A Raman spectral probe on polar w-ZnS nanostructures and surface optical phonon modes in nanowires

In the present study, different morphologies of ZnS nanostructures have been synthesized through a hydrothermal method and their Raman spectral modes are investigated. Raman scattering from surface optical (SO) modes has been seen and identified as a strange shoulder band of LO at 340 cm-1 in nanowires (NWs) with a hexagonal wurtzite structure of ZnS in air medium. X-ray diffraction (XRD) and transmission electron microscopy (TEM) techniques have been used to confirm the hexagonal phase and the modulation in the surface during the growth process, which causes the translational symmetry breaking to activate the SO mode. The appearance of a strong SO mode in NWs has been obviously confirmed by the frequency downshift of the SO mode in different dielectric media with dielectric constants ranging from 1 to 2.56. The SO phonon mode shift due to the roughness in the NW faces has been estimated from the wave-vector that activates the SO mode and an approximate dielectric continuum (DC) model has been used to understand the SO modes in NWs. The surface perturbation responsible for the activation of the SO mode has been estimated and is compared with the surface modulation along the growth axis of the NW from the TEM images.