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com/science/article/pii/S2211285521009678
Manuscript_9409754f5291a3319f79308b40c10c20

Near-infrared absorbing polymer acceptors enabled by selenophene-fused core

and halogenated end-group for binary all-polymer solar Cells with efficiency

over 16%

Qunping Fana, Huiting Fub, Zhenghui Luoc, Jiyeon Ohd, Baobing Fana, Francis Lina,
Changduk Yangd, and Alex K.-Y. Jena,b,e,f,*

a
Department of Chemistry, City University of Hong Kong, Kowloon 999077, Hong
Kong, China
b
Department of Materials Science and Engineering, City University of Hong Kong,
Kowloon 999077, Hong Kong, China
c
Department of Chemistry, Hong Kong University of Science and Technology,
Kowloon 999077, Hong Kong, China
d
Department of Energy Engineering, School of Energy and Chemical Engineering,
Perovtronics Research Center, Low Dimensional Carbon Materials Center, Ulsan
National Institute of Science and Technology (UNIST), 50 UNIST-gil, Ulju-gun,
Ulsan 44919, South Korea
e
Department of Materials Science and Engineering, University of Washington,
Box352120, Seattle, Washington, USA
f
Hong Kong Institute for Clean Energy, City University of Hong Kong, Kowloon
999077, Hong Kong, China
E-mail addresses: alexjen@cityu.edu.hk (A. K.-Y. Jen)

© 2021 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
Abstract: Due to the vigorous development of polymerized small-molecule acceptors

(PSMAs), all-polymer solar cells (all-PSCs) have made tremendous advancement

recently. However, their power conversion efficiencies (PCEs) are still restricted by

the lack of PSMAs with desirable optoelectronic properties, especially the ability to

capture the near-infrared photons. To resolve this, two near-infrared absorbing

PSMAs, namely PY2Se-F and PY2Se-Cl, with a selenophene-fused core and

halogenated end-group are developed. Combining the synergistic effects of selenium

and fluorine (F)/chlorine (Cl) substitutions in broadening absorption and enhancing

intermolecular interactions, PY2Se-F and PY2Se-Cl show significantly red-shifted

absorption (30-40 nm) and reasonably deep-shifted lowest unoccupied molecular

orbital (LUMO) levels compared with the pristine PY2S-H and fluorinated PY2S-F.

When replacing F with Cl on the end-group, the PY2Se-Cl shows a better blend

morphology with polymer donor PM6, compared with the PY2Se-F-based one,

leading to better charge transport. As a result, the PM6:PY2Se-Cl-based all-PSCs

achieve an impressive PCE of 16.1% with both high short-circuit current density (Jsc)

of 24.5 mA cm-2 and fill factor (FF) of 0.743, which are among the highest values in

the reported binary all-PSCs so far. Notably, this is the first example of chlorinated

end-group derived PSMAs. Combining with the low-cost merit of chlorination,

PY2Se-Cl shows great potential in the practical applications of efficient all-PSCs.

Keywords: all-polymer solar cells; halogenation; near-infrared absorbing polymer

acceptors; power conversion efficiencies; selenophene

2
1. Introduction

Recently, organic solar cells (OSCs) as an emerging clean-energy source, with the

advantages of lightweight, low-cost fabrication, and potential flexibility and

semi-transparency, have made significant progress [1-4]. Thanks to the rapid

advancements of fused-ring small-molecule acceptors (SMAs) with a typical

molecular backbone of A-DA'D-A (A: acceptor, D: donor) configuration, like Y6 and

its derivatives with strong absorption in near-infrared (NIR) region and low energy

loss in devices [4-6], the state-of-the-art power conversion efficiencies (PCEs) of over

18% have been achieved in the SMA-based OSCs [7-12]. All-polymer solar cells

(all-PSCs) consisting of tightly entangled polymer donor and polymer acceptor are

considered as the most promising candidate for practical applications in wearable

electronics due to their superior stability under thermal and mechanical stresses

[13-16].

