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Electroactive filament electrodes were synthesized by wet-spinning of cellulose nanofibrils (CNF) followed by femtosecond pulse laser deposition of ZnO (CNF@ZnO). A layer of conducting conjugated polymers was further adsorbed by in situ polymerization of either pyrrole or aniline, yielding systems optimized for electron conduction. The resultant hybrid filaments were thoroughly characterized by imaging, spectroscopy, electrochemical impedance, and small- and wide-angle X-ray scattering. For the filaments using polyaniline, the measured conductivity was a result of the synergy between the inorganic and organic layers, while the contribution was additive in the case of the systems containing polypyrrole. This observation is rationalized by the occurrence of charge transfer between ZnO and polyaniline but not that with polypyrrole. The introduced conductive hybrid filaments displayed a performance that competes with that of metallic counterparts, offering great promise for next-generation filament electrodes based on renewable nanocellulose.
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Tin-based perovskite solar cells (PSCs) are promising environmentally friendly alternatives to their lead-based counterparts, yet they currently suffer from much lower device performance. Due to variations in the chemical properties of lead (II) and tin (II) ions, similar treatments may yield distinct effects resulting from differences in underlying mechanisms. In this work, a surface treatment on tin-based perovskite is conducted with a commonly employed ligand, iso-butylammonium iodide (iso-BAI). Unlike the passivation effects previously observed in lead-based perovskites, such treatment leads to the recrystallization of the surface, driven by the higher solubility of tin-based perovskite in common solvents. By carefully designing the solvent composition, the perovskite surface is effectively modified while preserving the integrity of the bulk. The treatment led to enhanced surface crystallinity, reduced surface strain and defects, and improved charge transport. Consequently, the best-performing power conversion efficiency of FASnI3 PSCs increases from 11.8% to 14.2%. This work not only distinguishes the mechanism of surface treatments in tin-based perovskites from that of lead-based counterparts, but also underscores the critical role in designing tailor-made strategies for fabricating efficient tin-based PSCs.
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Single-atom catalysts, known for their high activity, have garnered significant interest. Currently, single-atom catalysts were prepared mainly on 2D substrates with random distribution. Here, we report a strategy for preparing arrayed single Pt (Pt1) atoms, which are templated through coordination with phosphotungstic acids (PTA) intercalated inside hexagonally packed silicate nanochannels for a high single Pt-atom loading of ca. 3.0 wt %. X-ray absorption spectroscopy, high-angle annular dark-field scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy, in conjunction with the density-functional theory calculation, collectively indicate that the Pt single atoms are stabilized via a four-oxygen coordination on the PTA within the nanochannels' inner walls. The critical reduction in the Pt-adsorption energy to nearly the cohesive energy of Pt clustering is attributed to the interaction between PTA and the silicate substrate. Consequently, the transition from single-atom dispersion to clustering of Pt atoms can be controlled by adjusting the number density of PTA intercalated within the silicate nanochannels, specifically when the number ratio of Pt atoms to PTA changes from 3.7 to 18. The 3D organized Pt1-PTA pairs, facilitated by the arrayed silicate nanochannels, demonstrate high and stable efficiency with a hydrogen production rate of ca. 300 mmol/h/gPtâapproximately twice that of the best-reported Pt efficiency in polyoxometalate-based photocatalytic systems.
