Thermodynamic Stability of Intergranular Amorphous Films in Bismuth‐Doped Zinc Oxide

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Abstract
It is shown that the solid‐state equilibrium configuration of Bi‐doped ZnO grain boundaries is a nanometer‐thick amorphous film. Polycrystalline Bi‐doped ZnO was investigated using high‐resolution transmission electron microscopy (HRTEM) and scanning transmission electron microscopy (STEM). The equilibrium state below the eutectic temperature and at 1 atm total pressure was approached from three different routes: samples were cooled from above the eutectic temperature (Teutectic= 740°C), processed entirely below the eutectic temperature, and desegregated by high applied pressure (1 GPa) followed by annealing at ambient pressure to restore segregation. In all instances, the final state is an amorphous intergranular film 1.0‐1.5 nm in thickness. The results show that a thin intergranular film in this system has lower free energy than the crystal‐crystal grain boundary. The implications of these results for creation of electrically active grain boundaries in zinc oxide varistors are discussed.