Before 2017, most of the polymer acceptors only demonstrated low PCEs of <12%

in all-PSCs due to their shortcomings, such as low extinction coefficient of ~10-4 cm-1

for the naphthalene/perylene diimide-based ones and narrow absorption window

limited in 300-700 nm for the B←N-bridged ones (Fig. S1) [14,17,18]. To overcome

the above-mentioned deficiencies, Li et al. reported a novel design strategy by

polymerizing small molecule acceptors (PSMAs) to construct efficient polymer

acceptors with desirable optoelectronic properties similar to their SMA precursor and

excellent mechanical properties [19]. As a demonstration of this strategy, PZ1 being

the first PSMA obtained a record PCE of 9.19% in all-PSCs [20], as it inherits the

3
merits of its SMA precursor (IDIC-C16), including a wide absorption spectrum of

300-800 nm, high extinction coefficient of >105 cm-1, and relatively high-lying lowest

unoccupied molecular orbital (LUMO) level of -3.86 eV. In the following years,

numerous PSMAs based on IDIC derivatives have been reported and achieved PCEs

approaching 13% (Fig. S2) [21-23], which testifies the effectiveness of this strategy.

Recently, benefiting from the excellent absorbance in the NIR region (800-900 nm)

and small photovoltage losses in Y-series SMAs, the Y-series PSMAs have achieved

the PCEs of over 14% in binary all-PSCs due to both high short-circuit current

densities (Jsc) of 20-24 mA cm-2 and high open-circuit voltages (Voc) of 0.88-0.95 V

(Fig. S3) [24-36]. To further broaden the absorption spectra of Y-series PSMAs,

fluorine (F) atoms have been introduced onto end-group (mono-fluorinated in the 4-,

5/6-, or 7-position, and difluorinated in the 4,6-positions), enhancing the PCEs of

binary all-PSCs to over 15% (Fig. S4) [37-39]. However, compared to the Y-series

SMAs with 5,6-difluorinated end-groups, such as the most classical Y6 [4], the

above-mentioned PSMAs with fluorinated end-group possess rather limited

absorption spectra [37-39], mainly due to the weakened intramolecular charge transfer

(ICT) between fused-ring core and end-group in their precursors.

Plenty of studies indicate that, due to the better orbital overlap in the π-conjugated

systems and more polarizable delocalized electron cloud of selenium (Se) atom

compared to sulfur (S) atom, selenophene shows enhanced quinoidal character and

weakened aromaticity compared to thiophene, rendering much lower bandgap and

significantly improved Jsc in photovoltaic materials based on selenophene unit than

4
their thiophene-based counterparts, especially in the previously reported Y-series

SMAs with a selenophene-fused core (Fig. S5) [40-46]. Recently, the introduction of

selenophene-fused DA'D core has also been carried out to broaden the optical

absorption of Y-series PSMAs [29]. Compared to the Se-free PFY-0Se,

selenophene-fused PFY-3Se has a ~30 nm red-shifted absorption and better

charge-transporting properties, which boosts the Jsc from 20.9 to 23.6 mA cm-2 in

all-PSCs [29]. Although the above two strategies of fluorination on end-group and

selenophene-fusion on DA'D core have shown great effectiveness in improving

optical absorption and device efficiency, there is still a strong need to further broaden

the absorption window in order to compete with the classical Y-series SMAs for

improving the PCE of all-PSCs.

By combining the aforementioned two effective molecular design strategies, two

novel PSMAs, namely PY2Se-F and PY2Se-Cl, with a selenophene-fused DA'D core

and different halogen atoms of F and chlorine (Cl) substituted end-groups were

designed and synthesized, as shown in Scheme 1. Notably, this is the first example of

chlorinated end-group derived PSMAs, although chlorination is simpler and cheaper

than fluorination in synthesis [47,48]. For a better comparison, two additional PSMAs

of the pristine PY2S-H and fluorinated PY2S-F were also prepared. Compared to

PY2S-H, PY2S-F shows a ~10 nm red-shifted absorption and a slightly deeper-lying

LUMO level, while both PY2Se-F and PY2Se-Cl exhibit significantly red-shifted

absorption onset of ~40 nm and reasonably deep-shifted LUMO levels. Moreover, the

introduction of Se and halogen atoms into the polymer backbone enables these

5
PSMAs to show variable crystallinity, molecular packing, and electron mobility,

resulting in different physical processes in their devices. In the all-PSCs pairing with

