Journal of Computational Electronics (2019) 18:951–961

https://doi.org/10.1007/s10825-019-01339-x

A theoretical investigation of the optoelectronic performance of some

new carbazole dyes
Souad El Mzioui1 · Si Mohamed Bouzzine1,2   · Mohamed Bourass3 · Mohammed Naciri Bennani4 ·
Mohamed Hamidi1

Published online: 8 May 2019

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Abstract
Density functional theory and time-dependent approaches are applied for theoretical investigation of a new class of novel
carbazole-based d–D–π–A-type dyes, where the carbazole moiety is the main electron donor, bithiophene behaves as a
π-bridge, and cyanoacetic acid as an electron acceptor for all the studied dyes, whereas the terminal electron donor unit is
varied to thiophene, thienothiophene, carbazole, dimethoxyphenyl, and indole. The influence of the terminal electron donor
on the optoelectronics properties is investigated for the dyes in isolated state and in chloroform solvent. Their absorption
spectra and electronic and structural properties are evaluated and discussed. The theoretical results show that all the dyes
exhibit excellent optoelectronic properties. In particular, D5 with indole as the terminal electron donor moiety has potential
­ iO2 solar cells based on its red-shifted absorption spectrum, reduced energy gap,
for use as a sensitizer for nanocrystalline T
lowest λtotal value, and higher ΔGInject and ΔGReg values.

Keywords  Carbazole · d–D–π–A structure · Electronic properties · DSSCs · DFT · TD-DFT

1 Introduction conversion efficiencies. To date, devices using ruthenium-

In the two decades since first reported by O’Regan and Grät-
zel [1], dye-sensitized solar cells (DSSCs) have attracted
great interest in the field of materials science [2], owing to
their potential advantages of low cost, easy production, flex-
ibility, and transparency compared with traditional silicon
solar cells [3, 4]. These devices contain coordination com-
plexes of ruthenium, which have received significant atten-
tion due to their photophysical and photochemical proper-
ties, which afford DSSCs with extremely high photoelectric
* Si Mohamed Bouzzine
mbouzzine@yahoo.fr
1
Equipe d’Electrochimie et Environnement, Faculté des
Sciences et Techniques, Université Moulay Ismaîl, B.P 509,
Boutalamine, Errachidia, Morocco
2
Centre Régional des Métiers d’Education et de formation,
B.P 8, Drâa Tafilalet, Errachidia, Morocco
3
ECIM/LIMME, Faculty of sciences Dhar El Mahraz,
University Sidi Mohamed Ben Abdallah, Fez, Morocco
4
Equipe du Matériaux et Catalyse Appliqués, Département
de Chimie, Faculté des Sciences, Université Moulay Ismail,
B.P. 11201, Zitoune, Meknes, Morocco
based dyes with a cobalt electrolyte have achieved power
conversion efficiencies above 12% [5]. However, these dyes
are barely appropriate for use in profitable and environmen-
tally responsible photovoltaic systems, due to their con-
tent of the noble metal ruthenium, which is expensive and
requires a difficult purification process, limiting the wide-
spread application of DSSCs [6]. For this reason, organic
dyes have been the subject of exhaustive research efforts,
because of their easy synthesis, high molar extinction coef-
ficient, tunable absorption spectral response from the visible
to infrared region, as well as environmentally friendly nature
and inexpensive production techniques [7, 8]. Recently,
much work has been done on this type of dye to improve the
conversion efficiency, achieving significant levels ranging
from 7.1% in 1991 to 13% in 2014 [9].
Most organic dyes are designed to have a
donor–linker–acceptor (D–π–A) dipolar structure, due to
its effective photoinduced intramolecular charge-transfer
characteristics [10]. Such organic dyes with carbazole [11],
triphenylamine [12–14], indole and indoline [15–18] as the
donor group have been developed, resulting in reports of
DSSCs with remarkable efficiency. Carbazole and its deriva-
tives are crucial groups among the aromatic heterocyclic

