Non-fullerene Acceptors Research Articles

From Molecules to Devices: A Multiscale Approach to Evaluating Organic Photovoltaics.

Due to their efficient molecular design, nonfullerene acceptors (NFAs) have significantly advanced organic photovoltaics (OPVs). However, the lack of models to screen and evaluate candidate NFAs based on the resulting device performance has impeded the rapid development of high-performance molecules. This work introduces a computational framework utilizing a kinetic Monte Carlo (kMC) model to derive device parameters from molecular properties computed through first principles. By analyzing the quantum chemical properties of diverse dimeric conformers, we estimate the relative probabilities of microscopic processes such as charge separation, recombination, and transport along with charge transfer state formation in the active layer of OPVs. These probabilities set up a random walk of charge carriers in a grid with disordered molecular sites, allowing us to track their average behavior and calculate key device parameters. Our model consistently predicts measured device parameters, including the short-circuit current and open-circuit voltage, for OPVs with diverse NFAs with high accuracy. Additionally, we applied the model to evaluate donor-acceptor combinations of known compounds and newly designed NFA molecules, identifying high-performing pairs. This model offers a computationally efficient approach for designing novel NFA molecules and optimizing the OPV performance.

Molecular models of PM6 for non-fullerene acceptor organic solar cells: How DAD and ADA structures impact charge separation and charge recombination.

The quadrupole moment of a non-fullerene acceptor (NFA) generated by the constituent electron donor (D) and acceptor (A) units is a significant factor that affects the charge separation (CS) and charge recombination (CR) processes in organic photovoltaics (OPVs). However, its impact on p-type polymer domains remains unclear. In this study, we synthesized p-type molecules, namely acceptor-donor-acceptor (ADA) and donor-acceptor-donor (DAD), which are components of the benchmark PM6 polymer (D: benzodithiophene and A: dioxobenzodithiophene). Planar heterojunction films, a model of bulk heterojunction, were prepared using ADA, DAD, and PM6 as the bottom p-type layers and Y6 NFA as the top n-type layer. Flash-photolysis time-resolved microwave conductivity, femtosecond transient absorption spectroscopy, and quantum mechanical calculations were employed to probe the charge carrier dynamics. Our findings reveal that while the subtle difference in quadrupole moment and energy gradient of the p-type materials has a minimal influence on CS, the molecular type (ADA or DAD) significantly affects the bulk CR. This study expands the understanding of how the p-type component and its conformation at the p/n interface impact the CS and CR in OPVs, highlighting the critical role of molecular donors in optimizing device performance.

Fluorination or Not in Small Molecule Solar Cells: Achieving a Higher Efficiency with Halogen-Free End Group.

Fluorination is an efficient strategy for improving organic solar cells (OSCs) efficiency, particularly by fluorinating the end group of emerging nonfullerene acceptors. Here, the fluorination effect was investigated by using small molecule donors with fluorine-free (SBz) and fluorinated (SBz-F) end groups, paired with the emerging nonfullerene acceptor Y6. Interestingly and unexpectedly, fluorination of the end group negatively affects OSCs efficiency, with fluorine-free SBz:Y6 OSCs achieving a higher power conversion efficiency (PCE) of 11.05 % compared to the fluorine-containing SBz-F:Y6 blends (PCE=9.61 %). Analysis of space-charge limited currents reveals lower and unbalanced hole/electron mobility in SBz-F:Y6 compared to the SBz:Y6 blends. These findings are further supported by charge recombination dynamics and donor-acceptor miscibility analyses.

Acceptor End‐functionalization of Naphthalenediimide Bithiophene Oligomers

AbstractOligomeric materials combine advantageous properties of both their small molecule and polymeric counterparts. Utilizing oligomers as non‐fullerene acceptors (NFAs) has been shown to be extremely useful for the development of organic solar cells with high efficiency, reproducible performance and long‐term stability. Here we report on two series of synthetically simple acceptor‐terminated oligomers A−T2‐(NDI−T2)n‐A with naphthalene diimide (NDI) and bithiophene (T2) cores up to the trimer (n =1,2,3). Termination of the oligomers is done using the strong acceptors (A) dicyanomethylene‐indanone (IC) and rhodanine (RD). Upon acceptor termination in the presence of piperidine (pip) as base, oligomers with pip‐substituted tricyclic end groups are obtained in high yield. We investigate the effect of oligomer length and acceptor end group on opto‐electronic properties and crystallinity. Both IC‐ and RD‐termination increase electron affinity compared to the parent, non‐functionalized cores. UV‐vis absorption in solution slightly redshifts as the chain length increases without showing a distinct aggregation. Asymmetric termination with hexylphenyl‐substituted indacenodithiophene (IDT) and IC is also possible. All symmetric oligomers show a strong tendency for crystallization, with the oligomer having the tricyclic end group exhibiting the highest melting enthalpy and temperature. The asymmetric IDT−T2‐NDI−T2‐IC oligomer is amorphous.