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We have demonstrated the molecular-weight effects of adding homopolystyrene (hPS) on the evolution of perforated layers and double gyroids in polystyrene-block-poly(methyl methacrylate)-based films during isothermal annealing. Two homopolystyrenes of 2.8 and 17 kg mol-1 were used. To prepare blend films, PS-b-PMMA and hPSx (x: 2.8 or 17) were mixed at a weight-fraction ratio of 75/25 in toluene and then spin-coated at SiOx/Si. Spin coating inevitably produced films with thick edges at the periphery of the substrate. The structural evolution of the spun films was in situ characterized by grazing incidence small-angle X-ray scattering (GISAXS). The annealed films were then characterized using a scanning electron microscope (SEM). We found that thin middle regions behaved differently from thick beads for the films. The middle of the blend films mainly formed perforated layers with different spatial orders and orientations, depending on the molecular weight of added hPS chains. Hexagonally perforated layers quickly formed at 205 °C for PS-b-PMMA/hPS2.8 films. However, when hPS17 was used instead of hPS2.8, perforated layers formed with defects in PS-b-PMMA/hPS17 films annealed at 205 °C. Annealing at 240 °C improved the spatial order and orientation of perforated layers for a PS-b-PMMA/hPS17 film. Nevertheless, annealing at 240 °C inversely depressed the in-plane spatial order of perforated layers for a PS-b-PMMA/hPS2.8 film. The depression in the in-plane spatial order is ascribed to a dilution effect of added short chains. Compared to the middle regions, the thick beads went through several metastable phases, such as perpendicularly oriented perforated layers and double gyroids.
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Due to their versatile applications, perovskite quantum dot (PQD)-based optoelectrical devices have garnered significant research attention. However, the fundamental packing behavior of PQDs in thin films and its impact on the device performance remain relatively unexplored. Drawing inspiration from theoretical models concerning packing density with size mixtures, this study presents an effective strategy, namely, binary-disperse mixing, aimed at enhancing the packing density of PQD films. Comprehensive grazing-incidence small-angle X-ray characterization suggested that the PQD film consists of three phases: two monosize phases and one binary mixing phase. The volume fraction and population of the binary-size phase can be tuned by mixing an appropriate amount of large and small PQDs. Furthermore, we performed multi-length-scale all-atom and coarse-grained molecular dynamics simulations to elucidate the distribution and conformation of organic surface ligands, highlighting their influence on PQD packing. Notably, the mixing of two PQDs of different sizes promotes closer face-to-face contact. The densely packed binary-disperse film exhibited largely suppressed trap-assisted recombination, much longer carrier lifetime, and thereby improved power conversion efficiency. Hence, this study provides fundamental understanding of the packing mechanism of perovskite quantum dots and highlights the significance of packing density for PQD-based solar cells.
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Liposome development is of great interest owing to increasing requirements for efficient drug carriers. The structural features and thermal stability of such liposomes are crucial in drug transport and delivery. Reported here are the results of the structural characterization of PEGylated liposomes via small- and wide-angle X-ray scattering and an asymmetric flow field-flow fractionation (AF4) system coupled with differential refractive-index detection, multi-angle light scattering (MALS) and dynamic light scattering. This integrated analysis of the exemplar PEGylated liposome formed from hydrogenated soy phosphatid-yl-choline (HSPC) with the addition of cholesterol reveals an average hydro-dynamic radius (R h) of 52â nm with 10% polydispersity, a comparable radius of gyration (R g) and a major liposome particle mass of 118â kDa. The local bilayer structure of the liposome is found to have asymmetric electronic density profiles in the inner and outer leaflets, sandwiched by two PEGylated outer layers ca 5â nm thick. Cholesterol was found to effectively intervene in lipid chain packing, resulting in the thickening of the liposome bilayer, an increase in the area per lipid and an increase in liposome size, especially in the fluid phase of the liposome. These cholesterol effects show signs of saturation at cholesterol concentrations above ca 1:5 cholesterol:lipid molar ratio.
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The black-to-yellow phase transition in perovskite quantum dots (QDs) is more complex than in bulk perovskites, regarding the role of surface energy. Here, with the assistance of in situ grazing-incidence wide-angle and small-angle X-ray scattering (GIWAXS/GISAXS), distinct phase behaviors of cesium lead iodide (CsPbI3 ) QD films under two different temperature profiles-instant heating-up (IHU) and slow heating-up (SHU) is investigated. The IHU process can cause the phase transition from black phase to yellow phase, while under the SHU process, the majority remains in black phase. Detailed studies and structural refinement analysis reveal that the phase transition is triggered by the removal of surface ligands, which switches the energy landscape. The lattice symmetry determines the transition rate and the coexistence black-to-yellow phase ratio. The SHU process allows longer relaxation time for a more ordered QD packing, which helps sustain the lattice symmetry and stabilizes the black phase. Therefore, one can use the lattice symmetry as a general index to monitor the CsPbI3 QD phase transition and finetune the coexistence black-to-yellow phase ratio for niche applications.
