Ternary Devices Research Articles

A benzobisoxazole-based polymer assisting high efficiency polymer solar cells

Ternary strategy is an effective method to optimize photovoltaic process and improve device performance. In this work, a benzobisoxazole-based conjugated polymer PBBO was designed and employed as the guest component for PM6:BTP-eC9 based devices. The polymer PBBO shows a large band gap of 2.16 eV and strong photoluminescence property, with efficient energy transfer observed between PBBO and PM6. The ternary blends not only form a cascaded energy level distribution, but also an alloy-like structure, which can effectively promote the exciton dissociation, charge transfer and efficiently suppress charge recombination. As a result, the power conversion efficiency (PCE) of the ternary device is substantially improved from 17.50% to 18.66% with the incorporation of PBBO guest component. Meanwhile, the ternary device shows good stability with retaining 86% of initial efficiency after storage for 2000 hours. This research demonstrates that the polymer PBBO would be an excellent photovoltaic material to optimize the performance of polymer solar cells.

Non-halogenated Solvent-Processed Organic Solar Cells with Approaching 20 % Efficiency and Improved Photostability.

The development of high-efficiency organic solar cells (OSCs) processed from non-halogenated solvents is crucially important for their scale-up industry production. However, owing to the difficulty of regulating molecular aggregation, there is a huge efficiency gap between non-halogenated and halogenated solvent processed OSCs. Herein, we fabricate o-xylene processed OSCs with approaching 20 % efficiency by incorporating a trimeric guest acceptor named Tri-V into the PM6:L8-BO-X host blend. The incorporation of Tri-V effectively restricts the excessive aggregation of L8-BO-X, regulates the molecular packing and optimizes the phase-separation morphology, which leads to mitigated trap density states, reduced energy loss and suppressed charge recombination. Consequently, the PM6:L8-BO-X:Tri-V-based device achieves an efficiency of 19.82 %, representing the highest efficiency for non-halogenated solvent-processed OSCs reported to date. Noticeably, with the addition of Tri-V, the ternary device shows an improved photostability than binary PM6:L8-BO-X-based device, and maintains 80 % of the initial efficiency after continuous illumination for 1380 h. This work provides a feasible approach for fabricating high-efficiency, stable, eco-friendly OSCs, and sheds new light on the large-scale industrial production of OSCs.

Non‐halogenated Solvent‐Processed Organic Solar Cells with Approaching 20 % Efficiency and Improved Photostability

AbstractThe development of high‐efficiency organic solar cells (OSCs) processed from non‐halogenated solvents is crucially important for their scale‐up industry production. However, owing to the difficulty of regulating molecular aggregation, there is a huge efficiency gap between non‐halogenated and halogenated solvent processed OSCs. Herein, we fabricate o‐xylene processed OSCs with approaching 20 % efficiency by incorporating a trimeric guest acceptor named Tri‐V into the PM6:L8‐BO‐X host blend. The incorporation of Tri‐V effectively restricts the excessive aggregation of L8‐BO‐X, regulates the molecular packing and optimizes the phase‐separation morphology, which leads to mitigated trap density states, reduced energy loss and suppressed charge recombination. Consequently, the PM6:L8‐BO‐X:Tri‐V‐based device achieves an efficiency of 19.82 %, representing the highest efficiency for non‐halogenated solvent‐processed OSCs reported to date. Noticeably, with the addition of Tri‐V, the ternary device shows an improved photostability than binary PM6:L8‐BO‐X‐based device, and maintains 80 % of the initial efficiency after continuous illumination for 1380 h. This work provides a feasible approach for fabricating high‐efficiency, stable, eco‐friendly OSCs, and sheds new light on the large‐scale industrial production of OSCs.

Nonvolatile Ternary Memory Devices Based on MoO3 Nanoparticles Embedded in Conjugated Copolymer with Hierarchy Charge Traps

Nonvolatile Ternary Memory Devices Based on MoO₃ Nanoparticles Embedded in Conjugated Copolymer with Hierarchy Charge Traps

Impact of alloy‐like phase on energy loss mitigation in multi‐component organic photovoltaics

AbstractThe multi‐component strategy has proven effective in advancing the performance of organic photovoltaics (OPVs), enhancing photocurrent and fill factor through spectral complementarity and morphology optimization. However, the open‐circuit voltage (VOC) mechanism in multi‐component systems lacks systematic investigation. In this study, we explore the influence of alloy‐like phases on energy level distribution and energy loss mechanisms in multi‐component OPVs. Appropriate modulation of donor alloy‐like phases maintains the original intermolecular stacking, enhances component compatibility, reduces acceptor aggregation, and improves acceptor phase purity, mitigating non‐radiative recombination losses. Additionally, suitable alloy‐like phase modulation elevates charge transfer (CT) states, reducing the gap between CT and local exciton state, lowering reorganization energy, and alleviating radiative recombination loss below the bandgap. Through synergistic optimization (layer‐by‐layer method with solid additive), ternary devices based on Y6 acceptor achieve a notable 19.41% power conversion efficiency, offering new insights for the analysis of the energy loss of the multi‐component OPVs.

