Effect of polycrystallinity on the optical properties of highly oriented ZnO grown by pulsed laser deposition

We report the results of photoluminescence and reflectance measurements on highly c-axis oriented polycrystalline ZnO grown by pulsed laser deposition. The samples measured were grown under identical conditions and were annealed in-situ at various temperatures for 10-15 min. The band-edge photoluminescence spectra of the material altered considerably with an increase in grain size, with increased free exciton emission and observable excitonic structure in the reflectance spectra. The green band emission also increased with increasing grain size. A deformation potential analysis of the effect of strain on the exciton energy positions of the A- and B-excitons demonstrated that the experimental exciton energies could not be explained solely in terms of sample strain. We propose that electric fields in the samples due to charge trapping at grain boundaries are responsible for the additional perturbation of the excitons. This interpretation is supported by theoretical estimates of the exciton energy perturbation due to electric fields. The behaviour of the green band in the samples provides additional evidence in favour of our model.