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We investigate the properties of ultrathin 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) films using a combination of tip-enhanced photoluminescence and unsupervised machine learning. We expose nanoscale spectral heterogeneities that can be understood on the basis of the interplay between vibronic effects, intermolecular excitons, and intramolecular excitons in PTDCI films. [ABSTRACT FROM AUTHOR]

Here, the effect of thermal annealing (TA) on the stability of solution‐sheared thin films of the semiconducting polymer poly[2,5‐bis(2‐octyldodecyl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione‐3,6‐diyl)‐alt‐(2,2′;5′,2′';5′',2′"‐quaterthiophen‐5,5′"‐diyl)] (PDPP4T) against the original coating solvent is studied, and it is shown that TA significantly improves the solvent resistance of semiconducting polymer films. Specifically, after the thin films are annealed at or above a critical temperature, the thin film thickness is largely retained when exposed to the original solvent, while for lower annealing temperatures material loss occurs, i.e., the thin film thickness is reduced due to rapid dissolution. The results of various techniques including grazing‐incidence wide‐angle x‐ray scattering (GIWAXS), atomic force microscopy (AFM), and ultraviolet‐visible‐near infrared (UV–vis‐NIR) absorption spectroscopy suggest physical changes as the cause for the increased solvent resistance. Such annealed films also show stable electrical characteristics in bottom‐gate, top‐contact (BGTC) organic field‐effect transistors (OFETs) even after solvent exposure. In initial tests, a multitude of technologically relevant polymers show such behavior, underlining the potential impact of such temperature treatments for the fabrication of multi‐layer polymer devices. [ABSTRACT FROM AUTHOR]

Absorption and emission in polymer aggregates is studied theoretically, taking into account excitonic (intermolecular) coupling, exciton-phonon (EP) coupling, and disorder, all treated on equal footing within a generalized Holstein Hamiltonian with numerically generated eigenmodes and energies. The disorder is modeled as a Gaussian distribution of molecular transition frequency offsets of width σ and spatial correlation length l0. Both herringbone (HB) and lamellar aggregate morphologies are considered. The emission spectral line shape is shown to undergo marked changes in response to increasing disorder, with the intensity of the ac-polarized 0-0 emission peak generally increasing relative to the replica intensities (0-1,0-2,...) as σ increases and/or as l0 decreases. This is contrary to the behavior of the b-polarized component of the 0-0 intensity, which, in HB aggregates, decreases with increasing disorder. Comparisons are made to analogous trends in oligomer aggregates. Analytical results are obtained in the strong EP coupling regime appropriate for conjugated polymers while treating the disorder perturbatively. A method for uniquely determining σ and l0 from the emission and absorption spectra is presented. Applications are made to absorption and low-temperature emission in thin films of regioregular poly(3-hexylthiophene), with excellent agreement between theory and experiment obtained for a spatial correlation length of only 3–4 molecules. [ABSTRACT FROM AUTHOR]

Nonfused ring electron acceptors (NFREAs) are promising candidates for future commercialization of organic solar cells (OSCs) due to their simple synthesis. Still, the power conversion efficiencies (PCEs) of NFREA‐based OSCs have large room for improvement. In this work, by merging end group halogenation and side chain engineering, we developed four A–D–A'–D–A type NFREAs, which we refer to as EH‐4F, C4‐4F, EH‐4Cl, and C4‐4Cl. Single crystal X‐ray diffraction revealed that multiple intermolecular S···F interactions between cyclopentadithiophene and 5,6‐difluoro‐3‐(dicyanomethylene)indanone could cause an unfavorable dimer formation, leading to ineffective π–π stackings in EH‐4F and C4‐4F, whereas no such dimer was found in EH‐4Cl and C4‐4Cl after replacing with 5,6‐dichloro‐3‐(dicyanomethylene)indanone. Moreover, although the shorter n‐butyl side chain resulted in a closer molecular packing in C4‐4Cl, EH‐4Cl (2‐ethylhexyl substitution) with proper crystallinity exhibited enhanced face‐on orientation in thin film, which is favorable for vertical charge transport and further reducing charge recombination. As a result, a PCE of 13.0% is obtained for EH‐4Cl‐based OSC with a fill factor of 0.70. This work highlights the importance of molecular packing and orientation control toward future high‐performance A–D–A'–D–A type NFREAs. [ABSTRACT FROM AUTHOR]

Conjugated polymers exhibit a unique portfolio of electrical and electrochemical behavior, which – paired with the mechanical properties that are typical for macromolecules – make them intriguing candidates for a wide range of application areas from wearable electronics to bioelectronics. However, the degree of oxidation or reduction of the polymer can strongly impact the mechanical response and thus must be considered when designing flexible or stretchable devices. This tutorial review first explores how the chain architecture, processing as well as the resulting nano- and microstructure impact the rheological and mechanical properties. In addition, different methods for the mechanical characterization of thin films and bulk materials such as fibers are summarized. Then, the review discusses how chemical and electrochemical doping alter the mechanical properties in terms of stiffness and ductility. Finally, the mechanical response of (doped) conjugated polymers is discussed in the context of (1) organic photovoltaics, representing thin-film devices with a relatively low charge-carrier density, (2) organic thermoelectrics, where chemical doping is used to realize thin films or bulk materials with a high doping level, and (3) organic electrochemical transistors, where electrochemical doping allows high charge-carrier densities to be reached, albeit accompanied by significant swelling. In the future, chemical and electrochemical doping may not only allow modulation and optimization of the electrical and electrochemical behavior of conjugated polymers, but also facilitate the design of materials with a tunable mechanical response. [ABSTRACT FROM AUTHOR]

Fabrication of multilayer thin films of solution‐processable organic semiconductors has great potential in organic electronics, but adopting existing thin‐film techniques to attain this is highly cumbersome. Herein, a unique unidirectional floating film transfer method has been utilized, which allows the facile fabrication of large area and oriented thin films of conjugated polymers. This method has successfully fabricated and characterized multilayer and oriented thin films of regioregular poly(3‐hexylthiophene) without having any adverse effect on the underlying layers. Optical characterizations reveal that fabricated thin films are anisotropic with a dichroic ratio of 2.2 having a single layer thickness of 14.5 nm. X‐ray diffraction results demonstrate uniformity in the crystallinity of the multilayered thin film with comparable crystallite size and interplanar spacing with purely edge‐on molecular orientation. The organic field effect transistor fabricates using multilayer thin films and also exhibits a uniform and saturated charge carrier mobility of about 0.1 cm2 V−1 s−1. [ABSTRACT FROM AUTHOR]

