Halogenation Strategy: Simple Wide Band Gap Nonfullerene Acceptors with the BODIPY-Thiophene-Backboned Polymer Donor for Enhanced Outdoor and Indoor Photovoltaics.

Researchers have been motivated to develop photovoltaic systems that can efficiently convert artificial light into power with the growing use of indoor electrical devices for the Internet of Things. Understanding the impact of molecular design strategies involving morphological optimization through the terminal group of the non-fullerene acceptors (NFAs) is crucial. This is critically important to enhancing the photovoltaic efficiency of organic photovoltaic devices under diverse irradiation conditions. Halogenation of terminal groups proves to be a standout approach for adjusting energy levels, refining light-harvesting capabilities, crystallinity, and bolstering the intermolecular stacking in NFAs. Herein, we have designed two simple NFAs, DICTF-4F and DICTF-4Cl, to explore the dihalogenation (F and Cl) effect on the terminal group on the optical and electrochemical properties. After combining with the BODIPY-thiophene-backboned donor polymer P(BdP-HT), the organic solar cells (OSCs) using an optimized active layer with P(BdP-HT):DICTF-4F and P(BdP-HT):DICTF-4Cl attained a power conversion efficiency (PCE) of about 8.03 and 14.16%, respectively, under 1 sun illumination. Moreover, the OSC-based P(BdP-HT):DICTF-4Cl active layer showed a PCE approaching 24% under 1000 lx indoor conditions.

Bithieno[3,4-c]pyrrole-4,6-dione-Based Wide-Bandgap Donor Polymers for Efficient Polymer Solar Cells.

The polymer solar cells (PSCs) have garnered substantial interest owing to their lightweight, cost-effectiveness, and flexibility, making them ideal for large-scale roll-to-roll manufacturing. In this study, two wide-bandgap (WBG) donor polymers, PFBiTPD and PClBiTPD, utilizing bithieno[3,4-c]pyrrole-4,6-dione (BiTPD) as the electron-accepting unit and fluorinated/chlorinated benzo[1,2-b:4,5-b']dithiophene (BDT) as the electron-donating moiety are designed and synthesized. The polymers demonstrated large optical bandgaps (exceeding 1.80 eV) and are blended with ITIC-4F to form the active layers in PSCs. The PFBiTPD-based devices showed a well-dispersed fibrillar network, facilitating efficient charge generation and transport. Thus, these devices attained a power conversion efficiency (PCE) of 8.60%, featuring a fill factor (FF) of 62.89%, an open-circuit voltage (Voc) of 0.88 V and a short-circuit current density (Jsc) of 15.54 mA cm-2. In contrast, PClBiTPD-based devices displayed lower performance due to less favorable morphology. The study underscores the importance of polymer design and morphology control in optimizing the photovoltaic performance of PSCs.

Dimerized M-series Acceptors with Low Diffusion Coefficients for Efficient and Stable Polymer Solar Cells.

As the simplest oligomeric acceptors, dimerized acceptors (DAs) are easier to synthesize, and more importantly, they can retain good intermolecular interaction and photovoltaic properties of their parent small-molecule acceptors (SMAs). Nevertheless, currently most efficient DAs are derived from banana-shaped acceptors and they might suffer from inferior device stability with high diffusion coefficients. Herein, we design and synthesize two planar DAs (DMT-FH and DMT-HF) by bridging two linear-shaped M-series SMAs with a thiophene unit. The effects of fluorination position on the diffusion coefficients, power conversion efficiencies (PCEs) and stability of the DAs are systematically studied. Our results suggest that DMT-HF with fluorination on the ending indanone groups shows enhanced intermolecular interactions, improved PCE and stability compared with the counterpart (DMT-FH) with fluorination on the central indanone groups. Further optimization on the DMT-HF-based devices yields an outstanding PCE of 17.17%, which is the highest among all linear-shaped SMA-based DAs. Notably, with the low diffusion coefficient (3.36×10-24 cm2 s-1) of DMT-HF, the resulting device retains over 93% of the initial PCE after 5000 h of continuous heating at 85 oC, suggesting its excellent thermal stability. The results highlight the importance of intermolecular interaction and fluorination for achieving efficient and stable polymer solar cells.

