The synthesis of a novel naphthalenediimide (NDI)-bithiazole (Tz2)-based polymer [P(NDI2OD-Tz2)] is reported, and structural, thin-film morphological, as well as charge transport and thermoelectric properties are compared to the parent and widely investigated NDI-bithiophene (T2) polymer [P(NDI2OD-T2)]. Since the steric repulsions in Tz2 are far lower than in T2, P(NDI2OD-Tz2) exhibits a more planar and rigid backbone, enhancing π-π chain stacking and intermolecular interactions. In addition, the electron-deficient nature of Tz2 enhances the polymer electron affinity, thus reducing the polymer donor-acceptor character. When n-doped with amines, P(NDI2OD-Tz2) achieves electrical conductivity (≈0.1 S cm ) and a power factor (1.5 µW m K ) far greater than those of P(NDI2OD-T2) (0.003 S cm and 0.012 µW m K , respectively). These results demonstrate that planarized NDI-based polymers with reduced donor-acceptor character can achieve substantial electrical conductivity and thermoelectric response.
We investigated the impact of Singly Occupied Molecular Orbital (SOMO) energy on the n-doping efficiency of benzimidazole-derivatives. By designing and synthesizing a series of new air-stable benzimidazole-based dopants with different SOMO energy levels, we demonstrated that an increase of the dopant SOMO energy by only ~0.3 eV enhances the electrical conductivity of a benchmark electron-transporting naphthalenediimide-bithiophene polymer by more than one order of magnitude. By combining electrical, X-ray diffraction, and electron paramagnetic resonance measurements with density functional theory calculations and analytical transport simulations, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, crystallinity of the doped polymer as a function of the dopant SOMO energy. Our findings strongly indicate that charge and energy transport are dominated by the (relative) position of the SOMO level, whereas morphological differences appear to play a lesser role. These results set molecular-design guidelines for next-generation ntype dopants.
Doping of organic semiconductors is a powerful tool to optimize the performance of various organic (opto)electronic and bioelectronic devices. Despite recent advances, the low thermal stability of the electronic properties of doped polymers still represents a significant obstacle to implementing these materials into practical applications. Hence, the development of conducting doped polymers with excellent long-term stability at elevated temperatures is highly desirable. Here, we report on the sequential doping of the ladder-type polymer poly(benzimidazobenzophenanthroline) (BBL) with a benzimidazole-based dopant (i.e., N-DMBI). By combining electrical, UV–vis/infrared, X-ray diffraction, and electron paramagnetic resonance measurements, we quantitatively characterized the conductivity, Seebeck coefficient, spin density, and microstructure of the sequentially doped polymer films as a function of the thermal annealing temperature. Importantly, we observed that the electrical conductivity of N-DMBI-doped BBL remains unchanged even after 20 h of heating at 190 °C. This finding is remarkable and of particular interest for organic thermoelectrics.
Two new conjugated polymers are synthesized based on a novel donor–acceptor–acceptor (D–A–A) design strategy with the intention of attaining lower lowest unoccupied molecular obital levels compared to the normally used D–A strategy. By coupling two thieno‐benzo‐isoindigo units together via the phenyl position to give a new symmetric benzene‐coupled di‐thieno‐benzo‐isoindigo (BdiTBI) monomer as an A–A acceptor and thiophene (T) or bithiophene (2T) as a donor, two new polymers PT‐BdiTBI and P2T‐BdiTBI are synthesized via Stille coupling. The two polymers are tested in top gate and top contact field effect transistors, which exhibit balanced ambipolar charge transport properties with poly(methyl methacrylate) as dielectric and a high hole mobility up to 1.1 cm2 V–1 s–1 with poly(trifluoroethylene) as dielectric. The polymer films are investigated using atomic force microscopy, which shows fibrous features due to their high crystallinity as indicated by grazing incidence wide‐angle X‐ray scattering. The theoretical calculations agree well with the experimental data on the energy levels. It is demonstrated that the D–A–A strategy is very effective for designing low band gap polymers for organic electronic applications.
Transfer printing techniques based on tunable adhesives that enable heterogeneous integration of materials in desired layouts are essential for developing existing and envisioned systems such as flexible electronics and micro‐LED (µ‐LED) displays. Here, a novel thermal controlled tunable adhesive, which not only has the ability of eliminating the interfacial adhesion for printing but also provides a new strategy for enhancing the interfacial adhesion for pick‐up is reported. The tunable adhesive features cavities filled with air on the surface. This simple construct offers thermal controlled suction and thrust with their amplitudes on the order of a few tens of kPa within 100 °C temperature change, which enables a reliable damage‐free transfer printing. Systematically theoretical and experimental studies reveal the underlying thermal induced pressure change mechanism and provide insights into the design and operation of the thermal controlled tunable adhesive. Demonstrations of this smart adhesive in manipulation of various surfaces and transfer printing of micro‐scale Si inks and µ‐LEDs illustrate its unusual capabilities for deterministic assembly by transfer printing.
Diketopyrrolopyrroles (DPP) have been recognized as a promising acceptor unit for construction of semiconducting donor–acceptor (D–A) polymers, which are typically flanked by spacers such as thiophene rings via a carbon–carbon single bond formation. It may suffer from a decrease in the coplanarity of the molecules especially when bulky side chains are installed. In this work, the two N atoms in the DPP unit are further fused with C-3 of the two flanking thiophene rings, yielding a π-expanded, very planar fused-ring building block (DPPFu). A novel DPPFu-based D–A copolymer (PBDTT-DPPFu) was successfully synthesized, consisting of a benzo[1,2- b :4,5- b ′]dithiophene (BDTT) unit as a donor and a DPPFu unit as an acceptor. For comparison, the unfused DPP-based counterpart PBDTT-DPP was also synthesized. Two dodecyl alkyl chains were attached to thiophene rings of DPP moieties to ensure good solubility of the DPPFu-based polymer. The influence of the ring-fusion effect on their structure, photophysical properties, electronic properties, molecular packing, and charge transport properties is investigated. Ring-fusion enhances the intermolecular interactions of PBDTT-DPPFu polymer chains as indicated by density functional theory calculation and analysis of electrostatic potential and van der Waals potential and results in significantly improved molecular packing for both the in-plane and out-of-plane directions as suggested by X-ray measurements. Finally, we correlate the molecular packing to the device performance by fabricating field-effect transistors based on these two polymers. The charge carrier mobility of the ring-fused polymer PBDTT-DPPFu is significantly higher as compared to the PBDTT-DPP polymer without ring-fusion, although PBDTT-DPPFu exhibited a much lower number-average molecular weight of 17 kDa as compared to PBDTT-DPP with a molecular weight of 108 kDa. The results from our comparative study provide a robust way to increase the interchain interaction by ring-fusion-promoted coplanarity.
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