polymer donor PM6, three PSMAs of PY2S-H, PY2S-F, and PY2Se-F achieved

gradually increased PCEs from 14.8% to 15.6% due to both increased Jsc and fill

factor (FF). When replacing F atom with Cl atom on the end-group of PSMAs, the

PM6:PY2Se-Cl blends showed a better active layer morphology compared to that of

PM6:PY2Se-F blends, which is beneficial to obtain better charge transport in devices,

leading to a higher FF of 74.3%. As a result, the PM6:PY2Se-Cl-based all-PSCs

achieved an impressive PCE of up to 16.1%, which is one of the highest values in the

reported binary all-PSCs so far.

Scheme 1. (a) End-groups and (b) DA'D cores applied to PSMAs in this work. (c)
Molecular structures of four PSMAs, namely PY2S-H, PY2S-F, PY2Se-F, and
PY2Se-Cl, and (d) the corresponding synthetic routes.

2. Results and discussion

Molecular structures and synthetic routes of four PSMAs are shown in Scheme

1c,d. The key monomers of ICBr-F [38], ICBr-Cl [49], and BP2Se-CHO [29] were

6
synthesized according to literatures. The final monomers of Y2SBr-H, Y2SBr-F,

Y2SeBr-F, and Y2SeBr-Cl were synthesized and characterized via 1H NMR, 13

C

NMR, and mass spectra measurements (Fig. S6-S8), respectively. The synthetic

procedures are provided in the Supporting Information. By using high-temperature gel

permeation chromatography with 1,2-dichlorobenzene as the eluent, the

number-average molecular weights (Mn) and dispersity (Ð) were measured as 11.1

kDa/1.70 for PY2S-H, 10.4 kDa/1.54 for PY2S-F, 12.5 kDa/1.69 for PY2Se-F, and

10.5 kDa/1.75 for PY2Se-Cl, respectively. All four PSMAs show good solubility in

common solvents with gentle heating under stirring, such as chloroform and toluene.

The optical properties of four PSMAs were studied. In thin-films, compared to the

pristine PY2S-H, PY2S-F shows a slightly red-shifted absorption of ~10 nm (Fig. 1a),

as fluorination enhances the electron-withdrawing strength of end-group. By

introducing additional Se atoms onto the central core, PY2Se-F and PY2Se-Cl show

further broadened absorption of ~30 nm compared with PY2S-F, implying the

effectiveness of our molecular design strategy in broadening absorption window.

Different from the previous reports that SMAs with chlorinated end-group tend to

have red-shifted absorption compared to their fluorinated analogues [50],

selenophene-fused PY2Se-F and PY2Se-Cl display similar absorption spectra, which

could be due to the steric hindrance effect of chlorine atoms lowering the coplanarity

of conjugated backbone. A similar phenomenon was observed in the previous report

[51]. Compared to the Se-free PY2S-H and PY2S-F, the PY2Se-F and PY2Se-Cl

show significantly increased absorption coefficient from 1.03×105 to 1.27×105 cm-1

7
(Fig. S9), which helps to capture more photons. The absorption peaks of PY2S-H,

PY2S-F, PY2Se-F, and PY2Se-Cl in neat films are located at 810, 818, 839, and 837

nm, respectively. Thus, PY2Se-F and PY2Se-Cl are more complementary to PM6 in

terms of optical absorption compared with those from PY2S-H and PY2S-F (Fig. 1b).

Compared with the classical SMA, Y6 [4] and state-of-the-art PSMA, PY2F-T [39]

with difluorinated end-group, both PY2Se-F and PY2Se-Cl show red-shifted

absorption peaks and/or onset (Fig. S10). Different from the similar absorption

spectra of PY2Se-Cl and PY2Se-F in neat films, PY2Se-Cl shows a blue-shifted

absorption compared to PY2Se-F in dilute chloroform (Fig. S11). The larger red-shift

from the solution to the neat film indicates that PY2Se-Cl neat film has better

dispersion in solution, which may improve its adjustability in the film-forming

process.