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.

Rational design of quinoline-based D-A system to accomplish a switching from binary to ternary memory devices

Quinoline-based small organic molecules containing anthracene and phenanthrene in a donor-acceptor (D-A) system have been designed and synthesized. The photophysical and electrochemical properties convey a better charge transfer possibility for the compounds with an ethylene bond between the D-A system than those without the ethylene bond. Through a red shift in the absorption spectra, the smaller band gap of the compounds (2.69–2.73 eV). Therefore, the memory behavior of the compounds also changed from binary to ternary, availing a better charge storage density in the systems. Even though all the compounds exhibited a non-volatile WORM memory performance with charge transfer and trapping as the major phenomenon behind the charge transport in the systems, the mechanism of compounds with the ethylene bridge between the D-A system differs due to the molecular orientation of the compounds. These compounds initially undergo a molecular ordering leading to a better channel for the charge transfer in the film, which takes the devices from OFF to ON1 state, followed by the charge transfer and trapping leading to an ON2 state. This guided the ternary WORM memory behavior of the compounds with a threshold voltage as low as - 0.8 V and an on/off current ratio of 104. The devices tend to show significant stability over 100 reading cycles and 4000 s under the constant stress of 0.5 V, making these devices perfect candidates for multilevel storage memory.

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.

Two Completely Non‐Fused Ring Acceptors Working in an Alloy‐Like Model for Efficient and Stable Organic Solar Cells

AbstractSimple chemical structure and simplified synthesis process of active layer materials are critical for advancing the practical application of organic solar cells. Herin, two completely non‐fused ring electron acceptors BTZT‐2Cl and BTZT‐4Cl are developed. BTZT‐4Cl exhibits an enhanced absorption band, increases electrostatic potential differences with D18, and improves crystallinity and molecular packing properties. Consequently, the binary device based on BTZT‐4Cl displays a markedly improved efficiency of 14.12%, compared to the BTZT‐2Cl‐based device, which only achieves a moderate efficiency of 11.25%. More importantly, an alloy‐like structure can be formed by incorporating a small amount of high miscibility and compatibility BTZT‐2Cl. The ternary blend exhibits more compact molecular packing, efficient exciton dissociation, and an extended charge carrier lifetime due to the formation of an alloy‐like structure. The ternary device achieves a decent efficiency of 15.41% with superior thermal stability and a high T80 lifetime over 1600 h after being aged at 65 °C. These results establish it as the most efficient among devices based on completely non‐fused ring acceptors with both high efficiency and voltage. This study demonstrates a simple material design strategy and high‐performance device optimization techniques, which are critical for advancing practical applications in the OSC field.

3D Crystal Framework Regulation Enables Se‐Functionalized Small Molecule Acceptors Achieve Over 19% Efficiency

AbstractSe‐functionalized small molecule acceptors (SMAs) exhibit unique advantages in constructing materials with near‐infrared absorption, but their photovoltaic performance lags behind that of S‐containing analogs in organic solar cells (OSCs). Herein, two new Se‐containing SMAs, namely Se‐EH and Se‐EHp, are designed and synthesized by regulating bifurcation site of outer alkyl chain, which enables Se‐EH and Se‐EHp to form different 3D crystal frameworks from CH1007. Se‐EH displays tighter π–π stacking and denser packing framework with smaller‐sized pore structure induced by larger steric hindrance effect of outer alkyl chain branched at 2‐position, and a higher dielectric constant of PM6:Se‐EH active layer can be obtained. OSCs based on PM6:Se‐EH achieved very high PCEs of 18.58% in binary and 19.03% in ternary devices with a high FF approaching 80% for Se‐containing SMAs. A more significant alkyl chain steric hindrance effect in Se‐EH adjusts the molecular crystallization to form a favorable nanofiber interpenetrating network with an appropriate domain size to reduce rate of sub‐ns recombination and promote balanced transport of carriers. This work provides references for further design and development of highly efficient Se‐functionalized SMAs.

