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1,4-Azaborine based unfused non-fullerene

Cite this: J. Mater. Chem. A, 2023, 11,
acceptors for organic solar cells†
3653
Shihao Chen,‡a Minghao Dong,‡a Yuanqing Bai,a Yuting Chen,a Yuang Fu,b Lin Shao,a
Xinhui Lu,b Chunchen Liu, *a Kai Zhang, a Hongbin Wu a and Fei Huang *a

1,4-Azaborine, containing both boron and nitrogen in an aromatic hydrocarbon, displays unique electronic
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properties compared with its all-carbon analogue and shows great potential as a multiresonant thermally
activated delayed fluorescence material. However, conjugated molecules featuring 1,4-azaborine for
organic solar cells (OSCs) have not yet been explored. In this study, two novel acceptor–donor–
acceptor (A–D–A) conjugated molecules, ABBT-BO and ABBT-DT, using dithieno-1,4-azaborine as the
core D unit have been designed and synthesized. Both molecules exhibited excellent solubility, strong
and broad absorption and appropriate energy levels, enabling them to be promising candidates for non-
fullerene acceptors (NFAs). It was found that the shorter alkyl chain of ABBT-BO could endow the device
with superior morphology, resulting in more sufficient exciton dissociation, improved carrier transport
and suppressed charge recombination. Impressively, PM6:ABBT-BO based OSCs achieved a power
Received 25th November 2022
Accepted 15th January 2023
conversion efficiency (PCE) of 10.07% with an open-circuit voltage (VOC) of 0.900 V, a short-circuit
current density (JSC) of 16.41 mA cm−2, and a fill factor (FF) of 68.16%, which is the highest efficiency
DOI: 10.1039/d2ta09188g
reported for NFAs featuring BN-heteroarenes. This work demonstrates the significant potential of 1,4-
rsc.li/materials-a BN-heteroarenes for constructing novel NFAs toward high-performance OSCs.

synthesize appealing heteroarenes for constructing novel NFAs

Introduction toward high-performance OSCs.19–22
Organic solar cells (OSCs), as a promising renewable energy BN-heteroarenes, which employ both boron and nitrogen in
technology, have attracted great attention due to their distinct aromatic hydrocarbons, display unique electronic properties
advantages of light weight, exibility, semitransparency and compared with their all-carbon analogues and have shown great
solution processability.1–6 In the past few decades, great efforts potential for applications in organic electronics.23 Boron and
have been devoted to exploring various photoactive materials to nitrogen atoms can form a B)N coordinate bond or a B–N
promote the power conversion efficiency (PCE) of OSCs.7–13 In covalent bond (Fig. 1a).24 BN-heteroarenes embedded with
the past few years, the PCE of OSCs has soared to 19% mainly a B)N coordinate bond exhibit an electron-decient nature
owing to the discovery of small molecule non-fullerene accep- because of the positive charge of the nitrogen atom, which thus
tors (NFAs).14,15 In contrast to the fullerene acceptors, NFAs has been widely utilized for constructing various polymer and
possessed strong near-infrared (NIR) absorption and easy small molecule acceptors in OSCs.25–27 Meanwhile, BN-
structure-modication and readily tuned electronic energy heteroarenes featuring a B–N covalent bond are also competi-
levels.16,17 Nowadays, a lot of attention has been paid to the tive candidates for constructing conjugated materials for
structure optimization of typical NFAs of ITIC and Y6 deriva- organic electronics.28 Azaborines is the basic B–N covalent
tives, whereas NFAs based on novel conjugated backbones lack heteroarene, where two carbon atoms are respectively replaced
exploration.18 Therefore, it is of signicance to design and with boron and nitrogen atoms. According to the relative posi-
tions of B and N atoms, azaborines are classied as three
isomers: 1,2-azaborine, 1,3-azaborine and 1,4-azaborine
(Fig. 1a). Due to its worst thermodynamic stability, conjugated
a
State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer polymers/molecules containing 1,3-azaborine have not yet been
Optoelectronic Materials and Devices, School of Materials Science and Engineering,
explored.29 Very recently, Duan and co-workers successfully
South China University of Technology, Guangzhou, 510640, P. R. China. E-mail:
[email protected]; ms[email protected] employed 1,2-azaborine to construct polymer donor and small
b
Department of Physics, The Chinese University of Hong Kong, New Territories, Hong molecule NFAs for OSCs, and considerable device performances
Kong 999077, China were achieved.30,31
† Electronic supplementary information (ESI) available. See DOI: Compared with its 1,2- and 1,3-isomers, 1,4-azaborine
https://doi.org/10.1039/d2ta09188g exhibits moderate thermodynamic stability32 and some unique
‡ S. Chen and M. Dong contributed equally to this work.

