Ternary Organic Solar Cells Research Articles

An Indacenodithienothiophene-Based Wide Bandgap Small Molecule Guest for Efficient and Stable Ternary Organic Solar Cells.

The strategic and logical development of the third component (guest materials) plays a pivotal and intricate role in improving the efficiency and stability of ternary organic solar cells (OSCs). In this study, a novel guest material with a wide bandgap, named IDTR, is designed, synthesized, and incorporated as the third component. IDTR exhibits complementary absorption characteristics and cascade band alignment with the PM6:Y6 binary system. Morphological analysis reveals that the introduction of IDTR results in strong crystallinity, good miscibility, and proper vertical phase distribution, thereby realizing heightened and balanced charge transport behavior. Remarkably, the novel ternary OSCs have exhibited a significant enhancement in photovoltaic performance. Consequently, open-circuit voltage (VOC), short-circuit current (JSC), and fill factor (FF) have all witnessed substantial improvements with a remarkable power conversion efficiency (PCE) of 18.94% when L8-BO replaced Y6. Beyond the pronounced improvement in photovoltaic performance, superior device stability with a T80 approaching 400h is successfully achieved. This achievement is attributed to the synergistic interplay of IDTR, providing robust support for the overall enhancement of performance. These findings offer crucial guidance and reference for the design and development of efficient and stable OSCs.

High Luminescence Stability Enables Reduced Burn‐In Voltage Loss in Organic Solar Cells

Although organic solar cells (OSCs) have received increasing attention because of their high device efficiencies, the fundamental mechanism governing their photostability remains elusive. Herein, the effect of the luminescence stability of the acceptor components on the burn‐in voltage loss of binary and ternary OSCs is demonstrated. A systematic characterization reveals that the acceptor component experiences an abnormal decrease in luminescence under photoaging—specifically, photoinduced luminescence quenching—because of a photoinduced conformational change. This phenomenon increases nonradiative recombination in blends and thus causes a substantial nonradiative voltage loss of OSCs. Moreover, an introduction of a third component with high luminescence stability can effectively reduce the burn‐in voltage loss of OSCs. A composition‐dependent photostability study of the resultant ternary OSCs reveals that the reduction in the burn‐in voltage loss of OSCs is mainly driven by the third component distributed in the mixed phase; high luminescence stability of this component effectively prevents the increase in nonradiative voltage loss by photoaging. The results suggest that improving the luminescence stability of the acceptor components can be an effective method for highly stable photovoltaics with greatly reduced burn‐in voltage loss.

Guest Acceptors with Lower Electrostatic Potential in Ternary Organic Solar Cells for Minimizing Voltage Losses.

The ternary strategy, in which one guest component is introduced into one host binary system, is considered to be one of the most effective ways to realize high-efficiency organic solar cells (OSCs). To date, there is no efficient method to predict the effectiveness of guest components in ternary OSCs. Herein, three guest compositions (i.e., ANF-1, ANF-2 and ANF-3) with different electrostatic potential (ESP) are designed and synthesized by modulating the electron-withdrawing ability of the terminal groups through density functional theory simulations. The effects of the introduction of guest component into the host system (D18:N3) on the photovoltaic properties are investigated. The theoretical and experimental studies provide a key rule for guest acceptor in ternary OSCs to improve the open-circuit voltage, that is, the larger ESP difference between the guest and host acceptor, the stronger the intermolecular interactions and the higher the miscibility, which improves the luminescent efficiency of the blend film and the electroluminescence quantum yield (EQEEL) of the device by reducing the aggregation-caused-quenching, thereby effectively decreasing the non-radiative voltage loss of ternary OSCs. This work will greatly contribute to the development of highly efficient guest components, thereby promoting the rapid breakthrough of the 20% efficiency bottleneck for single-junction OSCs.