As exhibited in Fig. S12 and Fig. 1c, the highest occupied molecular orbital

(HOMO) and LUMO energy levels were probed by cyclic voltammetry measurement

as -5.76/-3.87 eV for PY2S-H, -5.78/-3.91 eV for PY2S-F, -5.76/-3.93 eV for

PY2Se-F, and -5.75/-3.93 eV for PY2Se-Cl, respectively. With similar absorption

spectra, selenophene-fused PY2Se-F and PY2Se-Cl display almost same HOMO and

LUMO levels, while Se-free PY2S-H and PY2S-F have relatively higher LUMO

levels.

To investigate the effects of inserting halogen and Se atoms into polymeric

backbone on molecular packing properties in neat film, grazing incidence wide-angle

X-ray scattering (GIWAXS) measurements were performed (Fig. 1d,e and Table S1).

8
In the out-of-plane (OOP) direction, all the PSMA neat films exhibit the strong (010)

diffraction peaks located at 1.55-1.58 Å-1 with similar crystallite coherence lengths

(CCLs) of 2.20-2.37 nm, suggesting the similar and intense π-π stacking of polymeric

backbones. Notably, four PSMAs possess similar π-π stacking d-spacing of ~4.00 Å,

while the halogenated and/or selenophene-fused PY2S-F, PY2Se-F, and PY2Se-Cl

show obviously smaller lamellar d-spacing of 15.2-16.8 Å calculated from (001)

peaks in the in-plane (IP) direction compared with the pristine PY2S-H (18.4 Å).

Moreover, by inserting halogen and Se atoms into polymeric backbone, PSMAs

obtained gradually increased electron mobilities (μe) from 8.01×10−4 to 10.8×10−4 cm2

V-1 s-1 as retrieved by the space-charge-limited-current (SCLC) method (Fig. S13 and

Table S2), while selenophene-containing PY2Se-F and PY2Se-Cl achieved similar μe

values.

9
Fig. 1. (a) Absorption spectra of four PSMA neat films and (b) the corresponding
blend films. (c) Energy level diagrams of active materials. (d) GIWAXS 2D-profiles
and (e) the corresponding line-cuts of four PSMA neat films.

To study the effects of inserting halogen and Se atoms into molecular backbone on

photovoltaic performance, all-PSCs with a device structure of ITO/PEDOT:PSS/PM6:

PSMA/ PFN-Br/Ag were fabricated, and the corresponding fabrication processes were

provided in the Supporting Information. For a clear comparison, the current

density-voltage (J-V) curves of four optimal all-PSCs with different PSMAs are

displayed in Fig. 2a and the related photovoltaic data are summarized in Table 1,

respectively. The pristine PY2S-H achieved a PCE of 14.8% with a high Voc of 0.941

V, Jsc of 22.3 mA cm-2, and FF of 0.707 in all-PSCs, which are comparable to the

reported analogue PY-IT with shorter side-chains [30]. By introducing F atom onto

molecular backbone, PY2S-F obtained a slightly higher PCE of 15.1% due to the

optimized trade-off between Voc (0.920 V) and Jsc (23.3 mA cm-2). After further

introducing Se atom, PY2Se-F and PY2Se-Cl achieved continuously increased Jsc of

~24.5 mA cm-2 and slightly decreased Voc of ~0.885 V due to the significantly

broadened absorption spectra and slightly deeper-lying LUMO levels. When Cl was

introduced instead of F onto end-group, PY2Se-Cl obtained a higher FF of 0.743 than

PY2Se-F with an FF of 0.722, which results in an impressively high PCE of 16.1% in

the binary all-PSCs (Fig. 2b and Table S3).

As shown in Fig. 2c, external quantum efficiency (EQE) measurements were

performed to verify the reliability of Jsc values in this work. Compared to the

10
PY2S-H-based device, the PY2S-F-based device shows a slightly red-shifted EQE

response of ~10 nm, while the PY2Se-F- and PY2Se-Cl-based devices exhibit

obviously broadened EQE response of ~40 nm, which is consistent with the

absorption spectra of PSMA neat films and related blend films (Fig. 1a,b). Moreover,

all the all-PSCs achieved high EQE response with the maximum values close to 80%,

while the devices based on PY2S-F, PY2Se-F, and PY2Se-Cl with halogen and/or Se

substitutions have slightly improved EQE values compared to that of one based on

PY2S-H, indicating efficient photon capture and charge generation. As a result, with

the introduction of halogen and Se atoms into PSMAs, the related all-PSCs achieved

gradually increased integrated Jsc values from 21.9 to 23.8 mA cm-2, which is well

consistent with the ones from J-V measurement.

