Dyes and Pigments 220 (2023) 111657

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Dyes and Pigments

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

Effect of terminal fluorination of indenoindene-cored non-fullerene

molecular acceptors for photovoltaic application
Almas Zulfiqar a, b, Arfa Abrar Malik c, Haijun Fan a, *, Xiaozhang Zhu a, b, **
a
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190,
People’s Republic of China
b
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 101408, People’s Republic of China
c
CAS Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing,
100190, People’s Republic of China

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

Keywords: Two new non-fullerene molecule acceptors (NFAs), IDTIC and IDTIC-4F, based on a 5,10-dihydroindeno[2,1-a]
Organic photovoltaics indene core and 4H-cyclopenta[1,2-b:5,4-b’]dithiophene (CPDT) bridges, were designed and synthesized. The
Non-fullerene molecular acceptors fluorine-terminated IDTIC-4F shows a larger bathochromic shift than the non-fluorinated IDTIC. When blending
Indenoindene
with a PBDB-T polymer donor to fabricate organic solar cells, the IDTIC and IDTIC-4F acceptors respectively
Cyclopentadithiophene
showed power conversion efficiencies (PCEs) of 5.60% and 6.77%. The PBDB-T:IDTIC-4F device performed
Fluorination
better on Jsc and FF, which was attributed to the morphological evolution due to terminal fluorinated design of
NFAs. Comparatively, the terminal fluorinated IDTIC-4F contributes to the formation of a more uniform film with
less traps, which improves the charge transport and reduces the bimolecular recombination within the device.
The work demonstrates that terminal fluorination of NFAs is an efficient design to modifying the morphology and
performance of non-fullerene organic photovoltaics.

1. Introduction
When a photovoltaic semiconductor absorbs the UV–Vis light
strongly bounded excitons generate [1–3], which can efficiently split
into free charge carriers by constructing bulk-heterojunction type
photovoltaic devices [4]. Fullerene derivatives have been contributing
to the rapid performance improvement of organic photovoltaics (OPVs)
within last two decades [5,6]. Along with the development of material
sciences, non-fullerene molecular acceptors (NFAs) are emerging as an
appealing alternative for high performance OPVs. The fundamental
structure of both type materials dramatically affects the performance [7,
8]. As known, the fullerenes are ball-shape with featuring typical
isotropic character [9–11], while the NFAs are more anisotropic due to
planar configurations, designed based on enhancing π–π interaction and
better charge carrier delocalization consideration [12–14].
Currently, A–D–A type NFAs are popularly designed [15–17]. With
concepts and structures gradually evolved, NFAs- have achieve high
PCEs of over 19% [18–20]. An advantage of A–D–A design is on the
easily-tuned molecular energy levels and absorptions, which affects the
open-circuit voltage (Voc) and short-circuit current (Jsc) of a photovol­
taic device closely. To achieve both high Voc and Jsc for efficient NFAs,
delicately manipulating the intramolecular charge transfer interactions
between the donor and acceptor moieties is essential. In order to
enhance the push-pull effect within molecules, strong electron-donating
cores and/or electron-withdrawing end groups were widely introduced.
We have reported a centrosymmetric E-stilbene with 14 π-electrons and
more sp3 carbon bridge, indenoindene, which showed potential as effi­
cient core building block for NFAs [21]. Further improved design of
NFAs highly rely on the better understanding to the complicated inter­
action between the main buildings blocks, which deserves more explore.
Meanwhile, attaching halogen atoms such as fluorine et al. onto NFAs
has been proved to be useful. The highly electronegative fluorine atoms
help to lower the energy levels without causing large steric hindrance,
and also can strengthen the inter/intramolecular interactions via
non-covalent interacting. Therefore, NFAs with enhanced absorption,
suitable energy levels and better charge transport were widely reported

* Corresponding author.
** Corresponding author. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of
Sciences, Beijing, 100190, People’s Republic of China.
E-mail addresses: fanhai2008@iccas.ac.cn (H. Fan), xzzhu@iccas.ac.cn (X. Zhu).

