and Uinject is the electron
M8 5.25 2.84 2.41 - 1.59 0.45 0.96 1.49 injection efficiency. For the same DSSCs with only dif-
ferent dyes, just as for the organic dyes under study, it is
reasonable to assume that gcollect is a constant. Therefore,
Ainject and LHE will be the contributing factors to enhance
JSC.

123
Theoretical and Conceptual Framework to Design Efficient Dye-Sensitized Solar Cells (DSSCs):…
Light Harvesting Efficiency (LHE)
The LHE is an important factor for exploring the role of
dye molecule in DSSCs for absorbing the photons and
injecting the photo-excited electrons to the conduction
band of TiO2. According to Eq. 3, large LHE leads to high
Jsc, hence, enhance the efficiency of DSSCs. LHE of
investigated compounds are calculated [56] using Eq. 4
and results are presented in Table 1.
LHE ¼ 1  10f
In this Eq. 4, f represents the oscillating strength of dyes
related to the absorption energy (E00). LHE of all studied
compounds are found to be in the narrow range of 0.95 to
0.99 and close to each other. LHE of IC-2 is found to be
0.96. Results from Table 1 implies that substitution of p-
bridges slightly changed the f value and increases the LHE
in designed compounds particularly in M3, M5 and M7
with LHE values 0.98, 0.98 and 0.99 respectively. Highest
LHE value 0.99 is observed in M7. This implies that all
dyes will give photocurrent response. Thus, it is confirmed
that structural modeling by p-conjugated bridges affects
the LHE values and would be an important strategy to
enhance the LHE, hence DSSCs efficiency.
Electron Injection (DGinject) and Dye
Regeneration (DGreg)
According to Eq. 3, JSC can also be improved by improving
Uinject which is directly linked with the driving force of the
electron injection (DGinject) from the photo-induced excited
states of dye molecule to the TiO2 surface. Usually, large
DGinject results in large Uinject values. Computation of
electron injection rate is very useful to study photovoltaic
data which can be calculated using Eq. 5 [57].
dye 
TiO2
DGinject ¼ EOX  ECB
TiO2
In this equation, ECB is the reduction potential of the

conduction band of TiO2. Edye
OX represents the excited state
oxidation potential energy which can be determined
employing Eq. 6 [58].
dye
dye
EOX ¼ EOX  kICT
max
where EOXdye
is the ground state reduction potential which is
equal to the –EHOMO [59]. kICT
max is the vertical transition
energy.
dye dye
DGinject, EOX and EOX for IC-2 and M1–M8 are cal-
culated using above formulas and results are presented in
Table 1. We remark that DGinject is found to be negative in
all studied compounds which imply that excited stat of dye
molecules lies above the CBE of TiO2. Thus, electron
injection process in studied dye molecules will be
spontaneous and favoring the electron injection from
excited state of dye to the CBE of TiO2. The DGinject of
studied dyes is found to be in the range of - 1.59 to
- 1.12 eV and decreases in the following order: M4 [
M7 [ M1 [ M6 [ M3 [ IC-2 [ M5 [ M2 [ M8.
The driving force of regeneration (DGreg) is another
factor which influences the efficiency of the DSSCs. In
order to achieve the faster electron transfer process, it is
necessary to lower regeneration value. The DGreg of all dye
molecules are calculated using Eq. 7 [60] and results are
ð4Þ
given in Table 1.
dye
DGreg ¼ EOX  Eredox ð7Þ
where Eredox is the redox potential of electrolyte. The
electrolyte redox
E of commonly used iodide/triiodide redox couple is
about 4.8 eV [61, 62]. The DGreg of M2, M3, M5, M6, M7
and M8 are computed to be lower than IC-2 (0.91 eV).
This indicates that designed compounds hold adequate
potential to obtain high PCE of the DSSCs. The preceding
discussion shows that the improvement in LHE, DGreg, of
designed dyes as compared to parent one (IC-2) would
show higher JSC. On the basis of computed results of above
factor, M7 might be the most favorable candidate for
sensitizing the DSSCs performance. Furthermore, results of
this study also indicate that these indolocarbazole dye
derivatives can be systematically modified through the
various p-spacers for the DSSCs and other optoelectronic
applications.
Conclusions
Eight new chemical derivatives (M1–M8) of high-perfor-
mance experimentally synthesized DSSC dye IC-2 were
designed by a molecular engineering approach whose aim
ð5Þ
was to apply DFT and TDDFT calculations to discover
related dyes with improved DSSC performance. From
results, it is concluded that p-bridges in M1–M8 success-
fully lowered the HOMO–LUMO energy gap from 3.11 eV
in IC2 to 2.61 eV in M7. The LUMO levels of all designed
dyes are much higher than the conduction band of TiO2,
ð6Þ suggesting that the photo-excited electron escapes easily
from dye to TiO2. Absorbance wavelength in the visible
region suggests that M1–M8 can be good member for
DSSCs properties. Maximum red shifted absorption spec-
trum 436.05 nm was observed in M7 with low transition
energy (2.86 eV), highest transition moment (4.15 a.u) and
oscillating strength (1.863) as compared to parent IC-2 and
among all studied dyes. The Voc and DGinject of studied
dyes are ranges from 0.92 to 1.51 eV and - 1.59 to
- 1.12 eV respectively, indicating that these values are
123

sufficient for an efficient electron injection process. High-
est LHE value 0.99 is observed in M7. Results indicate that
p-bridges in M1–M8 would show better power conversion
efficiency (PCE) than IC2. Dye M7 with p-bridge 5-(thi-
azol-5yl)thiazole is found to be the most promising can-
didate for highly effective DSSCs applications due to least
HOMO-LUMO gap, highest absorption wavelength, high-
est LHE and reasonably good DGinject, DGreg, and Voc
values. It is expected that this work can provide a new
strategy and guidance for experimental scientists and trig-
ger them to synthesize these new dyes and further confirm
the excellent performance of these dyes in optoelectronic
applications.
Acknowledgements The authors are thankful to the financial support
from Saudi Aramco Project # CHEM-2409.
Compliance with Ethical Standards
Conflict of interest No conflicts declared.
Associated Content Optimized Cartesian coordinates of our studied
compounds are available in supporting information file
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