In order to elucidate room-temperature ͑RT͒ ferromagnetism ͑FM͒ in ZnO, we have analyzed a multitude of experimental publications with respect to the ratio of grain-boundary ͑GB͒ area to grain volume. FM only appears if this ratio exceeds a certain threshold value s th . Based on these important results nanograined pure and Mn-doped ZnO films have been prepared, which reveal reproducible RT FM and magnetization proportional to the film thickness, even for pure ZnO films. Our findings strongly suggest that grain boundaries and related vacancies are the intrinsic origin for RT ferromagnetism.

Dense nanograined pure and Mn-doped Zn1−xMnxO polycrystals with x ranging between 0.1–34 at. % were synthesized by the wet chemistry method from butanoate precursors. Pure and Mn-doped ZnO possesses ferromagnetic properties only if the ratio of grain boundary (GB) area to grain volume sGB exceeds a certain threshold value sth. The polycrystals in this work satisfy these conditions and, therefore, reveal ferromagnetic properties. The observed dependence of saturation magnetization on the Mn concentration shows an unexpected nonmonotonous behavior. The increase in saturation magnetization at low Mn concentration is explained by the injection of divalent Mn2+ ions and charge carriers into pure ZnO. The decrease in saturation magnetization between 0.1 and 5 at. % Mn can be explained by the increase in the portion of Mn3+ and Mn4+ ions. The second increase in saturation magnetization above 5 at. % Mn is explained by the formation of multilayer Mn segregation layer in ZnO GBs. The shape of the dependence of saturation magnetization on Mn concentration is different for the Mn-doped nanograined ZnO manufactured by different methods. It is most probably controlled by the topology of GB network (ferromagnetic GB foam) in the ZnO polycrystals.

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