2,5-dichloro-3,4-diiodothiophene as a versatile solid additive for high-performance organic solar cells

Volatile solid additive (SA) with diverse chemical structures has been proved to be an alternative to prepare high-efficient organic solar cells (OSCs). While, various organic photovoltaic materials raise challenges in selecting suitable SAs during the device optimization. Herein, based on the simple and commonly used thiophene unit, we proposed a perhalogenated 2,5-dichloro-3,4-diiodothiophene (SA-T5) as the SA for the device optimizations. As results, the capacity of SA-T5 in optimizing molecular packings of small-molecular acceptor L8-BO, dimeric acceptor DL8, and polymeric acceptor PY-DT based blend films has been demonstated. Their optimized morphologies assisted by SA-T5 contribute to the suppressed charge recombination and enhanced charge transportation, resulting in their improved short-circuit current density and fill factor, simultaneously. In comparsion with as-cast devices, SA-T5-treated devices showed significantly improved power conversion efficiencies (PCEs) of 18.8 % for PM6:L8-BO, 17.8 % for PM6:DL8, and 17.6 % for PM6:PY-DT, respectively. Furthermore, the potential of SA-T5 in obtaining high-performance ternary OSCs was also confirmed, for example, a 18.1 % efficiency was realized in PM6:DL8:L8-BO based device. To our knowledge, the performance of these SA-T5-treated devices reaches the best results of different acceptor-based OSCs. Importantly, this work provides a rare and successful case to develop versatile SAs for high-performance OSCs.

Designing a Novel Wide Bandgap Small Molecule Guest for Enhanced Stability and Morphology Mediation in Ternary Organic Solar Cells with over 19.3% Efficiency.

In this study, a novel wide-bandgap small molecule guest material, ITOA, designed and synthesized for fabricating efficient ternary organic solar cells (OSCs) ITOA complements the absorbance of the PM6:Y6 binary system, exhibiting strong crystallinity and modest miscibility. ITOA optimizes the morphology by promoting intensive molecular packing, reducing domain size, and establishing a preferred vertical phase distribution. These features contribute to improved and well-balanced charge transport, suppressed carrier recombination, and efficient exciton dissociation. Consequently, a significantly enhanced efficiency of 18.62% for the ternary device is achieved, accompanied by increased short-circuit current density (JSC), fill factor (FF), and open-circuit voltage (VOC). Building on this success, replacing Y6 with BTP-eC9 leads to an outstanding PCE of 19.33% for the ternary OSCs. Notably, the introduction of ITOA expedites the formation of the optimized morphology, resulting in an impressive PCE of 18.04% for the ternary device without any postprocessing. Moreover, the ternary device exhibits enhanced operational stability under maximum power point (MPP) tracking. This comprehensive study demonstrates that a rationally designed guest molecule can optimize morphology, reduce energy loss, and streamline the fabrication process, essential for achieving high efficiency and stability in OSCs, paving the way for practical commercial applications.

Tert-butyl carbazole modified non-fused ring electron acceptor generating high triplet state energy level for efficient organic solar cell

Two-dimensional side-chain plays a crucial role in the construction of efficient non-fused ring electron acceptors (NFREAs). Herein, we introduce a novel NFREA, PCT-4Cl, featuring a tert-butyl carbazole side-chain, and investigate its optoelectronic properties. Notably, PCT-4Cl exhibits a small singlet-triplet energy gap (ΔEST) of 0.25 eV. Blending PCT-4Cl with host eC9 or C8C8–4Cl acceptor extends the lifetime of singlet excitons and exciton diffusion length in the blend films. Moreover, the high energy level of the triplet state (ET1) in PCT-4Cl facilitates efficient transfer of triplet excitons to eC9 or C8C8–4Cl. The addition of PCT-4Cl to PM6:eC9 also leads to a longer crystallization time, restraining eC9 aggregation and enhancing crystallinity in the ternary blend films. Consequently, power conversion efficiencies (PCEs) of 18.84 % and 15.17 % are achieved based on the optimized ternary devices of PM6:eC9:PCT-4Cl (1:1:0.2, wt./wt./wt.) and PM6:C8C8–4Cl:PCT-4Cl (1:1:0.2, wt./wt./wt.), respectively, surpassing the performance of PM6:eC9 (17.34 %) and PM6:C8C8–4Cl (14.05 %). Furthermore, leveraging 2PACz as a hole transporting layer elevates the PCEs of the ternary OSCs to 19.25 % and 15.53 %. These findings underscore the significant role of the tert-butyl carbazole side-chain in elevating the ET1 of NFREA for efficient charge transfer, as well as its role in modulating the crystallinity, presenting a promising pathway for achieving high performance in both binary and ternary OSCs.