Fig. 2. (a) The J-V curves of the PM6:PSMA-based all-PSCs under the illumination
of AM 1.5G, 100 mW cm-2. (b) Plots of PCE against Jsc for the all-PSCs reported

11
previously with PCEs over 10% and in this study. (c) The EQE spectra of the
optimized all-PSCs. (d) The curves of Jph versus Veff of all-PSCs.

Table 1. Photovoltaic parameters of the PM6-based all-PSCs with different PSMAs.

D:A Voc [V] Jsc [mA cm-2][a] FF PCE [%][b]

PM6:PY2S-H 0.941 22.3 (21.9) 70.7 14.8 (14.7±0.1)

PM6:PY2S-F 0.920 23.3 (22.7) 70.5 15.1 (14.9±0.2)
PM6:PY2Se-F 0.885 24.4 (23.7) 72.2 15.6 (15.4±0.2)
PM6:PY2Se-Cl 0.884 24.5 (23.8) 74.3 16.1 (15.8±0.3)
[a] The integrated Jsc in parenthesis were calculated from the EQE spectra. [b] The average PCEs
in parenthesis were calculated from 10 devices.

To probe why the introduction of halogen and Se atoms into PSMAs can improve

both Jsc and FF values in devices, the exciton dissociation probabilities P(E,T) and

charge-transporting properties of four all-PSCs were systematically investigated. As

shown in Fig. 2d of the plots of photocurrent (Jph) vs effective voltage (Veff), with the

introduction of F and Se atoms onto PSMAs, the related all-PSCs exhibited gradually

increased P(E,T) values from 80.0% to 81.9% under the maximal power output

condition. Moreover, compared with the PY2Se-F-based device, the PY2Se-Cl-based

device achieved a further higher P(E,T) of 83.7%. As illustrated in Fig. S14 and Table

S2, the introduction of halogen and Se atoms onto polymeric backbone, the

corresponding blend films in devices show similar hole-mobility (µ h) of ~5.0×10-4

cm2 V-1 s-1 but gradually increased µ e from 7.18×10-4 to 9.64×10-4 cm2 V-1 s-1,

respectively. The higher charge mobility and P(E,T) values are expected to achieve

12
faster charge transport, less space charge accumulation, and more effective exciton

dissociation and charge extraction in all-PSCs for achieving higher Jsc and FF.

Fig. 3. (a) TEM images, (b) GIWAXS profiles and (c) the corresponding line-cuts of
the four blend films, respectively.

To further understand why the PY2Se-Cl-based all-PSCs can achieve a higher PCE

among the four all-PSCs, the active layer morphologies were further probed by

carrying out transmission electron microscopy (TEM) and GIWAXS measurements.

As shown in Fig. 3a, all the four active layers show similar TEM morphologies. As

shown in Fig. 3b,c, compared to the diffraction peaks in the IP direction, all the four

blend films with different PSMAs possess stronger (010) and (100) diffraction peaks

in the OOP direction, implying a mixed orientation of “face-on” and “edge-on”. The

four blend films show similar d-spacing of ~3.90 Å from π-π stacking, which is

consistent with the phenomenon from the related PSMA neat films (Fig. 1d,e). For the

13
(001) peaks in the IP direction, all the blend films also exhibit similar lamellar

d-spacing of 20.3-20.9 Å, which are consistent with the PM6 neat film with a

d-spacing of 20.8 Å (Fig. S15 and Table S1). For the (010) peaks from the OOP

direction, it is different from that PY2S-F neat film shows a similar but slightly

increased CCL (23.663 Å) and much higher diffraction intensity compared to PY2S-H

(22.013 Å), PM6:PY2S-F blend film has much lower CCL (16.695 Å) and diffraction

intensity compared to PM6:PY2S-H blend film (19.520 Å), which may be due to the

better miscibility between PM6 and PY2S-F. A similar phenomenon has also been

observed in the previous work, that is, when two strong crystalline molecules are

blended, increased miscibility and reduced crystallinity can be obtained [52]. As a

result, the PM6:PY2S-F-based device obtains a lower FF. Notably, when using Cl

atom instead of F atom in the selenophene-fused PSMAs, the PM6:PY2Se-Cl blend

film shows a much higher CCL value of 8.61 nm compared to the PM6:PY2Se-F

blend film with a 6.50 nm, which partly explains that the PM6:PY2Se-Cl-based

device has a higher FF.