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Fig. 1 (a) The classification of BN-heteroarenes featuring azaborines. (b) Chemical structures of PM6, ABBT-BO and ABBT-DT. (c) Schematic
energy diagram of PM6, ABBT-BO and ABBT-DT. (d) Normalized absorption spectra in chloroform solution. (e) Normalized absorption spectra of
neat films.

electronic properties due to the different p-electron distribu- noncovalent interactions. Both molecules exhibit good solu-
tions and dipole moments.29 Since the rst 1,4-azaborine-con- bility, strong NIR absorption, and appropriate energy levels,
taining anthracene was reported in 1961,33 numerous 1,4-BN- making them competitive candidates for NFAs. As a result,
heteroarenes have been designed and synthesized. In partic- OSCs with ABBT-BO/DT as acceptors have been successfully
ular, p-extended conjugated molecules featuring 1,4-azaborine fabricated. It was found that the length of branched alkyl chains
have attracted great interest due to their potential in multi- in the nitrogen atom of 1,4-azaborine will make a distinct
resonant thermally activated delayed uorescence (MR-TADF) difference to the exciton dissociation, carrier transport and
materials.34–36 However, to the best of our knowledge, conju- charge recombination in devices. Eventually, the optimal
gated molecules featuring 1,4-azaborine for OSCs are still PM6:ABBT-BO device achieved a PCE of over 10% due to its
unexplored. Therefore, it is necessary to design and synthesize superior morphology, higher exciton dissociation, increased
1,4-BN-heteroarene based donor/acceptors for OSCs and inves- carrier lifetime and suppressed charge recombination. To the
tigate the impact of 1,4-azaborine on material properties as well best of our knowledge, it is the highest performance for OSCs
as device performance. based on small molecule NFAs featuring BN-heteroarenes. As
Herein, dithieno-1,4-azaborine was used, for the rst time, the rst attempt to design and synthesize 1,4-BN-heteroarene
as the core unit to construct two novel A–D–A-type small based NFAs, this study may provide some inspiration for
molecule NFAs, ABBT-BO and ABBT-DT (Fig. 1a and b). The developing more BN-containing NFAs for high-performance
molecular skeleton exhibits good planarity because of the nearly OSCs.
planar structure of 1,4-azaborine and intramolecular S/O

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Paper Journal of Materials Chemistry A

Results and discussion absorption peak at 792 nm, slightly red-shied relative to that at
778 nm of ABBT-DT. Accordingly, optical bandgaps of 1.57 and
Materials synthesis and characterization 1.59 eV were deduced for ABBT-BO and ABBT-DT, respectively.
The synthetic routes of ABBT-BO and ABBT-DT are shown in The complementary absorption with PM6 and appropriate
Fig. S1 and S2.† Intermediates 2 with a butyl-octyl chain and 6 energy levels make these two 1,4-azaborine-containing mole-
with a decyltetradecyl chain were both obtained in a one-pot cules competitive candidates for NFAs in OSCs.
palladium-catalysed Buchwald–Hartwig cross-coupling reac-
tion with sequential formation of two C–N bonds. The incor- Calculated geometry and electronic properties
poration of a long alkyl chain on the nitrogen atom was
Density-functional theory (DFT) calculations were conducted to
essential to ensure sufficient solubility for the fabrication of
investigate the molecular geometry and energy levels at the
devices using the spin-coating method. The key intermediates 3
B3LYP/6-311+g(d,p) level using the Gaussian 16 package. To
and 7 were then generated by a selective Friedel–Cras-type C–
simplify the calculations, all alkoxy and alkyl chains were
H borylation from commercially available reagent PhBCl2.37
respectively replaced by methoxyl and methyl groups. As shown
Aer converting compound 3 and 7 to their respective bis-
in Fig. 2a, the conjugated skeleton exhibited good coplanarity
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tributyltin derivatives, 4 and 8, target NFAs (ABBT-BO and

