We report on an inelastic (Raman) light scattering study of the local structure of amorphous GeTe films. A detailed analysis of the temperature-reduced Raman spectra has shown that appreciable structural changes occur as a function of temperature. These changes involve modifications of atomic arrangements such as to facilitate the rapid amorphous-to-crystal transformation, which is the major advantage of phase-change materials used in optical data storage media. A particular structural model, supported by polarization analysis, is proposed being compatible with the experimental data as regards both the structure of a-GeTe and the crystallization transition. The remarkable difference between the Raman spectrum of the crystal and the glass can thus naturally be accounted for.
The polymer chain conformation under confinement and the morphology of the nanohybrid materials are investigated in hydrophilic polymer/layered silicate nanocomposites. A series of poly(ethylene oxide)/sodium montmorillonite hybrids were synthesized utilizing melt intercalation with compositions covering the complete range from pure polymer to pure clay. Intercalated nanocomposites with mono- and bilayers of PEO chains are obtained in all cases. The intercalated chains as well as the ones adsorbed on the outer surface of the clay particles remain purely amorphous; their conformation, however, exhibits different characteristics from those of the amorphous neat polymer melt. It is only for compositions where a large amount of excess polymer exists outside the completely full galleries that the polymer crystallinity is recovered.
For the case example of GeTe, we demonstrate that the use of techniques that probe the average structure may lead to misleading conclusions regarding the nature of phase change. GeTe is a narrow band-gap semiconductor and a ferroelectric with the simplest conceivable structure that-according to previous studiesundergoes a ferroelectric-to-paraelectric displacive phase transition at ϳ705 K. In this work, we provide direct experimental evidence that, contrary to the existing paradigm, the local distortion remains essentially unchanged with temperature and argue that the previous conclusion about the displacive nature of the ferroelectric-to-paraelectric transition was due to misinterpretation of Bragg diffraction, a technique that is only sensitive to the average structure and does not "see" random local distortions. The reported results have far-reaching implications for other materials exhibiting displacive phase transitions where conclusions have been reached based on results obtained using averaging techniques.
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