https://doi.org/10.1016/j.dyepig.2023.111657
Received 29 June 2023; Received in revised form 17 August 2023; Accepted 29 August 2023
Available online 30 August 2023
0143-7208/© 2023 Elsevier Ltd. All rights reserved.
A. Zulfiqar et al.
Fig. 1. Molecular structure of IDTIC, IDTIC-4F and PBDB-T.
[22–26]. For example, ITIC was studied as one of state of the art NFAs
[27–29]. Li et al. compared the photovoltaic performance of OPVs based
on ITIC and its fluorinated analogues, m-ITIC-2F and m-ITIC-4F [30].
The two acceptors with fluorine both show red-shifted optical absorp­
tion, better molecular packing and improved electron mobility
compared to m-ITIC. Fluorination of NFAs can also help to reduce the
voltage loss (Vloss) of devices, which highly depends on the bandgap of
the donor and acceptor and their energy level over-lapping [31,32]. He
et al. discussed the role of fluorine based on two ladder-type [33] NFAs,
DTCCIC and DTCCIC-4F and found that the fluorinated one performed
much better than the other, which mainly due to improved morphology
with much reduced Vloss (0.85 V vs 1.01 V) [34]. However, the effect of
fluorination for indenoindene-based NFAs remain unclear. Besides,
incorporating bridges between the core and terminals may modify the
push-pull effect, as number of acceptor2-acceptor1-donor-
acceptor1-acceptor2 (A2–A1–D–A1–A2) type molecules cases demon­
strated [35–38]. For example, the introduction of a thieno[3,4-b]thio­
phene bridge into an indacenodithophene (IDT) molecule creates ATT1,
which achieves top efficiency among solar cells using PTB7-Th donor
mainly by expanding the photo absorption. In contrast, introducing
benzothiadiazole into an indenoindene-based molecule produces IBR,
which obtains an extraordinary Voc reaching 1.16 eV, among the highest
values reported for single junction organic solar cells. As a useful bridge,
cyclopentadithiophene (CPDT) have been widely adopted in optoelec­
tronic devices such as OPVs and OFETs et al. [39–41] due to multiple
advantages such as its rigid coplanar structure which benefits the π-π
interaction for electron donation [39], and its five-membered internal
rings with more sites for well addressing the dissolving and processing
issue. Introducing CPDT may adjust the push-pull effect for
indenoindene-based NFAs and mainly contribute to an enhanced Jsc for
its electron-rich character. However, introducing long alkyl chains onto
CPDT may influence molecular packing and deep understanding to­
wards a balanced design for appreciate bridges is in dire need.
Herein, we designed and synthesized two new NFAs for investigating
above-mentioned effect. The molecular structures of 2,2’-((2Z,2′Z)-
((6,6’-(5,5,10,10-tetrakis(2-butyloctyl)-5,10-dihydroindeno[2,1–a]
indene-2,7-diyl)bis(4H-cyclopenta[1,2-b:5,4-b’]dithiophene-6,2-diyl))
bis(methanylylidene))-bis(3-oxo-2,3-dihydro-1H-indene-2,1-diyli­
dene))dimalononitrile (IDTIC) and 2,2’-((2Z,2′Z)-((6,6’-(5,5,10,10-tet­
rakis(2-butyloctyl)-5,10-dihydroindeno[2,1–a]indene-2,7-diyl)bis(4H-
