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Suppression of energy disorder by incorporating a

small-molecule acceptor into binary all-polymer
Published on 19 October 2023. Downloaded by Qingdao University on 11/2/2023 [Link] PM.

Cite this: DOI: 10.1039/d3ee02700g

solar cells†
Ye Xu,abc Jingwen Wang,af Tao Zhang,af Zhihao Chen,a Kaihui Xian, d Zi Li,a
Yang-Hui Luo,b Long Ye, d Xiaotao Hao, e Huifeng Yao *ab and
Jianhui Hou *af

Organic photovoltaic cells based on disordered materials suffer significant energy losses that limit the
power conversion efficiencies (PCEs). For all-polymer solar cells (all-PSCs), the complicated blend
morphology caused by the high probability of chain entanglement will exacerbate this situation. Here,
we designed an alternating copolymer donor, PDBQx-TCl, based on dithieno[2,3-d:2 0 ,3 0 -d 0 ]benzo[1,2-
b:4,5-b 0 ]dithiophene and dithieno[3,2-f:2 0 ,3 0 -h]quinoxaline units and studied its application in all-PSCs.
By blending with the polymer acceptor PY-IT, the device obtained a moderate PCE of 16.8%. We then
incorporated a small-molecule acceptor, BTA3-4F, into the PDBQx-TCl:PY-IT blend, which not only
Received 15th August 2023, tuned the optical absorption and aligned energy levels but also suppressed the energy disorder by
Accepted 17th October 2023 optimizing the blend morphology. As a result, the ternary device recorded an outstanding PCE of 18.6%,
DOI: 10.1039/d3ee02700g which is much higher than the binary all-PSC. This work demonstrates that suppressing energy disorder
by adding small molecules into binary all-PSCs is a feasible approach to improve photovoltaic
[Link]/ees performance.

Broader context
Recently, organic photovoltaic cells have experienced remarkable progress, witnessing rapid enhancements in power conversion efficiencies (PCEs). In comparison
to their inorganic or organic/inorganic hybrid counterparts, organic materials, while inherently less ordered, have substantial energetic disorders. This stands as a
pivotal challenge that restricts the advancement of PCEs. For all-polymer solar cells (all-PSCs) that consist of both polymeric donors and acceptors, morphology
control becomes a huge challenge. Here, we study the impacts of energy disorder on the charge transport/recombination processes. Furthermore, we present a
feasible strategy to counter this energy disorder by introducing a complementary third component. We design a polymer donor, PDBQx-TCl, and a small-molecule
acceptor, BTA3-4F, for fabricating solar cell devices. Our findings underscore that the introduction of BTA3-4F into the polymer blend PDBQx-TCl:PY-IT can
effectively optimize the morphology and thus get a decreased energy disorder. As a result, the PCE gets a significant improvement from 16.8% to 18.6%.

Introduction
a
State Key Laboratory of Polymer Physics and Chemistry, Beijing National
Laboratory for Molecular Sciences, CAS Research/Education Center for Excellence
Organic solar cells possess appealing features such as intrinsic
in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, flexibility and excellent mechanical properties, making them
100190 Beijing, China. E-mail: hjhzlz@[Link] viable candidates for lightweight and wearable energy supply.1,2
b
School of Chemistry and Chemical Engineering, Southeast University, Nanjing, When compared to their inorganic counterparts, the use of
211189, China. E-mail: yaohf@[Link]
c
amorphous and less crystalline organic materials results in
State Key Laboratory of Photovoltaic Science and Technology, Trina Solar,
Changzhou, 213031, China
larger energy disorders,3 leading to more severe charge recom-
d
School of Materials Science and Engineering, Tianjin Key Laboratory of Molecular bination. Hence, the design of novel photoactive materials and
Optoelectronic Sciences, Tianjin University and Collaborative Innovation Center of the exploration of feasible morphology optimization strategies
Chemical Science and Engineering (Tianjin), Tianjin 300350, China to suppress energy disorder are of great importance.4,5 Over the
e
School of Physics, State Key Laboratory of Crystal Materials, Shandong University,
past few years, the development of electron acceptors has
Jinan, Shandong 250100, China
f
China University of Chinese Academy of Sciences, 100049 Beijing, China
substantially contributed to rapid enhancements in power
† Electronic supplementary information (ESI) available. See DOI: [Link] conversion efficiencies (PCEs).6,7 An important attribute of
10.1039/d3ee02700g non-fullerene acceptors (B25 meV) in comparison to fullerene