Tetracyclic aromatic lactam-substituted tin-free donors for high-efficiency ternary organic solar cells via regulation of pre-aggregation and crystallization kinetics

Organic solar cells (OSCs) are rapidly developed for next-generation photovoltaic technologies due to low-cost and solution-processability etc. However, so far high-efficiency organic photovoltaic materials are typically prepared by multi-step Stille reactions, which are neither cost-efficient nor atom-economic, even raise safety concerns and incompatible with large-scale process. Large-scale industrial production of photovoltaic materials through simple, cost-effective, and green chemistry remains to be addressed. In this work, we present a case where two isomeric small-molecule donors based on polycyclic aromatic lactams (PAL) unit, named oPh2F and pPh2F with wide-bandgap and high-crystallinity, were designed and synthesized by atom-economic direct C-H activation strategy, modulates pre-aggregation and crystallization kinetics of host system PM6:Y6, induce distinct morphology evolution and effectively boost photovoltaic performance. The best power conversion efficiency (PCE) of 18.40 % for pPh2F-based ternary devices are found to be a fruit of improved light-harvesting ability, favorable vertical phase separation with enhanced crystallinity, the separated crystallization process of host materials and the higher and more balanced charge transport. To our knowledge, this study achieved the highest PCE among PM6:Y6-based ternary OSCs containing tin-free small-molecule donor, which not only highlights the great potential of PAL-based photovoltaic materials, but also promotes the integration of renewable energy with green chemistry.

π-Extended giant dimeric acceptor as a third component enables highly efficient ternary organic solar cells with efficiency over 19.2%

Ternary strategy with a suitable third component is a successful strategy to improve the photovoltaic performance of organic solar cells (OSCs). Very recently, Y-series based giant molecule acceptors or oligomerized acceptors have emerged as promising materials for achieving highly efficient and stable binary OSCs, while application as third component for ternary OSCs is limited. Here a novel π-extended giant dimeric acceptor, GDF, is developed based on central Y series core fusion and rigid BDT as linker, and then incorporated into the state-of-the-art PM1:PC6 system to construct ternary OSCs. The GDF has a near planar backbone, resulting in increased π-conjugation, excellent crystallinity, and good electron transport capacity. When GDF is introduced into the PM1:PC6 system, it ensues in a cascade like the lowest unoccupied molecular orbitals (LUMO) energy level alignment, a complementary absorption band with PM1 and PC6, higher and balanced hole and electron mobility, slightly smaller domain size, and a higher exciton dissociation probability for PM1:PC6:GDF (1:1.1:0.1) blend film. As a consequence, the PM1:PC6:GDF (1:1.1:0.1) ternary OSC achieves a champion PCE of 19.22%, with a significantly higher open-circuit voltage and short-circuit current density, compared to 18.45% for the PM1:PC6 (1:1.2) binary OSC. Our findings show that employing a π-extended giant dimeric acceptor as a third component significantly improves the photovoltaic performance of ternary OSCs.

Tailoring the Molecular Planarity of Perylene Diimide-Based Third Component toward Efficient Ternary Organic Solar Cells.

Incorporating a third component into binary organic solar cells (b-OSCs) has provided a potential platform to boost power conversion efficiency (PCEs). However, gaining control over the non-equilibrium blend morphology via the molecular design of the perylene diimide (PDI)-based third component toward efficient ternary organic solar cells (t-OSCs) still remains challenging. Herein, two novel PDI derivatives are developed with tailored molecular planarity, namely ufBTz-2PDI and fBTz-2PDI, as the third component for t-OSCs. Notably, after performing a cyclization reaction, the twisted ufBTz-2PDI with an amorphous character transferred to the highly planar fBTz-2PDI followed by a semi-crystalline character. When incorporating the semi-crystalline fBTz-2PDI into the D18:L8-BO system, the resultant t-OSC achieved an impressive PCE of 18.56%, surpassing the 17.88% attained in b-OSCs. In comparison, the addition of amorphous ufBTz-2PDI into the binary system facilitates additional charge trap sites and results in a deteriorative PCE of 14.37%. Additionally, The third component fBTz-2PDI possesses a good generality in optimizing the PCEs of several b-OSCs systems are demonstrated. The results not only provided a novel A-DA'D-A motif for further designing efficient third component but also demonstrated the crucial role of modulated crystallinity of the PDI-based third component in optimizing PCEs of t-OSCs.

Crossbreeding Effect of Chalcogenation and Iodination on Benzene Additives Enables Optimized Morphology and 19.68% Efficiency of Organic Solar Cells.

