Optik - International Journal for Light and Electron Optics 239 (2021) 166787

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Optik
journal homepage: www.elsevier.com/locate/ijleo

Original research article

DFT molecular modeling studies of D-π-A-π-D type

cyclopentadithiophene-diketopyrrolopyrrole based small
molecules donor materials for organic photovoltaic cells
Rania Zaier, Sahbi Ayachi *
Laboratory of Physico-Chemistry of Materials (LR01ES19), Faculty of Sciences of Monastir (FSM), Avenue of the Environment, 5019, Monastir,
University of Monastir, Tunisia

A R T I C L E I N F O A B S T R A C T

Keywords: A novel six D-π-A-π-D type compounds containing small molecules from cyclopentadithiophene
Cyclopentadithiophene (CPDT) and diketopyrrolopyrrole building (DPP) units were designed, as donors, for improving
Bulk hetero-junction solar cells the efficiency of bulk hetero-junction solar cells. The geometries of the title compounds were
Density functional theory
optimized using the density functional theory at the hybrid functional B3LYP in combination with
Transition density matrix
the 6− 311 g(d,p) basis set. Electronic structures, photo-physical, optical and intra-molecular
Intra-molecular charge transfer
charge transfer properties have been investigated. The contour plots of the transition density
matrix have been simulated for all compounds and used to evaluate the hole-electron localization,
the donor-acceptor interaction as well as the electronic excitation processes in their excited states.
The new designed donors have shown a large absorption in the visible range with interesting hole
transport properties, resulted from their rigid-planar structures. The open circuit voltage and the
fill factor were estimated. The present computational study showed that tuning the building
blocks of the organic materials dispose a potential approach for further enhance the performance
of small molecules donor materials in bulk hetero-junction (BHJ) organic solar cells.

1. Introduction

Organic photovoltaic present a promising solar power generation comparing to their inorganic counterparts, allowing low-
environmental impact with the benefits of cost-effective and flexibility [1–5]. In this context, research into bulk hetero-junction
(BHJ) Organic solar cells (OSCs) incorporating organic donor materials and fullerene derivatives as acceptors succeeded to achieve
a noticeable progress in term of device performance [6,7].
Recently, small molecules OSCs (SMOSCs) have been emerged as alternative OPV devices to the conventional photovoltaic
regarding their several advantages, particularly, the well-defined molecular structure, the easy synthetic process and the high charge
transfer [8–13].
Improving the efficiency of small molecules is mainly based on controlling the highest molecular orbital (HOMO) and the lowest
unoccupied molecular orbital (LUMO) energy levels, reducing the band gap for broader absorption in the visible range that results in
enhancing the photovoltaic performances of the application such as the short-circuit current density (Jsc) and open voltage circuit
(Voc) [14–16]. Thus, to insure a large Voc, which is an important photovoltaic parameter, the energy difference between HOMO of

* Corresponding author.
E-mail address: ayachi_sahbi@yahoo.fr (S. Ayachi).

https://doi.org/10.1016/j.ijleo.2021.166787
Received 28 July 2020; Received in revised form 11 January 2021; Accepted 16 March 2021
Available online 20 March 2021
0030-4026/© 2021 Elsevier GmbH. All rights reserved.
R. Zaier and S. Ayachi Optik 239 (2021) 166787

Scheme 1. Molecular structures of the six studied small-molecule donor materials.

donor and LUMO of acceptor should be higher, as the Voc expression is the following [5,17,18]:
1[ ⃒ ⃒]
Voc = |HOMOdonor | − ⃒LUMOacceptor ⃒ − 0.3 V (1)
e

Where, 0.3 V is an empirical value for efficient charge separation. Donor materials with suitable energy levels are required for
improved light harvesting response. The challenge of realizing small molecules that possess narrow band gap and high photo-physical
properties is a delicate compromise. For dealing with this approach, a judicious building blocks selection of small molecules based BHJ
is required.
Recently, D-π-A-π-D molecular architecture has shown potential designs for efficient small molecule donor materials as they
contribute to lowering the band gap by the ICT in between the electron donating and electron withdrawing blocks inside the con­
jugated framework and controlling the energy levels by tuning the donor and acceptor moieties within the molecule [19–22].
CPDT is one of the promising electron donating units that have shown the reliability of being used in high performance applications
due to the unique electron characteristics promoted by the fused thiophene ring derivatives, the rigidity and the high structure
planarity [23–25]. Diketopyrrolopyrrole (DPP) was selected as an acceptor cored block since it has been used as an electron deficient
pattern to design photovoltaic materials [26–28].
In this work, we report a theoretical investigation based on the photo-physical properties and photovoltaic performances of a series
of D-π-A-π-D type CPDT-DPP based small molecules as donor materials, as depicted in Scheme 1, namely D1CB1, D2CB1, D1CB2,
D2CB2, D1CB3 and D2CB3, for being blended with fullerene-based acceptor to form BHJ active layers. For the design concept of the
studied molecules, two types of weak- (carbonyl group) and strong-(dicyanomethelene) electron-withdrawing groups were bridged on
CPDT units in order to investigate their effect on the optoelectronic properties of the studied molecules.

