Raman Spectroscopy and DFT calculations for the Electronic Structure Characterization of Conjugated Polymers

In the last three decades, there has been a broad academic and industrial interest in conjugated polymers as semiconducting materials for organic electronics. Their applications in polymer light-emitting diodes (PLEDs), polymer solar cells (PSCs), and organic field-effect transistors (OFETs) offer opportunities for the resolution of energy issues as well as the development of display and information technologies1. Conjugated polymers provide several advantages including low cost, light weight, good flexibility, as well as solubility which make them readily processed and easily printed, removing the conventional photolithography for patterning2. A large library of polymer semiconductors have been synthesized and investigated with different building blocks, such as acenes or thiophene and derivatives, which have been employed to design new materials according to individual demands for specific applications. To design ideal conjugated polymers for specific applications, some general principles should be taken into account, including (i) side chains (ii) molecular weights, (iii) band gap and HOMO and LUMO energy levels, and (iv) suited morphology.3-6 The aim of this study is to elucidate the impact that substitution exerts on the molecular and electronic structure of π-conjugated polymers with outstanding performances in organic electronic devices. Different configurations of the π-conjugated backbones are analyzed: (i) donor-acceptor configuration, (ii) 1D lineal or 2D branched conjugated backbones, and (iii) encapsulated polymers (see Figure 1). Our combined vibrational spectroscopy and DFT study shows that small changes in the substitution pattern and in the molecular configuration have a strong impact on the electronic characteristics of these polymers. We hope this study can advance useful structure-property relationships of conjugated polymers and guide the design of new materials for organic electronic applications.

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.

Effect of organic amendments on the afforestation performance of plant species on degraded semiarid conditions

Vegetation plays a fundamental role in soil conservation, so it is common to consider an increase in vegetation cover as one of the techniques to mitigate the effects of desertification in Mediterranean forest environments. There are two factors limiting the establishment and growth of seedlings in dry environments: (i) an excessive radiation and, (ii) the limited availability of water during the summer drought. During an afforestation plan, soil preparation is always necessary to reduce sapling mortality. The goal of this study was to analyze the effect of various organic amendments on soil according to chemical and hydrological properties, and to assess the effects of these parameters on an afforestal proposal under Mediterranean climate conditions. Five amendments were applied in an experimental set of plots: straw mulching (SM); mulch with chipped branches of Aleppo Pine (PM); TerraCotten hydroabsobent polymers (HP); sewage sludge (RU); sheep manure (SH) and control (C). Plots were afforested following the same spatial pattern, and amendments were mixed with the soil at the rate 10 Mg ha -1 . Under bare soil conditions (C), most of mortalities occurred during the summer period of the first year. A substantial positive effect of SM, PM and HP on the survival rates have been clearly observed. Conversely, when the soil was amended with SH, the survival rate quickly decreased or remained more or less constant regarding to C. In this study, the lack of differences on chemical properties indicates that there may exist other reasons to justify the differences that were found in the pattern of vegetation. However, regarding to the hydrological properties some differences have been found. In C, soils were registered below the wilting point during 4 months a year, and therefore, in the area of water unusable by plants. These months were coinciding with the summer Mediterranean drought and can justify the high mortality found on plants. Conversely, in SM, PM and HP, soil moisture remained below the wilting point less period than C and, the plant available water was also higher. In these treatments, the survival sapling rates measured were the highest. SH showed water holding capacity slightly more limited than C. For this treatment, the survival sapling rates measured were the lowest. In conclusion, from a land management standpoint, the PM, SM and HP have been proved as a significant method to reduce sapling mortality rates during the Mediterranean summer drought.