Non-fused Nonfullerene Acceptors with an Asymmetric Benzo[1,2-b:3,4-b', 6,5-b"]trithiophene (BTT) Donor Core and Different AcceptorTerminal Units for Organic Solar Cells.

Here in, we have designed two new unfused non-fullerene small molecules using asymmetric benzo[1,2-b:3.4-b', 6,5-b"]trithiophene (BTT) as the central donor core and different terminal units i. e., 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (NFA-4) and 1,3-diethyl-2-thioxodi hydropyrimidine-4,6 (1H,5H)-dione (NFA-5) and examined their optical and electrochemical properties. Using a wide band-gap copolymer D18, organic solar cells (OSCs) based on bulk heterojunction of D18:NFA-4 and D18:NFA-5 showed overall power conversion efficiency (PCE) of about 17.07 % and 11.27 %, respectively. The increased PCE for the NFA-4-based OSC, compared to NFA-5 counterpart, is due higher value of short circuit current (JSC), open circuit voltage (VOC), and fill factor (FF). Following the addition of small amount of NFA-5 to the binary bulk heterojunction D18:NFA-4, the ternary organic solar cells attained a PCE of 18.05 %, surpassing that of the binary counterparts due to the higher values of which is higher than that for the binary counterparts and attributed to the increased values of JSC, FF, and VOC. The higher value of JSC is linked to the efficient use to excitons transferred from NFA-5 to NFA-4 with a greated dipole moment than NFA-5 and subsequently dissociated into a free charge carrier efficiently.

Enhancing the Efficiency and Stability of Inverted Perovskite Solar Cells and Modules through Top Interface Modification with N‐type Semiconductors

The interface modification between perovskite and electron transport layer (ETL) plays a crucial role in achieving high performance inverted perovskite photovoltaics (i‐PPVs). Herein, non‐fullerene acceptors (NFAs), known as Y6‐BO and Y7‐BO, were utilized to modify the perovskite/ETL interface in i‐PPVs. Non‐polar solvent‐soluble NFAs can effectively passivate surface defects without structural damage of the underlying perovskite films. Additionally, the improved PCBM ETL induced by NFAs modification significantly accelerates the electrons extraction. As a result, both Y6‐BO and Y7‐BO exhibit more effective interface modification effects compared to traditional PI molecules. The power conversion efficiency (PCE) of the inverted perovskite solar cell (i‐PSC) modified with Y7‐BO reaches 25.82%. Moreover, the adoption of non‐polar solvents and the superior semiconductor properties of Y7‐BO molecules also enable perovskite solar modules (i‐PSM) with effective areas of 50 cm2, 400 cm2, and 1160 cm2 to achieve record efficiencies of 23.05%, 22.32%, and 21.1% (certified PCE), respectively, making them the best PCE reported in the literature. Importantly, enhanced interface mechanical strength between the perovskite and PCBM layer results in significantly improved environmental and operational stability of the cells. The cells modified with Y7‐BO maintained 94.4% of the initial efficiency after 1522 hours of maximum power point aging.

Enhancing the Efficiency and Stability of Inverted Perovskite Solar Cells and Modules through Top Interface Modification with N-type Semiconductors.

