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Research Article
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19.10% Efficiency and 80.5% Fill Factor Layer-by-Layer
Organic Solar Cells Realized by 4-Bis(2-Thienyl)Pyrrole-
2,5-Dione Based Polymer Additives for Inducing Vertical
Segregation Morphology
Mingwei Zhou, Chentong Liao, Yuwei Duan, Xiaopeng Xu, Liyang Yu, Ruipeng Li,
and Qiang Peng*
The morphology plays a key role in determining the charge generation and
collection process, thus impacting the performances of organic solar cells
(OSCs). The limited selection pool of additives to optimize the morphology
of OSCs, especially for the emerging layer-by-layer (LbL) OSCs, impeding
the improvements of photovoltaic performances. Herein, a new method of
using conjugated polymers as the additives to optimize the morphology for
improving the photovoltaic performances of LbL-OSCs is reported. Four poly-
mers of PH, PS, PF, and PCl are developed with different side chains.
These polymers exhibit poor performances as donor materials and additives
in the BHJ devices, due to the unsuitable energy level alignment and unfa-
vorable molecular interactions. By contrast, they can be served as efficient
additives to optimize the PM6 fibril matrix for facilitating the penetration of
BTP-eC9 and forming an intertwined D/A bicontinuous network with a ver-
tical segregation. Such morphology is optimized by side chain engineering,
which enables the progressive improvement of the charge separation and
collection. As a result, adding a small amount of PCl as the additive, the
optimized morphology contributes to a champion PCE of 19.10% with a high
FF of 80.5%.
M. Zhou, C. Liao, X. Xu, L. Yu, Q. Peng
School of Chemical Engineering and State Key Laboratory
of Polymer Materials Engineering
Sichuan University
Chengdu 610065, P. R. China
E-mail: qiangpeng@scu.edu.cn
Y. Duan
Key Laboratory of Applied Surface and Colloid Chemistry
Ministry of Education
Shaanxi Key Laboratory for Advanced Energy Devices
Shaanxi Engineering Lab for Advanced Energy Technology
School of Materials Science & Engineering
Shaanxi Normal University
Xi’an 710119, P. R. China
R. Li
National Synchrotron Light Source II Brookhaven National Lab
Suffolk, Upton, NY 11973, USA
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.202208279.
DOI: 10.1002/adma.202208279
Adv. Mater. 2022, 2208279 2208279 (1 of 11)
1. Introduction
Benefiting from the successful design of
non-fullerene acceptors (NFAs) and device
engineering, organic solar cells (OSCs)
have witnessed rapid progress in the last
few years. The state-of-the-art OSCs have
exceeded 19% power conversion efficiency
(PCE),[1–7] showing their great prospects
in commercial applications. Such high-
performance OSCs have predominately
employed a bulk heterojunction (BHJ)
structure in the photoactive layer, which
is formed by the spontaneous phase sepa-
ration of a pre-mixed solution of electron
donor (D) and acceptor (A) materials
during film deposition.[7,8] It is well estab-
lished that a bicontinuous and interpen-
etrating network created by the phase
separation of D and A materials in BHJ
photoactive layer is beneficial for exciton
diffusion and dissociation, charge transfer,
and collection.[9–12] For this purpose, many
useful morphology optimization strate-
gies have been developed, such as thermal
annealing (TA), solvent vapor annealing (SVA), solvent aging
(or delayed processing), opting additives, etc.[13–17] Despite sig-
nificant progresses being made, it is still challenging to pre-
cisely control and elucidate the BHJ morphology, as it is rather
complex (often multiple length scales) and comprises multiple
components, such as molecular crystallinity and packing ori-
entation, domain size and purity, miscibility, as well as vertical
composition distribution.[18–20] All these morphology compo-
nents play decisive roles in determining the ultimate photovol-
taic performances, which can be easily disturbed by different
processing and ambient conditions.[21,22] Specifically, the one-
step spin-coating method usually affords the intimately mixed
BHJ morphology with low molecular crystallinity and phase
purity,[23] and the resultant thermodynamically formed BHJ
morphology is also inadequate for achieving suitable vertical
phase separation, effective charge transfer and collection, which
needs fine and rigorous morphology control via adding addi-
tives, post treatments and interfacial modification.[21] Moreover,
BHJ blend films optimized by multiple strategies inevitably
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surfer from reproducibility issues, which impedes their transi-
tion from laboratorial research of small-area devices to indus-
trial production of large-area solar cell panels.[11,21,24]
Alternatively, processing the donor and acceptor materials
sequentially (layer-by-layer, LbL) to form a desired p-i-n-like
structure of the photoactive layer has become a competitive
option to circumvent the complicated morphology evolution
associated with conventional one-step deposition.[21,25] Such a
two-step procedure allows us to optimize the microstructure
of each layer independently, which enables us to overcome the
incompatibility arising from the thermodynamic miscibility
between the donor and acceptor materials, broadening the pro-
cessing window for fine-tuning molecular packing.[6,23,25,26] The
interdiffusion between the D and A layers can be controlled
by carefully selecting processing conditions to form favorable
vertical composition distribution with sufficient D/A interfaces,
and each layer can maintain its high crystallinity.[21,23,25,27,28] In
such an ideal morphology, the separated holes and electrons
migrate respectively into pure D and A domains and transport
more smoothly to the respective electrodes, which is beneficial
to inhibit bimolecular charge recombination and enhance the
charge collection efficiency.[6,28] These advantages, especially
the more tunable and flexible processing conditions, make the
LbL-OSCs have great potential for the scalable production of
large-area devices in the near future.[6]
With regard to the morphology optimization of LbL-OSCs,
the microstructure of underlying polymer donor layer plays
a key role in determining the vertically penetrated depth of
acceptor and sufficiency of D/A interfaces.[10,28–31] During film
deposition, polymer donors with adequate crystallinity force the
polymer chains to self-assemble into a well-defined nanofibril
