MgH_2 thin films deposited by one-step reactive plasma sputtering

摘要

The morphology, crystal structure, hydrogen content, and sorption properties of magnesium hydride thin films prepared by reactive plasma-assisted sputter deposition were investigated. Few micrometers-thick films were deposited on Si and SiO_2/Si substrates, at low pressure (0.4 Pa) and close to room temperature using (Ar + H_2) plasma with H_2 fraction in the range 15-70%. The microstructure and hydrogen content of the films are closely related to the surface temperature and hydrogen partial pressure during the deposition process. Operating in pulsed-plasma mode allows the hydrogenation rate of the MgH_2 thin film to top up to 98%, thereby producing a nearly fully hydrogenated film in a single-step process. The positive effect of the pulsed process is explained by the significant decrease in the whole energy flux incident on the surface and the favourable impact of the transient process for the rearrangement/relaxation of the materials. As for the hydrogen storage properties, desorption experiments and cycling of the films show the destabilizing effect of Mg_2Si formation at the interface between the film and the Si substrate resulting in a drastically increased desorption kinetics compared to less reactive SiO_2 substrate. However, the reaction is regrettably not reversible upon hydrogenation and the hydrogen storage capacity is consequently reduced upon cycling. Nevertheless, the deposition process carried out on inert substrates would offer true potential for reversible storage. Finally, our experimental results, which show the possibility to preferentially grow the metastable medium pressure γ-MgH_2 phase, open possibilities for the synthesis of more complex metastable phases such as magnesium-based ternary compounds.