Volatile solid additives have attracted increasing attention in optimizing the morphology and improving the performance of currently dominated non-fullerene acceptor-based organic solar cells (OSCs). However, the underlying principles governing the rational design of volatile solid additives remain elusive. Herein, a series of efficient volatile solid additives are successfully developed by the crossbreeding effect of chalcogenation and iodination for optimizing the morphology and improving the photovoltaic performances of OSCs. Five benzene derivatives of 1,4-dimethoxybenzene (DOB), 1-iodo-4-methoxybenzene (OIB), 1-iodo-4-methylthiobenzene (SIB), 1,4-dimethylthiobenzene (DSB) and 1,4-diiodobenzene (DIB) are systematically studied, where the widely used DIB is used as the reference. The effect of chalcogenation and iodination on the overall property is comprehensively investigated, which indicates that the versatile functional groups provided various types of noncovalent interactions with the host materials for modulating the morphology. Among them, SIB with the combination of sulphuration and iodination enabled more appropriate interactions with the host blend, giving rise to a highly ordered molecular packing and more favorable morphology. As a result, the binary OSCs based on PM6:L8-BO and PBTz-F:L8-BO as well as the ternary OSCs based on PBTz-F:PM6:L8-BO achieved impressive high PCEs of 18.87%, 18.81% and 19.68%, respectively, which are among the highest values for OSCs.

Small molecule donor third component incorporating thieno[3,2-b]thiophene unit enables 19.18% efficiency ternary organic solar cells with improved operational stability

The rational design of the third component to enhance the efficiency and stability of organic solar cell (OSC) is a critical and challenge. Herein, a thieno[3,2-b]thiophene (TT) substituted wide-bandgap small molecule donor BTTC, was designed, synthesized and incorporated into the state-of-the-art PM6:L8-BO binary to construct ternary OSC. The rigid side chain and planar molecule skeleton enables strong crystallinity and complementary absorption with binary system. The introduction of BTTC enhanced the molecular packing, fibril-like film and preferred vertical phase separation, yielding balanced and higher charge transport, more efficient exciton dissociation and suppressed charge recombination. Besides, lower energy loss was attained and thus leading to higher open-circuit voltage (VOC). Consequently, the introduction of BTTC achieved the highest efficiency of 18.8% along with extended operational stability. Furthermore, replacing L8-BO to BTP-eC9 further boosted the ternary PCE to 19.18%, standing one of the best charge management in ternary OSC. This work presents efficient rigid side chain substitution strategy to construct the third component of small molecule donor for high performance ternary OSCs with comprehensively improved photovoltaic parameters. This strategy broadens the selection of guest materials toward realizing the actual commercial application of OSCs.

Efficient Ternary Organic Solar Cells with Suppressed Nonradiative Recombination and Fine-Tuned Morphology via IT-4F as Guest Acceptor.

The large open circuit voltage (VOC) loss is currently one of the main obstacles to achieving efficient organic solar cells (OSCs). In this study, the ternary OSCs comprising PM6:BTP-eC9:IT-4F demonstrate a superior efficiency of 18.2 %. Notably, the utilization of the medium bandgap acceptor IT-4F as the third component results in an exceptionally low nonradiative recombination energy loss of 0.28 V. The desirable energy level cascade is formed among PM6, BTP-eC9, and IT-4F due to the low-lying HOMO and LUMO energy levels of IT-4F. More importantly, the VOC of PM6:BTP-eC9:IT-4F OSCs can reach as high as 0.86 V, which is higher than both binary OSCs without sacrificing JSC and FF. Besides, this strategy proved that IT-4F can not only broaden the absorption range but also work as a morphology modifier in PM6:BTP-eC9:IT-4F OSCs, and there also exists efficient energy transfer between BTP-eC9 and IT-4F. This result provides a promising way to suppress the nonradiative recombination energy loss and realize higher VOC than the two binary OSCs in ternary OSCs to obtain high power conversion efficiencies.

18.63% Efficiency of Ternary Organic Solar Cells Achieved via Nonhalogenated Solvent and Hot Spin‐Coating Process

AbstractThe solubility problem of conjugated polymers in nonhalogenated solvents limits the application of nonhalogenated solvents in Organic solar cells (OSCs). By combining with a hot spin‐coating process, efficient PM6:BTP‐BO‐4F:GS‐ISO ternary OSCs are prepared by employing o‐xylene as a solvent. After adding 10 wt% content of GS‐ISO to PM6:BTP‐BO‐4F, the surface morphology in the active layers is improved and the charge extraction, transport, and collection in OSCs are enhanced. Compared with the efficiency of PM6:BTP‐BO‐4F OSCs (16.25%), an efficiency of 18.63% is achieved for PM6:BTP‐BO‐4F:GS‐ISO ternary OSCs. Moreover, PM6:BTP‐BO‐4F:GS‐ISO ternary OSCs with an efficiency of 14.13% are prepared in air. The work provides a new strategy for preparing efficient and environmentally friendly OSCs using green solvents.