due to the nearly planar 1,4-azaborine and S/O noncovalent
ABBT-DT) were then obtained via a Stille coupling reaction
interactions, which might be benecial for the intermolecular
followed by a Knoevenagel condensation reaction. Notably, the
packing and thus, improving the charge mobility.42–46 As shown
incorporation of alkoxy groups was in favor of the coplanarity of
in Fig. 2b, the HOMO energy level was mainly delocalized on the
the target molecules for the conformational “locks” via S/O
core dithieno-1,4-azaborine and alkoxyl thiophene moieties,
interactions38,39 as well as upshiing of HOMO energy levels for
whereas the LUMO energy level was distributed along the whole
a red-shied absorption.40 The molecular structures were thor-
molecule, indicating efficient p–p* conjugation between boron
oughly conrmed by 1H/13C nuclear magnetic resonance (NMR)
atoms with adjacent thiophenes.47 The calculated HOMO/
and matrix-assisted laser desorption/ionisation time-of-ight
LUMO was −5.99/−3.94 eV. The discrepancy between DFT
(MALDI-TOF) analyses (Fig. S11–S22†). Both NFAs exhibited
calculation results and CV measurements may be derived from
sufficient solubility in common organic solvents, such as chlo-
the intermolecular packing of ABBT-BO/ABBT-DT that was
roform, chlorobenzene and toluene, enabling the solution
generally ignored in the calculations.48
processability for neat and blend lms.
The electrostatic potential (ESP) is a physical property that
can reect the static charge distribution of a molecule, and it
Photophysical properties has been usually investigated to speculate the molecular
packing behaviour49 and the exciton dissociation progress in
The highest occupied molecular orbital (HOMO)/lowest unoc-
OSCs.50 As shown in Fig. 2c and S4,† negative ESP distributions
cupied molecular orbital (LUMO) energy levels were measured
for boron and its adjacent carbon atoms and positive distribu-
to be −3.97/−5.71 eV for ABBT-BO and 3.97/−5.72 eV for ABBT-
tions for nitrogen and its adjacent carbon atoms were observed,
DT by cyclic voltammetry (CV) tests (Fig. 1c and S3†). A negli-
indicating the obvious dipole moment between boron and
gible difference was observed for the electronic energy levels of
nitrogen atoms, which was similar to the ESP distribution in the
these two molecules. Absorption spectra of ABBT-BO and ABBT-
core of Y-series NFAs. The negative ESP distribution at the B-
DT in chloroform solution and neat lms are shown in Fig. 1d
side region was supposed to enhance the electron-accepting
and e, and the corresponding data are outlined in Table 1.
ability. Eventually, due to the incorporation of electron-
The length of the branched alkyl chain in 1,4-azaborine
decient B atoms, these molecules displayed similar ESP
made negligible difference to the solution absorption for ABBT-
distributions with Y-series NFAs51,52 along the conjugated
BO and ABBT-DT, both of which exhibited an identical peak
backbone, which was speculated to facilitate the intermolecular
located at 673 nm (Fig. 1d). Notably, both ABBT-BO and ABBT-
packing53,54 and exciton dissociation.
DT exhibited a maximum absorption coefficient of over 1.40 ×
105 M−1 cm−1, (Fig. S8†) which was comparable to that of the
star acceptor Y6.41 In thin lms, the absorption spectra of both Dielectric constant measurement
molecules exhibited a red-shi over 40 nm relative to those in Organic semiconductors typically have low dielectric constants
solution, resulting in a strong and broad absorption in the (3r < 3), resulting in high exciton binding energy of hundreds of
region of 500–800 nm (Fig. 1e). The ABBT-BO lm exhibited an meVs. A higher 3r is persistently pursued for organic

