In polymeric semiconductors, charge carriers are polarons, which means that the excess charge deforms the molecular structure of the polymer chain that hosts it. This results in distinctive signatures in the vibrational modes of the polymer. Here, we probe polaron photogeneration dynamics at polymer:fullerene heterojunctions by monitoring its timeresolved resonance-Raman spectrum following ultrafast photoexcitation. We conclude that polarons emerge within 300 fs. Surprisingly, further structural evolution on t50-ps timescales is modest, indicating that the polymer conformation hosting nascent polarons is not significantly different from that near equilibrium. We interpret this as suggestive that charges are free from their mutual Coulomb potential because we would expect rich vibrational dynamics associated with charge-pair relaxation. We address current debates on the photocarrier generation mechanism at molecular heterojunctions, and our work is, to our knowledge, the first direct probe of molecular conformation dynamics during this fundamentally important process in these materials.

The synthesis and characterization of a series of poly(3-alkyltellurophene)s are described. Polymers are prepared by both electrochemical and Kumada catalyst transfer polymerization methods. These polymers have reasonably high molecular weights (M(n) = 5.4-11.3 kDa) and can be processed in a manner analogous to that of their lighter atom analogues. All examples exhibit red-shifted optical absorption, as well as solid-state organization, as evidenced by absorption spectroscopy and atomic force microscopy. Overall, the synthesis and characterization of these materials open up a wide range of future studies involving tellurium-based polyheterocycles.

Concurrence of the vibrational coherence and ultrafast electron transfer has been observed in polymer/fullerene blends. However, it is difficult to experimentally investigate the role that the excited-state vibrational coherence plays during the electron transfer process since vibrational coherence from the ground- and excited-electronic states is usually temporally and spectrally overlapped. Here, we performed 2-dimensional electronic spectroscopy (2D ES) measurements on poly(3-hexylthiophene) (P3HT) films. By Fourier transforming the whole 2D ES datasets (S(λ1,T̃2,λ3)) along the population time (T̃2) axis, we develop and propose a protocol capable of separating vibrational coherence from the ground- and excited-electronic states in 3D rephasing and nonrephasing beating maps (S(λ1,ν̃2,λ3)). We found that the vibrational coherence from pure excited electronic states appears at positive frequency (+ν̃2) in the rephasing beating map and at negative frequency (-ν̃2) in the nonrephasing beating map. Furthermore, we also found that vibrational coherence from excited electronic state had a long dephasing time of 244 fs. The long-lived excited-state vibrational coherence indicates that coherence may be involved in the electron transfer process. Our findings not only shed light on the mechanism of ultrafast electron transfer in organic photovoltaics but also are beneficial for the study of the coherence effect on photoexcited dynamics in other systems.

Plants tend to attract diseases quite similar to human beings. Pesticides tend to be used to control such diseases. An alternative route, at least as far as damages from insects is concerned, envisions the application of pheromones. These cause a disorientation of male insects so that they are no longer able to locate the females, which finally gives rise to suppression of reproduction. The approach considered in this paper is based on the release of pheromones from polymer carriers, in particular, from nanofibers webs as obtained by electrospinning. These may be distributed across the field quite similar to spider webs. The pheromones are required to be incorporated in sufficiently high concentrations in the nanofibers via electrospinning and to be released from the nanofibers for a sufficiently long time expanding over several weeks to months. Polyamide 6 as well as cellulose acetate was used as a polymer carrier in the investigations reported in this contribution. Studies reveal that fluid pheromones can, in fact, be incorporated in the nanofibers to more than 33 wt%. They may undergo a nanoscalar phase separation within the fibers during electrospinning. Furthermore, thermogravimetric studies revealed via in vitro release studies that the pheromones are released from the nanofibers in a nearly linear fashion over a period covering many weeks. Copyright © 2009 John Wiley & Sons, Ltd.

In this study, a generally applicable strategy is described to manipulate the optical properties of a wide range of polymer semiconductors in the solid state. Blending these materials with a non-conjugated, polar polymer matrix is found to be the processing key to a drastic change and red-shift of the absorption characteristics.