Non-Fully Conjugated Dimerized Giant Acceptors with Different Alkyl-Linked Sites for Stable and 19.13 % Efficiency Organic Solar Cells.

Achieving both high power conversion efficiency (PCE) and device stability is a major challenge for the practical development of organic solar cells (OSCs). Herein, three non-fully conjugated dimerized giant acceptors (named 2Y-sites, including wing-site-linked 2Y-wing, core-site-linked 2Y-core, and end-site-linked 2Y-end) are developed. They share the similar monomer precursors but have different alkyl-linked sites, offering the fine-tuned molecular absorption, packing, glass transition temperature, and carrier mobility. Among their binary active layers, D18/2Y-wing has better miscibility, leading to optimized morphology and more efficient charge transfer compared to D18/2Y-core and D18/2Y-end. Therefore, the D18/2Y-wing-based OSCs achieve a superior PCE of 17.73 %, attributed to enhanced photocurrent and fill factor. Furthermore, the D18/2Y-wing-based OSCs exhibit a balance of high PCE and improved stability, distinguishing them within the 2Y-sites. Building on the success of 2Y-wing in binary systems, we extend its application to ternary OSCs by pairing it with the near-infrared absorbing D18/BS3TSe-4F host. Thanks to the complementary absorption within 300-970 nm and further optimized morphology, ternary OSCs obtain a higher PCE of 19.13 %, setting a new efficiency benchmark for the dimer-derived OSCs. This approach of alkyl-linked site engineering for constructing dimerized giant acceptors presents a promising pathway to improve both PCE and stability of OSCs.

Non‐Fully Conjugated Dimerized Giant Acceptors with Different Alkyl‐Linked Sites for Stable and 19.13 % Efficiency Organic Solar Cells

AbstractAchieving both high power conversion efficiency (PCE) and device stability is a major challenge for the practical development of organic solar cells (OSCs). Herein, three non‐fully conjugated dimerized giant acceptors (named 2Y‐sites, including wing‐site‐linked 2Y‐wing, core‐site‐linked 2Y‐core, and end‐site‐linked 2Y‐end) are developed. They share the similar monomer precursors but have different alkyl‐linked sites, offering the fine‐tuned molecular absorption, packing, glass transition temperature, and carrier mobility. Among their binary active layers, D18/2Y‐wing has better miscibility, leading to optimized morphology and more efficient charge transfer compared to D18/2Y‐core and D18/2Y‐end. Therefore, the D18/2Y‐wing‐based OSCs achieve a superior PCE of 17.73 %, attributed to enhanced photocurrent and fill factor. Furthermore, the D18/2Y‐wing‐based OSCs exhibit a balance of high PCE and improved stability, distinguishing them within the 2Y‐sites. Building on the success of 2Y‐wing in binary systems, we extend its application to ternary OSCs by pairing it with the near‐infrared absorbing D18/BS3TSe‐4F host. Thanks to the complementary absorption within 300–970 nm and further optimized morphology, ternary OSCs obtain a higher PCE of 19.13 %, setting a new efficiency benchmark for the dimer‐derived OSCs. This approach of alkyl‐linked site engineering for constructing dimerized giant acceptors presents a promising pathway to improve both PCE and stability of OSCs.

Recent Advances in Selenium‐Containing Non‐fullerene Acceptors for High‐Performance Organic Solar Cells

AbstractThe diversity in molecular structures and solution processability of non‐fullerene acceptors (NFAs), particularly those containing selenium (Se), plays a pivotal role in advancing organic solar cells (OSCs). Among various molecular design strategies, the introduction of selenium atoms, characterized by their large covalent radius, loose electron cloud, and strong polarization properties, can enhance intermolecular Se‐Se interactions and improve the electron‐donating capability of π‐cores. This approach is considered a significant avenue for optimizing the photovoltaic performance of active layer materials. In this review, we provide a comprehensive summary of recent advancements in selenium‐containing acceptor molecules. These include ITIC‐based fused ring NFAs, Y6‐based fused ring NFAs, Y6‐based polymer acceptors, non‐fused ring electron acceptors and their application in tandem and ternary OSCs. Additionally, we analyze the future prospects and development of selenium‐containing NFAs with the goal of achieving OSC efficiencies exceeding 20 %.

