Heterogeneous growth of continuous ZIF-8 films on low-temperature amorphous silicon

Thin amorphous silicon films, deposited at low temperature by Inductively Coupled Plasma Chemical Vapor Deposition, have, for the first time, been employed as substrate for ZIF-8 growth. In order to investigate the role of the surface chemistry on the nucleation process, films have also been grown on other silicon-based substrates such as H-terminated Si(1 0 0), SiO 2 and quartz. Film preparation was carried out at room temperature using a mixed Zn nitrate and imidazole solution in methanol or ethanol. Using methanol, continuous ZIF-8 films were obtained on amorphous Si and H-terminated Si(1 0 0), while less homogeneous films were formed on the other surfaces. In ethanol, slower growth rates occurred and thinner films, compared to the ones in methanol, were obtained. These slower rates highlight the different effects of the four surfaces on the growth process. These differences have been related to the silanol density of the surfaces and to the Lewis basic strength which affect imidazole moiety deprotonation. H-terminated Si(1 0 0) and amorphous Si turned out to be the most reactive surfaces, whereas on quartz and, especially, on SiO 2 reactivity was much lower. Experimental results have been validated by the DFT modelling of the proton exchange, which takes place between the imidazole group and the surface. Finally, the VOCs adsorption capability of ZIF-8 films grown on amorphous silicon has been evaluated through temperature desorption experiments.