Non-monotonous size-dependent photoluminescence and excitonic relaxations in nanostructured ZnO thin films

The size dependence of room-temperature photoluminescence (PL) accompanied with near-band-edge emission (NBE) and defect-associated green emission (GE) was investigated using high-quality crystalline nanostructured ZnO thin films with grain sizes varying from 29 nm to 2 nm. The size dependence of correlated intensities of the PL bands was pursued in correlation with structural and defect evolution revealed by X-ray photoelectron spectroscopy (XPS) and previous studies of XRD and Raman scattering. In contrast to the influence of thermally activated reconstruction and changes in defect densities, quantum size effects emerging at grain sizes below a critical value, i.e., d(c) ∼ 10 nm were inspected in relation to the observed blueshift in the bandgap and correlated variations in the size dependence of the intensity of NBE and GE. Taking into account the geometry-modelled relative emission efficiency, (i) the observed overall linear size dependence of the relative intensity I(NBE)/I(GE) was consistent with assuming a 1.05 nm-thick GE-active surface layer, and (ii) a local maximum of I(NBE)/I(GE) emerging near grain radius R ≈ 4 nm was identified in relation to the theoretically predicted local minimum in size-dependent exciton radiative lifetime due to the intrinsic quantum nature of excitons confined in ZnO. Our results have provided new insights into non-monotonous size-dependent PL of ZnO, which can benefit future photoelectronic device design by taking advantage of the size-controlled stability of confined excitons in nanostructured thin films and luminescent quantum dots.