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952 Journal of Computational Electronics (2019) 18:951–961

compounds, exhibiting robust electron-donating ability
[19]. Because of their specific electrochemical and optical
properties [20, 21], excellent structural stability, and copla-
narity with the donor and acceptor units, these units have
been commonly used as a functional construction block in
the D–π–A architecture to produce organic photoconduc-
The short-circuit photocurrent density ( JSC ) can be deter-
mined from the integral of the product of the light harvest-
ing efficiency of photons at wavelength λ, i.e., LHE(λ), the
electron injection efficiency 𝜑inject , and the charge collection
efficiency 𝜂collect [25–27], thus

∫
tors and nonlinear optical materials. Furthermore, the con- Jsc = LHE(𝜆)𝜑inject 𝜂collect d𝜆.
gested structure of the carbazole molecule is advantageous (2)
𝜆
for avoiding intramolecular aggregation [12]. Cyanoacrylic
acid is usually used as an electron acceptor moiety due to Another factor determining the efficiency of a DSSC
the presence of the cyanide group, which has good electron is the response of the dye to the incident light. The light
attraction properties. A π-bridge is used to link the electron harvesting efficiency (LHE) should be as high as possible
donor and acceptor, which helps to spread the electron den- to maximize the photocurrent response. The LHE can be
sity and facilitate charge separation upon excitation. The use expressed as [28]
of a π-bridge offers the advantages of broadening the maxi-
mum absorption peak, tuning the higher occupied molecular LHE = 1 − 10−f , (3)
orbital (HOMO) and lowest un-occupied molecular orbital where f represents the oscillator strength of the dye for a
(LUMO) levels, and reducing the charge recombination. given wavelength.
Among the compounds frequently used as the π-bridge, Calculation of the electron injection rate from the dye
thiophene and its derivatives, in particular bithiophene, to the conduction band of the T­ iO2 semiconductor and the
display better charge-transfer properties, making them can- regeneration of the dye by the electrolyte is very useful for
didate π-bridge moieties for dye sensitizers with a lower studying the photovoltaic performance. The following equa-
energy gap and enhanced photocurrent [22]. However, the tion can be used to calculate the change in free energy (in
major disadvantage of these organic dyes is that they may eV) corresponding to electron injection and regeneration
form aggregates on the surface of the semiconductor [23], [29, 30]:
thereby reducing the photoconversion efficiency. To address
dye∗ TiO
this, researchers have developed strategies to develop highly ΔGInject = EOX − ECB 2 and ΔGReg = EI− ∕I3− − EHOMO ,
effective sensitizers. One of the most important tactics (4)
where EOX is the excited-state oxidation potential energy of
dye*
employed is to modify organic dyes by varying their critical
the dye, ECB 2 is the reduction potential of the T
­ iO2 conduc-
TiO
constituents. In this regard, the current study provides an
tion band ( ECB 2 = −4.0 eV), and EI− ∕I3− is the ­I−/I3− redox
TiO
interesting advance by incorporating various terminal elec-
potential ( EI− ∕I3− = −4.8 eV) [29, 31]. EOX can be estimated
dye*
tron donors to obtain sensitizers that can enhance the optical
and electrophysical properties of DSSCs. as [32]
In this work, we investigate a series of D–π–A-type
dye* dye
organic dyes with carbazole as the electron donor (D), bith- EOX = EOX − Eexc , (5)
iophene as the π-conjugated bridge, and cyanoacrylic acid
where EOX is the oxidative potential energy in the ground
dye
as the electron acceptor (A). Substitution of carbazole by
various terminal electron donors (d), viz. thiophene, thien- state of the dye and Eexc is the electronic vertical transition
energy corresponding to λmax [32]. EOX can be estimated as
dye
othiophene, carbazole, 1,3-dimethoxyphenyl, and indole,
results in the formation of five organic dyes, namely D1–5. the negative of EHOMO [29].
The structural, optical, and electrochemical properties of the Voc can be approximately estimated using the analytical
compounds are investigated. relationship [33]

TiO
1.1 Parameter estimation equations VOC = ELUMO − ECB 2 . (6)