The interface modification between perovskite and electron transport layer (ETL) plays a crucial role in achieving high performance inverted perovskite photovoltaics (i-PPVs). Herein, non-fullerene acceptors (NFAs), known as Y6-BO and Y7-BO, were utilized to modify the perovskite/ETL interface in i-PPVs. Non-polar solvent-soluble NFAs can effectively passivate surface defects without structural damage of the underlying perovskite films. Additionally, the improved PCBM ETL induced by NFAs modification significantly accelerates the electrons extraction. As a result, both Y6-BO and Y7-BO exhibit more effective interface modification effects compared to traditional PI molecules. The power conversion efficiency (PCE) of the inverted perovskite solar cell (i-PSC) modified with Y7-BO reaches 25.82%. Moreover, the adoption of non-polar solvents and the superior semiconductor properties of Y7-BO molecules also enable perovskite solar modules (i-PSM) with effective areas of 50 cm2, 400 cm2, and 1160 cm2 to achieve record efficiencies of 23.05%, 22.32%, and 21.1% (certified PCE), respectively, making them the best PCE reported in the literature. Importantly, enhanced interface mechanical strength between the perovskite and PCBM layer results in significantly improved environmental and operational stability of the cells. The cells modified with Y7-BO maintained 94.4% of the initial efficiency after 1522 hours of maximum power point aging.

High-sensitivity pump-probe spectroscopy with a dual-comb laser and a PM-Andi supercontinuum.

Amplifier-based pump-probe systems, while versatile, often suffer from complexity and low measurement speeds, especially when probing samples require low excitation fluences. To address these limitations, we introduce a pump-probe system that leverages a 60-MHz single-cavity dual-comb oscillator and an ultra-low noise supercontinuum. The setup can operate in equivalent time sampling or in programmable optical delay generation modes. We employ this system to study the wavelength-dependent excited-state dynamics of the non-fullerene electron acceptor Y6, a compound of interest in solar cell development, with excitation fluences as low as 1 nJ/cm2, well below the onset of nonlinear exciton annihilation effects. Our measurements reach a shot-noise limited sensitivity in differential transmission of 3.4·10-7. The results demonstrate the system's potential to advance the field of ultrafast spectroscopy.

Optimizing Exciton Diffusion and Carrier Transport for Enhanced Efficiency in Q‐PHJ and BHJ Organic Solar Cells

AbstractExciton diffusion and carrier transport are two critical factors that determine the efficiency of organic photovoltaics (OPVs). However, the relationship between these two factors has not been extensively studied. Designing non‐fullerene acceptors (NFAs) with efficient diffusion coefficients and high electronic transmittance is a key area of focus. In this study, materials for bulk‐heterojunction (BHJ) and quasiplanar‐heterojunction (Q‐PHJ) devices are synthesized to validate the desired differences in crystallinity. The single crystal of BOBO4Cl‐βδ demonstrated the most compact packing structure, with an improved planar configuration and closer π···π distances, resulting in higher electron mobility and superior exciton diffusion coefficient. Consequently, BOBO4Cl‐βδ‐based devices achieved a power conversion efficiency (PCE) of 17.38% in Q‐PHJ, compared to a lower PCE of 14.75% in BHJ devices. Furthermore, incorporating BOBO4Cl‐βδ into the D18/L8‐BO Q‐PHJ system increased the PCE from 17.98% to 18.81%, one of the highest values recorded for Q‐PHJ devices. This improvement is attributed to strong crystallinity of BOBO4Cl‐βδ, which enhances the packing arrangement and improves the exciton diffusion coefficient. Our work highlights the importance of molecular design with tunable exciton diffusion and carrier transport for BHJ and Q‐PHJ OPV architectures and reveals the relationship between them, which contributes to the achievement of high‐performance NFAs.

Asymmetric Alkyl Chain Engineering for Efficient and Eco-Friendly Organic Photovoltaic Cells.

Recent advancements in organic photovoltaic (OPV) cells have resulted in power conversion efficiencies (PCEs) surpassing 20%. However, the use of halogen solvents in the fabrication of OPV cells raises concerns due to their potential environmental and health impacts. In this work, a novel non-fullerene small molecule acceptor BO-AM-4F, featuring an asymmetric alkyl chain design that includes a 2-butyloctyl and a unique 6-(hexylamino)-6-oxohexyl chain is synthesized. This design significantly improves molecular packing, crystallinity, and electrostatic potential distribution compared to the controlled acceptor DBO-4F, which possesses symmetric 2-butyloctyl chains. When combined with the polymer donor PBDB-TF and processed using the non-halogen solvent o-xylene, the BO-AM-4F-based OPV cell achieves an impressive PCE of 18.0%, surpassing the 16.6% PCE observed in the PBDB-TF:DBO-4F device. Furthermore, the PBDB-TF:BO-AM-4F system demonstrates enhanced photostability and thermal stability compared to its DBO-4F counterpart. These findings emphasize asymmetric alkyl chain engineering as an effective strategy for developing high-performance, environmentally friendly OPV materials. This represents a significant step towards sustainable OPV technology.