matrix, in which NFAs can penetrate into the fibril mesh to
form a bicontinuous network morphology.[27] In this scenario,
it is crucial to rationally choose appropriate processing condi-
tions to modulate the aggregation of the polymer matrix. For
instance, PM6 is a commonly used donor polymer to fabricate
highly efficient LbL-OSCs, which shows good crystallinity and
self-assembly capability.[10,24,25,28,29,31–41] Nevertheless, in most
cases, the PM6 layer is directly casted from single solvents,
such as chloroform (CF),[31,35–38] chlorobenzene (CB)[32–34,42–44]
or o-xylene (o-XY),[40,41,45] etc., which cannot necessarily guar-
antee the adequate self-aggregation and polymer matrix for-
mation.[24] To optimize the morphology, the solvent additives
used in the traditional BHJ structure, such as 1,8-diiodooctane
(DIO)[10,34,38,40,41] and 1-chloronaphthalene (CN),[28,36,37,42–44]
were added to the acceptor solution to help swell the polymer
matrix. They do have positive effects on swelling the polymer
matrix for improving the vertical segregation of acceptors, but
they cannot induce significant impact on the already formed
polymer matrix film.[10] Adding additives directly into the donor
polymer solution could be more effective to finely tune the pol-
ymer microstructures, but it is still seldom studied.[10,24,28,29,39]
Only limited additives based on small molecules were applied
successfully to optimize the morphology of PM6 film for LbL-
OSCs,[24,28,29,39] and the underlying working mechanism needs
to be fully understood. For these reasons, hardly any LbL-OSCs
could realize a high fill factor (FF), which is closely related
to the active layer morphology, over the 80% threshold,[24,31]
leaving a large room for further development.
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In this work, we report the rational active layer morphology
optimization by introducing appropriate conjugated polymer
additives into the donor polymer solution for improving the
photovoltaic performances of LbL-OSCs (Figure 1). A series of
4-bis(2-thienyl)pyrrole-2,5-dione (BPD) based polymers, namely
PH, PS, PF and PCl, were designed and synthesized
by modifying the side chains of benzo[1,2-b:4,5-b′]dithiophene
(BDT) blocks (Figure 1a). The strong dipole moment of BPD
block was expected to induce intermolecular interaction with
the host polymer donor, while the side chain engineering (sul-
furation, fluorination, and chlorination) would enable to fur-
ther tune the interaction strength, thus optimizing the fibril
morphology. The morphology optimization ability of these
polymers as additives was investigated in the PM6/BTP-eC9
system (Figure 1b). In the BHJ blends, these polymer additives
exhibited limited effect on the morphology optimization, but
induced a more mixed phase of donor and acceptor materials.
By contrast, the addition of these polymer additives into the
pristine PM6 film could promote the polymer chain aggrega-
tion to form a more adequate polymer fibril matrix, facilitating
the penetration of BTP-eC9 into the polymer matrix and forma-
tion of intertwined D/A bicontinuous network with a favorable
vertical segregation. Such morphology was further optimized
by modifying the interaction strength between the host PM6
donor and the polymer additives via elaborate side chain engi-
neering, which enabled us to improve the charge separation
and collection progressively. As a result, adding a small amount
of PCl as the additive into the PM6 layer, the optimized ver-
tical phase separation morphology in the resulting LbL devices
contributed a champion PCE of 19.10% with a decently high FF
of 80.5%, which is a new record for the LbL-OSCs.
2. Results and Discussion
2.1. Materials Synthesis and Characterization
The synthetic routes of the polymers are shown in in Figure 1c,
and the synthetic details are provided in Supporting Informa-
tion. The amination of dibromide (1) with a 2-butyoctyl-1-amine
gave alkyl-substituted 3,4-dibromo-1-(2-butyoctyl)-pyrrole-2,5-
dione (2). The Stille-coupling reaction between compounds 2
and 2-(tributylstannyl)thiophene in the presence of Pd(PPh3)4
as a catalyst gave 3,4-bis(2-thienyl)-1-(2-butyoctyl)-pyrrole-2,5-
dione (3). Compound 4 was then brominated with N-bromo-
succinimide (NBS) to form the monomer M1 with a high yield
of 80%. The target polymers were obtained by Stille-coupling
of M1 with the specific organic tin monomers in the presence
of Pd2(dba)3/P(o-tolyl) as the catalyst. The molecular structure
of M1 was confirmed by nuclear magnetic resonance (NMR)
spectra. All these polymers show good solubility in common
solvents, such as chlorobenzene (CB) and chloroform (CF). As
determined by gel permeation chromatography with CF as the
eluent, the number-average molecular weight (Mn) and poly-
dispersity index (Ð) were measured as 44.8 kDa/1.47 for PH,
41.0 kDa/1.75 for PS, 40.9 kDa/1.69 for PF and 52.1 kDa/1.55
for PCl, respectively. The comparable molecular weights can
help to clarify the side chain effects on the overall properties. All
these polymers have good thermal stability with decomposition
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Figure 1. a) The chemical structures the polymer additives. b) The chemical structures of PM6 and BTP-eC9. c) The synthetic routes of polymer addi-
tives. d) Schematic illustration of active layer deposition of the BHJ and LbL-OSCs.
temperatures (Td, 5% weight loss) over 330 °C (Figure S1,
Supporting Information).
2.2. Basic Properties and Application Potential
as Polymer Donors
The UV–vis–NIR absorption spectra of these polymers in
diluted CF solutions and as films are shown in Figures 2a
and 2b, respectively. Owing to their same conjugated back-
bones, these polymers showed similar absorption profiles
in both solution and film state. Clearly red-shifted absorp-
tions were observed from solution to film state, indicating
the enhanced molecular packing of these polymers. The side
chain engineering has minimal effect on their optical bandgaps
(Egopt), which were estimated around 1.60 eV.
The frontier orbital levels of these polymers were meas-
ured by cyclic voltammetry (CV) experiments (Figure 2c).
The highest occupied molecular orbital (HOMO) and lowest
unoccupied molecular orbital (LUMO) levels were estimated
to be −5.55/−3.69 eV for PH, −5.60/−3.71 eV for PS,
−5.69/−3.83 eV for PF, and −5.71/−3.85 eV for PCl, respec-
tively (Figure 2d). These frontier energy levels were deeper than
the commonly used large bandgap polymer PM6 (HOMO/
LUMO = −5.41/−3.47 eV)[46] in NFA-based OSCs. These results