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Understanding the polydispersity of nanoparticles is crucial for establishing the efficacy and safety of their role as drug delivery carriers in biomedical applications. Detonation nanodiamonds (DNDs), 3-5 nm diamond nanoparticles synthesized through detonation process, have attracted great interest for drug delivery due to their colloidal stability in water and their biocompatibility. More recent studies have challenged the consensus that DNDs are monodispersed after their fabrication, with their aggregate formation poorly understood. Here, we present a novel characterization method of combining machine learning with direct cryo-transmission electron microscopy imaging to characterize the unique colloidal behavior of DNDs. Together with small-angle X-ray scattering and mesoscale simulations we show and explain the clear differences in the aggregation behavior between positively and negatively charged DNDs. Our new method can be applied to other complex particle systems, which builds essential knowledge for the safe implementation of nanoparticles in drug delivery.
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Organic A'-site ligand structure plays a crucial role in the crystal growth of 2D perovskites, but the underlying mechanism has not been adequately understood. This problem is tackled by studying the influence of two isomeric A'-site ligands, linear-shaped n-butylammonium (n-BA+ ) and branched iso-butylammonium (iso-BA+ ), on 2D perovskites from precursor to device, with a combination of in situ grazing-incidence wide-angle X-ray scattering and density functional theory. It is found that branched iso-BA+ , due to the lower aggregation enthalpies, tends to form large-size clusters in the precursor solution, which can act as pre-nucleation sites to expedite the crystallization of vertically oriented 2D perovskites. Furthermore, iso-BA+ is less likely to be incorporated into the MAPbI3 lattice than n-BA+ , suppressing the formation of unwanted multi-oriented perovskites. These findings well explain the better device performance of 2D perovskite solar cells based on iso-BA+ and elucidate the fundamental mechanism of ligand structural impact on 2D perovskite crystallization.
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Solving the contradiction between good solubility and dense packing is a challenge in designing high-performance nonfullerene acceptors. Herein, two simple nonfused ring electron acceptors (o-AT-2Cl and m-AT-2Cl) carrying ortho- or meta-substituted hexyloxy side chains can be facilely synthesized in only three steps. The two ortho-substituted phenyl side chains in o-AT-2Cl cannot freely rotate due to a big steric hindrance, which endows the acceptor with good solubility. Moreover, o-AT-2Cl displays a more ordered packing than m-AT-2Cl as revealed by the absorption measurement. When blended with polymer donor D18 for the fabrication of organic solar cells (OSCs), o-AT-2Cl-based devices exhibit a favorable morphology, more efficient exciton dissociation, and better charge transport. Consequently, the optimal OSCs based on D18:o-AT-2Cl exhibit a power conversion efficiency (PCE) of 12.8%, which is significantly higher than the moderate PCE (7.66%) for D18:m-AT-2Cl-based devices. Remarkably, o-AT-2Cl shows a higher figure-of-merit value compared with classic high-efficiency fused ring electron acceptors. As a result, our research succeeds in obtaining nonfused ring acceptors with cost-effective photovoltaic performance and provides a valuable experience for simultaneously improving solubility as well as ensuring ordered packing of acceptors through regulating the steric hindrance via changing the position of substituents.