Since the general mutual restriction between Voc and Jsc in devices, it is very

important to obtain a good trade-off between them in order to achieve a high PCE. To

probe why the all-PSCs based on PY2Se-F and PY2Se-Cl with halogen and Se

substitutions achieved a notably increased Jsc but still maintain a favorable high Voc,

the total energy loss (Eloss or ∆E) and its divided three parts of devices were analyzed

in detail. According to the detailed balance theory [53], the ΔE consists of the

following three parts:

14
 SQ SQ rad rad
∆ = g − oc = g − oc + oc − oc + oc − oc

SQ rad ,belowgap non −rad

= g − oc + ∆ oc + ∆ oc =∆ 1 +∆ 2 +∆ 3

As shown in Fig. S16, the Eg is calculated from the derivatives of EQE spectra

using the method of Rau [53]. With the introduction of halogen and Se atoms into

PSMAs, the devices show gradually decreased Eg from 1.455 to 1.415 eV, while the

devices based on PM6:PY2Se-F and PM6:PY2Se-Cl have almost same smaller values.

Under the assumption of absent non-radiative recombination and EQE being a

step-function, the maximum voltages (VocSQ) are estimated from the

Shockley-Queisser (SQ) limit as 1.190, 1.168, 1.153, and 1.156 V for the PY2S-H-,

PY2S-F-, PY2Se-F-, and PY2Se-Cl-based devices, respectively. If there is no

non-radiative recombination, the Voc of devices is defined as Vocrad, which can be

calculated from EQE tailing via highly sensitive Fourier Transform Photocurrent

Spectroscopy (FTPS) measurements. As shown in Fig. 4a and Table 2, the Vocrad

values are calculated as 1.140, 1.128, 1.104, and 1.106 V for the devices based on

PY2S-H, PY2S-F, PY2Se-F, and PY2Se-Cl, respectively.

Among three parts of Eloss, ΔE1 is generally equal to 0.25-0.30 eV in all solar cells,

which is inevitable and comes from the radiative recombination loss above the

bandgap. Herein, all four all-PSCs have similar ΔE1 of 0.261-0.265 eV, while the

device based on original PY2S-H shows a slightly higher ΔE1 value. ΔE2 comes from

the radiative recombination loss below the bandgap, which originates from the

non-step function absorption. Compared to the PY2S-H-based device with a ΔE2 of

0.050 eV, the device based on fluorinated PY2S-F gets a lower value of 0.040 eV,

while the devices based on PY2Se-F and PY2Se-Cl with both halogen and Se
15
substitutions show similar values of 0.049-0.050 eV. ΔE3 is defined as the

nonradiative recombination loss of devices, which can be estimated by measuring the

electroluminescence quantum efficiency (EQEEL). As shown in Fig. 4b, with the

decrease of Eg (or the red-shift of absorption spectra), these all-PSCs exhibit gradually

reduced EQEEL from 0.039% to 0.018%, while the devices based on Se-free PY2S-H

and PY2S-F have ~2 times higher EQEEL values than these based on Se-containing

PY2Se-F and PY2Se-Cl. According to the calculated equation of ΔE3 = -kTln(EQEEL),

the ΔE3 values were estimated as 0.203, 0.206, 0.224, and 0.220 eV for the devices

based on PY2S-H, PY2S-F, PY2Se-F, and PY2Se-Cl, respectively. Therefore, among

the four all-PSCs, the slightly higher Eloss (0.016-0.023 eV) of the all-PSCs based on

PY2Se-F and PY2Se-Cl can be attributed to the increased nonradiative recombination

loss, which may due to that the OSCs based on selenophene-containing photovoltaic

materials have the increased density of charge-transfer states as our previous report

[54]. As a result, when the PY2Se-F and PY2Se-Cl obtain obviously red-shifted

absorption, the related all-PSCs still achieve favorable Voc.

