Dual-donor (Zn(i) and V(O)) mediated ferromagnetism in copper-doped ZnO micron-scale polycrystalline films: a thermally driven defect modulation process.

The paper reports robust ferromagnetic Cu-doped ZnO micron-scale polycrystalline films via spin-coating using high-quality doped nanocrystals. A reliable magnetic response is observed in the 900 °C vacuum annealed film without any ferromagnetic contribution from other sources. Post-annealing treatment in terms of atmosphere and temperature can control the proportion of oxygen vacancies (V(O)) and zinc interstitials (Zn(i)) defects and further help to precisely regulate defect-related ferromagnetic behavior. Complex charge transfer processes derived from dual-donor (Zn(i) and V(O)) to Cu acceptor are revealed by photoluminescence (PL) and electron paramagnetic resonance (EPR) spectra. Based on the above, specific charge transfer (CT)-type Stoner splitting and indirect double-exchange mechanisms are proposed to understand the ferromagnetic origin. The improvable FM performance and annealing-specific modulation further indicate that a thermal driven process can delicately tailor the magnetic property of the transition metal ion-doped ZnO system.