Real-time correlation of crystallization and segmental order in conjugated polymers.

Modulating the segmental order in the morphology of conjugated polymers is widely recognized as a crucial factor for achieving optimal electronic properties and mechanical deformability. However, it is worth noting that the segmental order is typically associated with the crystallization process, which can result in rigid and brittle long-range ordered crystalline domains. To precisely control the morphology, a comprehensive understanding of how highly anisotropic conjugated polymers form segmentally ordered structures with ongoing crystallization is essential, yet currently elusive. To fill this knowledge gap, we developed a novel approach with a combination of stage-type fast scanning calorimetry and micro-Raman spectroscopy to capture the series of specimens with a continuum in the polymer percent crystallinity and detect the segmental order in real-time. Through the investigation of conjugated polymers with different backbones and side-chain structures, we observed a generally existing phenomenon that the degree of segmental order saturates before the maximum crystallinity is achieved. This disparity allows the conjugated polymers to achieve good charge carrier mobility while retaining good segmental dynamic mobility through the tailored treatment. Moreover, the crystallization temperature to obtain optimal segmental order can be predicted based on Tg and Tm of conjugated polymers. This in-depth characterization study provides fundamental insights into the evolution of segmental order during crystallization, which can aid in designing and controlling the optoelectronic and mechanical properties of conjugated polymers.

Facile Blending Strategy for Boosting the Conjugated Polymer Semiconductor Transistor's Mobility.

The optimization of field-effect mobility in polymer field-effect transistors (FETs) is a critical parameter for advancing organic electronics. Today, many challenges still persist in understanding the roles of the design and processing of semiconducting polymers toward electronic performance. To address this, a facile approach to solution processing using blends of PDPP-TVT and PTPA-3CN is developed, resulting in a 3.5-fold increase in hole mobility and retained stability in electrical performance over 3 cm2 V-1 s-1 after 20 weeks. The amorphous D-A conjugated structure and strong intramolecular polarity of PTPA-3CN are identified as major contributors to the observed improvements in mobility. Additionally, the composite analysis by X-ray photoelectron spectroscopy (XPS) and the flash differential scanning calorimetry (DSC) technique showed a uniform distribution and was well mixed in binary polymer systems. This mobility enhancement technique has also been successfully applied to other polymer semiconductor systems, offering a new design strategy for blending-type organic transistor systems. This blending methodology holds great promise for the practical applications of OFETs.

Recent Advances in Mechanically Robust and Stretchable Bulk Heterojunction Polymer Solar Cells.

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.

Covalent Cross-Linking of Diketopyrrolopyrrole-Based Organogels with Polydiacetylenes.

A new strategy toward functional materials with novel properties and well-defined structures has been developed through the topochemical polymerization of diacetylene-containing diketopyrrolopyrrole (DPP) derivatives. In order to enable the efficient photopolymerization and cross-linking of the materials, a rational design of DPP-based derivatives has been performed to incorporate amide moieties, thus enabling the formation of intermolecular hydrogen bonds and the formation of an organogel. The new materials showed good gelation properties in aromatic solvents, resulting in the formation of a dense fibrous network in the gel state. Upon UV irradiation, the supramolecular self-assemblies obtained were shown to be efficiently cross-linked through the conversion of diacetylene into polydiacetylene. A detailed investigation of new resulting materials was performed by a combination of morphological characterization tools, including X-ray diffraction, Raman spectroscopy, and atomic force microscopy. Our results demonstrate that the topochemical polymerization of diacetylene-containing DPP-based compounds is a promising strategy toward new electroactive and well-defined materials, without the use of catalysts or additives, thus creating new opportunities for the preparation and processing of π-conjugated materials.

Probing the Viscoelastic Property of Pseudo Free-Standing Conjugated Polymeric Thin Films.

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.