Density functional theory study of first-layer adsorption of ZrO2 and HfO2 on Ge(1 0 0)

Density functional theory was used to performed a survey of transition metal oxide (MO2 = ZrO2, HfO2) ordered molecular adsorbate bonding configurations on the Ge(1 0 0)-4 × 2 surface. Surface binding geometries of metal-down (O–M–Ge) and oxygen-down (M–O–Ge) were considered, including both adsorbate and displacement geometries of M–O–Ge. Calculated enthalpies of adsorption show that bonding geometries with metal–Ge bonds (O–M–Ge) are essentially degenerate with oxygen–Ge bonding (M–O–Ge). Calculated electronic structures indicate that adsorbate surface bonding geometries of the form O–M–Ge tend to create a metallic interfaces, while M–O–Ge geometries produce, in general, much more favorable electronic structures. Hydrogen passivation of both oxygen and metal dangling bonds was found to improve the electronic structure of both types of MO2 adsorbate systems, and induced the opening of true semiconducting band gaps for the adsorbate-type M–O–Ge geometries. Shifts observed in the DOS minima for both O–M–Ge and M–O–Ge adsorbate geometries are consistent with surface band bending induced by the adsorbate films, where such band bending extends much further into the Ge substrate than can be modeled by the Ge slabs used in this work.