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org Research Article

Enhancing the Performance of Small-Molecule Organic Solar Cells

via Fused-Ring Design
Shengxi Zhou, Dongdong Xia,* Shijie Liang, Baiqiao Liu, Jing Wang, Chengyi Xiao,* Zheng Tang,
and Weiwei Li*
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ABSTRACT: Organic solar cells (OSCs) as the promising green

energy technology have drawn much attention in the last two decades.
In comparison to polymer solar cells, small-molecule organic solar cells
(SMOSCs) have the advantages of precise chemical structure and
molecular weight, purification feasibility, batch reproducibility, etc.
Despite of the recent advances in molecular design, the efficiencies of
SMOSCs are still lagging behind those of polymer-based OSCs. In this
work, a new small-molecule donor (SMD) with a fused-ring-connected
bridge denoted F-MD has been designed and synthesized. When F-MD
was applied into SMOSCs, the F-MD:N3 blends exhibited a power
conversion efficiency (PCE) of over 13%, which is much higher than
that of the linear π-bridged molecule L-MD based devices (8.12%).
Further studies revealed that the fused-ring design promoted the
planarity of the molecular conformation and facilitated charge transport in OSCs. More importantly, this strategy also lowered the
crystallinity and self-aggregation of the films, and hence optimized the microstructure and phase separation in the corresponding
blends. Thereby, the F-MD-based blends have been evidenced to have better exciton dissociation and reduced charge recombination
in comparison with the L-MD counterparts, explaining the enhanced PCEs. Our work demonstrates that the fused-ring π-bridge
strategy in small-molecule-donor design is an effective pathway to promote the efficiency of SMOSCs as well as enhance the diversity
of SMD materials.
KEYWORDS: small-molecule organic solar cells, small-molecule donors, fused-ring structure, charge transport, phase separation

■ INTRODUCTION
Organic solar cells, including polymer solar cells (PSCs) and
as a π-bridge have been rarely reported. Currently, the high-
performance non-fullerene small-molecule acceptors (NF-
small-molecule solar cells (SMOSCs), have been considered as SMAs) of the A-D-A type including ITIC, Y6, and their
analogues usually consist of a large fused core instead of a
promising technologies due to the merits of large-area
nonfused structure.24,34−36 The “fused-ring” strategy has
application, flexibility, and light weight.1−11 In comparison
achieved huge success in high-performance OSCs due to the
with polymers, small molecules have the merit of well-defined
following reasons: (1) large conjugated and fused chemical
chemical structures, monodispersed molecular weight, and
structures guarantee broad absorption, which improves the
easily tuned properties, which is beneficial for the device
harvesting of sunlight; (2) a fused-ring structure always enables
reproducibility and ease in establishing the physical model to
small molecules to have better coplanarity due to fewer degree
understand the structure−performance relationship.12−19 Re-
of freedom (single bonds have many possibilities of free
cently, with the rapid evolution of non-fullerene acceptors
rotation) and hence enhances the aggregated property and the
(NFAs), PSCs have achieved PCEs over 18% in single-junction
electron delocalization; (3) fused and nonfused molecules have
devices.20−24 However, SMOSCs have shown slow progress
different crystallinities so as to influence phase separation and
and displayed PCEs of 17% in ternary devices25 and of 15% in
phase purity in D/A blends.37−40 For instance, the fused ring
binary systems,26 lagging behind the PSCs. The reasons are the
limited strategies for donor molecule design and the difficulty
to control the morphology, thereby suppressing the develop- Received: November 15, 2021
ment of SMOSCs. Accepted: January 18, 2022
Most of the high-performance SMOSCs are based on Published: January 31, 2022
molecular donors containing linear terthiophene as a π-bridge,
such as B1,27 BTR,28 and L-MD (Figure 1a)29 as well as their
derivatives,30−33 while small-molecule donors with a fused ring

© 2022 American Chemical Society https://doi.org/10.1021/acsami.1c22135

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Figure 1. Chemical structures of conjugated molecules and their frontier energy levels: (a) linear L-MD; (b) the fused F-MD; (c) the acceptor N3;
(d) (i) Stille reaction using Pd(PPh3)4 in toluene at 120 °C for 24 h and (ii) Knoevenagel reaction using piperidine in chloroform, refluxed at 80 °C,
overnight; (e) energy level diagram.

