2024.11.22

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Polymerized Small Molecular Acceptors for

Efficient and Stable All-Polymer Solar Cells

Junji Jianga, Jiuxing Wanga,*, Jiawang Yanga, and Jianguo Tanga,*

a
Institute of Hybrid Materials, National Center of International Research for Hybrid Materials

Technology, National Base of International Science & Technology Cooperation, College of

Materials Science and Engineering, Qingdao University, Qingdao, Shandong 266071, P. R.

China.

Corresponding Author

*E-mail: jiuxingwang@qdu.edu.cn. *E-mail: tang@qdu.edu.cn.

Keywords: Polymerized small molecular acceptors; All-polymer solar cells; Power conversion

efficiency; Molecular design; Stability.

1
Abstract

All-polymer solar cells (all-PSCs) have achieved outstanding performance due to the rapid

development of polymerized small molecular acceptors (PSMAs). As a new type of polymer

acceptor, PSMAs have the advantages of polymer and small molecular acceptors, including

superior mechanical and thermal stabilities, excellent film-forming capabilities, wide and strong

absorption, and fine-tuned molecular energy levels and stacking behaviors. However, there is

still a long way to go to realize the commercial applications of all- PSCs. Here, we mainly focus

on the methodological principles for designing of PSMAs that will be comprehensively analyzed

and summarized. Besides, the miscibility and crystalline behaviors between binary/ternary

active-layer components are presented appending with the discussion on impacts of device

techniques on the PSMAs-based polymer matrix morphology. Finally, the main challenges and

latent opportunities are displayed, and the future innovation directions of PSMAs are extracted

and outlined.

Abstract Graphic

2
1. Introduction

The total energy projected by the sun to the earth every year is statistically more than 100

times the known reserves of fossil fuels [1]. The exploitation and utilization of light energy can

effectively alleviate the problems of traditional fossil fuels, such as non-renewable and severely

environmental pollution. Therefore, it is necessary to continuously develop and boom the solar

energy technologies especially abundance of solar energy resources. Polymer solar cells (PSCs)

have attracted a lot of attention and researches due to its potential advantages, such as the rapid

increase in power conversion efficiencies, viability of cost-effective roll-to-roll technology,

better mechanical robustness and diverse stability (thermal-stability, photo-stability and

mechanical stability), accompanying with wearable and portable characteristics due to the light

weight and bendable feature [2-8]. Pushing forward by mixing with well-matched polymer

donors (PDs), employing ternary/quaternary strategy and innovating device technology, a

number of cases showed that the power conversion efficiencies (PCEs) of all-PSCs based on

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PSMAs have exceeded 19%, very close to meet the standard of the commercial application for

organic photovoltaics (OPVs) [9-11]. All-PSCs have great potential of being in the lead on the

accomplishment of industrial production for OPVs.

Active layer as the kernel functioning part of the PSCs devices comprises the p-type donor (D)

and the n-type acceptor (A) mixing together to form heterojunction of the photovoltaic

semiconductor. Based on the special operating-principle (as illustrated in Figure 1) of organic

solar cells (OSCs) and the fact that the proper phase separation and ordered packing knitted in

D/A interface can allow for lowering the exciton diffusion length, improving exciton dissociation

efficiency, providing sufficient charge transporting channels and suppressing overly massive bi-

molecule recombination. Therefore, appropriate miscibility between donors and acceptors and

proper crystallinity and domain purity of each ones are pre-requisite to produce good active layer

morphology thus for obtaining high device parameters of the open- circuit voltage (VOC), the

short circuit current density (JSC) and the fill factor (FF) and realizing stable all-PSCs [12]. It is

known that the PCE of the solar cell device has the proportional correlation to VOC, JSC and FF.

By virtue of this, it’s of essence to acquire a profound and systematic understanding on the

kinetic mechanism for film-forming process and what elements an idea photoactive layer

morphology should possess or rather, the intricate relationships between morphology and blend-

film properties [13,14]. Besides, developing varieties of morphology-maneuvering method is

also technically indispensable for fulfilling the breakthrough of all-PSCs performances through

morphology engineering. All the morphological issues in terms of PSCs can not avoid the topic

that the fundamental and ubiquitous phenomenon of intermolecular interactions and its

regulation from molecular level which is significant to handle the difficulties in balancing the

D/A miscibility and crystallization capability of each photo-active component, rendering the

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benign solubility of the materials when undergoing solvent-processing, contriving the

interpenetrating networks with good vertical phase distribution, realizing the stable large-area

photoactive layer through blade coating process [4,5,15-17]. Overall details will be displayed

and discussed in main part of the text. In recent years, more concentration were cast in better and

extended understanding on relationship between internal molecular-structure of polymer donors

and polymer acceptors and their aggregation properties, the works included but not limited to the

side-chain and hetero-atom engineering, and discreet selection of polymer donors to compatibly

match and combine with PSMAs to form binary and ternary component systems [16,18-21]. It

worth noted that the PSMAs tend to have lower molecular energy levels than their small

molecular options thus to be more competitive in opting matching polymer donors, thus being

more prone to obtain high VOCs in the devices [22]. To adapt the diversified demands in

responding range of the spectrum, PDs can be designed with definition of the wide, medium and

narrow bandgap polymer donors [23]. Delicately-designed wide/ultral-wide bandgap polymer

donors can always display the eminent spectrum response in short-wave range and deep-lying

HOMO energy level to effectively furnish the harmonious optical-absorption and advantaged VOC

for the D/A-heterojunction device [24,25]. However, the rise researches in semi-translucent

photovoltaics brings the bright future to narrow band gap PDs and PAs in versatile applications

[26]. With the development of narrow bandgap non-fullerene acceptors and its polymerized

counterparts, the sake of more complementary absorbance is appealing to the appearance of new

wide band gap donor materials beyond PBDB-T, PM6 and D18, which are found to be

extensively potential of preparing high-performance all-PSCs [27-29].

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Figure 1. The schematic illustration of the organic photovoltaic device architecture and

operation mechanism of the all-PSCs.

Unlike donors, the progresses made in acceptor materials usually featured being representative

and saltatory, as which can be categorized into fullerene acceptors and non-fullerene acceptor

materials, while non-fullerene acceptors were further classified into non-fullerene small

molecular acceptors (NFSMAs) and polymer acceptors (Figure 2).

6
Figure 2. Evolution of acceptor materials.

As the first-generation fullerene-based acceptor material, hints of photo-induced charge

transfer has early been found to exist in between conjugated polymers and C60 with unique

spherical structure [30,31]. However, C60 have the disadvantage it self in poor solubility which

then became the main barrier for efficiency improvement of the OSCs. Since the C60 came out in

about 1995, fullerene derivatives had occupied the leading position of electronic acceptor

materials for a long period [32]. PC61BM and PC71BM, as classical acceptor materials, benefiting

from high electron mobility, isotropic electron transport ability and good compatibility with

donor materials, the PCE of their corresponding devices increased from 1% to about 11% [33].

However, fullerene type acceptors have inherent defects, such as high synthetic cost, difficulty in

adjusting electronic energy levels through chemical modifications, weak intermolecular packing

which resulted in poor active-layer morphology and weak photon utilization in especially the

infrared region [34]. Developing new type acceptor materials for efficient solar cells was in

imperative demand since the poor qualities of fullerene-type acceptors as such above [35].

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Compared with fullerene acceptors, NFSMAs gives priority to overcoming the drawbacks of

molecular structure and absorption, and has unique advantages such as narrow band gap, high

absorbance, and readily tunable electronic energy levels [36,37]. In 2015, as a star molecule in

SMAs with unique acceptor-donor-acceptor (A-D-A) type electron distribution, ITIC gained a

typical planar conformation and effective molecular stacking alongside an extended and stronger

absorption in thin film which with an excellent solvent-processability, was designed and

synthesized by Zhang et al [38]. Compared with fullerene acceptors, the low exciton binding

energy and low device energy loss could be the very promising reasons for non fullerene

acceptors (NFAs) to stand out to be the second-generation acceptor materials. In 2019, Zou et al.

prepared and synthesized Y6 [39], which was gifted an extraordinary performance marking the

milestone in evolution of acceptor materials with remarkably extended near-infrared absorption

and high absorption coefficient, intensely relatable to its unique molecular structure being of the

A-D-A’-D-A which was comprehensively taken from the merits of IDIC and its derivatives with

an exceptional electron-deficient benzodithiazole (BT) locating on the central position of the

molecular structure.

As the another consideration of the acceptor material, conventional PAs featuring the D-A

architecture resemble the most of PDs, while the absorption intensity of which is usually found

to be lagging behind with the PDs among the same period, which seriously hinders the stride

towards high-performance all-PSCs. Nevertheless, the PAs have still drawn much of researchers’

attention due to their eminent advantages over NFSMAs, for example, the good film-forming

properties, fine compatibility with polymer donors, light-exposure stability and characteristic

mechanical robustness and stretchability [40-42]. Noticeably, the advances in PAs inextricably

relied on the development of NFSMAs or rather even be propelled with in the same pace. At

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present, most of the polymer acceptors with outstanding performance are based on perylene

diimide (PDI) [43], naphthalene-bis(dicarboximide) (NDI) [44], or B←N-bridged bipyridine

building blocks. However, the weak absorption in the near-infrared region (NIR) severely limits

the performance of the device [45]. Aiming at enlarging the amplitude of polymer acceptors with

good NIR absorption properties, the Polymerized small molecular acceptors arose in response

with concept of ideally striking a balance between small molecular acceptors and polymeric

acceptors.

Figure 3. (a) Structure of PSMAs, and (b) advantages of PSMAs.

9
As unremitting endeavors cast on discovery of new structure-performance correlations and

breakthrough of numerous shortages, in 2017, Zhang et al. proposed the conception of PSMAs

and its design guideline with successful fruition of PZ1 implementing all-PSCs with PCE over

10% when combined with polymer donor PM6, almost being on par with the SMA parental [46].

The PSMAs strategy refers to the construction of new PAs by connecting high-performance

NFSMAs as the key electron-deficient building block one-by-one through relatively electron-rich

π-linkage (Figure 3a), so PSMAs definitely combine the advantages of NFSMAs and PAs

(Figure 3b) to pave the road towards efficient and stable all-PSCs. Indacenodithiophene (IDT),

indacenodithienothiophene (IDTT), benzothiadiazole (BT), benzotriazole (BTA) and quinoxaline

(Qx) are often found as the central nuclear unit. The coplanarity of IDT can play a positive role

in charge transfer for PSMAs [47]. IDTT with prolonged π-conjugate length built upon IDT can

facilitate the electron delocalization and elevate the energy level and extend the linear molecular

orientation [48]. After Y6 invented, BT was extensively found to be fused into A-D-A system to

construct PSMAs with wave-shaped backbone configuration, and represented by benchmark PY-

IT from which the devices with achievement of over 15% PCE was realized [49]. These

polymers have good crystallinity and charge transfer properties due to the multiple packing

patterns of between backbones and more powerful electron push-pull effects. The N-sp 3 atom in

the BTA moiety can bring in more abundant electrons, which is of great helpful to enhance

photocurrent of the solar cells [50]. Qx-based 2-dimentional extended fused-core is promising to

provide flatter backbone configuration and more charge transfer, and even the chance to obtain

new polymerizing styles for the gains of extra molecular stacking. For example, the first PSMA

PZ1 reported by Zhang et al. showed good film-forming properties, with a PCE of 9.19% for

PBDB-T:PZ1-based devices [46]. L11 was synthesized by Guo et al. with Y6 analogues as

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building blocks. The PM6:L11-based device achieved a PCE of up to 11.1% [51]. The linkage

unit also have tremendous impact on conformation of PSMA skeleton so that the molecular

packing and orientation. Yan et al. prepared PFBDT-IDTIC by replacing the thiophene linkage

unit in PZ1 with a fluorinated BDT unit in 2019 [52]. Owing to the good electron mobility and

high absorption coefficients of PFBDT-IDTIC, the PCE of the device prepared based on the

PM6 donor was up to 10.3%. Incorporating different halogenation atoms on polymer backbone,

Yuan and his colleagues synthesized PSMAs of PIDIC2T, PIDIC2T2F and PIDIC2Cl,

respectively [53]. They found that halogen substitution in the polymer backbone significantly

promote intermolecular π-π stacking, which increased and balanced the electron mobility. By

virtue of this, PIDIC2T2Cl-based cells yielded 7.11% PCE much higher than that of

PIDIC2T2F- (4.96%) and PIDIC2T-bsaed ones (4.89%). In addition to the introduction of

halogen atoms, further structural modification and adjustment of the branched side-chains,

designing new type of fused-ring core and end-groups beyond existing building blocks can also

be very useful approaches to obtaining high-performance PSMAs. Different types of PSMAs

make sure the performances promotions in all-PSCs continuously pump out into view (Chart 1)

from the initial PCE of 9.9% to over 18%, almost in line with the level of NFSMA-based OSCs

[41]. However, it is still of necessity to investigate which factors affect the performance of

PSMAs materials, such as the packing issue which can be originated from the terminal motifs on

SMA unit taken up by polymerization sites, unlike those of SMAs being isolated from to better

stack together. And most recent concentrations on researches pointing at regulating polymeric

entanglement nature itself is also expected to further refining the polymer matrix morphology

and mechanical performance of the active-layer related to all-PSCs [54-56].

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Chart 1. Number of PSMAs papers in recent years.

Herein, we will summarize the PSMAs in recent years and divide them into five categories

according to the central core unit, including IDT, IDTT, BT, BTA, Qx and other types. Solely for

the BT part, based on enormous varieties of Y-family SMA units, cases in point for molecular

design and active-layer optimization strategies as well as the preparing techniques for the devices

will be unfolded to elaborate by overviewing the all-PSCs involving PSMAs with common

thiophene linkage. Particularly, the remain problem of polymerization concerning random

connections between SMA units and linking units, will also be included along with the mention

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of molecular-weight property which is also one of important polymeric attributes. Besides,

through subdividing the BT part into sections of PSMAs with different kinds of linkage, of

which the design principles and directions will be devoted for peering into. Most important, in

the classification of other type core based PSMAs, we will give deep insight into those subtle

design methods for PSMAs, which can lead all-PSCs to different development directions in

pursuing high efficiency or cutting producing cost and literally create the solvable conditions for

overcoming the drawbacks of PSMAs in the molecular level. Finally, the future opportunities

and developing directions for PSMAs and the challenges the all-PSCs is facing will be listed and

discussed, and the designing and optimizing methods for molecular and aggregating structure of

PSMAs will be profoundly summarized.

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Figure 4. The Schematic illustration of the classification of core-based PSMAs and the

methodological strategies of chemistry and physics for addressment of recently-faced issues.

2. Polymerized small molecular acceptors based on various core units

2.1. IDT-core based PSMAs

IDT as an important ingredient of electron-deficient core, of which PSMAs based off

(Figure 5) has been fully demonstrated good merits among narrow band gap acceptors for

highly-efficient PSCs [57,58]. Chemical modification methods reported to date, to the best our

knowledge, mainly involves linker modification with end-group (EG) design and pertinent

region-random/regular issue, through which the IDT-based PSMAs have witnessed an

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improvement in PCEs reaching about 12%. The details of design methods will be elucidated

covering bridging atoms introduction, side-chain and heteroatoms substitution etc. In addition,

NFSMA based on IDT cell is considered to be very promising because of their rigid and coplanar

molecular structure, which is conducive to charge transfer [59]. IDT has many chemically

modifiable sites, through which the molecular structure and performance can be optimized. For

example, adding four hexylphenyl around the fused-ring system of IDT can improve the

solubility and intermolecular interaction of the acceptor molecule [57,60,61], however, such

structure has not come up in reports of constructing IDT-based PSMAs yet. Furthermore, in the

light of being conveniently available to synthesizing the central-core and modifying the different

types of linkages through which the IDT-based PSMAs can be classified into four types as

follow, and what’s more, the unique centrosymmetric SMA framework and varieties of backbone

configuration induced by the copolymerizing points, IDT-type PSMAs shows excellent potential

in achieving breakthroughs towards the PCE of the all-PSCs [62].

Figure 5. Molecular structure and chemically modifiable sites of IDT-based PSMAs.

2.1.1. Thiophene linkage

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In 2017, PZ1 was designed and synthesized by Zhang et al, taking IDIC-C16 as the key

building block, and thiophene as the linking unit [46]. This design strategy not only reserved the

advantages of NFSMA IDIC-C16 (planar structure, high electron affinity, high absorbance), but

also showcased the advantages as a conjugated polymer (good film forming properties, better

long-term and large-area morphological stability). Except for the IDT-based SMA units, the

thiophene used as the linkage can also adjust the photoelectric properties of the material.

Compared with IDIC-C16, the energy level of PZ1 has better adaptability to the PBDB-T, thus

the PCE produced by the PBDB-T:PZ1-bsased polymer blends reached 9.19%. In 2019, Li et al.

selected fluorine-containing wide band gap (Eg) PM6 as the congener donor of PBDB-T [63].

The appropriate deviation of highest occupied molecular orbitals (HOMO) and lowest

unoccupied molecular orbital (LUMO) energy level between polymer donor and acceptor (PZ1)

granted sufficient driving force for exciton dissociation and reduced the energy loss ( ELOSS) to

achieving high-lying VOC. As a result, all-PSCs based on the PM6:PZ1 was demonstrated an

impressive PCE of 11.2%. In 2020, PIDTC-T was designed and synthesized by Yan et al [64].

Other than benzene-terminated structure of SMA unit in PZ1, the thiophene was harnessed to

construct the end group. In addition to being introduced into the active layer as an acceptor

material, PIDTC-T can be served as an involatile solid additive of PM6:Y6 system to promote

the solar cell efficiency. The same team later adopted traces of polymerized component namely

BN-T, featuring the typical B←N electron-deficient structure as the central core without IC

terminal group to construct ternary OSCs with PM6:PY-IT as the host system, whose polymeric

acceptor is featured by a monomer with A-D-A’-D-A configuration ubiquitously found in

designing high-performance PSMAs [65]. Finally with the weight ratio of 1:1:0.1 for PM6:PY-

IT:BN-T matrix, the corresponding all-PSC reached an impressive PCE of 16.03%

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outperforming that of 15.11% for binary PM6:PY-IT one, which could be attributed to

simultaneously reinforced VOC, JSC and FF, in the light of the finely interpenetrable crystalline

regions of D/A, the mitigated non-radiative energy loss and exceptional charge and energy

transfer pathway between phases of two acceptors. Notably, the ternary batches also showed a

best PCE of 15.5% well duplicable when film area close to 1 cm2.

It can be concluded that the modulation of terminal-group, regioregularity of polymer main

chain and donor matching are the dominant approaches to regulating performances of the IDT-T

(IDT as the core while thiophene as the linkage) based devices. More than that, to obtain high

PCE, bold yet careful modification of IDT central core for employment of third component such

like incorporating B←N interaction into central unit, is also an effective mean.

Figure 6. Chemical structures for IDT core-based PSMAs with thiophene as the linking unit.

17
Table 1. Performance parameters for IDT-core based PSMAs with thiophene linking unit.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PZ1 -5.74 -3.86 1.55 PBDB-T 0.830 16.05 68.99 9.19 [46]

PZ1 -5.74 -3.86 1.55 PM6 0.96 17.1 68.2 11.2 [63]

PIDTC-T -5.99 -4.05 1.55 PM6 0.815 16,19 63.3 8.35 [64]

PY-IT:BN-T -5.64 -3.79 N.A. PM6 0.951 22.63 73.6 15.85 [65]

N.A. = not available.

2.1.2. Bithiophene linkage

In 2020, Yuan et al. prepared PIDIC2T, PIDIC2T2F and PIDIC2T2Cl, and studied the

effects of different halogen atoms on the photovoltaic properties of the materials [53]. Despite

the LUMOs and Egs of these polymer acceptors were almost the same, the halogen atom played a

significant role in facilitating the charge transfer behaviors of both between the polymer

acceptors and within the D/A interfaces. With the donor PM6, the PCE of chlorinated acceptor-

based device worked out the best (7.11%) among the three other devices. When paired with

donor PBDB-T, PIDIC2T2Cl still obtained higher PCE (5.13%) and higher VOC (0.82 V). In

2021, polymer acceptor P2TF was prepared with fluorinated bithiophene as linking unit by

Huang et al [66]. In order to reach the objective of scaled-up production, different isomers of

NFSMA units were compared and studied. It found that the geometry of the two isomers (Figure

7a-b) possessed a similar planar degree (Figure 7c-d) thus a negligible discrepancy in their

molecular packing and the optoelectronic properties. As shown in Figure 7e-f, there was only a

tiny gap between their energy levels. In addition, IDIC-TF-3 exhibited more asymmetric (Figure

18
7g-h), resulting in higher permanent dipole moment (1.50 vs. 1.41 D). These optimization

processes significantly improve the charge generation and dissociation process of the device.

Figure 7. The (a) and (b) are the isomers of IDIC-TF-4 and IDIC-TF-3, respectively. DFT

simulated structural geometry of (c) IDIC-TF-4 and (d) IDIC-TF-3. DFT calculated molecular

energy levels of (e) IDIC-TF-4 and (f) IDIC-TF-3. Permanent dipole moments of (g) IDIC-TF-4

and (h) IDIC-TF-3 [66]. Copyright 2021 Elsevier. (i) Structure of IDT core-based PSMAs of

bithiophene as linking unit.

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Table 2. Performance parameters for IDT-core based PSMAs with bithiophene type linking

units.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PIDIC2T -5.65 -3.85 1.54 PM6 0.90 10.47 52.0 4.89 [53]

PIDIC2T2C
-5.67 -3.87 1.55 PM6 0.90 12.66 62.0 7.11 [53]
l

PIDIC2T2F -5.73 -3.89 1.55 PM6 0.90 12.81 43.0 4.96 [53]

PIDIC2T -5.65 -3.85 1.54 PBDB-T 0.80 9.07 41.0 2.97 [53]

PIDIC2T2C
-5.67 -3.87 1.55 PBDB-T 0.82 10.75 60.0 5.34 [53]
l

PIDIC2T2F -5.73 -3.89 1.55 PBDB-T 0.85 9.00 53.0 4.07 [53]

P2TFa -5.79 -3.93 1.58 PM6 0.95 16.84 66.57 10.65 [66]

a
Treated with 2% CN and thermal annealing at 110 ℃ for 3 min.

2.1.3. Benzodithiophene (BDT) linkage

Yan et al. replaced the thiophene linking unit in PZ1 with fluorinated BDT unit in 2019 to

prepare PFBDT-IDTIC [52]. Thanks to the good electron mobility and high absorption

coefficient of PFBDT-IDTIC, the VOC derived from PM6 working as the donor was as high as

0.96 eV along with an impressive PCE of 10.3%. Matching with donor polymer PBDB-T, the

electron mobility lowered a bit due to the higher HOMO energy level of PBDB-T, leading to a

significant drop in PCE to about 8.0%. In 2021, fused with sulfur (S), and silicon (Si) atom in

BDT-type linking unit, two PSMAs named PSF-IDIC and PSiF-IDIC were synthesized by Chen

et al. in order [67]. The distinction of heteroatoms in side chains on of linking units hardly affect

the energy levels and band gaps, while the inferior film morphology and weakened exciton

20
dissociation and charge migrating behaviors subjected to which were unexpectedly observed as

the introduction of silicon atoms. PBI-α/β were prepared by Li et al. [68], distinguished from the

isomerism of ID end groups (TCN-α/β). In comparison, the PBI-α carried out the lower VOC

(0.930 V) but gave a short-circuit current density (JSC) (19.0% mA cm-2) above that of the PBI-β,

which could be ascribed to the more obvious molecular stacking effect of PBI-β in turn bolstered

the ordered π-π stacking in donor skeleton and improved the Eloss of the corresponding device,

which could also plausibly account for the reason that fill factor (FF) of PBI-β (0.684%)

outshone that of PBI-α (0.646%). In addition, PBI-α has a wider absorption spectrum than PBI-β,

resulting in higher JSC of PBI-α-based devices. In 2022, PBDT was prepared and synthesized by

Cui et al [69]. The all-PSCs based on the PTQ10:PBDT blend demonstrated a PCE of 8.13%

with a VOC of 1.08 V, a JSC of 12.27 mA cm-2, and an FF of 62%. The strong electron donating

ability and good planar structure of BDT provided a suitable energy level with PSMAs (HOMO

= -5.84 eV, LUMO = -3.78 eV), showing a narrow gap of HOMO energy level with the donor

(HOMO = -5.54 eV, LUMO = -2.98 eV), and thus improving the VOC of the device.

