An Instantaneous Recombination Rate Method for the Analysis of Interband Recombination Processes in ZnO Crystals

Time-resolved photoluminescence (TRPL) analysis is often performed to assess the qualitative features of semiconductor crystals using predetermined functions (e.g., double- or multi-exponentials) to fit the decays of PL intensity. However, in many cases—including the notable case of interband PL in direct gap semiconductors—this approach just provides phenomenological parameters and not fundamental physical quantities. In the present work, we highlight that within a properly chosen range of laser excitation, the TRPL of zinc oxide (ZnO) bulk crystals can be described with excellent precision with second-order kinetics for the total recombination rate. We show that this allows us to define an original method for data analysis, based on evaluating the “instantaneous” recombination rate that drives the initial slope of the decay curves, acquired as a function of the excitation laser fluence. The method is used to fit experimental data, determining useful information on fundamental quantities that appear in the second-order recombination rate, namely the PL (unimolecular) lifetime, the bimolecular recombination coefficient, the non-radiative lifetime and the equilibrium free-carrier concentration. Results reasonably close to those typically obtained in direct gap semiconductors are extracted. The method may represent a useful tool for gaining insight into the recombination processes of a charge carrier in ZnO, and for obtaining quantitative information on ZnO excitonic dynamics.