The synthesis of MLD-derived mesoporous ZnO with 20% of porosity is demonstrated and studied by advanced in situ characterization techniques.

Deriving mesoporous ZnO from calcinated, molecular layer deposited (MLD) metal-organic hybrid thin films offers various advantages, e.g., tunable crystallinity and porosity, as well as great film conformality and thickness control. However, such methods have barely been investigated. In this contribution, zinc-organic hybrid layers were for the first time formed via a three-step MLD sequence, using diethylzinc, ethanolamine, and maleic anhydride. These zinc‑organic hybrid films were then calcinated with the aim of enhancing the porosity of the obtained ZnO films. The saturation curves for the three-step MLD process were measured, showing a growth rate of 4.4 ± 0.2 Å/cycle. After initial degradation, the zinc-organic layers were found to be stable in ambient air. The transformation behavior of the zinc-organic layers, i.e., the evolution of the film thickness and refractive index as well as the pore formation upon heating to 400, 500, and 600 °C were investigated with the help of spectroscopic ellipsometry and ellipsometric porosimetry. The calculated pore size distribution showed open porosity values of 25%, for the sample calcinated at 400 °C. The corresponding expectation value for the pore radius obtained from this distribution was 2.8 nm.

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Organic adlayers on inorganic substrates often contain adatoms, which can be incorporated within the adsorbed molecular species, forming two-dimensional metal–organic frameworks at the substrate surface. The interplay between native adatoms and adsorbed molecules significantly changes various adlayer properties such as the adsorption geometry, the bond strength between the substrate and the adsorbed species, or the work function at the interface. Here, we use dispersion-corrected density functional theory to gain insight into the energetics that drive the incorporation of native adatoms within molecular adlayers based on the prototypical, experimentally well-characterized system of F4TCNQ on Au(111). We explain the adatom-induced modifications in the adsorption geometry and the adsorption energy based on the electronic structure and charge transfer at the interface.