Figure 2. Density functional theory (DFT) calculated optimized molecular structures and the frontier energy levels of (a) L-MD and (b) F-MD.

thieno[3,2-b]-thiophene (TT) has been widely used to
construct conjugated polymers to enhance backbone copla-
narity and crystallinity.41−46 Cao et al. incorporated the TT
unit into a small-molecule donor, enhancing the molecular
coplanarity and aggregated property. These features resulted in
highly efficient SMOSCs in contrast to a molecular donor
containing the linear 2,2′-bithiophene unit as a π-bridge (PCEs
changed from 5.71% for a linear species to 7.57% for a fused-
ring species).47 However, the incorporation of the fused-ring π-
bridge into the design of small-molecule donors (seen in Table
S1) has been rarely reported in comparison with polymer
donors and non-fullerene acceptors.
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Therefore, in this work, we utilized a fused-ring π-bridge unit
to construct a small-molecule donor and provided a systematic
comparison with its linear counterpart. Benzodithiophene
(BDT) with alkylthiophene side units as the core was selected
due to its superior advantages in designing conjugated
materials.48,49 The resulting small-molecule donor F-MD
(the structure is shown in Figure 1b) with rhodamine as end
groups was obtained through a simple two-step reaction with
Stille cross-coupling and Knoevenagel condensation, and the
donor L-MD29 with terthiophene as the bridge (as shown in
Figure 1a) was also synthesized according to the literature.29
SMOSCs based on F-MD as donor provided PCEs of up to
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Figure 3. (a) Normalized absorption spectra in CF solution (dashed lines) and thin films (solid lines), (b) CV curves vs Fc/Fc+ in thin films, and
(c) heating and cooling plots of DSC (second cycle) for the molecules L-MD and F-MD.

Table 1. Thermal, Optical, and Electrochemical Properties of the Small-Molecule Donors Used in This Work
material Td (°C) λmaxsol (nm)a λmaxfilm (nm)b λonsetfilm (nm) Egopt (eV)c HOMOCV (eV)d LUMOCV (eV)e
L-MD 391 506 590 725 1.71 −5.24 −3.49
F-MD 403 605 581 715 1.73 −5.30 −3.51
a
Absorption maximum in chloroform solution. bAbsorption maximum in thin-film state. cThe optical band gap was calculated through the onset of
the absorption edge. dEHOMO = −4.80 eV − Eox. eELUMO = −Ered − 4.80 eV.

Figure 4. (a) Device geometry of the SMOSCs, (b) J−V curves under AM1.5G (100 mW/cm2) illumination, and (c) the corresponding external
quantum efficiency (EQE) curves based on L-MD:N3 and F-MD:N3 blended films annealed at 100 °C. (d) Effective voltage bias Veff (Vbias − V0)
versus photocurrent Jph (Jlight − Jdark) and (e) Jsc and (f) Voc values versus light intensities based on the best performance of the L-MD:N3 and F-
MD:N3 films.

13.25%, while the PCE based on L-MD as donor was 8.12%.
The physical, crystalline, and optoelectrical properties of the
two molecules were systematically studied. The work
demonstrates that fused-ring design is an efficient method to
develop small-molecule donors for high-performance SCOSCs.
2. RESULTS AND DISCUSSION
2.1. Synthesis. We used an optimized synthetic route to
construct F-MD in comparison to L-MD,29 in which the key
precursor M2 containing −CHO and stannyl units was
developed. Therefore, two steps, including Stille cross-coupling
and Knoevenagel condensation, were performed to obtain F-
MD (Figure 1c and Scheme S1). F-MD was purified by
column chromatography in a high yield of over 85%. The
target products were characterized by nuclear magnetic
7095
resonance (1H NMR and 13C NMR) and MALDI-TOF mass
spectrometry. F-MD exhibited excellent solubility in organic
solvents, such as CF (chloroform), CB (chlorobenzene), and
dichloromethane, and showed excellent thermal stability as
confirmed by thermogravimetric analysis (TGA), as presented
in Figure S1.