cyclopenta[1,2–b:5,4–b’]dithiophene-6,2-diyl))bis(methanylylidene))
bis (5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalo­
nonitrile (IDTIC-4F) were shown in Fig. 1. Cyclopentadithiophene
(CPDT) free of dissolution-assisting alkyl chains were incorporated to
bridge the indenoindene core and malononitrile terminals based on dual
considerations of enhancing intermolecular interaction and adjusting π
conjugation within molecules. The frontier molecular orbital energy
levels of designed IDTIC and IDTIC-4F were calculated by DFT at the
B3LYP/6-31G** level (Fig. S1 in the Supporting Information). As shown,
the IDTIC-4F molecule possesses both lowered HOMO and LUMO levels
than IDTIC, suggests the feasibility of F introduction in indenoindene-
based NFAs for energy level tuning. Both NFAs were blended with a
PBDB-T polymer donor to fabricate organic solar cells (OSCs) for per­
formance evaluation. The optimal PCEs were achieved, 5.60% and
6.77% for IDTIC and IDTIC-4F acceptors respectively. Key parameter
2
Dyes and Pigments 220 (2023) 111657
differences of their photovoltaic performance were found on short-
circuit current (Jsc) and fill factor (FF), which reflects the multiple ef­
fects by terminal fluorination. First, combined data via UV absorption,
EQE and photovoltaic analysis consistently verifies that IDTIC-4F owns
higher molar extinction coefficient, stronger monochromatic photo-
conversion, more efficient exciton dissociation and lowered recombi­
nation, all favoring a higher Jsc compared to its IDTIC counterparts.
Secondly, detailed mobility measurement, recombination analysis,
miscibility and morphological characterization are all supporting an
obtained higher FF of IDTIC-4F device rather than the IDTIC one. The
work demonstrates that terminal fluorination is an efficient way to
adjusting the morphology and performance for non-fullerene organic
photovoltaics.
2. Experimental section
2.1. Materials
All reagents and starting materials were purchased from Aldrich,
Adamas or J&K and used without further treatment unless stated else.
Reactions sensitive to the air and moisture were carried out in a dry
apparatus protected by nitrogen or argon flow.
2.2. Measurements
Bruker Fourier 300 and Advance 400 spectrometers were used for
1
HNMR (Hydrogen Nuclear Magnetic Resonance) and 13CNMR (Carbon
Nuclear Magnetic Resonance) measurements. All samples were dis­
solved in CDCl3 with TMS as internal standard. The UV–Vis absorption
spectra were recorded by a spectrometer. Three electrode system of
CHI620D potentiostat instrument was used for cyclic voltammetry (CV)
measurements. The HOMO and LUMO energy levels were calculated by
equations: EHOMO = – (Eox‒EFe+4.8) eV and ELUMO = – (Ered–EFe+4.8)
eV, where Ered and Eox represent the onsets of reduction and oxidation
potentials respectively, and EFe is the half-wave potential of ferrocene.
Atomic force microscopy (AFM) images of films were recorded in a
Nanoscope IIIa AFM (Digital Instruments) operating system in a tapping