indicated that these polymers could be potentially used as
donor materials in NFA-based OSCs for obtaining high open-
circuit voltage (Voc).
The application potential of these newly developed poly-
mers as electron donors in NFA-based OSCs was studied by
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fabricating the OSCs with a conventional structure of indium
tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):poly(styrenes
ulfonate) (PEDOT:PSS)/active layer/PNDIT-F3N/Ag. BTP-eC9
(Figure 1b) was used as the electron acceptor. The detailed
fabrication procedure is presented in Supporting Information.
As shown in Figure 2e and Table S1, Supporting Information,
OSCs using PH as the donor achieved a Voc of 0.874 V, which
was higher than the PM6 based devices (0.84 V).[47] However,
the moderate short-current density (Jsc) of 18.57 mA cm−2
and very low FF of 47.37% limited to the PCE to 7.69%. The
Voc was increased to 0.895 V for PS based devices, owing
to the lower HOMO level. However, the largely decreased Jsc
of 14.23 mA cm−2 and lower FF of 46.47% lowered the PCE to
5.92%. These variation trends were also observed from PS
to PF based devices, the enlarged Voc of 0.932 V but dramati-
cally decreased Jsc of 3.64 mA cm−2 and FF of 42.79% resulted
in the poorer PCE of 1.45%. Furthermore, PCl based devices
afforded the lowest PCE of 0.54%, due to the synchronously
lowered Voc of 0.920 V, Jsc of 1.58 mA cm−2 and FF of 36.90%
compared to PF based devices. The degressive performances
was also confirmed by the external quantum efficiency (EQE)
spectra (Figure 2f ), the integral current density from the EQE
curves (JEQE) were 17.85, 13.24, 2.97 and 1.49 mA cm−2 for
PH, PS, PF and PCl based devices, respectively. The
progressively lowered PCE might be mainly due to the hardly
matched energy level alignment between the donor polymers
and BTP-eC9 acceptor (HOMO/LUMO = −5.67/−4.10 eV).[46]
Especially, PF and PCl have even deeper HOMO levels
than BTP-eC9, which are unfavorable for efficient charge
separation.
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Figure 2. Normalized UV–vis–NIR absorption spectra of the polymers a) in CF solutions and b) in film state. c) CV curves of the polymers. d) Energy
level diagram of the polymers and BTP-eC9 acceptor. e) J–V curves of the NFA-based OSCs using the polymers as electron donors. f) EQE spectra of
the NFA-based OSCs using the polymers as electron donors.
2.3. Application Potential as Polymer Additives
The application potential of these polymers that acted as addi-
tives were studied first by adding a trace amount of them into
the host BHJ layer of PM6:BTP-eC9 blend in the device of
ITO/PEDOT:PSS)/active layer/PNDIT-F3N/Ag. The addition
amount of these additives was determined to be 2.5 wt% rela-
tive to the host PM6 donor (Figure S2a and Table S2, Sup-
porting Information). The detailed fabrication procedure is
presented in Supporting Information. As shown in Figure 3a
and Table 1, the control devices without any additive obtained
as a high Voc of 0.851 V and Jsc of 26.72 mA cm−2. Whereas,
the moderate FF of 73.83% limited the PCE to 16.80%. Using
DIO as the additive, the Voc was not changed, while the sig-
nificantly increased FF of 77.6% and slightly enhanced Jsc
of 27.05 mA cm−2 resulted in the obviously improved PCE
of 17.87%. By comparison, the devices using the four poly-
mers as the additives exhibited little changes of the photo-
voltaic parameters. Among them, PF showed a slightly
higher Jsc of 26.78 mA cm−2 and FF of 74.83%, thus leading
to the mildly larger PCE of 16.95%. The additive effects on
the photovoltaic performances were also investigated by the
EQE measurements (Figure 3b). The devices based on DIO
additive exhibited a higher EQE response over all the absorp-
tion range than the other devices, which indicated the larger
JEQE. The calculated JEQE values were close to the Jsc values
obtained from the J–V curves (Table 1). These results demon-
strated these polymers could not serve as effective additives
to improve the performances of BHJ devices based on the
PM6:BTP-eC9 blend.
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In contrast to the minimal effects in the BHJ devices, we
found these polymers could largely improve the performances
of LbL devices. The addition amount of these additives in the
LbL devices was also determined to be 2.5 wt% relative to the
host PM6 donor (Figure S2b and Table S3, Supporting Informa-
tion). The control PM6/BTP-eC9 devices delivered a good Voc of
0.848 V, Jsc of 26.68 mA cm−2 and FF of 76.72%, give rising to the
PCE of 17.36% (Figure 3c and Table 1). Adding a small amount of
DIO into the PM6 layer, the slightly increased Jsc of 27.20 mA cm−2
and FF of 77.73% resulted in the higher PCE of 17.93%. Adding
a small amount of PH as the polymer additive into the PM6
layer, the resulting devices still showed no obvious photovoltaic
changes with a slightly enhanced PCE of 17.54%. Nevertheless, a
prominently enhanced PCE of 18.14% was achieved in the PS
additive-based devices, owing to the enhanced Jsc of 27.42 mA cm−2
and FF of 78.66%. Using PF as the polymer additive, the Jsc
was further improved to 27.76 mA cm−2 and FF of 79.06%, which
resulted in a higher PCE of 18.72%. Moreover, a champion PCE
of 19.10% was realized by introducing PCl as the polymer addi-
tive (certified as 18.93%, Figure S3, Supporting Information),
due to the higher Jsc of 27.81 and FF 80.50%. The enhanced
device performances were also confirmed by the EQE measure-
ments (Figure 3d and Table 1). To our best knowledge, this is
the first report of LbL devices that realize a high PCE of over
19% and FF of over 80% at the same time (Figure 3e and Table
S4, Supporting Information). As summarized in Figure 3f, both
the FF and PCE values for the BHJ and LbL devices modified
by various additives exhibited different variation trends, which
indicated the different working mechanism of these polymers in
these two types of devices.
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Figure 3. a) J–V curves of the BHJ devices without and with various additives. b) EQE curves of the BHJ devices without and with various additives.
c) J–V curves of the LbL devices without and with various additives. d) EQE curves of the LbL devices without and with various additives. e) The
summarized PCE versus FF plots of the LbL OSCs (the lines are guides to the eye). f) The comparison of FF and PCE values for BHJ and LbL devices
optimized by various additives.