Optimizing Double-Fibril Network Morphology via Solid Additive Strategy Enables Binary All-Polymer Solar Cells with 19.50% Efficiency.

Double-fibril network morphology (DFNM), in which the donor and the acceptor can self-assemble into a double-fibril structure, is beneficial for exciton dissociation and charge transport in organic solar cells. Herein, it is demonstrated that such DFNM can be constructed and optimized in all-polymer solar cells (all-PSCs) with the assistance of 2-alkoxynaphthalene volatile solid additives. It is revealed that the incorporation of 2-alkoxynaphthalene can induce a stepwise regulation in the aggregation of donor and acceptor molecules during film casting and thermal annealing processes. Through altering the alkoxy of 2-alkoxynaphthalene solid additives, both the intermolecular interactions and molecular miscibility with the host materials can be precisely tuned, which allows for the optimization of the molecular aggregation process and facilitation of molecular self-assembly, and thus leading to reinforced molecular packing and optimized DFNM. As a result, an unprecedented efficiency of 19.50% (certified as 19.1%) is obtained for 2-ethoxynaphthalene-processed PM6:PY-DT-X all-PSCs with excellent photostability (T80 = 1750 h). This work reveals that the optimization of DFNM via solid additive strategy is a promising avenue to boosting the performance of all-PSCs.

Over 18.2% efficiency of layer-by-layer all-polymer solar cells enabled by homoleptic iridium(III) carbene complex as solid additive.

The vertical phase distribution of active layers plays a vital role in balancing exciton dissociation and charge transport for achieving efficient polymer solar cells (PSCs). The layer-by-layer (LbL) PSCs are commonly prepared by using sequential spin-coating method from donor and acceptor solutions with distinct solvents and solvent additives. The enhanced exciton dissociation is expected in the LbL PSCs with efficient charge transport in the relatively neat donor or acceptor layers. In this work, a series of LbL all-polymer solar cells (APSCs) were fabricated with PM6 as donor and PY-DT as acceptor, and triplet material m-Ir(CPmPB)3 is deliberately incorporated into PY-DT layer to prolong exciton lifetimes of active layers. The power conversion efficiency (PCE) of LbL APSCs is improved to 18.24% from 17.32% by incorporating 0.3 wt% m-Ir(CPmPB)3 in PY-DT layer, benefiting from the simultaneously enhanced short-circuit current density (JSC) of 25.17 mA cm-2 and fill factor (FF) of 74.70%. The enhancement of PCE is attributed to the efficient energy transfer of m-Ir(CPmPB)3 to PM6 and PY-DT, resulting in the prolonged exciton lifetime in the active layer and the increased exciton diffusion distance. The efficient energy transfer from m-Ir(CPmPB)3 to PM6 and PY-DT layer can be confirmed by the increased photoluminescence (PL) intensity and the prolonged PL lifetime of PM6 and PY-DT in PM6 + m-Ir(CPmPB)3 and PY-DT + m-Ir(CPmPB)3 films. This study indicates that the triplet material as solid additive has great potential in fabricating efficient LbL APSCs by prolonging exciton lifetimes in active layers.

Improving Miscibility of Polymer Donor and Polymer Acceptor by Reducing Chain Entanglement for Realizing 18.64 % Efficiency All Polymer Solar Cells.

All-polymer solar cells have experienced rapid development in recent years by the emergence of polymerized small molecular acceptors (PSMAs). However, the strong chain entanglements of polymer donors (PDs) and polymer acceptors (PAs) decrease the miscibility of the resulting polymer mixtures, making it challenging to optimize the blend morphology. Herein, we designed three PAs, namely PBTPICm-BDD, PBTPICγ-BDD and PBTPICF-BDD, by smartly using a BDD unit as the polymerized unit to copolymerize with different Y-typed non-fullerene small molecular acceptors (NF-SMAs), thus achieving a certain degree of distortion and giving the polymer system enough internal space to reduce the entanglements of the polymer chains. Such effects increase the chances of the PD being interspersed into the acceptor material, which improve the solubility between the PD and PA. The PBTPICγ-BDD and PBTPICF-BDD displayed better miscibility with PBQx-TCl, leading to a well optimized morphology. As a result, high power conversion efficiencies (PCEs) of 17.50 % and 17.17 % were achieved for PBQx-TCl : PBTPICγ-BDD and PBQx-TCl : PBTPICF-BDD devices, respectively. With the addition of PYFT-o as the third component into PBQx-TCl : PBTPICγ-BDD blend to further extend the absorption spectral coverage and finely tune microstructures of the blend morphology, a remarkable PCE of 18.64 % was realized finally.