In short, sulfur atom is a promising functional method towards building efficient BDT-based

linker unit for IDT-based PSMA, whereas the functional atoms inserted in BDT linkage should

be carefully selected with investigation of the internal intermolecular-interactions since the issue

of morphology control. The thiophene-terminated end group could afford certain polymerization

sites for obtaining regularly-grown chain of PSMA thus to facilitate orderly packing and improve

photovoltaic performances of the device. Finally, novel side chains like aromatically conjugated

benzene are in serious need to be developed and researched.

21
Figure 8. Chemical structures for IDT core-based PSMAs with BDT as the linking unit.

Table 3. Performance parameters for IDT-core based PSMAs with BDT type linking units.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PFBDT-IDTIC -5.78 -3.85 1.62 PBDB-T 0.83 14.05 66 8.0 [52]

PFBDT-IDTIC -5.78 -3.85 1.62 PM6 0.96 15.27 68 10.3 [52]

PSF-IDIC -5.68 -3.89 1.64 PM6 0.97 15.67 66.97 10.18 [67]

PSiF-IDIC -5.73 -3.88 1.65 PM6 0.99 13.47 62.15 8.29 [67]

PBI-α -5.8 -3.7 1.63 PM6 0.93 19.0 64.6 11.4 [68]

PBI-β -5.8 -3.6 1.70 PM6 1.03 16.1 68.4 11.3 [68]

PIDT -5.71 -3.74 1.66 PTQ10 1.10 14.19 66.0 10.19 [69]

PBDT -5.84 -3.78 1.66 PTQ10 1.07 12.31 62 8.13 [69]

22
2.1.4. Other type linkage

PIDT (Figure 9) was synthesized by Cui et al. alongside PBDT mentioned in 2.1.3 section.

Owing to excellent electron-donating property of IDT shaped linker, the LUMO energy level of

the PIDT got upward with a higher VOC of 1.10 eV for the PSC compared to PBDT-based one.

Moreover, the more uniform phase separation in PIDT:PTQ10-based device was found with a

more effective charge transport and extraction and less energy loss, which benefited a lot to the

enhanced JSC and FF [69]. In 2020, based on IDIC-C16, Wang et al. used three different bridging

atoms (C, Si, and Ge) in the link unit to synthesize three different PSMAs:PF2-DTC, PF2-DTSi

and PF2-DTGe [70]. It is found that the Si as the bridging atoms had a great influence on the

crystallinity, the extinction coefficient and the electron mobility in corresponding PSMA. The

relevant absorption onsets of these polymer acceptors were basically about 785 nm, resulting in a

50 nm red shifted absorption compared with the corresponding SMA (IDIC-C16), which

provided a better adaptation to donor PM6. The LUMO energy level was close to -3.88 eV for

IDIC-C16, but the HOMO level moved upward, which contributed to narrowing the band gap, so

the JSC can be improved without sacrificing VOC. In 2022, Liu et al. linked IDIC derivative as the

acceptor unit, thiophene as main donor unit, and thiophene-linked NDI as the secondary donor

building block [71]. The polymer acceptors were PTer-N10, PTer-N25 and PTer-N50 by

adjusting the molar ratios of NDI. The introduction of NDI can adjust the molecular structure to

regulate the energy level, reduce the aggregation between molecules and ensure the good

solubility of the acceptor. Ternary PSMAs have good optical absorption, good morphology and

charge mobility in the blend films, and the consequent PCE based on PM6:PTer-N25 reached the

highest value of 11.94%. Currently, a strategy combining double electron-withdrawing building

blocks using IDIC and DPP (diketopyrrolopyrrole) afforded by Wang et al. was meant for

23
obtaining a regiorandom polymerized small molecule, namely P(IDIC-2TDPPEh), for the sake

of good electrophilic effect and charge transport property of DPP [72]. Whereas, because of the

severe issue on charge split and transporting caused by excessive aggregating-morphology

(implicated by uniform surface and imperceptibly effective phase separation evidenced by AFM)

together with an unsatisfied fluorescence quenching rate (estimated as 54%), finally the best PCE

of only 1.57% with rather low JSC of 4.88 mA cm−2 and FF of 38.32% produced by the PBDB-

T:P(IDIC-2TDPPEh)-based device.

In brief, based on varieties of fused-ring building blocks with efficient electron mobility and

absorption properties including dithienocyclopentacarbazole (DTC), IDT, NDI, and DPP, the

hetero atom strategy along with side-chain and ter-polymer engineering were conducted to

construct linking units to enhance especially crystallinity and electron mobility of the PSAMs. It

should be highlighted that the bridging atoms still requires more researches gave it an easy yet

effective way to modulate the photoelectric performance and enhance the robustness of the solar-

cells.

24
Figure 9. Chemical structures for IDT-core based PSMAs with other type linking units.

Table 4. Performance parameters for IDT-core based PSMAs with other type linking units.

HOMO LUMO Egopt VOC JSC FF PCEmax


Acceptor Donors Ref.
(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PF2-DTC -5.76 -3.90 1.57 PM6 0.97 14.11 60.8 8.31 [70]

PF2-DTSi -5.74 -3.87 1.57 PM6 0.99 16.48 66.1 10.77 [70]

PF2-DTGe -5.78 -3.90 1.57 PM6 0.97 14.48 57.6 8.09 [70]

PTer-N10 -5.80 -3.94 1.86 PM6 0.91 10.54 56.70 5.43 [71]

PTer-N25 -5.66 -3.98 1.68 PM6 0.94 19.52 65.13 11.94 [71]

PTer-N50 -5.61 -3.93 1.68 PM6 0.94 14.49 62.84 8.56 [71]

P(IDIC-2TDPPEh) -5.59 -3.91 1.47 PBDB-T 0.84 4.88 38.32 1.57 [72]

25
2.2. IDTT core based PSMAs

Compared with IDT, IDTT (Figure 10) has longer fused conjugate core, so that the

corresponding polymer has smaller optical band gap, higher absorption coefficient, higher

HOMO energy level and enhanced charge transfer performance [48]. With the increase of the

size of oligothienoacene units, the lowest energy absorption peak is basically unchanged, the

energy gap of HOMO and LUMO of IDTT will be reduced by about 0.2 eV, and the degree of

delocalization will be higher, due to the expansion of π-conjugation system alone the polymer

backbone [73]. Actually, the thought about expansion of conjugated spacer towards IDTT lighted

the road to the upcoming Y-series star- molecules. Beyond that, bidirectional conjugation

extension inclines to be whereby electron-donating substitution of phenyl and its derivatives for

higher absorption and π-packing, while the elongated branched/nonbranched alkyl side-chains

can be conducted to the same R-positions (Figure 10), in order to improve solubility for PSMAs

so as to better blend with the donor polymers. Except for the SMA unit refinement, linkers

always witnesses to be highly tunable with multiple categories can covering the thiophene, the

fused tricyclic unit likely containing heteroatoms, and even the ones with insertion of nonfused

spacer which brings the polymer acceptors with good flexibility and elasticity. The relationships

between different EGs and performances of related PSMAs need to be exploited and discovered

through adjusting the changeable main-rings and halogenated atoms in EG units.

26
Figure 10. Molecular structure and chemically modifiable sites of IDTT-based PSMAs.

Taking ITIC as the construction unit and thiophene unit as the link unit, a novel n-type π-

conjugated polymer (PN1) was obtained by Zhang et al [74]. In their work, the meta-

alkoxybenzene was attached with a bulky alkyl to help improve the solubility and extinction

coefficient. Owing to the ordered molecular orientation and dominant face-on packing to form

ideal blend morphology, PCE can be up to 10.5%. As a novel PSMAs, PT-IDTTIC was

polymerized by Yan and co-workers with IDTT-C18 as the central core unit, IC as the end group

and thiophene as the linking unit [48]. And the maximum PCE based on that reached 12.06%.

Compared with the PZ1, the band gap width of PT-IDTTIC reduced from 1.55 eV to 1.49 eV

with the absorption coefficient as high as 2.41 × 10 5 cm−1. Sharing the identical donor polymer

PM6, the performances of related device fairly improved in line with the VOC increasing from

0.94 V to 0.97 V. This can probably be ascribed to a very small voltage loss (Vloss) only of 0.52 V

found in the device. Benefiting from the stretched octadecyl group, the solubility in solvent was

guaranteed. Two PSMAs, PF3-DTCO and PF3-DTC, were prepared on the basis of ITIC-C16

acceptor unit and C-O/C bridged donor unit DTCO/DTC by Wang et al. Compared with PF2-

DTC, the increased conjugated length of the acceptor unit ensured PF3-DTC a wider absorption

spectrum and higher absorption coefficient. Moreover, the introduction of C-O bridges also

improved the morphology and electron mobility of the active layer blends. Compared to the

mixture based on PF2-DTC with a root mean square roughness (Rq) of 2.24 nm, a significant

increase in that of the PF3-DTC-based mixture presented to be 6.56 nm. This possibly meant an

inadequate phase separation which in turn suppressed the exciton dissociation, charge extraction

and charge transfer processes, resulting in lower Jsc and FF values in the PF3-DTC-based

27
device. Based on IDIC-C16 and ITIC as the building block, terpolymer acceptors were

developed by Su et al [75]. By adjusting the ratio of the two SMA monomers, the corresponding

optical and electrical properties can be easily customized. Among the series, PM6:PF1-TS4-60

had the best performance. Comparatively speaking, the PCE value of 6.17% for PF1-TS4-based

device was nearly slumped by half of the terpolymer device (9.31%) for the reason of poor JSC

and FF. With the increase of the content of ITIC components, the absorption spectrum of the

acceptor gradually red shifted, and as a result, PF1-TS4-60 based device obtained the highest

external quantum efficiency (EQE) value close to 70%, which was of validity to improve the

conversion between photon and electron.

In a word, the molecular bandgaps are highly boosted with enlarged light coefficients in

IDTT-core based PSMAs in comparison with IDT-based ones. However, the modification could

be remotely influential of enhancing PCEs maybe since the uncoordinated impacts on the VOC

and the JSC values. Nevertheless, the chain engineering and linker customization should be

classic and instructive to be noticed. For one case in point, phenyl-flanked ITIC showcased

considerable strength in face-on behavior between the polymer-chains to render well-oriented

aggregation and optimized morphology so as to boost FF of the devices. Besides, the C-O

bridged linkage to create PSMAs is promising to strengthen the absorption and to more than

well-define the blending morphology, thus benefiting the JSC and FF.

28
Figure 11. Chemical structures for IDTT-core based PSMAs.

Table 5. Performance parameters for IDTT-core based PSMAs.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PN1 -5.71 -3.85 1.55 PM6 1.00 15.2 69.0 10.05 [74]

PT-IDTTIC -5.59 -3.86 1.49 PM6 0.97 17.96 67.0 11.69 [48]

PF3-DTC -5.73 -3.91 1.55 PM6 0.97 13.77 58.5 7.83 [76]

PF3-DTCO -5.71 -3.95 1.50 PM6 0.94 15.75 68.2 10.13 [76]

PF1-TS4 -5.75 -3.89 1.55 PM6 0.99 11.21 55.6 6.17 [75]

PF1-TS4-20 -5.73 -3.89 1.55 PM6 0.99 13.73 59.7 8.12 [75]

29
PF1-TS4-40 -5.73 -3.9 1.55 PM6 0.99 14.67 60.8 8.83 [75]

PF1-TS4-60 -5.71 -3.9 1.55 PM6 0.99 15.3 61.4 9.31 [75]

PF1-TS4-80 -5.7 -3.91 1.55 PM6 0.97 15.51 60.3 9.16 [75]

2.3. BT core-based PSMAs

Benzodithiazole (Figure 12) as an electron-withdrawing moiety with benign electron-

withdrawing property, frequently appearing in constructing the (non) fused A-type central core

to fine tune the electron affinity and intra-/inter-molecular electronic interactions of the polymer

acceptors for a typical instance of PY-IT, the solar cells based on which have already achieved

over 19% PCEs [49]. Most BT based polymers have high crystallinity, good charge migration

characteristics, low band gaps and excellent optoelectronic properties and so on [77]. BT is

widely used as one of important conjugate debris of OSCs. In this part, we will not only show

what researchers have done to adjust the molecular structure and chemical component of BT-

based PSMAs for improvements of all-PSC performances from perspective of linking units, but

also the systematic molecular design and device optimization will be particularly detailed as in

the offshoot of the assortment of thiophene-based linker. As we illustrated in Figure 12, one can

technically subdivide the PSMA structure into two instrumental building blocks: SMA unit and

π-linkage which all have regularity of the strategy-for-object to be traced, i.e., for SMA part, the

X means the heteroatom like Se in the fused spacer to replace the traditional S atom to broaden

absorption and improve photocurrent, α and β represents the unsettled alkyl side-chains in

outer/inner position of the backbone to enhance the solubility and regulate the molecular

stacking, energy level and intermolecular interactions. The EG essentially featuring 1,1-

dicyanomethylene-3-indanone (IC) in conjunction with the (non) halogenated substitutions

30
conducted is usually found to be adjusted to achieve the excellent photovoltaic performance

simply through thiophene or acene as the terminated part. All these SMA strategies will be

analyzed through cases study together with the polymer issues of regional isomerism and

molecular-weight differences, as the molecular design part for 2.3.1 section. The ternary devices

and device techniques will also be summed up in the same part given the large number of

fruition focused through around PSMAs constituted by BT-core and thiophene-linker. The

commonly used linkers based on such as T (thiophene), BDT (benzodithiophene), BTI

(bithiophene imide) and Se, and other linkers (design principles for linking units) will also be

systematically summarized as the breakdown for the section of BT core unit.

Figure 12. Molecular structure and chemically modifiable sites of BT-based PSMA.

2.3.1. Thiophene linkage

(a) Cases Analysis of Molecular-Level Design for High Performance BT-Based PSMAs with

Linker Thiophene towards All-PSCs

31
Based on the brilliant electron-affinity property of benzodithiophene and the thiophene

conjugate-linker being simple yet effective to fine-tune the molecular stacking and charge

transport, continuous emergence of novel structure of PSMAs based on BT core and thiophene

linkage has fully demonstrated the great potential of improving device performance through

careful design of SMA unit, properly dealing with the dispersity of polymer mass and

randomness of polymerization sites at IC end-groups, and smartly employing random ter-

polymerization strategy.

In 2021, Alex K.-Y. Jen and his team stepwise introduced F atom and Se respectively into

end-group and fused BT-core on Y6-consisted PSMA named PY2S-H to construct PY2Se-F

[78], then further replaced the F atom with Cl atom to obtain PY2Se-Cl, enabling the gradual

enhancement of PCEs with marginal rise in JSCs and evident improvement in FF values for these

PSMAs based devices when paired with suitable donor PM6, ascribed to the red-shifted

absorption (30-40 nm), reasonably deep-lying LUMO energy level and optimized molecular

arrangements for orderly packing, resulting further from the strengthened effect of

intermolecular interactions since the cooperative work of selenium and F/Cl atoms. In

comparison with PY2Se-F, PY2Se-Cl promoted a lot in FF from 72.2% to 74.3% and thus

reached a superior PCE (16.1% versus 15.6%), because of the optimal morphology to facilitate

the charge transport and transfer which can be referred to the growing values from 6.50

(PM6:PY2Se-F film) to 8.61 nm (PM6:PY2Se-Cl film) by what CCLs suggested. Whereas, the

voltage loss got upward in PY2Se-F/Cl-based devices owing to the great ICT effect caused by

synergistic influence of selenium and halogenated atoms. Min et al. introduced two fluorine

substituents onto PYT to prepare PY2F-T [79]. PM6:PY2F-T devices implemented 15% PCEs,

when the third component PYT was added, the PCE of the devices can reach about 17%. The

32
introduction of PYT effectively promoted the exciton separation and balanced the charge

extraction in the active layer. Huang et al. prepared a new polymer acceptor PFA1 by

introducing fluorine atoms on random positions of end-group [80]. The PCE of all-PSCs

fabricated with donor polymer PTzBI-oF was 15.11%. In addition, when the donor polymer was

displaced by the PM6 and PBDB-T, the PCEs of the binary devices still kept performing well in

turn with 13.75% and 14.20%. It observed that chemical fragment of IC-F-T in PFA1 exhibited a

slightly higher torsional potential barrier (Figure 13). The strong intra-chain coplanarity and

rigidity caused by the non-covalent bond interaction between F atom and S atoms greatly

enhanced the charge transport. Compared with the fluorine-free PY5T (It is the name also known

as PJ1 in other articles), a bathochromic shift at 815 nm in absorption peak along with an

improved extinction coefficient (9.4 × 104 cm−1) happened to the PFA1 solid-film. Replacing the

common IC end groups with CPTCN units, PYTT-1, PYTT-2, and PYTT-3 were prepared by

Min et al. by changing locations of the sulfur atom on end-groups and the linker unit substitution

positions [81]. The best PCE of PBDB-T:PYTT-2-based device exhibited the highest value of

14.32% among that of others while PBDB-T:PYTT-1 and PBDB-T:PYTT-3 devices exhibited

inferior to be respectively 13.54% and 12.41%. PBDB-T:PYTT-3 blend film was more flat and

uniform than that of PBDB-T:PYTT-1 and PBDB-T:PYTT-2, which could suggest an over-

mixed morphology (Figure 14a-c). The GIWAXs diffraction peaks of PYTT-1 and PYTT-2 thin

films in (010) direction all markedly located at qz = 1.70 Å-1, qz = 1.62 Å-1 respectively (Figure

14g), in line with the finely proper D/A compatibility of the both active layers.

33
Figure 13. (a) Potential energy surface scan of model compounds IC-H-T and IC-F-T, simulated

by a density functional theory method at the B3LYP/6-31G* level. (b) Absorption spectra of

blend films [80]. Copyright 2020 American Chemical Society.

34
Figure 14. Contact-mode AFM surface scans (20 × 20 and 5 × 5 μm 2) of (a) PBDB-T:PYTT-1,

(b) PBDB-T:PYTT-2, and (c) PBDB-T:PYTT-3. Two-dimensional (2D) GIWAXS patterns for

the (d) PBDB-T PYTT-1, (e) PBDB-T:PYTT-2, and (f) PBDB-T:PYTT-3 blend films. (g) One

dimensional (1D) GIWAXs line curves with respect to the in-plane (IP) and OOP directions,

acquired from the critical incident angle of 0.13° [81]. Copyright 2021 American Chemical

Society.

Jen et al. prepared PYT-1S1Se, PYT-2S and PYT-2Se by contriving an asymmetric

selenophene skeleton [82]. Compared with S, Se atom has more orbital overlap and delocalized

35
electron being more polarizable in π-conjugated system, which significantly improves the charge

transport and narrows the Eg width for the PSMAs. Compared with selenium-free option PYT-2S

and symmetrically selenium-containing counterpart PYT-2Se, the all-PSC based on PYT-1S1Se

not only optimized JSC (24.1 mA cm−2) and VOC (0.926 V), but also obtained a remarkably low

Eloss of 0.502 eV. In parallel, the same group implemented the two Se atoms in the middle

thiophene ring of the fused-spacer [83]. The resulting PSMA PFY-2Se gained a high PCE over

14% owing to the desirable external quantum efficiency and high fill factor. However, the

incompetent PCE value compared to PYT-2Se with different Se-hybridized positions would be

fascinating to be uncovered. Side chain tailoring proposed by Sun et al. succeeded in breaking

through the record PCE of binary all-PSC then, in which four PSMAs designated as PY-X

sharing with identical L8-BO framework as the SMA unit but the varying branched alkyl chains

substituted on pyrrole motif of SMA building block.[18] Owing to the molecular assembly of

SMA-HD that arranged similarly with L8-BO within the single crystal, the PY-HD polymerized

through which proved a decent 16.41% PCE considering the favorable packing distance to boost

the charge transport. Based on this, the PY-DT with a expanded length of side chains further

heightened the PCE up to 16.76% (the highest one among the other PY-Xs) due mainly to the

well-defined phase separation, up-shifted LUMO level, leading to relatively high VOC with

suppressed non-radiative recombination loss of 0.18 eV which is comparable to the crystalline

silicon solar cells) while the PY-DH fell in the lowest one (14.86%), which can be accused from

the sizable steric- hindrance that caused an inferior crystallinity in blend film thus an

unsatisfactory charge properties. Jen et al. prepared a series of PSMAs PY2S-H, PY2S-F,

PY2Se-F and PY2Se-Cl [78]. With the synergistic effect of selenium and fluorine/chlorine

substitution on broadening absorption and enhancing intermolecular interaction, PY2Se-F and

36
PY2Se-Cl exhibited a significant red-shifted absorption compared with the control PY2S-H and

PY2S-F. When Cl was substituted with F on the end group, the blend morphology consisting of

PY2Se-Cl and polymer donor PM6 established better than that of PY2Se-F, resulting in better

charge transfer. All-PSCs based on PM6:PY2Se-Cl achieved an impressive PCE of up to 16.1%.

Zhang et al. reported a novel PSMAs PNT with benzene-extended end-group of SMA unit [84].

With excellent electron delocalization property, the PNT exhibited a notably broadened

absorption (600-900 nm) with a narrow bandgap of 1.37 eV, gifting the optimized device

(additive-treated with CN) based on PBDB-T:PNT an extraordinary JSC of 24.4 mA cm-2. In

short, the optimized blend film of PBDB-T:PNT showcased a favorable molecular stacking and

stark trend of crystallizing as well as more clear fibrils texture, leading to efficient charge

extraction and collection with a high PCE of 13.7% for corresponding device. Two regiorandom

PSMAs called PYFCl-T, and PYF&PYCl-T, were newly synthesized containing asymmetrically

substituted F and Cl atoms respectively in the terminal groups on each side of SMA unit [85].

The binary devices based on PM6:PYFCl-T and PM6:PYF&PYCl-T under best condition

showed a slight discrepancy in PCEs (14.03% vs. 13.38% for the former and latter in turn) due to

the suboptimal VOC and FF which may be caused by relatively intense self-aggregation of

PYF&PYCl-T in mixing morphology. However, when PYFCl-T (10 wt%) was introduced into

PM6:PY-IT host system as the third component, the intermixing phase of original blend was

immensely mediated with a more suitable phase separation and reasonable reservation of pure

domain. With refined-modulation of morphology and supplementary absorption being beneficial

for exciton generation and efficient charge behavior, the PCE of PM6:PY-IT:PYFCl-T-based

device utterly improved to 18.12%, standing out from that of PM6:PYFCl-T binary one

(14.03%) and PM6:PY-IT:PYF&PYCl-T ternary one (16.56%), with a VOC of 0.940 V, a Jsc of

37
25.76 mA cm−2, and an FF of 74.84%. With good merits of asymmetric configuration of PSMAs’

backbone in mind, A-D1-A’-D2-A-structured monomer featuring S-shape was innovatively

synthesized by Duan et al. by removing one thiophene ring from the electron-donating block of

Y6 [86]. The polymer chains of PSMA prepared by this can grow randomly during

polymerization and rendered the target PAY-IT a high molecular weight with low batch-to-batch

sensitivity (molecular weight of PAY-IT ranged from 18.3 to 26.2 kDa with the related PCEs

values spanning within 14.4%–14.9%), promising the enormous availability of skeleton-

asymmetric strategy in all-PSCs. Moreover, benefiting from the well co-planarity and charge

transport, the CN+TA treated PM6:PAY-IT-based device demonstrated the best PCE reaching

14.9% with a prominent VOC of 0.94 V and an FF of 0.73, though the efficiency still lag behind

its classic PM6:PY-IT counterpart, which can presumably be attributed to the downward energy

level, enlarged optical bandgap and weaker aggregate behavior that was resulted from the

random skeleton conformation of PAY-IT versus PY-IT, requiring furthermore optimization.

