Structural transformations in nanosized zirconium oxide

Structural properties of calcined ZrO₂ nanopowders having various sizes were investigated by Raman spectroscopy, x-ray diffraction, and high-resolution transmission electron microscopy. For grain sizes of the order of a few nanometers the Raman spectrum is typical of an amorphous material as is the corresponding x-ray diffractogram. As the size of the grains increases, the spectra progressively evolve towards that of a crystallized sample, furthermore, two regimes of growth, vitreous and crystalline, are evidenced. As opposed to the acoustical, the optical branches exhibit a strong discontinuity near the amorphous-crystalline transition. From the analysis of the Raman spectra as a function of size one can infer the phonon dispersion curves that has so far been inaccessible by neutron diffraction. A simple analysis using a classic elastic model shows that the Raman frequencies of the acoustical phonon bands of the nanograins are linearly dependent upon their size.