Surface Modification of ZnO Nanotubes by Ag and Au Coatings of Variable Thickness: Systematic Analysis of the Factors Leading to UV Light Emission Enhancement.

Surface modification by plasmonic metals is one of the most promising ways to increase the band-to-band excitonic recombination in zinc oxide (ZnO) nanostructures. However, the metal-induced modulation of the UV light emission depends strongly on the production method, making it difficult to recognize the mechanism responsible for charge/energy transfer between the semiconductor and a metal. Therefore, in this study, the ZnO/Ag and Au hybrids were produced by the same, fully controlled experimental approach. ZnO nanotubes (NTs), fabricated by a template-assisted ALD synthesis, were coated by metals of variable mass thickness (1-6.5 nm thick) using the electron beam PVD technique. The deposited Ag and Au metals grew in the form of island films made of metallic nanoparticles (NPs). The size of the NPs and their size distribution decreased, while the spacing between the NPs increased as the mass of the deposited Ag and Au metals decreased. Systematic optical analysis allowed us to unravel a specific role of surface defects in ZnO NTs in the processes occurring at the ZnO/metal interface. The enhancement of the UV emission was observed only in the ZnO/Ag system. The phenomena were tentatively ascribed to the coupling between the defect-related (DL) excitonic recombination in ZnO and the localized surface plasmon resonance (LSPR) at the Ag NPs. However, the enhancement of UV light was observed only for a narrow range of Ag NP dimensions, indicating the great importance of the size and internanoparticle spacing in the plasmonic coupling. Moreover, the enhancement factors were much stronger in ZnO NTs characterized by robust DL-related emission before metal deposition. In contrast to Ag, Au coatings caused quenching of the UV emission from ZnO NTs, which was attributed to the uncoupling between the DL and LSP energies in this system and a possible formation of the ohmic contact between the Au metal and the ZnO.