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acceptors (B45 meV) is their suppressed Urbach energy, which performance of all-PSCs, both polymer design and blend morphol-
is a key factor accounting for decreased voltage loss in resulting ogy optimization should consider energy disorder.
devices.8 The top-performing cells using polymer donor/Y6-type In this study, we design a polymer donor named PDBQx-TCl
acceptor combinations have recorded over 19% PCEs with through the alternating copolymerization of dithieno[2,3-d:
small energy disorders of approximately 25 meV.9 Furthermore, 2 0 ,3 0 -d 0 ]benzo[1,2-b:4,5-b 0 ]dithiophene (DTBDT) and dithieno-
controlling the morphology of the active layer plays a critical [3,2-f:2 0 ,3 0 -h]quinoxaline (DTQx) units. PDBQx-TCl possesses an
role in restricting energy disorder.10 For instance, by introdu- optical bandgap (Eopt g ) of 2.04 eV with a low-lying ionization
cing the solid additive 1,3,5-trimethoxybenzene, which exhibits potential of 5.23 eV. By blending it with PY-IT, the all-PSCs
a perfect electrostatic match with the non-fullerene acceptor achieve a good PCE of 16.8%. We then incorporate a small-molecule
BTP-eC9, intermolecular packing can be fine-tuned, resulting acceptor named BTA3-4F into the PDBQx-TCl:PY-IT blend to opti-
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in suppressed energy disorder and minimized non-radiative mize performance. BTA3-4F not only complements the absorption
recombination losses.11 spectrum within the 500–750 nm range but also elevates the energy
All-polymer solar cells (all-PSCs) consisting of conjugated level of the acceptor. Interestingly, the addition of BTA3-4F serves as
polymers as both donors and acceptors have garnered significant an effective morphology modulator that induces enhanced inter-
attention due to their unique advantages of superior flexibility molecular packing and greater phase separation, resulting in a
and stability.12–14 Compared to the extensively studied cells based decrease in Urbach energy from 29.2 to 25.1 meV. Consequently,
on polymer donors and small-molecule acceptors, substituting due to simultaneous improvements in short-circuit current density
polymer acceptors with small-molecule counterparts increases (JSC), open-circuit voltage (VOC), and fill factor (FF), the ternary
morphological complexity considerably.15 The high degree of devices attain a maximum PCE of 18.6%. This work demonstrates
chain entanglement in all-polymer blends causes additional that the suppression of energy disorder in binary all-PSC through
energy disorder.16 Since 2017, the design strategy involving the incorporation of a complementary third component is a viable
polymerized small-molecule acceptors has been developed, strategy for enhancing photovoltaic performance.
significantly enhancing the PCEs of all-PSCs.17–21 Currently, only
a limited variety of polymer donors can effectively match with
typical polymer acceptors like PY-IT. Designing new polymer Results and discussion
donors has been proven to be an effective approach to improving
PCEs.22 Additionally, concerning morphology optimization, some In our prior research,25 we discovered that copolymers utilizing
results suggest that incorporating a small amount of small- alternating benzodithiophene (BDT) and DTQx units exhibit
molecule acceptors into the polymer blend could induce ordered exceptional performance in all-PSCs. Here, we substituted BDT
intermolecular packing, leading to simultaneous improvements in with its derivative, DTBDT, to design the polymer PDBQx-TCl
efficiency and stability.23,24 To further enhance the photovoltaic (Fig. 1a). The extension of conjugated fused rings can enhance

Fig. 1 (a) Molecular structure, (b) calculated DOSs, (c) molecular orbitals, and (d) temperature-dependent absorption of the polymer PDBQx-TCl.

