Grain boundary layers in nanocrystalline ferromagnetic zinc oxide

The complete solubility of an impurity in a polycrystal increases with decreasing grain size, because the impurity dissolves not only in the crystallite bulk but also on the grain boundaries. This effect is especially strong when the adsorption layers (or the grain boundary phases) are multilayer. For example, the Mn solubility in the nanocrystalline films (where the size of grains is ∼20 nm) is more than three times greater than that in the ZnO single crystals. The thin nanocrystalline Mn-doped ZnO films in the Mn concentration range 0.1–47 at % have been obtained from organic precursors (butanoates) by the “liquid ceramic” method. They have ferromagnetic properties, because the specific area of the grain boundaries in them is greater than the critical value [B.B. Straumal et al., Phys. Rev. B 79, 205206 (2009)]. The high-resolution electron transmission microscopy studies show that the ZnO nanocrystalline grains with the wurtzite lattice are separated by amorphous layers whose thickness increases with the Mn concentration. The morphology of these layers differs greatly from the structure of the amorphous prewetting films on the grain boundaries in the ZnO:Bi₂O₃ system.