Meanwhile, λ+, λ−, and λtotal for a DSSC are described by

The power conversion efficiency (η) of a DSSC is closely
Bouzzine et al. [34, 35] as
associated with its short-circuit photocurrent density ( JSC ),
open-circuit potential ( VOC ), and fill factor (FF) as well as
𝜆total = [𝜆+ + 𝜆− ] = E0± − E±± + E±0 − E0 , (7)
[ ] [ ]
the intensity of the incident light ( IS ). This can be expressed
as follows [24]: where λ+, λ−, and λtotal are the hole, electron, and total
VOC JSC FF reorganization energy, respectively, and E0± is the cation or
𝜂= × 100%. (1) anion energy, calculated using the optimized structure of
IS

13
Journal of Computational Electronics (2019) 18:951–961 953

the neutral molecule, E±± is the cation or anion energy cal-
culated using the optimized cation or anion structure, E±0
is the neutral molecule energy calculated in the cationic or
anionic state, and E0 is the neutral molecule energy in the
ground state.
The ionization potential can also be calculated using the
following equations:
PIadiabatic = E++ − E0 PIvertical = E0+ − E0 ,
AEadiabatic = E−− − E0 AEvertical = E−0 − E0 .
2 Computational method
All calculations are carried out in isolated state and in chlo-
roform solvent using the Gaussian 09 package [36]. The
ground-state geometry is fully optimized using density
functional theory (DFT) with the hybrid functional B3LYP
[37], and the unpaired electron spin densities of radical
cations are calculated using the UB3LYP with the same
6–31G (d,p) basis set [38]. Moreover, the study by Fahim
et al. [39] on different functionals and basis sets revealed
that BH and HLYP are among the best functionals to give
better results for the excited state. To compare with these
result, excited-state calculations are also carried using time-
dependent (TD) DFT with B3LYP and BHandHLYP [40]
using the same basis set to simulate the ultraviolet–visible
(UV–Vis) absorption spectra in chloroform solvent with the
polarizable continuum model of solvation (CPCM) [41, 42].
The graphical presentation of the calculated optical
absorption spectra is simulated using the GAUSSVIEW
program [43], and plots of the optical absorption spectra are
(8) simulated using Origin 6.0 software [44]. The energy levels
of the molecular orbitals and isodensity plots are extracted
(9)
to show the electronic density distribution used to describe
the optical and electronic properties of the sensitizers. The
semiconductor ­TiO2 and iodine/iodide redox couple are used
respectively for electron injection and dye regeneration in
the DSSC. The cationic and anionic states of the dyes are
optimized at the B3LYP/6–31G (d,p) level to calculate the
total reorganization energy (λtotal).
3 Results and discussion
We study a series of carbazole-based organic dyes, where
the thiophene unit linked to carbazole (Fig. 1) is considered
as the terminal electron donor, applying different electron

Fig. 1  The chemical structure of Di d3

the studied dyes
θ3

d2 d4 H
d1
S
OH
N
S
θ4
θ1 θ2
C O

N
Di

S D3 :
D1 : CH3

S CH3

D1 : H3CO OCH3
CH3

S
D4

D5 : N CH3

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954 Journal of Computational Electronics (2019) 18:951–961

-83889,10 These results show that the conformer correspond-

-83889,15 ing to θ4 = 0° is more stable compared with that corre-
-83889,20 sponding to θ4 = 180°, with an energy barrier of 0.03 eV
-83889,25 (Table 1). In addition, as shown in Fig. 3, the ­C2–C3 bond
Energy (eV)

