Dimeric acceptors have demonstrated significant potential for the simultaneous realization of high efficiency, good stability, and even stretchability in organic solar cells (OSCs). However, most dimeric acceptors suffer from compromised efficiency due to insufficient morphological control. Herein, we design and synthesize three head-to-head flexible alkyl-chain-linked dimeric acceptors, CH-E2, CH-E6, and CH-E10, along with their monomeric counterpart CH-E1, by systematically varying the alkyl linker lengths via esterification. This synthetic approach avoids conventional metal-catalyzed coupling reactions, eliminating the need for expensive catalysts and toxic intermediates, such as organotin reagents. Results demonstrate that the linker lengths critically govern molecular conformations, packing motifs, and aggregation behavior. The binary PM6:CH-E6 and ternary PM6:CH-E6:CH-E1 devices, benefiting from favorable film microstructures, enhanced charge carrier dynamics, and reduced Eloss, achieve PCEs of 19.17 and 20.14%, respectively. Furthermore, the flexible alkyl chain linkage inhibits molecular diffusion, thereby stabilizing the active layer morphology under thermal and mechanical stress. Thus, CH-E6-based devices exhibit significantly improved MPP operational stability and thermal endurance. The crack-onset strain (COS) of the PM6:CH-E6 blend film reaches 20%, twice that of PM6:CH-E1.

Connection topology dictates the conductance level in cyclopentadienone junctions, while functional groups provide synergistic control, with a single group exerting opposite effects in different pathways.

Three conjugated molecules, i.e., DPP-Qc, DPP-2FQc, and DPP-2ClQc, with a thiophene-flanked diketopyrrolopyrrole (DPP) core and 2-[4-oxonaphthalen-1(4H)-ylidene]malononitrile (Qc), 2-(6,7-difluoro-4-oxonaphthalen-1(4H)-ylidene)malononitrile (2FQc) or 2-(6,7-dichloro-4-oxonaphthalen-1(4H)-ylidene)malononitrile (2ClQc) termini were synthesized. All three molecules possess optical bandgaps (E-g) < 1.0 eV and the lowest unoccupied molecular orbital (LUMO) energy levels < -4.3 eV. The incorporation of F and Cl atoms into the termini results in a bathochromic shift of the absorption spectra and a decrease of LUMO energy levels. Organic thin-film transistors (OTFTs) based on these molecules all exhibited n-type transport characteristics with electron mobility (mu(e)) exceeding 0.1 cm(2) V-1 s(-1). DPP-2FQc delivered the best device performance with mu(e) up to 0.33 cm(2) V-1 s(-1), attributed to its most appropriate film morphology.

Abstract Incorporation of quinoidal units into conjugated polymers provides an effective strategy for the development of n-type materials; however, the synthesis of polymerizable quinoidal building blocks remains challenging. Herein, we report a molecular design strategy that enables the construction of polymerizable quinoidal diketopyrrolopyrrole (DPP) units by introducing aromatic rings adjacent to the electron-withdrawing termini. Based on this approach, three conjugated polymers, PQT, PQTz, and PQCN, were synthesized with varied flanking units and terminal groups. While all polymers exhibit deep LUMO energy levels down to –4.45 eV, their charge transport properties differ markedly. PQT and PQTz display delocalized frontier molecular orbitals and nearly planar backbones, leading to unipolar n-type transport with maximum electron mobilities of 0.52 and 0.0048 cm2 V–1 s–1 respectively. In contrast, PQCN exhibits localized orbitals and a distorted backbone, resulting in suppressed charge transport. Benefiting from its broad absorption and efficient electron transport, PQT further enables photodetection and imaging applications, demonstrating clear photoresponse across the visible to NIR region. Furthermore, doped PQT achieves an electrical conductivity of 1.85 S cm–1 and a power factor of 14.5 μW m–1 K–2 in thermoelectrics.