Fig. 4. (a) FTPS-EQE spectra and (b) EQEEL curves of the all-PSCs based on PY2S-H,
PY2S-F, PY2Se-F, and PY2Se-Cl, respectively. (c) Diagrams of three parts of energy
losses.

16
 Table 2. Detailed Eloss of the all-PSCs based on PY2S-H, PY2S-F, PY2Se-F, and
PY2Se-Cl.

Eg EQEEL qVoc qVocSQ qVocrad ∆E ∆E1 ∆E2 ∆E3

Acceptors
[eV] [%] [eV] [eV] [eV] [eV] [eV] [eV] [eV]

PY2S-H 1.455 0.039 0.941 1.190 1.140 0.514 0.265 0.050 0.203

PY2S-F 1.430 0.035 0.920 1.168 1.128 0.510 0.262 0.040 0.206

PY2Se-F 1.415 0.018 0.885 1.153 1.104 0.530 0.262 0.049 0.224

PY2Se-Cl 1.417 0.020 0.884 1.156 1.106 0.533 0.261 0.050 0.220

3. Conclusions

Two novel NIR absorbing PSMAs, namely PY2Se-F and PY2Se-Cl, containing a

selenophene-fused DA'D core and halogenated end-groups were developed.

Compared to the Se-free PY2S-H and fluorinated PY2S-F, PY2Se-F and PY2Se-Cl

show obviously red-shifted absorption spectra (30-40 nm) with reasonably

deep-shifted LUMO level. Moreover, the introduction of Se and halogen atoms, four

PSMAs display different crystallinity, molecular packing, and electron mobility,

resulting in different morphologies and device physical properties. In the PM6-based

all-PSCs, PY2Se-F and PY2Se-Cl achieved improved PCEs with both higher Jsc and

FF than those of PY2S-H and PY2S-F. When replacing F with Cl atom on end-group

of PSMAs, PM6:PY2Se-Cl shows a more optimized blend morphology compared

with that of PM6:PY2Se-F, leading to optimal charge transport and a higher FF. As a

result, the PM6:PY2Se-Cl-based all-PSCs achieved an impressive PCE of 16.1% with

both high Jsc of 24.5 mA cm-2 and FF of 0.743, which is one of the highest values
17
reported for the binary all-PSCs so far. Combining with the low-cost merit of

chlorination, PY2Se-Cl shows great potential for the practical applications using

efficient all-PSCs.

Acknowledgements

Q.F. and H.F. contributed equally to this work. A.K.-Y.J. thanks for the

sponsorship of the Lee Shau-Kee Chair Professor (Materials Science). This work was

supported by the APRC Grant of the City University of Hong Kong (9380086),

Innovation and Technology Fund (ITS/497/18FP and GHP/021/18SZ), the Office of

Naval Research (N00014-20-1-2191), the Air Force Office of Scientific Research

(FA9550-18-1-0046), the GRF grant (11307621) from the Research Grants Council of

Hong Kong, Guangdong Major Project of Basic and Applied Basic Research

(2019B030302007), Guangdong-Hong Kong-Macao Joint Laboratory of

Optoelectronic and Magnetic Functional Materials (2019B121205002), and the

Fundamental Research (Discipline Arrangement) Project funding from the Shenzhen

Science and Technology Innovation Committee (JCYJ20180507181718203). The

authors also thank Dr. Shanshan Chen from Chongqing University for help with

GIWAXS measurement.

Notes and references

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22
Qunping Fan received his Ph.D. degree in Applied Chemistry from the College of
Chemistry, Chemical Engineering, and Materials Science at Soochow University in
2018. He was a postdoctoral researcher at the Department of Chemistryand Chemical
Engineering, Chalmers University of Technology, Sweden, from 2018 to 2020. Now,
he is a postdoctoral researcher at the Department of Chemistry, City University of
Hong Kong. His research interests focus on the synthesis and application of organic
photovoltaic materials.

Huiting Fu received her B.S. degree from the University of Science and Technology
Beijing and Ph.D. degree from the Institute of Chemistry, Chinese Academy of
Sciences (ICCAS). Now she is a postdoctoral researcher at the Department of
Materials Science and Engineering, City University of Hong Kong. Her research
interest focuses on the development and characterization of materials and devices for
organic photovoltaic applications.

