Regulation of Magnetic Behavior and Electronic Configuration in Mn-Doped ZnO Nanorods through Surface Modifications

In this research, Mn-doped ZnO nanorods were synthesized by a solvothermal method and their magnetic behavior was tuned from paramagnetism to ferromagnetism via a change in their surface environment. The structure and electronic configuration of Mn ions were investigated by means of X-ray diffraction and X-ray absorption fine structure to understand the surface-controlled magnetic properties. The surface electronic configuration was studied by Mn L-3,L-2-edge XANES, which were simulated using the ligand field multiplet theory and the ligand-to-metal charge transfer effects. The results pointed out that Mn3+ ions occupy distorted tetrahedronal sites near the surface region and different surface modifications produce changes in the Mn 3d-anion p hybridization strength. A midgap state with strong O-2p character has been also recognized at the O K-edge XANES, and the density of such a state is strongly related to the observed ferromagnetism. This research represents a novel promising route for tuning the magnetic behavior of nano-dilute magnetic semiconductor systems via surface atomic changes.