Thermal transport properties in acceptor‐doped thiophene‐based polymer films such as poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) and poly[2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] (PBTTT) are investigated using the cross‐plane 3‐omega method. A bilayer structure consisting of polymer semiconductors sequentially doped with 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ) and poly(methylmethacrylate) (PMMA) on a Si substrate is originally prepared by spin coating and employed to prevent leakage current from a heater wire during the 3‐omega measurements. Nondoped PBTTT thin film reveals an intrinsic cross‐plane thermal conductivity of 0.49 W m−1 K−1, which is higher than that for nondoped P3HT film (0.20 W m−1 K−1). X‐ray diffraction (XRD) analysis suggests that higher crystallinity of PBTTT films may result in higher thermal conductivity. The intrinsic thermal conductivity of P3HT and the interfacial thermal resistance between PMMA and P3HT are slightly increased at a low doping concentration (0.01 mg mL−1) and decreased at a higher doping concentration of 0.1 mg mL−1, whereas F4TCNQ doping reduces these values monotonously in the case of PBTTT layers. Furthermore, excess doping occurs only for P3HT and increments both intrinsic thermal conductivity and thermal resistance at PMMA/P3HT interface. The observed trend in the cross‐plane thermal transport caused by the sequential doping can be attributed to the differences between P3HT and PBTTT in their crystallinity and effective doping levels. [ABSTRACT FROM AUTHOR]

Circularly polarized luminescence (CPL) plays an important role in the development of advanced optical devices. However, the design of CPL-active materials with a decent dissymmetry factor is still challenging. Here, we report CPL-active transparent thin films made from optically active ruthenium complexes [Ru(bpy)3]2+ embedded in chiral inorganic frameworks. Due to the unique chiral-in-chiral combination, the obtained [Ru(bpy)3][Zn2(C2O4)3] displays CPL activity with a dissymmetry factor of 5 × 10−3. The CPL measurements show that the luminescence dissymmetry factor can be effectively enhanced by one order of magnitude when an optically active [Ru(bpy)3]2+ complex is incorporated into a chiral inorganic framework compared to its solution form. This study not only emphasizes the potential of constructing CPL-active thin films with coordination polymers but also points out the importance of introducing extra chiral environment to improve the CPL effect. [ABSTRACT FROM AUTHOR]

Self‐assembled nanocrystals (NCs) into superlattices (SLs) are alternative materials to polycrystalline films and single crystals, which can behave very differently from their constituents, especially when they interact coherently with each other. This work concentrates on the Superradiance (SR) emission observed in SLs formed by CsPbBr3 and CsPbBrI2 NCs. Micro‐Photoluminescence spectra and transients in the temperature range 4–100 K are measured in SLs to extract information about the SR states and uncoupled domains of NCs. For CsPbBr3 SLs with mostly homogeneous SR lines (linewidth 1–5 meV), this work measures lifetimes as short as 160 ps, 10 times lower than the value measured in a thin film made with the same NCs, which is due to domains of near identical NCs formed by 1000 to 40 000 NCs coupled by dipole–dipole interaction. The thermal decoherence of the SR exciton state is evident above 25 K due to its coupling with an effective phonon energy of ≈8 meV. These findings are an important step toward understanding the SR emission enhancement factor and the thermal dephasing process in perovskite SLs. [ABSTRACT FROM AUTHOR]

To impart high stretchability to semiconducting polymers, researchers have used a photocrosslinking approach based on the nitrene chemistry of an azide‐incorporated molecular additive. However, understanding of the molecular design of azide crosslinkers with respect to their effects on the electrical and mechanical properties of semiconducting polymer thin films is lacking. In this study, the effects of an azide photocrosslinker's molecular length and structure on the microstructural, electrical features, and stretchability of photocrosslinked conjugated polymer films is investigated. For a systematic comparison, a series of nitrene‐induced photocrosslinkers (n‐NIPSs) with different numbers of ethylene glycol repeating units (n = 1, 4, 8, 13) that bridge two tetrafluoro‐aryl azide end groups is synthesized. Two semicrystalline conjugated polymers and two nearly amorphous conjugated polymers are co‐processed with n‐NIPSs and crosslinked by brief exposure to UV light. It is found that, among the synthesized n‐NIPSs, the shortest one (1‐NIPS) is the most efficient in improving the stretchability of crosslinked indacenodithiophene‐benzothiadiazole films and that the improvement is achieved only with nearly amorphous polymers, not with semicrystalline conjugated polymers. On the basis of systematic studies, it is suggested that crosslinking density in amorphous regions is important in improving thin film stretchability. [ABSTRACT FROM AUTHOR]

Singlet exciton fission is a spin-allowed process in organic semiconductors by which one absorbed photon generates two triplet excitons. Theory predicts that singlet fission is mediated by intermolecular charge-transfer states in solid-state materials with appropriate singlet-triplet energy spacing, but direct evidence for the involvement of such states in the process has not been provided yet. Here, we report on the observation of subpicosecond singlet fission in mixed films of pentacene and perfluoropentacene. By combining transient spectroscopy measurements to nonadiabatic quantum-dynamics simulations, we show that direct excitation in the charge-transfer absorption band of the mixed films leads to the formation of triplet excitons, unambiguously proving that they act as intermediate states in the fission process. [ABSTRACT FROM AUTHOR]

Downscaling the semiconductor into ultrathin film is of vital importance to high‐performance field–effect transistors (FETs), but the high‐mobility FETs based on conjugated polymer monolayers have been rarely realized. Especially, the lack of high‐performance n‐type polymer monolayer FETs hinders the development of complementary integrated circuits. Herein, by fine‐tuning the supramolecular assembly of two thiazole flanked naphthalene diimide‐based conjugated polymers, the ≈2.5 nm‐thick monolayers with well‐defined fibrillar morphology are grown in a controllable way, where the one‐dimensional solution‐state structures are inherited. The resultant monolayer FETs show the electron mobility up to 0.25 cm2 V−1 s−1, among the record for n‐type polymer monolayer FETs. More importantly, the first demonstration of polymer monolayer complementary integrated circuits is present, and a record‐high inverter gain of 113 is achieved, which is also identical to the best polymer thin‐film inverters. [ABSTRACT FROM AUTHOR]