Providing a Photovoltaic Performance Enhancement Relationship from Binary to Ternary Polymer Solar Cells via Machine Learning.

Ternary polymer solar cells (PSCs) are currently the simplest and most efficient way to further improve the device performance in PSCs. To find high-performance organic photovoltaic materials, the established connection between the material structure and device performance before fabrication is of great significance. Herein, firstly, a database of the photovoltaic performance in 874 experimental PSCs reported in the literature is established, and three different fingerprint expressions of a molecular structure are explored as input features; the results show that long fingerprints of 2D atom pairs can contain more effective information and improve the accuracy of the models. Through supervised learning, five machine learning (ML) models were trained to build a mapping of the photovoltaic performance improvement relationship from binary to ternary PSCs. The GBDT model had the best predictive ability and generalization. Eighteen key structural features from a non-fullerene acceptor and the third components that affect the device's PCE were screened based on this model, including a nitrile group with lone-pair electron, a halogen atom, an oxygen atom, etc. Interestingly, the structural features for the enhanced device's PCE were essentially increased by the Jsc or FF. More importantly, the reliability of the ML model was further verified by preparing the highly efficient PSCs. Taking the PM6:BTP-eC9:PY-IT ternary PSC as an example, the PCE prediction (18.03%) by the model was in good agreement with the experimental results (17.78%), the relative prediction error was 1.41%, and the relative error between all experimental results and predicted results was less than 5%. These results indicate that ML is a useful tool for exploring the photovoltaic performance improvement of PSCs and accelerating the design and application with highly efficient non-fullerene materials.

Layer-by-Layer-Processed All-Polymer Solar Cells with Enhanced Performance Enabled by Regulating the Microstructure of Upper Layer.

The layer-by-layer (LBL) fabrication method allows for controlled microstructure morphology and vertical component distribution, and also offers a reproducible and efficient technique for fabricating large-scale organic solar cells (OSCs). In this study, the polymers D18 and PYIT-OD are employed to fabricate all-polymer solar cells (all-PSCs) using the LBL method. Morphological studies reveal that the use of additives optimizes the microstructure of the active layer, enhancing the cells' crystallinity and charge transport capability. The optimized device with 2% CN additive significantly reduces bimolecular recombination and trap-assisted recombination. All-PSCs fabricated by the LBL method based on D18/PYIT-OD deliver a power conversion efficiency (PCE) of 15.07%. Our study demonstrates the great potential of additive engineering via the LBL fabrication method in regulating the microstructure of active layers, suppressing charge recombination, and enhancing the photovoltaic performance of devices.

Precisely Controlling Polymer Acceptors with Weak Intramolecular Charge Transfer Effect and Superior Coplanarity for Efficient Indoor All-Polymer Solar Cells with over 27% Efficiency.

Indoor photovoltaics (IPVs) are garnering increasing attention from both the academic and industrial communities due to the pressing demand of the ecosystem of Internet-of-Things. All-polymer solar cells (all-PSCs), emerging as a sub-type of organic photovoltaics, with the merits of great film-forming properties, remarkable morphological and light stability, hold great promise to simultaneously achieve high efficiency and long-term operation in IPV's application. However, the dearth of polymer acceptors with medium-bandgap has impeded the rapid development of indoor all-PSCs. Herein, a highly efficient medium-bandgap polymer acceptor (PYFO-V) is reported through the synergistic effects of side chain engineering and linkage modulation and applied for indoor all-PSCs operation. As a result, the PM6:PYFO-V-based indoor all-PSC yields the highest efficiency of 27.1% under LED light condition, marking the highest value for reported binary indoor all-PSCs to date. More importantly, the blade-coated devices using non-halogenated solvent (o-xylene) maintain an efficiency of over 23%, demonstrating the potential for industry-scale fabrication. This work not only highlights the importance of fine-tuning intramolecular charge transfer effect and intrachain coplanarity in developing high-performance medium-bandgap polymer acceptors but also provides a highly efficient strategy for indoor all-PSC application.