38
Figure 15. Chemical structures for BT-core based PSMAs with thiophene linkers (classified by

factors of different modification methods for SMA units).

39
Table 6. Performance parameters of the PSCs embracing PSMAs modified through varieties of

chemical methods.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PY2F-T -5.71 -3.84 1.37 PM6 0.87 24.2 71.2 15.0 [79]

PY2F-T:PYT -5.71 -3.84 1.37 PM6 0.9 25.2 76.0 17.2 [79]

PFA1 -5.74 -3.84 1.41 PTzBI-oF 0.87 23.96 72.67 15.11 [87]

PYTT-1 -5.66 -3.82 1.5 PBDB-T 0.93 20.66 70.35 13.54 [81]

PYTT-2 -5.73 -3.83 1.52 PBDB-T 0.91 22.0 71.53 14.32 [81]

PYTT-3 -5.76 -3.88 1.46 PBDB-T 0.82 21.99 68.47 12.41 [81]

PYT-2S -5.65 -3.72 1.41 PM6 0.94 22.3 70.7 14.8 [82]

PYT-1S1Se -5.61 -3.75 1.39 PM6 0.92 24.1 73.0 16.3 [82]

PYT-2Se -5.59 -3.79 1.37 PM6 0.91 23.9 71.4 15.5 [82]

[83]
PFY-2Se -5.64 -3.91 1.45 PBDB-T 0.88 23.4 72.0 14.7

PY2S-H -5.76 -3.87 1.46 PM6 0.94 22.3 70.7 14.8 [78]

PY2S-F -5.78 -3.91 1.43 PM6 0.92 23.3 70.5 15.1 [78]

PY2Se-F -5.76 -3.93 1.42 PM6 0,89 24.4 72.2 15.6 [78]

PY2Se-Cl -5.75 -3.93 1.42 PM6 0.88 24.5 74.3 16.1 [78]

PNT -5.60 -3.80 1.37 PBDB-T 0.87 24.4 64.4 13.7 [84]

PY-HD -5.52 -3.94 N.A. PM6 0.94 24.05 72.8 16.41 [18]

PY-OD -5.60 -3.84 N.A. PM6 0.94 23.95 73.2 16.53 [18]

PY-DT -5.60 -3.83 N.A. PM6 0.95 23.73 74.4 16.76 [18]

PY-DH -5.65 -3.76 N.A. PM6 0.96 21.39 72.3 14.86 [18]

PYFCl-T -5.66 -3.73 1.40 PM6 0.93 23.32 64.83 14.03 [85]

PYF&PYCl-T -5.69 -3.76 1.38 PM6 0.91 23.51 62.74 13.38 [85]

40
PY-IT:PYFCl-T N.A. N.A. N.A. PM6 0.94 25.76 74.84 18.12 [85]

PY-IT:PYF&PYCl-T N.A. N.A. N.A. PM6 0.93 24.55 72.78 16.56 [85]

N.A. = not available.

PYT with subsequently increased molecular weights denoted as PYTL, PYTM and PYTH

were prepared by Min et al [88]. The Eloss of PYTM ranked the highest 0.544 eV with the middle

molecular weight, whereas the PYTL and PYTH respectively got suboptimal Eloss values of 0.532

eV and 0.528 eV. PJ1 was designed and synthesized by Huang et al [89]. The Mn and Mw of PJ1-

L, PJ2-M and PJ3-H were 7.3 kDa and 17.2 kDa, 11.0 k Da and 25.1 kDa and 23.3 kDa and 39.0

kDa. With the increment of Mn, the absorption edge red shifted, and the extinction coefficient

tended to rise. The absorption intensity for thin film of PJ3-H at 600-900 nm was very strong

with the extinction coefficient as high as 1.39 × 10 5 cm-1. The PCE of PBDB-T:PJ1-H-based

device reached the maximum of 14.4% among other control ones. Yang et al. developed regio-

regular polymer acceptors PA-5 and PA-6 with different relative molecular weights.[90] The

solar cell based on PA-6-H had large phase separation by virtue of its limited solubility accused

from overly large molecular weight. However, PA-5 crystallized more orderly, leading to higher

JSC and FF and the corresponding devices gave 16.11% photovoltaic performance.

Based on the regional isomerization phenomenon of the PSMAs, fluorinated PYT materials

(named PYF-T-o and PYF-T-m respectively) were synthesized by Yan et al [91]. It is

demonstrated that the superior backbone configuration of the PYF-T-o reinforced the inter-chain

stacking so as to promote the charge transportation. PM6:PYF-T-o-based devices showcased the

maximum PCE of 15.2% with photovoltaic performance much better than the non-fluorinated

41
PYT-featured one. Three polymer acceptors were prepared, named PY-IT, PY-OT, and PY-IOT,

by Yang et al [92]. The PM6:PY-IT-based device exhibited maximum PCE of 15.05% with VOC

of 0.933 V, JSC of 22.30 mA cm−2 and FF of 72.3%. In the sequence of PY-OT, PY-IOT, PY-IT,

the absorption edge of the three acceptor materials gradually red-shifted. Li et al. deliberately

synthesized two PSMAs named PBTO and PBTO-γ recently in 2024 [93]. Since good backbone

planarity and balanced and fast charge transport benefiting from structural lock of S-O

noncovalent interaction and introduction of regioregularity in PBTO-γ, as a result, such polymer

acceptor brought a top-notch PCE recorded as 11.42% for the device. When PBDB-T served as

the donor part in active layer, the PCE of PBTO-based solar cells decreased by over 50%,

because of the undesired grain-size and disordered intermixing nano-fibers which were

detrimental to realizing high photocurrent density. Ma et al. developed three isomeric PSMAs

through regular/random chlorination and copolymerization position on terminal IC group of

SMA unit. Systematically research revealed that two resulting PSMA referred to PY2Se‐Cl‐o

and PY2Se‐Cl‐ran presented a decent phase-separating morphology in films blended from with

PM6, leading to higher charge mobility and less recombination. Hence, the device based on

PM6:PY2Se‐Cl‐ran-blend won the highest 16.23% PCE, accompanying with extremely close

value of 16.17% for PM6:PY2Se‐Cl‐o one, but the superior device ductility and photostability

was belong to the former one given the better state of entanglement in the morphology arising

from the higher molecular weight. In addition, the excessive mixing morphology should be

responsible for the dramatically poor PCE of PY2Se‐Cl‐m-involved cells, which underscore the

significance of rational isomer design in PSMAs-based photovoltaic realm [94]. By transforming

the polymerization site of conventional PSMA, Chen et al. proposed two PSMAs namely SP-T

and SP-TT featuring conjugation extension in branched direction [95]. It is confirmed that SP-T

42
with single thiophene possessed a more planar molecular configuration than that of SP-TT

relying upon bithiophene linker, which ensured more condensed and ordered π-π stacking in the

blended film (PM6:SP-T) and more distinct fibrous morphology visualized by AFM images,

which was disparate from the relatively sparse and imperceptible one observed for PM6:SP-TT,

can partially be explained by immoderate miscibility between donor and acceptor. Consequently,

superior 13.54% PCE was achieved by PM6:SP-T-based device with fantastic charge carrier

extraction time of 0.28 μs and a charge carrier lifetime of 0.37 ms charted by TPV and TPC

measurements, highlighting the underlying value of readily adjusting configuration of PSMA

through isomerizing its chemical structure toward the efficient all-PSCs. Huang et al. exquisitely

opted long branched alkyl side chains to enhance solute-solvent interaction to prepare PIR-C39,

PRi-C39 and PRo-C39 [96]. Regular skeletons aided the intramolecular charge transfer and

intermolecular interaction, nay due to the smaller backbone warping conducive to better

intermolecular stacking, consequently PRi-C39 showed more red-shifted absorption than PRo-

C39 in the film. PCE of PTzBI-Si:PRiC39- and PTzBI-Si:PRoC39-containing devices also

reached about 14.4% and 13.4%. Regio-regular PSMA named PBTO-γ was designed using

nonfused BT-core by Li et al [93]. Due to the more favorable molecular packing nature and

better crystallinity, the device based on PBDB-T:PBTO-γ showed a higher photocurrent and thus

the PCE realized a fairly boost to 11.42% from the randomly copolymerized PBTO based one.

43
Figure 16. Chemical structures for BT-core based PSMAs (classified by factors of regional

isomerism and different molecular weights).

44
Table 7. Performance parameters of the PSCs embracing PSMAs modified on the basis of

polymer nature.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

L11 -5.73 -4.34 1.39 PM6 0.95 18.0 64.3 11.1 [51]

PYTL -5.73 -3.92 1.46 PM6 0.93 20.92 64.51 12.55 [51]

PYTM -5.69 -3.92 1.47 PM6 0.93 21.78 66.33 13.44 [51]

PYTH -5.69 -3.93 1.49 PM6 0.95 17.14 52.91 8.61 [51]

PJ1-L -5.68 -3.83 1.43 PBDB-T 0.89 20.3 69.0 12.3 [89]

PJ1-M -5.67 -3.83 1.42 PBDB-T 0.88 21.6 70.0 13.2 [89]

PJ1-H -5.64 -3.82 1.41 PBDB-T 0.9 22.3 70.0 14.1 [89]

PA-6-L -5.67 -3.80 1.43 JD40 0.92 22.13 72.99 14.81 [90]

PA-6-M -5.65 -3.78 1.42 JD40 0.92 22.42 72.41 14.99 [90]

PA-6-H -5.65 -3.75 1.45 JD40 0.92 20.53 67.36 12.78 [90]

PA-6-L -5.67 -3.80 1.43 JD40 0.92 22.13 72.99 14.81 [90]

PA-6-M -5.65 -3.78 1.42 JD40 0.92 22.42 72.41 14.99 [90]

PA-6-H -5.65 -3.75 1.45 JD40 0.92 20.53 67.36 12.78 [90]

PYF-T-o -5.73 -3.81 1.38 PM6 0.90 23.3 72.4 15.2 [91]

PYF-T-m -5.73 -3.77 1.38 PM6 0.95 4.6 32.7 1.4 [91]

PY-IT -5.68 -3.94 1.39 PM6 0.93 22.3 72.3 15.05 [92]

PY-OT -5.69 -3.9 1.42 PM6 0.95 16.82 62.6 10.04 [92]

PY-IOT -5.68 -3.92 1.41 PM6 0.94 19.71 65.6 12.12 [92]

PY2Se‐Cl‐o −5.75 −3.93 1.34 PM6 0.89 24.48 74.3 16.17 [94]

PY2Se‐Cl‐m −5.70 −3.87 1.34 PM6 0.96 5.22 35.3 1.76 [94]

PY2Se‐Cl‐ran −5.73 −3.91 1.35 PM6 0.90 24.16 74.4 16.23 [94]

PIR-C39 -5.67 -3.81 1.43 PTzBI-Si 0.89 19.6 66.0 11.3 [96]

45
PRi-C39 -5.71 -3.79 1.42 PTzBI-Si 0.90 23.1 69.4 14.3 [96]

PRo-C39 -5.65 -3.86 1.44 PTzBI-Si 0.83 22.1 73.2 13.3 [96]

SP-T -5.75 -3.87 N.A. PM6 0.89 20.61 73.72 13.54 [95]

SP-TT -5.70 -3.83 N.A. PM6 0.87 15.61 71.62 9.76 [95]

N.A. = not available.

Terpolymer strategy for developing PSMAs can feature both characteristics of being readily

available and effective of performance advancing as what have been extensively reported.

Triggered by this, Sun et al. attempted to copolymerize two monomers named SMA-C11 and

SMA-DT respectively with non-branched and branched side chains substituted on β-position of

the thiophene motifs of SMA [97]. As anticipated, the corresponding device (PM6:PY-82) with

20% molar ratio of SMA-DT yielded the best PCE value (17.15%), which topped the PM6:PY-

C11- (the PSMA with 100% SMA-DT) and PM6:PY-DT-based (the PSMA with 0% SMA-DT)

devices, along with intermediate VOC value but higher JSC and FF, owing to the fine-tuned

morphology by terpolymer with more reasonable diameter of fibrillar region forming within

blend films can be observed (10.19, 14.92, and 23.09 nm for PM6:PY-C11, PM6:PY-82, and

PM6:PY-DT blends, respectively), thus leading to faster hole transfer across the binodal and

synchronously charge recombination and non-radiative recombination abating. Moreover, the

optimized morphology of M6:PY82 also contributed to the mechanical flexibility of the related

device, affording another avenue to address wearable use of all-PSCs utilizing PSMAs. Other

than terpolymerized acceptors, Ying et al. prepared the chemically random terpolymer donor P1-

co-25%P2 [98]. This donor optimized the π-π stacking, compatibility and phase separation, being

conducive to exciton diffusion and charge transport. The binary all-PSCs constructed by

integrating P1-co-25%P2 with PYFT exhibited an impressive PCE of 14.67%. Designing

PSMAs with unique polymer shape such like long side-chain-hanging polymeric acceptors is an

46
interesting research topic found to be beneficial to promote optoelectronic properties and

morphology evolution for the device. Most recently, terpolymerization strategy was resorted by

Min et al. by randomly incorporating TYTz-4F as pendant into Y-series based polymer backbone

to acquire PSMAs denoted as PY-TYTz-x with x values indicating the molar ratios of TYTz-4F

component [99]. Owing to the decreased aggregation of blend film with more interpenetrating

fiber-like networks favorable for charge separation and transport, the PY-TYTz-5 based rigid

and flexible devices showed the best PCE of 18.14% and 16.17% respectively, outshining the

PY-TYTz-0 with a linear skeleton.

47
Figure 17. Chemical structures for BT-core based PSMAs derived from ternary polymerization

strategy.

Table 8. Performance parameters of the PSCs embracing PSMAs modified through ter-polymer

strategy.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

48
PY-82 -5,64 -3.88 N.A. PM6 0.95 23.82 75.8 17.15 [97]

P1-co-
PYFT -5.74 -3.84 1.41 0.83 23.51 73.09 14.67 [98]
25%P2

PY-TYTz-0 −5.70 −3.96 N.A. PM6 0.919 25.15 72.10 16.68 [99]

PY-TYTz-2.5 −5.74 −3.92 N.A. PM6 0.926 25.52 74.96 17.71 [99]

PY-TYTz-5 −5.72 −3.92 N.A. PM6 0.926 25.74 76.12 18.14 [99]

PY-TYTz-10 −5.73 −3.93 N.A. PM6 0.922 25.46 72.33 17.00 [99]

N.A. = not available.

As a whole, the four aspects of optoelectronic and morphological properties should be

integrally considered and addressed for PSMAs designing: i) Gain strong near-infrared

absorption to be complementary with polymer donors. Generally speaking, it can be benefited

from the Se atoms with weak electron-affinity inserted in the conjugate-backbone. The

conjugation-extension of end-group and moderate halogenation are also favorable for dense

aggregation and reduced band-gaps to realize high absorption coefficients. ii) Reach a high VOC

via low Eloss and reasonable energy gap between LUMO level of PSMAs and HOMO level of

polymer donor. To handle this, the key is to reasonably chlorinate the PSMA, conduct side chain

engineering, design regioregular and length-fitting polymer acceptor, in order to enhance the

difference of electrostatic potential between D/A with relatively high energy of CT state (ECT)

of the acceptor material and reduce the trap-state density and energy disorders originating from

the disorganized polymer-chain orientation and excessive entanglement. iii) Ensure intermediate

co-palanarity and suitable intermolecular interactions between inter-chains of PSMAs to achieve

optimum molecular packing and ordering, which is indispensable to efficient charge dynamics

process in OPVs. As we can concluded, constructing properly halogenated atoms and taking full

use of the non-covalent interactions of end-groups are the pivotal and urgent project. Besides, the

49
subtle modulation of polymerization position associating with the T-linker and EG is also

significant and un-negligible. iv) Fine-tune the miscibility between p- and n-type polymeric

semiconductors to realize favorable phase separation to allow for effective exciton split and

reduction of recombination, i.e., kind of morphology in which pure domain phase yet with an

ordered and intimate connection across D/A interface. For this issue, tailoring long side chains of

SMA unit for PSMAs and taking method of terpolymerization should be the obviously effective

ways to tune the overlarge phase separation. More important, the miscibility-based anticipation

and forecasting should be indispensable.

(b) Cases Analysis of Effects of Ternary Blend Strategy conducted to PSMAs on All-PSCs

Ternary all-PSCs can be easily found to be two types: polymer donor/polymer

donor/polymer acceptor (D1:D2:A) and polymer donor/polymer acceptor/polymer acceptor

(D:A1:A2), they are all impactful to boost the performances since the alignment of energy level,

absorption, charge and exciton properties and phase-separating morphology can undergo a

refinement compared to their corresponding binary ones, yet only when the mutual miscibility of

the ternary polymer-matrix got properly consolidated [100].

An instructional model for prediction of mechanical property (especially for the tensibility

and the elastic modulus) of the ternary polymer blends from miscibility and morphology analysis

has been established in 2023 by Ye et al [101]. To the best of their knowledge, four typical types

of ternary systems can be divisionally proposed by employing serial contents of PTQ10, PTVT-

T, PNDI and PPCBMB respectively as the third components to inter-react with the host systems.

The introduced PTQ10, PTVT-T and PPCBMB can effectively improve the mechanical stability

of the blends mainly because of the decrease in the degree of the crystallinity while the more

50
flexible PNDI yielded more chain entanglement and amorphous region which obviously

enhanced the resilliance of the related blends. They pointed out that the mechanical properties of

the third component can be selective to affect those of the blends due to the miscibility between

the third components and the host systems, for example, although the elastic modulus of the

PTVT-T is higher than the PTQ10, the elastic modulus values of the corresponding blends

increased more slower in the former when their contents increased, as a result of the more

miscible PTQ10 to be dispersed within the blends. The specific information on relationships of

the miscibility (χ value), morphology and the mechanical properties can be referred to the Figure

18.

Figure 18. The relationship between miscibility and morphology of ternary blend films. (a) The

relationship between four typical types of aggregated structures and their corresponding χ values.

51
(b)–(e) Melting temperatures of four third components blended with polymer donor PM6 and

polymer acceptor PYF-IT/PY-IT, respectively. (f) χ values distributions of four third-component

polymers with the host donor (PM6) and host acceptor (PYF-IT/PY-IT). (g) Diagram of the

distribution of various third-component polymers in four ternary blend films [101]. Copyright

2023 Royal Society of Chemistry.

In 2022, a chlorinated PSMA named PYCl-T with A-D-A’-D-A structured backbone of SMA

unit similar to that of classical PY-IT, was reported by Li et al. and blended into PM6:PY-IT

system at weight proportion of 20% accounting for PY-IT [102]. Due to proper miscibility and

stair shaped arrangement of frontier orbital energy levels among three polymers, an over 16%

PCE was gained by PM6:PY-IT:PYCl-T ternary device while 1 cm 2 area fellow one can

maintain in that of 15.52%, supported especially by extremely low interaction parameter of 0.007

K benign enough to realize highly packing ordering within PY-IT:PYCl-T blend, and a proper

one determined to be 0.035 K between PM6 and PY-IT:PYCl-T film to obtain uniform fibrous

texture for donor-acceptor phase. Ye et al. demonstrated that introducing 50% PYF-IT (the

fluorinated version of PY-IT) into PM6:PY-IT can make best benefits for the PCE improvement

of devices causally with fill factor significantly increasing from 70.1% (the PYF-IT free one) to

75.0% and even lead flexible large-area device to an impressively high PCE of 14.5% [103]. It

can practically ascribed to the impediment of aggregation of PM6 in binary system by the

appropriate insertion of PYF-IT, resulting in a proper domain spacing along with distinguishable

interpenetrating networks of the highly-tangled polymer matrix, thus such nano-morphology not

only heightened the exciton dissociation efficiency and balanced the charge transport, yet above

all, the decreased crystallinity and fully entanglement of chains also grant merits of stretchability

52
and long-term thermal tolerance for PM6:PY-IT:PYF-IT ternary device (as reflected in Figure

19). Following year, Min et al. ingenuously proposed a chlorinated PSMA PY-2Cl rather

compatible with the previously reported PY-1S1Se and intensive to long-waved absorption, as a

guest acceptor to add into PM6:PY-1S1Se host system [104]. Because of the formation of well-

miscible alloy-like acceptor phase, the PY-1S1Se:PY-2Cl (interaction value was 0.03 K) binary

blend achieved a reinforced molecular packing and ordering with a modest acceptor-based

domain size of 34 nm in ternary film (suggesting the well-manipulated phase separation), bit of

larger than that of PM6:PY-1S1Se, favorable for the exciton diffusion (prolonged L D of 8.80 nm

vs. 7.98 nm for PM6:PY-1S1Se binary one) and superior results regarding device physics

(suppressed non-radiative recombination and energy disorder which are crucial to fine-regulated

FF), as well as more complementary and stronger photon harvesting. Upon advantages of

solidified morphology, the ternary device based on PM6:PY-1S1Se:PY-2Cl showcased a

desirable operation stability and a exceedingly high PCE of 18.2% with a high JSC of 25.74 mA

cm-2

Figure 19. (a) The evolution plots of normalized PCE with storage time for the three blend films

53
and the extrapolated T80 lifetime. (b) The diagram of the tensile testing of blend films for FOW

and FOE measurement. (c) The comparison of COS of the films with varied PYF-IT contents

tested by the FOE method. (d) The stress-strain curves of PM6:PY-IT, PM6:PYF-IT, and

PM6:PY-IT:PYF-IT (50%) blend films tested by the FOW method. (e) The J-V curves of 1.0

cm2 large-area cells based on the optimized PM6:PY-IT:PYF-IT blend and their binaries. (f)

Bending test results of flexible cells. The experiments were all conducted at a radius of 5 mm

[103]. Copyright 2022 Wiley Online Library.

and an extraordinary FF of 77.2%. Li et al. proved the alleviated burn-in loss for all-PSCs

through introducing the PTQ10 as the guest donor into PQM-Cl:PY-IT host at a rational ratio of

20 wt% (given the lowest PCE loss ratio for “burn-in” devices with series of PTQ-10 content),

signifying the optimized lifetime and stability for the ternary sample, along with an improved

efficiency and ductility [105]. The ternary devices suffering light soaking alongside the fresh

ones were fabricated by authors to comprehend the underlying reason for burn-in loss

suppression after precisely treating of PTQ-10. As illustrated in Figure of length scales

(involving pure acceptor phase (2Rg) and mixed phase (χDAB)) versus the PTQ-10 content, the 2Rg

and χDAB were observed to be 26 and 21 nm for fresh devices with 20% PTQ-10 incorporation,

unveiling even more comparably balanced and reasonable D-A intermixing morphology for

boosting JSC and FF generally maintained from PQM-Cl:PY-IT binary one, while the other blend

films with higher ratio of PTQ-10 exhibited pronounced increasing in χ DAB values to break the

phase-distribution-balance which was approved to be detrimental for device efficiency.

