RESUMEN
Conjugated polymers with ethylene glycol-type side chains are commonly used as channel materials in organic electrochemical transistors (OECTs). To improve the performance of these materials, new chemical structures are often created through synthetic routines. Herein, we demonstrate that the OECT performance of these polymers can also be improved by changing their density-of-state (DOS) profile through solvent engineering. Depending on the solvent polarity, it solvates the backbone and side chains of the conjugated polymer differently, leading to differences in molecule orientation, π-stacking paracrystallinity, and film defects, such as grain boundaries and pinholes. This then results in a change in the DOS profile of the polymer. A more intense and narrow-width DOS distribution is usually observed in organic films with an "edge on" orientation and fewer film defects, while films with a "face on" orientation and apparent defects show a broadened DOS profile. The OECT devices that use the polymer film with a more intense and narrow-width DOS profile exhibit a better-normalized transconductance and figure-of-merit µC* than those with a broadened DOS profile (0.74 to 4.29 S cm-1 and 3.5 to 14.3 F cm-1 V-1 s-1). This study provides useful insights into how the DOS profile affects the mixed ionic-electronic conduction performance and presents a new avenue for improving n-type OECT materials.
RESUMEN
The general strategy for n-type organic thermoelectric is to blend n-type conjugated polymer hosts with small molecule dopants. In this work, all-polymer n-type thermoelectric is reported by dissolving a novel n-type conjugated polymer and a polymer dopant, poly(ethyleneimine) (PEI), in alcohol solution, followed by spin-coating to give polymer host/polymer dopant blend film. To this end, an alcohol-soluble n-type conjugated polymer is developed by attaching polar and branched oligo (ethylene glycol) (OEG) side chains to a cyano-substituted poly(thiophene-alt-co-thiazole) main chain. The main chain results in the n-type property and the OEG side chain leads to the solubility in hexafluorineisopropanol (HFIP). In the polymer host/polymer dopant blend film, the Coulombic interaction between the dopant counterions and the negatively charged polymer chains is reduced and the ordered stacking of the polymer host is preserved. As a result, the polymer host/polymer dopant blend exhibits the power factor of 36.9 µW m-1 K-1, which is one time higher than that of the control polymer host/small molecule dopant blend. Moreover, the polymer host/polymer dopant blend shows much better thermal stability than the control polymer host/small molecule dopant blend. This research demonstrates the high performance and excellent stability of all-polymer n-type thermoelectric.
RESUMEN
The ability of n-type polymer thermoelectric materials to tolerate high doping loading limits further development of n-type polymer conductivity. Herein, two alcohol-soluble n-type polythiophene derivatives that are n-PT3 and n-PT4 are reported. Due to the ability of two polymers to tolerate doping loading more significantly than 100 mol%, both achieve electrical conductivity >100 S cm-1 . Moreover, the conductivity of both polythiophenes remains almost constant at high doping concentrations with excellent doping tunability, which may be related to their ability to overcome charging-induced backbone torsion and morphology change caused by saturated doping. The characterizations reveal that n-PT4 has a high doping level and carrier concentration (>3.10 × 1020 cm-3 ), and the carrier concentration continues to increase as the doping concentration increases. In addition, doping leads to improved crystal structure of n-PT4, and the crystallinity does not decrease significantly with increasing doping concentration; even the carrier mobility increases with it. The synergistic effect of these two leads to both n-PT3 and n-PT4 achieving a breakthrough of 100 in conductivity and power factor. The DMlmC-doped n-PT4 achieves a power factor of over 150 µW m-1 K-2 . These values are among the highest for n-type organic thermoelectric materials.