Direct arylation polycondensations (DArP), including the DArP of C─Br and C─H monomers and oxidative DArP of C─H monomer(s), are characterized by their atom economy and simplicity compared with conventional transition-metal-catalyzed polycondensations. In the past decade, DArP have emerged as promising protocols for synthesizing high-performance polymer semiconductors used in organic thin-film transistors (OTFTs), organic solar cells (OSCs), organic electrochemical transistors (OECTs), etc. Several existing high-performance polymer semiconductors with high molecular weight and low structural defects have been successfully synthesized via optimizing the polymerization conditions of C─Br/C─H DArP, achieving device performances comparable to or even exceeding the counterparts obtained from conventional methods. Particularly, new C─H monomers, such as β-halogenated thiophene derivatives and 5-thiazoyl-terminated aryls, have been designed with consideration of both the enhancement of C─H-bond reactivity and semiconducting properties of the resulting polymers, enabling the synthesis of novel conjugated polymers with superior semiconducting properties via DArP as efficient as conventional protocols such as Stille and Suzuki polycondensations. In this article, we summarize the progress in high-performance polymer semiconductors synthesized via DArP as mentioned above and discuss mechanistic insights underlying the improved polymerization outcomes.

The solution aggregation structures of conjugated polymers are pivotal in determining their film morphology and optoelectronic properties, yet the relationship between solution aggregation and device performance remains elusive in organic photodiode (OPD) systems. Herein, we introduce the first examination of solution aggregation structures of all-polymer OPD blends, with a focus on how molecular entanglement modulates aggregation behavior and subsequent photodiode performance of low-cost poly(3-pentylthiophene). Using small-angle neutron scattering and freeze-dried imaging, we provide a comprehensive analysis of the solution-state aggregation behavior of poly(3-pentylthiophene) and its evolution in the blend, revealing profound impacts on film morphology and device performance. With finely optimized aggregation, the resulting all-polymer OPD achieves a record-high specific detectivity of ∼4×1013 Jones at zero bias, outperforming all bulk heterojunction (BHJ)-type self-powered OPDs reported to date. This device also demonstrates remarkable thermal stability, with negligible performance degradation after over 800 h of thermal annealing at 85 °C. Furthermore, the self-powered OPD exhibits excellent performance across a broad spectral range, enabling its application in both water quality monitoring and biosensing. This work offers new insights into the solution aggregation behavior of conjugated polymers in OPDs and highlights the importance of resolving solution aggregation in optimizing device function.

The advancement of stretchable organic photovoltaics is hindered by a fundamental trade-off between high optoelectronic performance and mechanical durability, in particular, a challenge rooted in the complex microstructure of conjugated polymers and their blends. This review addresses a critical literature gap on the microstructure of various conjugated polymer systems by systematically examining how multiscale microstructural evolution, from solution-state aggregation to solid-state morphology and dynamic response under strain, can be characterized, understood, and rationally controlled. Analysis begins with how advanced X-ray and neutron scattering techniques elucidate the formative solution-aggregation structures that dictate the final solid-state morphology. Subsequently, multiscale characterization methods for thin films are reviewed, alongside material design strategies, such as elastomeric modifiers, engineered to optimize phase-separated morphologies for simultaneous conductivity and mechanical flexibility. A key focus is the transition beyond static X-ray scattering analysis to explore the dynamic evolution of microstructure under mechanical stretching, thereby underscoring the pivotal role of in situ and operando characterization in revealing deformation and failure mechanisms. By integrating insights across these scales, this review aims to distill rational design principles, offer a coherent processing-structure-performance framework, and provide a complete picture for the predictive design of next-generation intrinsically robust stretchable photovoltaics and related electronics.