Compared with fresh devices at 20% PTQ-10 component, the burn-in processed ones performed

almost identical χDABg and 2Rg, can be explained by the complementary tendency in degradation

54
direction of PTQ-10 (inclined to shrink) and PQM-Cl (prefer to swell) phase in the inner of bulk

films to balance the D-A interpenetrating networks, according to the CLs (coherent lengths)

values of PQM-Cl:PY-IT and PTQ-10:PY-IT blends, further theoretically and really suggesting

the delicately regulating ratios of each component to build up ternary matrix is of significance in

concurrently enhancing operational stability and efficiency of all-PSCs. Most recently, A brand

new polymer donor named QQ1 with unique imide-fused dithienoquinoxaline as the A unit was

subtly designed by Zhou’s group and proved to work well with the PY-IT as the polymeric

acceptor (the more extended absorption especially in short-wave range, the deep HOMO energy

level to fit with PY-IT for higher VOC, the more appropriate intermixing property with PY-IT and

more precedent face-on packing couple with decent crystallites formation, in comparison with

PBDB-T:PY-IT cluster) to construct binary all-PSCs, with a incredibly high PCE (18.81%)

topping almost all the non-halogenated OSCs reported up to now [11]. Worth noting, the F-

BTA3 as the third component was further introduced into QQ1:PY-IT and contributed to uplift

the VOC from 0.917 V to 0.904 V with PCE of up to 19.20%, as a result of shallower LUMO level

of which. PJ2 was prepared by Huang et al. with additional thiophene spacer to be fused into

polymer backbone of analogue PJ1 which would be discussed below [106]. Limited by the weak

aggregation ability, the PJ2 was difficult to be solely used as acceptor material. However, it can

be used as a mediator to improve the compatibility of PBDB-T:PJ1 active layer when prepared

three components. Under the condition of easy preparation, the best PCE of PBDB-T:PJ1:PJ2

based device is 14.28%. Hao et al used the ternary assisted continuous solution deposition (SSD)

strategy to adjust the vertical component distribution of all PSC (based on PM6/PY-IT:PDI-2T

active layer), and realized 16.03% excellent PCE [107]. PDI-2T was served as the third

component to assist exciton diffusion and charge transfer of PM6. Interestingly, SSD was

55
demonstrated to be an effective way to customize the vertical phase distribution under the

condition of suppressing the density of trap states and optimizing the exciton yields, which can

improve the charge transfer ability and exciton diffusion length by inhibiting non-radiative

recombination. The solar cells prepared by Tao et al. based on PM6:PY-IT:PC 71BM active layer

had achieved excellent PCE of 16.36% [108].Thanks to the deeper energy level, excellent

electron transport characteristics and unique spherical structure of PC 71BM, the active layer

effectively improved the driving force of charge transfer.

Ternary devices embracing the third guest component of acceptors or donors has garnered

extensive attention in improving PCEs and mechanical performances for all polymer solar cells,

in which active layer can undergo evolution in crystallizing ability, molecular aggregation and

orientation, alloy-like interior micro-structure with enhancement of domain purity along with

considerable diminishing in trap-state within formed films and optimal phase separation with

high-quality transfixed fibrils, therefore providing extra charge transfer and transport channel to

facilitate more efficient photon-to-electron conversion of device. The miscibility (could be

figured as intermolecular noncovalently interactions) between three polymers can be tuned

through selection of materials being structurally similar and of complementary performances,

which can enhance the FF. Multistage energy-level alignment between guest components and

main active systems are requisite and primal to the high VOC, should also be required in

considerations. Likewise, the complementary absorption should also be emphasized to notice for

the improvement in JSC. More interestingly, the flexible ternary devices with good mechanical

stability can be conducted through introduction of weakly-aggregated third component while the

thermal stability of the device are found to be related to the enhancement of crystallinity and

formation of morphological lock by addition of intermediating polymer.

56
Table 9. The effects of ternary device strategy on performance parameters of PSMAs-based all-

PSCs.

active-layer Proportion of VOC JSC FF PCEmax Ref.

each component (V) (mA cm-2) (%) (%)

(w/w/w)

PM6:PY-IT N.A. 0.925 23.35 71.05 15.35 [102]

PM6:PYCl-T N.A. 0.907 19.76 70.80 12.69 [102]

PM6:PY-IT:PYCl-T 1:1:0.2 0.920 24.64 73.31 16.62 [102]

PM6:PY-IT:PYF-IT 1:0.6:0.6 0.92 24.1 75.0 16.6 [103]

PQM-Cl:PTQ10:PY-IT (fresh) 0.8:0.2:1.2 0.943 24.80 78.9 18.45 [105]

PQM-Cl:PTQ10:PY-IT (soaked) 0.8:0.2:1.2 0.939 24.56 77.3 17.85 [105]

PM6:PY-1S1Se N.A. 0.927 24.22 72.30 16.5 [104]

PM6:PY-2Cl N.A. 0.868 24.09 69.69 14.8 [104]

PM6:PY-1S1Se:PY-2Cl N.A.:1:0.2 0.914 25.15 77.2 18.2 [104]

QQ1:PY-IT N.A. 0.904 26.49 78.57 18.81 [11]

PM6/PY-IT:PDI-2T N.A. 0.949 23.97 70.48 16.03 [107]

PM6:PY-IT:PC71BM 1:1:0.2 0.942 25.06 69.27 16.36 [108]

N.A. = not available.

(c) Cases Analysis of Device Optimization towards All-PSCs

The device technology respecting to the PSMAs-based all-PSCs is always developed

around the conundrums about practical application of the solar cells concerning green-solvent

processing, mass production and stable and optimized morphology being such like well phase

separating and distributing which can be technically realized by additives strategy and sequential

57
deposition method respectively. Here we will summarize some representative advancement made

in all-PSCs based on PSMAs with BT-core.

Zhang et al. creatively incorporated a series content of PM6 in acceptor layer of PY-IT and

then deposited the blend on pure PM6 layer that had been spin-coated on the substrate [109]. The

additive-treated LBL device based on PM6:PY-IT won the best increasing in PCE from 16.04%

to 17.45% precisely under condition of 10 wt% PM6 insertion, principally influenced by the

more exciton dissociation channel afforded by extra D:A interface within donor-lacking top of

PY-IT layer, which perfectly handled the conundrum of too large distance for exciton diffusion

from acceptor phase to donor one commonly happening in active-layer concerning LBL-

processed planar hetero-junction. The systematic research also revealed a climb-up-then-decline

trend in correlation that the incorporated PM6 content (the extreme point locates approximately

at 10 wt%) versus the external quantum efficiency, packing and orientation degree of blended

films, as well as charge split and transport properties and resulting FF values, indicating the

effective way that properly mingling donor polymer with PSMA-based solution to prepare

acceptor layer towards efficient LBL-based all-PSCs. Organic solar cells with inverted structure

have been commonly deemed as impactful approach for the stable and long-lifetime photon-to-

electron conversion. Stroke by this, PM6 and PY-DT as the typical combination to constitute

active layer were selected by Guo’s team to fabricate all-PSCs involving both inverted and

conventional device configuration which were all conducted by BHJ and LBL processing [110].

With a large proportion of PY-DT aggregated close to the ITO electrode which was regarded to

be with high work function to use to collect the photo-generated electron, the PM6:PY-DT-based

inverted LBL device only performed a terrible PCE of 12.41% due basically to the forbidden

charge transfer from the acceptor PY-DT to the donor PM6 according to the Förster energy

58
transfer principle, particularly when compared with the conventional LBL-deposited one that

showed up the highest 17.24% efficiency among the devices fabricated in this research.

Meanwhile, the PCE of conventional device based on BHJ morphology exhibited relatively

inferior than the LBL one, resulting from the optimal vertical-distribution of components and

efficient exciton diffusion in donor-based phase because of the fine self-absorption property of

PM6. It is widely considered that the kernel to refine the molecular packing and blending

morphology through additives is fine-tuning the intermolecular interactions as to electron donor

and acceptor. Hence, Chen et al. exquisitely designed three isomeric solid additives named SA-

T1, SA-T2 and SA-T3 (SA-series), featuring the perhalogenated dibromothiophenes with

iodination and possessing potentially better polarizability and crystallinity than their fluorinated

counterparts [111]. As GIWAXs and Flory-Huggins parameters suggested, since the boosted

crystallinity and packing behavior of PM6 and PY-IT in blend films with the more optimized

miscibility, the SA-treated PM6:PY-IT devices showed much higher PCE than the as-cast ones,

especially for that of 18.3% demonstrated by the device prepared through treatment of SA-T1,

which was considered to be amidst the top rankings in the binary all-PSCs because of the best

charge dynamics process with extraordinary JSC and FF of 24.80 mA cm-2 and 76.5% and the

outstanding thermal and thickness-dependent stability. Lately, two small molecular additive

C5Ph and C6Ph were adopted into PBQx-TF:PY-IT all-polymer system and proved a noticeable

PCE improvement from 16.91% to 18.02% especially after traces of loading of C5Ph, reported

by Chu et al. [10], due basically to the independently enhanced molecular ordering and

crystallinity for both donor and acceptor, which was deeply revealed and certified to be as a

result of noncovalently pincer-shaped bonding interactions built between end-cap of SMA unit of

PY-IT and phenyl in side chains of C5Ph. Most strikingly, the pseudo-plane-heterojunction

59
(PPHJ) devices of PBQx-TF:PM6/PY-IT with C5Ph incorporation showed a supremely high

efficiency of 19.01% with an FF quite approaching 80%, as a reflection of entire evolution of

morphology even with a reinforcement of subcrystallinity, and decline of trap-state density and

tremendously optimized charge and exciton properties. Noted, the intimate bridge-connection

between the inter-chains of PY-IT by the C5Ph also furnished ternary all-PSCs with eminent

mechanical flexibility and stability, by which, was tight enough for the phase separation of active

layer to fully resile back to the initial state after bending tests. Duan et al. prepared PBDB-

T:PYT based devices through LBL treatment (Figure 20) and different additives (PCE for

16.05%) [112]. In addition, film of PBDB-T:PYT with heat treatment improved the lamellar

ordering of PBDB-T and helped form the PYT polymer fibrils. Moreover, a bimodal-like

morphology with two phases cohesively permeating throughout one another was observed in the

vertical direction. It effectively improved the exciton splitting efficiency. Huang et al. refined the

spin coating treatment, so that the maximum PCE can arrive up to 14.34% [106]. When the

rotation speed was changed from 1800 rpm to 6000 rpm, the corresponding PCE also increased

from 13.44% to 14.34%. Limited by solubility, further increasing the solution concentration had

little effect.

Overviewing above progresses, the technology of device preparation assumed a significant

position in optimizing morphology by improving degree of molecular arrangement, stacking and

crystallinity, as well as by refining interactions between donor and acceptor and their vertical

component distribution with respect to substrate, technically through approaches like

incorporating solid or solvent additives and conducting layer-by-layer (LBL) method, which are

favorable to photo-generated exciton dissociation and charge transport and resolving the

ubiquitous thermal-stability issue appearing in PSCs, also enabling the flexible electronics with

60
high stretchability coupling with excellent recovery ability. Besides, as the spin-coating method

gradually replaced by large-area blade-coating technique, a solid foundation was laid for

incoming industrilization of all-PSCs with promising PSMAs as acceptors. All these

advancements encouraged people to endeavor more efforts on innovation of device processing

methods to solve those cutting-edge difficulties.

Figure 20. (a) Chemical structures of PBDB-T (electron donor) and PYT (electron acceptor),

and device architecture of the all-PSCs employed in this work. (b) Schematic diagram of the

regulation of the microstructures of the polymer donor and acceptor via solvent additive [112].

Copyright 2021 Elsevier.

Table 10. The effects of device technics optimization on performance parameters of PSMAs-

based all-PSCs.

61
Acceptor HOM LUMO Egopt Donors VOC JSC FF PCEmax Device Ref.

O (eV) (eV) (V) (mA (%) (%) preparation

(eV) cm-2) method

PY-DT -5.60 -3.83 N.A. PM6 0.96 21.31 71.31 14.59 Inverted BHJ [110]

PY-DT -5.60 -3.83 N.A. PM6 0.96 19.98 64.71 12.41 Inverted LbL [110]

Conventional
PY-DT -5.60 -3.83 N.A. PM6 0.97 23.54 73.22 16.72 [110]
BHJ

Conventional
PY-DT -5.60 -3.83 N.A. PM6 0.97 23.83 74.60 17.24 [110]
LBL

Additive SA-
PY-IT N.A. N.A. N.A. PM6 0.93 25.61 76.5 18.3 [111]
T1

Additive SA-
PY-IT N.A. N.A. N.A. PM6 0.93 25.55 75.7 17.9 [111]
T2

Additive SA-
PY-IT N.A. N.A. N.A. PM6 0.93 24.57 75.9 17.4 [111]
T3

PY-IT N.A. N.A. N.A. PM6 0.95 23.25 64.1 14.1 As cast [111]

Additive
PY-IT N.A. N.A. N.A. PBQx-TF 0.92 24.30 77.61 17.37 [10]
C6Ph

Additive
PY-IT N.A. N.A. N.A. PBQx-TF 0.92 24.68 79.25 18.02 [10]
C5Ph

PBQx- Additive
PY-IT N.A. N.A. N.A. 0.91 26.08 79.91 19.01 [10]
TF:PM6 C5Ph

PYT -5.71 -3.70 N.A. PBDB-T 0.91 20.70 0.64 12.00 As-cast [112]

PYT -5.71 -3.70 N.A. PBDB-T 0.9 21.96 0.67 13.31 TA [112]

PYT -5.71 -3.70 N.A. PBDB-T 0.9 22.92 0.74 15.17 CN [112]

PYT -5.71 -3.70 N.A. PBDB-T 0.91 22.68 77.0 16.05 CN+TA [112]

a
Acceptor layer of PY-IT with wt 10% PM6 blended in.

N.A. = not available.

62
2.3.2. BDT Linkage

Numerous works pertinent to BDT-based linkage have been successfully down with PCEs

of PSMAs-based all-PSCs palpably boosted from around 9% to beyond 15%, principally through

halogenation and length-regulation of the side-chains on bulk BDT to fine-tune the morphology

and fully take virtues of the BDT (good chain rigidity and extended conjugate distance). Zhou et

al. earlier prepared PSMAs, named as A701, using Y6 derivatives as building blocks and BDT as

link units [113]. Employing PBDB-T as the donor and A701 as the acceptor, PCE can reach

10.7% at the highest. Due to good light-harvesting ability, the absorption coefficient was as high

as 6.85 × 104 cm−1 and the JSC was 18.27 mA cm−2. PG1 possessing structure similar to A701 was

synthesized by Li et al [114]. They used BDT-T as the linking unit as expansion in branched

direction to tune the packing capability and the solubility. When added 4% of CN additive,

PBDB-T:PG-based device can reach the best PCE of 11.5%. Wang and fellow workers linked

BDT-T unit to prepare PF5-Y5 including Y5 as the building block [115]. The PCE based on

PBDB-T:PF5-Y5 device optimally performed to be 14.45% mainly by the virtue of wide and

high absorption of SMA unit Y5. PYN-BDT and PYN-BDTF were prepared by Su et al [116].

The highest PCE yield was 13.22% for PBDB-T:PYN-BDTF-based devices. The best PCE

generating from PM6:PYN-BDTF device was 9.08%. Leaving out VOC, thanks to the fluorinated

acceptor, whether the donor was PM6 or PBDB-T, the photovoltaic performance of PYN-BDTF

was substantially better than that of PYN-BDT. Series of PSMAs regiorandom (RRd)-C12, RRd-

C20, and RRd-C24 as well as regioregular (RRg)-C20 and RRg-C24) proposed by Kim et al.

proved that can obtain more suitable aggregation and crystallization properties of polymers by

adjusting the side chain structure and changing the regional regularity of the main chain. PCEs of

63
the corresponding devices made a linear advancement with the increase of side chain length

(Figure 21) [117]. It should be noted that the longer side chains of PSMAs endowed the polymer

with higher solubility and RRg-backbone can reduce the defects of molecular arrangement in the

crystallized region and strengthen the inter-chain interactions, resulting in a higher crystallinity

and better photoelectronic properties.

To summarize, through precisely regulation of side-chains in both SMA unit and linkage help

widen and heighten the optical-absorption of the PSMA materials treated by BDT-spacer, and

what’s more, the intermolecular interactions between acceptor/acceptor and donor/acceptor could

be enhanced to provide more efficient JSC yield by simply introduction of fluorine or chlorine in

side chain of the linker BDT. Furthermore, conjunctive impact of the regioregular contact

between SMA/linker and the length of side-chain at inner position on polymer skeleton

configuration and aggregation behavior is notable and of significance as to the crystallinity and

mixing morphology.

Figure 21. Schematic illustrations of different blend morphology depending on the PSMA types

[117]. Copyright 2022 Wiley Online Library.

64
Figure 22. Chemical structures for BT-core based PSMAs with BDT type linking unit.

Table 11. Performance parameters for BT-core based PSMAs with BDT-type linking units.

65
Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

A701 -5.61 -3.8 1.42 PBDB-T 0.92 18.27 64 10.7 [113]

PG1 -5.66 -3.81 1.49 PBDB-T 0.94 17.8 69 11.5 [114]

PF5-Y5 -5.52 -3.84 1.5 PBDB-T 0.95 20.65 74 14.45 [115]

PYN-BDT -5.6 -3.76 1.38 PBDB-T 0.87 21.33 65 12.06 [116]

PYN-BDTF -5.67 -3.77 1.38 PBDB-T 0.86 22.28 69 13.22 [116]

PYN-BDT -5.6 -3.76 1.38 PM6 0.97 14.36 52 7.24 [116]

PYN-BDTF -5.67 -3.77 1.38 PM6 0.96 16.6 57 9.08 [116]

RRd-C12 -5.63 -3.96 1.44 PBDB-T 0.93 19.14 54 9.39 [117]

RRd-C20 -5.66 -3.97 1.44 PBDB-T 0.93 19.67 63 11.59 [117]

RRd-C24 -5.68 -3.99 1.46 PBDB-T 0.93 20.34 67 12.18 [117]

RRG-C20 -5.66 -3.95 1.41 PBDB-T 0.88 23.54 73 15.12 [117]

RRG-C24 -5.68 -3.93 1.42 PBDB-T 0.88 21.67 71 13.53 [117]

2.3.3. BTI and Selenophene Linkage

The selenophene and BTI are frequently used as linking unit in PSMAs with respectively

the electron-donating and electron-withdrawing properties, in order to promote the electron

transfer and transport as well as reinforce the ordered packing. Interestingly, the intensified

intra-/intermolecular interactions (n-π conjugation) to facilitate molecular stacking and charge

transfer produced by the selenophene and BTI are a bit of different, i.e., the electronic

delocalization induced by selenophene and adjacent conjugate system is more eminent since the

relatively lower restriction of lone-pairs in outermost shell of Se, while the high conductance of

BTI-based semiconducting materials is more dependent on its charge-transfer effect in between

adjacent conjugate unit [118].

66
A novel narrow band gap polymer acceptor L14 was reported by Guo et al [51]. When

matching with donor PM6, the device made 14.3% best PCE with JSC and FF values of 20.6 mA

cm−2 and 72.1% respectively. The rigid and coplanar backbone and good electron-accepting

property of BTI building block could account for strong electron mobility of L14 (8.7 × 10 −4 cm2

V−1 s−1) and the prominent optical absorption. Guo et al. studied the effects of different green

solvents on morphology of PM6:L14-based active-layer [119]. The solubility in 1,2,4-TMB and

o-XY solvents was found to be higher than in CS2 (b.p. of 46 ℃). In o-XY (b.p. of 144 ℃),

annealing duration was shorter, and the PCE was characterized by 15.6%. Compared to the

performances of the devices derived from other solvents, PCEs assigned to CS2, 1,2,4-TMB and

CF reduced to 13.03%, 13.84% and 14.61% respectively. It can be further explained by that the

increased crystallinity implied by the more ordered and compact molecular stacking in both

lamellar and π-π direction facilitated the electron transport capacity for the green solvent-treated

devices. PSMAs named as L15 and MBTI were further proposed by Guo et al.[120] Compared

with the acceptor material L14, L15 and MBTI featured a regioregular configuration along the

polymeric skeleton. The PCE of PM6:L15-based device reached over 15.22% with a high JSC

value of 22.21 mA cm−2, thanks to the high absorption coefficient, whereas the only 7.8% PCE

was harvested by PM6:MBTI-based device. However, when MBTI as the third component to be

added in the PM6:L15 system, maximum PCE displayed by 16.18%. Different from the bi-

component based photoactive layer, a multi-component system referred to as “S11” with

compound PM6, L15 and their block polymer named as PM6-b-L15 was obtained by Guo et al.

through convenient and cost-effective one-pot notion [121]. In this case, the S11 substantially

outperformed its analogue S9 with dominant PM6-b-PY-IT in both PCE (11.78% vs. 9.34%), FF

(52.15% vs. 70.11%) and thermal stability, since the subtly optimized compound active layer

67
where the long chain entanglement of dominant PM6-b-L15 enabled a well-interlaced fibrillar

network by suppressed the over aggregation of minority PM6 and L15 while which in turn filled

the nanovoids to restrict the chain motion to form a frozen morphology, leading to a more

balanced charge transfer with prolonged device lifetime and well-kept optoelectronic

performance (>80% PCE retention after 1000 h), when two-component PM6:L15 system was set

for further comparison. Li et al. synthesized regiorandom PS-Se [19]. The PS-Se-based devices

reached the best PCE of 13.83% lower than that of PN-Se-based control one. Impressively, the

optical absorption of PS-Se film red-shifted by 24 nm due mainly to the strengthened π-π

interaction and the enhanced degree of polymerization albeit with the poorer PCE it obtained,

implying the great potential in use of high performance photovoltaic acceptors. Y5-A-B PSMAs

were prepared by Kim et al. where “A” stood for selenophene (Se)/biselenophene (BiSe) and

“B” represented the backbone regioregularity (In/Mix/Out) [122]. The maximum PCE of 13.38%

was achieved by Y5-Se-In. The dihedral angles of between adjacent BT cores and IC groups for

different molecular structures are given out in the Figure 23. For θBT-BT, from small to large were

Y5-Se-In (13.70°), Y5-BiSe-Out (14.50°), Y5-Se-Out (35.10°), Y5-BiSe-In (52.09°), in turn,

while θIC-IC ranked as Y5-Se-In (12.50°), Y5-BiSe-Out (18.30°), Y5-BiSe-In (43.94°), Y5-Se-Out

(52.40°). Y5-Se-In got the smallest plane angle in favor of denser stacking between chains,

which could be as a result of the highest charge mobility of Y5-Se-In among other control

devices.

68
Figure 23. Side views of structural models of (a) Y5-Se PAs and (b) Y5-BiSe PAs using DFT

calculations by B3LYP/6-31G (d, p) model. The blue squares and orange triangles indicate the

planes of the IC and BT units, respectively. θIC-IC presents the plane angle between two

neighbouring IC units linked by a donating moiety while θBT-BT indicates the plane angle between

two near BT units [122]. Copyright 2021 Wiley Online Library.

PFY-0Se, PFY-1Se, PFY-2Se, and PFY-3Se with gradually enhanced degree of impact

from selenium were synthesized by Jen et al [83]. Despite the VOCs presented a drop trend with

the increasing number of Se, the JSC and FF slightly improved since the red-shifted absorption

(about 30 nm from PFY-0Se to PFY-3Se), reduced Eloss and stronger inter-molecular interactions.

As indicated by the (010) diffraction peaks of PFY-0Se, PFY-1Se, PFY-2Se, and PFY-3Se

locating at 1.56 Å-1, 1.58 Å-1, 1.60 Å-1, 1.61 Å-1, the best packing behavior of the PFY-3Se film

achieved being consistent with the highest charge mobility among the four blend films.

To summarize, the regioregular connection of BTI in PSMA furnishes the adequately planar

backbone architecture and considerably high JSC and offsets the unnecessary charge

recombination loss versus the randomly copolymerized counterpart. The one-pot method based

on BTI-linker also showcases the potential in easy preparation of efficient single-component

active material. Aside from BTI, linker selenophene is also promising in constructing high-

69
performance PSMAs with decent JSCs. Specifically, synergistic effect of Se in π-linker and in

SMA chain-block favors both the JSC and FF of the device. It should also be noted that

copolymerizing mode of being in/out as to the biselenophene affects completely different from

as the selenophene does on polymer chain growth for adjustment of the chain packing and

orientation.

Figure 24. Chemical structures for BT-core based PSMAs with BTI or selenophene type linking

unit.

Table 12. Performance parameters of BT-core based PSMAs with BTI/Se-Type linking units.