A method is presented to manipulate the final morphology of roll‐to‐roll slot‐die coated poly(3‐hexylthiophene) (P3HT) by optically exciting the p‐type polymer in solution while coating. These results provide a comprehensive picture of the entire knowledge chain, from demonstrating how to apply the authors' method to a fundamental understanding of the changes in morphology and physical properties induced by exciting P3HT while coating. By combining results from density functional theory and molecular dynamics simulations with a variety of X‐ray experiments, absorption spectroscopy, and THz spectroscopy, the relationship between morphology and physical properties of the thin film is demonstrated. Specifically, in P3HT films excited with light during deposition, changes in crystallinity and texture with more face‐on orientation and increased out‐of‐plane charge mobility are observed. [ABSTRACT FROM AUTHOR]

We show that chiral Frenkel excitons yield intense circularly polarized luminescence with an intrinsic dissymmetry factor in emission glum as high as 0.08. This outstanding value is measured through thin films of cyanine J‐aggregates that form twisted bundles. Our measurements, obtained by a Mueller polarization analysis, are artifact‐free and reveal a quasi‐perfect correlation between the dissymmetry factors in absorption, gabs, and in emission glum. We interpret the bisignate dissymmetry factors as the signature of a strong coupling between chiral Frenkel excitons longitudinally excited along the bundles. We further resolve by polarimetry analysis the split in energy between the excited states with a Davydov splitting as small as 28 meV. We finally show the anti‐Kasha nature of the chiral emission bands with opposite optical chirality. These mirror‐imaged emissive chiroptical features emerge from the structural rigidity of the bundles that preserves the ground‐ and excited‐state chirality. [ABSTRACT FROM AUTHOR]

The solid‐state molecular orientation of conjugated polymers is of vital importance for their charge transport properties, where the edge‐on orientation with π‐stacking direction parallel to the surface is generally preferable to achieving high‐mobility planar field‐effect transistors. However, so far, little is known about the origin of packing‐orientation formation in thin films. Here, it is shown that the solution‐state supramolecular structure of widely studied PffBT4T‐based polymers can be reversibly tuned between 1D worm‐like and 2D lamellar structures for the same polymer/solvent system through solution temperature. Such dimensionality in solution determines the solid‐state packing orientation of the polymer chains, where edge‐on and face‐on textures are generated from solutions with 1D and 2D structures, respectively. More importantly, the transition temperature of solution‐state supramolecular dimensionality is in excellent agreement with that of solid‐state packing orientation. These experimental observations unambiguously demonstrate the predominant roles of solution‐state supramolecular assembly in solid‐state molecular orientation, which is further verified using different molecular weight batches and other two representative polymers. The findings provide new insights into the growth mechanism of polymer semiconductors during transistor fabrication, and open prospective pathways for boosting device performance of solution‐processable plastic electronics. [ABSTRACT FROM AUTHOR]

We present a combined experimental and theoretical study to solve the unit-cell and molecular arrangement of the tetracene thin film (TF) phase. TF phases, also known as substrate induced phases (SIPs), are polymorphs that exist at interfaces and decisively impact the functionality of organic thin films, e.g., in a transistor channel, but also change the optical spectra due to the different molecular packing. As SIPs only exist in textured ultrathin films, their structure determination remains challenging compared to bulk materials. Here, we use grazing incidence X-ray diffraction and atomistic simulations to extract the TF unit-cell parameters of tetracene together with the atomic positions within the unit-cell. [ABSTRACT FROM AUTHOR]

Doping is an effective method to improve the electrical properties of organic semiconductors or insulators. However, current progress in organic n‐doping is limited relative to pdoping. Benzimidazole derivatives are representative organic n‐type dopants that have been widely applied, e. g. 1,3‐dimethyl‐2‐phenyl‐2,3‐dihydro‐1H‐benzo [d] imidazole (DMBI); its active unit is the phenyl tertiary carbon structure. Here, we designed and synthesized 11 small organic molecules with different phenyl tertiary carbon structures that were constituted by different heteroatoms (O, S, N) and several tertiary carbons to adjust the n‐doping performance. These molecules were then applied to dope polyalkylfluorene‐based organic semiconductor PFN to get a composite solid film. After optimization, the electrical conductivities of the prepared films were all enhanced by about three orders of magnitude. After experimentation and analysis, we confirmed that those dopants can effectively transfer their electrons to the host material. In addition, introducing the N atom to tertiary carbon and conjugating heteroatom with an aromatic ring improved its doping efficiency, but strong phase separation performance may result in limits on further heightening of conductivity. Therefore, these results are important for research into organic n‐type dopants. [ABSTRACT FROM AUTHOR]

Recent advances in quantum optics allow for exploration of boson dynamics in dissipative many-body systems. However, the traditional descriptions of quantum dissipation using reduced density matrices are unable to capture explicit information of bath dynamics. In this work, efficient evaluation of boson dynamics is demonstrated by combining the multiple Davydov Ansatz with finite-temperature timedependent variation, going beyond what state-of-the-art density matrix approaches are capable to offer for coupled electron-boson systems. To this end, applications are made to excitation energy transfer in photosynthetic systems, singlet fission in organic thin films, and circuit quantum electrodynamics in superconducting devices. Thanks to the multiple Davydov Ansatz, our analysis of boson dynamics leads to clear revelation of boson modes strongly coupled to electronic states, as well as in-depth description of polaron creation and destruction in the presence of thermal fluctuations. [ABSTRACT FROM AUTHOR]

The investigation of size confinement and chain orientation within the microstructure of a polymer thin film is very important for electronic device applications and fundamental research. Here, we present single step methodology for the synthesis of solution-processable poly (3-hexylthiophene) (P3HT) nanofibers via a self-assembly process. The formation of P3HT nanofibers is confirmed by atomic force microscopy. The synthesized nanofibers are characterized by UV-visible absorption, photoluminescence, and Raman spectroscopy. The aggregation type of self-assembled P3HT is studied by both UV-visible absorbance and photoluminescence spectroscopy. The exciton bandwidth in polymer films is calculated by following the Spano's H-aggregate model and found to be 28 meV. Raman spectroscopy is used to identify the various stretching modes present in nanofibers. The structural investigation using grazing angle X-ray diffraction of nanofibers reveals the presence of alkyl chain ordering. We have fabricated organic Schottky diodes with P3HT nanofibers on indium tin oxide (ITO) coated glass with configuration Al/P3HT/ITO, and current density-voltage characteristics are subsequently used for extracting the electronic parameters of the device. We have also discussed the charge transport mechanism at the metal/polymer interface. [ABSTRACT FROM AUTHOR]