Selenium substitution for dielectric constant improvement and hole-transfer acceleration in non-fullerene organic solar cells

Dielectric constant of non-fullerene acceptors plays a critical role in organic solar cells in terms of exciton dissociation and charge recombination. Current acceptors feature a dielectric constant of 3-4, correlating to relatively high recombination loss. We demonstrate that selenium substitution on acceptor central core can effectively modify molecule dielectric constant. The corresponding blend film presents faster hole-transfer of ~5 ps compared to the sulfur-based derivative (~10 ps). However, the blends with Se-acceptor also show faster charge recombination after 100 ps upon optical pumping, which is explained by the relatively disordered stacking of the Se-acceptor. Encouragingly, dispersing the Se-acceptor in an optimized organic solar cell system can interrupt the disordered aggregation while still retain high dielectric constant. With the improved dielectric constant and optimized fibril morphology, the ternary device exhibits an obvious reduction of non-radiative recombination to 0.221 eV and high efficiency of 19.0%. This work unveils heteroatom-substitution induced dielectric constant improvement, and the associated exciton dynamics and morphology manipulation, which finally contributes to better material/device design and improved device performance.

Efficient all-small-molecule organic solar cells processed with non-halogen solvent

All-small-molecule organic solar cells with good batch-to-batch reproducibility combined with non-halogen solvent processing show great potential for commercialization. However, non-halogen solvent processing of all-small-molecule organic solar cells are rarely reported and its power conversion efficiencies are very difficult to improve. Herein, we designed and synthesized a small molecule donor BM-ClEH that can take advantage of strong aggregation property induced by intramolecular chlorine-sulfur non-covalent interaction to improve molecular pre-aggregation in tetrahydrofuran and corresponding micromorphology after film formation. Tetrahydrofuran-fabricated all-small-molecule organic solar cells based on BM-ClEH:BO-4Cl achieved high power conversion efficiencies of 15.0% in binary device and 16.1% in ternary device under thermal annealing treatment. In contrast, weakly aggregated BM-HEH without chlorine-sulfur non-covalent bond is almost inefficient under same processing conditions due to poor pre-aggregation induced disordered π-π stacking, indistinct phase separation and exciton dissociation. This work promotes the development of non-halogen solvent processing of all-small-molecule organic solar cells and provides further guidance.

Fluorinated benzimidazole-based conjugated polymers for ternary memory devices

The application of fluorinated materials in optoelectronic devices has been extensively studied, yet their potential in polymer-based memory devices still needs to be explored. The strategic manipulation of electron donors and electron acceptors to enhance the electron properties of material represents a valid approach to advancing data storage performance. The acceptor unit plays a crucial role in charge trapping, by fluorinating acceptor unit, the polymer electron affinity can be further modulated, leading to optimized carrier injection. In this work, we have synthesized three donor-acceptor-type (D-A-type) conjugated polymers, employing benzimidazole-isoindole electron acceptors substituted with different numbers of fluorine atoms. These polymers were utilized as active layers and integrated into indium-tin-oxide/active layer/aluminum devices through a straightforward fabrication process. These devices exhibit excellent ternary non-volatile memory performance and demonstrate sustained stability even after 103 cycle numbers. Notably, the PM4Fbzo-based device achieves impressively low threshold voltages of −0.55 V and −0.80 V, accompanied by a switching current ratio surpassing 104. These exceptional outcomes show the tremendous potential of fluorinated benzimidazole-isoindole-based materials for ternary storage applications, showcasing them as one of the promising candidates for the next generation of materials.

Over 19 % Efficiency Organic Solar Cells Enabled by Manipulating the Intermolecular Interactions through Side Chain Fluorine Functionalization.

Fluorine side chain functionalization of non-fullerene acceptors (NFAs) represents an effective strategy for enhancing the performance of organic solar cells (OSCs). However, a knowledge gap persists regarding the relationship between structural changes induced by fluorine functionalization and the resultant impact on device performance. In this work, varying amounts of fluorine atoms were introduced into the outer side chains of Y-series NFAs to construct two acceptors named BTP-F0 and BTP-F5. Theoretical and experimental investigations reveal that side-chain fluorination significantly increase the overall average electrostatic potential (ESP) and charge balance factor, thereby effectively improving the ESP-induced intermolecular electrostatic interaction, and thus precisely tuning the molecular packing and bulk-heterojunction morphology. Therefore, the BTP-F5-based OSC exhibited enhanced crystallinity, domain purity, reduced domain spacing, and optimized phase distribution in the vertical direction. This facilitates exciton diffusion, suppresses charge recombination, and improves charge extraction. Consequently, the promising power conversion efficiency (PCE) of 17.3 % and 19.2 % were achieved in BTP-F5-based binary and ternary devices, respectively, surpassing the PCE of 16.1 % for BTP-F0-based OSCs. This work establishes a structure-performance relationship and demonstrates that fluorine functionalization of the outer side chains of Y-series NFAs is a compelling strategy for achieving ideal phase separation for highly efficient OSCs.