2.2. DFT Calculations. The density functional theory
(DFT) method was calculated with the B3LYP/6-31G basis
set to obtain optimal molecule geometries and the orbitals of
L-MD and F-MD (Figure 2). The two donor molecules show
similar planar skeletons, while the dihedral angle of F-MD
between the BDT core and 4H-cyclopenta[1,2-b:5,4-b′]-
dithiophene (CPDT) plane is 7°. This angle is smaller than
the 13° for L-MD with a terthiophene unit as the π-bridge.
Since a better planarity of the fused-structure donor is helpful
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Table 2. Optimal Photovoltaic Parameters of OSCs with a Conventional Device Configuration
active layer treatment Voc (V)
L-MD:N3 as cast 0.90 (0.85 ± 0.079)
thermal annealinga 0.80 (0.80 ± 0.005)
F-MD:N3 as cast 0.83 (0.83 ± 0.003)
thermal annealinga 0.82 (0.82 ± 0.004)
a
The active layers were thermally annealed at 100 °C for 5 min. bThe average PCEs of OSCs were obtained from six parallel devices.
for π−π stacking of the molecules, an efficient charge transport
pathway would be generated in the OSC devices. The
calculated highest-occupied molecular orbital (HOMO) and
lowest-unoccupied molecular orbital (LUMO) levels are −2.82
eV and −4.93 eV for L-MD, and −2.92 eV and −5.05 eV for F-
MD, respectively.
2.3. Optical and Thermal Properties. Optical absorption
spectra of L-MD and F-MD in dilute chloroform solution and
spin-coated films are presented in Figure 3a. In the solution
state, there are different optical absorptions between L-MD
and F-MD with maximum peaks at 506 and 605 nm,
respectively. Notably, the absorption onset of F-MD was
enormously red shifted in comparison to that of L-MD,
indicating that the fused-ring π-bridge donor has a
preaggregation behavior in solution.50,51 This would be helpful
for F-MD to form pure crystalline domains in blended thin
films. From the solution to the film state, the two SMDs
exhibited bathochromically shifted and broader absorptions,
indicating the formation of molecular packing in the solid state.
Despite of the different absorption in solution, the absorption
range (412−724 nm) of F-MD in films was similar to that of
L-MD. We speculate that L-MD has better crystallinity than F-
MD in thin films, which will result in a huge difference in
morphology and photovoltaic performance.
The HOMO and LUMO levels of L-MD and F-MD were
also obtained via cyclic voltammetry (CV) with reference to
ferrocene/ferrocenium (Fc/Fc+) (Figure 3b). The CV results
indicate that L-MD possesses HOMO and LUMO levels of
−5.24 and −3.49 eV, while the energy levels of F-MD are
downshifted to −5.30 and −3.51 eV, respectively. It is worth
noting that the fused π-bridge design can downshift the
HOMO level of F-MD, which is beneficial for higher open-
circuit voltage (Voc) in OSCs.
The thermal properties of the conjugated molecules were
then studied by differential scanning calorimetry (DSC), as
shown in Figure 3c. Both of the SMDs exhibited a pair of peaks
in the heating and cooling cycle, while the peaks of L-MD
showed a higher enthalpy (ΔH) in comparison to F-MD. This
illustrated the better crystallinity of L-MD, which is consistent
with the absorption analysis. All of the optoelectrical and
thermal properties are summarized in Table 1.