2.4. Morphology Properties out-of-plane direction, corresponding to the lamellar stacking

Grazing incidence wide angle X-ray scattering (GIWAXS)
measurements were performed to study the additive effect on
the crystallinity and molecular packing behaviors. As shown in
Figure S4, Supporting Information, the four polymer additives
exhibited good crystalline nature and preferred face-on packing
with well-defined (100) diffractions around 2.87 nm−1 in the in-
plane direction and (010) diffractions around 16.8 nm−1 in the
distance (dl) of 2.19 nm and π–π stacking distance (dπ) of
0.374 nm, respectively. From PH to PS, PF and PCl, the
diffraction intensity and crystal coherent length (CCL) values
for both (100) and (010) diffractions were increased gradually,
indicating the improved molecular crystallinity. In compar-
ison, the pristine PM6 film coexisted in face-on and edge-on
packings (Figure 4). The (100) and (010) peaks were located at
2.90 nm−1 and 17.4 nm−1, respectively, corresponding to the

Table 1. Photovoltaic parameters of the devices without or with various additives.

Device Additive Voc [V] Jsc [mA cm−2] JEQEb) [mA cm−2] FF [%] PCE [%]
BHJ w/o 0.851 (0.851 ± 0.002)a)
26.72 (26.55 ± 0.16) 26.05 73.83 (73.16 ± 0.72) 16.80 (16.52 ± 0.16)
DIO 0.851 (0.850 ± 0.002) 27.05 (26.97 ± 0.20) 26.41 77.60 (76.48 ± 0.67) 17.87 (17.53 ± 0.24)
PH 0.850 (0.850 ± 0.002) 26.52 (26.34 ± 0.24) 25.80 74.26 (73.40 ± 0.86) 16.72 (16.44 ± 0.24)
PS 0.845 (0.846 ± 0.004) 26.68 (26.48 ± 0.25) 25.91 74.43 (73.55 ± 0.58) 16.78 (16.47 ± 0.22)
PF 0.846 (0.847 ± 0.002) 26.78 (26.59 ± 0.17) 26.12 74.83 (74.07 ± 0.64) 16.95 (16.68 ± 0.23)
PCl 0.846 (0.846 ± 0.002) 26.70 (26.58 ± 0.12) 26.01 74.46 (73.71 ± 0.52) 16.82 (16.58 ± 0.17)
LbL w/o 0.848 (0.847 ± 0.003) 26.68 (26.47 ± 0.16) 26.01 76.72 (75.93 ± 0.79) 17.36 (17.02 ± 0.23)
DIO 0.848 (0.846 ± 0.003) 27.20 (27.00 ± 0.21) 26.18 77.73 (77.36 ± 0.45) 17.93 (17.67 ± 0.19)
PH 0.851 (0.849 ± 0.003) 26.74 (26.50 ± 0.20) 26.09 77.06 (76.45 ± 0.54) 17.54 (17.20 ± 0.21)
PS 0.851 (0.850 ± 0.002) 27.42 (27.19 ± 0.23) 26.58 78.66 (78.14 ± 0.52) 18.35 (18.05 ± 0.24)
PF 0.853 (0.850 ± 0.004) 27.76 (27.49 ± 0.22) 26.67 79.06 (78.73 ± 0.47) 18.72 (18.05 ± 0.15)
PCl 0.853 (0.851 ± 0.003) 27.81 (27.53 ± 0.18) 27.04 80.50 (79.57 ± 0.71) 19.10 (18.64 ± 0.23)

a)Theaveraged values with standard deviations in the parentheses were calculated from 10 individual devices; b)The integrated current densities were calculated from the
EQE curves.

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Figure 4. GIWAXS patterns of PM6 film a) without additive, b) with DIO additive, and c) with PCl additive. d) The corresponding in-plane and out-
of-plane line-cuts. e) Zoom-in diffraction peaks of PM6 films treated without and with different additives. f) The summarized CCL values for the (100)
and (010) diffraction peaks of PM6 films treated without and with different additives (the lines are guides to the eye).

shorter dl of 2.16 nm and dπ of 0.361 nm. These results indi-
cated that PM6 had more compact molecular packing than the
polymer additives. Adding the PCl additive to the PM6 film,
the CCL for (100) and (010) diffractions were increased from
65.0 to 70.6 Å and from 21.8 to 24.6 Å, respectively, showing
the enhanced molecular packing intensity. While using DIO
as the additive, the CCLs were further enlarged to 72.4 Å for
(100) diffraction and 26.5 Å for (010) diffraction, implying that
the DIO additive had more impact on the molecular packing
order. The enhanced molecular packing by DIO additive could
also be observed in the BHJ blend film based on PM6:BTP-eC9
(Figure S5, Supporting Information). However, contrary to
the pristine film, the lowered molecular packing order was
observed in the PM6:BTP-eC9 blend film after being modified
by PCl additive.
To find the reason why the polymer additive induced dif-
ferent molecular packing behaviors in pristine PM6 film and
the BHJ film, we performed the droplet contact angle measure-
ments (Figures S6 and S7, and Table S5, Supporting Informa-
tion). The surface energies (γ) were calculated to be 29.7 and
38.24 mJ m−2 for PM6 and BTP-eC9, respectively. The γ dif-
ference forced the phase separation of the polymer donor and
NFA during film deposition. For these polymer additives, the
γ were 31.73, 32.15, 32.98 and 33.94 mJ m−2 for PH, PS,
PF and PCl, respectively, which were in the range between
PM6 and BTP-eC9. Therefore, it was expected to promote the
PM6 aggregation by adding these polymer additives, thus
leading to the improved polymer crystallinity. Compared to
other polymer additives, the larger γ discrepancy between PCl
and PM6 could enable higher ordered packing of PM6 donor,
which agreed well with the better performance of the LbL
devices when using PCl additive. The γ of the PM6:additive
(1:1 by weight) films were increased to 30.36, 30.91, 31.17 and
32.85 mJ m−2 for PH, PS, PF and PCl based blends,
respectively. Therefore, these polymer additives might enhance
the miscibility between the PM6 donor and BTP-eC9 acceptor
in the BHJ blends, thus weakening the phase separation. This
could explain the ineffectiveness of these polymer additives in
improving the performances of the BHJ devices. However, it
still not explained why the LbL devices using polymer additives
performed better than those using DIO additive, considering
that DIO could lead to higher ordered PM6 packing than the
polymer additives in the LbL active layers.
To get in-depth of the morphology evolution, atomic force
microscopy (AFM) and transmission electron microscopy (TEM)
measurements were conducted. The BHJ films without addi-
tive and with the polymer additives exhibited minimal changes,
along with the root-mean-square roughness (Rq) values around
0.9–1.0 nm (Figures S8 and S9, Supporting Information). Thin
nanofibers could be observed in the AFM phase images and
TEM images. By comparison, the BHJ film with DIO addi-
tive exhibited significantly enhanced phase separation with a
larger Rq of 1.51 nm. The AFM phase images and TEM showed
better interpenetrating networks with wider fibrils, favoring the
charge transport. These results explained the reason that the
performance of the BHJ devices was improved by DIO additive.