2. Computational details

In this study, all the calculations were performed by means of Gaussian 09 software package [29]. The ground state geometry
optimizations of the designed molecules were fully simulated using density functional theory (DFT) combined with B3LYP hybrid
functional at 6− 311 g(d,p) basis set in gaseous phase [30–34]. The frontier molecular orbitals (FMOs) including HOMOs and LUMOs
and the gap energies were investigated to obtain insight into the structures and their related electro-optical properties. The energies of
neutral, cationic and anionic states were determined to investigate the electronic properties such as the ionization potential (IP) and
electron affinity (EA). Based on the optimized geometries, the optical properties including the maximum absorption wavelengths
(λmax ) and the oscillator strengths (f) were computed using time dependent DFT (TD-DFT) at B3LYP/6-311 g(d,p) level of theory [35,
36]. TDM maps that are used to investigate electron-hole coherence correlation of charge transfer based on electronic transitions, were
produced using Multiwfn [37]. Moreover, the reorganization energy of hole, hole integral rate and hole transport rate have been
simulated to elucidate the charge transfer properties. The open circuit voltage (VOC) and the fill factor (FF) were calculated in order to
investigate the photovoltaic properties. Finally, the Scharber diagram was used to estimate the power conversion efficiency (PCE) of
the designed small molecules.

3. Results and discussion

3.1. Structural properties

The ground state optimized geometries of all the studied molecules are simulated and illustrated in Fig. 1. The global optimization
parameters including the total energy of system and dipole moment are listed in Table 1. Due to the symmetry of the electron pair
arrangement, the considered materials exhibit electrical dipole moments close to zero. The molecular structure stability is strongly

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Table 1
Calculated total energies (Hartree) and dipole moments (Debye) at the DFT//B3LYP/6-311
g(d,p) level.
Total energy Dipole moment

D1CB1 − 4260.131073 0.001010

D2CB1 − 4557.315246 0.000800
D1CB2 − 4260.075478 0.000100
D2CB2 − 4556.609334 0.000003
D1CB3 − 4906.026215 0.000200
D2CB3 − 5203.210402 0.000056

Table 2
Optimized geometry structural parameters of the investigated molecules.
D1CB1 D2CB1 D1CB2 D2CB2 D1CB3 D2CB3

Bond length (Å)

L1 1.431 1.431 1.421 1.423 1.424 1.424
L2 1.433 1.434 1.433 1.434 1.432 1.433
L3 1.433 1.433 1.434 1.434 1.433 1.433

Dihedral angle (deg.)

φ1 0.02110 0.01448 0 0.00226 0.00106 0.00265
φ2 0.00658 0.00956 0 0.02940 0.00033 0.000101

Fig. 1. Optimized geometries of the studied molecules.

related to the lower total energy system [38]. The discrepancy of total energy values is evidently related to the difference of cored block
and CPDT-bridge building groups in term of atomic energy.
The selected geometry parameters were calculated and summarized in Table 2. All the optimized structures display high planarity
originating from the S—H, S—N and O—H intra-molecular non-covalent interactions established between the different blocks of the
molecules, as mentioned in Fig. 1. The high planarity enhances the molecular stability and rigidity.
The bridge bonds define the bonds link between the donor, acceptor and π-spacer elements are determined to get insight into the
intra-molecular interactions among the various building blocks [39]. As shown in Table 2, the bridge lengths of all the studied
structures are ranged from 1.421 to 1.434 Å. They are shorter than the typical C–C single band (1.54 Å) and higher than C– – C double
bond (1.33 Å) indicating a strong interaction originating from the high delocalization of electrons that leads to better ICT within the
framework. In addition, the dihedral angles between the different fragments of the materials considered were determined and listed in
Table 2. We found that the obtained values were almost 0◦ showing the high planarity of these structures which is a beneficial factor for
enhancing the charge mobility and thus an efficient charge transfer (CT) [40].
Additionally, in order to define the electronic properties and molecular stability, Molecular Electrostatic Potential Surfaces (MEPS)
were carried out (Fig. 2) as it is related to the electron density and dispose a powerful tool to reveal the reactive sides of the molecule
[41]. The colors displayed in the MEP denote the different electrostatic potential values and charge distribution within the molecules.
Hence, the electron rich regions with high negativity (red) are located at oxygen and nitrogen atoms while the electron deficient
regions with high positivity (blue) are mainly located at hydrogen atoms. From the MEP plots, we reveal the dominance of green color
referring to the zero potential.

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Fig. 2. Molecular Electrostatic Potential (MEP) of studied molecules [D1CB1 (a), D2CB1 (b), D1CB2 (c), D2CB2 (d), D1CB3 (e), D2CB3 (f)].

Table 3
Electronic properties calculated at the DFT//B3LYP/ 6-311 g(d,p) level of theory.
Compound EH− 1 (eV) EH (eV) EL (eV) EL+1 (eV) ΔEgap (eV) IP(eV) EA (eV)

D1CB1 − 5.67 − 4.96 − 3.25 − 2.98 1.71 5.70 2.52

D2CB1 − 5.89 − 5.11 − 3.79 − 3.75 1.32 5.84 3.08
D1CB2 − 5.59 − 4.96 − 3.28 − 2.91 1.68 5.67 2.54
D2CB2 − 5.57 − 4.90 − 3.55 − 3.51 1.35 5.61 2.84
D1CB3 − 5.62 − 5.04 − 3.40 − 2.95 1.64 5.75 2.64
D2CB3 − 5.83 − 5.20 − 3.78 − 3.72 1.42 5.90 3.09

Fig. 3. Frontier molecular orbital contour plots for the studied molecules.