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intermolecular stacking, potentially suppressing energy disor- primary peak gradually diminishes, indicating a pre-aggregation
der. The introduction of chlorinated thiophenes as conjugated effect. This feature is recognized as a significant characteristic of
side chains will result in a downshift of the lowest unoccupied highly efficient polymer donors,26 contributing to the formation
molecular orbital (LUMO) energy level. Using the density func- of a nano-scale fibrillar blend morphology (Fig. S1a, ESI†), which
tional theory (DFT), we optimized the molecular geometry and can induce an appropriate phase separation when blended with
calculated the density of states (DOS) for the PDBQx-TCl non-fullerene acceptors. The thermal stability of PDBQx-TCl was
molecular model at the B3LYP/6-31G(d,p) level. As depicted in evaluated through thermogravimetric analysis (TGA). As dis-
Fig. 1b, analysis of the DOS composition reveals that the DTQx played in Fig. S1b (ESI†), the decomposition temperature for a
fragment has a more significant impact on both the highest 5% weight loss is approximately 380 1C. The crystalline property
occupied molecular orbital (HOMO) and LUMO than the and molecular orientation were probed using grazing-incidence
Published on 19 October 2023. Downloaded by Qingdao University on 11/2/2023 [Link] PM.

DTBDT fragment. Molecular electrostatic potential (ESP) and wide-angle X-ray scattering (GIWAXS) measurements. As shown
frontier orbit maps are illustrated in Fig. 1c. The most con- in Fig. S1c (ESI†), both (010) and (100) diffraction peaks are
jugated surface of PDBQx-TCl exhibits negative ESP, with the evident in the out-of-plane (OOP) direction, indicating the coex-
lowest values localized around the nitrogen atoms. The esti- istence of face-on and edge-on molecular packing. Extracted line-
mated HOMO/LUMO levels are 4.97/2.39 eV, slightly higher cut profiles in Fig. S1d (ESI†) reveal intermolecular p–p and
than those of the BDT-based polymer PBQx-TCl.22 This energy lamellar distances of 3.74 and 21.7 Å, respectively. Applying the
level shift likely originates from the stronger electron-donating Lambert–Beer law, we determined the absorption coefficient to
feature of DTBDT, potentially unfavorably affecting the VOCs of be 1.01  105 M cm1, showing robust light-harvesting capability
resulting solar cell devices. PDBQx-TCl was synthesized using (Fig. S2, ESI†).
the conventional Still coupling reaction (Scheme S1, ESI†). The Fig. 2a depicts the chemical structures of the polymer
polymer can be processed using solvents such as chloroform, acceptor PY-IT and the newly designed small-molecule acceptor
chlorobenzene, and toluene. Gel permeation chromatography BTA3-4F. PY-IT has been effectively employed in fabricating
measurements yield a number-average molecular weight of highly efficient all-PSCs. From previous works, we observed that
44 kDa and a polydispersity index of 2.9. the middle-bandgap BTA3 series possesses significant utility as
We conducted UV-vis spectra measurements of PDBQx-Cl in optical, electrical, and morphological modulators, enhancing
chlorobenzene at varying temperatures ranging from 0 to binary device performance.27,28 Given the well-established effec-
110 1C. As depicted in Fig. 1d, the principal absorption band tiveness of fluorination in organic semiconductor design,29–33 we
falls within the 400–620 nm range at a low temperature of 0 1C, employed a fluorination-based strategy. This involved substitut-
with the maximum absorption peak observed at 578 nm. As the ing the alkyl-benzotriazole moiety with its bis-fluorine substituted
solution temperature increases, the absorption intensity of the counterpart. Detailed synthetic procedures (Scheme S2, ESI†) and

Fig. 2 (a) Chemical structures of PY-IT and BTA3-4F. (b) Absorption spectra and (c) energetic levels of PDBQx-TCl, BTA3-4F, and PY-IT in the film state.

