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.

Physical Aging Behavior of the Side Chain of a Conjugated Polymer PBTTT.

This paper provides a viewpoint of the technology of the fast-scanning calorimetry with the relaxation behavior of disordered side chains of poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-C12) around the glass transition temperature of the side chains (Tg,γ). PBTTT is an ideal model of the high-performance copolymer of poly(alkylthiophenes) with side chains. The γ1 relaxation process of the disordered side chains of PBTTT was detected as a small endothermic peak that emerges before the γ2 relaxation process. It shows an increase with increasing temperature as it approaches the glass transition temperature of the disordered side chains of PBTTT. The ductile-brittle transition of PBTTT in low temperatures originating from the thermal relaxation process is probed and illustrated by physical aging experiments. The signature is shown that the relaxation process of the disordered side chain of PBTTT at low temperatures varies from Arrhenius temperature dependence to super Arrhenius temperature dependence at high temperatures. These observations could have significant consequences for the stability of devices based on conjugated polymers, especially those utilized for stretchable or flexible applications, or those demanding mechanical robustness during tensile fabrication or use in a low-temperature environment.

Tuning Conjugated Polymer Chain Packing for Stretchable Semiconductors.

In order to apply polymer semiconductors to stretchable electronics, they need to be easily deformed under strain without being damaged. A small number of conjugated polymers, typically with semicrystalline packing structures, have been reported to exhibit mechanical stretchability. Herein, a method is reported to modify polymer semiconductor packing-structure using a molecular additive, dioctyl phthalate (DOP), which is found to act as a molecular spacer, to be inserted between the amorphous chain networks and disrupt the crystalline packing. As a result, large-crystal growth is suppressed while short-range aggregations of conjugated polymers are promoted, which leads to an improved mechanical stretchability without affecting charge-carrier transport. Due to the reduced conjugated polymer intermolecular interactions, strain-induced chain alignment and crystallization are observed. By adding DOP to a well-known conjugated polymer, poly[2,5-bis(4-decyltetradecyl)pyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione-(E)-1,2-di(2,2'-bithiophen-5-yl)ethene] (DPPTVT), stretchable transistors are obtained with anisotropic charge-carrier mobilities under strain, and stable current output under strain up to 100%.

Conjugated Carbon Cyclic Nanorings as Additives for Intrinsically Stretchable Semiconducting Polymers.

Molecular additives are often used to enhance dynamic motion of polymeric chains, which subsequently alter the functional and physical properties of polymers. However, controlling the chain dynamics of semiconducting polymer thin films and understanding the fundamental mechanisms of such changes is a new area of research. Here, cycloparaphenylenes (CPPs) are used as conjugated molecular additives to tune the dynamic behaviors of diketopyrrolopyrrole-based (DPP-based) semiconducting polymers. It is observed that the addition of CPPs results in significant improvement in the stretchability of the DPP-based polymers without adversely affecting their mobility, which arises from the enhanced polymer dynamic motion and reduced long-range crystalline order. The polymer films retain their fiber-like morphology and short-range ordered aggregates, which leads to high mobility. Fully stretchable transistors are subsequently fabricated using CPP/semiconductor composites as active layers. These composites are observed to maintain high mobilities when strained and after repeated applied strains. Interestingly, CPPs are also observed to improve the contact resistance and charge transport of the fully stretchable transistors. ln summary, these results collectively indicate that controlling the dynamic motion of polymer semiconductors is proved to be an effective way to improve their stretchability.

Multi-scale ordering in highly stretchable polymer semiconducting films.

Stretchable semiconducting polymers have been developed as a key component to enable skin-like wearable electronics, but their electrical performance must be improved to enable more advanced functionalities. Here, we report a solution processing approach that can achieve multi-scale ordering and alignment of conjugated polymers in stretchable semiconductors to substantially improve their charge carrier mobility. Using solution shearing with a patterned microtrench coating blade, macroscale alignment of conjugated-polymer nanostructures was achieved along the charge transport direction. In conjunction, the nanoscale spatial confinement aligns chain conformation and promotes short-range π-π ordering, substantially reducing the energetic barrier for charge carrier transport. As a result, the mobilities of stretchable conjugated-polymer films have been enhanced up to threefold and maintained under a strain up to 100%. This method may also serve as the basis for large-area manufacturing of stretchable semiconducting films, as demonstrated by the roll-to-roll coating of metre-scale films.

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.

Highly stretchable polymer semiconductor films through the nanoconfinement effect.

Soft and conformable wearable electronics require stretchable semiconductors, but existing ones typically sacrifice charge transport mobility to achieve stretchability. We explore a concept based on the nanoconfinement of polymers to substantially improve the stretchability of polymer semiconductors, without affecting charge transport mobility. The increased polymer chain dynamics under nanoconfinement significantly reduces the modulus of the conjugated polymer and largely delays the onset of crack formation under strain. As a result, our fabricated semiconducting film can be stretched up to 100% strain without affecting mobility, retaining values comparable to that of amorphous silicon. The fully stretchable transistors exhibit high biaxial stretchability with minimal change in on current even when poked with a sharp object. We demonstrate a skinlike finger-wearable driver for a light-emitting diode.

Synthesis of Site-Specific Dye-Labeled Polymer via Atom Transfer Radical Polymerization (ATRP) for Quantitative Characterization of the Well-Defined Interchain Distance.

Novel difunctional initiators that incorporate Förster/fluorescence resonance energy transfer (FRET) pairs are generated to carry out atom transfer radical polymerization of styrene, methyl methacrylate, and n-butyl methacrylate monomers by an efficient manner. Based on the chemical structures of the initiators, the locations of the fluorophore moiety are dictated to be in the center of the chain with accurately quantified chain functionality (>90% labeling ratio). The site-specific integration of FRET dyes into separate polymer chain centers allows for characterization of the well-defined interchain distance quantitatively based on the response between these fluorescent probes. The reliability of this technique is verified in bulk state, which is in well agreement with the theoretical ones. This well-defined FRET system is expected to be a promising candidate to provide a distinct physical image at a microscopic level regarding scaling chain dimension, chain interpenetration, and polymer compatibility.