Materials design for ambipolar devices: tuning orbital energetics in oligothiophene-naphthalimides semiconductors

Ambipolar organic field-effect transistors (OFETs), which can efficiently transport both holes and electrons, using a single type of electrode, are currently of great interest due to their possible applications in complementary metal oxide semiconductor (CMOS)-like circuits, sensors, and in light-emitting transistors. Several theoretical and experimental studies have argued that most organic semiconductors should be able to transport both types of carrier, although typically unipolar behavior is observed. One factor that can compromise ambipolar transport in organic semiconductors is poor solid state overlap between the HOMO (p-type) or LUMO (n-type) orbitals of neighboring molecules in the semiconductor thin film. In the search of low-bandgap ambipolar materials, where the absence of skeletal distortions allows closer intermolecular π-π stacking and enhanced intramolecular π-conjugation, a new family of oligothiophene-naphthalimide assemblies have been synthesized and characterized, in which both donor and acceptor moieties are directly conjugated through rigid linkers. In previous works we found that oligothiophene-napthalimide assemblies connected through amidine linkers (NDI derivates) exhibit skeletal distortions (50-60º) arising from steric hindrance between the carbonyl group of the arylene core and the sulphur atom of the neighbored thiophene ring (see Figure 1). In the present work we report novel oligo- and polythiophene–naphthalimide analogues NAI-3T, NAI-5T and poly-NAI-8C-3T, in which the connections of the amidine linkage have been inverted in order to prevent steric interactions. Thus, the nitrogen atoms are directly connected to the naphthalene moiety in NAI derivatives while they were attached directly to the thiophene moiety in the previously investigated NDI-3T and NDI-5T. In Figure 1 is depicted the calculated molecular structure of NAI-3T together with that of NDI-3T showing how the steric interactions are not present in the novel NAI derivative. The planar skeletons in these new family induce higher degree of crystallinity and the carrier charge transport can be switched from n-type to ambipolar behaviour. The highest FET performance is achieved for vapor-deposited films of NAI-3T with mobilities of 1.95x10-4cm2V-1s-1 and 2.00x10-4cm2V-1s-1 for electrons and holes, respectively. Finally, these planar semiconductors are compared with their NDI derivates analogues, which exhibit only n-type mobility, in order to understand the origin of the ambipolarity in this new series of molecular semiconductors.

The influence of organic amendments on soil aggregate stability from semiarid sites

Restoring the native vegetation is the most effective way to regenerate soil health. Under these conditions, vegetation cover in areas having degraded soils may be better sustained if the soil is amended with an external source of organic matter. The addition of organic materials to soils also increases infiltration rates and reduces erosion rates; these factors contribute to an available water increment and a successful and sustainable land management. The goal of this study was to analyze the effect of various organic amendments on the aggregate stability of soils in afforested plots. An experimental paired-plot layout was established in southern of Spain (homogeneous slope gradient: 7.5%; aspect: N170). Five amendments were applied in an experimental set of plots: straw mulching; mulch with chipped branches of Aleppo Pine (Pinus halepensis L.); TerraCotten hydroabsobent polymers; sewage sludge; sheep manure and control. Plots were afforested following the same spatial pattern, and amendments were mixed with the soil at the rate 10 Mg ha-1. The vegetation was planted in a grid pattern with 0.5 m between plants in each plot. During the afforestation process the soil was tilled to 25 cm depth from the surface. Soil from the afforested plots was sampled in: i) 6 months post-afforestation; ii) 12 months post-afforestation; iii) 18 months post-afforestation; and iv) 24 months post-afforestation. The sampling strategy for each plot involved collection of 4 disturbed soil samples taken from the surface (0–10 cm depth). The stability of aggregates was measured by wet-sieving. Regarding to soil aggregate stability, the percentage of stable aggregates has increased slightly in all the treatments in relation to control. Specifically, the differences were recorded in the fraction of macroaggregates (≥ 0.250 mm). The largest increases have been associated with straw mulch, pinus mulch and sludge. Similar results have been registered for the soil organic carbon content. Independent of the soil management, after six months, no significant differences in microaggregates were found regarding to the control plots. These results showed an increase in the stability of the macroaggregates when soil is amended with sludge, pinus mulch and straw much. This fact has been due to an increase in the number cementing agents due to: (i) the application of pinus, straw and sludge had resulted in the release of carbohydrates to the soil; and thus (ii) it has favored the development of a protective vegetation cover, which has increased the number of roots in the soil and the organic contribution to it.