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Chitosan is a naturally derived biodegradable polymer with abundancy, sustainability, and ease of chemical modification. Polyurethanes are a family of elastic biocompatible polymers, and composites of polyurethanes have versatile properties and applications. Chitosan-polyurethane composites were recently developed but had insufficient strength and limited stretchability. In the current study, cellulose nanofibers (CNFs) were integrated in chitosan-polyurethane composites to prepare stretchable and anisotropic materials. A biodegradable polyurethane was first synthesized, end-capped with aldehyde to become dialdehyde polyurethane (DP) nanoparticles, and added with CNFs to prepare the DP-CNF composite crosslinker (DPF). The waterborne DPF crosslinker was then blended with chitosan solution to make polyurethane-CNF-chitosan (DPFC) composites. After blending, DPFC may form hydrogel in ~33 min at room temperature, which confirmed crosslinking. Composite films cast and dried from the blends showed good elongation (~420.2 %) at 60 °C. Anisotropic films were then generated by tension annealing with pre-strain. The annealed films with 200 % pre-strain exhibited large elastic anisotropy with ~4.9 anisotropic ratio. In situ SAXS/WAXS analyses unveiled that rearrangement and alignment of the microstructure during tension annealing accounted for the anisotropy. The anisotropic composite films had the ability to orient the growth of neural stem cells and showed the potential for biomimetic and tissue engineering applications.
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Quitosana , Nanofibras , Nanofibras/química , Quitosana/química , Celulose/química , Poliuretanos/química , Anisotropia , Espalhamento a Baixo Ângulo , Difração de Raios X , PolímerosRESUMO
Mixed-cation hybrid perovskite nanocrystal (HPNC) with high crystallinity, color purity, and tunable optical bandgap offers a practical pathway toward next-generation displays. Herein, a two-step modified hot-injection combined with cation compositional engineering and surface treatment to synthesize high-purity cesium/formamidinium lead bromide HPNCs(Cs1-x FAx PbBr3 ) is presented. The optimized Cs0.5 FA0.5 PbBr3 light-emitting devices (LEDs) exhibit uniform luminescence of 3500 cd m-2 and a prominent current efficiency of 21.5 cd A-1 . As a proof of concept, a self-healing polymer (SHP) integrated with white LED backlight and laser prototypes exhibited 4 h autonomous self-healing through the synergistic effect of weak reversible imine bonds and stronger H-bonds. First, the SHP-HPNCs-initial and SHP-HPNCs-cut possess high long-term stability and dramatically suppressed lead leakage as low as 0.6 ppm along with a low leakage rate of 1.11 × 10-5 cm2 and 3.36 × 10-5 cm2 even over 6 months in water. Second, the Cs0.5 FA0.5 PbBr3 HPNCs and SHP-induced shattered-repaired perovskite glass substrate show the lowest lasing threshold values of 1.24 and 8.58 µJ cm-2 , respectively. This work provides an integrative and in-depth approach to exploiting SHP with intrinsic and entropic self-healing capabilities combined with HPNCs to develop robust and reliable soft-electronic backlight and laser applications.
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Site-selectively chemical bioconjugation of peptides and proteins can improve the therapeutic exploration of modified protein drugs. Only 3.8% natural abundance of phenylalanine in protein and nearly 90% of proteins contain at least one phenylalanine residue in their sequenced, showing the potential in biopharmaceutical utility of the phenylalanine bioconjugation. However, the covalent bioconjugation of native phenylalanine is one of the most challenging problems in protein modification. Herein, an approach to protein modification is described that relies on a photoredox method for the site-selective bioconjugation of phenylalanine. This methodology has been validated on peptides as well as protein insulin using a straightforward and mild condition. In addition, based on characterization by near-UV CD spectroscopy and small angle X-ray scattering (SAXS), this pyrazole labeling approach permitted the insulin hexamer to completely dissociate into the monomeric form, thus making it a potential candidate for use as rapid-acting insulin for the treatment of diabetes.