ABSTRACT The accelerated adoption of thermoplastic elastomers (TPEs) is driving a critical shift toward wearable electronics and highly durable energy technologies that are both mechanically durable and high‐performing. This feature‐article systematically examines the rapidly expanding role of TPEs across key device platforms, specifically organic photovoltaics and thermoelectrics, and explores how TPEs enable their synergistic integration with other crucial functionalities such as light‐emitting diodes, thin‐film transistors, photodetectors, and electrochemical transistors within advanced flexible energy systems. The integration of TPEs in various devices enables unprecedented improvements in both mechanical robustness and electronic functionality critical for sustained energy performance. The distinctive two‐phase microstructure of TPEs, which combines dynamically reversible physical crosslinks with flexible soft segments, enables tunable mechanical behavior and superior interfacial compatibility. This architecture allows TPEs to serve multiple critical functions, as flexible substrates, encapsulation layers, adhesion promoters, and toughening agents, significantly improving stretchability, structural adaptability, and performance retention under mechanical deformation for energy conversion and storage applications. By critically analyzing recent breakthroughs, this review formulates essential design guidelines and persistent challenges for optimizing TPE‐incorporated devices. Collectively, this work underscores the transformative and practical potential of TPEs in realizing advanced, intelligent, and highly durable energy‐harvesting and power‐supply systems for next‐generation wearable applications.

Efficient direct arylation polymerization (DArP) largely relies on the rational design of C-H monomers. In the current paper, three thiophene-flanked diketopyrrolopyrrole (ThDPP) derivatives, i.e., FDPP, ClDPP, and CNDPP, in which the beta-positions of thiophene rings are substituted with electron-withdrawing groups (EWG) fluorine (F), chlorine (Cl), and cyano (CN) groups, respectively, were synthesized as C-H monomers. The DArP of the C-H monomers with ThDPP and selenophene-flanked DPP (SeDPP) C-Br monomers underwent efficiently, affording six low bandgap conjugated polymers, i.e., PFTh, PClTh, PCNTh, PFSe, PClSe, and PCNSe, with high molecular weights. The polymers based on FDPP and ClDPP (PFTh, PClTh, PFSe, and PClSe) show n-type-dominant ambipolar transport behavior. Of the four polymers, PFSe delivered the best device performance with maximum hole and electron mobilities of 0.76 and 1.86 cm2 V-1 s-1, respectively. CN substitution substantially lowers the LUMO energy level of the polymers. Consequently, the CNDPP-based polymers PCNTh and PCNSe exhibited unipolar n-type transport characteristics with electron mobilities up to 0.42 cm2 V-1 s-1. The beta-EWG substitution provides an effective strategy to concurrently enhance DArP reactivity and tune polymer properties without increasing backbone complexity. This work suggests poly(diketopyrrolopyrrole-alt-bichalcogenophene) as a versatile platform for the rational design of high-performance polymer semiconductors.

This study introduces a novel organic memristor based on a blend of ruthenium trichloride (RuCl3) and polyvinylpyridine-polystyrene copolymer (PVPS), designed for neuromorphic computing applications. The device operates on a redox-based mechanism, circumventing the challenges associated with conductive filament formation, and displays both digital and analog switching behaviors. This dual functionality enables rapid binary switching, suitable for digital applications, as well as fine-tuned conductance modulation, mimicking synaptic plasticity in neuromorphic systems. Key features of the device include nonvolatility, a high yield rate of 76%, and a large ION/IOFF ratio of 102, making it ideal for information storage and neuromorphic applications. Furthermore, the memristor demonstrates high robustness in noisy environments, with a recognition accuracy of up to 92.72% in a facial recognition task under 40% Gaussian noise. These results suggest that the Ru-PVPS-based memristor is a promising candidate for AI hardware, offering energy-efficient, scalable, and biologically inspired computing solutions.