3.2. Frontier molecular orbitals (FMOs) analysis

The frontier molecular orbitals (FMOs) investigation provides potential descriptions about the electron delocalization and electron
transport abilities within the conjugated framework. To examine the impact of the donor and acceptor fragments on the electro-optical
properties of the studied molecules, the HOMO and LUMO energy levels, the band gap, the ionization potential (IP), the electron
affinity (EA) and the open-circuit voltage(Voc)were simulated using the DFT/B3LYP/6-311 g(d,p) level and listed in Table 3. The
FMOs were carried out at the optimized ground state geometries and depicted in Fig. 3.
As shown in Fig. 3, the HOMOs were distributed over the entire molecule. By contract, the LUMOs were mainly located over the

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Fig. 4. Density of states (DOS) for the studied molecules. The intrinsic Fermi levels (EF) lies in the middle of the band gaps.

Fig. 5. Simulated HOMO/LUMO energy levels and band gaps of donor molecules with PC70BM.

cored blocks of the acceptor fragments. These distributions indicate high electron delocalization and important CT takes place within
the designed molecules.
The density of states (DOS) were carried out and depicted in Fig. 4. The DOS plots show high delocalization of energy levels
resulting from the synchronal reaction of donor and acceptor units as well as the π-spacer effect for reinforcing the delocalization.
These observations are well confirmed by the visualized variation of HOMOs and LUMOs electron distributions.
Table 3 clearly shows the variation of FMOs energy level values and the band gap energies. These small molecules exhibit relatively
small band gaps in the range of 1.32− 1.71 eV, that favors the electron excitation and charge transfer within the molecules. Similarly,
we interested to calculate electronic structure of PC70BM, as acceptor moiety, in chloroform solution. In Fig. 1S (see, Supplemental
data), optimized structure of PC70BM and corresponding orbital energy, as well as the 2D molecular electrostatic map have shown.
Herein, we refereed to ref [41] in order to support the obtained results. The HOMO and LUMO energies of PC70BM, measured by
square-Wave Voltammetry are − 6.20 and − 4.0 eV, respectively. It is worth noting that the calculations are returning slightly different
values, due to the polarity of the used solvent. In addition, we have shown the strong accepting properties of PC70BM regarding its 2D
molecular electrostatic map.
The extracted orbital energies for all optimized donor structures were depicted in Fig. 5 together with the experimental HOMO/
LUMO energy levels of PC70BM acceptor reported in a previous work [42] to better figure out the electronic and charge transfer
properties of the studied systems.
The LUMO levels of these donors are in accordance with the LUMO level of the PC70BM acceptor. This character is quite important
for BHJ solar cells for facilitating the electron transfer from the donor to PC70BM acceptor, thus, improving the electron mobility.
As shown in Fig. 5, there is a variation of HOMO and LUMO energy levels while tuning the conjugated structure of the investigated
small molecules. This variation is related to the electronic effect of oxygen and sulfur atoms of DPP derivatives. In addition, there is a
remarkable decrease in term of band gap energies of molecules containing dicyanomethylene groups compared to those containing
carbonyl groups. This result could be explained by the high electron withdrawing character of dicyanomethylene that affects the
electron distribution and the interactions within the backbone.
An efficient OSC depends on high electron and hole injection abilities in between the donor and acceptor compounds within the
active layer. Therefore, the ionization potential (IP) and electron affinity (EA) are used to better describe the charge separation, charge
collection and charge transfer of the investigated molecules. Where, the IP of the donor which describes the ability of donor to liberate

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Fig. 6. Experimental and theoretical optical absorption spectra for CPDT molecule.

Fig. 7. Optical absorption spectra for studied molecules.

an electron should be lower than that of the acceptor. Whereas, the EA of acceptor should be larger than that of donor in order to
facilitate the charge carriers injection and transport [43]. The studied compounds exhibit relatively suitable IP and EA values around
5.7 eV and 2.6 eV, respectively. Hence, the considered materials exhibit impressive electronic properties making them interesting

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Table 4
Calculated electronic transition energy Eex (eV), maximum absorption wavelengths, λmax (nm), oscillator strength (f), and light harvesting efficiency
(ηλ).
Compound Eex λmax f major configuration ηλ

D1CB1 1.9823 625 0.7631 H→L (92%), H→L+1 (5%)

1.5531 798 1.7989 H→L (94%), H→L+2 (4%) 0.9841
D2CB1 1.8226 680 1.6593 H→L+2 (98%) 0.9780
1.0987 1128 0.2749 H→L (93%), H-1→L+1 (5%)
D1CB2 1.9450 637 0.5052 H→L+2 (87%), H→L (7%)
1.5640 792 2.2728 H→L (92%), H→L+2(6%) 0.9946
D2CB2 1.7539 706 2.4255 H→L+2 (91%), H→L (5%) 0.9962
1.0627 1166 0.4026 H→L (90%), H-1→L+1 (6%)
D1CB3 1.9242 644 0.1914 H→L+2 (87%), H→L (5%)
1.5467 801 2.3051 H→L (95%), H→L+2 (5%) 0.9950
D2CB3 1.6803 737 1.1021 H→L+2 (60%), H-1→L+2 (30%) 0.9209
1.1318 1095 0.3962 H→L (88%), H-1→L+1 (7%)

compounds for OSC applications.