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Fenilalanina , Proteínas , Fenilalanina/química , Espalhamento a Baixo Ângulo , Difração de Raios X , Proteínas/química , Peptídeos/química , Insulina/químicaRESUMO
The device efficiency of PM6:Y6-based nonfullerene organic solar cells is fast advanced recently. To maintain organic solar cells (OSCs) with high power conversion efficiency over 16% in long-term operation, however, remains a challenge. Here, a novel non-volatile additive, an open-cage [60]fullerene (8OC60Me), is incorporated into PM6:Y6-based OSCs for high-performance with high durability. With optimized addition of 1.0 wt % 8OC60Me, the PCE value of PM6:Y6/8OC60Me OSCs can be promoted to 16.5% from 15.0%. Most strikingly, such a high PCE performance can maintain nearly 100% for over 500 h at room temperature; at an elevated operation temperature of 80 °C, the PCE can be stabilized above 15.0% after 45 h of operation. Grazing incidence small- and wide- angle X-ray scattering studies reveal improved orientation and crystallinity of Y6 in a fractal-like network structure of PM6 in PM6:Y6/8OC60Me films under in situ annealing, parallel to the enhanced electron mobility. Analysis of charge distributions lines up possible van der Waals interaction between the thienyl/carbonyl moiety of 8OC60Me and difluorophenyl-based FIC-end groups of Y6. This result is of great contrast to those devices with the best-selling PC61BM as the additivesâ8OC60Me might be of interest to be incorporated into future Y6-based OSCs for concomitantly improved PCE and excellent stability.
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Rationally utilizing and developing synthetic units is of particular significance for the design of high-performance non-fullerene small-molecule acceptors (SMAs). Here, a thieno[3,2-b]pyrrole synthetic unit was employed to develop a set of SMAs (ThPy1, ThPy2, ThPy3 and ThPy4) by changing the number or the position of the pyrrole ring in the central core based on a standard SMA of IT-4Cl, compared to which the four thieno[3,2-b]pyrrole-based acceptors exhibit bathochromic absorption and upshifted frontier orbital energy level due to the strong electron-donating ability of pyrrole. As a result, the polymer solar cells (PSCs) of the four thieno[3,2-b]pyrrole-based acceptors yield higher open-circuit voltage and lower energy loss relative to those of the IT-4Cl-based device. What is more, the ThPy3-based device achieves a power conversion efficiency (PCE) (15.3%) and an outstanding fill factor (FF) (0.771) that are superior to the IT-4Cl-based device (PCE = 12.6%, FF = 0.758). The ThPy4-based device realizes the lowest energy loss and the smallest optical band gap, and the ternary PSC device based on PM6:BTP-eC9:ThPy4 exhibits a PCE of 18.43% and a FF of 0.802. Overall, this work sheds light on the great potential of thieno[3,2-b]pyrrole-based SMAs in realizing low energy loss and high PCE.
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The large non-radiative recombination is the main factor that limits state-of-the-art organic solar cells (OSCs). In this work, two novel structurally similar oligomers (named 5BDTBDD and 5BDDBDT) with D-A-D-A-D and A-D-A-D-A configuration are synthesized for high-performance ternary OSCs with low energy loss. As third components, these PM6 analogue oligomers effectively suppress the non-radiative recombination in OSCs. Although the highest occupied molecular orbital (HOMO) levels of 5BDTBDD and 5BDDBDT are higher than that of PM6, the oligomers enabled ultra-high electroluminescence quantum efficiency (EQEEL ) of 0.05% and improved VOC , indicating suppressing non-radiative recombination overweighs the common belief of deeper HOMO requirement in third component selection. Moreover, the different compatibility of 5BDTBDD and 5BDDBDT with PM6 and BTP-BO4Cl fine-tunes the active layer morphology with synergistic effects. The ternary devices based on PM6:5BDTBDD:BTPBO4Cl and PM6:5BDDBDT:BTP-BO4Cl achieve a significantly improved PCEs of 17.54% and 17.32%, representing the state-of-the art OSCs processed by green solvent of o-xylene. The strategy using novel oligomer as third component also has very wide composition tolerance in ternary OSCs. This is the first work that demonstrates novel structurally compatible D-A type oligomers are effective third components, and provides new understanding of synergetic energy loss mechanisms towards high performance OSCs.