Simultaneously achieving high electrical conductivity and optical transparency remains a formidable challenge for polymers. In this study, we addressed this challenge by preparing a conjugated polymer (PBT) using a carbonyl-terminated quinoidal unit that was synthesized via a newly developed method. PBT is lightly colored because its absorption band is located in the infrared region with minimal absorption in the ultraviolet and visible regions. This unique feature allows infrared photodetection and imaging without sacrificing visible clarity and minimizing interference from visible light. Upon doping, the infrared absorption band in the spectrum of PBT is almost completely suppressed, resulting in broad-spectrum transparency from 300 to 2500 nm with a maximum transmittance of up to 98%. The excellent optical transparency, combined with a close match between the transmission and solar spectrum, ensures that doped PBT has a minimal impact on the color rendering index of light, thereby preserving the color fidelity of objects. Furthermore, the electrical conductivity of doped PBT exceeds 100 S cm-1, the highest reported for intrinsically transparent conjugated polymers. As an active material, doped PBT has been successfully used to fabricate transparent thermoelectric devices. These results highlight the potential of PBT for innovative applications in next-generation transparent electronics.

n-Type conjugated polymers are mainly synthesized by the conventional cross-coupling polymerizations, such as Stille polycondensation, which require prefunctionalized organometallic intermediates and raise concerns regarding toxicity. Here, we report the synthesis of benzodifurandione-based conjugated polymers via a synthetic strategy that combines direct arylation for monomer construction with metal-free aldol polycondensation for polymer formation, thereby eliminating the need for prefunctionalized organometallic intermediates. By introducing different numbers of fluorination on the BDOPV unit, two polymers, P2FB2Tz and P4FB2Tz, are synthesized. Both polymers exhibit deep-lying LUMO energy levels of down to-4.45 eV, enabling unipolar n-type charge transport with electron mobilities of similar to 0.15 cm2 V-1 s-1. Although increased fluorination enhances backbone planarity and further lowers the LUMO energy level of P4FB2Tz, it suppresses n-doping efficiency due to restricted dopant diffusion into the polymer matrix. As a result, the less planar polymer (P2FB2Tz) delivers superior thermoelectric performance, with a conductivity of 3.13 S cm-1 and a power factor of 7.98 mu W m-1 K-2 after N-DMBI doping.

Side chain structures have a significant influence on the solution preaggregation and thin-film microstructures of conjugated polymers (CPs) and are thus one of the key structural parameters determining the charge transport properties of CPs. Herein, a series of isoindigo-based n-type CPs appending carbosilane side chains with varying Si-branching positions, named BmSiC12 (m = 3-8, representing the number of CH2 units between the Si atom and the conjugated backbone), were synthesized via direct arylation polymerization. The effect of branching positions of carbosilane side chains on solution preaggregation, thin-film microstructures, and semiconducting properties of BmSiC12 was systematically investigated. These properties of BmSiC12 exhibit an obvious odd-even dependence on m as m ≤ 6. The polymers with even m tend to form larger one-dimensional (1D) fibrous aggregate in solution and higher long-range order in thin film, and thus display more efficient charge transport in organic thin-film transistors (OTFTs). The odd-even effect gradually diminishes as the m value increases to above 6. Among the polymers, B4SiC12 and B6SiC12 form the largest solution preaggregates and highly aligned thin films, achieving maximum OTFT electron mobilities up to 3.65 and 3.95 cm2 V-1 s-1, respectively.

Organic batteries using abundant and recyclable organic electrode materials provide a sustainable and environmentally friendly alternative to commercial lithium-ion batteries1-5, which rely on resource-limited mineral-derived inorganic electrode materials6-8. However, the practical use of organic batteries has been severely hindered by the intrinsic insulation and dissolution of organic electrode materials9,10. Here we report practical organic batteries using an n-type conducting polymer cathode, poly(benzodifurandione) (PBFDO), which exhibits excellent mixed ionic and electronic transport and low solubility. The PBFDO cathode maintains its n-doped state throughout the electrochemical processes and exhibits stable and reversible redox characteristics, high electrical conductivities and significant lithium-ion diffusion coefficients, without the need for additional conductive additives. Consequently, ultrahigh-mass-loading polymer cathodes, with mass loadings up to 206 mg cm-2, are realized, delivering a high areal capacity of 42 mAh cm-2 and demonstrating robust cycling stability. Furthermore, practical 2.5 Ah lithium-organic pouch cells were fabricated, achieving an impressive energy density of 255 Wh kg-1. Notably, the conducting polymer cathode operates efficiently over a wide temperature range from -70 °C to 80 °C and demonstrates excellent flexibility and safety, marking considerable potential for applications in extreme conditions and wearable electronics.