2.4. Photovoltaic Properties. To obtain the results of the
photovoltaic performance of the two small-molecule donors, L-
MD and F-MD as electron donors were utilized to fabricate
OSCs with a conventional configuration. The conjugated small
molecules paired with the electron acceptor N352 to fabricate
bulk-heterojunctions with the architecture of ITO/PE-
DOT:PSS/active layer/PDINO/Ag.53 The devices were
systematically optimized, with regard to the ratio of donor
and acceptor, using different additives and various post-
treatments (thermal annealing and solvent annealing), as
shown in Tables S2−S6. The optimized J−V and EQE curves
www.acsami.org Research Article
Jsc (mA/cm2) FF PCEb (%)
1.61 (1.61 ± 0.039) 0.20 (0.21 ± 0.013) 0.29 (0.27 ± 0.012)
19.89 (20.02 ± 0.12) 0.52 (0.51 ± 0.009) 8.05 (7.97 ± 0.11)
20.90 (19.61 ± 0.69) 0.51 (0.50 ± 0.014) 8.78 (8.21 ± 0.40)
23.65 (22.87 ± 0.71) 0.68 (0.69 ± 0.014) 13.25 (13.01 ± 0.19)
are presented in Figure 4b,c, and the photovoltaic parameters
are presented in Table 2.
The as-cast L-MD-based devices exhibited a relatively low
PCE of 0.29%, while the PCE was enhanced to 8.05% with a
Voc of 0.80 V, a short-circuit current density (Jsc) of 19.89 mA/
cm2, and a fill factor (FF) of 0.52, respectively, through
thermal annealing (TA). We also changed the post thermal
annealing conditions, including temperature and treatment
time, to optimize the SMOSC cells (depicted in Table S5).
Similarly, the optimal F-MD:N3 blends with post-annealing
treatment provided a high PCE of 13.25% with a Voc of 0.82 V,
a Jsc of 23.65 mA/cm2, and a high FF of 0.68 (Figure 4b and
Table 2). Considering the relatively low HOMO offsets
between F-MD/L-MD and N3, we obtained the steady-state
photoluminescence (PL) spectra of neat N3, L-MD:N3, and F-
MD:N3 films (Figure S2). The PL quenching efficiencies of
95.1% (F-MD:N3) and 97.8% (L-MD:N3) indicated that the
holes were effectively transferred from N3 to F-MD or L-MD
molecules.54,55 The distinction in Jscs of SMD-based blended
films is also reflected in ethe xternal quantum efficiency (EQE)
spectra (Figure 4c). Both blends exhibited photoresponses in a
wide range of 300−950 nm. However, the EQE value of the F-
MD:N3 blend was over 70% in this region, which was
obviously higher than that of the L-MD:N3 films. We speculate
that the thermal annealing method could improve light
utilization and morphology in SMD:N3 blended films, which
further facilitate charge generation in OSCs.
We conducted voltage loss analysis to explain the different
Vocs of L-MD:N3- and F-MD:N3-based cells, which are shown
in Figure S3 and Table S7. The optical band gap (Eg) of N3
was defined by the intersection of the PL and absorption
spectra, which was 1.39 eV (Figure S3). The energy levels of
the charge transfer state (ECT) of the cells based on L-MD:N3
and F-MD:N3 are defined by fitting to the low-energy part of
the EQE and electroluminescence (EL) spectra using Marcus
theory.56 They exhibited similar ECT values of 1.308 eV for L-
MD:N3 and 1.317 eV for F-MD:N3 (Figure S3). Generally,
there are three parts of voltage loss in OSCs: the voltage loss
from the CT state (ΔECT), radiative recombination (ΔVrad),
and nonradiative recombination (ΔVnonrad).57 As shown in
Table S7, the cells based on L-MD:N3 and F-MD:N3
exhibited similar ΔECT and ΔVrad values but different ΔVnonrad
values (0.305 eV for L-MD:N3 and 0.204 eV for F-MD:N3).
The difference in nonradiative recombination results in a ca.
0.1 eV voltage loss, which is reponsible for the higher Vocs in F-
MD:N3-based cells.