mode. Transmission electron microscopy (TEM) was performed using a
JEOL 2200FS instrument at 160 kV accelerating voltage.
2.3. Synthesis
4H-cyclopenta[1,2–b:5,4–b’]dithiophene-2-carbaldehyde (1):
POCl3 (0.1 g, 0.67 mmol) was added into the C2H4Cl2:DMF (3 ml, 5:1 in
volume) solution of CPDT (100 mg, 0.56 mmol) at 0 ᵒC under inert at­
mosphere. After 5 h stirring at 0 ᵒC, 10 ml saturated sodium acetate
solution was added into the reaction mixture and the solution was
stirred for additional 2 h at RT. The organic solution was extracted by
CH2Cl2 and dried over MgSO4. The residue was purified by column
chromatography using petroleum ether (PE) and CH3COOC2H5 (10:1)
and the yield is 37%. 1HNMR (400 MHz, CDCl3): δ 9.850 (s, 1H), δ 7.714
(s, 1H), δ 7.423 (d, J = 4 Hz, 1H), δ 7.152 (d, J = 4 Hz, 1H), δ 3.634 (s,
2H). 13CNMR (100 MHz, CDCl3): δ 182.68, 153.93, 149.47, 149.29,
143.23, 137.94, 131.81, 129.33, 123.19, 32.03. HRMS (MALDI-TOF):
m/z calc. for C10H7OS2 [M]+: 206.9933; found 206.9934.
A. Zulfiqar et al.
Scheme 1. Synthesis of IDTIC and IDTIC-4F.
6-bromo-4H-cyclopenta[1,2–b:5,4–b’]dithiophene-2-carbalde­
hyde (2): N-Bromosuccinimide (NBS) (110.35 mg, 0.62 mmol) was
added into a THF solution (10 ml) of 4H-cyclopenta[1,2–b:5,4–b’]
dithiophene-2-carbaldehyde (103 mg, 0.5 mmol) at 0 ᵒC under inert
atmosphere. The reaction mixture was stirred for 5 h at 0 ᵒC and then 10
ml water was added. The organic solution was extracted by CH2Cl2 and
dried over MgSO4. The residue was purified by column chromatography
using PE and CH3COOC2H5 (10:1) with a yield of 84%. 1HNMR (400
MHz, CDCl3): δ 9.847 (s, 1H), δ 7.699 (s, 1H), δ 7.160 (s, 1H), δ 3.619 (s,
2H). 13CNMR (100 MHz, CDCl3): δ 182.66, 152.47, 148.48, 143.56,
138.29, 131.55, 126.23, 115.91, 32.48. HRMS (MALDI-TOF): m/z calc.
for C10H4BrOS2 [M]+: 282.888145; found 282.888524.
6,6’-(5,5,10,10-tetrakis(2-butyloctyl)-5,10-dihydroindeno
[2,1–a]indene-2,7-diyl)bis(4H-cyclopenta[1,2–b:5,4–b’]dithio­
phene-2-carbaldehyde) (IDT): 2,2’-(5,5,10,10-tetrakis(2-butyloctyl)-
5,10-dihydroindeno[2,1–a]indene-2,7-diyl)bis(4,4,5,5-tetramethyl-
1,3,2-dioxaborolane) (127.5 mg, 0.11 mmol) was dissolved into 12 ml
THF and 6-bromo-4H-cyclopenta[1,2–b:5,4–b’]dithiophene-2-carbalde­
hyde (74 mg, 0.26 mmol) was added. Tetrakis(triphenylphosphine)
palladium (6.5 mg, 0.05 mmol) catalyst was then added. All above
operation was under nitrogen. After adding K2CO3 (1 M, 2 ml), the flask
was tightened up hard. The reaction mixture was stirred at 80 ᵒC over­
night and extracted by dichloromethane (DCM) after cooling down.
Before evaporating DCM the solution was dried by MgSO4. The residue
was purified by column chromatography using PE:DCM eluent. 60 mg
dark reddish product was obtained (yield: 41%). 1HNMR (400 MHz,
CDCl3): δ 9.855 (s, 2H), δ 7.718 (s, 2H), δ 7.620 (s, 2H), δ 7.536 (d, J = 8
Hz, 2H), δ 7.385 (s, 2H), δ 7344 (d, J = 8 Hz, 2H), δ 3.684 (s, 4H), δ
2.060 (s, 8H), δ 1.254–0.621 (m, 92H). HRMS (MALDI-TOF): m/z calc.