Improving Optoelectronic Properties of Acceptor–Donor–Acceptor‐Type Non‐Fullerene Acceptors Containing Extended Fused Ring Donor Units for Efficient Organic Semiconductors

Developing efficient small molecule‐based non‐fullerene acceptors (NFAs) has gained huge attention in fabricating high‐efficiency and stable organic solar cells (OSCs). Herein, we designed and characterized eight new NFAs for OSCs. To investigate the potential of these newly designed NFAs series (IBH1–IBH8) for OSCs, various advanced quantum chemical simulation approaches are used and compared with the synthetic reference molecule IBH–R. Due to the extended donor cores, the IBH1–IBH8 molecules possess strong intramolecular and intermolecular interactions, which helps improve the thin‐film surface crystallinity. Moreover, the designed IBH1–IBH8 molecules present improved UV–visible absorption, narrower bandgaps, lower excitation, and binding energies, and improved photovoltaic characteristics. Furthermore, the impact on the intrinsic properties such as transition density matrix, density of state, electrostatic potential, distribution of frontier molecular orbitals, and reorganizational energies of holes and electrons are estimated. Additionally, the charge‐transfer phenomenon by establishing a donor:acceptor blend (PTB7–Th:IBH4) is analyzed, their geometric analyses are studied, and a good charge‐shifting process is found at the donor:acceptor interface. With these results, we demonstrated the enhancements in the optoelectronic and photovoltaic characteristics of OSCs by performing a simple end‐capped modulation. Hence, these molecules are recommended for the development of efficient and cost‐effective OSCs.

Polymerized non-fullerene small molecular acceptor as a versatile electron-transport material for 24.50 % efficiency inverted perovskite solar cells with extended spectral response

Development of novel non-fullerene electron-transport materials (ETMs) with excellent optoelectronic properties, good thermal and chemical stability, and defect passivation capability is of great significance for improving the device performance of inverted perovskite solar cells (PSCs). In this work, a polymerized non-fullerene small molecular acceptor with narrow bandgap named PY-DFT is rationally designed and synthesized. The resultant materials not only exhibits great hydrophobicity, thermal and chemical stability, but also maintains the excellent electron-transport properties of Y-type small molecule. Moreover, the electron-rich units in PY-DFT finely passivates the surface defects in perovskite. Consequently, an exceptional PCE of 24.50 % has been achieved for the champion device based on PY-DFT ETM, which is the highest efficiency for inverted PSCs based on non-fullerene ETMs to date. Notably, PY-DFT provides an extra current density of 0.25 mA/cm2 in the near-infrared light response region, where the intrinsic perovskite film has no spectral response, demonstrating attractive advantages in rationally utilization of solar spectrum. The target device without encapsulation also demonstrates good long-term operational stability. This work paves a new avenue for designing photo-active non-fullerene electron-acceptor towards efficient and stable inverted PSCs.

Reducing Non-Radiative Energy Losses in Non-fullerene Organic Solar Cells.

With the rapid advancement of non-fullerene acceptors (NFAs), the power conversion efficiency (PCE) of organic solar cells (OSCs) has surpassed the 20% threshold, highlighting their considerable potential as next-generation energy conversion devices. In comparison to inorganic or perovskite solar cells, the open-circuit voltage (Voc) of OSCs is constrained by substantial non-radiative energy losses (ΔEnr), leading to values notably below those anticipated by the Shockley-Queisser limit. In OSCs, non-radiative energy losses are intimately associated with the electroluminescent quantum efficiency (EQEEL) of charge transfer states, which is in turn directly affected by the photoluminescence quantum yield (PLQY) of acceptor materials. Consequently, enhancing the PLQY of low-bandgap acceptor materials has emerged as a pivotal strategy to effectively mitigate ΔEnr. This review article delves into the intrinsic correlation between molecular structure and PLQY from the vantage point of acceptor material design. It further explores methodologies for designing acceptor materials exhibiting high PLQY, with the ultimate goal of realizing OSCs that combine high efficiency with minimal ΔEnr.