N
-83889,30
1
2 3
OH O length (1.4256 Å) for the conformer E (θ4 = 0°) is slightly
-83889,35 S 4 4
shorter than those of the other conformers E (θ4 = 180°)
O 1
-83889,40 N S
2 3 OH
­(C2–C3 = 1.4294 Å), indicating excellent electron delocali-
-83889,45 zation between the bithiophene and cyanoacrylic acid in the
-83889,50 conformer E (θ4 = 0°). Furthermore, note that, in the same
-83889,55
conformer, E depends on the steric effects caused by the
0 20 40 60 80 100 120 140 160 180 attraction of the adjacent atoms in space; for example the
Angle θ= ( S1-C2-C3-C4) ­S1–N (3.34634 Å) and ­S1–C5 distances (3.12436 Å) in E
(θ4 = 0°) are greater than the ­H1–N (2.56502 Å) and –C5
Fig. 2  Scan of the dihedral angle θ4 = (S1–C2–C3–C4) of dye D1 (2.5440 Å) distances in conformer E (θ4 = 180°; Fig. 3).
The results of these theoretical calculations are confirmed
by various similar results in literature [45, 46].
Table 1  Electronic properties of conformers E (θ4 = 0°) and E
(θ4 = 180°) 3.2 Geometry structural properties
Conformer EHOMO ELUMO Egap Emolecule ΔE (eV)
(eV) (eV) (eV) (eV) The geometrical values for all the studied dyes are presented
in Table 2 (bond length) and Table 3 and Fig. 4 (dihedral
E (θ4 = 0) −5.40 −2.94 2.47 −83,892.35
angles). Dyes D3, D4, and D5 present shorter bond lengths
E (θ4 = 180) −5.38 −2.90 2.48 −83,892.32 0.03
in the ground and doped states compared with dyes D1 and
D2. Furthermore, in the doped state, the bond lengths in
dyes D3–5 are significantly decreased in comparison with
donors such as thienothiophene, carbazole, 1,3-dimethoxy- those in the ground state, especially ­d2 and ­d4. These results
phenyl, and indole to form five organic dyes, namely D1–5, indicate that the connection between the cyanoacrylic
respectively, to find a molecular structure offering good acid and bithiophene is crucial for enhancing the separa-
optoelectronic properties for use in DSSCs. tion and transfer of charge. As mentioned above, to obtain
the optimized structure of the oxidized dyes, we start from
3.1 Conformation of cyanoacrylic acid the optimized structure of the neutral form. The structural
parameters of the dyes in polaronic states are illustrated in
To establish a proper conformation of the cyanoacrylic Tables 2 and 3 to reveal the change in the structures of the
acid with the bithiophene, we first carry out a conforma- compounds. Compared with the neutral dye, the simple
tional study of 2-cyano-3-(bithiophene-3-yl) acrylic acid. bonds become shorter, while the double ones become longer.
The ground-state potential energy surface (PES) scan of The interring bonds are longer than normal double bonds.
the dihedral angle θ4 = (S1–C2–C3–C4) between the bithio- These results are comparable to those reported by Bouzzine
phene and cyanoacrylic acid moieties is performed at the et al. [34, 47].
B3LYP/6–31G (d,p) level from 0° to 180° in increments of At the same time, the dihedral angle values (Table 3)
30°. The results are shown in Fig. 2. show that θ2 and θ4 are coplanar (on the order of 179°),

Fig. 3  Calculations of the distances between adjacent atoms in space for D1

13
Journal of Computational Electronics (2019) 18:951–961 955

Table 2  Distances (Ǻ) in all dyes in the ground and exited state, calculated at B3LYP/6–31G (d,p) level
Dye Distance
d1 d2 d3 d4
Ground state Doped state Ground state Doped state Ground state Doped state Ground state Doped state

D1 1.392 1.407 1.443 1.417 1.468 1.468 1.425 1.394

D2 1.393 1.408 1.443 1.416 1.467 1.467 1.426 1.394
D3 1.390 1.407 1.442 1.417 1.486 1.486 1.425 1.393
D4 1.389 1.406 1.442 1.418 1.487 1.488 1.424 1.393
D5 1.389 1.406 1.442 1.418 1.471 1.474 1.424 1.393

Table 3  Dihedral angles (°) of all the dyes in the ground and exited state, calculated at B3LYP/6–31G (d,p) level
Dye Angle
θ1 θ2 θ3 θ4
Ground state Doped state Ground state Doped state Ground state Doped state Ground state Doped state