Efficient Dual Mechanisms Boost the Efficiency of Ternary Solar Cells with Two Compatible Polymer Donors to Exceed 19.

Ternary strategyopens a simple avenue to improve the power conversion efficiency (PCE) of organic solar cells (OSCs). The introduction of wide bandgap polymer donors (PDs) as third component canbetter utilize sunlight andimprove the mechanical and thermal stability of active layer. However, efficient ternary OSCs (TOSCs) with two PDs are rarely reported due to inferior compatibility and shortage of efficient PDs match with acceptors. Herein, two PDs-(PBB-F and PBB-Cl) are adopted in the dual-PDs ternary systems to explore the underlying mechanisms and improve their photovoltaic performance. The findings demonstrate that the third components exhibit excellent miscibility with PM6 and are embedded in the host donor to form alloy-like phase. A more profound mechanism for enhancing efficiency through dual mechanisms, that are the guest energy transfer to PM6 and charge transport at the donor/acceptor interface, has been proposed. Consequently, the PM6:PBB-Cl:BTP-eC9 TOSCs achieve PCE of over 19%. Furthermore, the TOSCs exhibit better thermal stability than that of binary OSCs due to the reduction in spatial site resistance resulting from a more tightly entangled long-chain structure. This work not only provides an effective approach to fabricate high-performance TOSCs, but also demonstrates the importance of developing dual compatible PD materials.

Ternary Organic Solar Cells—Simulation–Optimization Approach

Ternary Organic Solar Cells—Simulation–Optimization Approach

Controllable Exciton Diffusion Length and Ultrafast Charge Generation in Ternary Organic Solar Cells

Comprehensive SummaryCharge generation, a critical process in the operation of organic solar cell (OSC), requires thorough investigation in an ultrafast perspective. This work demonstrates that the utilization of alloy model for the non‐fullerene acceptor (NFA) component can regulate the crystallization properties of active layer films, which in turn affects exciton diffusion and hole transfer (HT), ultimately influencing the charge generation process. By incorporating BTP‐eC7 as a third component, without expanding absorption range or changing molecular energy levels but regulating the ultrafast exciton diffusion and HT processes, the power conversion efficiency (PCE) of the optimized PM6:BTP‐eC9:BTP‐eC7 based ternary OSC is improved from 17.30% to 17.83%, primarily due to the enhancement of short‐circuit current density (JSC). Additionally, the introduction of BTP‐eC7 also reduces the trap state density in the photoactive layer which helps to reduce the loss of JSC. This study introduces a novel approach for employing ternary alloy models by incorporating dual acceptors with similar structures, and elucidates the underlying mechanism of charge generation and JSC in ternary OSCs.

Wide‐Bandgap Polymers with a C(sp3)─F Polyfluoride Backbone Enable High‐Efficient Ternary Organic Solar Cells

AbstractFluorination strategy is demonstrated to be a successful approach for optimizing the electron distribution and morphology of organic photovoltaic materials. The previous works focus on introducing only a few C(sp2)─F bonds into conjugated backbone or C(sp3)─F bonds into sidechains. Herein, a new strategy by introducing C(sp3)─F polyfluoride unit into the backbone is proposed, wherein the fluorine atoms are not involved into the conjugation but can promote the intermolecular interaction between backbones. Two wide‐bandgap fluoropolymers are prepared and employed as the third component for ternary organic solar cells. As expected, even if there are six fluorine atoms in a single repeat unit, the relevant fluoropolymers possess complementary absorption and aligned energy levels. More importantly, the polyfluoride backbone affords adequate non‐covalent interactions, consequently enhancing the polymer aggregation and packing order, which is verified by a fibril‐like morphology in the blend film with the host polymer PM6 and only 10 wt.% fluoropolymer. In addition, the decreased surface energy caused by polyfluoride unit is beneficial for the improvement of domain purity and the formation of nanoscale phase separation between donor and acceptor materials. As a result, the fluoropolymer‐assisted ternary device displays a higher efficiency of 18.74% compared with the binary device (17.39%).