To get insights into the charge transport in F-MD-based
cells, the space-charge-limited current (SCLC) measurement
was performed. The device geometry of ITO/PEDOT:PSS/
active layers/MoO3/Ag was applied to obtain the hole mobility
(μh), and the device structure of ITO/ZnO/active layers/
PDINO/Ag was exploited to obtain the electron mobility (μe)
(Figure S4). The mobilities were obtained from SCLC
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Figure 5. AFM (a, c) height and (b, d) phase images (3 × 3 μm2) of (a, b) L-MD and (c, d) F-MD thin films fabricated from chloroform.
GIWAXS images along with the corresponding profiles in thin films of (e) neat L-MD, (f) L-MD:N3, (g) neat F-MD, and (h) F-MD:N3.

Table 3. Crystallographic Parameters Exacted from the IP and OOP GIWAXS Profiles of L-MD:N3 and F-MD:N3 Blend Films
IP direction OOP direction
(010) (100)
−1 −1 −1
active layer q (Å ) d (nm) fwhm (Å ) a
CL (nm) q (Å ) d (nm) fwhm (Å−1) CLa (nm)
L-MD:N3 1.72 0.37 0.30 1.87 0.32 1.98 0.06 9.7
IP direction OOP direction
(100) (010)
−1 −1 −1
q (Å ) d (nm) fwhm (Å ) a
CL (nm) q (Å ) d (nm) fwhm (Å−1) CLa (nm)
F-MD:N3 0.34 1.87 0.08 6.73 1.82 0.35 0.46 1.23
a
CL (coherence length) = 2πk/f whm, here the shape factor k is 0.9.

measurement by using the equation as shown in eq 1. The μhs
of L-MD:N3- and F-MD:N3-based devices are 2.22 × 10−4
and 1.46 × 10−3 cm−2 V−1 s−1, and the calculated μe values of
L-MD:N3 and F-MD:N3 devices are 3.97 × 10−5 and 1.97 ×
10−4 cm−2 V−1 s−1, respectively. F-MD:N3 based devices
present the enhanced hole and electron mobilities, which is
beneficial for charge extraction and responsible for the elevated
Jsc and better photovoltaic performance.
The photocurrent density (Jph) versus effective voltage was
tested to study the exciton dissociation and extraction
processes of the SMOSCs, and the plots are presented in
Figure 4d. In the equation Jph = JL − JD, JL is the current
density measured under illumination conditions and JD is the
dark current density. On the other hand, Veff = V0 − VA, where
V0 is the voltage when Jph = 0, and VA represents the applied
bias voltage.58 In Figure 4d, the values of Jph for F-MD-based
devices reach saturation (Jsat) more quickly in comparison with
L-MD-based devices. After the value of Jsat is obtained, the Jph/
Jsat value for estimating the exciton dissociation performance
(P(E,T)) can be calculated, where the E and T parameters are
the electric field and room-temperature conditions, respec-
tively.59 Under the circumstances of short circuiting and the
maximum power output, the Jsc/Jsat values for exciton
dissociation efficiency and Jmax power/Jsat values for charge
collection efficiency were calculated. The values of F-MD:N3
devices are 98.28% and 76.29%, respectively, which are higher
than 92.56 and 64.51% for L-MD:N3 devices. This indicates a
better exciton dissociation and extraction process in F-MD-
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based OSCs, which is consistent with its high photocurent
density and FF.
Furthermore, the light-intensity (Plight) dependences of Jsc
and Voc were measured to analyze the charge recombination
properties (Figure 4e,f). From previous works, for a slope of
the Jsc versus light-intensity line with an α value close to 1, the
bimolecular recombination would dominate. The α values are
0.981 and 0.963 for F-MD-/L-MD-based devices, indicating
the more severe bimolecular recombination in L-MD-based
cells. However, in the Voc versus light intensity plots, the slopes
are related to monomolecular recombination, also named
Shockley−Read−Hall (SRH) recombination. The curves were
fitted according to the equation Voc ∝ nkBT/(q ln I),27 where
kB is the Boltzmann constant, T is the Kelvin temperature, and
q is the elementary charge, respectively. As shown in Figure 4f,
the value of the L-MD-based binary device is 1.85 kBT/q in
comparison with 1.50 kBT/q for the F-MD-based device. This
implies less trap-assisted recombination occurred in F-MD-
based devices, which is in the agreement with the better
photovoltaic performance of F-MD:N3 devices.