Short-wavelength infrared (SWIR) organic photodetectors (OPDs), particularly all-polymer ones, hold substantial commercial promise in vital monitoring and imaging. However, the development of all-polymer SWIR OPDs has been limited by the lack of high-performance n-type ultralow-bandgap polymer semiconductors. Herein, we report two dual-acceptor polymers (ThDPP-CNBTz and ThDPP-CNBSz), with dicyano-benzothiadiazole/benzoselenidazole as strong acceptor units, diketopyrrolopyrrole as a sub-strong acceptor unit, and thiophene as a donor moiety. Both polymers possess ultralow optical bandgaps and deep HOMO/LUMO, making them ideal acceptor materials for all-polymer SWIR OPDs. Owing to more efficient charge generation and transport, ThDPP-CNBTz-based all-polymer OPDs show superior responsivity ≥0.150 A W-1 from 780 to 1060 nm. The ThDPP-CNBSz-based OPDs show lower noise currents, attributed to the larger thermal activation energy of dark current and lower trap density. As a result, ThDPP-CNBTz- and ThDPP-CNBSz-based OPDs deliver similar specific detectivity, exceeding 1012 Jones in the spectral range of 780-1140 nm and 350-1240 nm, respectively. Furthermore, ThDPP-CNBTz-based stretchable OPDs show a small performance attenuation after 1000 cycles of stretching at 20% strain, heralding potential application in wearable vital monitoring. By monolithically integrating PDPP-3T:ThDPP-CNBTz-based OPDs with silicon-based readout integrated circuits, high-resolution imaging has also been demonstrated for infrared penetration and material discrimination.

Despite recent advances in stretchable polymer semiconductors, the trade-off between charge mobility and mechanical properties remains outstanding using conventional physical or chemical strategies. Herein, we introduce transesterification crosslinking in hydroxy-modified poly(indacenodithiophene-alt-benzothiadizole)s (OH-IDTBT-5%) using a polyurethane elastomer crosslinker containing a polycaprolactone segment (PU-PCL), to simultaneously enhance the elastic recovery rate, elastic modulus (similar to 1.5 GPa) and hole mobility, while maintaining exceptional ductility (COS > 100%, epsilon(F) similar to 30%). The crosslinked network restricts plastic deformation, yielding an outstanding elastic recovery rate (>90% at 4% strain) with delayed plastic deformation onset strain (PdOS similar to 100%). Notably, the crosslinking reaction passivated detrimental hydroxy groups and enhanced mobility to 2.13 cm(2) V-1 s(-1), which remained relatively consistent even after 500 stretching cycles at 70% strain. Importantly, the crosslinking films exhibited excellent robustness against organic solvents by retaining over 90% fraction after soaking. Our strategy provides an opportunity for high-performance stretchable semiconductors, by overcoming not only the trade-off between charge transport properties and mechanical durability in general, but also the sacrifice of ductility in chemical crosslinking systems.