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characterizations are provided in the ESI.† The absorption coeffi- To investigate the photovoltaic performance of PDBQx-TCl
cient of BTA3-4F was determined to be 1.28  105 M cm1 in all-PSCs, we employed a device configuration of ITO/PED-
(Fig. S3, ESI†). Subsequently, we evaluated the UV-vis absorption OT:PSS/active layer/PDINN (N,N 0 -bis{3-[3-(dimethylamino)pro-
spectra of the materials as thin films. Illustrated in Fig. 2b, the pylamino]propyl}perylene-3,4,9,10-tetracarboxylic diimide)/Ag.
main absorption bands of PDBQx-TCl and BTA3-4F span the Detailed information regarding device processing conditions
400–600 and 500–700 nm ranges, respectively. By contrast, PY-IT can be found in the ESI.† Photovoltaic performances under
exhibits complementary absorption within the 600–900 nm standard test conditions for PDBQx-TCl:BTA3-4F, PDBQx-TCl:
region. The blend of three materials is expected to have a good PY-IT, and PDBQx-TCl:BTA3-4F:PY-IT devices are depicted in
match with the solar radiative spectrum. We then assess the Fig. 3a, with corresponding electrical parameters collected in
energy levels of the new materials through cyclic voltammetry Table 1. The optimized PDBQx-TCl:BTA3-4F-based device
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measurements, with the results plotted in Fig. 2c and Fig. S4 achieves a maximum PCE of 10.5%, with a VOC of 1.05 V, a
(ESI†). Compared to our previous report on PBQx-TCl, PDBQx-TCl JSC of 13.9 mA cm2, and a FF of 72.0%. For the PDBQx-TCl:PY-
exhibits a subtle energetic upshift in both ionic potentials (IP) IT-based device, although the VOC decreases to 0.910 V, the
and electron affinities (EA). This can be attributed to the electron- expanded light absorption range of PY-IT enhances the JSC to
rich nature of DBDT. Fluorine substitution on BTA3-4F results in 23.5 mA cm2, yielding a good PCE of 16.8%. By integrating the
a downshift of both IP and EA due to its pronounced electron- high VOC of the PDBQx-TCl:BTA3-4F blend into the PDBQx-
withdrawing properties. This is also evident in the corresponding TCl:PY-IT-based system, the ternary cell based on PDBQx-
more positive ESP, which is presented in Fig. S5 (ESI†). The TCl : BTA3-4F : PY-IT (1 : 0.2 : 1, w/w) exhibits an elevated VOC
enhanced disparities in energetic levels and ESP between of 0.934 V. Moreover, the complementary absorption character-
PDBQx-TCl and BTA3-4F may be beneficial for the charge istics of BTA3-4F contribute to enhanced light response in the
transfer. Furthermore, the energetic levels of PDBQx-TCl and ternary blend. Consequently, the ternary device attains an
BTA3-4F establish a cascade energetic distribution with the efficiency of 18.6%, accompanied by simultaneous improve-
polymer acceptor PY-IT, which was further confirmed by the ments in JSC, VOC, and FF, which is among the top PCEs
ESP distribution and calculated molecular levels of the PY-IT achieved in PSCs containing polymer donors and polymer
given in Fig. S6 (ESI†). acceptors (Table S1, ESI†).34,35 We understand that the ternary

Fig. 3 (a) J–V, (b) EQE curves, (c) Photo-CELIV, (d) Pdiss, (e) EQEEL, and (f) trap densities of the three devices.

Table 1 The detailed photovoltaic parameters of all-PSCs

Active layer VOC (V) JSC (mA cm2) Jcal (mA cm2) FF (%) PCE (%)a
PDBQx-TCl:BTA3-4F 1.05 13.9 13.6 72.0 10.5 (10.2  0.2)
PDBQx-TCl:PY-IT 0.910 23.5 23.0 78.6 16.8 (16.5 0.3)
PDBQx-TCl : BTA3-4F : PY-IT (1 : 0.2 : 1) 0.934 24.9 24.3 79.8 18.6 (18.2  0.3)
a
Average values with standard deviation are obtained from 10 independent cells.

