Bi-directional Kirkendall effect in coaxial microtube nanolaminate assemblies fabricated by atomic layer deposition.

The solid-state reaction within a coaxial Al2O3/ZnO/Al2O3 multilayered microtubular structure can be used to prepare discrete microtube-in-microtube ZnAl2O4 spinel assemblies through a Kirkendall void production mechanism at 700 degrees C. In contrast with previous studies of the nanoscale Kirkendall effect, the reaction observed here proceeds through a bi-directional vacancy diffusion mechanism wherein ZnO species diffuse into inner- and outer-Al2O3 concentric layers, thereby resulting in vacancy supersaturation and void production between two isolated spinel microtubes. Low-temperature atomic layer deposition (ALD) of Al2O3 and ZnO enables the fabrication of complex coaxial multilayered microtubes with precise control of the starting film thicknesses and relative composition. When a molar excess of ZnO is present between two Al2O3 layers, electron microscopy images reveal incomplete ZnO consumption after annealing at 700 degrees C. At higher initial Al2O3 concentrations, however, complete reaction with ZnO is observed, and the size of the Kirkendall gap between isolated spinel microtubes appears to be directly influenced by the thickness of the intermediate ZnO layer.