Complexes of some transition-metal salts and emeraldine base of polyaniline were synthesized and characterized by UV-vis-IR spectroscopy, morphology studies, and conductivity measurements. Depending on the inorganic salt used, two extreme cases of doping were distinguished. The first regime of doping resulted in films of grained morphology, with a relatively high conductivity of up to 10 -1 S/cm and electronic absorption spectra showing features of both pseudo-protonic doping and oxidation of the polymer backbone. IR absorption spectra were consistent with interaction of the benzenoid groups of the polymer with metal cations. The second regime of doping resulted in a smoother film morphology without grains, but with poor conductivity, normally not more than 10 -3 S/cm, and higher solvent concentration in the film. Electronic and IR absorption spectra were consistent with pseudoprotonation of the polymer backbone. On the basis of the obtained data, a model of the macromolecular polyaniline-transition-metal salt complex is proposed.
Nanorods and nanotubes as photoactive materials as well as electrodes in photovoltaic cells have been launched a few years ago, and the literature in this field started to appear only recently. The first steps have shown both advantages and disadvantages of their application, and the main expectation associated with their effective charge transport has not been realized completely. This article aims to review both the first and the recent tendencies in the development and application of nanorod and nanotube materials in photovoltaic cells. Two basic techniques of synthesis of crystalline nanorod structures are described, the top-down and bottom-up approaches, respectively. Design and photovoltaic performance of solar cells based on various semiconductor nanorod materials, such as TiO2, ZnO, CdS, CdSe, CdTe, CuO, Si are presented and compared with respective solar cells based on semiconductor nanoparticles. Specific of synthesis and application of carbon nanotubes in photovoltaic devices is also reviewed.
The exciton, an excited electron–hole pair bound by Coulomb attraction, plays a key role in photophysics of organic molecules and drives practically important phenomena such as photoinduced mechanical motions of a molecule, photochemical conversions, energy transfer, generation of free charge carriers, etc. Its behavior in extended π-conjugated molecules and disordered organic films is very different and very rich compared with exciton behavior in inorganic semiconductor crystals. Due to the high degree of variability of organic systems themselves, the exciton not only exerts changes on molecules that carry it but undergoes its own changes during all phases of its lifetime, that is, birth, conversion and transport, and decay. The goal of this review is to give a systematic and comprehensive view on exciton behavior in π-conjugated molecules and molecular assemblies at all phases of exciton evolution with emphasis on rates typical for this dynamic picture and various consequences of the above dynamics. To uncover the rich variety of exciton behavior, details of exciton formation, exciton transport, exciton energy conversion, direct and reverse intersystem crossing, and radiative and nonradiative decay are considered in different systems, where these processes lead to or are influenced by static and dynamic disorder, charge distribution symmetry breaking, photoinduced reactions, electron and proton transfer, structural rearrangements, exciton coupling with vibrations and intermediate particles, and exciton dissociation and annihilation as well.
An excimer in J-aggregates has been often considered as a self-trapped exciton originating from the free exciton excited on the same aggregate and relaxed through interaction with vibronic modes. Here we show that other types of excimers due to intermolecular off-diagonal interactions can be observed in J-aggregates of thiamonomethinecyanine dyes. These excimers arise owing to free excitons too, but they possess a longer formation time of more than 100 ps, indicating migration of free excitons to the excimer formation site, where they interact with a guest species in the ground state. Formation of the excimers occurs in solutions as a power law of concentration with an exponent of 1.5, showing that an excited aggregate should be twice longer than a ground-state guest species, consistent with the exciton coherence length of four molecules versus one dimer, respectively. Unlike the self-trapped exciton, lower temperatures lead to significant suppression of the observed excimer emission.
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