Table 1 Optical and electrochemical properties of ABBT-BO and ABBT-DT

lmax
lonset
Acceptors Solution Film [lm] Eopt
g [eV] EHOMO [eV] ELUMO [eV] Eg [eV] 3 [M−1 cm−1]

ABBT-BO 673 719 792 1.57 −5.71 −3.97 1.74 1.44 × 105
ABBT-DT 673 713 778 1.59 −5.72 −3.97 1.75 1.45 × 105

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Fig. 2 (a) Molecular geometries obtained by DFT calculations. (b) Calculated frontier molecular orbitals of the molecules, (c) ESP distribution on
the molecular surface of the ABBT-BO/DT backbone. (d) Dielectric constant versus frequency.

semiconductors to promote exciton dissociation and charge Photovoltaic performance

transport accompanied by decreased geminate and non-
Photovoltaic devices were fabricated with a conventional
geminate recombinations.55 Considering the unique dipole
conguration of ITO/PEDOT:PSS/PM6:ABBT-BO or ABBT-DT/
moment and electronic properties of a 1,4-azaborine unit, the 3r
PNDIT-F3N60/Ag. PM6 was selected as the polymer donor due to
values of ABBT-BO, ABBT-DT and Y6 were measured using the its matched energy levels and complementary absorption with
parallel-plate capacitance measurement with impedance spec- ABBT-BO/DT. The current density–voltage (J–V) curves of the
troscopy. The 3r values were obtained from the equation: C =
devices are shown in Fig. 3a, and the optimized performance
303rA/d, where C is the capacitance, 30 is the permittivity of free
parameters are summarized in Table 2. The PM6:ABBT-DT
space, A is the device area, and d is the thickness of the test lm.
device exhibited an open circuit voltage (VOC) of 0.902 V, a short
As shown in Fig. 2d, the 3r values were plotted as a function of
circuit current density (JSC) of 12.29 mA cm−2 and a ll factor
the frequency. Y6 showed an 3r of 3.64, consistent with the re-
(FF) of 56.11%, yielding a poor PCE of 6.24%. However, the
ported studies.56 A slightly lower 3r of 3.36 was observed for
PM6:ABBT-BO device achieved a PCE of 10.07% with an VOC of
ABBT-DT; however, ABBT-BO exhibited an 3r value of 4.05, even 0.900 V and a signicantly higher JSC of 16.41 mA cm−2 and FF
higher than that of Y6, which was speculated to facilitate the of 68.16%. To the best of our knowledge, this is the highest PCE
exciton dissociation in organic electronics.57,58 The lower
reported to date for small molecule NFAs featuring BN-
dielectric constant of ABBT-DT may be ascribed to the longer
heteroarenes.
alkyl chain that reduces the number of polarizable molecular
units in a given volume.59

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Fig. 3 (a) J–V characteristics and (b) EQE spectra of the optimal OSCs. (c) PL spectra of PM6 and PM6:NFA blend films. (d) Jph–Veff relationships
of PM6:ABBT-BO and PM6:ABBT-DT. (e) VOC versus light intensity curves and (f) JSC versus light intensity curves of PM6:ABBT-BO and
PM6:ABBT-DT.

