The morphology of active layer plays a critical role in determining the photovoltaic performance of organic solar cells(OSCs). However, binary blends often suffer from suboptimal phase separation, which limits the efficiency of OSCs. Herein, two bridging polymer acceptors(PAs)-benzodithiophene-(2-ethylhexyl)oxy(BDT-C2C4) and benzodithiophene-octyloxy(BDT-C-8)-are designed and synthesized by combining a benzodithiophene(BDT) unit as the donor moiety[poly({4,8-bis[5-(2-ethylhexyl)-4-fluorothiophen-2-yl]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}){5,8-bis[4-(2-butyloctyl)thiophen-2-yl]dithieno[3',2':3,4]}, D18], and a2,2 '-((2Z,2 ' Z)-{[12,13-Bis (2-butyloctyl)-12,13-dihydro-3,9-dinonylthieno[2,3]thieno[3,2-b]pyrrolo[4,5-g]thieno[2,3-b]indole-2,10-diyl] bis(methanylylidene)}bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(Y6) derivative as the acceptor moiety. BDT-C2C4 and BDT-C-8 are functionalized with (2-ethylhexyl)oxy and octyloxy side chains on the BDT unit, respectively. Both PAs show complementary absorption and cascaded energy levels with the donor D18 and the acceptor 2,2 '-((2Z,2 ' Z)-{[12,13-bis(3-ethylheptyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno [2 '',3 ''& ratio;4 ',5 ']thieno[2 ',3 '& ratio;4,5]pyrrolo[3,2-g]thieno[2 ',3 '& ratio;4,5]thieno[3,2-b]indole-2,10-diyl]bis(methaneylylidene)}bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile(N3), but BDT-C-8 exhibits better compatibility with D18 and N3 compared to BDT-C2C4. When incorporated as a third component into the D18 & ratio;N3 blend, both PAs improve the active layer morphology. In particular, the D18 & ratio;N3 & ratio;BDT-C-8 blend shows significantly optimized morphology, featuring reduced phase separation and a fibrous network structure. As a result, the device based on D18 & ratio;N3 & ratio;BDT-C-8 achieves a power conversion efficiency of 18.18%, significantly higher than that of the device based on D18 & ratio;N3(ca.17.37%). This work presents a compatibilizer strategy for optimizing blend morphology towards high-performance ternary OSCs.

Aerogels are renowned for their ultralow density and superior thermal insulation. However, the poor adhesion of traditional aerogels, arising from their porous surfaces and rigid frameworks, presents a significant challenge for integration into functional systems. Inspired by the core-shell architecture of expanded thermoplastic polyurethane (ETPU) beads, which feature a thermoplastic shell enabling thermally activated adhesion and a resilient core ensuring mechanical recovery, we developed self-assembled adhesive aerogel capsules (SAACs). SAACs emulate this decoupling strategy with a porous chitosan/silica aerogel (CTS/SA) core preserving the thermal insulation, while an adhesive chitosan/carboxylated nitrile rubber (CTS/XNBR) shell enables adhesion. Through electrostatically-based self-assembly and freeze-drying, negatively charged XNBR encapsulates a positively charged CTS/SA scaffold, forming a core-shell structure. SAACs can be thermally processed at mild temperatures (≤ 80°C) to adhere into 3D assemblies, conform to irregular shapes, and adhere to diverse substrates. Despite their adhesive capability, SAACs retain low density, low thermal conductivity (30-39 mW·m-1·K-1), and inherent flame retardancy. Unlike conventional aerogels or ETPU, SAACs combine the thermal processability of elastomers with the insulation and fire resistance of aerogels, offering a promising platform for applications in on-site thermal management, energy conservation, and fire protection.

Polymer crystallization theory has been studied for almost a hundred years, but remains a huge challenge in polymer science. Traditional polymer crystallization studies are mainly based on flexible polymers and the typical crystalline units are stems, whose length are much larger than the length of Kuhn segments (LK). However, the crystallization behavior of chain segments with lengths below LK is not well understood. In the case of conjugated polymers, their strong chain rigidity leads to a larger LK, which will help us to observe the crystallization behavior of chain segments of length around the LK. In this review, we summarize the unique crystallization behaviors of conjugated polymers and discuss some deeper understanding of polymer crystallization inspired by conjugated polymer crystallization. First, current polymer crystallization theories are briefly reviewed and their limitations are discussed. Then, the special crystalline features of conjugated polymers are summarized, including a prior backbone ordering or side chain ordering, a transition from chain-folded to chainextended crystallization with increasing chain rigidity, preferred growth directions, novel rhizoid crystal morphology, and paracrystallinity. Afterwards, several deeper insights into polymer crystallization are discussed, such as direct evidence for chain-folding and chain-extending, conformational order before interchain stacking, intermediate states between amorphous and crystalline structures, and new crystallization models based on chain motion. Finally, a concise summary is provided, followed by several current challenges.