3.3. Optical absorption properties

The CPDT plays the role of donor building block in the molecules under investigation. Fig. 6 presents the experimental optical
absorption spectrum that has been carried out in chloroform solution together with the simulated spectrum obtained using the TD-
DFT/B3LYP/6-311 g(d,p) level of theory. As shown in Fig. 6, the CPDT exhibits an absorption in the ultra-violet region with a
maximum of 260 nm. There is an overlap between the simulated and experimental spectra indicating the reliability of the used
theoretical method.
The solar absorption spectral range and the intensity of absorption are basic for the value of short-circuit current density (JSC) of
organic solar cell. The JSC is a function of the photon number S () over the whole frequencies given by the solar spectrum and the
external quantum efficiency (EQC) expressed as [44]:
∫
JSC = q EQE.S(λ)dλ (2)

Where, EQE is defined as the product of light harvesting efficiency (ηλ), exciton diffusion efficiency (ηED), charge separation efficiency
(ηCS), and charge collection efficiency (ηCC). It is noted from this expression that the absorption ability of the donor material is a key
factor for improving the solar cell efficiency. The light harvesting efficiency (ηλ) is in correlation with the oscillator strength (f) of the
specific optical absorption wavelength as follows [45]:

ηλ = 1 − 10− f
(3)
To estimate the optical properties of the studied molecules, TD-DFT approach was used as cost-effective method [46].The simulated
optical absorption spectra were carried out together with the corresponding oscillator strengths using the TD-DFT/B3LYP/6-311 g(d,p)
level in gaseous phase as shown in Fig. 7. The calculated excited energy (Eex,), maximum absorbance wavelength (λmax), oscillator
strength (f), major configuration and light harvesting efficiency (ηλ) of the first excited state transition are listed in Table 4.
As it can be seem in Fig. 7, all the studied compounds exhibit a maximum absorption band in the range between 600 nm and 800 nm
covering an important part of the solar spectrum knowing that the maximum absorbance in the solar spectrum is about 700 nm [47].
We found that there is a red shift in the order of D1CB2 < D1CB1 < D1CB3 < D2CB1 < D2CB2 < D2CB3 indicating the effect of the
bridge groups as well as the DPP derivatives in improving the optical properties.
The maximum peaks are mainly raised from HOMO to LUMO electronic transition, as noted in Table 4, indicating a strong electron
displacement from the ground state (S0) to the first excited state (S1). These maxima are ascribed to the local excited (LE) and ICT
emissions within the conjugated frameworks between donor and acceptor blocks. The optical absorption spectra are outlined as major
large oscillator strength with low excitation energy and a series of small oscillator strengths with high excitation energies.
For D1CB1, D1CB2 and D1CB3, a weak absorption peak is observed in the range around 600 nm that can be generated from π→π*
transition in the carbonyl group of CPDT donor blocks [48,49]. In contrast, for D2CB1, D2CB2 and D2CB3, there is a broad absorption
band in the range of 900− 1400 nm. This band is attributed to the intra-molecular charge transfer (ICT) from the sulfur rich electron to
the electron withdrawing dicyanomethylene group within CPDT units [50].
A promising organic donor material should exhibit a large light harvesting efficiency (ηλ) [51] to reach the high photocurrent
signal. From Table 4, the considered materials show high ηλ values close to one that is required for high performances OSC devices.
Overall, the molecules under investigation have shown an interesting optical absorption that covers the amount of visible range as
well as the near infrared zone which leads to photo-physical properties and JSC enhancement.

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Fig. 8. TDM plots for investigated molecules in the first excited state (S1)[D1CB1 (a), D2CB1 (b), D1CB2 (c), D2CB2 (d), D1CB3 (e), D2CB3 (f)].

Fig. 9. EDD maps [D1CB1 (a), D2CB1 (b), D1CB2 (c), D2CB2 (d), D1CB3 (e), D2CB3 (f)].

3.4. Intra-molecular charge transfer (ICT) properties

The ICT investigation provides an idea about the ability of exciton dissociation into free charges that is one of the key factors for
improving the donor material efficiency. The effective exciton separation of donor material reinforces the photo-generated charge
carriers, and then the JSC.

3.4.1. Transition density matrix (TDM)

The ICT properties are basically related to the electronic transitions nature. To evaluate this kind of transitions, TDM was carried
out for the investigated compounds in the first excited state (S1) as illustrated in Fig. 8. TDM is a helpful tool to analysis the electron
excitation process and the electron-hole coherence [52,53]. Besides, TDM provides information about the donor and acceptor in­
teractions in the first excited state along the molecular framework.
As shown in Fig. 8, the electron-hole coherences are concentrated over the diagonal element in S1 indicating a delocalized tran­
sition. The strong distribution in the diagonal box (D-D) and (A-A) demonstrated high π→π* electronic transitions and consequently the
probability of electron-hole coherence over donor and acceptor moieties.
For compounds D1CB1, D1CB2 and D1CB3, the electron-hole coherences are mainly localized over the donor and acceptor frag­
ments in the diagonal box and off-diagonal box (D-A). This localization demonstrates the weak ICT character between the donor and
acceptor units in the first excited state. The strong coupling of electrons and holes in these compounds could explain the difficult
excitons dissociation. Hence, a weak ICT takes place within the molecular structure.
Variously, the electron-hole coherences localization for D2CB1, D2CB2 and D2CB3 are chiefly observed at diagonal box (D-D) with
weaker coefficient of donor-acceptor correlation. The weak coherences help the escape of exciton from the Coulomb attraction more