The spectra of external quantum efficiency (EQE) are dis- exciton dissociation behaviours in OSCs (Fig. 3d). The Jph/Jsat
played in Fig. 3b. Both devices achieved a broad photo response value is dened as exciton dissociation efficiency, where Jph and
in the region of 400–800 nm, coinciding well with the combined Jsat respectively represent the photogenerated and saturation
absorption of PM6 and ABBT-BO/DT. Impressively, a thoroughly current density. The Jph/Jsat values were calculated to be 97.1%
stronger photo response was achieved for the PM6:ABBT-BO and 90.4% for PM6:ABBT-BO and PM6:ABBT-DT based devices.
device, which was in a good agreement with its higher JSC. As The higher Jph/Jsat value of the PM6:ABBT-BO based device
a result, JSC values of 15.61 and 12.07 mA cm−2 were deduced for suggests its more efficient exciton dissociation, which is
PM6:ABBT-BO and PM6:ABBT-DT, respectively, both of which consistent with the above PL-quenching results.
agree well with the JSC results obtained from the J–V curves The curves of JSC or VOC versus the light intensity (Plight) were
(within 5% error), validating the authenticity of device data. plotted to study the recombination behaviours in ABBT-BO/DT
To elucidate the underlying mechanism for the performance based devices. As shown in Fig. 3e, the Plight dependence of the
difference between ABBT-BO and ABBT-DT based devices, VOC was tted to reveal the trap-assisted recombination. The
exciton dissociation, charge recombination, carrier lifetime and slope approaching 1KT/q means weaker trap-assisted recombi-
transport were investigated. Photoluminescence (PL) emission nation in the devices (K is the Boltzmann constant, T is the
spectra of neat PM6 and PM6:ABBT-BO/DT lms are shown in temperature in units of kelvin, and q is the elementary charge).
Fig. 3c, and the PL emission of PM6 (excited at 615 nm) was The slopes for PM6:ABBT-BO and PM6:ABBT-DT devices were
largely quenched in both blend lms, indicating efficient deduced to be 1.23 and 1.56KT/q, respectively, indicating the
exciton dissociation at D/A interfaces. However, it should be severer trap-assisted recombination in PM6:ABBT-DT devices.
noted that the PL quenching efficiency of the PM6:ABBT-BO Additionally, the curves of JSC versus Plight were measured
lm (97%) is slightly higher than that of the PM6:ABBT-DT one (Fig. 3f) to clarify the bimolecular recombination. The rela-
(95%), showing more sufficient exciton dissociation in the tionship between JSC and Plight can be described as JSC f Plighta,
former lm. The photocurrent density (Jph) versus effective where a is the exponential factor which would be close to 1
voltage (Veff) curves were measured to gain further insight into when there is negligible bimolecular recombination. The slopes

Table 2 Photovoltaic parameters of the optimized solar cells based on ABBT-BO and ABBT-DT under standard AM 1.5 G illumination, 100 mW
cm−2

Entry VOC [V] JSC [mA cm−2] FF [%] PCEavea [%] PCEmax [%]

PM6:ABBT-BO 0.900 16.41 68.16 10.02
0.05 10.07

PM6:ABBT-DT 0.905 12.29 56.11 6.15
0.05 6.24
a
Average of more than 5 individual devices.

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extracted for PM6:ABBT-BO/ABBT-DT devices were 0.974 and The transient photovoltage (TPV) and transient photocurrent
0.959, respectively, indicating the weaker bimolecular recom- (TPC) decay measurements were also carried out to thoroughly
bination in the PM6:ABBT-BO device. The higher exciton understand charge properties including carrier lifetime,
dissociation efficiency, and lower trap-assisted and bimolecular recombination and extraction in devices. As shown in Fig. 4d,
recombination together veried the higher FF and JSC for the transient photovoltage decay lifetime of ABBT-BO and
PM6:ABBT-BO devices. ABBT-DT based devices was 190 and 137 ms, respectively. The
Moreover, the Platform for All-In-One Characterization of longer lifetime indicates the weaker premature recombination
Solar Cells and OLED (PAIOS) was used to gain insight into the of charge carriers in the PM6:ABBT-BO device. The TPC
charge recombination within active layers in operating measurement was conducted under short-circuit conditions,
devices.61–63 The charge density for devices based on ABBT-BO/ which reects the time from charge generation to charge
DT were shown as a function of bias light intensity (Fig. 4a). The collection by the electrode.64 A shorter TPC means more effi-
charge lifetime (s) was extracted from the transient photo- cient carrier transport and extraction progress in OSCs. By
voltage (TPV) decay dynamics. Obviously, at the same light tting the TPC curves as shown in Fig. 4e, the charge extraction
intensity, the PM6:ABBT-BO device exhibited higher carrier time was calculated to be 0.27 and 0.41 ms for ABBT-BO and
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density, suggesting the reduced charge recombination and thus ABBT-DT based devices, respectively. Overall, the results of TPV
higher photocurrent generation. Additionally, the PM6:ABBT- and TPC measurements indicated that the improvement of the
BO active layer displayed a higher s value than its ABBT-DT charge transfer and collection were signicantly enhanced in
counterpart in a wide range of light intensities (Fig. 4b). ABBT-BO based devices.
Furthermore, charge-extraction (CE) measurements were per- The hole (mh) and electron (me) mobilities were also
formed at various light intensities to estimate carrier densities measured by the space-charge-limited-current (SCLC) method
(n) for PM6:ABBT-BO/DT devices(Fig. 4c). An increased n value (Fig. S6 and S7†). The mh/me of PM6:ABBT-BO and PM6:ABBT-DT
can be obtained for the ABBT-BO based device, which agrees devices were 7.20/5.38 × 10−5, and 5.16/3.52 × 10−5 cm2 V−1
well with its higher JSC. The bimolecular recombination rate s−1, respectively. Accordingly, the mh/me ratio of 1.34 and 1.47
constants krec were then calculated from the s and n values were calculated for PM6:ABBT-BO and PM6:ABBT-DT devices,
according to krec = 1/(l + 1)ns (l is the recombination order). As respectively. Apparently, PM6:ABBT-BO based devices exhibited
shown in Fig. 4d, krec for the ABBT-DT based device was higher and more balanced charge transport, contributing to its
signicantly larger than that for the ABBT-BO based one. All of higher FF and JSC.
these results further revealed that the superior performance of Moreover, energy losses (Eloss) in ABBT-BO and ABBT-DT
the ABBT-BO based device was mainly derived from a higher based devices were measured by using the Fourier-transform
carrier lifetime and density, and reduced carrier recombination. photocurrent spectrum (FTPS) (Fig. S9†).65 In general, Eloss in