Stretchable near-infrared organic photodetectors (NIR OPDs) are crucial for the development of wearable and implantable electronics. However, these devices commonly underperform compared to their rigid counterparts, primarily due to the lack of high-quality stretchable transparent electrodes. Here, we develop silver nanowires (AgNWs)/thermoplastic polyurethane (TPU) composite electrodes by introducing 3-[N-tris(hydroxymethyl)methylamino]-2-hydroxypropanesulfonic acid sodium salt (HOS). The resulting AgNWs-HOS/TPU electrodes show impressive optical transmittance and low sheet resistance (12 Ω·sq-1), comparable to ITO/glass electrodes. Notably, the incorporation of HOS significantly improves the adhesion between AgNWs and TPU, ensuring a low sheet resistance (21.3 Ω·sq-1) even under mechanical deformation of 80%. Consequently, the AgNWs-HOS/TPU-based stretchable OPDs exhibit a record-high shot-noise-limited specific detectivity (D*shot) of 5.58 × 1013 Jones at 800 nm, comparable to rigid devices. Moreover, these stretchable devices maintain a D*shot > 1013 Jones after 500 stretching cycles at 50% strain and sustain a D*shot over 1013 Jones under continuous stretching at 30% strain for over 80 min, ranking as the highest value among stretchable OPDs in photovoltaic mode reported so far. Furthermore, the stretchable NIR OPDs are successfully applied in pulse signal detection, imaging, and optical communication, and they are capable of accurate signal detection after cyclic stretching, which demonstrates great potential in wearable and implantable devices.

In this study, a tetraphenylethylene-based dicyclophane with an o-carborane framework was constructed. This material exhibits excellent dual-state emission in both solution and solid states, demonstrating solvent-dependent orange-to-blue fluorescence in solution and bright green emission as a solid. Moreover, this dicyclophane has special responses to nucleotides and C60.

With merits of good solution processability, intrinsic flexibility, etc, organic/organic interconnecting layers (ICLs) are highly desirable for tandem organic photovoltaics (OPVs). Herein, an n‐doped cross‐linked organic electron transport layer (ETL), named c‐NDI‐Br:PEI is developed, via a simple in situ quaternization reaction between bromopentyl‐substituted naphthalene diimide derivative (NDI‐Br) and polyethylenimine (PEI). Due to strong self‐doping, c‐NDI‐Br:PEI films exhibit a high electrical conductivity (0.06 S cm −1 ), which is important for efficient hole and electron reombination in ICL of tandem OPVs. In addition, the cross‐linked ETLs show strong work function modulation ability, and good solvent‐resistance. The above features enable c‐NDI‐Br:PEI to function as an efficient ETL not only for single‐junction OPVs, but also for tandem devices without any metal layer in ICL. Under solar radiation, the single‐junction device with c‐NDI‐Br:PEI as ETL achieves a power conversion efficiency (PCE) of 18.18%, surpassing the ZnO‐based device (17.09%). The homo‐ and hetero‐tandem devices with m‐PEDOT:PSS:c‐NDI‐Br:PEI as ICL exhibit remarkable PCEs of 19.06% and 20.06%, respectively. Under 808 nm laser radiation with a photon flux of 57 mW cm −2 , the homo‐tandem device presents a superior PCE of 38.5%. This study provides a new ETL for constructing all‐solution‐processed organic/organic ICL, which can be integrated in flexible and wearable devices.

Organic memristors, integrating chemically designed resistive switching and mechanical flexibility, present promising hardware opportunities for neuromorphic computing, particularly in the development of next-generation wearable artificial intelligence devices. However, challenges persist in achieving high yield, controllable switching, and multi-modal information processing. In this study, we introduce an efficient distribution of conversion bridges (EDCB) strategy by dispersing organic semiconductor (poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene], PBTTT) in elastomer (polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene, SEBS). This innovative approach results in memristors with exceptional yield, high stretchability, and reliable switching performance. By fine-tuning the semiconductor content, we shift the primary charge carriers from ions to electrons, realizing modulable non-volatile, and volatile duo-mode memristors. This advancement enables multi-modal signal processing at distinct operational mechanisms-non-volatile mode for image recognition in convolutional neural networks (CNNs) and volatile mode for dynamic classification and prediction in reservoir computing (RC). A fully analog RC hardware system is further demonstrated by integrating the distinct volatile and non-volatile modes of the EDCB-based memristor into the dynamic neuron network and the linear regression layer of the RC respectively, achieving high accuracy in online arrhythmia detection tasks. Our work paves the way for high-yield organic memristors with mechanical flexibility, advancing efficient multi-mode neuromorphic computing within a unified memristor system integrating volatile and non-volatile functionalities.image