All-polymer solar cells (all-PSCs) suffer from significant challenges of large-scale aggregation and phase separation due to poor compatibility between donor and acceptor polymers. In this study, we introduce volatile solid additives to regulate intermolecular interactions and improve blending miscibility, thereby controlling aggregation and phase separation. Both computational and experimental results reveal that the key to this regulation lies in the strong electrostatic potential coupling between the solid additive and the polymer acceptor. This selective interaction modulates the aggregation behavior during film deposition and thermal annealing, enabling a gradual phase evolution. Further analysis indicates that the strong electrostatic coupling reduces aggregate size and promotes more ordered molecular packing, ultimately optimizing the film morphology. As a result, all-PSCs based on PM6/PY-IT incorporating the solid additive 2-BDBF exhibit a significantly improved power conversion efficiency of 18.62%, representing an increase compared to 14.93% ender the control conditions. This work demonstrates that solid additives with engineered electrostatic interactions offer an effective strategy to tune intermolecular forces, optimize morphology evolution, and boost device performance in all-PSCs.

Poly(vinyl alcohol) (PVA) film is a crucial material that impacts the polarization performance, color tone, transmittance, and other important optical properties of the polarization film. However, the coffee ring effect, caused by differences in evaporation rates, significantly decreases the uniformity of the PVA film. In this study, we propose a strategy to mitigate the evaporation rate at the edges of droplets by introducing solvent vapors (increasing humidity), thereby inhibiting the coffee ring effect. For this purpose, PVA aqueous solutions were dried at four different relative humidity levels from 30 % RH to 90 % RH. When the humidity was 70 % RH or higher, the coffee ring profile disappeared, resulting in a uniform deposit. This is because higher humidity slows down the drying rate at the edges of the droplet and restricts the radial flow from the center to the outside of the droplet. The discovery was applied to the preparation of large-area PVA films (20 cm x 30 cm) by blade coating. At 90 % RH, the uniform thickness part of the PVA film was 90 %, with a thickness difference of 6 mu m between the edge and center, which is much smaller than that of 21 mu m at 30 % RH. This method enables the formation of a large, uniformly thick film without altering the properties of the solution itself, providing theoretical and technical guidance for improving industrial processing and preparing PVA films with high uniformity.

The scalable fabrication of stretchable conjugated polymer films via solution printing is essential for their practical application in large-area wearable electronics. However, the printed conjugated polymer films typically exhibit high crystallinity, limiting their mechanical deformability. Herein, we propose a plasticizer-assisted printing strategy to simultaneously enhance the stretchability and electrical performance of films based on the conjugated polymer poly(3-(5-(5-methylselenophen-2-yl)thiophen-2-yl)-6-(5-methylthiophen-2-yl)-2,5-bis(4-octyltetradecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione) (P(TDPP-Se)). The incorporation of a plasticizer trioctyl trimellitate (TOTM) promotes P(TDPP-Se) aggregation in initial solution, facilitates chain alignment under flow field, and shorten solidification process, thereby restricting randomly polymer crystallization. Consequently, a low-crystallinity film with favorable edge-on orientation, strong chain alignment and improved chain dynamics is realized, which effectively alleviates crystallites fragmentation and crack propagation under large strain. The TOTM-plasticized film exhibits approximately 2-fold improvements in fracture strain and charge mobility, along with superior mobility retention under 100% strain in comparison to the neat film. This study provides a feasible approach for microstructure control in printed stretchable conjugated polymer film.

