Role of interfacial energy and crystallographic orientation on the mechanism of the ZnO + Al2O3 → ZnAl2O 4 solid-state reaction: I. reactivity of films deposited onto the sapphire (110) and (012) faces

The initial steps of the reaction between ZnO and Al2O 3 have been investigated with X-ray diffraction, atomic force microscopy, and X-ray absorption spectroscopy at the Zn-K edge starting from 45 nm thick zincite films deposited onto (110)- and (102)-oriented sapphire single crystals. The formation of nonequilibrium phase(s) has been detected for both orientations. For the (001)zincite ∥ (110)sapphire interface, the rate-determining step is the motion of the interface(s); the growth of the spinel layer is linear with time, with a rate constant k = 1.1(2) × 10-9 cms-1 at 1000 C. At the (110) zincite ∥ (012)sapphire interface, the reaction shows dumped oscillations. The results are discussed along with a comparison with previous results on thinner films to clarify the role of interfacial free energy and crystallographic orientation. © 2013 American Chemical Society.