for C84H116O2S4 [M]+: 1284.7852; found 1284.7855.
2,2’-(((6,6’-(5,5,10,10-tetrakis(2-butyloctyl)-5,10-dihy­
droindeno[2,1–a]indene-2,7-diyl)bis(4H-cyclopenta
[1,2–b:5,4–b’]dithiophene-6,2-diyl))bis(methylene))bis(3-oxo-2,3-
dihydro-1H-indene-2-yl-1-ylidene))dimalononitrile (IDTIC): IDT
(22 mg, 0.02 mmol) was dissolved in 12 ml chloroform and INCN (28
mg, 0.14 mmol) was added. The solution was deoxygenated in nitrogen
for 20 min and 4 drops of pyridine catalyst was added. The reaction
mixture was stirred for 12 h at 45 ᵒC and then filtered with methanol
3
Dyes and Pigments 220 (2023) 111657
after cooling down. The crude residue was purified by flash chroma­
tography with PE:DCM (1:4). 18 mg dark blue product was obtained
(yield: 64%). 1HNMR (400 MHz, CDCl3): δ 8.909 (s, 2H), δ 8.641 (d, J =
6.4 Hz, 2H), δ 7.881 (d, J = 6 Hz, 2H), δ 7.811 (s, 2H), δ 7.699 (s, 4H), δ
7.668 (s, 2H), δ 7.598 (d, J = 6.8 Hz, 2H), δ 7.444 (s, 2H), δ 7.394 (d, J =
7.6 Hz, 2H), δ 3.740 (s, 4H), δ 2.103 (s, 8H), δ 1.254–0.71 (m, 92H).
13
CNMR (100 MHz, CDCl3): δ 187.50, 159.78, 158.67, 157.16, 155.85,
153.45, 149.30, 140.30, 138.99, 137.92, 137.81, 137.11, 136.32,
135.88, 133.61, 132.93, 129.12, 124.01, 123.55, 122.35, 119.72,
119.48, 118.81, 117.62, 114.22 66.20, 53.26, 41.73, 37.37, 34.10,
33.52, 33.35, 32.81, 30.93, 28.81, 28.73, 27.45, 26.55, 25.18, 24.23,
22.11, 21.95, 21.70, 21.66, 13.12, 13.04, 12.98. HRMS (MALDI-TOF):
m/z calc. for C108H124N4O2S4 [M]+: 1636.8602; found 1636.8593.
2,2’-((2Z,2′Z)-((6,6’-(5,5,10,10-tetrakis(2-butyloctyl)-5,10-
dihydroindeno[2,1–a]indene-2,7-diyl)bis(4H-cyclopenta
[1,2–b:5,4–b’]dithiophene-6,2-diyl))bis(methanylylidene))bis
(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalo­
nonitrile (IDTIC-4F): IDT (5 mg, 0.004 mmol) was dissolved in 10 ml
THF and INCN–4F was added. The solution was then deoxygenated in
nitrogen for 30 min with 1 drop pyridine catalyst added. The reaction
was kept at 65 ᵒC for 15 h and was filtered by methanol after cooling
down. The raw product was purified by silica gel column chromatog­
raphy with PE:DCM (1:4). 3.7 mg dark blue product was obtained (yield:
55%). 1HNMR (400 MHz, CDCl3): δ 8.879 (s, 2H), δ 8.489 (q, J = 3.2 Hz,
2H), δ 7.820 (s, 2H), δ 7.675 (s, 2H), δ 7.645 (d, J = 7.6 Hz, 2H), δ 7.609
(d, J = 7.2 Hz, 2H), δ 7.462 (s, 2H), δ 7.405 (d, J = 8 Hz, 2H), δ 3.763 (s,
4H), δ 2.103 (s, 8H), δ 1.545–0.647 (m, 92H). 13CNMR (100 MHz,
CDCl3): 186.10, 160.89, 158.91, 158.60, 157.34, 157.30, 156.96,
156.91, 155.51, 155.38, 155.36, 152.91, 152.78, 150.62, 141.48,
141.46, 139.42, 138.74, 138.09, 137.27, 137.25, 136.52, 136.47,
134.40, 130.03, 124.66, 120.77, 120.55, 118.80, 118.68, 114.82,
114.66, 112.36, 112.18, 67.50, 54.29, 42.70, 35.35, 35.09, 34.52,
34.35, 33.81, 31.97, 31.93, 29.81, 29.80, 29.76, 29.73, 28.45, 27.54,
26.18, 25.23, 23.12, 22.95, 22.71, 22.67, 22.65, 14.14, 14.05, 14.00,
13.98. HRMS (MALDI-TOF): m/z calc. for C108H120F4N4O2S4 [M]+:
1708.8225; found 1708.8231.
A. Zulfiqar et al. Dyes and Pigments 220 (2023) 111657