The extension of polymer fibrils is anticipated to enhance charge transport in organic solar cells (OSCs).However, further extending the length of polymer fibrils remains challenging due to the weak inter-molecular interactions among polymer chains. This work reports a fibrillization strategy that enablespronounced extension of polymer donor D18 fibrils (from 264 nm to 391 nm) by selectively strengtheningpacking between the acceptor units (A) in D18 fibrils. By introducing a volatile solid additive, 2,4-dichloro-5-cyanothiazole (DCCTz), dipole-dipole interactions are established between the additive and the A unitsof the polymer donor D18, effectively reducing the energetic barrier for intermolecular packing. Importantly,the extended fibril network and optimized molecular packing are well preserved in D18/L8-BO layer-by-layer (LbL) processed active layers without disturbing acceptor ordering. Consequently, this optimizeddonor fibril morphology facilitates charge transport and collection in D18/L8-BO LbL fabricated organicsolar cells (OSCs), yielding a significantly improved power conversion efficiency of 19.30%. This workdemonstrates an effective strategy to carefully control the dipole-dipole interaction between the solidadditive and polymer donor, offering a promising approach for advancing the performance of OSCs.

Developing more sustainable and high-performance rubber composites is critical for sustainable manufacturing. Pyrolysis carbon black (CBp) from waste tires is a promising circular filler, yet its reinforcing efficiency is often limited by its poor interfacial interaction with rubber matrices. Inspired by how metal coordination bonds endow biological materials with high mechanical performance, we propose a simple metal-coordination strategy to strengthen the CBp–natural rubber (NR) interface by introducing Zn 2+ . The resulting composite exhibits comprehensive mechanical enhancement, achieving a 26.9% increase in tensile strength—among the highest improvements reported for CBp-reinforced systems. Moreover, the composite demonstrates exceptional resistance to permanent deformation, retaining 98.8% of its original shape after 45,000 compression cycles. This is primarily attributed to the formation of a unique 4-coordinate structure involving Zn 2+ between the CBp and the NR matrix, which significantly enhances the interfacial interaction between them. This work elucidates an efficient and scalable interfacial reinforcement mechanism and provides a viable strategy toward designing high-performance and sustainable rubber composites.

Organic photodetectors (OPDs) possess lightweight and mechanical flexibility, making them ideal for skin-conformal wearable health monitoring devices. However, achieving simultaneously high stretchability and optoelectronic performance remains a critical challenge. Here, we report an elastomer-semiconductor blend strategy with promising applicability across multiple representative donor-acceptor systems, introducing a low-cost commercial thermoplastic polyester elastomer (TPEE) into the high-performance blend system to achieve remarkable stretchability and mechanical stability while maintaining high optoelectronic performance. The TPEE forms a continuous, ductile network at 50% content without significantly compromising the morphology or charge transport of the conjugated molecules. The resulting blend film achieves a fracture strain of 224% while retaining competitive optoelectronic performance with responsivity (R-max) of 0.295 A W-1 and specific detectivity (D-noise*) > 9 & times; 10(11) Jones. The stretchable devices retain excellent performance under 100% strain or after 1000 stretching cycles at 50% strain (R-max > 0.2 A W-1, D-noise* > 3 & times; 10(11) Jones). As proof of concept, we demonstrate their reliable operation in wearable near-infrared oximeters, delivering accurate heart rate and blood oxygen readings even under strain and prolonged air exposure. This work highlights the potential of commercial elastomers in advancing high-performance, intrinsically stretchable optoelectronic systems for practical health monitoring applications.

Differences in solvent selection for small molecules and polymers used in inkjet printing and the compatible binary ink formulations.