D1 127.75 98.26 178.84 179.98 151.08 150.39 179.95 179.94

D2 126.91 99.03 178.77 179.96 150.21 149.67 179.92 179.97
D3 130.43 95.12 176.14 179.85 141.02 141.16 179.81 179.96
D4 131.83 85.75 172.66 179.88 134.64 133.81 179.76 179.93
D5 131.9 101.02 171.45 179.37 143.72 139.22 179.84 179.78

180 indicating that the geometry is slightly twisted. This explains

the same geometrical property observed for the three dyes
170
D3, D4, and D5.
θ1
Dihedral angle (°)

160
150
140
130
120
D1 D2 D3
Dye
Fig. 4  Variation of the dihedral angle of all the dyes
due to the extended π-bond conjugation in all the studied
dyes. Meanwhile, the angle θ1 increases with the increase
of the donor strength and the decrease from the ground to
doped state, indicating high coplanarity for D3, D4, and D5,
having a high conjugation effect compared with D1–2. In
addition, θ3 is twisted out of the plane with increasing donor
strength, which can help inhibit the close intermolecular
π–π aggregation. This variation of the molecular geometry
can be attributed to the steric effects caused by the terminal
electron donor, especially for D3, D4, and D5, which have
a larger terminal electron donor compared with D1 or D2,
θ2
θ3
4 Electronic properties
θ4
To clarify the effect of the terminal electron donor on the
electronic properties of the studied dyes for use in DSSCs,
quantum-chemical analysis is performed by varying the elec-
D4 D5
tron donor ability. The results of this analysis of the frontier
molecular orbital energies (HOMO and LUMO) and the
energy gap of these dyes, together with experimental values
for compound D1 (when hexyl is substituted by methyl), are
presented in Table 4, while energy level diagrams showing
the HOMO and LUMO are presented in Fig. 5. After study-
ing the effect of the chain on the optoelectronic properties
of compound D1, Mziou et al. [48] found that variation of
the length of the alkyl chain had no effect on the optoelec-
tronic properties. That is why we limited the analysis of
compound D1 to only methyl. The LUMO lies above the
conduction band of T ­ iO2 (−4.00 eV in vacuum) [2], provid-
ing a thermodynamic driving force for good electron injec-
tion. Meanwhile, the HOMO lies below the iodide redox
potential (−4.80  eV in vacuum) [49], leading to quick
regeneration of the studied dyes and sun geminate charge
recombination between the oxidized dye and photoinjected

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956 Journal of Computational Electronics (2019) 18:951–961

Table 4  The HOMO, LUMO, and energy gap values (eV) of all the 50000
dyes calculated at the B3LYP/6–31G (d,p) level (a) D1
45000

Molar Extinction Coefficient (1/M -1 cm -1)

D2
Dye EHOMO (eV) ELUMO (eV) Egap (eV) 40000 D3
D4
35000 D5
D1 −5.24 −2.87 2.37
30000
−5.65a −3.19a 2.46a
25000
D2 −5.18 −2.90 2.28
D3 −5.08 −2.79 2.29 20000

D4 −5.06 −2.73 2.33 15000

D5 −4.93 −2.76 2.18 10000

a 5000
 Experimental values [48]
0

300 400 500 600 700 800 900 1000 1100 1200

-2,75 Wavelength (nm)

-3,00
HOMO
-3,25 LUMO
60000 (b)

Molar Extinction Coefficient (1/M -1 cm-1)

-3,50
D1
-3,75 50000 D2
2,37
Energy (eV)

2,33 D3
TiO2 2,29
-4,00 2,28 D4
2,18
-4 eV 40000 D5
-4,25

-4,50 30000
-4,75 I -/I3-
-4,8 eV 20000
-5,00

-5,25
D1 D2 D3 D4 D5 10000

0
Fig. 5  Diagram of the HOMO and LUMO levels of all the studied
250 300 350 400 450 500 550 600 650 700
dyes obtained at the B3LYP/6–31G (d,p) level
Wavelength (nm)