2.5. Morphology and Crystallinity Investigation. In
order to study the morphology of F-MD- and L-MD-based
films, atomic force microscopy (AFM) measurements were
utilized to analyze the surface morphology for these blended
films, as shown in Figure 5a−d. Although the root-mean-
square (RMS) value of the F-MD:N3 film is 3.02 nm,
exceeding the value of 1.32 nm for the L-MD:N3 system, the
L-MD:N3 blended film exhibited larger crystalline domains in
comparison to the F-MD:N3 film. This indicates that the L-
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MD:N3 blended film presented a large phase separation in
comparison to the F-MD:N3 blend. The proper phase
separation of F-MD:N3 blends between the donor and
acceptor parts may be beneficial for charge separation and
hinder the charge recombination probability, which further
influences the Jscs and FFs in the F-MD-based devices.
To investigate the crystallinity and molecular packing
properties of the two molecules, grazing incidence wide-angle
X-ray scattering (GIWAXS) methods were utilized to measure
the neat films and corresponding blended films.60 The 2D
GIWAXS imagess are shown in Figure 5, and the crystallo-
graphic parameters of the two blended films obtained by
GIWAXS measurements are summarized in Table 3. For the
neat L-MD films, there are clear π−π stacking (010) peaks at
1.73 Å−1 in the in-plane (IP) direction and lamellar packing
(h00) in the out-of-plane (OOP) direction (Figure 5e and
Table S8), which reveals that the neat L-MD films favor an
“edge-on” orientation with the alkyl chain direction of the L-
MD molecules being perpendicular to the glass in consid-
eration of the previous DFT calculations. When they were
blended with the acceptor N3, the blended films showed a
similar molecular packing mode with slightly decreasing
crystallinity (Figure 5f). The lamellar packing distance for
the L-MD:N3 film is 1.98 nm for the (100) diffraction peaks in
the OOP direction, and the π−π interaction distance is 0.37
nm for the (010) diffraction peaks at the IP direction (Table
3). In contrast, the pristine F-MD films showed a mixed
molecular orientation (Figure 5g and Table S9) and the F-
MD:N3 films presented a “face-on” dominated packing motif
with the OOP π−π stacking at the position of 1.82 Å−1 (Figure
5h and Figure S4). Therefore, the molecular packing mode of
the F-MD:N3 film enabled more favorable charge transport in
the vertical direction61 and facilitated the higher photocurrent
of F-MD:N3 based devices. The lamellar packing distance for
the F-MD:N3 film is 1.87 nm for the (100) diffraction peaks in
the IP direction. In addition, the (100) coherence lengths
(CLs) of the L-MD:N3 film in the OOP direction were
calculated to be 9.7 nm, while the CL value was 6.73 nm for F-
MD:N3 blends in the IP direction (Table 3). Similarly, the CL
value at the (010) peak for the L-MD:N3 film was larger than
that for F-MD:N3 blends, indicating the better crystallinity of
the L-MD:N3 blends. This means that the fused-ring π-bridge
design can effectively decrease the crystallinity and reduce self-
aggregation in the blended films, resulting in better phase
separation.62−64 This is also in agreement with the AFM
measurements.
3. CONCLUSIONS
In summary, a new type of SMD with a fused conjugated π-
bridge structure (F-MD) has been designed and synthesized.