23
Zhenghui Luo received his Ph.D. degree in 2019 from Wuhan University, Wuhan for
his study in the field of organic photovoltaics under the direction of Professor Chuluo
Yang. From 2019 to 2021, he was a postdoctoral fellow in Professor He Yan's group
at HKUST. Since 2021, he has been full professor at Hubei University. His research
interests focus on the synthesis and application of organic photovoltaic materials.

Jiyeon Oh is in the combined master's and doctorate course for Energy Engineering
in Ulsan National Institute of Science and Technology (UNIST, south Korea). Before
coming to UNIST, she received BS in 2016 in Advanced Materials Chemistry at
Korea University. She joined Professor Changduk Yangs group in 2017. Her main
research is device physics of organic solar cells.

Baobing Fan earned his B.S. degree in 2013 from Soochow University. In 2018, he
obtained his Ph.D. degree from South China University of Technology, focusing on

24
highly efficient materials for organic solar cells (OSCs). He also worked as a visitor at
the Friedrich-Alexander-Universität Erlangen-Nürnberg, where he studied the energy
loss and long-term stability of OSCs. Then he worked as a postdoc at South China
University of Technology from 2018. In 2020, he joined City University of Hong
Kong as a postdoc. He currently investigates the performance and stability of OSCs
based on near-infrared photovoltaic materials.

Francis Lin received his B.S. degree in Chemistry from the National Taiwan
University in 2013 and Ph.D. degree of Chemistry from the University of Washington
in 2019, and is currently a postdoctoral fellow at Alex Jen Research Group in the City
University of Hong Kong. He has an interdisciplinary expertise including the design,
synthesis and processing of multifunctional organic and organic/inorganic hybrid
materials, and develops a broad research interest into the field of solar energy
conversion and energy storage, such as organic photovoltaics, Perovskite solar cells
and Li-ion batteries.

Changduk Yang obtained his Ph.D. degree from the Max Planck Institute for
Polymer Research (Germany) in 2006 under Prof. Klaus Müllen. He finished his
postdoctoral training in 2009 at the University of California Santa Barbara (U.S.) with
25
Prof. Fred Wudl. In March 2009, he has joined UNIST. He serves on the editorial
board for Polymer (South Korea) and works as a fulltime professor at UNIST. His
research focus is on the development of organic semiconducting materials and
multifunctional molecule-related self-assembly for various applications, including
organic optoelectronics, perovskites, triboelectric generators, and secondary batteries.

Alex K.-Y. Jen is the Lee Shau-Kee Chair Professor of Materials Science and Chair
Professor of Chemistry and Materials Science of the City University of Hong Kong.
He had also served as the Provost of CityU during 2016-2020. He received his Ph.D.
from the University of Pennsylvania in USA. Prior to CityU, he served as the
Boeing-Johnson Chair Professor and Chair of the Department of Materials Science &
Engineering at the University of Washington, Seattle. He was also appointed as Chief
Scientist for the Clean Energy Institute endowed by the Washington State Governor.
His interdisciplinary research covers organic/hybrid functional materials and devices
for photonics, energy, sensors, and nanomedicine.

26
 Graphical Abstract

A novel near-infrared absorbing polymer acceptor PY2Se-Cl with a selenophene-fused core

and chlorinated end-group was developed. In binary all-PSCs, PY2Se-Cl achieved a record

PCE of 16.1% with both high Jsc of 24.5 mA cm-2 and FF of 0.743. Combining the low-cost

merit of chlorination, PY2Se-Cl shows great potential in the applications of efficient

all-PSCs.

Keywords: all-polymer solar cells, halogenation; near-infrared absorbing polymer acceptors;

power conversion efficiencies; selenophene

Qunping Fana, Huiting Fub, Zhenghui Luoc, Jiyeon Ohd, Baobing Fana, Francis Lina,

Changduk Yangd, and Alex K.-Y. Jena,b,e,f,*

Near-infrared absorbing polymer acceptors enabled by selenophene-fused core and

halogenated end-group for binary all-polymer solar Cells with efficiency over 16%