Temperature dependent photoluminescence processes in ZnO thin films grown on sapphire by pulsed laser deposition

Temperature dependence of the photoluminescence (PL) transitions in the range of 10–300 K was studied for ZnO thin films grown on sapphire by pulsed laser deposition. The low temperature PL spectra were dominated by recombination of donor bound excitons (BX) and their phonon replicas. With increasing temperature, free exciton (FX) PL and the associated LO phonon replicas increased in intensity at the expense of their bound counterparts. The BX peak with line width of ∼6 meV at 10 K exhibited thermal activation energy of ∼17 meV, consistent with the exciton-defect binding energy. The separation between the FX and BX peak positions was found to reduce with increasing temperature, which was attributed to the transformation of BX into the shallower donor bound exciton complexes at consecutive lower energy states with increasing temperature, which are possible in ZnO. The energy separation between FX peak and its corresponding 1-LO phonon replica showed stronger dependence on temperature than that of 2-LO phonon replica. However, their bound counterparts did not exhibit this behavior. The observed temperature dependence of the energy separation between the free exciton and it is LO phonon replicas are explained by considering the kinetic energy of free exciton. The observed PL transitions and their temperature dependence are consistent with observations made with bulk ZnO crystals implying high crystalline and optical quality of the grown films.