The impact on chiral aggregation in solution processed and thermally annealed thin films of two indolenine and one anilino squaraines with chiral (S)‐citronellyl functionalization at the nitrogen of the squaraine backbone is investigated. A pseudo polymorphic crystal structure is obtained for one of the indolenine squaraines, but thin films of both compounds are basically non‐aggregated and truly isotropic as evidenced by spectroscopic ellipsometry. The anilino squaraine coalesces and readily aggregates to circular dichroic but discontinuous thin films. The extent of circular dichroism correlates with the morphology of the samples, which is quantified by Mueller matrix polarimetry in combination with atomic force microscopy. The shape of the CD spectra reinforces the hybrid Frenkel and charge‐transfer excitonic nature of the characteristic double hump signatures within unpolarized absorbance spectra of previously investigated non‐chiral anilino squaraines with linear alkyl chain functionalization. Such excitonic CD offers an additional design parameter for next‐generation opto‐electronic devices. [ABSTRACT FROM AUTHOR]

In biological imaging, red‐to‐infrared emissive dyes facilitate direct visualization of molecular interactions, through deep tissue penetration, along with minimal tissue damage. This work uses simple systems based on a single dye‐doped polymeric thin film for distributed feedback and random lasing investigations. As active compounds, novel push‐pull luminescent diphenylaminofluorene derivatives are used, functionalized with different acceptor groups. Integration of such luminescent dyes with a transparent polymeric medium allows fabrication of real‐time lasing tunability in the first biological window (650–950 nm). The observed spectral tuning of 150 nm is a groundbreaking value obtained in a single‐dye system. [ABSTRACT FROM AUTHOR]

Doping polymer semiconductors is a central topic in plastic electronics and especially in the design of novel thermoelectric (TE) materials. In this contribution, it has been demonstrated that doping of oriented semicrystalline P3HT thin films with the dopant tris(4‐bromophenyl)ammoniumyl hexachloroantimonate), known as magic blue (MB), helps reach charge conductivities of 3000 S cm−1 and TE power factors of 170 ± 30 μW mK−2 along the polymer chain direction. A combination of transmission electron microscopy, polarized optical absorption spectroscopy, Rutherford backscattering, and TE property measurements helps clarify the conditions necessary to achieve such high charge conductivities. A comparative study with different dopants demonstrates that the doping mechanism is intimately related to the semicrystalline structure of the polymer and whether crystalline, amorphous or both phases are doped. The highest charge mobilities are observed when the dopant MB is preferentially located in the amorphous phase of P3HT, leaving the structure of P3HT nanocrystals almost unaltered. In this case, the P3HT nanocrystals are doped from their interface with the surrounding amorphous phase. These results indicate that doping preferentially the amorphous phase of semicrystalline polymer semiconductors is an effective strategy to reduce polaron localization, enhance charge mobilities, and improve TE power factors. [ABSTRACT FROM AUTHOR]

Two D‐A copolymers consisting of fused ring pyrrolo‐dithieno‐quinoxaline acceptors are synthesized with different donor units, i.e., benzodithiophene (BDT) with alkylthienyl (P134) and 2‐ethylhexyloxy (P117) side chains. These copolymers are used as donors and a narrow bandgap acceptor Y6 to fabricate bulk heterojunction polymer solar cell devices. Owing to the strong electron‐deficient fused ring pyrrolo‐bithieno‐quinoxaline and weak alkyl thienyl side chains in BDT, the polymer solar cells (PSCs) based on P134:Y6 attain the power conversion efficiency (PCE) of 15.42%, which is higher than the P117:Y6 counterpart (12.14%). The superior value of PCE for P134:Y6 can be associated with more well‐adjusted charge transport, weak charge recombination, proficient exciton generation, and dissociation into free charge carriers and their subsequent charge collection owing to the dense π–π stacking distance and more considerable crystal coherence length for the P134:Y6 thin films. This investigation confirms the great potential of a strong acceptor‐weak donor tactic for developing efficient D‐A copolymers consists of quinoxaline acceptor for PSCs. [ABSTRACT FROM AUTHOR]

A series of non‐fullerene acceptors based on perylene monoimides coupled in the peri position through phenylene linkers were synthesized via Suzuki‐coupling reactions. Various substitution patterns were investigated using density functional theory (DFT) calculations in combination with experimental data to elucidate the geometry and their optical and electrochemical properties. Further investigations of the bulk properties with grazing incidence wide angle X‐ray scattering (GIWAXS) gave insight into the stacking behavior of the acceptor thin films. Electrochemical and morphological properties correlate with the photovoltaic performance of devices with the polymeric donor PBDB‐T and a maximum efficiency of 3.17 % was reached. The study gives detailed information about structure–property relationships of perylene‐linker‐perylene compounds. [ABSTRACT FROM AUTHOR]

Solution-processable precrystalline nanowires (NWs) of conjugated polymers (CPs) have garnered significant attention in fundamental research based on crystallization-driven self-assembly and in the roll-to-roll fabrication of optoelectronic devices, such as organic field-effect transistors, diodes, and solar cells. The highly crystalline NWs manufactured using a suitable solvent system ensure the improved performance of the solution-processable devices. Herein, we report a comprehensive understanding of how solubility-considering binary solvent selectivity and their mixing rates affect the growth of poly(3-hexylthiophene) (P3HT) into NWs and the transfer of the crystallinity and molecular orientation of precrystalline NWs determined in solutions to thin film. The crystal growth rate was controlled by varying the mixing rate of a good solvent (chloroform, CF) and various orthogonal solvents (marginal-, poor-, and non-solvents) with respect to the P3HT. Highly crystalline P3HT NWs were successfully obtained by slow diffusion of orthogonal solvents into a good solvent, even when non-solvents with vastly different Hansen solubility parameters to P3HT, such as acetonitrile and methanol, were used. The crystallinity and molecular orientation of precrystalline NWs were determined by the solvent quality and mixing rate, and their transfer efficacy was rationalized by considering the difference in the surface energies and boiling points between binary solvents. The large difference between CF and acetonitrile led to the formation of rapid, massive large aggregates of P3HT with precrystalline P3HT NWs after CF evaporation, providing the thin film deterioration. As a result, the well-defined NWs with high crystallinity, long conjugation length, and highly ordered edge-on molecular orientation were successfully fabricated in a mixed solvent of chloroform and hexane showing small differences in boiling point and surface tension, exhibiting the high charge-carrier mobilities in thin film devices. [ABSTRACT FROM AUTHOR]