Fig. 4 (a) Charge density versus light intensity. (b) The carrier lifetimes and densities under different illumination intensities. (c) Charge lifetime
versus charge density. (d) Bimolecular recombination rate constant krec extracted from s and n. (e) TPV and (f) TPC characterization of
PM6:ABBT-BO and PM6:ABBT-DT.

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solar cells can be divided three parts: (1) DE1 is the intrinsic PM6:ABBT-DT lm. A root-mean-square roughness (Rq) of
radiative recombination loss in the Shockley–Queisser limit, 2.54 nm was observed for the PM6:ABBT-BO lm, remarkably
which is inevitable for all photovoltaic cells. (2) DE2 is the larger than 6.07 nm for the PM6:ABBT-DT one. The superior
additional radiative recombination energy loss, originating blend morphology of PM6:ABBT-BO was supposed to facilitate
from the extra absorption within the bandgap active layer in exciton dissociation, charge transport and eventually improve
BHJ OSCs. (3) DE3 results from the non-radiative recombination the device performance.
at the D/A interface in OSCs. As shown in Table S1,† the The Flory–Huggins interaction parameters (c) were calcu-
incorporation of different alkyl side chains showed weak lated to investigate the miscibility of PM6 with ABBT-BO and
impacts on Eloss. Unfortunately, a relatively high value of over ABBT-DT (Fig. S23 and Table S3†). According to the equation:
pffiffiffiffiffiffi pffiffiffiffiffiffi
0.70 eV was calculated for both ABBT-BO and ABBT-DT based cDA ¼ Kð gD  gA Þ2 ; where K is a constant, g is the surface
devices compared to Y6 based devices, which probably resulted energy, and D and A refer to donor and acceptor, respectively.
in the inferior Jsc and FF of the ABBT-BO/DT based device The c parameters were calculated to be 0.10 K and 0.28 K for
relative to the state-of-the-art devices. PM6:ABBT-BO and PM6:ABBT-DT, respectively. The higher c
parameter of PM6 and ABBT-DT prefers to form oversized
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Morphology phase separation, which is consistent with the TEM and AFM
It is well recognised that the nanoscale morphology of the active images.
layers is intimately connected with the exciton dissociation, Grazing-incidence wide angle X-ray scattering (GIWAXS) was
charge transport and recombination in OSCs.66 Transmission performed to reveal the intermolecular packing of ABBT-BO/DT
electron microscopy (TEM) and atomic force microscopy (AFM) lms as well as PM6:ABBT-BO/DT lms. Their 2D-GIWAXS
results were obtained as shown in Fig. 5. The homogeneously patterns and line-cut proles are presented in Fig. 6 and S9.†
distributed nanober microstructures in the PM6:ABBT-BO lm For the neat lms, PM6 had reections at approximately 0.99
were supposed to be favourable for exciton dissociation and Å−1 in the out-of-plane (OOP) direction and a weak lamellar
charge transport. In contrast, obvious island-like agglomeration stacking peak at approximately 0.30 Å−1 in the in-plane (IP)
could be observed in the PM6:ABBT-DT lm, leading to the direction (Table S2†). The p–p stacking peak could be attrib-
oversized phase separation caused by the ordered packing of uted to the reection at 1.74 Å−1 in the OOP direction, with a d-
the longer alkyl chain in ABBT-DT as reported in previous spacing of 3.22 Å. However, there were weak p–p stacking peaks
studies.67,68 As shown in the AFM images, the PM6:ABBT-BO but strong lamellar stacking peaks at approximately 0.33 Å in
lm showed a smoother top surface compared to the the OOP direction for both ABBT-BO and ABBT-DT neat lms,