The intrachain and interchain charge transport in conjugated polymer films mainly depends on the crystalline and amorphous regions, as well as the connectivity between the ordered domains. The microstructure of the conjugated polymer films is known to be influenced by the solution aggregation and the film formation kinetics. However, a mechanistic understanding of the polymer chain assembly has been hindered by the lack of in situ monitoring. In this study, we systematically controlled the solution aggregation and chain assembly pathways of P(NDI2OD-T2) by mixing a mutual solvent chloroform (CF) with a backbone selective solvent 1-fluoronaphthalene (FN). Our investigation, combining static characterization (UV-vis, TEM, AFM, and 2D-GIWAXS) with in situ UV-vis and in situ 2D-GIWAXS, not only revealed the structure of solutions and films but also mapped the dynamic film-formation pathway, identifying key intermediates essential for evolving toward an optimized morphology. In the CF + 10 v% FN solvent, as revealed by in situ UV-vis absorption spectroscopy, the polymer chains first disentangled into single chains, then assembled into weakly aggregated intermediates, and finally developed into strongly aggregated species. This sufficient rearrangement process facilitated the formation of a well-ordered fibrous morphology with increased edge-on content (with a relative degree of crystallinity, rDOC, of 1.74). In contrast, the films cast from the pure CF solution exhibited fine fibers with poor ordering (rDOC = 1.00), whereas the pure FN solution led to large-sized aggregates (rDOC = 1.09) owing to the poor solubility. As a result, the electron mobility of the CF + 10 v% FN film reached 0.120 cm2 V-1 s-1, higher than that of the CF film (0.056 cm2 V-1 s-1) and the FN film (0.083 cm2 V-1 s-1), respectively. Upon thermal annealing, the electron mobility of the CF + 10 v% FN film further increased to 0.336 cm2 V-1 s-1, resulting from a tighter backbone packing driven by the evaporation of residual FN.

Conjugated polymer-based block copolymers (BCPs) are important materials as they incorporate the optoelectronic properties of conjugated polymers and unique microphase-separated properties of BCPs. The ability to tailor the two basic phase behaviors (crystallization and microphase separation) within conjugated BCPs is highly desirable to not only control their physical properties, but also strengthen the fundamental understanding of rod-like BCPs. However, the crystallization of semirigid conjugated polymers has not been well elucidated compared to traditional flexible polymers. Moreover, the phase behaviors of conjugated BCPs are much less understood than those of classical coil-coil BCPs from both theoretical and experimental aspects. In this Viewpoint we begin with a brief introduction of chain stiffness and the crystallization of conjugated polymers. After introducing the phase behaviors of BCPs including coil-coil, rod-coil, and rod-rod types, we discuss recent advances in the interplay and competition between crystallization and microphase separation within conjugated BCPs, as well as their applications in organic electronics. Finally, ongoing challenges and future perspectives will be discussed.

Stretchable organic solar cells (OSCs) hold significant promise as light-harvesting power sources in wearable electronics. Physical blending highly-deformable elastomer into rigid photovoltaic components represents a simple and effective approach to enhance film stretchability. However, the mechanical and photovoltaic performance of elastomer-based active layers are generally inferior to those achieved through chemical approaches. Herein, we report a high-performance stretchable active layer that combines photo crosslinking with sequential deposition of an elastomer-based ternary system poly[2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-5,5'-(5,8-bis(4-(2-butyloctyl)thiophen-2-yl)dithieno[3',2':3,4;2'',3'':5,6]benzo[1,2-c][1,2,5]thiadiazole)] (D18)/2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene)bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalonitrile) (Y6): polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS), achieving a power conversion efficiency of 15.38% and a crack-onset strain of 35.91%. Crosslinking D18 with an azide compound ethane-1,2-diyl bis(4-azido-2,3,5,6-tetrafluorobenzoate) (2BX) in the bottom layer not only produces a 3D covalent network, but also results in a low-crystallinity film with a reduced glass transition temperature. These structure changes contribute to delayed large-scale chain slippage and enhanced strain energy dissipation, leading to approximately 100% and 40% improvements in the stretchability of D18 film and full active layer. Moreover, the charge generation and transport behaviors are just slightly affected with moderate microstructure change, enabling the device to retain 94% of initial efficiency. Ultimately, the optimal active layer achieves an efficiency-stretchability factor of 5.52%, ranking among the highest reported values for stretchable active layer systems.

Stretchable organic light-emitting diodes (OLEDs) are essential for display and interaction in wearable electronics. However, inkjet-printed silver nanowire (AgNW) films for OLED electrodes are limited by poor film uniformity, high surface roughness, and insufficient stretchability. Here, an integrated strategy is proposed to address these challenges through cosolvent modulation, substrate transfer, and junction soldering. Specifically, a high-viscosity cosolvent (1-pentanol) was introduced into the AgNW ink to suppress the outward capillary flow during drying. This effectively mitigated the coffee ring effect and significantly improved film uniformity. On this basis, the AgNW films were embedded into a thermoplastic polyurethane/polydimethylsiloxane (TPU/PDMS) elastomeric matrix via a substrate transfer process, utilizing the water solubility of the initial PEDOT:PSS substrate. This process reduced the root-mean-square surface roughness from 23.9 nm to 4.1 nm and the maximum peak-to-valley roughness from 188.2 nm to 29.9 nm. Furthermore, the inter-nanowire junctions were soldered using a small-molecule additive (4 '-pentyl-4-cyanobiphenyl, 5CB) to further enhance mechanical stability. This reduced the relative resistance change (R/R0) under 100% strain from 99 to 12. Based on the optimized electrodes, the fully inkjet-printed stretchable OLED devices were successfully fabricated. The devices exhibited a maximum luminance of 3141 cd m-2, corresponding to 84% of that of the spin-coated reference device. Under 100% strain, the devices retained 38% of the initial luminance. These results demonstrate a viable and scalable route toward high-performance, fully printed stretchable OLEDs.