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Table 5
Charge transfer properties.
Compound λhole thole khole

D1CB1 0.261 0.355 2.91 × 10+14

D2CB1 0.254 0.390 2.34 × 10+14
D1CB2 0.256 0.315 4.18 × 10+14
D2CB2 0.242 0.335 3.17 × 10+14
D1CB3 0.228 0.290 3.79 × 10+14
D2CB3 0.224 0.315 4.99 × 10+14

efficiently and then lead to further ICT. The excitons in these compounds conceivably be easily dissociated regarding their weak
electron-hole correlation coefficients, especially with the existence of CT from donors to dicyanomethylene groups [54].
As shown in Fig. 8, the correlation coefficients between donor and acceptor for D1CB1, D1CB2 and D1CB3 are higher than those for
D2CB1, D2CB2 and D2CB3. The coupling of electrons and holes in systems D1CB1, D1CB2 and D1CB3 is stronger which indicates the
hardness of exciton dissociation in these systems. Thus, compounds D2CB1, D2CB2 and D2CB3 may efficiently improve the Jsc ac­
cording to charge separation efficiency.
The electron density difference (EDD) was used to evaluate the charge separation and electron transfer process from S0 → S1 states
[45,55]. The EDD maps of the each compound were simulated and depicted in Fig. 9.
The region of electronic density depletion (blue color) and increment (purple color) are properly recognized showing the charge
transfer from donor to acceptor moieties for S0 → S1 transition. Particularly, in the case D2CB1, D2CB2 and D2CB3, there was a
remarkable charge transfer from CPDT main block to the dicyanomethylene bridge groups which is in accordance with the TDM
analysis.
From both TDM plots and EDD maps, we have clearly revealed the impact of the dicyanomethylene as a strong electron with­
drawing group on the charge transfer properties of these donors.

3.4.2. Charge transfer: Marcus theory

After light harvesting, the excitons created at donor/acceptor hetero-junction are dissociated into electrons and holes. Where, the
electrons will be injected from donor to acceptor in the active layer while the holes will be transferred within the donor material. Donor
materials with high hole transport capabilities are commendable as they strongly contribute on improving the JSC. The evaluation of
hole transport abilities is based on the hole transport rate (khole) that can be determined using Marcus theory as [56,57]:

2πt2hole π − λhole
(4)
1
khole = ( )2 exp( )
h λhole kB T 4kB T
Hence, h, kB and T are Planck’s constant, Boltzmann’s constant and the temperature (298 K), respectively. According to khole
expression, the key parameters required for hole transport abilities estimation are the hole transfer integral (thole) and the reorgani­
zation energy for hole transport (λhole ). The hole transfer integral is related to the intra-molecular stacking arrangement of molecules,
that can be estimated as [58]:
1
thole = (EH − EH− 1 ) (5)
2
EH-1 and EH are the energy levels of HOMO-1 and HOMO in the optimized ground state of the donor molecules, respectively [59].
The hole reorganization energy (λhole ) is the variation in system’s energy between neutral and charge states and is determined as
follows [60]:
] ( ) ]
λhole = [E0 (M + ) − E0 (M 0 ) + [E+ M 0 − E+ (M + ) (6)
( ) ( )
Where, E0 (M+ ) and E+ M0 are the energy of neutral/cation molecule in cationic/neutral structure. E0 M0 and E+ (M+ ) are the
energy of neutral/cationic molecule in ground state/ cation optimized structure.
The computed hole transport parameters λhole , thole and khole of all the studied molecules are listed in Table 5. The values of λhole are
found to be similar regarding the similar geometry relaxation. The thole values are nearby due to the sameness of the geometries of the
molecules under investigation. Mostly, the designed compounds exhibit excellent hole transport mobility because of the lower values
of λhole and the high values of khole. Overall, these compounds are good candidates for hole transport properties which may improve
the photovoltaic properties for the OSC devices.

3.5. Photovoltaic properties

The considered small molecules have shown interesting optoelectronic properties to be used as donors in BHJ organic solar cells.
The photovoltaic parameters are theoretically calculated and listed in Table 6. For obtaining an efficient electron injection from donor
to PC70BM (acceptor), the energy difference between LUMO of donor and LUMO of acceptor (ELL) should be in the range of 0.2− 1 eV

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Fig. 10. Orbital energy diagram for donor-acceptor pairing (A) and Energy loss (B) for BHJ-OSCs.

Table 6
Extracted parameters for organic photovoltaic.
Compound ELL (eV) Voc (V) FF ECT (eV) Eg − ECT (eV) ECT − eVOC (eV)

D1CB1 0.79 0.66 0.83 0.96 0.75 0.30

D2CB1 0.25 0.81 0.86 1.11 0.21 0.30
D1CB2 0.76 0.66 0.83 0.96 0.72 0.30
D2CB2 0.49 0.6 0.82 0.90 0.45 0.30
D1CB3 0.64 0.75 0.85 1.04 0.60 0.29
D2CB3 0.26 0.90 0.87 1.20 0.22 0.30

