If the medium surrounding a nano-grain does not support the vibrational wavenumbers of a material, the optical and acoustic phonons get confined within the grain of the nanostructured material. This leads to interesting changes in the vibrational spectrum of the nanostructured material as compared to that of the bulk. Absence of periodicity beyond the particle dimension relaxes the zone-centre optical phonon selection rule, causing the Raman spectrum to have contributions also from phonons away from the Brillouin-zone centre. Theoretical models and calculations suggest that the confinement results in asymmetric broadening and shift of the optical phonon Raman line, the magnitude of which depends on the widths of the corresponding phonon dispersion curves. This has been confirmed for zinc oxide nanoparticles. Microscopic lattice dynamical calculations of the phonon amplitude and Raman spectra using the bond-polarizability model suggest a power-law dependence of the peak-shift on the particle size. This article reviews recent results on the Raman spectroscopic investigations of optical phonon confinement in several nanocrystalline semiconductor and ceramic/dielectric materials, including those in selenium, cadmium sulphide, zinc oxide, thorium oxide, and nano-diamond. Resonance Raman scattering from confined optical phonons is also discussed.

Effect of confinement is investigated on optical phonons of different symmetries in the nanoparticles of zinc oxide with wurtzite structure using Raman spectroscopy. An optical phonon confinement model is used for calculating the theoretical line shapes, which exhibit different asymmetric broadening and shifts, depending on the symmetries of phonon and their dispersion curves. The best fit to the data is found for particle diameters consistent with those estimated using x-ray diffraction.

Raman spectroscopic investigations of phonons of different symmetries in anatase TiO2 nanocrystals synthesized by the sol−gel method are carried out. Out of six Raman active phonons, the line shapes of two Eg modes and one B1g mode have been analyzed quantitatively to distinguish between the contributions of laser-induced local heating, phonon confinement effects, and defects to the line broadening. The line shape asymmetry arising from confinement of optical phonons in the 397 cm−1 B1g mode is found to be of opposite nature than those in the 144 and 639 cm−1 Eg modes. This arises due to the negative dispersion of the 397 cm−1 B1g phonon dispersion curve. The measured spectra show larger broadening than those predicted by a phonon confinement model. The excess broadening, attributed to intrinsic defects, is found to be least for the 144 cm−1 Eg mode and largest for the 397 cm−1 B1g mode. In addition, finite laser power of the excitation wavelength is found to raise the temperature of the nanocrystals, with heating being maximum for the smallest size nanocrystals.

Raman spectroscopic measurements on negative-thermal-expansion (NTE) material zirconium tungstate Zr(WO4)2 at 20 K over the complete range of phonon frequencies yield 39 out of the predicted 54 optical phonons. The modes are assigned as lattice modes, and translational, librational and internal modes of the WO4 ion. High-pressure measurements in a diamond anvil cell (DAC) have revealed that in addition to the low-frequency rigid-unit modes (RUMs) several other phonons, including the bending modes of the WO4 ion, also exhibit negative Grüneisen parameter in the cubic phase. In the high-pressure orthorhombic phase above 0.3 GPa splitting of phonon modes is found to be consistent with the lowering of symmetry. Pressure-induced amorphization in this system at 2.2±0.3 GPa is argued to arise because a pressure-induced decomposition of the compound into a mixture of ZrO2 and WO3 is kinetically constrained. The temperature dependence of specific heat and thermal expansion coefficient are calculated and compared with reported results. In contrast to earlier models and calculations, which considered only the phonons below 8 meV (64 cm-1) to explain the NTE, it is shown that modes much higher than 8 meV also contribute significantly to NTE in this material.

Dilute aqueous polystyrene suspensions are found to exhibit a novel vapor-liquid condensation. Upon de-ionization, weakly interacting homogeneous suspensions below a critical particle concentration condense into a concentrated phase with liquidlike order and a dilute vapor phase. This phenomenon strongly suggests net attraction between particles at interparticle separation several times the particle diameter. The present results are understood on the basis of an effective interparticle model potential.

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