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.
Mechanical failure of π-conjugated polymer thin films is unavoidable under cyclic loading conditions, due to intrinsic defects and poor resistance to crack propagation. Here, the first tear-resistant and roomtemperature self-healable semiconducting composites is presented, consisting of conjugated polymers and butyl rubber elastomers. This new composite displays both record-low elastic modulus (< 1 MPa) and ultra-high deformability with fracture strain above 800%. More importantly, failure behavior is not sensitive to precut notches under deformation. Autonomous self-healing at room temperature, both mechanical and electronic, is demonstrated through physical contact of two separate films. The composite film also shows device stability in the ambient environment over five months due to muchimproved barrier property to both oxygen and water. Butyl rubber is broadly applicable to various Ptype and N-type semiconducting polymers for fabricating self-healable electronics to provide new resilient electronics that mimic the tear resistance and healable property of human skin.
There remains a lack of fundamental understanding in the role of backbone rigidity on the thermomechanical properties of conjugated polymers. Here, we provide the first holistic approach to understand the fundamental influence of backbone rigidity on an n-type naphthalene diimide-based conjugated polymer, denoted by PNDI-Cx, through insertion of a flexible conjugation break spacer (CBS). CBS lengths are varied from fully conjugated with zero alkyl spacer (PNDI-C0) to a seven-carbon alkyl spacer (PNDI-C7), with the CBS engineered into each repeat unit for systematic evaluation. Solution small-angle neutron scattering and oscillatory shear rheometry were employed to provide the first quantitative evidence of CBS influence over conjugated polymer chain rigidity and entanglement molecular weight (M e), demonstrating a reduction in the Kuhn length from 521 to 36 Å for fully conjugated PNDI-C0 and PNDI-C6, respectively, as well as a nearly consistent M e of ∼15 kDa upon the addition of CBS. Thermomechanical properties, such as elastic modulus and glass-transition temperature, were shown to decrease with an increasing length of CBS. An extraordinary ductility, upwards of 400% tensile strain before fracture, was observed for high-molecular-weight PNDI-C4, which we attribute to a high number of entanglements and disruption of crystallization. Furthermore, the deformation mechanism for PNDI-Cx was studied under strain through X-ray diffraction, polarized UV–vis spectroscopy, and atomic force microscopy. Overall, this work sheds light on the important role of backbone rigidity in designing flexible and stretchable conjugated polymers.
Conjugated polymers are emerging as promising building blocks for a broad range of modern applications including skin‐like electronics, wearable optoelectronics, and sensory technologies. In the past three decades, the optical and electronic properties of conjugated polymers have been extensively studied, while their thermomechanical properties, especially the glass transition phenomenon which fundamentally represents the polymer chain dynamics, have received much less attention. Currently, there is a lack of design rules that underpin the glass transition temperature of these semirigid conjugated polymers, putting a constraint on the rational polymer design for flexible stretchable devices and stable polymer glass that is needed for the devices’ long‐term morphology stability. In this review article, the glass transition phenomenon for polymers, glass transition theories, and characterization techniques are first discussed. Then previous studies on the glass transition phenomenon of conjugated polymers are reviewed and a few empirical design rules are proposed to fine‐tune the glass transition temperature for conjugated polymers. The review paper is finished with perspectives on future directions on studying the glass transition phenomena of conjugated polymers. The goal of this perspective is to draw attention to challenges and opportunities of controlling, predicting, and designing polymeric semiconductors, specifically to accommodate their end use.
Semiconducting donor-acceptor (D-A) polymers have attracted considerable attention towards 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 (T g ) with increasing side-chain length, which is further verified through coarse-grained molecular dynamics (CG-MD) simulations. Informed from experimental results, a mass-per-flexible bond model is developed to capture such observation through a linear This article is protected by copyright. All rights reserved. 3 correlation between T g and polymer chain flexibility. Using this model, a wide range of backbone T g 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 T g and modulus of future new D-A polymers.) The synthesis part was financially supported by the Natural Sciences and Engineering Research Council of Canada (NSERC) through a Discovery Grant (RGPIN-2017-06611), and by the Canadian Foundation for Innovation (CFI). M. U. O. thanks NSERC for a doctoral scholarship.
Intrinsic mechanical properties of sub-100 nm thin films are markedly difficult to obtain, yet an ever-growing necessity for emerging fields such as soft organic electronics. To complicate matters, the interfacial contribution plays a major role in such thin films and is often unexplored despite supporting substrates being a main component in current metrologies. Here we present the shear motion assisted robust transfer technique for fabricating free-standing sub-100 nm films and measuring their inherent structural–mechanical properties. We compare these results to water-supported measurements, exploring two phenomena: 1) The influence of confinement on mechanics and 2) the role of water on the mechanical properties of hydrophobic films. Upon confinement, polystyrene films exhibit increased strain at failure, and reduced yield stress, while modulus is reduced only for the thinnest 19 nm film. Water measurements demonstrate subtle differences in mechanics which we elucidate using quartz crystal microbalance and neutron reflectometry.
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.
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