70
Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

L14 -5.79 -4.40 1.39 PM6 0.96 20.6 72.1 14.3 [123]

L14a -5.79 -4.40 1.39 PM6 0.95 21.09 65.17 13.03 [119]

L14b -5.79 -4.40 1.39 PM6 0.95 20.97 69.53 13.84 [119]

L14c -5.79 -4.40 1.39 PM6 0.95 22.10 74.10 15.62 [119]

L14d -5.79 -4.40 1.39 PM6 0.95 21.17 72.35 14.61 [119]

L15 -5.75 -3.94 1.38 PM6 0.95 22.21 71.86 15.22 [120]

PS-Se -5.69 -3.88 N.A. PBDB-T 0.87 23.27 68.0 13.83 [19]

Y5-Se-Out -5.68 -4.24 1.44 PBDB-T 0.88 16.09 56.0 7.92 [122]

Y5-Se-Mix -5.68 -4.25 1.43 PBDB-T 0.89 17.95 58.0 9.33 [122]

Y5-Se-In -5.68 -4.28 1.40 PBDB-T 0.86 21.74 72.0 13.38 [122]

Y5-BiSe-Out -5.64 -4.22 1.42 PBDB-T 0.92 18.12 66.0 10.67 [122]

Y5-BiSe-Mix -5.64 -4.22 1.42 PBDB-T 0.92 17.44 60.0 9.58 [122]

Y5-BiSe-In -5.66 -4.25 1.41 PBDB-T 0.86 16.54 59.0 8.52 [122]

PFY-0Se -5.68 -3.88 1.51 PBDB-T 0.90 20.9 68.8 13.0 [83]

PFY-1Se -5.68 -3.89 1.50 PBDB-T 0.89 21.2 72.9 13.8 [83]

PFY-2Se -5.64 -3.91 1.45 PBDB-T 0.88 23.4 72.0 14.7 [83]

PFY-3Se -5.65 -3.92 1.50 PBDB-T 0.87 23.6 73.7 15.1 [83]

S9 -5.64 -3.68 N.A. S9 0.95 18.79 52.15 9.34 [121]

S11 -5.71 -3.74 1.38 S11 0.95 17.62 70.11 11.78 [121]

a
Based on CS2 solvent. b Based on 1,2,4-TMB solvent. c Based on o-XY solvent. d Based on CF

solvent. N.A. = not available.

2.3.4. Other Types Linkage

71
Our ensuing concentration will focus on overview about other linkers of PSMAs based on

BT core, for the sake of thoughtful designing principles and molecular perspectives for linkage

development to pump consecutive impetus into commercialized prospects of PSMA-based all-

PSCs. As one important part of PSMA, linking unit is highly flexible and convenient to be

modified to subtly regulate the optoelectronic properties, morphological stability for PSMAs.

Therefore, to discuss in detail, the structural design for the linkers would be strategically sorted

in this part to give a comprehensive guideline, such as the hetero atoms substituted or constituted

linkages, the side chain modified linkers and the linking units with (non) conjugated flexible

spacer expanded or electron-accepting unit extended.

Zhang et al. prepared PY-DF using fluorinated thiophene as the connecting unit [20]. PY-DF

had more coplanar and rigid molecular conformations, leading to better conjugated skeleton and

stronger inter-chain stacking, thereby improved the electron mobility and reduced the energy

disorder. All-PSC based on PY-DF gave 15.7% high PCE. Wang et al. studied the role of B←N

based building blocks as the electron-accepting component by preparing and comparing PBN25

and PBN25-CC [124]. The introduction of B←N unit palpably reduced the LUMO/HOMO

levels of the molecules and promoted the exciton dissociation with lower E LUMO/EHOMO of -3.85

eV/-5.59 eV for PBN25 than that of -3.93 eV/-5.74 eV for PBN25-CC, ensuring the former work

better with donor in OSCs. In addition, PBN25 film exhibited stronger crystallinity, which could

be one of the reasons for higher-lying electron mobility. All in all, PBN25-based devices

performed more eminent than PBN25-CC, along with a PCE of 14.36%, VOC, JSC and FF of 0.89

V, 22.62 mA cm−2 and 71.6% respectively. He et al. introduced two fluorine substituents in

bithiophene to serve as the linker, with marriage of the isomerizing strategy to prepare PBTIC-γ-

2F2T and PBTIC-δ-2F2T [125]. Thanks to good crystallinity and good compatibility, the PCE of

72
PM6:PBTIC-γ-2F2T reached 14.34% with a VOC of 0.95 V, a JSC of 22.56 mA cm−2 and an FF of

66.89%. The polymer configuration as to δ-position connection obtained stronger aggregation

and was almost insoluble in common solvents. To seek potential virtue of halogenation of PSMA

backbone, PY-2T2Cl as an efficient PSMA was originally reported by Yuan et al. via

copolymerizing Y5-derivative and chlorinated bithiophene [126]. Compared to its non-

chlorination counterpart PY-2T, PY-2T2Cl showcased a red-shifted absorption profile and

furnished the solid blend (PM6:PY-2T2Cl) with favorable crystallinity as characterized by more

evident separation of mixing phase due to the more planar molecular geometry and stronger

intermolecular interactions induced by chlorinated acceptor. The device based on PM6:PY-

2T2Cl delivered a certified PCE of 9.35% farther surpassing that of PM6:PY-2T one (5.34%),

with substantially boosted JSC of 16.3 mA cm-2 and impressive FF of 65%. Bao et al. synthesized

PY-BTz with bithiazole as the linking unit [127]. The best PCE of 16.4% was gained by PBDB-

TF0.25:PY-BTz-based device, much higher than that of 9.85% for the PY-2T-based control one,

in which the heteroatom N on the linking unit was replaced by H atom. Such high performance

lied basically in the red-shifted optical absorption with a narrow optical band-gap of 1.42 eV and

more π-stacking, induced by the enhanced electron coupling and tremendously subsided dihedral

angles as well as noncovalent interactions of N-O within the polymer backbone. Benefiting from

its vantages of co-planarity, the scalable device based on PY-BTz printed from solution-shearing

in ambient was also corroborated a 14.7% high PCE.

Motivated by the superb photovoltaic performance resulting from refined electronic and

molecular structure via selenophene-conducted polymer acceptors, combining with π-linker

engineering, Min et al. systematically studied the effects of linkage unit with different

heterocycles on the performances of resulting PSMAs [128]. Accordingly, PSMAs named PY-O,

73
PY-S and PY-Se synthesized respectively with furan, thiophene and selenophene as linkers

presented disparate electron mobilities in the state of blended films, where the PBDB-T:PY-Se

blends topped the other films with value of 3.28 × 10 –4 cm2 V–1 s–1 together with a quite close

hole-transport capability of 3.16 × 10 –4 cm2 V–1 s–1, fundamentally because of the suitable inter-

molecular interactions in donor-donor and donor-acceptor, which offered the much better

molecular ordering and optimal crystallites with well-maintained phase-separation, in contrast

with the PBDB-T:PY-O one exhibiting an excessively aggregated and relatively amorphous

morphology. Greatly thanks to the eminent D/A miscibility and robust intermolecular

interactions, the PBDB-T:PY-Se based devices made the highest efficiency (PCE = 15.48%),

storage stability and mechanical robustness in unison. Another selenoium-rich PSMA named

PY3Se-1V was polymerized by Alex K.-Y. Jen et al. through selenophene π-spacer and an

asymmetric SMA unit with a vinylene fragment unidirectionally inserted into [129]. Possessing

an optical absorption approaching 1000 nm benefiting from good electron-donating property and

well-matched energy levels with PBDB-T, CN-processed PY3Se-1V-based binary all-PSCs

performed a superior PCE of 13.2% with an FF of 0.659 which was much higher than the DIO-

treated congeneric one, for the reason of better interpenetrating morphology with a more even

surface respecting to the PBDB-T:PY3Se-1V-based blend. However, it is noted that DIO-

mediated device particularly gave a higher JSC value of 25.9 mA cm-2 and more intense EQE

responses, signaling more efficient charge transport with less recombination within a highly-pure

crystallizing domain.

74
Figure 25. Chemical structures for BT-core based PSMAs with other type linking unit featuring

the incorporation of hetero-atoms.

Table 13. The effects of heteroatoms in the linking units of PSMAs on PSCs performances.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PBN25 -5.74 -3.93 1.43 PM6 0.89 22.62 71.6 14.36 [124]

PBN25-CC -5.59 -3.85 1.44 PM6 0.91 12.4 63.5 7.17 [124]

PBTIC-γ-2F2T -5.56 -3.8 1.41 PM6 0.95 22.56 66.89 14.34 [125]

PBTIC-m-2F2T -5.59 -3.78 1.43 PM6 0.99 9.72 33.84 3.26 [125]

PBTIC-γ-2T -5.51 -3.77 1.42 PM6 0.08 0.91 24.83 0.02 [125]

75
PBTIC-δ-2F2T -5.58 -3.83 1.39 PM6 0.95 20.85 60.22 11.92 [125]

PY-DF -5.68 -3.76 1.43 PM6 0.97 23.1 70.2 15.7 [20]

PY-2T2Cl −5.63 −3.82 1.38 PBDB-T 0.87 16.32 65.0 9.35 [126]

PBDB-
PY-BTz −5.66 −4.24 1.42 25.8 0.917 0.67 16.4 [127]
TF0.25

PY-O -5.57 -3.78 1.45 PBDB-T 0.88 17.86 62.68 9.80 [128]

PY-S -5.55 -3.78 1.44 PBDB-T 0.90 22.84 69.71 14.16 [128]

PY-Se -5.56 -3.77 1.42 PBDB-T 0.89 23.52 73.85 15.48 [128]

PY3Se-1V -5.51 -3.90 1.25 PBDB-T 0.81 24.7 0.659 13.2 [129]

Side chain/group engineering for linkage units plays a pivotal role in fine-tuning

intra/intermolecular interactions and regulating the backbone conformation of the PSMAs. Li et

al. introduced a third functional unit into conventional PSMA to prepare terpolymer PTPBT-ETx

[130]. Based on PYT as the parental PSMA, the third functional unit 3-ethylesterthiophene (ET)

with ester group featuring high electronegativity was chose to copolymerize with PYT to obtain

a series of polymer acceptor materials by controlling the molar ratios of the monomers. ET can

induce non-covalent interactions within or between molecules to fine-tune the energy levels. As

shown in Figure 26a, with the increased proportion of the ET unit, LUMO energy level of

PSMAs gradually moved up, associating with the up-shifted trend of VOC values. The highest

PCE won by the corresponding devices was when the proportion of ET units located at 0.3,

otherwise, the PCEs started to slide down with maximum absorption peak of the thin-film going

through a tiny blue-shift (Figure 26b-c).

76
Figure 26. (a) Schematic energy level diagrams of the PTPBT-ETx polymer acceptors.

Normalized UV-vis absorption spectra of the PTPBT-ETxs (b) solutions in chloroform and (c)

solid film. (d) EQE spectra of the corresponding all-PSCs [130]. Copyright 2020 Wiley Online

Library.

PYEx was reported by Min et al. based off of the ternary copolymerization strategy [131].

By randomly replacing some SMA units of PYT with ester-substituted thiophene (EST) as a

linking block, a series of new PSMAs with were obtained and denoted as from PYE0 to PYE40.

PBDBT:PYE20-based devices showed the maximum PCE of 13.60% with VOC, JSC and FF of

0.905 V, 20.97 mA cm−2 and 71.63% respectively. Based on PY-TO with alkoxy-substituting

thiophene as linker, Li et al. introduced alkoxy groups into outer position of backbone of PY-TO

to further design and synthesize a PSMA named PO-TO, with a blue-shifted absorption and

medium bandgap of 1.53 eV in comparison with PY-IT and PY-TO, whereas a higher

absorbance as well as an increased LUMO energy level of -3.68 eV contributed to the

considerably high VOC of 1.04 V, resulting from its weakened ICT effect induced by non-

77
covalent bond within polymer backbone [132]. However, the final PCE and FF were slightly

undesirable for PO-TO based device when worked with ultra-broad bandgap polymer donor

PBQx-TF, much lower than PBQx-TF:PY-TO and PBQx-TF:PY-IT with PCE of 15.62% and

16.77%, respectively, attributing to the over-mixed blend morphology of PBQx-TF:PO-TO.

Noted, the PO-TO performed excellent in ternary cell based on PBQx-TF:PY-IT:PO-TO

(1:1:0.2, w/w/w) with significantly improved PCE of 17.71% from the PBQx-TF:PY-IT binary

system (16.77%) due to the complementary absorption and the enlarged VOC caused by splendid

energy level alignment. Shao et al. employed siloxane as the side chain of benzodithiophene-

based linkage to newly acquire PSMA PY-SiO with enhanced molecular aggregation echoed by

the red-shifted absorption peak stark at 793 nm, comparatively to its referenced sample PY-EH

with ethylhexyl-terminated side chains [133]. As a result, a proper phase separation was

implemented in the PBDB-T:PY-SiO-based blend films with ample free-volume of inter-chain to

aid the chain blocks to move and reconfigure when subjected with a strain, given the flexible

siloxane substituent. In a whole, the conventional solar cell based on PY-SiO offered a 12.04%

PCE outperforming the PBDB-T:PY-EH-consisted one (10.85%), even with an impressive 9.8%

PCE for the stretchable device and >70% retention under 20% strain. Chen et al. introduced

oligoethylene oxide (TOE) side chain into bithiophene linker unit to construct what was used as

the third component to copolymerize with PYT to prepare series of PSMAs, namely PYT-

TOE(x) [134]. As a third functional unit, TOE can improve the crystallization and carrier

mobility of PYT-based devices. The gradually upward LUMO energy level as TOE increased

elevated the VOC of the devices.

78
Figure 27. Chemical structures for BT-core based PSMAs with other type linking unit featuring

the tailoring of side-chains.

Table 14. The effects of side-chain engineering for the linking units of PSMAs on PSCs

performances.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PY-TO −5.73 −3.73 1.44 PBQx-TF 0.94 23.42 70.63 15.62 [132]

PO-TO −5.80 −3.68 1.53 PBQx-TF 1.04 20.51 64.42 13.75 [132]

PY-EH −5.48 −3.75 1.45 PBDB-T 0.91 18.12 65.20 10.85 [133]

PY-SiO −5.54 −3.77 1.43 PBDB-T 0.92 19.99 65.19 12.04 [133]

PTPBT -5.66 -3.85 1.42 PBDB-T 0.85 19.82 59.2 9.96 [130]

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PTPBT-ET0.1 -5.66 -3.85 1.42 PBDB-T 0.86 19.48 62.3 10.37 [130]

PTPBT-ET0.2 -5.66 -3.84 1.42 PBDB-T 0.86 20.78 65.5 11.76 [130]

PTPBT-ET0.3 -5.65 -3.83 1.42 PBDB-T 0.90 21.33 65.3 12.52 [130]

PTPBT-ET0.4 -5.66 -3.82 1.42 PBDB-T 0.9 21.22 55.3 10.56 [130]

PTPBT-ET0.5 -5.64 -3.82 1.42 PBDB-T 0.90 18.77 57.5 9.73 [130]

PTPBT-ET0.75 -5.6 -3.78 1.42 PBDB-T 0.90 14.5 38.8 5.08 [130]

PYE0 -5.58 -3.74 1.55 PBDB-T 0.91 19.72 70.54 12.67 [131]

PYE10 -5.57 -3.75 1.44 PBDB-T 0.9 20.93 69.43 13.09 [131]

PYE20 -5.58 -3.75 1.44 PBDB-T 0.91 20.97 71.63 13.6 [131]

PYE30 -5.6 -3.76 1.43 PBDB-T 0.88 21.63 70.18 13.28 [131]

PYE40 -5.6 -3.76 1.43 PBDB-T 0.86 22.24 68.12 13.04 [131]

PYT-TOE(10) -5.53 -3.96 1.44 PBDB-T 0.91 21.73 64.63 12.77 [134]

PYT-TOE(20) -5.54 -3.97 1.43 PBDB-T 0.91 18.75 61.41 10.49 [134]

PYT-TOE(30) -5.53 -3.96 1.43 PBDB-T 0.89 16.74 55.01 8.16 [134]

A variety of flexible spacers (Fs) have been becoming a hot research topic in PSMAs

because their non-conjugated part can endow polymer acceptors with decent solubility to make it

possible for the green-solvent process, and most of all, the ductile devices with soft aggregating

morphology based on which are showcasing the excellent mechanical properties and attracting

the keen-interests in flexible electronics. In the same vein, vinylene is a characteristic

representation of flexible spacer with concise conjugation which can considerably promote the

planarity of polymer backbone, thus the packing ordering and crystalline behavior of such kind

of PSMAs should be getting much progress from the aromatically fused ones. Min et al.

synthesized PYV with flexible vinylene which can reduce the number of rotatable C-C bonds on

the main chain to improve the ordered arrangement, so as to be favorable to the planarity of the

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polymer main chains and the π-π stacking and thus the charge transport and transfer behavior

[135]. PBDB-T:PYV-based devices obtained best PCE of 11.51%. Chen et al. synthesized PY-

V-γ as the regioregular version of the PYV [136]. The device was fabricated using PCBM or

PFBO-C12 as the third component. PFBO-C12 can effectively promote hole-transfer and

suppress charge recombination hence the device efficiency significantly increased from 16.9%

for binary devices to 18.0% for ternary all-PSCs. Moreover, the enhanced crystallinity and the

more fibril-textured morphology yet endowed the PFBO-C12-based ternary devices with better

stability and mechanical robustness. PY-V-γ was further researched and developed by Hu et al

[137]. Taking method of the sequential process (SQP) with non-halogenated toluene as the

solvent, the corresponding binary device showcased a PCE as high as 16.2%. With PJ1-γ added

into binary system, the best PCE for optimized device was up to 18%. Bumjoon J. Kim et al.

incorporated siloxane (SiO) as the flexible building block into the main chain of PSMA with

different molar ratios relative to the SMA unit [138]. The results indicated the maximum PCE

(13.5%) along with a high crack-onset-strain (COS) (15.2%) displayed by the all-PSC based on

PYSiO-10 (10% SiO), attributing to the favorable crystallinity of PYSiO-10-based blend film

with proper d-spacing (3.93 Å) and CL (2.10 nm) in the OOP direction, and a suitable domain

spacing of 45.2 nm revealed by resonant soft X-ray scattering (RSoXS) observation, implying

the most reasonable crystalline-induced morphology for charge transport and an exciton

dissociation, contrasting with the PYSiO-0 based one having a rather coarse Rq of 2.8 nm to be

harmful to the charge separation and to lead to brittle nature for the corresponding device. Wang

et al. incorporated non-conjugated spacers with various carbon numbers (0, 2, 4 and 8) into

bithiophene moiety to synthesize PSMAs named as from PYTS-C0 to PYTS-C8 with

nonlinearly-changed photovoltaic and mechanical properties in PSCs [139]. Owing to the effect

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of PYTS-C2 on regulating molecular aggregation and π-π stacking, the morphology and

solubility of PBDB-T:PYTS-C2-based active layer was fine-tuned with a significantly improved

PCE of 11.37% together with higher mechanical stretchability and robustness than those of

PYTS-C0-based ones. However, as increasing of spacer length, all the above performances

presented a sharp falling trend with over aggregation happened in mixing blends, which was

terrible for the effective charge extraction and transport with low generation of photocurrent and

EQE responses (PYTS-C4 and PYTS-C8 were determined to be 8.28 and 6.87 mA cm -2,

respectively). Chen et al. further demonstrated the reasonable incorporation of conjugation-

broken chain-spacer into backbone of PSMA can benefit great more for the devices processed

from large-area BC (blade coating) tactic rather than small-area SC (spin coating) method [6]. As

reported, two PSMAs named as PYTCl-A and PYTCl-B with their thiophene linkage and rigid

SMA-unit respectively replaced by non-conjugated flexible spacer, were newly designed and

synthesized. Due to the mild regulation of molecular aggregation with outstanding face-on

orientation, the SC-processed PYTCl-A-based devices showed better PCEs (16.03%) than those

of PYTCl-B ones (13.46%) with soft packing framework and PY-IT counterparts (15.36%) with

collapsed stacking assemblies. More intriguingly, when non-toxic TL served as the processing

solvent, the BC processed large area (1.21 cm 2) device (PM6:PYTCl-A) proved a decent PCE of

14.70% accompanying with an almost unchanged FF value from the one with a small active area,

while the PCE and FF obviously decreased in PM6:PY-IT-based device, highlighting the

significance of the compatibility of the BC method with the flexible chain blocks obtained from

exquisite molecular design. Besides, the large-area flexible devices with concurrently non-

conjugated spacer-containing PDs and PAs particularly presented a 15.54% high PCE with the

topmost ESF (a performance indicator of integral consideration of PCE and COS) index of

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3.12% for the PM6-A:PYTCl-A system, which stood out from either the PM6:PYTCl-A with a

higher PCE but a lower COS, or the PM6-B:PYTCl-B with superior COS yet a poorer PCE

value. A new polymer material NC-PY6 was prepared and synthesized by Chen et al [140].

D18:NC-PY6-based devices showed that the best PCE of 12.30% with VOC, JSC and FF of 0.87 V,

20.66 mA cm−2 and 68.42% respectively. The HOMO energy level of NC-PY6 and donor D18

lined well with only 0.05 eV energy offset to offer solar-cells high VOC values. Non-fully

conjugated PFY-2TS was synthesized by Wang et al.[141] The favorable molecular crystallinity

and aggregation properties of PFY-2TS were well-manipulated for the morphology of the active

layer in corresponding devices. Especially, The PBDB-T:PFY-2TS blend film exhibited a

smoother surface and more proper phase separation from AFM and TEM observations, which

were conducive to improve the charge transfer process, so as to obtain higher JSC and FF. Huang

et al. designed and compared PJTVT and PJTET by respectively introducing conjugated

thienylene-vinylene-thienylene (TVT) and non-conjugated thienylene-ethyl-thienylene (TET)

[142]. When paired with the donor JD40, one can observe more ordered π-π stacking and

enhanced face-on orientation within microstructure of PJTVT, which helped enhance the exciton

dissociation, the better charge transfer and swifter charge extraction, and thereby achieve the

better PCE (16.13% for the JD40:PJTVT). Peng et al. reported BTP-T2F and BTP-2T2F based

on dithienothiopheno[3,2-b]ss-pyrrolobenzothiadiazole (BTTP) as the linker unit [143]. BTTP-

based polymers offered the BTP-2T2F with relatively shallow HOMO energy levels and high

coefficients. Smaller dihedral angles also promoted and solidified the intermolecular

aggregation. Therefore, the binary device containing PTQ10:BTP-2T2F displayed a high 14.32%

PCE. By adding compatibilizer PBDTCL-TPD as the third component, higher PCE was obtained

in ternary blend all-PSCs. Chen et al. developed three novel non-conjugated polymer acceptors

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(PTH-Y, PTClm-Y and PTClo-Y) for all-PSCs [144]. It is found that the non-conjugated

polymer acceptor can effectively redeem the technique-efficiency compatibility between spin-

coating and blade-printing. Thanks to the action of chlorine atoms and good morphology, the

PCE of all PSCs based on PBDB-T:PTClo-Y ranked the highest value of 12.74%. In addition, in

the midst of the slow film-forming process of blade coating, the non-conjugated chain can be

conducive to the flexible skeleton to moving and avoiding the excessive aggregation of blend

films.

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85
Figure 28. Chemical structures for BT-core based PSMAs with other type linking unit featuring

the insertion of flexible spacers.

Table 15. The effects of flexible linking units of PSMAs on PSCs performances.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PYV -5.61 -3.89 1.39 PBDB-T 0.84 20.67 66.26 11.51 [135]

PYSiO-10 N.A. N.A. N.A. PBDB-T 0.92 21.62 0.67 13.52 [138]

PYT-C0 -5.77 -4.30 1.30 PBDB-T 0.92 11.99 11.99 4.84 [139]

PYTS-C2 -5.80 -4.24 1.43 PBDB-T 0.91 18.72 18.72 11.20 [139]

PYTCl-A −5.69 −3.92 1.42 PM6 0.94 23.49 73.04 16.16 [6]

PYTCl-B −5.69 −3.90 1.42 PM6 0.94 20.76 70.14 13.61 [6]

NC-PY6 -5.56 -3.92 1.44 D18 0.87 20.66 68.42 12.3 [140]

PFY-2TS -5.5 -3.85 1.46 PBDB-T 0.91 20.47 66.3 12.31 [140]

PJTET -5.56 -3.78 N.A. JD40 0.92 18.58 63.84 10.93 [145]

PJTVT -5.57 -3.77 N.A. JD40 0.89 23.75 76.4 16.13 [145]

BTP-T2F -5.9 -4.3 1.49 PTQ10 0.86 19.58 65.2 11.06 [143]

BTP-2T2F -5.87 -3.92 1.48 PTQ10 0.89 23.15 69.5 14.32 [143]

PTH-Y -5.55 -3.74 1.46 PBDB-T 0.96 12.01 57.2 6.57 [144]

PTHm-Y -5.6 -3.81 1.43 PBDB-T 0.94 15.86 55.3 8.25 [144]

PTHo-Y -5.61 -3.83 1.43 PBDB-T 0.95 20.21 66.5 12.74 [144]

N.A. = not available.