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device cannot be called all-PSC although the content of small- a logarithmic plot (Fig. S9b, ESI†), slopes (S) for the three
molecule is not large (20%, w/w). The impacts of this strategy devices are calculated at approximately 1.00, which implies that
on the mechanical property will be studied in our further work. bimolecular recombination is negligible for all three devices.
By applying the Mott–Schottky equation, the built-in potentials The overall efficiencies (Pdiss) of charge separation, transport,
of the three blends were deduced from impedance spectroscopy and collection are calculated as 91%, 93%, and 96% for PDBQx-
(Fig. S7, ESI†).36,37 Notably, the built-in potential of the ternary TCl:BTA3-4F, PDBQx-TCl:PY-IT, and PDBQx-TCl:BTA3-4F:PY-IT
device surpasses that of the PDBQx-TCl:PY-IT-based device by blends, respectively, as depicted in Fig. 3d.40 These results
20 mV. This enhancement will facilitate carrier transport and suggest that the improved current density in the ternary device
consequently improve the current density. should be connected to the suppressed trap-mediated recombi-
External quantum efficiency (EQE) measurements were con- nation, low bimolecular recombination, and high exciton dis-
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ducted to explore wavelength-dependent photoelectronic con- sociation efficiency.

version efficiencies and to corroborate the accuracy of the To study the origin of the enhanced VOC observed in the
measured JSC values. As presented in Fig. 3b, the PDBQx- ternary device, the voltage loss analysis was carried out based on
TCl:BTA3-4F-based device exhibits a photo response range from previous studies.41 Initially, the bandgaps were determined
300 to 750 nm. It attains a peak value of 78% at 520 nm, with an through the intersections of electroluminescence (EL) and EQE
additional shoulder peak reaching 71% at 650 nm. The photon spectra,42 yielding values of 1.79, 1.46, and 1.46 eV for PDBQx-TCl:
response of the PDBQx-TCl:PY-IT-based device covers a broader BTA3-4F, PDBQx-TCl:PY-IT, and PDBQx-TCl:BTA3-4F:PY-IT blends,
range from 300 to 900 nm, corresponding to an integrated respectively (Fig. S10, ESI†). Employing reduced EL and sensitive
current density of 23.0 mA cm2. Introducing the mid-bandgap EQE spectra (Fig. S11, ESI†), the energetic levels of the charge
acceptor BTA3-4F in the ternary blend leads to improved con- transfer state are fitted to be 1.77, 1.44, and 1.46 eV for PDBQx-
version efficiencies in the absorption range of BTA3-4F. Speci- TCl:BTA3-4F, PDBQx-TCl:PY-IT, and PDBQx-TCl:BTA3-4F:PY-IT
fically, the EQE values from 400 to 600 nm for the ternary device blends, respectively. By measuring the electroluminescence EQE
also exhibit enhancement, which may be related to the (EQEEL) (Fig. 3e), the non-radiative voltage loss (Enr-loss) can be
improved built-in potential. The photogenerated current den- quantified using the equation Enr-loss = ekBT ln(1/EQEEL)/q, where
sity is improved to 24.3 mA cm2. The calculated integrated kB represents the Boltzmann constant, T stands for the device
current densities are quite close to the measured current temperature, and q denotes the elementary charge. Notably, the
densities, indicating the accuracy of the photovoltaic para- ternary device exhibits decreased Enr-loss in comparison to the
