We demonstrate the newly developed technique Photomodulated Rayleigh Scattering spectroscopy in order to probe the electronic band structure of single semiconductor nanowires. We show that both the electronic transition energies and nanowire diameter can be measured simultaneously and with high accuracy in a single non-destructive measurement. We demonstrate our results for zincblende GaAs as well as wurtzite InP nanowires where we probed the band gaps and transition energies at both room and low temperatures. This technique should advance the study of optical properties of single nanowires as well as other types of nanostructures.
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