Fig. 6  Absorption spectra of all the studied dyes calculated at the a

electrons in the T
­ iO2 semiconductor [50]. Based on Table 4,
note that the LUMO energy levels were similar for all the
compounds, while the HOMO energies decrease in the
order D1 < D2 < D3 < D4 < D5, indicating that the HOMO
of the studied compound is influenced by the strong effect
of the terminal electron donor, leading to a reversal of the
order compared with the energy gap. The calculated Egap for
the dyes Di with i = 1–5 are in quite good agreement with
experimental results for the analogues compounds DWH1
and DWH2 obtained by Huang et al. [51]. Moreover, we
remark that D5 presents a high HOMO energy compared
with the other studied dyes, leading to a narrow gap for this
compound. Therefore, this dye is not too encumbered, like
the dyes D3 and D4, which may reflect the greater strength
of the terminal donor and the increased conjugation between
the donors and conjugated π-system.
5 Absorption spectra
The impact of the terminal electron donor on the absorp-
tion properties of the studied dyes is investigated in chlo-
roform solvent. The absorption spectra are shown in Fig. 6,
TD-B3LYP/6–31G (d,p) and b TD-BHandHLYP/6–31G (d,p) level in
chloroform solvent
and pertinent data are presented in Table 5. All the dyes
exhibit two distinctive absorption bands, one in the range
of 438–477 nm and another in the range of 603–667 nm,
when calculating the absorption at B3LYP level. The
former band can be assigned to the π–π* transition from
HOMO-2 to the LUMO, while the latter band corresponds
to intramolecular charge transfer (ICT) via the HOMO to
LUMO transition, when using the BHandHLYP functional,
as confirmed by our group [39]. We conclude new results,
with an absorption maximum in the range of 433–447 nm
attributed to intramolecular charge transfer corresponding
to an electron jump from the HOMO orbital towards the
LUMO. These results are in good agreement with those
reported by Huang et al. [51].
The band wavelengths of the ICT transition of the
studied dyes are classified in the following order: D2
(432.06) < D1 (433.26) < D4 (441.40) < D3 (442.62) < D5
(447.78). Dyes D1 and D2 show almost comparable values
of λmax, while D3, D4, and D5, with the longest terminal

13
Journal of Computational Electronics (2019) 18:951–961 957

Table 5  Computed absorption TD-B3LYP/6-31G (d,p) TD-BHandHLYP/6-31G (d,p)

wavelength (λ), oscillator
strength (f), and light harvesting E (eV) λ (nm) f λ (nm) E (eV) f LHE Major contribution
efficiency (LHE) for all the dyes
in chloroform solvent D1 2.06 603.24 0.366 433.26 2.86 1.2912 0.948 H → L (53%)
434a H → L+1 (11%)
2.83 438.27 1.021
D2 2.00 618.46 0.317 432.06 2.07 1.3800 0.958 H → L (49%)
H → L+1 (10%)
2.76 449.51 1.071
D3 1.99 623.28 0.339 442.62 2.80 1.2955 0.949 H−2 → L (38%)
H → L (50%)
2.60 477.39 0.507
D4 2.03 609.73 0.400 441.40 2.80 1.3129 0.951 H−1 → L (38%)
H → L (56%)
2.74 452.84 0.758
D5 1.86 667.58 0.309 447.78 2.76 1.2164 0.939 H → L (54%)
H → L+1 (10%)
H−2 → L (41%)
266 465.82 0.841
a
 Experimental values [48]