Raman spectroscopy is a powerful technique that enables fingerprinting of materials, molecules, and chemical environments by probing vibrational resonances. In many applications, the desired Raman signals are masked by fluorescence, either from the molecular system being studied, or from adjacent metallic nanostructures. Here, it is shown that wavelength‐modulated Raman spectroscopy provides a powerful way to significantly reduce the strength of the fluorescence background, thereby allowing the desired Raman signals to be clearly recorded. This approach is made use of to explore Raman scattering in the context of vibrational strong coupling, an area that has thus far been problematic to visualise. Specifically, strong coupling between the vibrational modes in a polymer and two types of confined light field, the fundamental mode of a metal‐clad microcavity, and the surface‐plasmon modes of an adjacent thin metal film are looked at. While clear advantages in using the wavelength‐modulated Raman approach are found, these results on strong coupling are inconclusive, and highlight the need for more work in this exciting topic area. [ABSTRACT FROM AUTHOR]

Combining side chain engineering and controlled alignment of PBTTT is an effective strategy to produce oriented thin films with improved thermoelectric performance when doped sequentially with the acceptor molecule hexafluoro‐tetracyanonaphthoquinodimethane (F6TCNNQ). The substitution of linear alkyl side‐chains (n‐C12) with a chain of identical length including an ether function (n‐C7OC4) leads to a new class of slightly polar PBTTT polymers, preserving the ease of synthesis and air stability of alkylated PBTTTs. This side‐chain modification improves the structural order of PBTTT backbones and the thermo‐mechanical properties of the polymer. It then can be oriented by high temperature rubbing up to 240 °C to reach very high dichroic ratios up to 20 thanks to enhanced cohesive forces within side‐chain layers. The side chain polarity of n‐C7OC4 helps to tune the polymer‐dopant interactions. A multi‐technique approach demonstrates that F6TCNNQ dopants are randomly oriented in the disordered side chain layers of n‐C7OC4 with some evidence of dopant clustering. The combination of improved alignment and random orientation of intercalated F6TCNNQ dopants helps reach a very high charge conductivity σ = 5 ⋅ 104 S cm−1 and a record power factor of 2.9 mW m−1 K−2 in the polymer chain direction. [ABSTRACT FROM AUTHOR]

Steady‐state and time‐resolved photoluminescence (PL) and electrophotoluminescence (E‐PL) have been recorded for bulk heterojunction samples of thin films of regio‐regular poly(3‐hexylthiophene) (P3HT) and methyl [6,6]‐phenyl‐C61‐butanoate (PCBM). The PL spectra of the bulk heterojunction samples showed a monotonic decrease of PL quantum yield with increased PCBM content in the film. The PL decay was measured with both a femtosecond up‐conversion technique and a time‐correlated single‐photon‐counting technique. The mechanism of PL quenching deviated from a simple Stern‐Volmer equation, explained in terms of an apparent static quenching with a sphere‐of‐action model and dynamic quenching. With increased content of PCBM, the static quenching played a dominant role. Upon application of an electric field, the E‐PL spectra of both P3HT and bulk heterojunction samples showed an enhanced quantum yield and incremented lifetime of PL of P3HT. The long‐range electron transfer from P3HT to PCBM was retarded upon application of an electric field; the field‐induced change increased with increasing PCBM content. [ABSTRACT FROM AUTHOR]

Conjugated polymer‐based block copolymers (CP‐BCPs) are an unexplored class of materials for organic thermoelectrics. Herein, the authors report on the electronic conductivity (σ) and Seebeck coefficient (α) of a newly synthesized CP‐BCP, poly(3‐hexylthiophene)‐block‐poly (oligo‐oxyethylene methacrylate) (P3HT‐b‐POEM), upon solution co‐processing with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and subsequently vapor‐doping with a molecular dopant, 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane (F4TCNQ). It is found that the addition of the hydrophilic block POEM greatly enhances the processability of P3HT, enabling homogeneous solution‐mixing with LiTFSI. Notably, interactions between P3HT‐b‐POEM with ionic species significantly improve molecular order and unexpectedly cause electrical oxidizing doping of P3HT block both in solution and solid‐states, a phenomenon that has not been previously observed in Li‐salt containing P3HT. Vapor doping of P3HT‐b‐POEM‐LiTFSI thin films with F4TCNQ further enhances σ and yields a thermoelectric power factor PF= α2σ of 13.0 µW m−1 K−2, which is more than 20 times higher than salt‐free P3HT‐b‐POEM sample. Through modeling thermoelectric behaviors of P3HT‐b‐POEM with the Kang‐Snyder transport model, the improvement in PF is attributed to higher electronic charge mobility originating from the enhanced molecular ordering of P3HT. The results demonstrate that solution co‐processing CP‐BCPs with a salt is a powerful method to control structure and performance of organic thermoelectric materials. [ABSTRACT FROM AUTHOR]

Using optical spectroscopy in solution and thin film, and supported by quantum chemical calculations, we investigated the aggregation process of the donor-acceptor type molecule p-DTS(FBTTH2)2. We demonstrate that cooling a solution induces a disorder-order phase transition that proceeds in three stages analogous to the steps observed in semi-rigid conjugated polymers. By analyzing the spectra, we are able to identify the spectral signature of monomer and aggregate in absorption and emission. From this we find that in films, the fraction of aggregates is near 100% which is in contrast to films made from semi-rigid conjugated polymers. [ABSTRACT FROM AUTHOR]