Polymerized-Small-Molecule Acceptors Featuring Siloxane-Terminated Side Chains for Mechanically Robust All-Polymer Solar Cells.

Flexible and stretchable organic solar cells (OSCs) show great promise in wearable and stretchable electronic applications. However, current high-performance OSCs consisting of polymer donors (PDs) and small-molecule acceptors (SMAs) face significant challenges in achieving both high power conversion efficiency (PCE) and excellent stretch-ability. In this study, we synthesized a new polymerized-small-molecule acceptor (P-SMA) PY-SiO featuring siloxane-terminated side chains and compared its photovoltaic and mechanical performance to that of the reference PY-EH with ethylhexyl-terminated side chains. We found that the incorporation of siloxane-terminated side chains in PY-SiO enhanced the molecular aggregation and charge transport, leading to an optimized film morphology. The resultant of all-polymer solar cells (all-PSCs) based on PBDB-T/PY-SiO showed a higher PCE of 12.04% than the PY-EH-based one (10.85%). Furthermore, the siloxane-terminated side chains also increased the interchain distance and provided a larger free volume for chain rotation and reconfiguration, resulting in a higher film crack-onset strain (COS: 18.32% for PBDB-T/PY-SiO vs 11.15% for PBDB-T/PY-EH). Additionally, the PY-SiO-based stretchable all-PSCs exhibited an impressive PCE of 9.8% and retained >70% of its original PCE even under a substantial 20% strain, exceeding the performance of the PY-EH-based stretchable all-PSCs. Our result suggests the great potential of the siloxane-terminated side chain for achieving high-performance and stretchable OSCs.

Polymerizing M-Series Acceptors for Efficient Polymer Solar Cells: Effect of the Molecular Shape.

Currently, high-performance polymerized small-molecule acceptors (PSMAs) based on ADA-type SMAs are still rare and greatly demanded for polymer solar cells (PSCs). Herein, two novel regioregular PSMAs (PW-Se and PS-Se) are designed and synthesized by using centrosymmetric (linear-shaped) and axisymmetric (banana-shaped) ADA-type SMAs as the main building blocks, respectively. It is demonstrated that photovoltaic performance of the PSMAs can be significantly improved by optimizing the configuration of ADA-type SMAs. Compared to the axisymmetric SMA-based polymer (PS-Se), PW-Se using a centrosymmetric SMA as the main building block exhibits better backbone coplanarity thereby resulting in bathochromically shifted absorption with a higher absorption coefficient, tighter interchain π-π stacking, and more favorable blend film morphology. As a result, enhanced and more-balanced charge transport, better exciton dissociation, and reduced charge recombination are achieved for PW-Se-based devices with PM6 as polymer donor. Benefiting from these positive factors, the optimal PM6:PW-Se-based device exhibits a higher power conversion efficiency (PCE) of 15.65% compared to the PM6:PS-Se-based device (8.90%). Furthermore, incorporation of PW-Se as a third component in the binary active layer of PM6:M36 yields ternary devices with an outstanding PCE of 18.0%, which is the highest value for PSCs based on ADA-type SMAs, to the best of the knowledge.

Metallic nanoparticles and hybrids of metallic nanoparticles/graphene nanomaterials for enhanced photon harvesting and charge transport in polymer and dye sensitized solar cells.