Fig. 2. Left: Normalized absorption spectra of IDTIC and IDTIC-4F in solution and films. Right: Energy level diagram of materials used for photovoltaic devices.

2.4. Device fabrication and characterization 3. Results and discussion

All photovoltaic devices were of an ITO/PEDOT:PSS/PBDB-T: 3.1. Materials preparation

acceptors/PDINO/Al layered structure. To fabricate the devices, ITO-
coated glass substrates (15 Ω sq− 1) were cleaned with de-ionized Scheme 1 shows the synthetic routes for target molecules. The
water, acetone, and isopropyl alcohol successively and treated by bridging CPDT block was synthesized according to reported literatures
ozone plasma for 20 min. Then a PEDOT:PSS (Bayer Baytron 4083, ~30 [42–44]. 4H-cyclopenta[1,2–b:5,4–b’]dithiophene-2-carbaldehyde (1)
nm) layer was spin-coated onto the substrates and were baked at 150 ◦ C were synthesized [45] and brominated to get 6-bromo-4H-cyclopenta[1,
for 15 min. The PEDOT-coated substrates were transferred into a glo­ 2–b:5,4–b’]dithiophene-2-carbaldehyde (2) [46]. The indenoindene
vebox filled with N2. Active layers were deposited by spin-coating an o- intermedium 2,2’-(5,5,10,10-tetrakis(2-butyloctyl)-5,10-dihydroindeno
dichlorobenzene (DCB) solution of PBDB-T:acceptors blends (10 mg/ml [2,1–a]indene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
for PBDB-T). A PDINO (2 mg/ml in CH3OH) solution was spin-coated was synthesized by a six-steps reaction [37]. The aryl dialdehyde in­
onto the annealed active layers to form an electron transporting layer. termediate (IDT) [47]was synthesized through a Suzuki coupling reac­
Finally, an aluminum (100 nm) layer were thermally evaporated at 4.0 tion of IDT and 2. IDTIC and IDTIC-4F were obtained via a Knoevenagel
× 10− 4 Pa to form the electrodes. A shadow mask was used to define the condensation reaction [21].
active area to be 0.05 cm2. The current density–voltage (J–V) charac­
teristics of all photovoltaic devices were measured under N2 using a
3.2. Optoelectronic and electrochemical properties
Keithley 2400 source meter. A 300 W xenon arc solar simulator (Oriel)
with an AM 1.5 global filter was used and operated at 100 mW cm− 2
The optoelectronic properties of IDTIC and IDTIC-4F were charac­
irradiation. The illumination intensity was corrected by using a silicon
terized by UV–Vis spectroscopy (Fig. 2). Both acceptors show broad
photodiode with a protective KG5 filter calibrated by the National
absorption in 600–900 nm. The peak absorption of IDTIC in solution
Renewable Energy Laboratory (NREL). The external quantum efficiency
appears at 686 nm and it is 709 nm for the film, giving a bathochromic
(EQE) was performed using a certified IPCE equipment (Zolix In­
shift of 23 nm. IDTIC-4F exhibits a larger bathochromic shift (~29 nm)
struments, Inc, SolarCellScan100).
compared to IDTIC. Due to the attachment of more electron-deficient
The carrier mobility was determined via a space-charge-limited-
fluorine atoms, the strengthened molecular polarity may enhance the
current (SCLC) method. Related electron and hole-only devices were
intermolecular π-π interaction in solid film state, which can be a reason
fabricated in configurations of ITO/ZnO/PBDB-T:acceptors/PDINO/Al
to this larger bathochromic shift. In solution, IDTIC-4F shows a larger
and ITO/PEDOT:PSS/PBDB-T:acceptors/MoO3/Al respectively. The
molar extinction coefficient (2.70 × 105 M− 1 cm− 1) than IDTIC-4F (1.46
active layers were processed at the same condition as described for
× 105 M− 1 cm− 1) at the maximum absorption peak, which may benefit
photovoltaic device fabrication. The mobility was determined by fitting
the generation of large photocurrent for photovoltaic application.
the dark current to a SCLC model, which is described as: J = 9ε0εrμ0V2/
The electrochemical properties of acceptors were tested by cyclic
8L3, where J is the current density, ε0 is the permittivity of the free space,
voltammetry (CV). The HOMO and LUMO energy levels of IDTIC-4F
εr is the relative permittivity of the material, μ0 is the zero-field mobility,
were − 5.68 eV and − 3.80 eV, both lower than those of IDTIC (− 5.47
V is the effective voltage in the devices and L is the thickness of the
eV and − 3.69 eV). The lowered LUMO energy level of NFAs were
active layer. V is defined as V = Vappl - Vbi, where Vappl is the applied
contributive to an enlarged driving force for fabricated BHJ OSCs, which
voltage and Vbi is the built-in voltage due to the relative work function
may benefit the charge separation. The bandgap of IDTIC-4F (1.88eV)
difference of the two electrodes.
were noticed to be larger than that of IDTIC (1.78eV), which is
reasonable considering the mesomeric contribution by fluorination
[48]. Beyond the major inductive electron-withdrawing effect, intro­
Table 1 ducing strong electronegative F atom can feature noticeable mesomeric
Photovoltaic parameters of PBDB-T:IDTIC and PBDB-T:IDTIC-4F devices. effect by its lone pair. This affect the LUMO more, and therefore results
Active layer Voc (V) Jsc (mA Jcal (mA FF PCE
in a net widening of band gap of IDTIC-4F relative to IDTIC.
cm− 2) cm− 2) (%)

PBDB-T:IDTIC 0.961 11.58 11.33 0.50 5.60 3.3. Photovoltaic performance

PBDB-T:IDTIC- 0.886 14.10 13.88 0.54 6.77
4F
OPV devices were fabricated in a conventional structure of indium