When it comes to the construction of electron distribution in the polymer chain, the variety

arrangement of D and A types of building blocks play a significant role in facilitating the

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electron transfer along the conjugated chains. Conventional A-π type PSMAs have boosted the

efficiency of binary all-PSCs to about 18%, while the other polymeric architecture like A-π-A-π

(extension of A-π) and fused-ring A-D/A-A frameworks, are rare and sparse of discussion about

pertinent interplay of structure-performance in the previous researches. Herein, some cases about

these special electronic structures implemented through building-block engineering will be

presented to inspire the later projects.

Fused-ring conjugated system is attractive and promising to be used in designing π-spacers of

the PSMAs to facilitate the charge transfer/transport properties. Guo et al. rationally constructed

an imide-fused biselenophene linkage to prepare a new acceptor-acceptor (A-A) type PSMA

named as PY5-BSeI with high molecular weight over 30 kDa [146]. In comparison with classic

D-A featured PY5-BSe, the absorption peak of the PY5-BSeI thin film red-shifted about 20 nm

with larger extinction coefficient due to the better aggregation and enhanced electron push-pull

effect. Besides, without the single bond affecting the planarity conformation between two

selenophene, the reduced dihedral angles was observed in PY5-BSeI with the all-fused linker,

which considerably prompted the ordered molecular packing and crystallinity, thereby

facilitating the charge transport. For another, the improved exciton diffusion and dissociation

behavior (TAS calculated time constants τ 1/τ2 were 1.06/20.64 and 0.89/17.04 ps, for PM6:PY5-

BSe and PM6:PY5-BSeI blend films, respectively) were mainly resulted from more uniform and

more compatible nano-fibrils presented in the blends. At last, PM6:PY5-BSeI-based device

obtained a tremendous PCE value of 17.77% with a high short-circuit current of 24.93 mA cm -2

and an FF of 75.83%, a lot superior to the PM6:PY5-BSe-based PSC. Another branch of fused-

ring linking unit features the electron-donating characteristic to construct A-D type PSMA. Most

recently, Tang et al. utilized fused thiophene[3,2-b]thiophene (TT) system to replace single-

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bond-containing dithiophene (2T) moiety to design and synthesize PSMAs PYTT [147]. Owing

to the good electron-donating performance of the TT unit, the LUMO energy level upshifted

with a narrower band-gap contributing to the widened absorption. What’s more, tighter π-π

stacking and more ordered crystalline could be observed within PM6:PYTT combination since

the more planar and rigid backbone endowed by the TT units other than the 2T. Benefiting form

the entirely improved optoelectronic properties, the final device based on PYTT 15.38% best

PCE and outstanding JSC of 24.94 mA cm-2, outperforming the PY2T one (PCEmax of 13.99% and

JSC of 22.50 mA cm-2).

Li and colleagues reported four A-π-A-π type PSMAs named in sequence as PY5-BTZ, PY5-

2TZ, PY5-PZ, and PY5-BT with typically electron-deficient BTz, TTz, Pz and BT introduced

into π-linker units [148]. As characterized that the PY5-BTZ exhibited the highest-lying LUMO

energy level of -3.72 eV, the biggest absorbance of 1.5 × 10 -5 cm−1 and the optimum miscibility

with polymer donor PBDB-T, the PCE of photovoltaic device prepared from the PBDB-T:PY5-

BTZ finally got the peak value (14.82%) among these devices, benefited by the most effective

charge transport with the lowest recombination and efficient exciton split. Later, two polymer

acceptors defined on whether the eyhylhexyl substitution position on two thiophene rings being

far from (PY5-TTz-FT) or close to (PY5-TTz-CT) the central TTz block of the linker, were

further synthesized by the same group [149]. Albeit with the relative higher LUMO energy level

and more complete and broader absorption exhibited by the thin-film of PY5-TTz-CT, the

excellent backbone planarity led to the over crystallinity and unfavorable aggregating

morphology of the corresponding blend film where the oversized grain even made the phase

separation indiscernible from the AFM height image with a fair homogeneous surface roughness.

Therefore, the PBDB-T:PY5-TTz-CT-based device was in tremendous shortage of photophysical

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and photovoltaic process and resulting FF value (51.8% vs. 68.4%) that put the ultimate PCE

(9.84% vs. 12.73%) in disadvantage, contrary to those of the PBDB-T:PY5-TTz-FT-based one.

Most recently, Peng et al. successfully reduced the inter-chain entanglement to furnish blend

morphology of the solar cells with good D/A miscibility, by smartly adopting the 1,3-

bis(thiophen-2-yl)-5,7-bis(2-ethylhexyl)benzo-[1,2-c:4,5-c’]dithiophene-4,8-dion (BDD) as the

bridging unit to construct three PSMAs named PBTPICm-BDD (regiorandom), PBTPICγ-BDD

(regioregular) and PBTPICF-BDD (with fluorine atoms on terminal groups) [54]. Benefiting

from that the certain torsional degrees of the non-fluorinated PBTPICγ-BDD resulted in a steric

hindrance (slightly higher than those of the PBTPICF-BDD one), the matching donor of PBQx-

TCl can intersperse well through the inter-chain voids and ensure a pretty proximity of the JSC

and FF values versus the PBTPICF-BDD for the corresponding devices, and thus leading to

superior PCEs (17.37% vs. 17.17%) due mainly to the higher VOC (0.944 V vs. 0.924 V).

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90
Figure 29. Chemical structures for BT-core based PSMAs with other type linking unit featuring

fused-ring functional segments.

Table 16. The effects of fused-ring functional segments in the linking units of PSMAs on PSCs

performances.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

PY5-BTZ −5.67 −3.72 1.44 PBDB-T 0.92 22.61 71.1 14.82 [148]

PY5-2TZ −5.70 −3.76 1.44 PBDB-T 0.89 20.82 68.4 12.73 [148]

PY5-PZ −5.71 −3.75 1.45 PBDB-T 0.89 19.91 68.2 12.10 [148]

PY5-BT −5.73 −3.78 1.43 PBDB-T 0.89 15.05 60.4 8.12 [148]

PY5-TTz-FT −5.70 −3.76 1.44 PBDB-T 0.89 20.82 68.4 12.73 [149]

PY5-TTz-CT −5.68 −3.71 1.33 PBDB-T 0.93 20.44 51.8 9.84 [149]

BTPICm-BDD -5.64 -3.75 1.42 PBQx-TCl 0.98 17.05 63.20 10.51 [54]

PBTPICγ-BDD -5.66 -3.79 1.41 PBQx-TCl 0.94 24.10 76.92 17.50 [54]

PBTPICF-BDD -5.65 -3.87 1.40 PBQx-TCl 0.92 24.15 76.93 17.17 [54]

PY5-BSe -5.67 -3.85 1.40 PM6 0.94 17.66 64.68 10.70 [146]

PY5-BSeI -5.76 -4.00 1.35 PM6 0.94 24.93 75.83 17.77 [146]

PY2T -5.78 -4.38 1.40 PM6 0.924 22.50 67.28 13.99 [147]

PYTT -5.71 -4.33 1.38 PM6 0.907 24.94 67.98 25.38 [147]

N.A. = not available.

In conclusion, based on some typically normal building blocks such as thiophene,

selenophene, bithiophene and BDT, halogenation (F, Cl) introduction, Se/N hetero-cycle

modulation and side chain tailoring are the classically effective design methods for linkages to

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well-define intra/inter-molecular interactions, long-range skeleton planarity, frontier orbital

energy level and miscibility with matching donors. More than those, adding functionalized

building blocks such as embedding a segment of flexible non-conjugated chain, which is

confirmed to be conducive to realize large-scale blade coating process and to gain decent

stretchability, and also, rigid/fused π-conjugation extension through incorporation of fused-ring

system along backbone direction greatly favors to good co-planar conformation and charge

transfer property in order to promote the photovoltaic performance.

2.4. BTA-Core Based PSMAs

Compared with BT, BTA (Figure 30) has weaker electron-efficient characteristic to impact

bandgap and optical absorption of the PSMAs and downshift the energy level. In general, with

synergistic conduction on engineering of the side-chain on the central N atom of BTA unit and

the linkage, the energy level, molecular absorption and the inter-chain packing along with

solubility could be finely-tuned [50,150]. Thanks to the fact that the alkyl chains in γ-position

(referred to Figure 30a) grants more abundant electron to the conjugated system, the

corresponding LUMO energy level could be improved to obtain higher open-circuit voltage and

more important, the bandgap of relavent PSMAs gets dropped [151]. The synergistic application

of BTA and selenophene-linker can broaden the UV-vis absorption range and improve the

single-component photoluminescence quantum yield without involving halogenated active-

material and toxic-solvent process, which helps to reduce the Eloss of the device and echos the

requirement of green energy development [152]. Moreover, the side-chain engineering regarding

to α and β position (Figure 30a) has also been extensively probed and developed through like

branched chain substitution in β and long-branched alkyl chain tailoring for α sites. These

modification mehods undoubtedly help make great advancement in PCEs of the devices,

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especially with shining properties of decreasing in Eloss and red-shifted absorption. Besides, due

to the extraodinary performances brought by BTA core-unit, the nonfused PSMAs on the basis

of BTA showcased excellent photon-to-electron conversion capability. The relevant chemical

optimization can be easily conducted on α-position (Figure 30b) of the BTA through

incoporation of the alkoxy groups or the halogenation atoms. The alkyl chains in γ-position

(Figure 30b) are occasionally modified to seek for the fitting photoelectric properties and chian-

packings. Ipso facto, the Se atoms could selectively appear in the X 1, X2 poitions while the

assymetric backbone can be realized by tailoring the thiophene-spacer marked with dotted line in

Figure 30 to further enhance the photovoltaic performance likewise the BT-based PSMAs.

These unimplemented modifications should be promising to exist in the later researches for a

supplement.

Figure 30. Molecular structure and chemically modifiable sites of BTA-based PSMAs.

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The A702 bearing a very short branched chain was synthesized by Zhou et al [153]. 3%

DIO optimized PBDB-T:A702-based devices showed the optimal PCE of 11.84% along with the

VOC, JSC and FF of 0.90 V, 21.93 mA cm −2 and 60% respectively. The electron and hole mobility

of PBDB-T:A702 based device were 1.02 × 10−4 cm2 V−1 s−1 and 2.10 × 10−4 cm2 V−1 s−1,

respectively, while those of PM6:A702-based device presented unbalanced (1.08 × 10 −4 cm2 V−1

s−1 and 5.34 × 10−6 cm2 V−1 s−1), which could account for the higher JSC and FF for the former

one. PN-Se was synthesized by Li et al [19]. Compared with PS-Se based on BT central core

unit, the film-state optical absorption of PN-Se red-shifted a lot, and the morphology for PN-Se-

based blend film showed more interpenetrating networks when matched with PBDB-T, mainly

benefiting from the regulating result of alkyl chain on the BTA. Thanks to better charge transport

performance with less charge recombination, the PCE for PN-Se-based device improved to

16.16% with overall enhanced VOC, JSC and FF values characterized by 0.907 V, 24.82 mA cm −2

and 71.8% respectively. PS1 was prepared by Ying et al. selecting thiophene as the linking unit

and Y1 as SMA part of the backbone [154]. The side chain substituting on the central BTA unit

enhanced the solubility of materials in non-chlorinated solvents to better form the crystalline film

with higher PCE (13.8%), as it confirmed that in the 2-MeTHF solvent, the absorption peak for

dissolved PS1 exhibited a red-shift from 796 nm to 810 nm and the absorption coefficient of

solid film performed bigger (7.0 × 10 4 cm−1 vs. 5.1 × 104 cm−1), than those in the CF solvent. At

the same time, trying different solution treatments, the PCE of PS1 got remotely improved in

conparison with SMA Y1, mainly resulting from the quite high and balanced hole/electron

mobility of 2.45 × 10−3 cm2 V−1 s−1/3.57 × 10−4 cm2 V−1 s−1 for PS1 film after treating with 2-

MeTHF. Not only the crystallinity of the PS1 showed significantly obvious with 2-MeTHF as

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the solvent (Figure 31), what’s more, more distinguishable and ordered light-dark interweaving

image of the blended D-A morphology characterized by the TEM can also be responsible for the

favorable exciton dissociation and the charge transport in 2-MeTHF-processed devices.

Figure 31. Two-dimensional grazing incidence wide-angle X-ray scattering patterns of PTzBI-

oF:PS1 blend films processed by (a) chloroform (CF) and (b) 2-MeTHF under optimum

conditions. Transmission electron microscopy images of PTzBI-oF: PS1 blend films processed

by (c) chloroform (CF) and (d) 2-MeTHF [154]. Copyright 2021 Royal Society of Chemistry.

PYV-Tz was synthesized by Min et al [135]. With more electron-rich property of BTA than

BT, the absorption spectrum of PYV-Tz red-shifted with improved absorption coefficient, and

the LUMO energy level elevated from -3.89 eV to -3.87 eV, compared to the PYV. What’s

more, PBDB-T:PYV-Tz blend with smoother surface improved the charge collection. Since

these advantages, higher VOC and JSC can be obtained by PYV-Tz-containing device. Two brand-

new narrow band gap PSMAs were prepared by Jen et al., denoted as PZT and PZT-γ [155].

Compared with PYT with BT as the core unit, the PCEs of PZT (region-random) and PZT-γ

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(region-regular) got remarkably improved. PZT-γ thin-film had wider absorption range and

higher electron mobility (5.75 × 10−4 cm2 V−1 s−1 vs. 7.53 × 10−4 cm2 V−1 s−1) due to certain

regional regularity of the polymer skeleton, outperforming the PZT. Thus, PBDB-T:PZT-based

devices reached PCE only of 14.5% lagging behind the PBDB-T:PZT-γ-based device (15.8%).

Triggered by the ordered polymer chain packing, the PBDB-T:PZT-γ-based films formed a

better blending morphology with high crystallinity. Duan et al. prepared PFBTz-TT and PBTz-

TT [156]. Fluorinated PFBTz-TT exhibited a more coplanar structure, higher absorption

coefficient (1.06 × 105 cm-1) and stronger inter-chain interaction. The high electron mobility

should be ascribed to the higher density of delocalized electron cloud, leading to an augment of

the charge transfer. Therefore, All-PSC based on PFBTz-TT showed 10.14% PCE with higher

JSC of 18.95 mA cm-2 and FF of 63%. With the benzotriazole as the fused-ring core and the

thiophene as the linkage, Sun and collaborators delved deep into how the side chains in β-

position impacted the performance of corresponding PSMAs, through copolymerization of PTz-

BO and PTz-C11 bearing respectively branched and non branched chains to induce distinct

spatial topology of polymers [157]. It demonstrated that the branched side chains profoundly

uplifted the LUMO energy level and broadened the bandgap of the PTz-BO, leading to reduced

voltage loss of device and enlarged extinction coefficient which were beneficial for the higher

EQEEL and VOC as well as the resulting PCE value of the device, in comparison with PBDB-

T:PTz-C11-based one, though the superior JSC gained by the latter essentially arose from its

broader optical-absorption range. Impressively, the ternary device proved an eminent PCE of

16.34% by introducing PTz-C11 as the third component into PBDB-T:PTz-BO, ascribing to

comprehensive advance in VOC, JSC and FF gifted by more enhanced light-response and

optimized micro-structure of fibril-networks. This work forcibly suggests the BTA-based fused

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ring acceptors possess an exclusive strength in designing efficient PSMAs for all-PSCs.

Intrigued by noncovalently fused-ring acceptors (NFRAs) being of low cost with simple

synthesis but high total yields, two groundbreaking PSMAs named PBTzO (fluorination) and

PBTzO-2F (without fluorination) were synthesized by Huang et al. using BTA as central core

with noncovalently interaction-containing conformation in molecular backbone. A tremendous

elevation in PCE from 1.08% to 11.04% was realized by two binary all-PSC devices when

fluorine atom substituted in terminal groups, along with the distinctly favorable PL quenching

efficiency, more balanced charge transportation, tighter π-π stacking and more organized fibril-

like phase separation for the PBTzO-2F-based solar cell, so contributing to the higher JSC and FF

values for PBDB-T:PBTzO-2F-based device compared to PBDB-T:PBTzO control one. Noted

that, the lower LUMO energy level of fluorinated PBTzO-2F was at no expense of VOC on

account of depressed Eloss [158]. Furthermore, two PSMAs named PYT and PYT-Tz were

synthesized by Min et al. to systematically fathom out the influence of BTA core in conjunction

with the side-chain tailoring in outer position of fused backbone, shedding light on the avenue to

refinement of molecular-designing for BTA-based PSMAs [159]. Stemming from replacing BT

with BTA and introducing shortened n-nonane side-chain into polymer backbone, PYT-Tz

exhibited higher LUMO energy level, luxuriant NIR-absorption response and bigger absorption

coefficient, could be accused from the declined electron-accepting ability of PYT-Tz and more

molecular coplanarity to be in favor of π-π interactions in thin film. More importantly, when

paired with classical polymer donor PBDB-T, compared with PYT, PYT-Tz showed higher and

more balanced carrier mobility, reduced charge recombination and superior charge extraction

behavior with lower extraction time of 0.25 μs, reasonably revealed the brilliant JSC (22.85 mA

cm-2) and FF (69.90%) values associating with PYT-Tz-based device from photophysics

97
perspective. Additionally, GIWAXs results showcased that PYT-Tz blend film generated a

stronger IP diffraction signal with larger CCL value in OOP direction, indicating more ordered

and effective crystalline of blend, in combination with AFM image which evidently presented

the compactly intermixed domains in PYT-Tz blend film. Except the upshifted LUMO energy

level of PYT-Tz acceptor, the notable decreased Eloss of related devices jointly enabled the

ultimate VOC to surpass that of PYT-based one, with a considerable value of 0.912 V. To flourish

the BTA fused core based PSMAs, Chen et al. used bithiophene as linkage to synthesize

polymerized acceptor PYBzDT [160]. Compared with thiophene linked counterpart PYBzT, the

extended conjugation length of PYBzDT worked less to improvement of PCE when paired with

J52 as the electron-donating material, despite of the more ordered lamellar and π-π stacking and

slightly higher electron mobility in blends. However, interestingly, the PYBzT based devices

exhibited more balanced charge transport, broader light absorption range, decreased charge

recombination, tighter intermolecular π-π packing and suitable miscibility, eventually PCEs of

10.67% with concurrently enhanced JSC and FF and nearly equivalent VOC were gained by

J52:PYBzT systems much better than PCEs of 8.69% for PYBzDT ones. As for reasons, the

inferior charge separation (P(E,T): 93.6% vs. 88.0%) and the transportation (μh/μe: 1.68 and 1,14)

as well as the charge recombination (α: 0.92 and 0.89 according to Jsc ∝ Plightα) could be ascribed

to the too miscible domains of PYBzDT and J52. Two regioregular polymer acceptors named

PFBTz-T-γ and PFBTz-T-δ with different polymerization sites in terminal groups of BTz-based

SMA building blocks, were synthesized by Duan et al. PFBTz-T-γ demonstrated a favorable

planar conformation with optimized π-π stacking which led to superior charge mobility, less

recombination and relative modest phase separation, when compared with PFBTz-T-δ after

mixing with PBDB-T as donor [161]. As a result, PBDB-T:PFBTz-T-δ based device performed a

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rather poor PCE by 0.52%, resulting from its excessively self-aggregated morphology, whereas a

much higher PCE of 9.72% was unveiled by PFBTz-T-γ-based one. Sun et al. synthesized three

PSMAs named PTz-Ph, PTz-Me, and PTz-H by adopting phenyl, methyl and hydrogen into outer

position of main chain with stepwise diminished steric hindrance [162]. It confirmed that such

particular spatial barrier was not the necessity in modulating aggregated morphology of PSMAs

and as anticipated, the photovoltaic performance subsequently enhanced for PTz-Ph-, PTz-Me-

and PTz-H-based devices, due to the more and more compact π-π stacking, favorable

crystallinity and uniform fibrillar morphology uncovered in their blend films with PBDB-T as

donor polymer. Taking advantages of the bathochromic absorption and the better exciton and

charge behaviors, PTz-H-based binary (PBDB-T:PTz-H) and ternary (PBDB-T:PTz-BO:PTz-H)

devices all performed fantastic photoelectric conversion of 16.53% and 18.16%, respectively.

In summary, the conjunctive effect of BTA central core and selenophene linkage significantly

improves the photocurrent and aggregating morphology. It particularly noted that the utilization

of selenophene linker and subtly customization of the side-chain in β-site of SMA unit can

effectively reduce the energy loss in the device. It also can be seen that the 2-decyldodecyl is a

competitive candidate to be used for side-chains in α-position because of its regulation role in

increasing the spatial hindrance to keep a proper polymer-chain conformation in long-range. It

also should be underscored that the processing-solvent selection is crucial for achieving suitable

intermolecular interactions between polymer chains so that the good rearrangement of chain

packing and aggregating morphology can be guaranteed. Besides, nonfused BTA-based PSMAs

displayed a powerful value in cost-cut all-PSCs in production realm, principally by the virtue of

the planar fused-linkage, certain and appropriate polymerization position and the non-covalently

interactions built upon the BTA-core and the neighbouring thiophene, which in turn affect the

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co-planar backbone architecture and charge transporting property with PCE of the device

surpassing 11%.

100
101
Figure 32. Chemical structures for BTA core-based PSMAs.

Table 17. Performance parameters for BTA-core based PSMAs.

Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

A702 -5.41 -3.74 1.39 PM6 0.94 5.16 36.0 1.75 [153]

a
A702 -5.41 -3.74 1.39 PM6 0.95 6.74 43.0 2.73 [153]

A702 -5.41 -3.74 1.39 PBDB-T 0.89 19.17 52.0 8.93 [153]

a
A702 -5.41 -3.74 1.39 PBDB-T 0.9 21.93 60.0 11.84 [153]

PN-Se -5.63 -3.85 N.A. PBDB-T 0.91 24.82 71.8 16.16 [19]

PS1b -5.56 -3.7 1.39 PTzBI-oF 0.92 21.45 61.36 12.1 [154]

c
PS1 -5.56 -3.7 1.39 PTzBI-oF 0.92 22.47 66.7 13.8 [154]

PYV-Tz -5.52 -3.87 1.34 PBDB-T 0.89 21.73 67.62 13.02 [135]

PZT -5.58 -3.76 1.39 PBDB-T 0.91 23.2 68.6 14.5 [155]

PZT-γ -5.57 -3.78 1.36 PBDB-T 0.90 24.7 71.3 15.8 [155]

PBTz-TT -5.41 -3.97 1.38 PBDB-T 0.84 16.01 51.0 6.85 [156]

PFBTz-TT -5.67 -4.12 1.42 PBDB-T 0.85 18.95 63.0 10.14 [156]

PTz-BO -5.58 -3.56 1.37 PBDB-T 0.93 23.88 69.8 15.56 [157]

PTz-C11 -5.56 -3.80 1.36 PBDB-T 0.88 25.20 69.2 15.36 [157]

PBTzO -5.35 -3.76 1.43 PBDB-T 0.89 2.90 41.74 1.08 [158]

PBTzO-2F -5.46 -3.91 1.40 PBDB-T 0.90 18.27 67.37 11.04 [158]

PYT-Tz -5.53 -3.77 1.40 PBDB-T 0.91 22.85 69.90 14.82 [159]

PYBzDT -5.51 -3.77 1.37 J52 0.85 21.00 48.71 8.93 [160]

PYBzT -5.55 -3.77 1.36 J52 0.85 23.10 55.43 11.22 [160]

PFBTz-T-γ -5.56 -3.82 1.42 PBDB-T 0.89 16.78 66.0 9.72 [161]

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PFBTz-T-δ -5.55 -3.79 1.47 PBDB-T 0.84 2.02 28.0 0.52 [161]

PTz-Ph -5.52 -3.78 1.36 PBDB-T 0.90 21.80 65.2 12.56 [162]

PTz-Me -5.49 -3.81 1.33 PBDB-T 0.84 24.10 70.3 14.22 [162]

PTz-H -5.47 -3.84 1.31 PBDB-T 0.83 26.23 73.6 16.28 [162]

a
add 3% DIO. b Solvent is CF. c Solvent is CF 2-MeTHF. N.A. = not available.

