Role of donor defects in stabilizing room temperature ferromagnetism in (Mn, Co) co-doped ZnO nanoparticles

We report the effects of co-doping ZnO with Co and Mn in an n-type environment on ferromagnetism (FM). Two sets of samples, Zn0.95-xCo0.04MnxO (0.000 ≤ x ≤ 0.02) and Zn0.95-yCoyMn0.04O (0.000 ≤ y ≤ 0.02), were synthesized by the chemical route with oxygen vacancies introduced via annealing in a forming gas (reducing the atmosphere). In addition to the magnetization, the particles were characterized by x-ray diffraction, diffuse reflectance spectroscopy and x-ray absorption near-edge emission spectroscopy. The Co and Mn ions were determined to be in the + 2 state in a tetrahedral symmetry, with no evidence of metallic Co or Mn. We find that while a purely Mn-doped sample exhibits weak FM at room temperature, the general effect of Mn as a co-dopant with Co, in an n-type environment, is to decrease the moment strongly. All of our results can be systematically explained within the context of defect mediated FM in these wide bandgap semiconductors, where the coincidence of the spin-split-impurity (defect) band states and the 3d states leads to the development of a net moment alongside the formation of spin polarons. (paper)