Gas phase nanoparticle production, manipulation and deposition is of primary importance for the synthesis of nanostructured materials and for the development of industrial processes based on nanotechnology. In this review we present and discuss this approach, introducing cluster sources, nanoparticle formation and growth mechanisms and the use of aerodynamic focusing methods that are coupled with supersonic expansions to obtain high intensity cluster beams with a control on nanoparticle mass and spatial distribution. The implication of this technique for the synthesis of nanostructured materials is also presented and applications are highlighted.
A systematic study of the shift and linewidth of the Eg Raman peak at 144 cm−1 of anatase TiO2 nanopowders, produced by a flame aerosol technique, is here presented. The analysis was performed as a function of the crystal domain size and of the degree of oxidation. In the nanopowders, a clear contribution of the stoichiometry defects to the peak shift was evidenced, while the peak width seems to be less affected by the oxygen content. The Raman peak behavior due to size reduction has been interpreted in the framework of a phonon quantum confinement model. A critical review of the different approaches to this model, adopted in the literature to explain the behavior of the anatase Raman spectra as a function of the domain size, is presented. In particular, the hypothesis of a three-dimensional isotropic model for the dispersion relations is discussed. This analysis evidences general limits in the application of the phonon confinement model to the study and characterization of nanoparticles and nanostructured materials, showing how an uncritical use of the confinement theory can yield distorted results
Nanostructured carbon films produced by supersonic cluster beam deposition have been studied by in situ Raman spectroscopy. Raman spectra show the formation of a sp2 solid with a very large fraction of sp-coordinated carbyne species with a long-term stability under ultrahigh vacuum. Distinct Raman contributions from polyyne and cumulene species have been observed, as well as different stabilities under gas exposure. Our experiments confirm theoretical predictions and demonstrate the possibility of producing a carbyne-rich pure carbon solid. The stability of the sp2-sp network has important implications for astrophysics and for the production of novel carbon-based systems.
Ab-initio calculations within Density Functional Theory combined with experimental Raman spectra on cluster-beam deposited pure carbon films provide a consistent picture of sp-carbon chains stabilized by sp 3 or sp 2 terminations, the latter being sensitive to torsional strain. This unexplored effect promises many exciting applications since it allows one to modify the conductive states near the Fermi level and to switch on and off the on-chain π-electron magnetism.
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