The influence of N‐substituents on the photovoltaic properties of singly bay‐linked perylene diimides (diPDIs) was systematically investigated to understand the aromatic‐aliphatic balance, which is beneficial for achieving high device performance in organic photovoltaic (OPV) systems. The synthesis of various N‐substituted diPDIs was successfully achieved using a newly developed one‐step procedure, resulting in sufficiently high yields. Detailed investigations of seven variants of diPDIs demonstrated that the primary alkyl substituents, particularly the 2‐ethylhexyl group, induce the self‐organized growth of thin films with high crystallinity. This is beneficial for enhancing the device performance of bulk heterojunction (BHJ) systems. The results presented herein reveal the important roles of alkyl side chains as hydrophobic solubilizing auxiliaries or primary determinants in the control of the active layer nanomorphology. This offers a valuable guideline that is essential for developing high‐performance organic semiconductor materials for future practical applications. [ABSTRACT FROM AUTHOR]

Combining high‐throughput experiments with machine learning accelerates materials and process optimization toward user‐specified target properties. In this study, a rapid machine learning‐driven automated flow mixing setup with a high‐throughput drop‐casting system is introduced for thin film preparation, followed by fast characterization of proxy optical and target electrical properties that completes one cycle of learning with 160 unique samples in a single day, a >10× improvement relative to quantified, manual‐controlled baseline. Regio‐regular poly‐3‐hexylthiophene is combined with various types of carbon nanotubes, to identify the optimum composition and synthesis conditions to realize electrical conductivities as high as state‐of‐the‐art 1000 S cm−1. The results are subsequently verified and explained using offline high‐fidelity experiments. Graph‐based model selection strategies with classical regression that optimize among multi‐fidelity noisy input‐output measurements are introduced. These strategies present a robust machine‐learning driven high‐throughput experimental scheme that can be effectively applied to understand, optimize, and design new materials and composites. [ABSTRACT FROM AUTHOR]

Organic semiconductors offer a flexibility in band gap tuning through different molecular lengths and have shown to be promising candidates for high‐performance electronic devices. While electronic properties have been extensively studied in many publications, the topic of thin film structure and molecular packing is still quite neglected. In this work, the thin film crystal structure of [6]phenacene (Fulminene) and [7]phenacene deposited on silicon substrates using the OMBD method as well as further studies with potassium deposition on [6]phenacene are investigated. Ex‐situ X‐ray and optical methods are employed to obtain an insight into the crystal structure and optical properties. The orientation of the molecules and the unit cell structure is calculated from the measured reciprocal space maps. Additionally, the influence of a possible interfacial doping mechanism by deposition of potassium on top of [6]phenacene is investigated. Thin films of [6]phenacene show a high crystallinity with a standing‐up configuration and a similar molecular structure and symmetry compared to [4]phenacene. [7]phenacene features two different apparently thickness‐dependent polymorphs (H and L) with a structure similar to [5]phenacene. These results reveal that odd/even parity, that is, even or odd number of benzene rings, directly influences the phenacene thin film structure. [ABSTRACT FROM AUTHOR]

Recently, many researchers have tried to develop stretchable semiconducting thin films that can maintain their electrical performance under stretching. However, the fabrication processes have not been sufficiently practical and feasible to be used for soft electronics. Here, a stretchable high‐performance organic semiconducting thin film is fabricated by exploiting simultaneous patterning and pinning of a polymer semiconductor solution on an elastomeric substrate in which creasing‐instability has occurred. As a result, a mesh‐like polymer semiconducting thin film having vacant regions in the crease centers and surrounding crystalline regions near them can be fabricated. Due to the mesh‐like morphology and the percolated crystalline regions, the polymer semiconducting thin film shows superior stretchability and charge‐transport performance compared to the reference flat polymer thin film. When incorporated into organic thin‐film transistors, the DPP‐DTT polymer semiconducting thin film maintains its high field‐effect carrier mobility (0.53 ± 0.03 cm2 (V s)−1) under a strain ε of 80% and is highly stable under repeated stretching cycles at an ε of 50%. [ABSTRACT FROM AUTHOR]

Recent advances in optoelectronics are often based on thin‐film organic semiconductors. Interesting organic semiconductors are given by squaraines, small molecules that show excitonic coupling with visible light and are thus suitable for applications in solar cells and light sensors. While such squaraine thin films have already been proven to be suitable for stimulation of neuronal model cells, the integration into, e.g., the human eye to support blind people necessitates forming thin layers on seamless substrates. Herein, squaraine films are spin‐coated on electrospun nanofiber mats and nanomembranes, prepared from polyacrylonitrile, and made conductive by spin coating with poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). The fibrous non‐woven texture of the nanofiber mats and membranes alters the thin film formation of the squaraine compound considerably compared with preparation on planar, nonsoaking substrates such as glass and polyethylene terephthalate (PET) foil demanding further engineering regarding material's choice and processing conditions. [ABSTRACT FROM AUTHOR]

Donor–acceptor (D–A) type semiconducting polymers have shown great potential for the application of deformable and stretchable electronics in recent decades. However, due to their heterogeneous structure with rigid backbones and long solubilizing side chains, the fundamental understanding of their molecular picture upon mechanical deformation still lacks investigation. Here, the molecular orientation of diketopyrrolopyrrole (DPP)‐based D–A polymer thin films is probed under tensile deformation via both experimental measurements and molecular modeling. The detailed morphological analysis demonstrates highly aligned polymer crystallites upon deformation, while the degree of backbone alignment is limited within the crystalline domain. Besides, the aromatic ring on polymer backbones rotates parallel to the strain direction despite the relatively low overall chain anisotropy. The effect of side‐chain length on the DPP chain alignment is observed to be less noticeable. These observations are distinct from traditional linear‐chain semicrystalline polymers like polyethylene due to distinct characteristics of backbone/side‐chain combination and the crystallographic characteristics in DPP polymers. Furthermore, a stable and isotropic charge carrier mobility is obtained from fabricated organic field‐effect transistors. This study deconvolutes the alignment of different components within the thin‐film microstructure and highlights that crystallite rotation and chain slippage are the primary deformation mechanisms for semiconducting polymers. [ABSTRACT FROM AUTHOR]

Accurate determination of the photoluminescence (PL) spectrum of molecules is crucial in many areas including molecular diagnostics, genome analysis, and organic electronics. However, interpretation of experimental spectra from thin films can be complicated by phenomena extrinsic to the site of photon emission such as optical interference and self‐absorption. In this study, the alteration of fluorescence spectral lineshape is modeled from a thin film due to extrinsic factors as function of film thickness, incident angle, bandgap, and Stokes shift. The method is experimentally verified for thin (<400 nm) layers of molecular semiconductors on quartz substrates. Finally, a chart is provided for estimating the magnitude of the error due to extrinsic factors in the bandshape of fluorescence spectra from thin films. This demonstrates that the 0‐0/0‐1 intensity ratio, an indicator of the nature of excitonic coupling, is especially sensitive to possibly unconsidered influence from extrinsic effects. [ABSTRACT FROM AUTHOR]