Solar energy is a sustainable option in the provision of affordable and clean energy. Conversion of solar energy to electricity requires the development of materials and technologies that are not only efficient but also cost-effective. Polymer solar cells (PSCs) and dye sensitized solar cells (DSSCs) are some of the cost-effective technologies for solar energy conversion. However, PSCs suffer from poor optical absorption and charge carrier mobility, while the major drawback to high efficiencies in DSSCs is charge carrier recombination. This article examines the potency of plasmonic metallic nanoparticles (MNPs) and hybrids of MNPs/graphene nanomaterials (GNMs) in mitigating these challenges. MNPs and MNPs/GNMs incorporated in these devices enhance light harvesting to extended wavelengths and improve charge transport. MNPs in the photoanode of DSSCs serve as cosensitizers to offer complementary optical absorption, while MNPs/GNMs as counter electrode yield high catalytic activity comparable to Pt. Simultaneous application of MNPs and/or MNPs/GNMs in PSCs' interfacial and active layers yield enhanced broadband optical absorption and effective charge transport. The mechanisms by which these nanomaterials enhance light harvesting in these devices are discussed in detail. The material characteristics that influence the performance of MNPs and MNPs/GNMs modified devices, such as MNPs size, shape, and morphology, are highlighted. Hence, this article presents perspectives and strategies on successful utilization of plasmonic MNPs and hybrids of MNPs/GNMs to mitigate the challenges of poor optical absorption and charge transport of PSCs and DSSCs for high efficiencies.

High-Efficiency Ternary Polymer Solar Cells with a Gradient-Blended Structure Fabricated by Sequential Deposition.

Acquiring the ideal blend morphology of the active layer to optimize charge separation and collection is a constant goal of polymer solar cells (PSCs). In this paper, the ternary strategy and the sequential deposition process were combined to make sufficient use of the solar spectrum, optimize the energy-level structure, regulate the vertical phase separation morphology, and ultimately enhance the power conversion efficiency (PCE) and stability of the PSCs. Specifically, the donor and acceptor illustrated a gradient-blended distribution in the sequential deposition-processed films, thus resulting in facilitated carrier characteristics in the gradient-blended devices. Consequently, the PSCs based on D18-Cl/Y6:ZY-4Cl have achieved a device efficiency of over 18% with the synergetic improvement of open-circuit voltage (VOC), short-circuit current density (JSC), and fill factor (FF). Therefore, this work reveals a facile approach to fabricating PSCs with improved performance and stability.

Dimeric Giant Molecule Acceptors Featuring N-type Linker: Enhancing Intramolecular Coupling for High-Performance Polymer Solar Cells.

Giant molecular acceptors (GMAs) are typically designed through the conjugated linking of individual small molecule acceptors (SMAs). This design imparts an extended molecular size, elevating the glass transition temperature (Tg) relative to their SMA counterparts. Consequently, it effectively suppresses the thermodynamic relaxation of the acceptor component when blended with polymer donors to construct stable polymer solar cells (PSCs). Despite their merits, the optimization of their chemical structure for further enhancing of device performance remains challenge. Different from previous reports utilizing p-type linkers, here, we explore an n-type linker, specifically the benzothiadiazole unit, to dimerize the SMA units via a click-like Knoevenagel condensation, affording BT-DL. In comparison with B-DL with a benzene linkage, BT-DL exhibits significantly stronger intramolecular super-exchange coupling, a desirable property for the acceptor component. Furthermore, BT-DL demonstrates a higher film absorption coefficient, redshifted absorption, larger crystalline coherence, and higher electron mobility. These inherent advantages of BT-DL translate into a higher power conversion efficiency of 18.49 % in PSCs, a substantial improvement over the 9.17 % efficiency observed in corresponding devices with B-DL as the acceptor. Notably, the BT-DL based device exhibits exceptional stability, retaining over 90 % of its initial efficiency even after enduring 1000 hours of thermal stress at 90 °C. This work provides a cost-effective approach to the synthesis of n-type linker-dimerized GMAs, and highlight their potential advantage in enhancing intramolecular coupling for more efficient and durable photovoltaic technologies.

Dithienoquinoxalineimide-Based Polymer Donor Enables All-Polymer Solar Cells Over 19 % Efficiency.