Fig. 5 (a and b) TEM height images and (c and d) AFM images of PM6:ABBT-BO and PM6:ABBT-DT.

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Fig. 6 2D GIWAXS patterns of (a) PM6:ABBT-BO, (b) PM6:ABBT-DT and (c) the corresponding out-of-plane (black lines) and in-plane (red lines)
line cuts.
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indicating the random intermolecular packing mode. For the Author contributions
blend lms, the alkyl-to-alkyl lamellar packing in the OOP
direction plays a crucial and decisive role in determining the Shihao Chen designed and synthesised the molecules, con-
crystalline structure. The p–p stacking peaks of the PM6:ABBT- ducted the experiments and draed the original manuscript.
BO and PM6:ABBT-DT lms were located at 1.83 and 1.80 Å−1 in Minghao Dong fabricated the organic solar cells and contrib-
the OOP direction, with a d-spacing of 3.07 and 3.12 Å, respec- uted to the data analyses. Yuanqing Bai contributed to the
tively. The stronger and intensive p–p stacking peaks indicated theoretical calculations. Yuting Chen and Hongbin Wu carried
that the incorporation of PM6 enhanced the crystallinity of out the energy loss measurement. Yuang Fu and Xinhui Lu
blend lms. The crystal coherence length (CCL), which is closely performed the GIWAXS measurement. Lin Shao helped in data
related to the charge transport and device performance, was curation. Kai Zhang helped in device data analyses. Chunchen
extracted from the GIWAXS line proles. The CCL was calcu- Liu and Fei Huang guided and supervised the whole project. All
lated to be 21.97, 32.50 and 32.84 Å for the p–p stacking peaks authors discussed the results and commented on the
located at approximately 1.80 Å−1 for PM6, PM6:ABBT-BO and manuscript.
PM6:ABBT-DT, respectively. The longer CCL of blends lms
indicates that more ordered domains and tighter p–p stacking
were formed, which was benecial for the charge transport and
Conflicts of interest
reduced charge recombination. The authors declare no conicts of interest.

Conclusions Acknowledgements
In summary, dithieno-fused 1,4-azaborine was innovatively This work was nancially supported by the National Key
used for constructing two novel A–D–A structural molecules, Research and Development Program of China
ABBT-BO and ABBT-DT. These molecules possessed desired (2019YFA0705900) funded by MOST, the Basic and Applied
solubility, broad absorption, appropriate energy levels, unique Basic Research Major Program of Guangdong Province (No.
ESP distribution, high dielectric coefficient and coplanar 2019B030302007), the National Natural Science Foundation of
conformation, making them promising candidates for NFAs. China (No. U21A6002), and the Guangdong-Hong Kong-Macao
The OSCs with PM6 as the donor and ABBT-BO/DT as acceptors Joint Laboratory of Optoelectronic and Magnetic Functional
have been successfully fabricated, and it was found that the Materials (No. 2019B121205002).
length of branched alkyl chains in 1,4-azaborine could make
a signicant difference to the device performance. Impressively, References
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