A continuous network with short-range aggregation structures in an amorphous matrix is widely recognized for achieving optimal electronic and mechanical performance of conjugated polymer films. The size and structural order of these aggregates critically determine the ability to accommodate and dissipate strain without disrupting the charge transport pathways. Here, we systematically investigated the effect of polymer chain dynamics on the evolution of aggregation structure for the conjugated polymer poly(indacenodithiophene-co-benzothiadiazole) (IDTBT) by controlling the annealing temperature (T- a). In the as-cast film, the polymer backbone remains kinetically trapped in a distorted conformation, leading to a loosely packed and disordered morphology. Thermal annealing at 100 degrees C, between the backbone glass transition temperatures (T- g) and the disaggregation temperature (T (disagg)), activates the segment motion, enabling reorganization into small, short-range ordered aggregates with an extended conformation. When annealed at 260 degrees C (T- a > T disagg), full chain mobility permits assembly into larger, more ordered aggregates with dense molecular packing. Consequently, the charge mobility increases from 0.92 cm(2) V-1 s(-1) in the as-cast film to 3.14 cm(2) V(-1 )s(-1) after annealing at 260 degrees C. Under strain, the film annealed at 100 degrees C retains its short-range aggregates, which facilitates efficient stress dissipation through interlayer slip and preserves charge mobility. In contrast, the film annealed at 260 degrees C exhibits premature fracture of the large ordered aggregates accompanied by restricted chain alignment. As a result, the film annealed at 100 degrees C maintains a charge mobility of 0.86 cm2 V-1 s-1 under 100% strain, whereas the 260 degrees C-annealed film exhibits a substantially lower mobility of 0.14 cm(2) V-1 s(-1). These results underscore the critical role of short-range aggregation structures in achieving high-performance stretchable conjugated polymer films.

Intrinsically stretchable polymer semiconductors (IS‐PSCs) exhibiting simultaneously high charge‐carrier mobility and robust mechanical properties are highly desired yet remain challenging for wearable electronics. Herein, a conjugated non‐aromatic stacking‐inhibiting ( CNASI ) design strategy is proposed by randomly embedding dithienyl‐dimethylcyclopentadiene (2TCp) units into a diketopyrrolopyrrole (DPP)‐based polymer backbone, obtaining a series of near‐linear and fully conjugated terpolymers containing different contents of 2TCp. Specifically, the geminal dimethyl substituents of 2TCp can introduce steric hindrance into the polymer backbone, effectively suppressing tight intermolecular π – π stacking interactions, while enhancing backbone conjugation and planarity owing to the introduction of a non‐aromatic polyene character. Finally, the optimized 2TCp‐15% terpolymer exhibits a high crack onset strain up to 160%, showing an over‐threefold improvement compared to the pristine PDPPT polymer. Moreover, it exhibits an improved initial charge‐carrier mobility ( µ m ax = 1.32 cm 2 V −1 s −1 ), together with excellent mobility retention and cyclic stability under mechanical strain, compared to PDPPT and a fully aromatic terthiophene‐based reference polymer. This study indicates that subtle modulation of interchain π–π interactions and backbone aromaticity via the novel CNASI strategy effectively balances the trade‐off between mechanical stretchability and electrical performance, providing a new approach for designing IS‐PSCs.