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Electron donors and acceptors in organic solar cells (OSCs) shall strike a favorable vertical phase separation that acceptors and donors have sufficient contact and gradient accumulation near the cathodes and anodes, respectively. Random mixing of donors/acceptors at surface will result in charge accumulation and severe recombination for low carrier-mobility organic materials. However, it is challenging to tune the vertical distribution in bulk-heterojunction films as they are usually made from a well-mixed donor/acceptor solution. Here, for the first time, it presents with solid evidence that the commonly used 1-chloronaphthalene (CN) additive can tune the donor/acceptor vertical distribution and establish the mechanism. Different from the previous understanding that ascribed the efficiency enhancement brought by CN to the improved molecular stacking/crystallization, it is revealed that the induced vertical distribution is the dominant factor leading to the significantly increased performance. Importantly, the vertical distribution tunability is effective in various hot nonfullerene OSC systems and creates more channels for the collection of dissociated carriers at corresponding organic/electrode interfaces, which contributes the high efficiency of 18.29%. This study of the material vertical distribution and its correlation with molecular stacking offers methods for additives selection and provides insights for the understanding and construction of high-performance OSCs.
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Prion protein is composed of a structure-unsolved N-terminal domain and a globular C-terminal domain. Under limited trypsin digestion, mouse recombinant prion protein can be cleaved into two parts at residue Lys105. Here, we termed these two fragments as the N-domain (sequence 23-105) and the C-domain (sequence 106-230). In this study, the structural properties of the N-domain, the C-domain, and the full-length protein were explored using small-angle X-ray scattering, analytical ultracentrifugation, circular dichroism spectroscopy, and the 8-anilino-1-naphthalenesulfonic acid binding assay. The conformation and size of the prion protein were found to change sensitively under the solvent conditions. The positive residues in the sequence 23-99 of the N-domain were found to be responsible for the enhanced flexibility with the salt concentration reduced below 5 mM. The C-domain containing a hydrophobic patch tends to unfold and aggregate during a salt-induced structural collapse. The N-domain collapsed together with the C-domain at pH 5.2, whereas it collapsed independently at pH 4.2. The positively charged cluster (sequence 100-105) in the N-domain contributed to protecting the exposed hydrophobic surface of the C-domain.
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Proteínas Intrinsicamente Desordenadas , Proteínas Priônicas , Animais , Dicroísmo Circular , Proteínas Intrinsicamente Desordenadas/química , Camundongos , Proteínas Priônicas/química , Domínios ProteicosRESUMO
In this study, we designed, synthesized, and characterized an A-D-A'-D-A-type indacenodithienothiophene (IDTT)-based molecular acceptor that exhibited a broader absorption range and higher lowest unoccupied molecular orbital energy level with a nearly comparable band gap compared to a well-known electron acceptor IT-M. The designed electron-deficient molecular acceptor FB-2IDTT-4Cl with a fluorinated benzene tether (FB), that is, p-tetrafluorophenylene divinylene, demonstrated long-wavelength absorption and high hole and electron charge mobility in the thin films blended with the electron donor PBDB-T for an inverted organic photovoltaic (OPV) binary device, resulting in a maximum power conversion efficiency (PCE) of 11.4%. Such a performance is comparably as high as that of the device with PBDB-T:IT-M, and particularly, it was 18.8% higher than that of the devices with ITIC-4Cl as the acceptor (PCE 9.1% ± 0.5%) and 24.9% higher than that of the devices with the thiophene-flanked benzothiadiazole-bridged acceptor CNDTBT-IDTT-FINCN (PCE 9.01% ± 0.13%). Furthermore, varying the illumination intensity from 200 to 2000 lux increased the Jsc and Voc values as well as the FF values, thus leading to increased PCE levels. In addition, the best PCE of the PM6:Y6 device with 1% FB-2IDTT-4Cl as additives was 16.9%. Our stability test showed that the PM6:Y6 standard device efficiency downgraded very soon either at room temperature or under thermal-annealing conditions. However, with the addition of 1% FB-2IDTT-4Cl as additives, the device efficiency still can be maintained at 90-95% in 500 h at room temperature and 95% at 20 h and 85-95% in 45 h at an annealing temperature of 80 °C. These findings demonstrate FB-2IDTT-4Cl to be a promising candidate as an electron acceptor with a fluorinated π-bridging fused-ring design for OPV applications.