F-MD possesses a BDT core, side chains, and terminal groups
(ethyl rhodamine) similar to those of other SMDs but uses
fused cyclopentathiophene as a π-bridge connecting unit. The
F-MD:N3-based OSCs can reach a better PCE of 9.59% in
comparison to the extremely low value of 0.29% of the donor
molecule L-MD with a linear bridge. After a thermal annealing
treatment, the F-MD based OSCs produced an obvious
enhancement in the PCE to 13.25%, which is the highest
performance among SMOSCs based on SMDs with a new
fused architecture, and is also comparable to those of state-of-
the-art SMOSCs. Further calculations and measurements
demonstrated that the fused-ring design effectively decreased
the crystallinity and reduces self-aggregation, enabling better
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phase separation in the blended films. These results reveal that
fused π-bridge-conjugated-based SMDs can successfully reach
a high photovoltaic performance in SMOSCs, which can be
used to design new conjugated materials.
4. EXPERIMENTAL SECTION
4.1. General Measurements. The 1H and 13C nuclear magnetic
resonance (NMR) spectra were measured with a 400 MHz
spectrometer (Bruker AVANCE) and tetramethylsilane (TMS) was
used as an internal standard. Fourier transform mass spectrometry
(FTMS) with high-resolution matrix-assisted laser desorption/
ionization (HR-MALDI) was carried out with a Varian 7.0T FTMS
instrument. Optical UV−vis−NIR absorption spectra were measured
with a U-2910 spectrophotometer; the slit width was 5.0 nm, and the
scan speed was 800 nm min−1. Cyclic voltammetry was performed
under an inert (N2) atmosphere; the scan rate was 0.1 V s−1, and the
electrolyte was tetrabutylammonium hexafluorophosphate in acetoni-
trile (1 M). Glassy carbon was used as the working electrode, Pt wire
was used as the counter electrode, and Ag/AgCl was used as the
reference electrode. The concentration of the electrolyte was
approximately 9 mg/mL. All potentials were corrected against Fc/
Fc+. Thermogravimetric (TGA) analysis data were obtained with a
thermogravimetric analyzer (PerkinElmer, TGA8000). Differential
scanning calorimeter (DSC) spectra of the small-molecule donors
were measured with a TA Instruments DSC250; the heating rate was
10 °C/min under a nitrogen atmosphere.
4.2. Atomic Force Microscopy (AFM) and GIWAXS. AFM was
conducted with a Multimode 8 atomic force microscope (Bruker) in
tapping mode. 2D scattering patterns were recorded using a Pilatus
2M detector, with the sample to detector distance calibrated using a
silver behenate reference standard. The measurements were
performed at the National Center for Nanoscience and Technology.
The sample and detector were enclosed in a vacuum chamber to
suppress air scatter. Scattering patterns were measured as a function of
the angle of incidence, with the data shown being acquired with an
angle of incidence near the critical angle that maximized scattering
intensity from the sample. Further details can be found in a previous
publication.60
4.3. Characterization of SMOSCs. The actual active area of all
the devices was 0.040 cm2. The J−V curves were measured using a 3A
solar simulator (XES-70S1, SAN-EI Electric Co., Ltd.) calibrated with
a standard Si photovoltaic cell loaded with KG5 filters (certificated by
the National Institute of Metrology) and a Keithley 2450 source-
measure unit under AM1.5G illumination at 100 mW cm−2. The EQE
data were obtained using a solar cell spectral response measurement
system (QE-R3011, Enli Technology Co. Ltd.). The thicknesses of
the films were measured by a surface profilometer (Dektak XT,
Bruker).
4.4. Hole and Electron Mobility (SCLC). SCLC mobility was
measured through the diode configuration ITO/PEDOT:PSS/active
layers/MoO3/Ag for hole mobility and ITO/ZnO/active layers/
PDINO/Ag for electron mobility by setting the dark current density
at 10−6 V and fitting the plots to a space-charge-limited form, where
SCLC is described by
9ε0 εr μ 0 V 2
J=
8L3 (1)
where J is the current density, L is the thickness of the active layer, μ0
is the hole or electron mobility, εr is the relative dielectric constant of
the transport media, ε0 is the permittivity of the vacuum (8.85 × 10−12
F m−1), V (=Vappl − Vbi) is the internal voltage of the device, Vappl is
the bias voltage, and Vbi is the built-in voltage of the two electrodes.
