The combination of Transparent Conductive Oxides, characterized by desired optical and electrical properties, with high barrier (hybrid and inorganic) films deposited onto flexible polymeric substrates, is of considerable importance, in order to improve the efficiency, lifetime and stability of Flexible Electronic Devices. In this work, ZnO thin films were deposited onto flexible high-barrier inorganic/polymeric and hybrid/polymeric substrates by Pulsed DC Magnetron Sputtering, at room temperature and by applying different target power voltages. In-situ and real-time Vis-farUV Spectroscopic Ellipsometry (SE) in the 1.5-6.5 eV spectral region has been employed in order to investigate the growth mechanisms of ZnO onto inorganic (SiO_x, AlO_x) and hybrid barrier films from the early stages of growth. The detailed study of the time evolution of the ZnO films’ thickness and optical properties (energy gap, absorption peaks, conductivity, etc.), in combination to the investigation of their bonding structure by in-situ and real-time FTIR SE (900-3500 cm^-1), has provided important insights on the layer and interface quality, which have a major impact on the final device performance. Finally, X-Ray Diffraction measurements revealed information on the nanostructural properties and on the effect of the applied power on the ZnO films’ crystallinity.

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