meters. We tested the device stability of the binary all-PSC binary devices, which may be connected to the reduced trap
and the ternary device under continuous light illumination. As density. The Mott–Schottky analysis was performed to assess the
provided in Fig. S8 (ESI†), we can find that the stability of both density of trap states (tDOS).43,44 The tDOS can be fitted using the
devices is not quite satisfying. By contrast, the ternary device eqn (1):
shows a marginal advantage over the binary cell. It’s worth
" #
noting that the stability of PSC, primarily utilizing polymer
Nt ðEt  E Þ2
donors and polymer acceptors, remains a critical research focus. Nt ðE Þ ¼ pffiffiffiffiffiffiffiffi exp  (1)
2ps 2s2
Further exploration of carrier transport and recombination
was conducted to elucidate the mechanisms behind the enhanced
photovoltaic performance observed in the ternary device. Photo- where Nt and Et represent the total density and the center of the
induced charge-carrier extraction by linearly increasing voltage tDOS, respectively, and s is the disorder parameter. As shown in
(photo-CELIV) measurements were employed to assess the mobi- Fig. 3f, all the devices exhibit widespread Gaussian distribution of
lities of the faster carrier component. Calculated from the data in tDOS, and the ternary device shows the narrowest peak widening.
Fig. 3c, the mobilities are determined as 1.48  104, 1.57  104, Additionally, the fitted Nt values also indicate that the ternary
and 2.12  104 cm2 V1 s1 for PDBQx-TCl:BTA3-4F-, PDBQx-TCl: device has the smallest tDOS (4.58  1016 cm3 for PDBQx-
PY-IT-, and PDBQx-TCl:BTA3-4F:PY-IT-based devices, respectively. TCl:BTA3-4F, 3.96  1016 cm3 for PDBQx-TCl:PY-IT, and 3.31 
The improved carrier transport within the ternary device will 1016 cm3 for PDBQx-TCl:BTA3-4F:PY-IT), which has a similar
contribute to the mitigation of bimolecular recombination, tendency with the integrated tDOS from Mott–Schottky spectra
thus yielding improvements in JSC and FF values. Recombina- (4.88  1016 cm3 for PDBQx-TCl:BTA3-4F, 4.52  1016 cm3 for
tion properties within the three devices were subsequently PDBQx-TCl:PY-IT, and 3.91  1016 cm3 for PDBQx-TCl:BTA3-4F:
examined through photovoltaic parameters under different PY-IT). The Urbach energy (EU), as an indicator of energy disorder,
light intensities.38,39 By fitting VOCs with light intensities on a was also measured. From the plots shown in Fig. S12 (ESI†), we
semilogarithmic scale (Fig. S9a, ESI†), trap-mediated charge can find that the ternary device possesses the lowest EU of 25.1
recombination can be analyzed. The determined slopes are 1.43, meV while PDBQx-TCl:BTA3-4F has the largest EU of 38.8 meV and
1.41, and 1.38 kBT/q for PDBQx-TCl:BTA3-4F, PDBQx-TCl:PY-IT, PDBQx-TCl:PY-IT possesses a EU of 29.2 meV. The result is
and PDBQx-TCl:BTA3-4F:PY-IT devices, respectively. This sug- consistent with the non-radiative analysis as well as the tDOS
gests more suppressed trap-mediated charge recombination in calculations. These results suggest that the tDOS and energetic
the ternary device. Based on the power law, JSC should exhibit disorder of the binary all-PSC is suppressed by adding the small
proportionality to light intensities. Through fitting the curve in molecule.