[61,62]. As shown in Table 6, all of the molecules exhibit low values of ELL that are in the order of D2CB1 (0.25 eV) < D2CB3 (0.26 eV)
< D2CB2 (0.49 eV) < D1CB3 (0.64 eV) < D1CB2 (0.76 eV) < D1CB1 (0.79 eV). This investigation showed the strong impact of the
well-designed molecular structure for facilitating the electron injection and then, improving the charge transfer within the active layer
in between donor and acceptor.
Charge transfer (CT) mechanism at the donor/acceptor (D/A) interface plays a major role in the development of high power
conversion efficiency (PCE) in BHJ-OSCs [63], which deeply affects the resulting competition between charge separation (CS) and
charge recombination (CR) [64]. Let us recall that efficient systems typically have ~ 0.3 eV offset in molecular orbital energy levels
between the donor and acceptor. This sets up an interfacial charge transfer (CT) state with an energy ECT < Eg (optical gap). Here, ECT
is the difference between LUMO energy of the donor (D) and HOMO energy of the acceptor (A): ECT = εA LUMO − εHOMO . Thus, we define
D

energy loss incurred during charge generation as: Eg − ECT and energy loss incurred during charge recombination, results from both
radiative and non-radiative CT state decay, as: ECT − eVOC (see Fig. 10). Accordingly, we provide a snashot of our current under­
standing of these two energy loss components and the results are summarized in Table 6. Altogether, the studied BHJ-OSCs demon­
strate energy losses ranging from ~ 0.3 to 0.75 eV. We believe that energies loss can be adjusted to zero and ~ 0.5 eV for charge
generation and charge recombination, respectively, to achieve high PCE in BHJ-OSCs.
The power conversion efficiency that describes the efficiency of the BHJ organic solar cell is related to the short-circuit current
density (JSC), the open circuit voltage (VOC), the fill factor (FF), and the incident photon to current efficiency (Pinc) which is given as
follows [65]:
JSC × VOC × FF
PCE = (7)
Pinc
From this expression, we can note that the fill factor (FF) is one of the important parameters that influence the PCE of the bulk
hetero-junction solar cells. The FF is estimated as [66]:
( )
eVoc
kB T
− ln eV oc
kB T
+ 0.72
FF = eVoc (8)
kB T
+1

Where, e, kB , T and VOC are the elementary charge, Boltzmann’s constant, temperature (298 K) and open circuit voltage, respectively.
The calculated values listed in Table 6 shows large FF (0.82− 0.87) which indicates a promising PCE.
The Scharber diagram [67] is widely used to estimate the PCE or an appropriate designed donor molecule in BHJ organic solar cell
composite with PC70BM as acceptor. The Scharber diagram defines the relation between the LUMO and the gap energy of donor as

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R. Zaier and S. Ayachi Optik 239 (2021) 166787

Fig. 11. Scharber diagram to estimate the power conversion efficiency for the studied compounds.

shown in Fig. 11. The PCE of the investigated molecules were in the range from 3.3%–8.2 %. These results have shown that tuning the
molecular structure, particularly the bridge group of the CPDT donor block within the designed compounds, owns a crucial impact on
the photovoltaic performances. Overall, the molecules under investigation exhibit interesting photovoltaic performances for promising
OSCs.

4. Conclusion

In this study, we reported a computational study based on the electronic, photo-physical and charge transport properties of novel
designed small and planar molecules by means of DFT and TD-DFT methods. These compounds were designed based on tuning the DPP
and CPDT derivatives with a D-π-A-π-D molecular architecture. According to the computed results, the bridge groups of the CPDT
donor block considerably affected the HOMO/LUMO energy levels while the DPP acceptor cored blocks mainly affected the optical
properties. The optical absorption covered mostly the solar spectrum with high light harvesting efficiency. The main excited state
properties have shown the effect of the bridge blocks in improving the light-harvesting capability and the efficiency of exciton
dissociation. The results demonstrated that these compounds are promising photovoltaic small molecules donor materials due to the
small reorganization energy, large Voc and high FF. Finally, the estimated PCE values using the Scharber diagram are found to reach
the 8.2 %. Based on this investigation, we suggest that the designed small molecules as donor materials are promising candidates for
high efficiency BHJ organic solar cells.

Declaration of Competing Interest

None.

Acknowledgements

The authors are grateful to Atef KRIR, English Language Institute, King Abdulaziz University for the language proofreading.

Appendix A. Supplementary data

Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.ijleo.2021.
166787.

References

[1] J. Lee, J.L. Hernandez, I. Pelse, J.R. Reynolds, C. Yang, J. Mat. Chem. C. 6 (2018) 10532.
[2] J. Zhao, Y. Li, G. Yang, K. Jiang, H. Lin, H. Ade, W. Ma, H. Yan, Nat. Energy. 1 (2016) 1.
[3] G. Deng, P. Yin, X. Zeng, G. Wang, J. Liang, C. Cui, P. Shen, Deyes Pigm. 171 (2019) 107687.
[4] A. Aghassi, C.D. Fay, J. Phys. Chem. Sol. 130 (2019) 136.
[5] R. Zaier, M.P. De La Cruz, F.L. De La Puente, S. Ayachi, J. Phys. Chem. Sol. (2020) 109532.
[6] F. Liu, Z. Zhou, C. Zhang, T. Vergote, H. Fan, F. Liu, X. Zhu, J. Am. Chem. Sci. 138 (2016) 15523.
[7] H. Kang, G. Kim, J. Kim, S. Kwon, H. Kim, K. Lee, Adv. Mat. 28 (2016) 7821.
[8] M. Nazim, S. Ameen, M.S. Akhtar, H.K. Seo, H.-S. Shin, RSC Adv. 5 (2015) 6286.
[9] H. Bin, J. Yao, Y. Yang, I. Angunawela, C. Sun, L. Gao, L. Ye, B. Qiu, L. Xue, C. Zhu, Adv. Mat. 30 (2018) 1706361.
[10] S.S. Bagde, H. Park, J.G. Han, Y. Li, R.B. Ambade, S.B. Ambade, B. Kim, S.H. Lee, Deyes Pigm. 137 (2017) 117.
[11] M.R. Busireddy, V.N.R. Mantena, N.R. Chereddy, B. Shanigaram, B. Kotamarthi, S. Biswas, G.D. Sharma, J.R. Vaidya, Org. Elect. 37 (2016) 312.

