RESUMO
n-Doped polymers with high electrical conductivity (σ) are still very scarce in organic thermoelectrics (OTEs), which limits the development of efficient organic thermoelectric generators. A series of fused bithiophene imide dimer-based polymers, PO8, PO12, and PO16, incorporating distinct oligo(ethylene glycol) side-chain to optimize σ is reported here. Three polymers show a monotonic electron mobility decrease as side-chain size increasing due to the gradually lowered film crystallinity and change of backbone orientation. Interestingly, polymer PO12 with a moderate side-chain size delivers a champion σ up to 92.0 S cm-1 and a power factor (PF) as high as 94.3 µW m-1 K-2 in the series when applied in OTE devices. The PF value is among the highest ones for the solution-processing n-doped polymers. In-depth morphology studies unravel that the moderate crystallinity and the formation of 3D conduction channel derived from bimodal orientation synergistically contribute to high doping efficiency and large charge carrier mobility, thus resulting in high performance for the PO12-based OTEs. The results demonstrate the great power of simple tuning of side chain in developing n-type polymers with substantial σ for improving organic thermoelectric performance.
RESUMO
The development of n-type conjugated polymers with high electrical conductivity (σ) has continued to pose a massive challenge in organic thermoelectrics (OTEs). New structural insights into the charge-carrier transport are necessitated for the realization of high-performance OTEs. In this study, three new n-type copolymers, named pNB, pNB-Tz, and pNB-TzDP, consisting of naphthodithiophenediimide (NDTI) and bithiopheneimide (BTI) units, are synthesized by direct arylation polymerization. The backbone orientation is altered by incorporating thiazole units into the backbone and tuning the branching point of the side chain. The alteration of the backbone orientation from face-on to bimodal orientation with both face-on and edge-on fractions significantly impacts the σ and the power factors (PFs) of the polymers. As a result, pNB-TzDP, with the bimodal orientation, demonstrates a high σ of up to 11.6 S cm-1 and PF of up to 53.4 µW m-1 K-2 , which are among the highest in solution-processed n-doped conjugated polymers reported so far. Further studies reveal that the bimodal orientation of pNB-TzDP introduces 3D conduction channels and leads to better accommodation of dopants, which should be the key factors for the excellent thermoelectric performance.
RESUMO
Conjugated polymers with high thermoelectric performance enable the fabrication of low-cost, large-area, low-toxicity, and highly flexible thermoelectric devices. However, compared to their p-type counterparts, n-type polymer thermoelectric materials show much lower performance, which is largely due to inefficient doping and a much lower conductivity. Herein, it is reported that the development of a donor-acceptor (D-A) polymer with enhanced n-doping efficiency through donor engineering of the polymer backbone. Both a high n-type electrical conductivity of 1.30 S cm-1 and an excellent power factor (PF) of 4.65 µW mK-2 are obtained, which are the highest reported values among D-A polymers. The results of multiple characterization techniques indicate that electron-withdrawing modification of the donor units enhances the electron affinity of the polymer and changes the polymer packing orientation, leading to substantially improved miscibility and n-doping efficiency. Unlike previous studies in which improving the polymer-dopant miscibility typically resulted in lower mobilities, the strategy maintains the mobility of the polymer. All these factors lead to prominent enhancement of three orders magnitude in both the electrical conductivity and the PF compared to those of the non-engineered polymer. The results demonstrate that proper donor engineering can enhance the n-doping efficiency, electrical conductivity, and thermoelectric performance of D-A copolymers.