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Figure 5. AFM a–c) height images, d–f) tapping phase images of PM6 films. a,d) Pristine PM6 film. b,e) PM6 with DIO. c,f) PM6 with PCl. TEM
images of the LbL films g) without additive, h) with DIO additive, and i) with PCl additive.

The as-cast PM6 film exhibited relatively weak self-assembly
nature with a small Rq of 1.02 nm (Figure 5). Short and dense
rodlike aggregations could be observed in the AFM phase
image. Such weak self-assembly was preserved in the LbL
film, which was confirmed by the TEM image. After adding
the polymer additives, the resultant films exhibited gradual
aggregation with even an enlarged Rq of 1.07, 1.11, 1.19 and
1.21 nm for PH, PS, PF and PCl modified PM6 film,
respectively (Figure S10, Supporting Information). On the other
hand, more fibril like PM6 films could be observed by adding
these polymer additives, especially for the PF and PCl modi-
fied films, facilitating the charge extraction and transport. In
comparison, the DIO additive induced the excessive aggrega-
tion of PM6 film with a rather large Rq of 1.53 nm (Figure 5).
The fibril width was also enlarged markedly, which could lead
to the reduced D/A interfaces for the worse charge separation.
The different polymer matrix induced by various additives
might have an impact on the penetration of acceptor molecule in
the following deposition of its solution. The penetration degree
of BTP-eC9 in the PM6 donor matrix was studied by time-of-
flight secondary ion mass spectrometry (TOF-SIMS) meas-
urements (Figure 6a–c). The F−, CN−, SO3− and InO− signals
denoted the PM6, BTP-eC9, PEDOT:PSS and ITO, respectively.
The higher CN− intensity at a shorter sputter time indicated the
aggregation of BTP-eC9 at the top surface. With increasing
the sputter time, the CN− intensity decreased fast in the LbL
film without additive. In contrast, the CN− intensity in the DIO
modified LbL film exhibited a variation trend almost like the F−
intensity. Whereas, the CN− intensity in the PCl modified LbL
film exhibited a variation trend between those without additive
and with DIO additive. Considering the time-of-flight secondary
ion mass spectrometry (TOF-SIMS) had limited depth resolu-
tion (tens of nanometers),[48] we also performed depth inde-
pendent X-ray photoelectron spectroscopy (XPS) measurements
to further investigate the penetration depth of BTP-eC9 in the
PM6 donor. As shown in Figure 6d–f, the N 1s signals mainly
denoted the BTP-eC9 acceptor. Compared with the bulk inside
of the active layer, the top surface showed quite different N 1s
signals, which was attributed to the unavoidable surface con-
tamination. For the control LbL film without additive, the inten-
sity of N 1s signals dropped when the film depth was above
50 nm and became weak above 80 nm (Figure 6d). In contrast,
the LbL film with DIO additive exhibited more stable N 1s sig-
nals from 10 to 100 nm (Figure 6e). Whereas, the intensity of

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Figure 6. Depth independent TOF-SIMS of the LbL films: a) without additive, b) with DIO additive, and c) with PCl polymer additive. Depth inde-
pendent N 1s signals of the LbL films obtained by XPS: d) without additive, e) with DIO additive, f) with PCl additive. Schematic illustration of the
vertical phase separation of the LbL films: g) without additive, h) with DIO additive, and i) with PCl additive.

N 1s signals of the LbL film with PCl additive retained high
within 70 nm depth and then dropped gradually (Figure 6f).
A trace amount of N 1s signals could still be detected when the
film depth reached 100 nm, which might be contributed by the
PCl additive. These results indicated the different penetration
depths of BTP-eC9 in the PM6 donor matrix, which could be
schematically illustrated as shown in Figure 6g–i. As aforemen-
tioned, the poor aggregation of PM6 film without additive had
a dense and short rodlike matrix with insufficient interspaces
between these domains, which restricted the deep penetration
of BTP-eC9 and left a more unpenetrated portion of polymer
layer (Figure 6g). Whereas, the excessive polymer chain aggre-
gation of PM6 induced by DIO additive led to the oversized
polymer domains and large interspaces between domains, the
acceptors were readily to fill into these interspaces and even
reached the bottom anode, forming large acceptor domains
with insufficient D/A interfaces as well as characterless vertical
segregation morphology (like a BHJ structure, Figure 6h). In
both conditions, the effective charge dissociation and transport
are restrained, leading to serious charge recombination and
lower photovoltaic performances. Fortunately, the addition of
the polymer additive induced the moderately enhanced PM6
aggregation with a more appropriate polymer matrix, favoring
the penetration of BTP-eC9 acceptor and formation of a more
ideal vertical segregation morphology (Figure 6i). The ideal
vertical segregation could facilitate the charge separation and
transport, thus resulting in the better device performances.
2.5. Charge Generation Kinetics
The charge generation kinetics was studied by femtosecond
transient absorption spectroscopy (fs-TAS) measurements. The
ground-state bleach (GSB) signals of PM6 and BTP-eC9 were
around 630 and 850 nm, respectively (Figure S11, Supporting
Information). An excitation wavelength of 780 nm was chosen
to excite the acceptor to study the electron transfer processes
(Figure 7). Here, the kinetics of 630 nm was chosen to repre-
sent the PM6 GSB dynamic owing to the photoexcited BTP-eC9
displayed almost no signal there. The rising kinetics of PM6
GSB in the active layers directly reflected the hole transfer pro-
cess, which could be fitted by biexponential function. The hole
transfer process consisted an ultrafast hole transfer process at
the D/A interface, as characterized by τ1, as well as a diffusion

