RESUMO
The performance of devices relying on organic electronic materials, such as organic field-effect transistors (OFET) and organic photovoltaics (OPV), is strongly correlated to the morphology of the conjugated material in thin films. For instance, several factors such as polymer solubility, weak intermolecular forces between polymers and fullerene derivatives, and film drying time impact phase separation in the active layer of a bulk heterojunction OPV device. In an effort to probe the influence of polymer assembly on morphology of polymer thin films and phase separation with fullerene derivatives, five terthiophene-alt-isoindigo copolymers were synthesized with alkyl side-chains of varying lengths and branching on the terthiophene unit. These P[T3(R)-iI] polymers were designed to have similar optoelectronic properties but different solubilities in o-dichlorobenzene and were predicted to have different tendencies for crystallization. All polymers with linear alkyl chains exhibit similar thin film morphologies as investigated by grazing-incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM). The main differences in electronic and morphological properties arise when P[T3(R)-iI] is substituted with branched 2-ethylhexyl (2EH) side-chains. The bulky 2EH substituents lead to a blue-shifted absorption, a lower ionization potential, and reduced ordering in polymer thin films. The five P[T3-iI] derivatives span hole mobilities from 1.5 × 10-3 to 2.8 × 10-2 cm2 V-1 s-1 in OFET devices. In OPV devices, the 2EH-substituted polymers yield open-circuit voltages of 0.88 V in BHJ devices yet low short-circuit currents of 0.8 mA cm-2, which is explained by the large phase separation observed by AFM in blends of P[T3(2EH)-iI] with PC71BM. In these P[T3(R)-iI] systems, the propensity for the polymers to self-assemble prior to aggregation of PC71BM molecules was key to achieving fine phase separation and increased short-circuit currents, eventually resulting in power conversion efficiencies of 5% in devices processed using a single solvent.
RESUMO
Very few studies have reported oriented crystallization of conjugated polymers directly in solution. Here, solution crystallization of conjugated polymers in a microfluidic system is found to produce tightly π-stacked fibers with commensurate improved charge transport characteristics. For poly(3-hexylthiophene) (P3HT) films, processing under flow caused exciton bandwidth to decrease from 140 to 25 meV, π-π stacking distance to decrease from 3.93 to 3.72 Å and hole mobility to increase from an average of 0.013 to 0.16 cm(2) V(-1) s(-1), vs films spin-coated from pristine, untreated solutions. Variation of the flow rate affected thin-film structure and properties, with an intermediate flow rate of 0.25 m s(-1) yielding the optimal π-π stacking distance and mobility. The flow process included sequential cooling followed by low-dose ultraviolet irradiation that promoted growth of conjugated polymer fibers. Image analysis coupled with mechanistic interpretation supports the supposition that "tie chains" provide for charge transport pathways between nanoaggregated structures. The "microfluidic flow enhanced semiconducting polymer crystal engineering" was also successfully applied to a representative electron transport polymer and a nonhalogenated solvent. The process can be applied as a general strategy and is expected to facilitate the fabrication of high-performance electrically active polymer devices.
RESUMO
A new solution-processable small-molecule containing electron-poor naphthalene diimide and tetrazine moieties has been synthesized. The optimized spin-coated n-channel OFETs on glass substrate shows electron mobility value up to 0.15 cm(2) V(-1) s(-1) . Inkjet-printed OFETs are fabricated in ambient atmosphere on flexible plastic substrates, which exhibits an electron mobility value up to 0.17 cm(2) V(-1) s(-1) and also shows excellent environmental and operational stability.