Emission-energy dependence of ultrafast P-emission decay in ZnO from bulk to nanofilm

We have performed time-resolved photoluminescence (PL) spectroscopy for ZnO thin films with thicknesses of 90, 460, and 2800 nm under intense excitation condition. We clearly observed the P emission due to inelastic exciton-exciton scattering. It was found that, in the 460- and 2800-nm thick samples, the decay time of the P emission considerably depends on the detection energy inversely proportional to the group velocity of the polariton in a bulk crystal with each factor of proportionality. In contrast, the energy dependence is less remarkable in the 90-nm thick sample. The decay times are basically shortened with a decrease in the film thickness. The thickness dependence of the P-emission-decay profiles is explained by considering the crossover from the polariton modes in the 2800-nm thick sample (bulk-like film) to the exciton-/photon-like modes in the 90-nm thick sample (nanofilm).