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Figure 7. fs-TAS spectra of the active layers. a) BHJ layer without additive. b) BHJ layer with DIO additive. c) BHJ layer with PCl additive. d) LbL layer
without additive. e) LbL layer with DIO additive. f) LbL layer with PCl additive. fs-TAS decay kinetics of the g) BHJ layers and h) LbL layers (pumped
at 780 nm, probed at 630 nm). i) Summarized τ1 and τ2 of the BHJ and LbL layers (the lines are guides to the eye).

mediated process controlled by domain size and aggregation
strongly, as characterized by τ2.[49] The τ1/τ2 were estimated to
be 0.35/9.48, 0.35/11.71 and 0.35/8.45 ps for the BHJ blends
without additive and with DIO and PCl additives, respec-
tively. These results showed the additives did not impact the
hole transfer process at the D/A interface but influenced the
exciton diffusion process. The larger τ2 of DIO modified BHJ
blend was associated with the enlarged phase separation and
domain size. Whereas, the reduced τ2 in the PCl modified
BHJ blend agreed with the improved miscibility between donor
and acceptor materials, which could lead to serious bimolecular
recombination of free charges. The τ1/τ2 values were estimated
to be 0.28/13.19, 0.33/13.82 and 0.22/12.24 ps for the LbL blends
without additive and with DIO and PCl additives, respectively.
The LbL films exhibited larger τ2 than the BHJ films, due to
the longer exciton diffusion distance in the vertical segregated
LbL films. However, LbL films had smaller τ1 than the BHJ
films, indicated the faster hole transfer at the D/A interfaces.
The PCl modified LbL film had smaller τ1 and τ2 values than
the other LbL films, which facilitated the more efficient charge
generation and lower monomer charge recombination. These
results could explain the reason that the PCl modified LbL
devices performed better performance than the other devices.
2.6. Device Stability and Generality
The photostability OSCs is an important factor when evalu-
ating their future application potentials. The photostability
of the encapsuled LbL-OSCs was tracked under continuous
illumination by using maximum power point (MPP) tracking
methods. As shown in Figure S12, Supporting Information,
the LbL devices without additive exhibited good stability with
85% of the initial PCE retained after 500 h continuous illumi-
nation. The DIO modified devices showed more obvious drop
of the PCE in the initial 200 h, which might be caused by the
negative effect of residual DIO additive. The PCE could retain
78% after 500 h continuous illumination. By comparison, the
PCl additive based devices exhibited better photostability with
91% of the PCE retained after 500 h continuous illumination,

