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Despite having favorable optoelectronic and thermomechanical properties, the wide application of semiconducting polymers still suffers from limitations, particularly with regards to their processing in solution which necessitates toxic chlorinated solvents due to their intrinsic low solubility in common organic solvents. This work presents a novel greener approach to the fabrication of organic electronics without the use of toxic chlorinated solvents. Low‐molecular‐weight non‐toxic branched polyethylene (BPE) is used as a solvent to process diketopyrrolopyrrole‐based semiconducting polymers, then the solvent‐induced phase separation (SIPS) technique is adopted to produce films of semiconducting polymers from solution for the fabrication of organic field‐effect transistors (OFETs). The films of semiconducting polymers prepared from BPE using SIPS show a more porous granular morphology with preferential edge‐on crystalline orientation compared to the semiconducting polymer film processed from chloroform. OFETs based on the semiconducting films processed from BPE show similar device characteristics to those prepared from chloroform without thermal annealing, confirming the efficiency and suitability of BPE to replace traditional chlorinated solvents for green organic electronics. This new greener processing approach for semiconducting polymers is potentially compatible with different printing techniques and is particularly promising for the preparation of porous semiconducting layers and the fabrication of OFET‐based electronics. [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]

Semiconducting donor–acceptor (D–A) polymers have attracted considerable attention toward the application of organic electronic and optoelectronic devices. However, a rational design rule for making semiconducting polymers with desired thermal and mechanical properties is currently lacking, which greatly limits the development of new polymers for advanced applications. Here, polydiketopyrrolopyrrole (PDPP)‐based D–A polymers with varied alkyl side‐chain lengths and backbone moieties are systematically designed, followed by investigating their thermal and thin film mechanical responses. The experimental results show a reduction in both elastic modulus and glass transition temperature (Tg) with increasing side‐chain length, which is further verified through coarse‐grained molecular dynamics simulations. Informed from experimental results, a mass‐per‐flexible bond model is developed to capture such observation through a linear correlation between Tg and polymer chain flexibility. Using this model, a wide range of backbone Tg over 80 °C and elastic modulus over 400 MPa can be predicted for PDPP‐based polymers. This study highlights the important role of side‐chain structure in influencing the thermomechanical performance of conjugated polymers, and provides an effective strategy to design and predict Tg and elastic modulus of future new D–A polymers. [ABSTRACT FROM AUTHOR]

Thermomechanical properties of polymers highly depend on their glass transition temperature (Tg). Differential scanning calorimetry (DSC) is commonly used to measure Tg of polymers. However, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring Tg in such type of polymers. The changes in specific heat capacity (Δcp) at Tg were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δcp from flexible polymer (0.28 J g−1 K−1 for polystyrene) to rigid CPs (10−3 J g−1 K−1 for a naphthalene diimide‐based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δcp at Tg by a factor of 10, confirming that backbone rigidity reduces the Δcp. Additionally, an increase in the crystalline fraction of the CPs further reduces Δcp. We conclude that the difficulties of determining Tg for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D‐A CPs with weak transition signals. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1635–1644 [ABSTRACT FROM AUTHOR]

Organic bulk heterojunction solar cells are promising candidates as future photovoltaic technologies for large‐scale and low‐cost energy production. It is, therefore, not surprising that research on the design and preparation of these types of organic photovoltaics has attracted a lot of attention since the last two decades, leading to constantly growing values of energy conversion and efficiency. Combined with the possibility of a large‐scale production via roll‐to‐roll printing techniques, bulk heterojunction solar cells enable the fabrication of conformable, light‐weight and flexible light‐harvesting devices for point‐of‐use applications. This perspective review will highlight the recent advances toward mechanically robust and intrinsically stretchable bulk heterojunction solar cells. Mechanically robust fullerene‐based and all‐polymer devices will be presented, as well as a comprehensive overview of the recent challenges and characterization techniques recently developed to overcome some of the challenges of this research area, which is still in its infancy. [ABSTRACT FROM AUTHOR]

Abstract: The understanding of the structure‐mechanical property relationship for semiconducting polymers is essential for the application of flexible organic electronics. Herein pseudo free‐standing tensile testing, a technique that measures the mechanical property of thin films floating on the surface of water, is used to obtain the stress–strain behaviors of two semiconducting polymers, poly(3‐hexylthiophene) (P3HT) and poly(2,5‐bis(2‐decyltetradecyl)‐3,6‐di(thiophen‐2‐yl)diketopyrrolo[3,4‐c]pyrrole‐1,4‐dione‐alt‐thienovinylthiophene (DPP‐TVT) donor–acceptor (D–A) polymer. To our surprise, DPP‐TVT shows similar viscoelastic behavior to P3HT, despite DPP‐TVT possessing a larger conjugated backbone and much higher charge carrier mobility. The viscoelastic behavior of these polymers is due to sub room temperature glass transition temperatures (Tg), as shown by AC chip calorimetry. These results provide a comprehensive understanding of the viscoelastic properties of conjugated D–A polymers by thickness‐dependent, strain rate dependent, hysteresis tests, and stress‐relaxation tests, highlighting the importance of Tg for designing intrinsically stretchable conjugated polymers. [ABSTRACT FROM AUTHOR]

Organic semiconducting donor–acceptor polymers are promising candidates for stretchable electronics owing to their mechanical compliance. However, the effect of the electron‐donating thiophene group on the thermomechanical properties of conjugated polymers has not been carefully studied. Here, thin‐film mechanical properties are investigated for diketopyrrolopyrrole (DPP)‐based conjugated polymers with varying numbers of isolated thiophene moieties and sizes of fused thiophene rings in the polymer backbone. Interestingly, it is found that these thiophene units act as an antiplasticizer, where more isolated thiophene rings or bigger fused rings result in an increased glass transition temperature (Tg) of the polymer backbone, and consequently elastic modulus of the respective DPP polymers. Detailed morphological studies suggests that all samples show similar semicrystalline morphology. This antiplasticization effect also exists in para‐azaquinodimethane‐based conjugated polymers, indicating that this can be a general trend for various conjugated polymer systems. Using the knowledge gained above, a new DPP‐based polymer with increased alkyl side chain density through attaching alky chains to the thiophene unit is engineered. The new DPP polymer demonstrates a record low Tg, and 50% lower elastic modulus than a reference polymer without side‐chain decorated on the thiophene unit. This work provides a general design rule for making low‐Tg conjugated polymers for stretchable electronics. [ABSTRACT FROM AUTHOR]