All-polymer solar cells (all-PSCs) have been regarded as one of the most promising candidates for commercial applications owing to their outstanding advantages such as mechanical flexibility, light weight and stable film morphology. However, compared to large amount of new-emerging excellent polymer acceptors, the development of high-performance polymer donor lags behind. Herein, a new D-π-A type polymer donor, namely QQ1, was developed based on dithienoquinoxalineimide (DTQI) as the A unit, benzodithiophene with thiophene-conjugated side chains (BDTT) as the D unit, and alkyl-thiophene as the π-bridge, respectively. QQ1 not only possesses a strong dipole moment, but also shows a wide band gap of 1.80 eV and a deep HOMO energy level of -5.47 eV, even without halogen substituents that are commonly indispensable for high-performance polymer donors. When blended with a classic polymer acceptor PY-IT, the QQ1-based all-PSC delivers an outstanding PCE of 18.81 %. After the introduction of F-BTA3 as the third component, a record PCE of 19.20 % was obtained, the highest value reported so far for all-PSCs. The impressive photovoltaic performance originates from broad absorption range, reduced energy loss, and compact π-π stacking. These results provide new insight in the rational design of novel nonhalogenated polymer donors for further development of all-PSCs.

Efficient and Stable All-Polymer Solar Cells Enabled by Dual Working Mechanism.

Ternary strategy with integration characteristics and adaptability is a simple and effective method for blooming of the performance of photovoltaic devices. Herein, a novel wideband gap polymer donor PBB2-Hs is synthesized as the guest component to optimize all-polymer solar cells (all-PSCs). High-energy photon absorption and long exciton lifetime of PBB2-Hs constitute efficient energy transfer. Good miscibility and cascade energy levels promote the formation of alloy-like structure between PBB2-Hs and host system. The dual working mechanisms greatly improve photon capture and charge transfer in active layers. Additionally, the introduction of PBB2-Hs also optimizes the ordered molecular stacking of acceptors and suppresses molecular peristalsis. Upon adding 15 wt% PBB2-Hs, the ternary all-PSC achieved a champion efficiency of 17.66%, and can still maintain 82% photostability (24 h) and 91% storage stability (1000 h) of the original PCE. Moreover, the strong molecular stacking and entanglement between PBB2-Hs and the host material increased the elongation at break of ternary blend film by 1.6 times (16.2%), allowing the flexible device to maintain 83% of the original efficiency after 800 bends (R = 5 mm). This work highlights the effectiveness of guest polymer on simultaneously improving photovoltaic performance, photostability and mechanical stability in all-PSCs.

Tethered Trimeric Small-molecular Acceptors through Aromatic-core Engineering for Highly Efficient and Thermally Stable Polymer Solar Cells.

Polymer solar cells (PSCs) rely on a blend of small molecular acceptors (SMAs) with polymer donors, where thermodynamic relaxation of SMAs poses critical concerns on operational stability. To tackle this issue, tethered SMAs, wherein multiple SMA-subunits are connected to the aromatic-core via flexible chains, are proposed. This design aims to an elevated glass transition temperature (Tg) for a dynamical control. However, attaining an elevated Tg value with additional SMA subunits introduces complexity to the molecular packing, posing a significant challenge in realizing both high stability and power conversion efficiency (PCE). In this study, we initiate isomer engineering on the benzene-carboxylate core and find that meta-positioned dimeric BDY-ß exhibits more favorable molecular packing compared to its para-positioned counterpart, BDY-α. With this encouraging result, we expand our approach by introducing an additional SMA unit onto the aromatic core of BDY-ß, maintaining a meta-position relative to each SMA unit location in the tethered acceptor. This systematic aromatic-core engineering results in a star-shaped C3h-positioned molecular geometry. The supramolecular interactions of SMA units in the trimer contribute to enhancements in Tg value, crystallinity, and a red-shifted absorption compared to dimers. These characteristics result in a noteworthy increase in PCE to 18.24 %, coupled with a remarkable short-circuit current density of 27.06 mA cm-2. More significantly, the trimer-based devices delivered an excellent thermal stability with over 95 % of their initial efficiency after 1200 h thermal degradation. Our findings underscore the promise and feasibility of tethered trimeric structures in achieving highly ordered aggregation behavior and increased Tg value in PSCs, simultaneously improving in device efficiency and thermal stability.

Binary All-polymer Solar Cells with a Perhalogenated-Thiophene-Based Solid Additive Surpass 18 % Efficiency.