2.5. Quinoxaline (Qx) Core Based PSMAs

To step up the possibility of industrialized production of PSMAs-based all-PSCs and fit the

practical and multi-scenario necessities, exploring novel electron-deficient core (EDC)/electron-

sufficient core (ESC) and refining/simplifying the synthetic strategy of corresponding PSMAs to

provide precious experiences on breakthroughs of efficiency bottlenecks and balance the

imperative efficiency-stability-cost issues, are essentially crucial and fundamental. According to

the difference of polymerization sites, classic EDC-type Qx-based PSMAs can be sorted as

traditional connecting style of “EG-linker” and newly-developed “core-linker”. The pith of goal

is to essentially completely play the eminent peculiarity of SMA units, which is refrained by the

occupation of polymerization sites on the end-groups of fused core, consequently leading to the

contorted polymer conformation, weakened impact of terminal-group on inter-molecular packing

patterns and difficulties in purification of regional isomers. Hopefully, the above drawbacks can

be tackled through extension of central EDCs to furnish abundance of reacting positions for

copolymerization to release the end-group (Figure 33b). Unusually, P-position can be

concurrently utilized to connect with linking units to form a 3-D polymer-network. Meanwhile,

as depicted in the Figure 33a, the newly-innovated cores have a trend to be employed in

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molecular modification like being halogenated on a two-dimensional skeleton for more efficient

electron transfer. Besides, the selection and modification for the linkages and side-chains on α, β-

position is a hot-topic being of significance to tune the energy level and absorption. Recent

researches started to focus attention on designing of fused moiety on the top of central-core

being served as one of important packing units (Figure 33a). Structure-performance

relationships on both EG-linker and core-linker featured Qx-based PSMAs will be exhausted as

follows by comparative analysis through some specific cases. Furthermore, as one would expect,

the X1, X2 mean to the altering-accessible sites with S atoms to be replaced by the Se atoms

selectively for pleasing photoelectric properties.

Figure 33. Molecular structure and chemically modifiable sites of Qx-based PSMAs.

2.5.1 EG-linker connected PSMAs based on Qx-core units

Chen et al. created two PSMAs designated as PZC16 and PZC17 based on difluoro-

substituted quinoxaline-extended core with respectively the non-aromatic ethynyl and vinylene

as the linkers [163]. Influenced by the conjugation extension along central-core direction and the

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notably reduced contortion angle between SMA unit and vinylene linker, the PZC17 matching

well with PM6 showcased well-miscible active-layer morphology with clear and more uniform

bi-continuous nanoscale networks mutually permeating within the solvent, signifying the

efficient exciton dissociation and charge transfer (quenching efficiency value of 80.0% in

contrast with 68.8% for PZC17 and PZC16 based devices respectively). Besides, the

PM6:PZC17-based blend films also demonstrated a more rapid and more balanced charge

transport, alleviated recombination, enormous decreasing in energy loss (0.599 eV vs 0.534 eV)

and thereby the remarkably enhanced JSC and FF, could be assigned to that the PZC-17 presented

a stronger IP and OOP orientation and close stacking distance coordinating with that of PM6 in

the blends. Ergo the PZC17-based device achieved a prominent PCE of 16.33% much higher

than that of only 9.22% for PM6:PZC16. Terrific PCE as high as 15.14% belonging to the

PZC17-based device with 1 cm2 area was top notch among the large-area all-PSCs. With good

performance of PZC2 in mind, Chen et al. continued designing and synthesizing a novel PSMA

named PZC24 essentially similar with PZC2 and when blended it with PM6, the binary device

corroborated a decent PCE of 16.82% with a rather high VOC of 0.946 V, outshining that of 0.936

V for PZC2 with a relative deeper-lying LUMO energy level [164]. Utilizing the same SMA

building block and the linking unit of PZC24, a dimer named CH-D1 further synthesized to serve

as the guest component to be introduced into PM6:PZC24. The PCE of ternary device can be up

to 17.40% with totally improved VOC, JSC and FF. Foremost, resulting from the notable impact of

CH-D1 on facilitating ordered and condensed molecular packing and mitigating the over-mixed

D:A interface (inferred by the interaction parameters among PM6, PZC24 and CH-D1), finally

the alloy-like acceptor-based phase (indicated by the more pronounced face-on diffraction peak

in ternary system) can form in the ternary blend films, leading to a higher domain purity with

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fibril size of 15.1 nm (PM6:PZC24:CH-D1) than 13.5 nm (PM6:PZC24), consequently

bolstering the fast charge transport and effective charge separation and alleviating the impaction

of space-charge limitation. Impressively, the ternary device constructed from PM6:PZC24:CH-

D1 exclusively exhibited an excellent mechanical robustness with high ductility. Therefore, the

PCE of flexible ternary device even approached 15.35% with satisfying photo-soaking stability

and thermal stability and excellent batch-to-batch reproducibility, fully suggesting the potential

of such other-core based PSMAs in use of ternary PSC.

2.5.2. Core-linker connected PSMAs based on Qx-core units

Chen et al. proposed the deep insight into neural-like π-conjugating PSMAs through

copolymerization of phenazine-core-based SMAs and linking units, in which they meanwhile

made two end-groups and central core as the reaction positions [165]. With non-fluorinated or

fluorinated linking units, two PSMAs TZ1 and TZ2 were synthesized to match with PM6 as the

donor and certified to have notable gap in PCEs (TZ2 of 7.41% vs. TZ1 of 4.06%), due to the

slightly red-shifted absorption spectra (caused by the stronger ICT effect), more distinct

bicontinuos interpenetrating networks and fine aggregation of the acceptors in the TZ2-based

blends, hence resulting in more efficient and higher charge separation and transportatiom with

less recombination and ultimately better JSC value of 14.25 mA cm-2, in contrast with that of 7.87

mA cm-2 as to the TZ1-based counterpart. Noticeably, the innovation of the radiated PSMAs

concededly expands the researching sightseeing of novel PSMAs with high performance.

Followed by next year, based on TZ2, they strove to address the intermolecular packing issue

that have long-term constrained the photovoltaic performances of the PSMAs based all-PSCs

[166]. They initially demonstrated the feasible conceive of SMA-pendant strategy, in which PX-

1 as the PSMA was copolymerized through the central core of SMA and the difluorinated

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thiophene spacer. Benefiting from the well aligned energy level between PX-1 and PM6,

complementary absorption, distinguished nanofiber network morphology, and fairly improved

pre-aggregation property of PX-1, in turn, a promising PCE of 12.36% was accomplished by the

non-additive treated device. With rational incorporation of 2-methoxynaphthalene (2-MN) as the

additive, the PM6:Y6 system proved even higher PCE of 13.55% with slightly improved CCL

along the OOP direction. Most of all, the release of end-groups offered plenty of modifiable sites

to further hybridizing with hetero atoms, hence to accommodate versatile stacking patterns and

reinforced photoelectric properties for the PSMAs to response requirements of highly-efficient

all-PSCs. Not very soon, the same group further copolymerized a PSMA called SH-1 by

harnessing the polymerization site on the fused thiophene of central ESC so that the remained

grafting fraction of SMA unit can be served as the charge transporting channel and regulate the

molecular packing [167]. Compared with the conventional structure of PSMAs, i.e., the SH-2

synthesized through end-group of SMA and linking unit exhibited a notable weakness in power

conversion efficiency (14.14% vs 6.55%), mainly because that the devices based on SH-1

displayed a smoother and more obvious fibrous network after blending with frequently used

donor PM6, plus the tighter and more ordered π-π aggregates formed in blends revealed by

GIWAXs. In contrary, the SH-2-based blend films got a large phase separation with RMS value

high-lying to be 10.2 nm with less crystallinity, which were not as suitable as the SH-1 was to

charge dissociation and transportation. Moreover, immensely enhanced intermolecular packing

slightly abated the Eloss of the PM6:SH-1-based device basically due to the lower non-radiative

combination. The photo-generating exciton property of SH-1 may lag behind the SH-2, since the

blue-shifted absorption with a larger optical bandgap due to its weaker ICT effect, nevertheless,

the JSC (21.03 mA cm-2 vs. 12.87 mA cm-2) and the FF (68.67% vs. 55.94%) of SH-1-based solar

107
cell all further exceeded the latter. He et al. made an expansion in quinoxilline with fused 2D

phenanthrene and acenaphthene to construct two different EDCs, which were utilized to further

synthesize the SMAs (PTIC-HD-4Cl and ATIC-HD-4Cl) and the PSMAs (PPTIC-HD-Th and

PATIC-HD-Th) [168]. Interestingly, two small molecular acceptors performed an dramatically

converse outcomes about aggregation properties of blended films incorporated with PBDB-T

into as the donor polymer, resulting in a great discrepancy in their PCEs, which involved the

complex packing pattern diversity of SMAs and PSMAs. Specifically, in terms of PPTIC-HD-Th

and PATIC-HD-Th featuring the disparate RMS of 10.15 and 1.40 nm and PCEs of 6.57% and

12.47% for corresponding devices, was confirmed to be with solubility of 23 and 29 mg mL −1 in

chlorobenzene at room temperature, meaning the self-aggregation effect of PPTIC-HD-Th likely

being stronger than that of PPTIC-HD-Th. The author later probed deeper into the acceptor-

based DFT calculations. As expected, the dihedral angles between the terminal groups and the

electron-donating cores of for PPTIC-HD-Th and PATIC-HD-Th were 0.13° and 0.57°, as well

as the binding energies of dominant CC (dimer configurations of cores to cores) and CT (cores to

terminal groups) configuration were determined by −34.98 and −36.90 kcal mol −1 for PTIC-HD-

4Cl, much lower than those of −27.89 and −26.98 kcal mol -1 for ATIC-HD-4Cl. All these results

were in agreement with the estimation of solubility and suggested more preference to tightly

aggregate, pack and arrange for polymer acceptor PPTIC-HD-4Cl during the solution processing,

intrinsically elucidated the reason for higher and more balanced charge transport with decreased

recombination and superior exciton dissociation behavior found in the PBDB-T:APTIC-HD-4Cl-

based devices, via revelation of close relationship among molecular structure (the differently

fused 2-D expansion of central core), aggregation structure and consequent performance of solar

cell devices (charge and exciton behaviors).

108
In a word, π-extended quinoxaline-based central-core has elevated the PCE of the binary

all-PSCs close to 18%, principally enabled by the expanded range of delocalized electron in the

light of 2-D conjugate-backbone of the PSMA, exquisite selection of linking units, and

reasonable fluorination conducted on the terminal position of central core and thiophene linkage.

Moreover, the subtle design of fused-ring extension of the Qx-core is crucial to avoid the

excessive molecular self-aggregation. On top of that, the connection between central core and the

thiophene technically provides new insights in molecular design to address the intractable issue

of inadequate polymer-chain packing.

109
Figure 34. Chemical structures for Qx-based PSMAs.

110
Table 18. Performance parameters of the PSCs corresponding to Qx-based PSMAs.
Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

SH-1 -5.68 -3.69 1.45 PM6 0.98 21.03 68.67 14.14 [167]

SH-2 -5.64 -3.76 1.38 PM6 0.91 12.87 55.94 6.55 [167]

PZC16 −5.61 −3.81 1.43 PM6 0.86 18.98 56.65 9.22 [163]

PZC17 −5.60 −3.79 1.44 PM6 0.93 23.38 75.54 16.33 [163]

N.A.
PPTIC-HD-Th -5.36 -3.59 PBDB-T 0.90 13.55 54.53 6.57 [168]

N.A.
PATIC-HD-Th -5.31 -3.58 PBDB-T 0.92 18.96 71.54 12.47 [168]

N.A.
PX-1 -5.67 -3.81 PM6 0.95 18.94 71.02 13.55 [166]

TZ1 -5.56 -3.72 1.46 PM6 0.93 7.99 54.6 4.06 [165]

TZ2 -5.57 -3.78 1.45 PM6 0.93 14,94 53.7 7.41 [165]

PZC24:CH-D1 −5.69 −3.70 1.43 PM6 0.95 24.23 75.25 17.40 [164]

PZC24 −5.69 −3.70 1.43 PM6 0.95 23.76 74.47 16.82 [164]

-5.59
PZC1 -3.72 1.44 PM6 0.92 22.10 67.88 13.83 [169]

-5.62
PZC2 -3.74 1.45 PM6 0.94 24.61 74.93 17.30 [169]

-5.64
PZC3 -3.75 1.46 PM6 0.95 22.34 73.97 15.75 [169]

N.A. = not available.

2.6. Other Core Based PSMAs

As shown in Figure 35, PSMAs with other fused/nonfused cores are also summarized to

display and explain their performances and applications in the purposes of thrifting the synthetic

cost and pursuing high industrial figure-of-merits. The non-fused-ring based PSMAs with

111
electron-donating cores can confront imperatives mainly at the planarity of backbone and

unfavorable electron transport between rings of polymer skeleton being aromatically isolated

which was preliminarily addressed by the incorporation of hetero atoms to induce the

noncovalent bonds (so called as the concept of “conformation locks”, initially proposed by

Huang et al. in 2012 [3]) between aromatic rings. As conveyed by the Figure 35a (nonfused

polymer series), such noncovalently bond can be achieved through alkoxy substituents in the α,

α- or the α, β-positions to form adjacently S-O inter-molecular interactions, while in Figure 35b

(fused polymer series), this extra Van der Waals interaction induced by the α-substituting alkoxy

side-chains can be revealed in centrosymmetric backbone where the π-spacer is connected at the

2, 3 sites instead of the 1, 2 ones. Apart from the alkoxy substituents, the γ-sites of the polymer

(Figure 35a) are to bear branched alkyl chains to enhance the solubility and fine-tune the inter-

chain stacking, same as the β positions in Figure 35b does. The halogen-atoms can be randomly

incorporated into EGs with definable numbers briefly suggested by the X position (Figure 35a-

b), and yet the X1, X2 can technically represent the Se-modifiable locations with latent

opportunities provided for performance improvements, would be attempted in following phase.

As far as we know, α-sites in Figure 35a should be very promising of being halogenated to fine-

tune the photovoltaic performance of such kind of PSMAs. Eventually, the selenophene and

BDT are the preferable linking units to be opted for the low-cost PSMA designing, for the sake

of efficient polymer stacking and electron mobility.

The matter is that the synthetic routes of such non-fused PSMAs only takes concisely few

steps and are prone to be solvent-processed, paving the road to seeking resolution for efficient

PSMAs toward being cost-effective and scalable.

112
Figure 35. Molecular structure and chemically modifiable sites of other-core based PSMAs.

2.6.1 Nonfused other-core-based PSMAs

Sun et al. chose 2,5-bis (alkyloxy) phenylene as central core to build a new type non-fused

regioregular PSMA named PDO, which was used to fabricate all-PSCs by stepwise depositing

the polymer donor PBDB-T and then the polymer acceptor [170]. The LBL device exhibited

distinct increment in JSC and FF from the conventional BHJ system, mainly attributing to the

well-maintained crystallization of PM6 and PDO in the blend film with highly ordered molecular

packing in both OOP and IP directions, which was of benefit to PDO to obtain the broader and

stronger absorption for exciton extraction, the high-quality fibril texture morphology for exciton

dissociation and furnish sufficient charge transporting pathway for higher and balanced carrier

mobility with suppressed recombination. Thanks to these optimal photovoltaic process, the

PBDB-T:PDO-based device using LBL method demonstrated a PCE of 9.68% ahead of the BHJ-

based one with that of 8.14%. Li et al. uncovered the subtle correlation between performance of

non-fused PSMAs and altered alkyl substitution position on its central core [171]. With two

alkoxy side chains located on the same side of benzene to be identified as the core of SMA unit,

polymerized acceptor P2 outshone its counterpart P1 with opposite-side substitution of identical

chains in PCE (9.14% vs. 8.09%), which can ascribed to the more ordered molecular packing as

113
suggested by more distinct IP diffraction peak shown in the blends comprising PBDB-T (donor)

and P2, compared to the P1-based one, implying a favorable charge extraction and

recombination process for more efficient charge transportation towards the electrodes (the μh/μe

for P1- and P2-based devices were 1.00 × 10 −4/ 2.54 × 10−4 cm2/V·s and 4.08 × 10−4/ 3.24 ×10−4

cm2/V·s). Apart from the enhanced JSC, the VOC for P2-based device also elevated from 0.855 V

to 0.881 V because of the lifted LUMO energy level. The best PCE for the PBDB-T:P2-based

device (9.33%) was higher than PDO-based BHJ one (8.14%) is perhaps due to the regulation

effect of F atoms and extra noncovalent interactions bridged from the O and S atoms. Li et al.

attempted to exploit the thieno[3,4-c]pyrrole-4,6-dione (TPD) served as EDC in non-fused

PSMA [172]. Thus, two PSMAs RP01 (regiorandom) and RP02 (regioregular) with dithiophene-

substituted BDT as the linking unit were synthesized in order to match with PM6. Since the

fantastic coplanarity produced by the conformation locks from TPD-based nonfused backbone

and well organized intermolecular interactions (dominated by the H-aggregation), the RP02

displayed a favorable absorption with λonsetfilm red-shifted from 811 to 839 nm for the sufficient

usage of near-infrared spectrum. In addition, the GIWAXs motifs unveiled that regioregular

RP02 arranged more orderly and tightly in blend films to crystallize into preferable nanofibers

interpenetrating with donors, reasonably accounting for the good charge transport property (μh/μe

indicated the 2.3 × 10−4/3.9 × 10−5 cm2 V−1 s-1 for PM6:PR01 while the 5.6 × 10−3/7.4 × 10−4 cm2

V−1 s-1 for M6:PR02) with low recombination. Most important is that replacing benzene ring with

TPD as the EDC made a noticeable progress in efficiencies of devices as 10.99% realized by the

PM6:RP02 system, signifying expanding the amplitude of the pool of efficient EDCs is essential

for further advancing the performances of nonfused PSMAs. Li et al. reported three non-fused

regio-random PSMAs named PBTI-H, PBTI-F, and PBTI-Cl with 2,5-dialkyloxy-1,4-phenylene

114
as the central core (benzene flanked by two alkoxyl) and differently halogenated thiophene-

substituted benzoditiophene as the linkage unit [173]. When matched them with PBDB-T, the

PBTI-Cl-based photovoltaic device carried out the highest PCE of 8.80% while the PBTI-F-

based one proved the lowest 6.20%, as a result of the red-shifted absorption and the modest

LUMO energy level (-3.75 eV) for PBTI-Cl, as well as the outstanding charge kinetics and the

best exciton dissociation property (Pdiss = 96.4%), along with a reasonable phase separation

obtained by the PBTI-Cl blend films, while a completely opposite trend was manifested by

PBTI-H-based films. All in all, PBDB-T:PBTI-Cl-based solar cells demonstrated overall

promotion in VOC, JSC and FF compared to the PBTI-H and PBTI-F control ones. More important,

the Cl-substituted nonfused core-based PSMA won the device a considerably high figure-of-

merit (FOM) value (29.69%) with a rather sensible synthetic complexity index (29.64%),

suggesting a great potential of this benzene-based non-fused core in application of economically

affordable PSMAs. Massive previous works have shown that the unique centrosymmetric

configuration of SMA building block, construction of noncovalently intra-molecular interactions

and incorporation of halogenated atoms are the critical strategy to implement optimal backbone

packing and thus morphology and performances of non-fused PSMAs. Considering these

matters, Huang and co-workers designed and synthesized a small molecule BF on which they

took further step to attain the PSMAs PBF [174]. Best trading off the performance and stability

and cost to aim at the commercial criteria as illustrated in Figure 36, the PBF refreshed the

record in the efficiency (12.61%) in scope of non-fused PSMAs with an industrial figure-of-

merit value of brilliant 0.309 among the other OSC alternatives. To fully take advantages of the

delicately designed molecular structure as such above, they combined them with well-fitted

polymer donor PBDB-T, the corresponding blend showcased higher JSC, FF and PCE,

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specifically, the more complete absorption, more optimized crystallinity and appropriate

miscibility of D/A with fine distribution of exciton generation. And more significantly, the

corresponding device also achieved superior storage stability (95.2% of initial PCE after

functioning for 800 h) and thermal stability along with quite satisfied preparation costs. Whereas,

there still probably be with some issues like energy loss of device to be dealt with given that

anomalous phenomenon that the higher LUMO level of PBF but the inferior VOC value in the

device compared to the SMA-based one.

Figure36. (a) The matrix analysis of parameters related to synthetic complexity (SC) value and

(b) efficiency-stability-cost balance in the “Golden Triangle”. (c) The industrial figure of merit

(i-FOM) against synthetic complexity of active layer (SCAL) plots of the representative systems.

Reprinted with permission from ref [174], Copyright 2023, Wiley Online Library.

2.6.1 Fused other-core-based PSMAs

Apart from nonfused PSMAs dominated by the genre of alkoxy-benzene core, novel-

concept central-cores for economy-friendly polymer acceptors featuring an IDTT-similar

structure have been proposed to implement commercially-desirable PSMAs. In 2023, Zheng et

al. developed two novel ladder-type heteroheptacene based PSMAs noted as the PW-OD and

PW-HD using alkoxy-substituted benzene as the central building block with branched 2-

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octyldodecyl or 2-hexyldecyl side-chains substituted on the main chains [175]. With the intense

impact of steric hindrance induced by the longer side chains, the PW-OD showcased less ordered

inter-chain packing and relative unfavorable aggregation and thus the bathochromic-shift

absorption, inferior fibrous morphology with lower crystallinity and suboptimal degree of

stacking along the OOP direction (as supported by GIWAXs that the π-π stacking distances of

3.74 and 3.69 Å and CL values of 12.29 and 12.85 Å, for the PW-OD and PW-HD, respectively),

which were ascertained to make enhancement of charge transport and transfer associating closely

with the promoted JSC and FF for the PW-HD-based PSCs. Whereas, the PW-HD-based device

was revealed with a dramatic drop in the VOC but a slightly increase in LUMO energy level of the

acceptor (-5.59 eV) compared to the PW-OD (-5.61 eV), considering the proportional correlation

between the bandgap and the VOC value, might be intrinsically explained by that the bonding

excitons were more easy to be split in the reinforced crystalline system of PW-HD-based blended

film. To generalize, such ladder-type PSMAs featuring a simple electron-deficient core with

well-defined side chains cast light on the designing of the EDCs yet with such issue as energy

loss urgent to be solved. Furthermore, the same group incorporated fluorine and chlorine atoms

respectively into linkers of phenazine-based PSMA to obtain two halogenated PAs named as

PZC2 and PZC3 along with the non-halogenated control sample, namely PZC1.[169] Owing to

the smallest torsion angle existing in backbone of PZC2, the relevant acceptor gained the most

coplanar and rigid conformation, conducive to more ordered inter-molecular stacking and thus

the most efficient charge dynamics with the lowest EU (Urbach energy loss) (the indicator of

trap-assisted recombination) with respect to PZC2-based device (PM6:PZC2), perfectly echoing

the related EQE curve presenting extended and stronger optical response. The suitable phase

separation reflected by the contact angle analysis also ensured PM6:PZC2-based device highest

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charge transfer. However, the conspicuous steric hindrance falling in between Cl and H atoms

seriously handicapped the effective aggregation of PZC3 and hence caused a drop in JSC and FF

values in comparison with those of PZC2-based device. At last, the PM6:PZC2-based device

realized the promising PCE of 17.30% even with a nearly peerless COS of 41.1%. Most recently,

the Zheng’s team reported a breakthrough in the photovoltaic performance of M-series based

PSMAs [176]. As copolymerization through SMAs symbolically featuring centrosymmetric and

axisymmetric configuration as building block along with selenophene as bridging unit, PW-Se

structurally resembling the IDTT core-based PSMAs has verified a stunning PCE of 15.65%

beating the PS-Se with that of only 8.90%. Comparably speaking, the torsion angle of between

SMA and linker ranged from 4.78° to 6.44° and 16.11° to 19.80° for the PW-Se and PS-Se

respectively, manifesting that the former acquired an outperformed packing property when

blended with donor PM6. The magnificent aggregation behavior of the PW-Se also rendered the

favorable absorption property (red-shifted absorption band and higher maximum extinction

coefficient) for efficient exciton and free charge generation. Particularly, a weaker miscibility

with PM6 furnished the PW-Se with a suitable phase separation and interpenetrated fibril-

network morphology in the blend films (suggested by rougher surface with root-mean-square

1.18 nm, compared to that of 0.93 nm of the control one allowing for its plummeted Flory–

Huggins interaction parameter values). With the all-around improvements in exciton and charge

properties, the JSC and FF both considerably enhanced for PM6:PW-Se with an acceptable PCE,

epitomizing a powerful contender for PSMAs-based photovoltaics. Given the high similarity of

backbone structure with IDTT, two M-series small molecules featuring a ladder-type

heteroheptacene skeleton carrying alkyl side chains with varied branched length, were proposed

by Zhu et al. to be individually employed in constructing two polymeric acceptors, named as PQ-

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HD (2-hexyldecyl) and PQ-OD (2-octyldodecyl), through a simple and economical way to

synthesize [177]. Beneficial from the shorten length of branched chains, the PQ-HD:PBDB-T-

based solar cell projected a more condensed aggregation, more intimately crystallized

arrangement along with a donor-and-acceptor-well-interweaved morphology with a small phase

separation and thus a good photovoltaic, mechanic and thermally stabilized performance with a

best PCE of 13.36% and a best COS (crack-onset strain) of 17.5% far too surpassing those of

PQ-OD:PBDB-T-based system (PCE = 10.87% and COS = 12.8%), and marked the highest

stretchability record among full-conjugated PSMAs by then.