4.5. Fabrication of OSC Devices. The photovoltaic devices were
fabricated with the structure glass/ITO/PEDOT:PSS/donor:accep-
tor/PDINO/Ag. The ITO-coated glass substrates were sequentially
cleaned with detergent, water, deionized water, anhydrous ethanol,
and isopropyl alcohol under ultrasonication for 15 min each and dried
by a nitrogen blow. This cleaned ITO was also treated with a UV−
https://doi.org/10.1021/acsami.1c22135
ACS Appl. Mater. Interfaces 2022, 14, 7093−7101
ACS Applied Materials & Interfaces
ozone cleaner (30 min). PEDOT:PSS (AI 4038) was spin-coated with
a speed of 4000 rpm. Then the substrates were subjected to thermal
annealing at 150 °C for 15 min. The active layers were spin-coated
from chloroform solutions onto the PEDOT:PSS/ITO substrate. The
thickness of active layers was controlled to be 100−110 nm. PDINO
(1 mg/mL using MeOH as solvent) was spin-coated with a speed of
3500 rpm (40 s). Finally, an 80 nm Ag film was vacuum-deposited
under a high vacuum (<1 × 10−6 Pa). The effective area of the cells
was 4 mm2.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsami.1c22135.
Literature summary, materials synthesis, TGA, solar cell
performance, PL, EQE, EL, and SCLC, GIWAXS
images, and NMR and HR-MALDI (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Chengyi Xiao − Beijing Advanced Innovation Center for Soft
Matter Science and Engineering & State Key Laboratory of
Organic−Inorganic Composites, Beijing University of
Chemical Technology, Beijing 100029, People’s Republic of
China; orcid.org/0000-0002-7253-7136;
Email: xiaocy@mail.buct.edu.cn
Weiwei Li − Beijing Advanced Innovation Center for Soft
Matter Science and Engineering & State Key Laboratory of
Organic−Inorganic Composites, Beijing University of
Chemical Technology, Beijing 100029, People’s Republic of
China; orcid.org/0000-0002-7329-4236;
Email: liweiwei@iccas.ac.cn
Dongdong Xia − Institute of Applied Chemistry, Jiangxi
Academy of Sciences, Nanchang 330096, People’s Republic of
China; Email: xiadongdong@iccas.ac.cn
Authors
Shengxi Zhou − Beijing Advanced Innovation Center for Soft
Matter Science and Engineering & State Key Laboratory of
Organic−Inorganic Composites, Beijing University of
Chemical Technology, Beijing 100029, People’s Republic of
China
Shijie Liang − Beijing Advanced Innovation Center for Soft
Matter Science and Engineering & State Key Laboratory of
Organic−Inorganic Composites, Beijing University of
Chemical Technology, Beijing 100029, People’s Republic of
China
Baiqiao Liu − Beijing Advanced Innovation Center for Soft
Matter Science and Engineering & State Key Laboratory of
Organic−Inorganic Composites, Beijing University of
Chemical Technology, Beijing 100029, People’s Republic of
China
Jing Wang − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, Center for Advanced
Low-dimension Materials, College of Materials Science and
Engineering, Donghua University, Shanghai 201620, People’s
Republic of China
Zheng Tang − State Key Laboratory for Modification of
Chemical Fibers and Polymer Materials, Center for Advanced
Low-dimension Materials, College of Materials Science and
Engineering, Donghua University, Shanghai 201620, People’s
Republic of China; orcid.org/0000-0003-0036-2362
Complete contact information is available at:
7099
www.acsami.org Research Article
https://pubs.acs.org/10.1021/acsami.1c22135
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This study is jointly supported by Beijing Natural Science
Foundation (JQ210065) and NSFC (52073016, 92163128,
21905018) of China. This work was further supported by the
Fundamental Research Funds for the Central Universities
(buctrc201828, XK1802-2), the opening Foundation of State
Key Laboratory of Organic-Inorganic Composites, Beijing
University of Chemical Technology (oic-202201006), and the
Jiangxi Provincial Department of Science and Technology (No.
20192ACB20009).
■
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