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which indicated that the polymer additive could not only boost
the photovoltaic performance but also improve the photo
stability.
Another important factor is the generality of the polymer
additive in improving the device performance of various
LbL-OSCs. In this regard, we added the PCl additive into other
D/A systems, PBDTF/Y6[50] d PNDTS-T/Y6-T[51] (Figure S13,
Supporting Information), and evaluated the device perfor-
mances. The PBDTF/Y6 and PNDTS-T/Y6-T based LbL devices
without PCl additives obtained PCEs of 12.59% and 14.05%
(Figure S14 and Table S6, Supporting Information), respec-
tively, which were comparable to the previous reports in BHJ
devices.[50,51] After adding 2.5 wt% PCl into the polymer layer,
the PCEs were remarkably enhanced to 13.92% for PBDTF/
Y6 and 15.68% for PNDTS-T/Y6-T based devices, respectively.
These results demonstrated the new developed polymer have
good application generality as additive in improving the device
performance of LbL-OSCs.
3. Conclusion
In summary, we reported here a new method of using con-
jugated polymers as the additives to optimize the active layer
morphology for improving the photovoltaic performances of
LbL-OSCs. A series of BPD based polymers, namely PH, PS,
PF and PCl, were provided by modifying the side chains
of benzo[1,2-b:4,5-b′]dithiophene (BDT) blocks. Owing to the
unsuitable energy level alignment and molecular interactions,
poor performances were observed when these polymers were
used as donor materials. On the other hand, these polymers
also induced lower crystallinity and more mixed phase when
used as additives in the BHJ layer based on PM6:BTP-eC9, thus
showing ineffectiveness in improving the performance of BHJ
devices. Interestingly, the addition of these polymer additives
into the pristine PM6 film could promote the polymer chain
aggregation to form more adequate polymer fibril matrix, facili-
tating the penetration of BTP-eC9 into the polymer matrix and
formation of intertwined D/A bicontinuous network with a
favorable vertical segregation. Such morphology was further
optimized by modifying the interaction strength between the
host PM6 donor and the polymer additives via elaborate side
chain engineering, which enabled us to improve progres-
sively the charge separation and collection. As a result, when
adding a small amount of PCl as the additive into the PM6
layer, the optimized morphology in the resulting LbL-OSCs
contributed a champion PCE of 19.10% with a decent high FF
of 80.5%. Moreover, besides the good generality application in
other LbL-devices, the devices stability could also be improved
by such polymer additive. The results demonstrate the rational
design of polymer additives is a promising method to optimize
the morphology for maximizing the device performances of
LbL-OSCs.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
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Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (NSFC, 21825502, 22075190, 21905185, and
22105135), the School Local Science and Technology Cooperation
Special Funds of Sichuan University Zigong City (2020CDYB-28), Special
Fund for Strategic Cooperation Between Sichuan University and Yibin
Municipal People’s Government (2020CDZG-6), and the Fundamental
Research Funds for the Central Universities (YJ201957, YJ202069, and
YJ202116). The authors also thank National Synchrotron Light Source II
(NSLS-II, Contract No. DE-SC0012704) Brookhaven National Laboratory
for providing GIWAXS experiment time.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
Research data are not shared.
Keywords
4-bis(2-thienyl)pyrrole-2, 5-dione, layer-by-layer processing, morphology,
nonfullerene solar cells, polymer additive
Received: September 9, 2022
Revised: October 27, 2022
Published online:
[1] K. Chong, X. Xu, H. Meng, J. Xue, L. Yu, W. Ma, Q. Peng,
Adv. Mater. 2022, 34, 2109516.
[2] L. Zhu, M. Zhang, J. Xu, C. Li, J. Yan, G. Zhou, W. Zhong,
T. Hao, J. Song, X. Xue, Z. Zhou, R. Zeng, H. Zhu, C. C. Chen,
R. C. I. MacKenzie, Y. Zou, J. Nelson, Y. Zhang, Y. Sun, F. Liu,
Nat. Mater. 2022, 21, 656.
[3] R. Sun, Y. Wu, X. Yang, Y. Gao, Z. Chen, K. Li, J. Qiao, T. Wang,
J. Guo, C. Liu, X. Hao, H. Zhu, J. Min, Adv. Mater. 2022, 34, 2110147.
[4] C. He, Y. Pan, Y. Ouyang, Q. Shen, Y. Gao, K. Yan, J. Fang, Y. Chen,
C.-Q. Ma, J. Min, C. Zhang, L. Zuo, H. Chen, Energy Environ. Sci.
2022, 15, 2537.
[5] Y. Cui, Y. Xu, H. Yao, P. Bi, L. Hong, J. Zhang, Y. Zu, T. Zhang,
J. Qin, J. Ren, Z. Chen, C. He, X. Hao, Z. Wei, J. Hou, Adv. Mater.
2021, 33, 2102420.
[6] W. Gao, F. Qi, Z. Peng, F. R. Lin, K. Jiang, C. Zhong, W. Kaminsky,
Z. Guan, C. S. Lee, T. J. Marks, H. Ade, A. K. Jen, Adv. Mater. 2022,
34, 2202089.
[7] Y. Wei, Z. Chen, G. Lu, N. Yu, C. Li, J. Gao, X. Gu, X. Hao, G. Lu,
Z. Tang, J. Zhang, Z. Wei, X. Zhang, H. Huang, Adv. Mater. 2022,
34, 2204718.
[8] X. Xu, Y. Li, Q. Peng, Adv. Mater. 2022, 34, 2107476.
[9] L. Zhu, M. Zhang, W. Zhong, S. Leng, G. Zhou, Y. Zou, X. Su,
H. Ding, P. Gu, F. Liu, Y. Zhang, Energy Environ. Sci. 2021, 14, 4341.
[10] Q. He, W. Sheng, M. Zhang, G. Xu, P. Zhu, H. Zhang, Z. Yao,
F. Gao, F. Liu, X. Liao, Y. Chen, Adv. Energy Mater. 2021, 11, 2003390.
[11] R. Yu, H. Yao, Y. Xu, J. Li, L. Hong, T. Zhang, Y. Cui, Z. Peng,
M. Gao, L. Ye, Z. a. Tan, J. Hou, Adv. Funct. Mater. 2021, 31,
2010535.
[12] I. Angunawela, L. Ye, H. Bin, Z.-G. Zhang, A. Gadisa, Y. Li, H. Ade,
Mater. Chem. Front. 2019, 3, 137.
© 2022 Wiley-VCH GmbH