Molecular Level Resolution of the Crucial Differences in the Morphologies of Non-Fullerene Acceptor Y Derivatives/Donor Polymer PM6 Heterogeneous Films

Characterizing the morphologies of nonfullerene acceptors (NFAs)/donor polymer layers with molecular resolution is crucially important for organic solar cells (OSCs), but remains challenging and insufficient currently. Herein, the morphologies of NFA Yn (n=5-7)/donor polymer PM6 heterogeneous films were revealed with molecular resolution through scanning tunnelling microscopy and analyzed through density functional theory (DFT) calculations. Y6 forms an interdigitated, ladder-like structure with PM6 which is verified as a kinetic product by the DFT calculations. After annealing, the ladder-like structure coexists with the energy-favorable phase separation one. The difference of the forming energy between the phase separation and ladder-like structure in Y7/PM6 and Y5/PM6 is obviously larger than the one in Y6/PM6, therefore, only the phase separation structure was observed before and after annealing in Y7/PM6 and Y5/PM6. Yn (n=5-7) shows rather different stacking in its neat domain. Y6 forms a face-to-face, dense packing pair with the lateral shift around half of a molecule. Y7 is a dense packing was well, but the stacking is the T type. Y5 forms an exact face-to-face style while its packing is not the dense one. The morphology differences of Yn (n=5-7)/PM6 films are closely related to the alterations of the ending groups in the backbones of Yn (n=5-7) molecules. Annealing reduce the surface-occupied ratio of Y5 and Y7 domains but does not change their stacking. The results are very valuable for the accurate morphology characterizations and the researches of related OSCs and optoelectronics.

Regulating Intermolecular Interactions and Film Formation Kinetics for Record Efficiency in Difluorobenzothiadizole‐Based Organic Solar Cells

AbstractThe difluorobenzothiadizole (ffBT) unit is one of the most classic electron‐accepting building blocks used to construct D‐A copolymers for applications in organic solar cells (OSCs). Historically, ffBT‐based polymers have achieved record power conversion efficiencies (PCEs) in fullerene‐based OSCs owing to their strong temperature‐dependent aggregation (TDA) characteristics. However, their excessive miscibility and rapid aggregation kinetics during film formation have hindered their performance with state‐of‐the‐art non‐fullerene acceptors (NFAs). Herein, we synthesized two ffBT‐based copolymers, PffBT‐2T and PffBT‐4T, incorporating different π‐bridges to modulate intermolecular interactions and aggregation tendencies. Experimental and theoretical studies revealed that PffBT‐4T exhibits reduced electrostatic potential differences and miscibility with L8‐BO compared to PffBT‐2T. This facilitates improved phase separation in the active layer, leading to enhanced molecular packing and optimized morphology. Moreover, PffBT‐4T demonstrated a prolonged nucleation and crystal growth process, leading to enhanced molecular packing and optimized morphology. Consequently, PffBT‐4T‐based devices achieved a remarkable PCE of 17.5 %, setting a new record for ffBT‐based photovoltaic polymers. Our findings underscore the importance of conjugate backbone modulation in controlling aggregation behavior and film formation kinetics, providing valuable insights for the design of high‐performance polymer donors in organic photovoltaics.

Tailoring Optoelectronic Properties of A-D-A Type Non-Fullerene Acceptors with Fused Aromatic Thiophene-Furan Bridges for Efficient Organic Photovoltaics

Tailoring Optoelectronic Properties of A-D-A Type Non-Fullerene Acceptors with Fused Aromatic Thiophene-Furan Bridges for Efficient Organic Photovoltaics

Theoretical study of star shaped benzotriindole based variant non-fullerene acceptors for efficient organic solar cells

Theoretical study of star shaped benzotriindole based variant non-fullerene acceptors for efficient organic solar cells

Elucidating the Advancement in the Optoelectronics Characteristics of Benzoselenadiazole-Based A2-D-A1-D-A2-Type Nonfullerene Acceptors for Efficient Organic Solar Cells.

