Formation and stability of crystalline and amorphous Al2O3 layers deposited on Ga2O3 nanowires by atomic layer epitaxy

Abstract

Although the crystalline α and γ phases are the most stable forms of alumina, small-diameter (<6 nm) nanoparticles are known to be completely amorphous, due to the surface energy being correspondingly lower for the less stable non-crystalline phase. Al2O3 films with a thickness of 5 nm grown by low temperature (200 °C) atomic layer deposition (ALD) on small-diameter (<20 nm) Ga2O3 nanowires (NWs), however, are identified by transmission electron microscopy as belonging to the α, γ, and possibly θ crystalline phases of Al2O3, while films deposited on larger diameter (>20 nm) NWs are found to be amorphous. Indeed, until recently, all Al2O3, films deposited by low-temperature ALD using trimethylaluminum and water have been reported to be amorphous, regardless of film thickness or substrate. The formation of a crystalline ALD film can be understood in terms of the energetics of misfit dislocations that maintain the registry between the ALD film and the NW substrate, as well as the influence of strain and surface energy. The decreasing energy of co-axial misfit dislocations with NW diameter results in a corresponding decrease in the contribution of the Al2O3/Ga2O3 interface to the free energy, while the interfacial energy for an amorphous film is independent of the NW diameter. Therefore, for NW cores of sufficiently small diameter, the free energy contribution of the Al2O3/Ga2O3 interface is smaller for crystalline films than for amorphous films, thereby favoring the formation of crystalline films for small-diameter NWs. For ALD Al2O3 films of 10 nm thickness deposited on small-diameter Ga2O3 NWs, however, only the first 5 nm of the ALD film is found to be crystalline, possibly due to well-established kinetic limitations to low temperature epitaxial growth.