www.advancedsciencenews.com
[13] S. Yoon, E.-Y. Shin, N.-K. Cho, S. Park, H. Y. Woo, H. J. Son,
J. Mater. Chem. A 2021, 9, 24729.
[14] X. Xu, Y. Li, Q. Peng, Nano Select 2020, 1, 30.
[15] C. Cui, Y. Li, Aggregate 2021, 2, e31.
[16] X. Xu, G. Zhang, L. Yu, R. Li, Q. Peng, Adv. Mater. 2019, 31,
1906045.
[17] X. Xu, L. Yu, H. Yan, R. Li, Q. Peng, Energy Environ. Sci. 2020, 13,
4381.
[18] T. Shan, K. Ding, L. Yu, X. Wang, Y. Zhang, X. Zheng, C. C. Chen,
Q. Peng, H. Zhong, Adv. Funct. Mater. 2021, 31, 2100750.
[19] L. Ye, Y. Xiong, S. Li, M. Ghasemi, N. Balar, J. Turner, A. Gadisa,
J. Hou, B. T. O’Connor, H. Ade, Adv. Funct. Mater. 2017, 27,
1702016.
[20] Y. Xiong, L. Ye, A. Gadisa, Q. Zhang, J. J. Rech, W. You, H. Ade,
Adv. Funct. Mater. 2019, 29, 1806262.
[21] R. Yu, X. Wei, G. Wu, Z. a. Tan, Aggregate 2021, 3, e107.
[22] W. Zhong, Q. Hu, L. Ying, Y. Jiang, K. Li, Z. Zeng, F. Liu, C. Wang,
T. P. Russell, F. Huang, Y. Cao, Sol. RRL 2020, 4, 2000148.
[23] Y. Zhang, B. Wu, Y. He, W. Deng, J. Li, J. Li, N. Qiao, Y. Xing,
X. Yuan, N. Li, C. J. Brabec, H. Wu, G. Lu, C. Duan, F. Huang,
Y. Cao, Nano Energy 2022, 93, 106858.
[24] X. Xu, L. Yu, H. Meng, L. Dai, H. Yan, R. Li, Q. Peng, Adv. Funct.
Mater. 2022, 32, 2108797.
[25] H. Fu, Z. Peng, Q. Fan, F. R. Lin, F. Qi, Y. Ran, Z. Wu, B. Fan,
K. Jiang, H. Y. Woo, G. Lu, H. Ade, A. K. Y. Jen, Adv. Mater. 2022,
34, 2202608.
[26] D. Zhang, W. Zhong, L. Ying, B. Fan, M. Li, Z. Gan, Z. Zeng,
D. Chen, N. Li, F. Huang, Y. Cao, Nano Energy 2021, 85, 105957.
[27] K. Weng, L. Ye, L. Zhu, J. Xu, J. Zhou, X. Feng, G. Lu, S. Tan, F. Liu,
Y. Sun, Nat. Commun. 2020, 11, 2855.
[28] X. Wang, L. Zhang, L. Hu, Z. Xie, H. Mao, L. Tan, Y. Zhang, Y. Chen,
Adv. Funct. Mater. 2021, 31, 2102291.
[29] R. Yu, G. Wu, Y. Cui, X. Wei, L. Hong, T. Zhang, C. Zou, S. Hu,
J. Hou, Z. Tan, Small 2021, 17, 2103497.
[30] X. Li, R. Zhu, Z. He, X. Du, H. Lin, C. Zheng, G. Yang, Z. Chen,
S. Tao, ACS Appl. Mater. Interfaces 2022, 14, 25842.
[31] C. He, Y. Pan, G. Lu, B. Wu, X. Xia, C. Q. Ma, Z. Chen, H. Zhu,
X. Lu, W. Ma, L. Zuo, H. Chen, Adv. Mater. 2022, 34, 2203379.
[32] Y. Zheng, R. Sun, M. Zhang, Z. Chen, Z. Peng, Q. Wu, X. Yuan,
Y. Yu, T. Wang, Y. Wu, X. Hao, G. Lu, H. Ade, J. Min, Adv. Energy
Mater. 2021, 11, 2102135.
Adv. Mater. 2022, 2208279 2208279 (11 of 11)
15214095, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.202208279 by Orta Dogu Teknik Universitesi, Wiley Online Library on [27/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advmat.de
[33] Y. Yang, E. Feng, H. Li, Z. Shen, W. Liu, J. Guo, Q. Luo, J. Zhang,
G. Lu, C. Ma, J. Yang, Nano Res. 2021, 14, 4236.
[34] S. Liu, D. Chen, X. Hu, Z. Xing, J. Wan, L. Zhang, L. Tan, W. Zhou,
Y. Chen, Adv. Funct. Mater. 2020, 30, 2003223.
[35] H. C. Wang, P. Cheng, S. Tan, C. H. Chen, B. Chang, C. S. Tsao,
L. Y. Chen, C. A. Hsieh, Y. C. Lin, H. W. Cheng, Y. Yang, K. H. Wei,
Adv. Energy Mater. 2021, 11, 2003576.
[36] J. Chen, J. Cao, L. Liu, L. Xie, H. Zhou, J. Zhang, K. Zhang, M. Xiao,
F. Huang, Adv. Funct. Mater. 2022, 32, 2200629.
[37] K. Jiang, J. Zhang, Z. Peng, F. Lin, S. Wu, Z. Li, Y. Chen, H. Yan,
H. Ade, Z. Zhu, A. K. Jen, Nat. Commun. 2021, 12, 468.
[38] L. Zhan, S. Li, X. Xia, Y. Li, X. Lu, L. Zuo, M. Shi, H. Chen,
Adv. Mater. 2021, 33, 2007231.
[39] S. Y. Park, C. Labanti, J. Luke, Y. C. Chin, J. S. Kim, Adv. Energy
Mater. 2022, 12, 2103237.
[40] Y. Zhang, K. Liu, J. Huang, X. Xia, J. Cao, G. Zhao, P. W. K. Fong,
Y. Zhu, F. Yan, Y. Yang, X. Lu, G. Li, Nat. Commun. 2021, 12, 4815.
[41] J. Wan, L. Zeng, X. Liao, Z. Chen, S. Liu, P. Zhu, H. Zhu, Y. Chen,
Adv. Funct. Mater. 2021, 32, 2107567.
[42] S. Karuthedath, Y. Firdaus, A. D. Scaccabarozzi, M. I. Nugraha,
S. Alam, T. D. Anthopoulos, F. Laquai, Small Struct. 2022, 3,
2100199.
[43] W. Xu, X. Ma, J. H. Son, S. Y. Jeong, L. Niu, C. Xu, S. Zhang,
Z. Zhou, J. Gao, H. Y. Woo, J. Zhang, J. Wang, F. Zhang, Small 2022,
18, 2104215.
[44] H. Fu, W. Gao, Y. Li, F. Lin, X. Wu, J. H. Son, J. Luo, H. Y. Woo,
Z. Zhu, A. K. Y. Jen, Small Methods 2020, 4, 2000687.
[45] S. Dong, K. Zhang, B. Xie, J. Xiao, H. L. Yip, H. Yan, F. Huang,
Y. Cao, Adv. Energy Mater. 2019, 9, 1802832.
[46] L. Hong, H. Yao, Y. Cui, P. Bi, T. Zhang, Y. Cheng, Y. Zu, J. Qin,
R. Yu, Z. Ge, J. Hou, Adv. Mater. 2021, 33, 2103091.
[47] Y. Cui, H. Yao, J. Zhang, K. Xian, T. Zhang, L. Hong, Y. Wang, Y. Xu,
K. Ma, C. An, C. He, Z. Wei, F. Gao, J. Hou, Adv. Mater. 2020, 32,
1908205.
[48] J. Brison, S. Muramoto, D. G. Castner, J Phys Chem 2010, 114, 5565.
[49] Q. Wu, W. Wang, Y. Wu, Z. Chen, J. Guo, R. Sun, J. Guo, Y. Yang,
J. Min, Adv. Funct. Mater. 2021, 31, 2010411.
[50] X. Xu, Y. W. Lee, H. Y. Woo, Y. Li, Q. Peng, Chem. - Eur. J. 2020, 26,
11241.
[51] X. Xu, K. Feng, Y. W. Lee, H. Y. Woo, G. Zhang, Q. Peng,
Adv. Funct. Mater. 2020, 30, 1907570.
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