We analyze the linear absorption spectrum of regioregular poly(3-hexylthiophene) films spun from a variety of solvents to probe directly the film microstructure and how it depends on processing conditions. We estimate the exciton bandwidth and the percentage of the film composed of aggregates quantitatively using a weakly interacting H-aggregate model. This provides a description of the degree and quality of crystallites within the film and is in turn correlated with thin-film field-effect transistor characteristics. [ABSTRACT FROM AUTHOR]

The solid state supramolecular interactions of diketopyrrolopyrrole derivatives (DPPs) and their correlation with thin film optical properties are of particular interest because of the applications of these materials in organic electronics. In this study, we report the single crystal X-ray structures of several phenyl DPP derivatives, containing 4-methoxyphenyl, 4-hydroxyphenyl and 4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl aryl units, and show how subtle changes in the substituent chains at side or end positions of the chromophore can lead to very different packing. They are compared to their phenyl counterpart to explore how the nature of both the alkyl chain and the aryl unit influence the optical properties that have been measured in solid and solution states. Importantly, for the three families of N-substituted compounds studied, the structures are changed by the conformation of the molecules and are apparently dominated by crystal packing effects where edge-to-face interactions are favoured rather than π stacking, with only one of the compounds showing a flat form, promoted by intermolecular contacts between the aromatic regions. It is therefore possible that the twist between DPP and phenyl units in crystals of DPPs results from edge-to-face interactions (rather than steric interactions between the N-substituent and the protons attached to the aromatic ring) that might be overcome in more extended structures. Hydrogen bonding dominates the packing to generate chains of DPP units for phenol derivatives. Remote bulky groups do affect the core conformation. The emission of the materials as thin films is dominated by local effects in the packing of the materials that are unique for each case as the structures are distinct from one another. Charge mobility (as calculated from the crystal structures) is not favoured because of twisted conformations and large displacement, but the sometimes high emission and large Stokes shift could make the materials interesting for other purposes, such as light emitters. [ABSTRACT FROM AUTHOR]

One important feature of organic semiconductors is their solution processability, which allows researchers to tune their aggregation states in solution and solid states and to control the processing conditions to reach desirable electronic and optoelectronic properties. Temperature is one of the most important processing parameters of organic semiconductors and has been studied extensively particularly for those conjugated small‐ and macro‐ molecules with strong temperature‐dependent aggregation properties. This minireview summarizes the temperature‐induced aggregation behaviors of organic semiconductors in solution, during solution casting and upon thermal annealing post‐treatment of solid‐state thin films. The influences of different aggregation states on the optoelectronic properties, in particular the photovoltaic properties, are discussed. The conclusions in this work will provide a rational guide to precisely control the aggregation states of organic semiconductors to fabricate high‐performance optoelectronic devices. [ABSTRACT FROM AUTHOR]

We report the design and testing of a custom-built experimental setup for dip-coating from volatile solutions under microgravity conditions onboard an aircraft. Function and safety considerations for the equipment are described. The equipment proved to work well, both concerning the safety and the preparation of thin films. No leakage of the solvents, nor the solvent vapors, was detected, not even in a situation with a fluctuating gravitational field due to bad weather conditions. We have shown that the equipment can be used to prepare thin films of polymer blends, relevant for organic solar cells, from solution in a feasible procedure under microgravity conditions. The prepared films are similar to the corresponding films prepared under 1 g conditions, but with differences that can be related to the absence of a gravitational field during drying of the applied liquid coating. We report on some introductory results from the characterization of the thin films that show differences in film morphology and structure sizes. [ABSTRACT FROM AUTHOR]

The rate of singlet fission, the process of generating two triplet excitons with photoexcitation of one singlet exciton, depends on a combination of singlet/triplet energy balance and intermolecular coupling. Here, we perform carboxylic acid functionalization of anthradithiophene (ADT) derivatives that results in hydrogen bonds that drive molecular orientation and strong electronic coupling of polycrystalline ADT thin films, leading to ultrafast singlet fission without significant enthalpic driving force. ADT with a single carboxylic acid group exhibits weak intermolecular coupling and slow and inefficient singlet fission, much like the parent ADT, and substitution of different alkylsilyl solubilizing groups has little effect. However, the addition of two carboxylic acid groups on either end of the long axis favors significant coupling and crystallinity in as‐deposited thin films that increase the effective singlet fission rate by roughly three orders of magnitude. The properties of the triplet pair, particularly its propensity to form long‐lived independent triplets, are also influenced by the degree of long‐range intermolecular coupling. The enhancement of intermolecular coupling specific to singlet fission using the ubiquitous cyclic hydrogen bonding motif could impact triplet pair utilization schemes in a variety of contexts. [ABSTRACT FROM AUTHOR]

Heterofission is a photophysical process of fundamental and applied interest whereby an excited singlet state is converted into two triplets on chemically distinct chromophores. The potential of this process lies in the tuning of both the optical band gap and the splitting between singlet and triplet energies. Herein, we report the time‐domain observation of heterofission in mixed thin films of the prototypical singlet fission chromophores pentacene and tetracene using excitation wavelengths above and below the tetracene band gap. We found a time constant of 26 ps for endothermic heterofission of a singlet exciton on pentacene in blends with low pentacene fractions, which was outcompeted by pentacene homofission for increasing pentacene concentrations. Direct excitation of tetracene lead to fast energy transfer to pentacene and subsequent singlet fission, which prevented homo‐ or heterofission of a singlet exciton on tetracene. [ABSTRACT FROM AUTHOR]