11
R. Zaier and S. Ayachi Optik 239 (2021) 166787

[12] H. Zhang, C. Wang, X. Li, J. Jing, Y. Sun, Sol. Energy Mater. Sol. Cel. 157 (2017) 71.
[13] N.F. Montcada, S. Arrechea, A. Molina-Ontoria, A.I. Aljarilla, P. de la Cruz, L. Echegoyen, E. Palomares, F. Langa, Org. Elect. 38 (2016) 330.
[14] P. Verstappen, I. Cardinaletti, T. Vangerven, W. Vanormelingen, F. Verstraeten, L. Lutsen, D. Vanderzande, J. Manca, W. Maes, RSC Adv. 6 (2016) 32298.
[15] P. Heinrichova, J. Pospíšil, S. Stříteský, M. Vala, M. Weiter, P. Toman, D. Rais, J. Pfleger, M. Vondráček, D. Šimek, J. Phys. Chem. C. (2019).
[16] A. Mishra, P. Bäuerle, Angew. Chem. Int. Ed. 51 (2012) 2020.
[17] Y.A. Duan, Y. Geng, H.B. Li, J.L. Jin, Y. Wu, Z.M. Su, J. Comp. Chem. 34 (2013) 1611.
[18] X. Liu, W. Shen, R. He, Y. Luo, M. Li, J. Phys. Chem. C. 118 (2014) 17266.
[19] K. Narayanaswamy, A. Venkateswararao, V. Gupta, S. Chand, S.P. Singh, Chem. Comm. 52 (2016) 210.
[20] S. Zeng, L. Yin, C. Ji, X. Jiang, K. Li, Y. Li, Y. Wang, Chem. Comm. 48 (2012) 10627.
[21] B. Yadagiri, K. Narayanaswamy, R. Srinivasa Rao, A. Bagui, R. Datt, V. Gupta, S.P. Singh, ACS Omega 3 (2018) 13365.
[22] H.Q. Xia, C.P. Kong, J. Wang, F.Q. Bai, H.X. Zhang, RSC Adv. 4 (2014) 50338.
[23] Z. Wang, L. Zhu, Z. Shuai, Z. Wei, Macromol. Rapid Comm. 38 (2017) 1700470.
[24] R. Domínguez, N.F. Montcada, P. de la Cruz, E. Palomares, F. Langa, Phys. Chem. Chem. Phys. 19 (2017) 3640.
[25] K. Brymora, L. Ducasse, A. Delaure, L. Hirsch, T. Jarrosson, C. Niebel, F. Serein-Spirau, R. Peresutti, O. Dautel, F. Castet, Deyes Pigm. 149 (2018) 882.
[26] A. Tang, C. Zhan, J. Yao, E. Zhou, Adv. Mat. 29 (2017) 1600013.
[27] A.D. Hendsbee, J.-P. Sun, L.R. Rutledge, I.G. Hill, G.C. Welch, J. Mater. Chem. 2 (2014) 4198.
[28] C. Maglione, A. Carella, R. Centore, P. Chávez, P. Lévêque, S. Fall, N. Leclerc, Deyes Pigm. 141 (2017) 169.
[29] G.W.T. M.J. Frisch, H.B. Schlegel, G.E. Scuseria, M.A. Robb, G.S. J.R. Cheeseman, V. Barone, B. Mennucci, G.A. Petersson, M.C. H. Nakatsuji, X. Li, H.P.
Hratchian, A.F. Izmaylov, J. Bloino, J.L.S. G. Zheng, M. Hada, M. Ehara, K. Toyota, R. Fukuda, M.I. J. Hasegawa, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T.
Vreven, J.E.P. J.A. Montgomery Jr., F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, V.N.S. K.N. Kudin, R. Kobayashi, J. Normand, K. Raghavachari, J.C.B. A.
Rendell, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, J.E.K. M. Klene, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, O.Y. R.E.
Stratmann, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, K.M. R.L. Martin, V.G. Zakrzewski, G.A. Voth, P. Salvador, S.D. J.J. Dannenberg, A.D. Daniels, O.
Farkas, J.B. Foresman, J.V. Ortiz, D.J.F. J. Cioslowski, Gaussian 09 (Revision A.01), Gaussian, Inc., Wallingford, CT.
[30] Y. Li, Y. Feng, M. Sun, Sci. Rep. 5 (2015) 13970.
[31] H. Hwang, H. Ko, S. Park, S.R. Suranagi, D.H. Sin, K. Cho, Org. Elect. 59 (2018) 247.
[32] S.H. Chou, H.C. Chen, C.K. Wang, C.L. Chung, C.M. Hung, J.C. Hsu, K.T. Wong, Org. Elect. 68 (2019) 159.
[33] R. Zaier, F. Mahdhaoui, S. Ayachi, T. Boubaker, J. Mol. Struct. 1182 (2019) 131.
