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Optical and structural experiments have been carried out on Si/ZnO thin films modified with ultra-thin gold layers of different thicknesses. ZnO was produced via Atomic Layer Deposition (ALD) and Au via Physical Vapor Deposition (sputtering). The structural properties of nanostructures were studied by XRD and AFM. Optical characterization was performed by absorbance, photoluminescence (PL) and spectroscopic ellipsometry (SE). A transition from cluster-to-thin films with the increase of Au thickness has been revealed from an analysis of optical and structural parameters. The analysis of optical features of the system has shown that slight changes of the localized plasmon absorption peaks in spectra make a significant contribution to complex refractive index of gold film and, as a result, leads to a strong enhancement of UV PL peak in the ZnO layer. The mechanism of the tailoring of ZnO optical features changes …