Single crystals of three at bay area tetraphenoxy‐substituted perylene bisimide dyes are grown by vacuum sublimation. X‐ray analysis reveals the self‐assembly of these highly twisted perylene bisimides (PBIs) in the solid state via imide–imide hydrogen bonding into hydrogen‐bonded PBI chains. The crystallographic insights disclose that the conformation and sterical congestion imparted by the phenoxy substituents can be controlled by ortho‐substituents. Accordingly, whilst sterically less demanding methyl and isopropyl substituents afford double‐stranded PBI chains of complementary P and M atropo‐enantiomers, single hydrogen‐bonded chains of homochiral PBIs are observed for the sterically more demanding ortho‐phenyl substituents. Investigation of the absorption and fluorescence properties of microcrystals and thin films of these PBIs allow for an unambiguous interpretation of these exciton systems. Thus, the J‐aggregates of the double‐stranded crystals exhibit a much larger (negative) exciton coupling than the single‐stranded one, which in contrast has the higher solid‐state fluorescence quantum yield. [ABSTRACT FROM AUTHOR]

Photoinduced oxidation (doping) of conjugated polymers by complexation with oxygen can have a significant impact on electronic properties and performance in device environments. Nanofiber model forms of poly(3‐hexylthiophene) (P3HT) are investigated using single molecule spectroscopy that possess similar morphological qualities as their bulk thin film counterparts yet, heterogeneity is confined to the spatial dimensions of these particles. Specifically, P3HT nanofibers assembled in anisole solutions contain both aggregated and nonaggregated (amorphous) chains with distinct electronic properties. Excitation intensity dependent photoluminescence (PL) emission imaging is then used to expose differences in oxygen affinity and reactivity upon photoexcitation. Nanofiber regions with low PL yields tend to show faster PL intensity saturation that also degrade much faster following periods of high excitation intensity soaking. Conversely, other regions show gains in PL intensity and virtually no saturation. These PL "gainer" and "loser" behaviors are assigned as originating from amorphous and aggregated P3HT chains, respectively. The apparent propensity of aggregated chains to undergo latent oxygen doping indicates a greater affinity probably due to a larger extent of electronic delocalization in these structures. The results shed new light on degradation factors studied frequently at the bulk material level, which often lacks sufficient sensitivity to specific structural forms. [ABSTRACT FROM AUTHOR]

Realizing high polymer chain orientation and ordered thin‐film microstructures is beneficial for efficient charge transport of conjugated polymers. However, achieving a high alignment degree remains a challenge due to the sensitive nature of polymers to the processing conditions. By simply varying concentrations during a dip‐coating method, the component of polymer aggregates that adopt the planar backbones is enlarged and the ensuing assembly process is promoted. Herein, highly oriented polymer thin films of an isoindigo‐based conjugated polymer (PII‐2T) are prepared to enhance polymer orientation resulting in a drastic booming in carrier mobilities of organic field‐effect‐transistors (OFETs). The maximum mobility from aligned polymer films increases by up to 8.3 cm2 V−1 s−1, which is tenfold beyond the value evaluated from the unaligned direction or traditional spin‐coated samples. The enhanced orientation can also reduce the adverse effects of the contact resistance and facilitate charge transport in transistors. This work demonstrates that the highly aligned conjugated polymer films can be approached by the dip‐coating method while offers a latent cornerstone toward understanding the critical role of processing‐related parameters in determining morphology of solution‐coated thin films. [ABSTRACT FROM AUTHOR]

The correlation between morphology and optoelectronic performance in organic thin‐film transistors based on blends of photochromic diarylethenes (DAE) and poly(3‐hexylthiophene) (P3HT) is investigated by varying molecular weight (Mw = 20–100 kDa) and regioregularity of the conjugated polymer as well as the temperature of thermal annealing (rt‐160 °C) in thin films. Semicrystalline architectures of P3HT/DAE blends comprise crystalline domains, ensuring efficient charge transport, and less aggregated regions, where DAEs are located as a result of their spontaneous expulsion from the crystalline domains during the self‐assembly. The best compromise between field‐effect mobility (μ) and switching capabilities is observed in blends containing P3HT with Mw = 50 kDa, exhibiting μ as high as 1 × 10−3 cm2 V−1 s−1 combined with a >50% photoswitching ratio. Higher or lower Mw than 50 kDa are found to be detrimental for field‐effect mobility and to lead to reduced device current switchability. The microstructure of the regioregular P3HT blend is found to be sensitive to the thermal annealing temperature, with an increase in μ and a decrease in current modulation being observed as a response to the light‐stimulus likely due to an increased P3HT‐DAE segregation, partially hindering DAE photoisomerization. The findings demonstrate the paramount importance of fine tuning the structure and morphology of bicomponent films for leveraging the multifunctional nature of optoelectronic devices. [ABSTRACT FROM AUTHOR]

A series of recently synthesized 1,3‐disubstituted imidazo[1,5‐a]pyridines (IPs) and ‐quinolines (IQs) targeting at increased efficiency of luminescence is investigated. The properties of molecules in solution as well as their change in the solid state are reported and assessed regarding possible application in organic electronics. The influence of increased ring size by substitution, e.g., exchanging phenyl to naphthalenyl, as well as pyridyl to quinolinyl moieties, and by means of a larger IQ fluorophore is discussed. A higher oscillator strength and quantum yield can be achieved. Frontier orbital energies are estimated based on cyclic voltammetry and density functional theory (DFT) calculations. Single crystals of molecules are grown. A red‐shift in the photoluminescence spectra found for crystals of IQs compared with those in solution is proposed to be caused by intermolecular coupling based on the parallel stacking of the enlarged fluorophore units. Thin films deposited by physical vapor deposition exhibit similar effects, showing promise as active layers in organic light‐emitting diodes (OLEDs). An amorphous morphology is inferred for these films from both spectral broadening in photoluminescence and atomic force microscopy. An OLED test structure is prepared, using the most efficient IQ lumophore and demonstrating the feasibility of obtaining electroluminescence from such thin films. [ABSTRACT FROM AUTHOR]

The mechano‐electrical properties of poly(3‐hexylthiophene) thin films are investigated as a function of their tie‐chain content. Tie chains play an indispensable role in enabling strain‐induced structural alignment and charge‐transport enhancement in the strain direction. In the absence of sufficient tie chains, the external mechanical force cannot induce any significant polymer backbone alignment locally or crystallite reorientation at the mesoscale. These samples instead undergo brittle fracture on deformation, with cracks forming normal to the direction of strain; charge transport in this direction is hindered as a consequence. This mechanistic insight on strain alignment points to the promise of leveraging tie‐chain fraction as a practical tuning knob for effecting the mechano‐electrical properties in conjugated polymer systems. [ABSTRACT FROM AUTHOR]