Published online by Cambridge University Press: 10 February 2011
It is shown that the solid state equilibrium configuration of ZnO grain boundaries saturated with Bi-doping is a nanometer-thick amorphous film. Polycrystalline ZnO samples doped with Bi2O3 were studied using high resolution transmission electron microscopy (HRTEM) and dedicated scanning transmission electron microscopy (STEM). Samples were equilibrated below the eutectic temperature (Teutectic = 740°C) and at 1 atmosphere pressure, starting from three different initial states: one was cooled from above the eutectic temperature; a second was processed entirely below the eutectic temperature; and the third was de-segregated by applying high pressure (1 GPa) followed by annealing at 1 atmospheric pressure. In all instances, ZnO grain boundaries contain an amorphous film 1.0–1.3 ran in thickness, corresponding to a Bi excess equivalent to approximately one monolayer.