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Fig. 4 (a) 2D TA profile and (b) TA spectra at different time delays of the ternary blend. TA dynamics of (c) PDBQx-TCl:BTA3-4F, (d) PDBQx-TCl:PY-IT,
and (e) PDBQx-TCl:BTA3-4F:PY-IT blends. (f) TA dynamics of the S1 signals probed at 1060 nm in pure polymer and the corresponding blends.

Through femtosecond transient absorption (TA) spectro- crystalline properties of the three blend films using atomic force
scopy, we investigate the excitation dynamics within the three microscopy (AFM) and grazing-incidence wide-angle X-ray scattering
blends. To analyze the dynamics of electron transfer, a 400 nm (GIWAXS) measurements. The AFM height images in Fig. 5a–c
pump was utilized to primarily excite the donor, PDBQx-TCl, suggest that the ternary blend exhibits the highest root-mean-
thereby initiating the onset of the electron transfer process. square (Rq) value of 2.14 nm, indicating a more robust aggregation.
Fig. S13 (ESI†) displays the TA profiles of PDBQx-TCl:BTA3-4F The ordered molecular stacking benefits the reduction of trap
and PDBQx-TCl:PY-IT blends, while the profiles of the ternary densities, consequently leading to an enhancement in carrier trans-
blend are presented in Fig. 4a and b. Notably, PDBQx-TCl, port. Corresponding phase images, as depicted in Fig. S14 (ESI†),
BTA3-4F, and PY-IT exhibit ground-state bleaching (GSB) signals demonstrate that all three blends show homogeneous fibrillar net-
at 576, 648, and 808 nm, respectively. In the binary PDBQx- works, which ensures an optimal balance between exciton dissocia-
TCl:PY-IT blend, a gradual rise of the PY-IT GSB signal is tion and carrier transport. The GIWAXS patterns are displayed in
observed, accompanied by pronounced GSB quenching of Fig. 5d–f, and the corresponding line-cut profiles are presented in
PDBQx-TCl, occurring on a timescale of B2.0 ps (Fig. 4c and Fig. 5g. We can find that all three blends exhibit a preferential face-
d). In contrast, within the ternary blend, the GSB rise for PY-IT on molecular packing. Notably, the PDBQx-TCl:BTA3-4F film shows
and the GSB quenching of PDBQx-TCl manifest more rapidly, a strong diffraction peak in the OOP direction at 1.72 Å1, coupled
transpiring at 1.0 and 1.2 ps, respectively (Fig. 4e). The inter- with a lamellar peak in the in-plane (IP) direction at 0.30 Å1. These
mediary role of BTA3-4F is evident in its GSB decay dynamics, features correspond to a p–p stacking distance of 3.65 Å and a
which markedly contrast between the binary and ternary blends. lamellar stacking distance of 20.9 Å. In contrast, the PDBQx-TCl:PY-
The decay lifetime of the BTA3-4F GSB signal spans around 10 ps IT blend shows a weaker diffraction signal. The introduction of
in the PDBQx-TCl:BTA3-4F binary blend, whereas it is less than 1 BTA3-4F induces a distinct improvement in crystallinity within the
ps in the ternary blend, suggesting an enhanced electron transfer ternary blend. A larger p–p stacking distance of 3.74 Å is also
process in the presence of BTA3-4F. Furthermore, a comparison observed. The crystalline coherent lengths are estimated as 26.9,
of exciton decay dynamics of the donor molecule across different 24.7, and 28.2 Å for PDBQx-TCl:BTA3-4F, PDBQx-TCl:PY-IT, and
blends was conducted. As depicted in Fig. 4f, the S1 exciton of PDBQx-TCl:BTA3-4F:PY-IT blend films, respectively.
PDBQx-TCl exhibits shorter lifetimes in the BTA3-4F and PY-IT
binary blends, with the shortest decay realized in the ternary
blend. These findings underscore the effectiveness of BTA3-4F in Conclusions
enhancing charge transfer by acting as a bridging component.
Since the device performance is highly linked to the morphol- In summary, our study focused on the suppression of energy
ogy, we conducted the characterizations of the nanostructure and disorder in binary all-PSCs. We designed a polymer donor

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Fig. 5 AFM height images of (a) PDBQx-TCl: BTA3-4F, (b) PDBQx-TCl:PY-IT and (c) ternary blends; 2D-GIWAXS patterns of (d) PDBQx-TCl:BTA3-4F, (e)
PDBQx-TCl:PY-IT, and (f) ternary blends. (g) 1D GIWAXS profiles of the blends.

PDBQx-TCl, which has a wide bandgap of 2.04 eV and a and Key Technology Research program, BE2022021) and the
pronounced pre-aggregation effect in the solution. By blending National Natural Science Foundation of China (22122905,
with the polymer acceptor PY-IT, the resulting cell achieved a 22075301, 52120105005). H. Yao was supported by the Start-
moderate PCE of 16.8% due to the large energy disorder. Then, up Research Fund of Southeast University (RF1028623263). Y.
we introduced a medium bandgap small-molecule acceptor Xu wants to thank the support from Jiangsu Funding Program
BTA3-4F into the polymer blend, which was found to be effective for Excellent Postdoctoral Talent (no. 2023ZB667). This work
in modulating the blend morphology. As a result, the trap density was carried out with the support of the Shanghai Synchrotron
was reduced and the carrier mobility was improved. Conse- Radiation Facility, beamline BL02U2.
quently, the PCE of the ternary PSC was boosted to an impressive
value of 18.6%. Our findings suggest that incorporating a ternary
element into binary all-polymer blends serves as an effective Notes and references
strategy to suppress the energy disorder, thus improving the
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