Over 19 % Efficiency Organic Solar Cells Enabled by Manipulating the Intermolecular Interactions through Side Chain Fluorine Functionalization

AbstractFluorine side chain functionalization of non‐fullerene acceptors (NFAs) represents an effective strategy for enhancing the performance of organic solar cells (OSCs). However, a knowledge gap persists regarding the relationship between structural changes induced by fluorine functionalization and the resultant impact on device performance. In this work, varying amounts of fluorine atoms were introduced into the outer side chains of Y‐series NFAs to construct two acceptors named BTP‐F0 and BTP‐F5. Theoretical and experimental investigations reveal that side‐chain fluorination significantly increase the overall average electrostatic potential (ESP) and charge balance factor, thereby effectively improving the ESP‐induced intermolecular electrostatic interaction, and thus precisely tuning the molecular packing and bulk‐heterojunction morphology. Therefore, the BTP‐F5‐based OSC exhibited enhanced crystallinity, domain purity, reduced domain spacing, and optimized phase distribution in the vertical direction. This facilitates exciton diffusion, suppresses charge recombination, and improves charge extraction. Consequently, the promising power conversion efficiency (PCE) of 17.3 % and 19.2 % were achieved in BTP‐F5‐based binary and ternary devices, respectively, surpassing the PCE of 16.1 % for BTP‐F0‐based OSCs. This work establishes a structure‐performance relationship and demonstrates that fluorine functionalization of the outer side chains of Y‐series NFAs is a compelling strategy for achieving ideal phase separation for highly efficient 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%).

Impact of Electrostatic Interaction on Vertical Morphology and Energy Loss in Efficient Pseudo-Planar Heterojunction Organic Solar Cells.

Although a suitable vertical phase separation (VPS) morphology is essential for improving charge transport efficiency, reducing charge recombination, and ultimately boosting the efficiency of organic solar cells (OSCs), there is a lack of theoretical guidance on how to achieve the ideal morphology. Herein, a relationship between the molecular structure and the VPS morphology of pseudo-planar heterojunction (PPHJ) OSCs is established by using molecular surface electrostatic potential (ESP) as a bridge. The morphological evolution mechanism is revealed by studying four binary systems with vary electrostatic potential difference (∆ESP) between donors (Ds) and acceptors (As). The findings manifest that as ∆ESP increases, the active layer is more likely to form a well-mixed phase, while a smaller ∆ESP favors VPS morphology. Interestingly, it is also observed that a larger ∆ESP leads to enhanced miscibility between Ds and As, resulting in higher non-radiative energy losses (ΔE3). Based on these discoveries, a ternary PPHJ device is meticulously designed with an appropriate ∆ESP to obtain better VPS morphology and lower ΔE3, and an impressive efficiency of 19.09% is achieved. This work demonstrates that by optimizing the ΔESP, not only the formation of VPS morphology can be controlled, but also energy losses can be reduced, paving the way to further boost OSC performance.

High‐Performance Ternary Organic Solar Cells with Enhanced Luminescence Efficiency and Miscibility Enabled by Two Compatible Acceptors

AbstractThe ternary strategy has proven to be an effective method for improving the efficiency of organic solar cells (OSCs). However, designing and selecting the third component still pose challenges. In this study, this issue is addressed by focusing on the PBDB‐T:Y18‐F binary system and introducing a new, strong luminescent, asymmetric small‐molecule acceptor (SMA) called L8‐CBIC‐Cl, which shares a similar skeleton with Y18‐F. The similarity in molecular framework facilitates good compatibility between the two acceptors, resulting in the formation of an alloy‐like acceptor phase. Furthermore, the norbornenyl‐modified end group in L8‐CBIC‐Cl contributes to its strong luminescent properties, which in turn leads to a low non‐radiative energy loss and a high open‐circuit voltage. Consequently, the PBDB‐T:L8‐CBIC‐Cl:Y18‐F based ternary devices realize a high power conversion efficiency (PCE) up to 17.01%, which is higher than PBDB‐T:Y18‐F device (14.49%). Importantly, L8‐CBIC‐Cl exhibits a good universality as a guest acceptor in other three binary systems (D18:Y6, D18:BTP‐eC9‐4F, and D18:L8‐BO). The D18:L8‐BO:L8‐CBIC‐Cl device shows an impressive efficiency of 19%. The work demonstrates that employing SMA with a high PLQY and better miscibility with host acceptor as the third component has a great potential for developing high‐efficiency ternary OSCs.