The potential applications of nonfullerene acceptors (NFAs) such as tunable band gaps, improved charge separation, wide-range absorption, enhanced power conversion efficiency, and operational stability make them highly favorable for organic photovoltaic applications. Herein, we designed eight novel structurally modified nonfused benzoselenadiazole (BSe)-based A2-D-A1-D-A2-type NFAs for efficient organic solar cells (OSCs). These newly modeled BSe-based NFA series contain BSe as the central core. We employed strong electron-withdrawing moieties at terminal acceptor A2 to further enhance the optical, optoelectronics, and photovoltaic characteristics of OSCs. These designed molecules (HNM1-HNM8) along with the synthetic reference molecule (HNM) were thoroughly characterized by using efficient and advanced quantum chemical simulation approaches. Thus, to ascertain the enhancement of both optical and photochemical response, a thorough density functional theory (DFT) study was carried out using the M062X level in association with the 6-31G(d,p) basis set. All of the investigated molecules (HNM1-HNM8) had their excited states calculated using the time-dependent density functional theory method. The newly designed molecules (HNM1-HNM8) presented narrower band gaps, improved absorption and optoelectronics properties, and reduced excitation and binding energies. The electrostatic potential, density of states, transition density matrix, ionization potential, and electron affinity analysis of this newly designed (HNM1-HNM8) series revealed a strong coherence with those of the reference HNM molecule. Electron density difference mapping allowed us to visualize the spatial movement of electrons between the donor and acceptor molecules during excitation. This insight helps us to understand the efficiency of charge separation and recombination processes that are critical for the performance of organic photovoltaics. The reorganization energy and charge transfer analysis suggests that HNM1-HNM8 molecules could act as NFAs for organic photovoltaic applications to enhance their efficiency further. The donor: acceptor charge transfer analysis was also carried out, which revealed that the PTB7-Th:HNM2 donor:acceptor complex shows a great charge transportation process at the donor-acceptor interface. Moreover, the photovoltaic analysis shows that the designed (HNM1-HNM8) NFA series has a great potential to produce improved open-circuit voltage and fill factor values, which may be helpful in enhancing the overall PCEs of the OSCs.

Nonadiabatic dynamical simulations to the radiative recombination of nonfullerene acceptor molecular excited states.

Improving the radiative recombination rate of nonfullerene acceptor (NFA) molecular excited states can help to promote their photoluminescence quantum yield and thus reduce the nonradiative energy loss in NFA-based organic solar cells. In this Letter, by developing a nonadiabatic dynamical simulation method, we clarify quantitative correlations of some typical characteristics of NFA molecules with their radiative recombination rates. For a single NFA molecule, the weakening of electron-phonon coupling and the strengthening of electron-push-pull potential can each improve the radiative recombination rate. For different NFA molecular aggregates, their radiative recombination rates are all reduced compared with a single molecule, where the A-to-A and A-to-D type J-aggregates have higher rates than D-to-D type H-aggregate. To further improve the radiative recombination rate of NFA molecular J-aggregates, we should increase the intermolecular distance, such as extending the side chain length.

Asymmetrified Benzothiadiazole‐Based Solid Additives Enable All‐Polymer Solar Cells with Efficiency Over 19 %

AbstractDisordered polymer chain entanglements within all‐polymer blends limit the formation of optimal donor‐acceptor phase separation. Therefore, developing effective methods to regulate morphology evolution is crucial for achieving optimal morphological features in all‐polymer organic solar cells (APSCs). In this study, two isomers, 4,5‐difluorobenzo‐c‐1,2,5‐thiadiazole (SF‐1) and 5,6‐difluorobenzo‐c‐1,2,5‐thiadiazole (SF‐2), were designed as solid additives based on the widely‐used electron‐deficient benzothiadiazole unit in nonfullerene acceptors. The incorporation of SF‐1 or SF‐2 into PM6 : PY‐DT blend induces stronger molecular packing via molecular interaction, leading to the formation of continuous interpenetrated networks with suitable phase‐separation and vertical distribution. Furthermore, after treatment with SF‐1 and SF‐2, the exciton diffusion lengths for PY‐DT films are extended to over 40 nm, favoring exciton diffusion and charge transport. The asymmetrical SF‐2, characterized by an enhanced dipole moment, increases the power conversion efficiency (PCE) of PM6 : PY‐DT‐based device to 18.83 % due to stronger electrostatic interactions. Moreover, a ternary device strategy boosts the PCE of SF‐2‐treated APSC to over 19 %. This work not only demonstrates one of the best performances of APSCs but also offers an effective approach to manipulate the morphology of all‐polymer blends using rational‐designed solid additives.