electron donors, present a small red-shift compared with
D1.
The greatest red-shift is found for D5 compared with the
other dyes, which can be attributed to the strong terminal
electron donor induced by the additional carbazole molecule,
while the other dyes have smaller terminal electron donors.
Comparing D3, D4, and D5 with the phenyl group, N, and O
atoms reveals that these compounds present greater overlap
than D1 and D2, which can be attributed to the steric effects
due to the two benzenes of the carbazole terminal donor in
D3. The observed overlap is low (in the case of D5 and D4
compared with D1 and D2).
The oscillator strength (f) is another descriptor that com-
municates the probability of absorption of electromagnetic
radiation by transitions between the energy levels of an atom
or molecule. The oscillator strength values of these dyes at
the maximum absorption are presented in Table 5, revealing
values in the range of 1.2912–1.3800. Besides the oscilla-
tor strength, another factor associated with the efficiency of
DSSCs is the light harvesting efficiency (LHE). The LHE of
these dyes must be as high as possible to maximize the photo-
current response. The LHE values for all these dyes range from
0.939 to 0.958 (Table 5). This slight difference between the
LHE values indicates that all the sensitizers will give similar
photocurrents.
6 Molecular orbital calculations
The electron density distributions of the HOMO and
LUMO of the studied dyes are plotted in Fig.  7. The
HOMO shows an antibonding character between two
adjacent fragments, while the LUMO shows a bonding
character.
In Fig. 7, we observe that the electron density of the
HOMO of all the studied dyes mainly originates from
π-orbitals of the donor consisting of carbazole and the
terminal electron donor as well as the π-linker unit. At the
same time, the electron density of the LUMO is strongly
localized on the cyanoacrylic acid unit and the π-linker for
all the studied compounds. The contribution of the elec-
tronic transition from the HOMO to LUMO is about 53%
for D1, D4, and D5, but about 50% for dyes D2 and D3.
Therefore, we believe that the electronic transition of all
dyes originates from the HOMO to the LUMO. The distri-
butions of the electron density of the HOMO and LUMO
indicate that, upon irradiation with photons, an excited
electron moves from the donor consisting of methyl-indole
and carbazole to the cyanoacrylic acid acceptor via the
π-linker group, ensuring efficient charge separation and
electron injection.

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958 Journal of Computational Electronics (2019) 18:951–961

6.1 Free energy and ionization potential
The ionization potential, electron affinity, hole reorganiza-
tion energy, electron reorganization energy, and total reor-
ganization energy are summarized in Table 6. A dye with
a small ionization potential allows effective hole injection
[52]. Therefore, the order for both the adiabatic and verti-
cal ionization potential is D5 < D3 < D4 < D2 < D1. The IP
values for dyes D3, D4, and D5 are lower than those of dyes
D1 and D2, especially for D5, indicating that hole creation is
easier for the compounds possessing an oxygen and nitrogen
heteroatom than for those possessing a sulfur heteroatom.
In addition, the ionization potential and the calculated λ +,
λ−, and λtotal values are also significant factors influenc-
ing the photovoltaic conversion of solar cells. A low λtotal
including the hole and electron reorganization energy might
improve Jsc. The calculated λtotal values of all the studied
dyes increased in the order D4 < D3 < D5 < D1 < D2, reveal-
ing that D4, D3, and D5 possess lower total reorganization
energy compared with D1 and D2. Furthermore, the hole
and electron reorganization energies are significant for high-
efficiency DSSCs; greater hole and electron reorganization
energies can lead to higher luminous efficiency [28]. It is
clear that the difference between 𝜆+ and 𝜆− for the designed
dyes D1–D5 increases in the order D4 < D5 < D3 < D1 < D2.
Thus, the differences in D3, D4, and D5 result in a more bal-
anced transport rate than for D1 or D2.
The free injection electron energy ΔGInject and ΔGReg are
important parameters to analyze the relationship between
the electronic structure and Jsc. Low ΔGInject and ΔGReg are
required for fast electron transfer. The calculated values of
these parameters are presented in Table 7. Note that ΔGInject

LUMO

HOMO

D1 D2 D3 D4 D5

Fig. 7  Visualization of the frontier molecular orbitals (FMOs) of all the dyes obtained at the B3LYP/6–1G(d,p) level