All in all, other cores dominated by simple nonfused alkoxy benzene showcase great potential

in designing low-cost and mechanically robust PSMAs. Generally speaking, through adjusting

the substituting position of alkoxy side-chains, properly incorporating halogenated atoms in EGs

and linkages, the molecular packing and bandgap can be obviously well-regulated. More than

that, π-spacer in the SMA unit takes significant part in the electron transfer and transport as well

as the ordered chain orientation and aggregation. Actually, when being with the number of fused

ring in the normal cyclic spacer cut down, the synthetic cost can be decreased while the chain

rigidity and charge transport property could be relatively poor, but it can be technically tackled

by introducing like bulky fused-ring linkage systems; On the other hand, when the π-spacer is

taken to fuse with central benzene core to be a ladder-type fused-ring conjugate-system, the more

electron mobility, narrower band-gaps, better skeleton planarity and more ordered inter-chain

interactions could be obtained within this type of PSMAs; Even more, when the two π-spacers

linearly arranged straight by the sides of benzene core, the electron delivery within the polymer

chain could be more efficient.

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Figure 37. Chemical structures for other-core based PSMAs.

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Table 19. Performance Parameters of the PSCs using other-core based PSMAs.
Acceptor HOMO LUMO Egopt Donors VOC JSC FF PCEmax Ref.

(eV) (eV) (eV) (V) (mA cm-2) (%) (%)

P1 -5.38 -3.82 1.40 PBDB-T 0.86 15.65 0.60 8.09 [171]

P2 -5.48 -3.84 1.48 PBDB-T 0.88 15.75 0.62 9.14 [171]

PDO (LBL) -5.34 -3.82 N.A. PBDB-T 0.85 19.09 59.7 9.68 [170]

PDO (BHJ) -5.34 -3.82 N.A. PBDB-T 0.88 17.56 52.9 8.14 [170]

RP01 −5.64 −3.61 1.53 PM6 0.97 9.61 43.0 4.00 [172]

RP02 −5.66 −3.60 1.48 PM6 0.91 19.19 63.0 10.99 [172]

PBF −5.42 −3.76 N.A. PBDB-T 0.84 21.54 69.35 12.61 [174]

PBTI-H −5.87 −3.75 1.62 PBDB-T 0.94 13.67 65.0 8.27 [173]

PBTI-F -5.92 −3.77 1.62 PBDB-T 0.93 12.40 54.0 6.20 [173]

PBTI-Cl −5.94 −3.75 1.61 PBDB-T 0.93 13.98 68.0 8.80 [173]

PW-OD −5.61 −4.06 1.40 PM6 0.85 14.95 50.65 6.47 [175]

PW-HD −5.59 −4.04 1.38 PM6 0.82 19.73 56.62 9.12 [175]

PW-Se −5.71 −4.04 1.31 PM6 0.82 25.64 74.05 15.65 [176]

PS-Se −5.74 −4.01 1.39 PM6 0.86 16.26 63.83 8.90 [176]

PQ-HD -5.53 -3.95 1.39 PBDB-T 0.79 24.28 69.66 13.13 [177]

PQ-OD -5.54 -3.95 1.41 PBDB-T 0.80 19.98 68.25 10.64 [177]

N.A. = not available.

3. Challenges and optunities

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As a kind of newly developed organic photovoltaic materials, PSMAs should be given high

value since its great potential in improving the performances of all-PSCs, adapting demanding of

large-area flexible solar-cell devices, and sustaining the stability of the device efficiency under

conditions of being unveiled in the persistent light and thermal. As newly designed molecules

unceasingly arose into view and technology of ternary devices and device technics gradually

developed, the power conversion efficiencies of the PSMAs-based devices has been greatly

improved to over 19%, catching up with and even outdoing its alternatives being based on small

molecular acceptors in the usage of solar energy source. Not only that, the wider space in green

solvent-processing and large-area flexible device with good morphological stability are waiting

to be further tackled with. Meanwhile, non-halogenated polymer acceptors with non-fused

central functional cores is also promising and being hopeful to dominate the future markets of

OPVs, given the reduction of detriment to people from the toxic chemical-elements existing in

the materials of the active-layer and extraordinarily high figure-of-merits of “performance-

stability-cost” golden triangle which is still difficult to be reached for the state-of-the-art

NFSMAs-based devices. As an effective way to achieve high performances and realize specially

functionalized applications for the all-PSCs, molecular design strategy through clarifying the

structure-performance relationship has been extensively disclosed and delved down deep,

particularly along with the PCEs of the all-PSCs being up continuously to a new platform, thus

the ingenious and wise molecule design should be the fundamental way and the great challenge

in reducing the lab-to-fab gap for the realm of OSCs which is being given an increasing value.

(1) Preparing the high-performance PSMAs with fully non halogen atoms towards efficient all-

PSCs: Halogenated substitution by switching H atoms to fluorine or chlorine in PSMAs is

confirmed to be effective and facile to promote PCEs of the corresponding all-PSCs. However,

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the halogen atoms can make damage to the environment and human body, which may go against

the common value of pursuing green and sustainability. It is well known that the operation

principles for OSC devices can be sorted in order into five parts: the donor and acceptor

materials absorbing the solar photons in different wave-range to generate the excitons, the

excitons diffusing and transferring to D/A interface, thereafter, the excitons dissociating into free

charge, the free charge transporting in channels across the certain materials, the electrodes with

different work function receiving the free charge. Thereby, in practice, from the molecule

engineering perspective, the above issue can be perfectly addressed if the intrinsic properties of

the PSMAs listed as below being well-regulated: the strong near-infrared absorbance, the proper-

lying HOMO and LUMO energy levels and with formed bandgaps as low as possible, the decent

inter-molecular packing and modest self-aggregation property, the device energy loss which is

originated from the energy offsets in between D/A binodals and non-radiative recombination, as

well as the active-layer morphology concerning benign D/A miscibility with uniformly

distributed micro-phase separation. On the other hand, the molecular engineering with respect to

the PSMAs can be basically divided into function unit (SMA part and linker part) modification,

and polymer design (of molecular weight and its distribution and introduction of regioisomerism

as well as copolymerization through multi-component), taking the polymer structures in different

dimensions into account that can dramatically affect the ultimate properties of the PSMAs and

the devices.

(2) Morphology controlling issue: In parallel, morphological issue should be comprehensively

considered through matching donor selection with prudence and thermaldynamic problems

involving miscibility between micro-phases and their long-term stability, considering the

entropy-decrease characteristics during film-coating process. As a matter of fact, organic

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semiconductor material has a intrinsic high exciton bonding energy hard for generated exciton to

timely dissociate due to the short hole-electron pair distance arising from the low dielectric

constant of the material, according to Shockle-Queisser (S-Q) theory, which is different from its

crystallized silicon alternative. Thereby, it is critical to form an energy offset/gap between donor

and acceptor materials to stimulate dissociation of the exciton at specific D/A interfaces. What’s

more, due to the short lifetime and diffusion distance of the exciton resulting from inevitable bi-

molecule recombination, the enough interface area should be guaranteed for swiftly efficient

charge dissociation. Thus, the development of device technics such like annealing treatment,

solvent option, additive modulation, device architecture and mixing mode of between D/A

(likewise BHJ or LBL), for desirable morphology-filming process from inter-permeating to inter-

aggregating then to crystallizing, is of imperative for fabricating OSCs devices with high

quantum efficiency, satisfying carrier mobility, low voltage loss with suppressed trap-state

density and energy disorder, good scalability, high photo-thermal stability, favoring to

breakthrough the S-Q limit in further raising of power conversion efficiency.

(3) Enriching and developing the PSMAs with high i-FOM (industrial figure-of-merit): The

PSMAs based on non-fused central core no doubt grants a brand new avenue towards the

commercialization of the organic solar cells. With the emergence of exceeding 12% PCE for the

non-fused PSMAs based device, reconsidering the multi-benefits of this kind of PSMAs is

becoming necessary and significant with more attraction received. Given the cumbersome and

relatively tricky process for synthesis of PSMAs with fused SMA and its extremely complex

purification with rather high cost of post-processing, the quantifying of total cost from original

agent synthesis to production separation and purification for PSMAs is in urgent need to

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instructionally propel the all-PSCs towards commercializing roads from the industrial

perspective. The widely confirmed indicator is i-FOM which can be defined as function (1):

i−FOM =(PCE × Stability )/ SC , (1)

Where the Stability refers to the PCE retention ratio of the device after treating under a certain

condition, while the SC corresponds to the cost of the entire procession of the polymeric

synthesis containing post-processing. With its inherent low synthetic complexity and stability of

chemical bond within the polymer chains, the nonfused core based PSMAs are always farther

ahead the other alternatives in i-FOM of the corresponding devices. It has been demonstrated

that the delicately designed the side-chainscan afford noncovalently intra-molecular interactions

with non-fused PSMAs to form an unique conformation lock of the polymer backbone, which is

of far significance to regulating the planarity and rigidity of the polymer skeleton, thus rendering

the ordered morphology with high crystallinity for the devices.

4. Conclusions and prospects

Based on the different central core of SMA unit, the design principle for PSMAs can be

technically divided into three parts: the SMA unit modification, the linker unit design and the

polymer design which is based off of self property of PSMAs embracing terpolymerization

engineering and the regional isomerism as well as the diversity of molecular weight. Developing

central cores of SMA as the kernel functioning part of photo-electronic properties of the PSMAs,

usually includes typical types like IDT, IDTT, BT, BTA, Qx and other cores in which we

classified them as fused and non-fused central cores to elucidate their meanings towards the

device performances and the cost. By the virtue of these exquisitely-designed central cores, the

device performances have got rapid boost with great advancement in commercial availability of

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PSMAs-based all-PSCs. The three elements in designing of PSMAs will be comprehensively

generalized as below together with the discussion about insights into structure-performance

relationships.

SMA unit design: (i) The hetero atoms can be substituted on polymer backbone or

introduced into aromatic ring to fine-tune the intra-/inter-molecular charge transfer and enhance

molecular stacking. Especially when the traditional sulfur atoms was replaced by Selenium

atoms in the polymer skeleton, the electron delocalization can be fairly facilitated with a

remarkably red-shifted absorption extending to above 1000 nm. Worth noting that the Cl and Se

atoms are found to be beneficial for the reduction of the Eloss due to the decreased bonding energy

within the corresponding devices, what can likewise take this effect is the π-extension of the

backbone, signifying the feasible ways to make a trade-off between JSC and VOC. (ii) Carefully

tailoring side-chains can regulate the intermolucular packing and molecular solubility which are

of significance to form the well-miscible D-A blending morphology and meanwhile, the energy

level can be subtly tuned by side chains with different length or branched styles. It is believed

that the rigorous side-chain modification should be the prior option in later works, cause that it

can readily modify the optoelectronic properties of the PSMAs with careful incorporation of

economy-friendly and relatively-green atoms for instances, the sulfur atoms, silicon atoms and

oxygen atoms into the certain chains to benefit the properties as the toxic halogen-atoms do. (iii)

The terminal-groups play a critical role in fine-tuning the molecular energy levels, enhancing

absorption coefficient and manipulating intra-/inter-chain packings, typically through the ways

of like halogenation, fused π-extension, or replacement of terminal benzene with thiophene. In

recent years, researchers have focused more attention on the configuration of PSMAs in

expectations of giving more rooms for end-groups to be utilized for more molecular packing. For

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example, the PffBQx-T synthesized by He et al. demonstrated an extra intra-molecular packing

between adjacent end-groups in single polymer since the each SMA unit lined tremendously

close to form a “double-decker” structure. (iv) Variety of fused central core unit is the dominant

factor on device performances. As a common donor unit, IDT has many excellent properties. The

coplanarity of molecular structure can be determined to a certain extent, which plays a positive

role in charge transfer. When the side chain structure changed, the solubility of the material will

also change. IDTT as a conjugation expanded version of IDT, can be more favorable to the

diminishing of optical band gap and the improvement of absorption coefficient. BT is introduced

into the monomer structure of A-DA’D-A as an acceptor unit, in between the central fused core

featuring D-A’-D architecture. These polymers have good crystallinity and charge transfer

properties. The N atom in BTA unit can intensify the distribution of electron cloud, theoretically

due to the lone pair electron of N-sp2 without participation in formation of π-conjugated system

can reduce the electron-donating nature. As a result, the corresponding LUMO energy level of

this kind of material is also higher than that of BT-based PSMAs. In addition, by customizing the

alkyl chain on the N atom, the appropriate solubility and crystallinity can be obtained, and the

morphological characteristics of the active layer can be improved to a certain extent, which is

very helpful to charge transfer and inhibit charge recombination. The PCEs for such type of

devices are prone to reach as high as 17%. Other type central cores generally consist of the

electron-rich benzene with ladder-type molecular configurations or quinoxaline-based electron-

deficient building blocks extended in 2-D direction, the former can take advantage of being

concisely synthesized and cost-cutting, while the latter strengthen particularly the center-center

aggregation of the polymer based thin-film, in favor of charge transport and offer more sites

available to further chemical modifying, and even make it possible for releasing the end-group

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unit from undertaking the role of the polymerization to obtain higher degree of molecular

packing. (v) It is approval that the asymmetric structure design for SMAs can supply great

enhancement in molecular dipole-dipole moment and polarity, fairly benefiting for the

unidirectional transferring of the electron and self-aggregating capability of between SMAs, and

thus making a huge achievement in the optical absorption and charge transporting even also the

alleviation of energy loss in the device. Likewise, the PSMAs in regionally non-axial symmetry

harvested from the copolymerization through asymmetric SMA (crafted by introducing different

hetero atoms, side chains, conjugated spacers or terminal-groups), have also shown the finer JSC

and FF compared to regional symmetric counterparts, nonetheless it’s still lack in revelation of

the inter-chain packing mode of such polymeric cluster and how it affect the performances. More

important is, the polymeric backbone with certain axisymmetric/centrosymmetric/completely-

asymmetric configuration has instrumental influence on the direction and length of the chain

growth amidst polymerizing, which in turn affect the polymeric conformation to technically

adjust the chain entanglement and ordered-packing.

For linking units, (i) thiophene, bithiophene, vinylene units were structurally simple and

easily tunable to be commonly reported in recent years. As frequently used connecting unit,

thiophene linking unit possesses the merits of being easy to access and chemical stability. Plus

that the twisting angles in polymer main chain can be mitigated to cause a planar skeleton

through the bithiophene strategy, the thiophene based PSMAs still symbolized the cutting-edge

PCEs. The use of bithiophene as the linkage was primarily meant to widen the conjugated chain

length to improve the degree of electronic delocalization and subtly regulate the HOMO/LUMO

energy level and so as to the optical-absorption. Vinylene can afford considerable co-planarity

with the polymer main-chain to achieve highly neat and compact inter-chain packing, mainly due

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to its simple double-bond structure to form more planar contact with neighbouring SMA to

relieve the misorientation of the bakobone. Many cases of PSMAs regarding vinylene have made

immense improvement in short-circuit current density being distinguished from the aromatic-

ring-based alternatives since the proposal of PYV. (ii) Fused linkages are known to be favorable

to the electron transferring and be effectively-resolvable to the optimization of the planarity

along with pertinent molecular-packing of the PSMA frameworks. BDT and its derivatives are

usually spotted in some reports because of their virtues in extending the conjugation length and

forming co-planar and rigid backbone structure. Also, BDT units can be modified by branching

different side-chains or halogenating with hetero atoms, for the sake of flexible devices or

enhance the aggregating and crystallized morphology. BTI and selenophene based linker units

featuring strong electron-withdrawing property have been proved to be quite useful to enhance

the spectrum coverage in long-wave range and obtain better charge transfer and transport. The

fused tricyclic system of BTI and metallicity of the selenophene are also conducive to the

elongation of the polymeric backbone planarity. When BTI and Se were used in conjunction to

obtain BSeI which was served as the A-type fused-ring π-spacer, with absolutely boosted

electron transfer and transport and chain-stacking, the regular binary cell implemented stunning

PCE of over 17%, manifesting the great strength of reasonable molecular-design for the linkages.

(iii) As to other linking units like non-conjugate-expanded flexible spacers are specially utilized

in designing bendable and wearable solar cell devices with eminent ductility and good resilience

under external pressures. The knack of remaining some extent mechanical robustness and

modulus is to take this type of linker into terpolymerization with other host polymers in proper

molar ratios to gain a relatively high degree of crystalline, which technically originates from the

suitable dispersing of amorphous region consisting of flexible blocks amidst the regular

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crystalline formation of orderly-packed chain-blocks.

Besides, what should also be highlighted is that there are three exclusive phenomena the

polymeric acceptors have: the regio-isomerism in configuration of PSMAs backbone directly

caused by the different sites of polymerization between SMA units and linker units, the

molecular weight distinction of PSMAs resulting from under different polymerizing conditions,

and ternary polymers concerning including the third SMA unit or the linker unit. In early years,

the regiorandom PSMAs based solar cells delivered PCEs tending to be less than 10% due to the

versatile backbone configurations that impeded the polymer-chain ordering and inter-chain

packing behaviors. It is inevitable because of the multiple active sites exist during the

polymerizing process. When regioregularity of the polymer backbone was introduced, the

efficiency and device stability improved a lot exactly for the PSMAs copolymerized from inner

position of the Y-type SMA, disparate to its counterpart polymerized from outer position of

SMA, by virtue of the more linear orientation and co-planar conformation for the former type

PSMAs accompanying with much higher crystallinity and charge transport and much descended

charge recombination. Not only being confined to varying the connecting positions between end-

group and linker, most recently, with the bulk pendant unit flanked the polymer main chain in

line, the “double decker” PSMAs is becdouboming popular since the terminal-group of the SMA

unit can be free to provide more efficient molecular packing and to be modified with hetero

atoms, and consequently the JSC and FF along with stability of the correlating all-PSCs

simultaneously enhanced. Through altering the linking mode of between SMA unit and linker, it

showcases the unlimited possibilities of PSMAs in creating high-performance acceptors.

Secondly, varied molecular weight of the PSMAs is a non-negligible element to profoundly

influence the degree of polymer chain-entanglement and aggregation and further the device

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performances. Generally speaking, the larger the molecular weight, the more stable and

crystallized mixing morphology the final devices would derive. In some studies, the PSMAs with

middle-lying molecular weight exhibited more ordered π-π stacking, stronger crystallinity and

more homogeneous mixed phase, thus outperforming the ones with light or high molecular

weight in fast and balanced charge transport and less recombination for the corresponding

devices. This can be deputed from the dissolving issue cased by the excessive molecular weight

and undesirable arrangement of polymer chains, ergo it’s urgent to develop new technics for the

device preparation or explore the appropriate processing solvent and annealing treatment

conditions to overcome the above difficulties. It being held a high regard for the terpolymer

strategy in exploiting novel high-performance PSMAs since it’s facile and effective to fruition.

Propelled by the terpolymer method, the PCEs for binary all-PSCs have already entered the rank

of being over 18%. It can subtly merge the merits of two components for instance, two SMAs or

linkers with different function or chemical features, in a single polymer, by just randomly or

segmentally copolymerizing one type of monomers into a host system. With gradually increased

incorporation of the third component, the photovoltaic of PSMAs reasonably go through a

nonlinear variation with a best circumstance for PCE existing in between. However, the

relationship between the molar ratios of each component and performance-stability trade-off is

still vague, and the exact situation for the balance between mechanical properties and

performance is yet to be discovered and confirmed. It should be noticed that the massive density

of the trap-state and energy disorder in the active layer resulting from the random distribution of

the host-guest components in polymer long-chain, which may severely disrupt the intermolecular

aggregation to disadvantage the efficient charge transport and transfer, therefore the

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compatibility between the third component and the host polymer should be fully considered

when designing or screening the molecular structure of the third component.

All in all, with exquisite molecular design, careful donor matching, delicate selection of the

third component and thoroughly-considered innovation of device processing, brighter future for

PSMAs-based all-polymer solar cells can be promising to prospect supposing the concurrent

fulfilled efficient PSMAs, the cooperatively-working polymer donors as well as the satisfying

blended-morphology. Besides, the all-PSCs towards commercial market is strategically

important considering the new conception about life and production built as the development of

technologies. Therefore, based on the guarantee of being high-efficient, there still be lots of

indexes and elements with respect to PSMAs-based all-PSCs must be noted. First of all, the

industrialized producing course of from PSMAs materials to the solar cell devices should be

implemented, that is, the curtailment of cost during synthesis of PSMAs, the printable large-area

devices, and the batch-to-batch reproducibility are to be appealed. What’s more, to meet the

requirement of practical application to serve for the mankind, the diversified purpose of use such

as bendable and wearable electronics with good thermal and mechanical stability, and the

detrimental degree of the nontoxic materials should be evaluated and considered. Most

important, the morphology control is now more and more mature and systematic, varieties of

approaches regarding chemical modification of molecules, ternary mixing blends and device

techniques are continuously emerging to realize more interpenetrating D/A networks, more

optimized component distribution, more crystallized D/A interface. These salutary methods will

undoubtedly propel the advancement of PSMAs-based all-PSCs in efficiency, stability and low-

cost to make it more resonated with the tendency of forthcoming commercialization.

CRediT authorship contribution statement

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Declaration of competing interest

The authors declare that they have no known competing financial interests or personal

relationships that could have appeared to influence the work reported in this paper.

Data availability

All relevant data are within the paper.

Acknowledgements

This work was supported by the Shandong Provincial Natural Science Foundation

(ZR2022MB068), the National Natural Science Foundation of China (51703104), the State Key

Project of International Cooperation Research (2023YFE0201100), the Program of Introducing

Talents of Discipline to Universities (“111” plan), the Double Hundred Foreign Expert Project of

Shandong Province, and the High-Level Discipline Program of Materials Science of Shan dong

Province.

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