[34] T.F. Lu, W. Li, J. Chen, J. Tang, F.-Q. Bai, H.-X. Zhang, Elect. Acta. 283 (2018) 1798.
[35] J.M. Ku, D.K. Kim, T.H. Ryu, E.H. Jung, Y. Lansac, Y.H. Jang, Bull. Korean Chem. Soc. 33 (2012) 1029.
[36] R. Zaier, S. Hajaji, M. Kozaki, S. Ayachi, Opt. Mater. 91 (2019) 108.
[37] T. Lu, F. Chen, J. Comp. Chem. 33 (2012) 580.
[38] D. Makhov, L. Lewis, Phys. Rev. Lett. 92 (2004) 255504.
[39] H.Q. Xia, J. Wang, F.Q. Bai, H.X. Zhang, Deyes Pigm. 113 (2015) 87.
[40] D. Liu, B. Kan, X. Ke, N. Zheng, Z. Xie, D. Lu, Y. Liu, Adv. Ener. Mater. 8 (2018) 1801618.
[41] H. Yao, Y. Cui, D. Qian, C.S. Ponseca Jr, A. Honarfar, Y. Xu, J. Xin, Z. Chen, L. Hong, B. Gao, J. Am. Chem. Sci. 141 (2019) 7743.
[42] S.K. Pal, T. Kesti, M. Maiti, F. Zhang, O. Inganas, S. Hellstrom, M.R. Andersson, F. Oswald, F. Langa, T. Osterman, J. Am. Chem. Sci. 132 (2010) 12440.
[43] M.C. Scharber, N.S. Sariciftci, Prog 38 (2013) 1929.
[44] N. Bérubé, V. Gosselin, J. Gaudreau, M. Côté, J. Phys. Chem. C. 117 (2013) 7964.
[45] A. Ostovan, Z. Mahdavifar, M. Bamdad, Polymer 126 (2017) 162.
[46] C. Adamo, D. Jacquemin, Chem. Soc. Rev. 42 (2013) 845.
[47] A. Azazi, A. Mabrouk, M. Chemek, D. Kreher, K. Alimi, Synt. Met. 198 (2014) 314.
[48] A.A. Youssef, S.M. Bouzzine, Z.M.E. Fahim, İ. Sıdır, M. Hamidi, M. Bouachrine, Physica B. 560 (2019) 111.
[49] F. Lincker, N. Delbosc, S. Bailly, R. De Bettignies, M. Billon, A. Pron, R. Demadrille, Adv. Funct. Mater. 18 (2008) 3444.
[50] Z. Wang, A. Putta, J.D. Mottishaw, Q. Wei, H. Wang, H. Sun, J. Phys. Chem. C. 117 (2013) 16759.
[51] S. Hedström, P. Henriksson, E. Wang, M.R. Andersson, P. Persson, Phys. Chem. Chem. Phys. 16 (2014) 24853.
[52] Q.Q. Pan, S.B. Li, Y. Wu, Y. Geng, M. Zhang, Z.M. Su, Org. Elect. 53 (2018) 308.
[53] W. Taouali, M.E. Casida, A.A.M. Darghouth, K. Alimi, Comp. Mater. Sci. 150 (2018) 54.
[54] S.B. Li, Y.A. Duan, Y. Geng, H.-Z. Gao, Y.-Q. Qiu, Z.M. Su, RSC Adv. 5 (2015) 29401.
[55] T. Mestiri, K. Alimi, Theor. Chem. Acc. 137 (2018) 133.
[56] Z.Z. Sun, Y.L. Xu, R. Zhu, H.Y. Liu, Org. Elect. 63 (2018) 86.
[57] L. Wang, G. Nan, X. Yang, Q. Peng, Q. Li, Z. Shuai, Chem. Soc. Rev. 39 (2010) 423.
[58] H. Liu, S. Kang, J.Y. Lee, J. Phys. Chem. B 115 (2010) 5113.
[59] X. Chen, F.Q. Bai, H.-T. Wang, H.-X. Zhang, Y. Tang, RSC Adv. 5 (2015) 47681.
[60] V.T.T. Huong, H.T. Nguyen, T.B. Tai, M.T. Nguyen, J. Phys. Chem. C. 117 (2013) 10175.
[61] M. Knupfer, App. Phys.A. 77 (2003) 623.
[62] R.A. Janssen, J. Nelson, Adv. Mat. 25 (2013) 1847.
[63] K. Vandewal, K. Tvingstedt, A. Gadisa, O. Inganäs, J.V. manca, Nat. Mater. 8 (2009) 904.
[64] J. Wiberg, L. Guo, K. Pettersson, D. Nilsson, T. Ljungdahl, J. Mårtensson, B. Albinsson, J. Am. Chem. Soci. 129 (2007) 155.
[65] H. Yao, L. Ye, H. Zhang, S. Li, S. Zhang, J. Hou, Chem. Rev. 116 (2016) 7397.
[66] L. Zhang, W. Shen, R. He, X. Liu, X. Tang, Y. Yang, M. Li, Org. Elect. 32 (2016) 134.
[67] M.C. Scharber, D. Mühlbacher, M. Koppe, P. Denk, C. Waldauf, A.J. Heeger, C.J. Brabec, Adv. Mat. 18 (2006) 789.

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