In this work we develop a simple theory for the green photoluminescence of ZnO quantum dots (QDs) that allows us to understand and rationalize several experimental findings on fundamental grounds. We calculate the spectrum of light emitted in the radiative recombination of a conduction band electron with a deeply trapped hole and find that the experimental behavior of this emission band with particle size can be understood in terms of quantum size effects of the electronic states and their overlap with the deep hole.We focus the comparison of our results on detailed experiments performed for colloidal ZnO nanoparticles in ethanol and find that the experimental evolution of the luminescent signal with particle sizeat room temperature can be better reproduced by assuming the deep hole to be localized at the surface of the nanoparticles. However, the experimental behavior of the intensity and decay time of the signal with temperature can be rationalized in terms of holes predominantly trapped near the center of the nanoparticles at low temperatures being transferred to surface defects at room temperature. Furthermore, the calculated values of the radiative lifetimes are comparable to the experimental values of the decay time of the visible emission signal.We also study the visible emission band as a function of the number of electrons in the conduction band of the nanoparticle, finding a pronounced dependence of the radiative lifetime but a weak dependence of energetic position of the maximum intensity.
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