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 (
The glass transition temperature (
- Award ID(s):
- 1921854
- PAR ID:
- 10153442
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 11
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract T g) 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 inpara ‐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 lowT g, 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‐T gconjugated polymers for stretchable electronics. -
Abstract 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 (
T g) 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 betweenT gand polymer chain flexibility. Using this model, a wide range of backboneT gover 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 predictT gand elastic modulus of future new D–A polymers. -
Abstract The morphological stability of an organic photovoltaic (OPV) device is greatly affected by the dynamics of donors and acceptors occurring near the device's operational temperature. These dynamics can be quantified by the glass transition temperature (
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Abstract Conjugated polymers consist of complex backbone structures and side‐chain moieties to meet various optoelectronic and processing requirements. Recent work on conjugated polymers has been devoted to studying the mechanical properties and developing new conjugated polymers with low modulus and high‐crack onset strain, while the thin film mechanical stability under long‐term external tensile strain is less investigated. Here we performed direct mechanical stress relaxation tests for both free‐standing and thin film floated on water surface on both high‐
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ABSTRACT Thermomechanical properties of polymers highly depend on their glass transition temperature (
T g ). Differential scanning calorimetry (DSC) is commonly used to measureT g 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 measuringT g in such type of polymers. The changes in specific heat capacity (Δc p ) atT g were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δc p from flexible polymer (0.28 J g−1K−1for polystyrene) to rigid CPs (10−3J g−1K−1for 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 Δc p atT g by a factor of 10, confirming that backbone rigidity reduces the Δc p . Additionally, an increase in the crystalline fraction of the CPs further reduces Δc p . We conclude that the difficulties of determiningT g 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