4
A. Zulfiqar et al.
Fig. 3. J–V and EQE curves of IDTIC and IDTIC-4F based photovoltaic devices.
Fig. 4. Plots of Jph–Veff and Jsc–Pin of IDTIC and IDTIC-4F based photovoltaic devices.
tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfo­
nate)(PEDOT:PSS)/PBDB-T:acceptors/PNDIO/Al, where PDINO was
used the cathode buffer layer. Device optimization was conducted by
varying D:A ratios, solvents, additives and blend concentrations. The
optimized photovoltaic parameters were summarized in Table 1 with
typical J-V curves plotted in Fig. 3. The optimal PCE of IDTIC-based
devices was 5.6% with an open circuit voltage (Voc) of 0.961 V, a
short-circuit current density (Jsc) of 11.58 mA cm− 2 and a fill factor of
0.50. Contrastively, IDTIC-4F-based devices obtained an optimal PCE of
6.77% with a Voc of 0.886 V, a Jsc of 14.10 mA cm− 2 and an FF of 0.54.
The IDTIC-4F acceptor performs comparatively better than IDTIC,
mostly attributed to the improved Jsc and FF.
As shown in Fig. 3, the EQE of both devices cover wide wavelength
ranges from 300 nm to 900 nm, corresponding well with the absorption
of PBDB-T, IDTIC and IDTIC-4. The EQE of IDTIC-4F-based devices
shows a maximum value oC2f 55% at 680 nm, while the strongest
response of IDTIC-based device is 52% (660 nm). The Jsc from J–V
measurement and those values calculated by integrating their EQE
curves were consistent. The IDTIC-based devices gave an integrated Jsc
of 11.33 mA cm− 2 with an error of 2.16% compared to the J–V measured
Jsc. On the contrary, the EQE-integrated Jsc of IDTIC-4F based device
was 13.88 mA cm− 2 with an error of 1.57%. It is obvious that IDTIC-4F
incorporated photovoltaic device contributes to larger Jsc values.
Fig. 4 shows the plots of photocurrent density (Jph) versus effective
voltage (Veff) of both devices. Veff is defined as Veff = V0 – V. In the
equation, V is the applied voltage and V0 is the voltage where Jph = 0. Jph
5
Dyes and Pigments 220 (2023) 111657
is defined as Jph = JL–JD, where JD and JL are current densities under
dark and illumination, respectively. Jph saturates when Veff approaches
~2 V for both devices. The ratio of Jph/Jsat reflects the charge dissoci­
ation and collection probability P(E,T). Under short circuit condition,
the P(E,T) for IDTIC and IDTIC-4F based devices were ~89% and ~92%
respectively, suggesting more efficient charge dissociation in latter
devices.
The dependence of light intensity (Plight) to Jsc reflects the condition
of charge recombination in devices, which was described as Jsc ∝ Pα. The
deviation of index α from 1 suggests the level of severe bimolecular
recombination. The α values of IDTIC based devices was 0.901 and that
of IDTIC-4F based ones was 0.933, which suggests less bimolecular
recombination in latter devices. It can be a reason to the better FF of
PBDT-T:IDTIC-4F devices. The charge transport properties were
measured and compared by a space charge-limited current (SCLC)
method (Fig. S2 and Table S9 in supporting information). The electron
mobility of PBDB-T:IDTIC and PBDB-T:IDTIC-4F blend films were 2.29
× 10− 4 and 3.81 × 10− 4 cm2 V− 1 s− 1, respectively, whose corresponding
hole mobility were 1.78 × 10− 4 and 3.12 × 10− 4 cm2 V− 1 s− 1. The PBDB-
T:IDTIC-4F blend shows both better μe and μh than PBDB-T:IDTIC, which
account for its relatively larger Jsc. As known, the faster transporting of
carriers contributes to the quicker sweeping-out of separated charges
with reducing the bimolecular recombination at certain levels. Howev­
er, as both devices show similarly large μe:μh ratios (>1.2), their low FFs
(<0.60) can be reasonable for that their overall recombination level
shall be significant, which consist with above Jsc-Plight dependence
A. Zulfiqar et al.
Fig. 5. AFM and TEM images of PBDB-T:IDTIC and PBDB-T:IDTIC-4F blends.
analysis.
3.4. Thin film morphology
The morphology of active layers was investigated by atomic force
microscope (AFM) and transmission electron microscopy (TEM) (Fig. 5).
The PBDB-T:IDTIC blend film shows a coarser surface with obvious large
aggregates while the PBDB-T:IDTIC-4F blend film is smoother and uni­
form, suggesting better intermixing. The root mean square (RMS) of
PBDB-T:IDTIC film was 9.01 nm, much higher than that of PBDB-T:
IDTIC-4F film (1.84 nm). The TEM images of the two blends were
contrastive, where uniform surface was also observed in PBDT-T:IDTIC-
4F blend film. It is worthy of noticing that though the fluorinated IDTIC-
4F shows stronger aggregation in pristine state, its blend film shows a
smaller RMS than the PBDB-T:IDTIC blend. This can be understood from
