Low wavenumber Raman scattering of the acoustic vibrational modes of nanoparticles was used for the determination of the size distribution of free dielectric and semiconductor nanoparticles and of nanoparticles embedded in matrices. The theoretical background as well as the experimental results for the free noninteracting nanoparticles and for the nanoparticles in strong interaction with a surrounding matrix is described. The approach is based on a 1/n dependence of the Raman light-to-vibration coupling coefficient and on the fact that each nanocrystallite of diameter D vibrates with its eigenfrequency n ∼ 1/D. The model calculation considers the inhomogeneous broadening due to contribution from the particles of different sizes, and homogeneous broadening due to interaction of particles with the matrix. The comparison of the calculated and experimental low wavenumber Raman spectra are presented for SnO 2 , TiO 2 and CdS free nanoparticles and TiO 2 , CdS x Se 1−x and HfO 2 nanoparticles embedded in a glass matrix. The particle-size distributions determined by Raman scattering were compared to those found by TEM measurements. Raman spectroscopy proved to be a simple, fast and reliable method for size-distribution measurements. By an inverse procedure, starting from the Raman spectra and known particle-size distribution, a new method for the determination of the mean sound velocities of longitudinal and transverse phonons of nanoparticles is described.
The influence of the addition of 1 mol% Tm2O3 on the nanocrystallization of LaF3 in a glass of composition 55SiO2–20Al2O3–15Na2O–10LaF3 (mol%) has been studied. Tm2O3 affects the phase separation in the glass and delays the onset of crystallization with respect to the undoped glass. Additionally, the maximum LaF3 crystal size is slightly greater than that in the undoped glass–ceramics. The microstructural and compositional changes in the glass matrix have been studied using several techniques, including viscosity, dilatometry, X‐ray and neutron diffraction (XRD, ND), quantitative Rietveld refinement, transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and Raman spectroscopy. Photoluminescence measurements indicate that the Tm3+ ions are distributed between the glassy matrix and LaF3 crystals. Eu2O3 has been used as structure probe and part of the Eu3+ ions are reduced to Eu2+ when incorporated in the LaF3 nano‐crystals. Up‐conversion spectra under IR‐excitation show a higher intensity of the blue emission in the Tm‐doped glass–ceramic compared with that in the glass.
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