Table 6  The ionization potential Dye IPa IPv EAa EAv 𝜆+ 𝜆− Δλ 𝜆total

(eV), electronic affinity (eV),
and total reorganization D1 6.14 6.27 −1.73 0.191 0.123 1.92 1.8 2.05
energy calculated at the DFT/
D2 6.03 6.14 −1.78 0.191 0.114 1.97 1.85 2.08
B3LYP/6–31G (d,p) level
D3 5.89 5.96 −1.68 0.196 0.074 1.87 1.80 1.95
D4 5.93 6.05 −1.62 0.204 0.117 1.82 1.71 1.94
D5 5.81 5.92 −1.65 0.199 0.106 1.85 1.74 1.96

Table 7  The free injection Dye dye

Eox 𝜆 (ICT) dye*
Eox ΔGInject ΔGReg Voc
energy, free regeneration
energy, and open-circuit voltage
D1 5.24 2.86 2.38 −1.62 −0.44 1.13
(eV) calculated at the DFT/
B3LYP/6–31G (d,p)/BH and D2 5.18 2.07 3.11 0.89 −0.38 1.10
HLYP/6–31G (d,p) levels D3 5.08 2.80 2.38 −1.62 −0.28 1.21
D4 5.06 2.80 2.26 −1.74 −0.26 1.27
D5 4.94 2.76 2.18 −1.82 −0.14 1.24

13
Journal of Computational Electronics (2019) 18:951–961 959
is negative for all the designed dyes, except compound D2,
which has a positive value (0.89), indicating that the excited
electron in the dye can escape easily into the conduction
band of ­TiO2, promoting the injection phenomenon. More-
over, the ΔGInject value calculated for all the studied dyes
increases in the order D5 < D4 < D1 = D3 < D2, and ΔGReg
in the order D1 < D2 < D3 < D4 < D5; these results reveal
that dye D5 with indole as the terminal donor exhibits a
high power conversion efficiency compared with the other
compounds ( ΔGInject = −1.82 eV and ΔGReg = −0.14 eV),
leading to a high IPCE. In addition, the values of Jsc and the
open-circuit voltage (Voc) also influence the global power
conversion efficiency. Based on Eq. (6), the Voc of the stud-
ied dyes increases in the order D4 > D5 > D3 > D1 > D2,
revealing that D5, D4, and D3 have larger Voc values than
D1 or D2. Based on these results, it can be concluded that a
low ΔGInject , low ΔGReg , and small λtotal as well as Voc could
result in a high efficiency. Consequently, the performance
of DSSCs sensitized using D5 may be superior to when
using other dyes, due to its favorable performance in terms
of the above-mentioned factors obtained from our theoreti-
cal results.
7 Conclusions
We investigate a series of carbazole-based dyes containing
different terminal electron donors to obtain high-perfor-
mance dyes for use in DSSCs. The geometrical, electronic
structure, and optical absorption properties and transition
characteristics of the frontier molecular orbitals of all the
studied dyes are calculated and discussed. Based on the com-
putational results, the role of the diverse terminal electron
donors in regulating the geometry, electronic structure, and
optical properties are evaluated, and the different parameters
affecting Voc and Jsc are discussed, with the aim of identify-
ing sensitizers with potential for use in DSSCs. The results
show that these dyes exhibit good optoelectronic properties
for application in DSSCs, in particular D5, with indole as
the terminal electron donor. The latter is found to be the best
photosensitizer due to its narrow energy gap, better opti-
cal properties, appropriate FMO energy levels, lowest λtotal
value, and higher ΔGInject and ΔGReg values compared with
the other studied dyes. Therefore, a DSSC sensitized using
D5 dye may exhibit good optoelectronic properties com-
pared with when using the other dyes, improving the overall
energy conversion efficiency.
Acknowledgements  The authors thank the Volubilis Program (No.
Ma/11/248) for the purchase of Gaussian 09 and Mr. Abderrah-
mane Babni, Assistant Professor, Polydisciplinary Faculty of Erra-
chidia Moulay Ismail University-Meknes, a teacher of English, who
helped us to correct grammatical and spelling mistakes.
Compliance with ethical standards 
Conflict of interest  The authors declare that they have no conflicts of
interest.
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