a miscibility view. When materials blend, the intermolecular interaction
and aggregation behavior may change largely, for that the miscibility
between donor and acceptor materials is also influential. Generally, low
miscibility may result in strong self-aggregation with oversized do­
mains, which reduces the efficiency of charge separation and charge
transport percolating pathways, while high miscibility may lead to
excessively mixed amorphous domains, which increases bimolecular
recombination. To clarify it, we conducted contact angle measurement.
Table S10 in the Supporting Information shows the surface energy of
PBDT-T, IDTIC and IDTIC-4F pristine films. Compared with IDTIC,
IDTIC-4F shows a closer surface tension to PBDT-T donor. The Flor­
y–Huggins interaction parameter (χ) for the two blends were determined
by a formula: χD–A = K ( γD −
√̅̅̅̅̅ √̅̅̅̅̅ 2
γ A ) , where χPBDT-T–IDTIC = 0.73K,
smaller than χPBDT-T–IDTIC-4F = 1.21K, suggesting better miscibility be­
tween PBDT-T and IDTIC. As too miscible blend tends to form exces­
sively mixed domains, the larger RMS of PBDT-T:IDTIC should be by this
reason. The morphological analysis supports the less bimolecular
recombination and higher FF of IDTIC-4F-based devices.
The morphological difference also reflects varied trap states within
the blends. To study the effects on electron injection due to morpho­
logical change, we fabricated electron-only devices with an ITO/ZnO/
PBDT-T:IDTIC(or IDTIC-4F)/PDINN/Ag configuration and measured
the dark current to derive the trap density. Fig. S3 displays the dark J-V
curves of the electron-only devices based IDTIC and IDTIC-4F logarith­
mically. The dot/square symbols are the experimental data points and
the solid lines are a fit to J ∝ Vm. At low voltages, the conduction is
Ohmic with m = 1 for both devices. Gradual trap-filling were observed
with the current rise in a medium voltage range. A trap-filled-limit-
voltage (VTFL) reaches following a trap-free Mott’s V2 law (SCLC re­
gion). As VTFL correlates with the trap density (Nt) in a function: VTFL =
eNtd2/2ε0εr, where e is the elementary charge, d is the thickness of blend
films, εr is the relative dielectric constant of the blends, ε0 is the vacuum
permittivity, therefore Nt can be determined. The VTFL of PBDT-T:IDTIC-
F device shifts to a lower voltage comparing with PBDT-T:IDTIC, sug­
gesting a low electron trap density. Quantitatively, the Nt of PBDT-T:
IDTIC-F device is 1.42 × 1017 cm− 3, lower than that of PBDT-T:IDTIC
6
Dyes and Pigments 220 (2023) 111657
(2.75 × 1017 cm− 3). This evidentially supports the analysis regarding
the superior morphology and performance of PBDT-T:IDTIC-4F devices.
4. Conclusions
Two new non-fullerene molecule acceptors, IDTIC and IDTIC-4F,
with indenoindene core and cyclopentadithiophene bridges, were
designed and synthesized to investigate the interplay between desig­
nated core-bridge design and terminal fluorination. The terminal fluo­
rination of indenoindene-cored NFA features a slightly enlarged
bandgap due to fluorine atoms’ mesomeric contribution. When blending
with a PBDB-T polymer donor, IDTIC-4F exhibited a promising PCE of
6.77%. The better performance of IDTIC-4F was attributed to its
enhanced intermolecular interaction by terminal fluorination, which
resulted in more optimal morphology with reduced trap density and
charge recombination within the photovoltaic blends. The results show
that the terminal fluorination is an efficient way to adjust the
morphology and performance of NFAs for OPV application.
CRediT authorship contribution statement
Almas Zulfiqar: carried out the synthesis of molecules, wrote the
draft, All authors reviewed the manuscript. Arfa Abrar Malik: provided
synthetic support, All authors reviewed the manuscript. Haijun Fan:
fabricated, characterized and optimized photovoltaic devices, inte­
grated the data, and, finalized the manuscript, All authors reviewed the
manuscript. Xiaozhang Zhu: proposed, and, supervised, the project, All
authors reviewed the manuscript.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
The authors thank the sponsorship of CAS-TWAS president fellow­
ship for international doctoral students, the financial supports by In­
ternational Partnership Program of Chinese Academy of Sciences
(027GJHZ2022036GC), and National Natural Science Foundation of
China (52225305, 22175187, 22171273).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.dyepig.2023.111657.
A. Zulfiqar et al. Dyes and Pigments 220 (2023) 111657

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