Morphological control of all-polymer blends is quintessential yet challenging in fabricating high-performance organic solar cells. Recently, solid additives (SAs) have been approved to be capable in tuning the morphology of polymer: small-molecule blends improving the performance and stability of devices. Herein, three perhalogenated thiophenes, which are 3,4-dibromo-2,5-diiodothiophene (SA-T1), 2,5-dibromo-3,4-diiodothiophene (SA-T2), and 2,3-dibromo-4,5-diiodothiophene (SA-T3), were adopted as SAs to optimize the performance of all-polymer organic solar cells (APSCs). For the blend of PM6 and PY-IT, benefitting from the intermolecular interactions between perhalogenated thiophenes and polymers, the molecular packing properties could be finely regulated after introducing these SAs. In situ UV/Vis measurement revealed that these SAs could assist morphological character evolution in the all-polymer blend, leading to their optimal morphologies. Compared to the as-cast device of PM6 : PY-IT, all SA-treated binary devices displayed enhanced power conversion efficiencies of 17.4-18.3 % with obviously elevated short-circuit current densities and fill factors. To our knowledge, the PCE of 18.3 % for SA-T1-treated binary ranks the highest among all binary APSCs to date. Meanwhile, the universality of SA-T1 in other all-polymer blends is demonstrated with unanimously improved device performance. This work provide a new pathway in realizing high-performance APSCs.

18.6% Efficiency All-Polymer Solar Cells Enabled by a Wide Bandgap Polymer Donor Based on Benzo[1,2-d:4,5-d']bisthiazole.

The limited selection of wide bandgap polymer donors for all-polymer solar cells (all-PSCs) is a bottleneck problem restricting their further development and remains poorly studied. Herein, a new wide bandgap polymer, namely PBBTz-Cl, is designed and synthesized by bridging the benzobisthiazole acceptor block and chlorinated benzodithiophene donor block with thiophene units for application as an electron donor in all-PSCs. PBBTz-Cl not only possesses wide bandgap and deep energy levels but also displays strong absorption, high-planar structure, and good crystallinity, making it a promising candidate for application as a polymer donor in organic solar cells. When paired with the narrow bandgap polymer acceptor PY-IT, a fibril-like morphology forms, which facilitates exciton dissociation and charge transport, contributing to a power conversion efficiency (PCE) of 17.15% of the corresponding all-PSCs. Moreover, when introducing another crystalline polymer acceptor BTP-2T2F into the PBBTz-Cl:PY-IT host blend, the absorption ditch in the range of 600-750 nm is filled, and the blend morphology is further optimized with the trap density reducing. As a result, the ternary blend all-PSCs achieve a significantly improved PCE of 18.60%, which is among the highest values for all-PSCs to date.

Regulating Phase Separation Kinetics for High-Efficiency and Mechanically Robust All-Polymer Solar Cells.

All-polymer solar cells (all-PSCs) possess excellent operation stability and mechanical robustness than other types of organic solar cells, thereby attracting considerable attention for wearable flexible electron devices. However, the power conversion efficiencies (PCEs) of all-PSCs are still lagging behind those of small-molecule-acceptor-based systems owing to the limitation of photoactive materials and unsatisfactory blend morphology. In this work, a novel terpolymer, denoted as PBDB-TFCl (poly4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b″]dithiophene-1,3-bis(2-ethylhexyl)-5,7-di(thiophen-2-yl)-4H,8H-benzo[1,2-c:4,5-c″]dithiophene-4,8-dione-4,8-bis(4-chloro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene), is used as an electron donor coupled with a ternary strategy to optimize the performance of all-PSCs. The addition of PBDB-TCl unit deepens the highest occupied molecular orbital energy level, reducing voltage losses. Moreover, the introduction of the guest donor (D18-Cl) effectively regulates the phase-transition kinetics of PBDB-TFCl:D18-Cl:PY-IT during the film formation, leading to ideal size of aggregations and enhanced crystallinity. PBDB-TFCl:D18-Cl:PY-IT devices exhibit a PCE of 18.6% (certified as 18.3%), judged as the highest value so far obtained with all-PSCs. Besides, based on the ternary active layer, the manufactured 36 cm2 flexible modules exhibit a PCE of 15.1%. Meanwhile, the ternary PSCs exhibit superior photostability and mechanical stability. In summary, the proposed strategy, based on molecular design and the ternary strategy, allows optimization of the all-polymer blend morphology and improvement of the photovoltaic performance for stable large-scale flexible PSCs.