'Sandwich'-like hybrid ZnO thin films produced by a combination of atomic layer deposition and wet-chemistry using a mercapto silane as single organic precursor

This study describes a straightforward preparation of hybrid organic-inorganic thin films containing a stable 'sandwich'-like structure of two atomic layer deposited (ALD) ZnO layers separated by a thin organosilane phase, which is built from a single organic component (3-mercaptopropyl)trimethoxysilane (MPTMS). Grafting of MPTMS on the first ALD ZnO layer was performed in solution and driven by the strong affinity of the terminal thiol functionality (-SH) towards ZnO. We demonstrate that under different reaction conditions, either MPTMS monolayers are prepared or a 5 nm thick cross-linked polymeric network is formed due to the self-condensation of silane, which covers the ALD ZnO surface. This film served as a soft template for the nucleation of an ALD ZnO top layer by creation of S-Zn and Si-O-Zn bonds at the upper interface, as confirmed by XPS measurements. An increase in surface roughness, as compared to the initial ZnO film, is observed after removal of the organic layer from the hybrid structure by calcination, which is accompanied by an improvement in UVA photocatalytic activity towards the degradation of methyl orange dye. Thus, MPTMS can be used as a sacrificial agent in combination with low temperature ALD processes for building rougher and photocatalytically efficient ZnO coatings.