RESUMEN
Tailoring organic semiconductors to facilitate mixed conduction of ionic and electronic charges when interfaced with an aqueous media has spurred many recent advances in organic bioelectronics. The field is still restricted, however, by very few n-type (electron-transporting) organic semiconductors with adequate performance metrics. Here, a new electron-deficient, fused polycyclic aromatic system, TNR, is reported with excellent n-type mixed conduction properties including a µC* figure-of-merit value exceeding 30 F cm-1 V-1 s-1 for the best performing derivative. Comprising three naphthalene bis-isatin moieties, this new molecular design builds on successful small-molecule mixed conductors; by extending the molecular scaffold into the oligomer domain, good film-forming properties, strong π-π interactions, and consequently excellent charge-transport properties are obtained. Through judicious optimization of the side chains, the linear oligoether and branched alkyl chain derivative bgTNR is obtained which shows superior mixed conduction in an organic electrochemical transistor configuration including an electron mobility around 0.3 cm2 V-1 s-1 . By optimizing the side chains, the dominant molecular packing can be changed from a preferential edge-on orientation (with high charge-transport anisotropy) to an oblique orientation that can support 3D transport pathways which in turn ensure highly efficient mixed conduction properties across the bulk semiconductor film.
RESUMEN
In the development of high-performance organic thermoelectric devices, n-type materials, especially with small molecule semiconductors, lags far behind p-type materials. In this paper, three small molecules are synthesized based on electron-deficient naphthalene bis-isatin building blocks bearing different alkyl chains with the terminal functionalized with 3-ethylrhodanine unit and studied their aggregation and doping mechanism in detail. It is found that crystallinity plays an essential role in tuning the doping behavior of small molecules. Molecules with too strong crystallinity tend to aggregate with each other to form large crystalline domains, which cause significant performance degradation. While molecules with weak crystallinity can tolerate more dopants, most of them exhibit low mobility. By tuning the crystallinity carefully, organic thermoelectric devices based on C12NR can maintain high mobility and realize effective doping simultaneously, and a high power factor of 1.07 µW m-1 K-2 at 100 °C is realized. This delicate molecular design by modulating crystallinity provides a new avenue for realizing high-performance organic thermoelectric devices.
RESUMEN
The primary challenge for n-type small-molecule organic electrochemical transistors (OECTs) is to improve their electron mobilities and thus the key figure of merit µC*. Nevertheless, few reports in OECTs have specially proposed to address this issue. Herein, we report a 10-ring-fused polycyclic π-system consisting of the core of naphthalene bis-isatin dimer and the terminal moieties of rhodanine, which features intramolecular noncovalent interactions, high π-delocalization and strong electron-deficient characteristics. We find that this extended π-conjugated system using the ring fusion strategy displays improved electron mobilities up to 0.043â cm2 V-1 s-1 compared to our previously reported small molecule gNR, and thereby leads to a remarkable µC* of 10.3â F cm-1 V-1 s-1 in n-type OECTs, which is the highest value reported to date for small-molecule OECTs. This work highlights the importance of π-conjugation extension in polycyclic-fused molecules for enhancing the performance of n-type small-molecule OECTs.
RESUMEN
Tuning the film morphology and aggregated structure is a vital means to improve the performance of the mixed ionic-electronic conductors in organic electrochemical transistors (OECTs). Herein, three fluorinated alcohols (FAs), including 2,2,2-trifluoroethanol (TFE), 1,1,1,3,3,3-hexafluoroisopropanol (HFIP), and perfluoro-tert-butanol (PFTB), were employed as the alternative solvents for engineering the n-type small-molecule active layer gNR. Remarkedly, an impressive µC* of 5.12 F V-1 cm-1 s-1 and a normalized transconductance of 1.216 S cm-1 are achieved from the HFIP-fabricated gNR OECTs, which is three times higher than that of chloroform. The operational stability has been significantly enhanced by the FA-fabricated devices. Such enhancements can be ascribed to the aggregation-induced structural ordering by FAs during spin coating, which optimizes the microstructure of the films for a better mixed ion and electron transport. These results prove the huge research potential of FAs to improve OECT materials' processability, device performance, and stability, therefore promoting practical bio-applications.
RESUMEN
Small-molecule semiconductors used as the channel of organic electrochemical transistors (OECTs) have been rarely reported despite their inherent advantages of well-defined molecular weight, convenient scale-up synthesis, and good performance reproducibility. Herein, three small molecules based on perylene diimides are readily prepared for n-type OECTs. The final molecules show preferred energy levels, tunable backbone conformation, and high film crystallinity, rendering them good n-type dopability, favorable volumetric capacities, and substantial electron mobilities. Consequently, the OECTs afford a record-low threshold voltage of 0.05 V and a normalized peak transconductance of 4.52 × 10-2 S cm-1, as well as impressive long-term cycling stability. Significantly, the OECTs utilized for hydrogen peroxide sensing are further demonstrated with a detection limit of 0.75 µM. This work opens the possibility of developing nonfullerene small molecules as superior n-type OECT materials and provides important insights for designing high-performance small-molecule mixed ion-electron conductors for OECTs and (bio)sensors.