Stretchable organic photodetectors (OPDs) are promising for wearable healthcare and biointegrated sensing, yet reconciling intrinsic stretchability with high optoelectronic performance remains challenging. Here, we develop ultra-stretchable, efficient, and mechanically robust OPDs enabled by an elastomer-mediated network, with a honeycomb-like morphology as a representative manifestation. This structure enables effective stress dissipation while preserving donor-acceptor packing, refining vertical phase separation, and suppressing trap formation. The optimized ternary blends achieve a leading combination of fracture strain (>500%), specific detectivity (Dnoise∗ > 3 × 1012 Jones), responsivity (>0.35 A W−1), and stable optoelectronic performance under 100% strain and after 1,000 stretch-release cycles. Multiscale characterization reveals that the elastomer network suppresses crack formation and stabilizes morphology evolution across multiple length scales. These devices enable reliable heart rate and blood oxygen saturation monitoring under large deformation and cyclic strain. This work highlights morphology modulation as an effective strategy for mechanically reliable stretchable optoelectronics.

Silica aerogels (SAs) impart low density and excellent thermal insulation to polymer systems, yet incorporating hydrophobic SAs into aqueous rubber latex systems remains challenging owing to their poor dispersibility and potential to destabilize the latex. Although previous studies have dispersed SAs in aqueous poly(vinyl alcohol) (PVA), the stability of such dispersions and their effectiveness as bridging media for latex integration have not been thoroughly evaluated, which limits their practical application in latex compounding. This study systematically examined how the surface chemistry governs hydrolytic stability, interfacial behavior, and latex compatibility in PVA-assisted aqueous processing. Two hydrophobic SAs were prepared: ethoxy-modified SA (E-SA) and methyl-modified SA (M-SA). Both initially formed a homogeneous PVA slurry, but E-SA rapidly hydrolyzed its surface -OCH2CH3 groups, releasing ethanol, becoming hydrophilic, and undergoing irreversible nanopore collapse. In contrast, M-SA maintains its structural integrity and hydrophobicity because its -Si(CH3)3 groups are highly resistant to hydrolysis. This divergence dictates the behavior during latex blending. The ethanol released from E-SA disrupts electrostatic and steric stabilization, inducing latex coagulation, whereas M-SA/PVA dispersions preserve colloidal stability across diverse latex systems. As a practical demonstration, M-SA-reinforced chlorosulfonated polyethylene (CSM) rubber latex composites show more than a 50% reduction in thermal conductivity while maintaining chemical resistance, enabling high-performance insulating protective gloves and coatings. This work establishes a critical link between aerogel surface chemistry and aqueous processing stability, providing a mechanistic foundation for the rational design of water-based rubber/silica aerogel composites and next-generation thermal insulation materials.

The deformation mechanisms of stretchable conjugated polymer films are critical for their electrical performance in wearable electronics. However, the effect of polymer chain motions on their deformation mechanisms remains underexplored. Herein, we propose that polymer segmental motion facilitates chain conformational changes under strain, thereby establishing efficient charge transport pathways in stretched films. This hypothesis is enabled by systematically examining the uniaxial stretching behavior of a high-mobility conjugated polymer, IDTBT, at varying temperatures. When the film is heated to 70 degrees C (near its glass transition temperature, T g), the segmental movement of the mainchains is substantially activated, providing sufficient free volume for chain rearrangement. Upon stretching to 50%, backbone planarization occurs, as evidenced by an increase in the I BT/I IDT Raman ratio from 2.42 to 2.80, accompanied by improved chain alignment with a high dichroic ratio of 1.37. Meanwhile, chain disentanglement and crystallite reorientation are facilitated by enhanced chain diffusion and slippage. Further stretching to 100% strain induces the self-assembly of adjacent stretched chains in the amorphous region into ordered aggregates/crystallites, leading to an approximate 2-fold increase in the relative degree of crystallinity. The reconstructed intra- and interchain transport pathways effectively enhance charge mobility, reaching 1.11 cm2 V-1 s-1 even under 100% strain. In contrast, stretching the film at 25 degrees C (well below T g ) to 100% strain, segmental motion remains restricted. This leads to pronounced cavitation and microcracking through chain scission and crystallite fragmentation, sharply reducing charge mobility from 0.82 to 0.48 cm2 V-1 s-1. When stretched at 90 degrees C (above T g), dramatic polymer motions reduce backbone planarity and crystallinity, yielding a moderate charge mobility of 0.89 cm2 V-1 s-1 at 100% strain. These results offer valuable insights for optimizing molecular design and operating conditions of conjugated polymers in wearable electronics.